L. A. Utracki (Auth.) - Commercial Polymer Blends-Springer US (1998) - 1

Commercial Polymer Blends
Commercial
Polymer Blends
L. A. Utracki
National Research Council of Canada,
Industrial Materials Institute,
and
Department of Chemical Engineering,
McGill University,
Montreal, QC,
Canada
runt SPRINGER-SCIENCE+BUSINESS MEDIA, B.V.

First edition 1998
© 1998 L.A. Utracki
Originally published by Chapman & Hall in 1998
Softcover reprint of the hardcover 1st edition 1998
Thomson Science is a division of International Thomson Publishing

Typeset in 9/11 Palatino by Pure Tech India Ltd, Pondicherry, India
Additional material to this book can be downloaded from http://extras.springer.com.
ISBN 978-0-412-81020-6 ISBN 978-1-4615-5789-0 (eBook)
DOI 10.1007/978-1-4615-5789-0
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Contents
Preamble xiii
Abbreviations in Appendices xvii
Part one
Polymer Science and Technology 1
1 Introduction 3
2 Polymer industry 8
2.1 Early period: 1800-1945 8
2.1.1 Modified natural polymers 10
2.1.2 Synthetic rubbers 17
2.1.3 Synthetic thermosetting polymers 19
2.1.4 Synthetic thermoplastic polymers 21
2.2 Growth period: post 1945 28
2.2.1 Commodity resins 28
2.2.2 Engineering resins 39
2.2.3 Specialty polymers 44
3 Development of polymer processing S3

3.1 Mixing 53
3.2 Extrusion 53
3.3 Compression molding 57
3.4 Transfer molding 57
3.5 Injection molding 59
3.6 Blow molding 60
3.7 Rotational molding 61
3.8 Thermoforming 62
4 Development of polymer science 63

4.1 Beginnings 63
4.2 Early polymers and polymerization reactions 66
4.2.1 Molecular weight determination 67
4.2.2 Free volume 69
4.2.3 Viscoelasticity 71
4.2.4 Radical polymerization 72
4.2.5 Anionic polymerization 73
vi Contents
4.2.6 Ziegler-Natta catalysis 73
4.2.7 Single-site metallocene catalysts 74
4.2.8 New polymerization methods and new polymers 76
5 Nomenclature of polymeric systems 78

5.1 Traditional 78
5.2 Copolymers 78
5.3 Non-linear macromolecules and macromolecular assemblies 81
5.4 Polymer blend terminology 81
Part Two
Technical and Economic Rationality for Polymer Blending 83
6 Reasons for, benefits and problems of blending 85

6.1 Compatibilization 86
6.2 Interphase 89
6.3 Compatibilization by addition of a copolymer 93
6.4 Reactive compatibilization 94
7 Morphology 98
7.1 Equilibrium morphology and phase inversion 98
7.2 Flow-imposed morphology 99
7.2.1 Flow-induced dispersion 100
7.2.2 Fibrillation 101
7.2.3 Flow-induced coalescence 102
7.2.4 Interlayer slip 102
7.2.5 Flow-induced encapsulation 102
8 Rheology 104
8.1 Introduction 104
8.2 Single-phase mixtures 104
8.3 Two-phase systems 105
8.4 Microrheology 106
8.5 Concentration dependence of viscosity 108
8.6 Dynamic flow 109
8.7 Compatibilization effects 112
8.8 Time-temperature superposition 114
8.9 Steady-state versus dynamic viscosities 114
8.10 Blend elasticity 115
8.11 Elongational flows 115
8.12 Conclusions 116
9 Development of polymer blends 117

9.1 Economy of blending 117
9.2 Developing commercial blends 118
9.3 Blend performance 122
9.3.1 Mechanical properties 122
9.3.2 Electrically conductive blends 126
9.4 Outline of polymer alloys and blends evolution 127
9.5 Conclusions and outlook 135
Contents vii
Part Three
Commodity Resin Blends 137
10 Styrenics: polystyrene and styrene copolymers 139

10.1 High impact polystyrene and its blends 140
10.1.1 HIPS with EPR 142
10.1.2 HIPS with block copolymers 142
10.2 SBR and blends 143
10.3 PS/PE and PS/modified-PE blends 144
10.3.1 Recycling 146
10.4 PS/acrylics blends 148
10.4.1 Miscible blends 148
10.4.2 Blends with static dissipative properties 151
10.5 ABS and its blends 153
10.5.1 High heat ABS 155
10.5.2 Weatherable ABS 156
10.5.3 Reactive acidified ABS 157
10.5.4 Methacrylate-Butadiene-Styrene copolymers, MBS 158
10.5.5 ABS/PVC blends 159
10.5.6 ABS/PC blends 161
10.5.7 ABS/PA blends 168
10.5.8 ABS/PEST blends 170
10.5.9 ABS/TPU blends 172
10.5.10 ABS/PSF blends 173
10.5.11 ABS/SMA blends 175
10.6 SBS block copolymer blends 176
10.6.1 SBS/SEBS blends with commodity resins 177
10.6.2 SBS/SEBS blends with engineering resins 181
10.6.3 SBS/SEBS blends with specialty resins 188
10.7 PS/PA blends 189
10.8 PS/POM blends 189
10.9 PS/PC blends 189
10.10 PS/polyester blends 190
10.11 PS/PPE blends 191
10.12 PS/PPS blends 193
11 Polyvinylchloride 194
11.1 PVC/NBR blends 195
11.2 PVC/acrylics blends 198
11.3 PVC/elastomer blends 202
11.4 PVC/polyalkene blends 203
11.5 PVC/CPE and PVC/CSR blends 203
11.6 PVC/polyurethane blends 207
11.7 PVC/EVAc and PVC/EVAc-VC blends 207
11.8 PVC/ABS blends 208
11.9 PVC/engineering resin blends 211
11.9.1 Blends with PEST 211
11.9.2 Blends with COPO 211
11.9.3 Blends with PC 212
11.9.4 Blends with POM 213
viii Contents
11.9.5 Blends with PI 213
11.9.6 Blends with PVP 214
12 Polyvinylidene halide blends 215

12.1 Polyvinylidene chloride blends 215
12.2 Polyvinylidene fluoride blends 216
12.2.1 PVDF/acrylics blends 217
12.2.2 PVDF/ engineering resin blends 218
13 Poly(methyl)methacrylate, PMA and PMMA, Blends 219

13.1 PMA blends 219
13.2 PMMA blends 219
13.2.1 Copoly(meth)acrylate blends 219
13.2.2 PMMA/Poly(meth)acrylate blends 221
13.2.3 PMMA/PVC blends 223
13.2.4 PMMA/PO blends 224
13.2.5 PMMA/elastomer blends 224
13.2.6 PMMA/PC blends 225
13.2.7 PMMA/PEST blends 226
13.2.8 PMMA/PPE blends 227
13.2.9 PMMA/PA blends 227
13.2.10 PMMA/POM blends 228
13.2.11 PMMA/PVDF blends 228
14 Polyethylene blends 230

14.1 PE/elastomer blends 231
14.1.1 Rubber blends 231
14.1.2 Atactic PP blends 232
14.1.3 CSR blends 232
14.1.4 pm blends 233
14.1.5 lonomer blends 233
14.2 PE/EPR or EPDM blends 234
14.3 PE/PE blends 235
14.3.1 LDPE/LLDPE blends 236
14.3.2 LLDPE/LLDPE blends 237
14.3.3 LDPE or LLDPE blends with HOPE 238
14.4 PE/PP blends 239
14.5 PE/PS blends 240
14.6 PE/styrenics blends 241
14.7 PE blends with acrylics 242
14.8 PE blends with other commodity polymers 243
14.9 PE blends with reduced permeability 244
14.10 Electrically conductive PE blends 245
14.11 Biodegradable PE blends 246
14.12 PE/PA blends 247
14.13 PE/PC blends 248
14.14 PE/PPE blends 250
14.15 PE/PEST blends 251
14.16 PE/POM blends 252
14.17 PE/specialty resin blends 253
Contents ix
15 Polypropylene 254
15.1 PPIPE blends 255
15.2 PPIPIB blends 258
15.3 PP blends with other polyalkenes 259
15.4 PPI elastomer blends 260
15.4.1 PPlrubber blends 260
15.4.2 PPIEPR or EPDM blends 261
15.4.3 PP I chlorinated elastomer blends 265
15.4.4 PP I styrenic elastomer blends 266
15.4.5 PP I acrylic elastomer blends 267
15.5 PP IPS blends 268
15.6 PPlEVAc blends 269
15.7 PPIPVC blends 270
15.8 PP blends with other commodity resins 270
15.9 PP biodegradable blends 270
15.10 PP I electrically conductive polymer blends 271
15.11 PP/engineering resin blends 271
15.11.1 PP/PA blends 271
15.11.2 PP IPC blends 275
15.11.3 PPIPEST blends 276
15.11.4 PPIPPE blends 278
15.11.5 PPlPOM blends 279
15.12 PP/specialty polymer blends 279
15.12.1 PP/PARA blends 280
15.12.2 PPILCP blends 281
15.12.3 PP blends with other specialty polymers 282
15.13 Summary 282
Part Four
Engineering Resin Blends 283
16 Polyamide blends 285

16.1 Early blends (up to 1970) 285
16.1.1 Early impact-modified blends 285
16.1.2 PA/PO early blends 286
16.1.3 PA/PA early blends 286
16.1.4 PAlABS early blends 286
16.1.5 Early PA blends with engineering resins 287
16.2 PAlcommodity resin blends 287
16.2.1 PA toughened blends 287
16.2.2 PAlelastomer blends 295
16.2.3 PA/PO rigid blends 304
16.2.4 PAlstyrenics blends 309
16.2.5 PA/vinyls blends 313
16.2.6 PA blends with TPU 313
16.2.7 PA blends with reduced permeability 314
16.2.8 Biodegradable or recyclable PA blends 317
16.3 PAlengineering resin blends 317
16.3.1 PA/PPE blends 317
16.3.2 PA(I)/PA(2) blends 323
16.3.3 PAlPARA blends 324
x Contents
16.3.4 PA/POM blends 325
16.3.5 PA/PEST blends 326
16.3.6 PA/PC blends 330
16.4 PA/specialty polymer blends 333
16.4.1 PA/PSF blends 333
16.4.2 PA/PPS blends 333
16.4.3 PA/ Phenoxy blends 334
16.4.4 PA/PVDF blends 335
16.4.5 PA/PEA blends 335
16.4.6 PA/PAI blends 336
16.4.7 PA/PEl blends 336
16.4.8 PA/LCP blends 336
17 Polyester blends 337

17.1 PEST blends with commodity resins 340
17.1.1 PET/PO blends 340
17.1.2 PBT blends 342
17.1.3 PEST/elastomer blends 345
17.1.4 PEST/styrenics blends 352
17.1.5 PET/SMA blends 356
17.1.6 PEST/acrylics blends 357
17.1.7 PEST/vinyl blends 360
17.2 PESf blends with engineering resins 361
17.2.1 PET blends with other PEST resins 361
17.2.2 PEST/PAr blends 364
17.2.3 PEST/PA blends 365
17.2.4 PEST/PC blends 367
17.2.5 PEST/PPE blends 374
17.2.6 PEST/paM blends 378
17.3 PEST blends with specialty resins 379
17.3.1 PEST/polysulfide blends 379
17.3.~ PEST/polysulfone blends 380
17.3.3 PEST/polyimide blends 381
17.3.4 PEST/PEA blends 382
17.3.5 PEST/LCP blends 382
17.3.6 PEST/inorganic glass blends 382
18 Polycarbonate blends 384

18.1 PC blends with commodity resins 384
18.1.1 PC/polyalkene blends 384
18.1.2 PC/styrenics blends 385
18.1.3 PC/acrylics blends 387
18.1.4 PC/PVC blends 388
18.1.5 PC/TPU blends 388
18.2 PC blends with engineering resins 389
18.2.1 PC/PA blends 389
18.2.2 PC/PEST blends 389
18.2.3 PC/PPE blends 391
18.2.4 PC/POM blends 393
18.3 PC blends with specialty resins 394
18.3.1 PC/siloxane resin blends 394
Contents xi
18.3.2 PC/PSF blends 394

18.3.3 PC/fluoropolymer blends 396
18.3.4 PC/polyimide blends 396
18.3.5 PC/PEl blends 397
18.3.6 PC/LCP blends 398
19 Polyoxymethylene (acetal resins) 399

19.1 POM blends with commodity resins 400
19.1.1 POM/acrylics blends 400
19.1.2 POM/TPU blends 401
19.2 POM blends with engineering resins 403
19.2.1 POM/POM blends 403
19.2.2 POM/PPE blends 404
19.3 POM blends with specialty resins 405
20 Polyphenyleneether 407
20.1 PPE blends with commodity resins 409
20.1.1 PPE/PS blends 409
20.1.2 PPE/PMMA blends 414
20.1.3 PPE/PE blends 414
20.1.4 PPE/PP blends 415
20.1.5 PPE/vinyl resin blends 415
20.2 PPE blends with engineering resins 416
20.2.1 PPE/PA blends 416
20.2.2 PPE/PEST blends 417
20.2.3 PPE/PC blends 418
20.2.4 PPE/POM blends 419
20.3 PPE blends with specialty resins 420
20.3.1 PPE/PPS blends 420
20.3.2 Other PPE blends with specialty polymers 422
20.4 Miscible PPE blends 425
21 Specialty resin blends 428

21.1 Polyarylene sulfide blends 428
21.1.1 PPS/PSF blends 429
21.1.2 PPS/PAr blends 430
21.1.3 PPS/PARA blends 430
21.1.4 PPS/PI blends 431
21.1.5 PPS/PAI blends 432
21.1.6 PPS/PEK blends 432
21.1.7 PPS blends with polysiloxanes 433
21.1.8 PPS/fluoropolymer blends 434
21.1.9 PPS/LCP blends 435
21.1.10 PPS/inorganic glass blends 435
21.2 Polysulfone blends 436
21.2.1 General 436
21.2.2 Summary of PSF blends 436
21.2.3 PSF blends with PAl, PI or PEl 438
21.2.4 PSF blends with fluoropolymers 439
21.2.5 PSF blends with PEK 439
21.2.6 Diverse PSF blends 440
xii Contents
21.3 Polyetheretherketone blends 440
21.4 Polyetherimide 443
21.5 Aromatic polyamides 447
21.6 Polyarylates 448
21.7 Molecular composites 449
21.8 Liquid crystal polymer blends 452
21.8.1 Introduction to LCP blends 452
21.8.2 LCP blends with commodity resins 454
21.8.3 LCP/PA blends 455
21.8.4 LCP/PC blends 455
21.8.5 LCP/PEST blends 456
21.8.6 LCP/PPE blends 459
21.8.7 LCP/PEI blends 460
21.8.8 PPS/LCP blends 461
21.8.9 PSF blends with LCP 462
21.8.10 LCP blends with other specialty resins 462
21.9 Electrically conductive polymer blends 464
21.9.1 Introduction 464
21.9.2 Static dissipation 464
21.9.3 Electrical conductivity 466
22 Recycling and biodegradable blends 469

22.1 Recycling 469
22.1.2 Compatibilization 470
22.1.3 PS/PE recycling 473
22.1.4 Polyalkene blends 475
22.1.5 Biodegradable or recyclable PA blends 477
22.1.6 Other blends 478
22.2 Biodegradable blends 480
22.2.2 Blends with polysaccharides 481
22.2.3 Blends with biodegradable synthetic polymers 482
22.2.4 Blends with other polymers 483
References 485
APPENDICES: 560
Appendix I List of international abbreviations for polymers 560
Appendix II List of the commercial blends 578
Appendix ill The major types of polymer blends. 614
Appendix IV Polymer blends discoveries and developments. 630
Index 644
Preamble
There are two approaches to science - analytical and synthetic - the former attempt-
ing to analyze selected phenomena to the greatest depth, while the latter tries to form
a coherent view of a broad number of events pertaining to a specific field. As is
evident from the list of Nobel prize winners, both approaches may lead to great
intellectual achievements. Nowadays, there is a growing tendency, especially among
younger researchers or practitioners, to favor the analytical method. The narrowing
of interest is also more evident in the curricula of the New World universities than in
the European ones. In consequence, industrial researchers and engineers tend to be
increasingly specialized. Without denying the importance of the analytical approach,
it is beneficial from time to time to look at a given domain from a different and/or
broader perspective.
Polymer science and technology are young. The technology (including that of
natural rubbers and modified biopolymers) barely stretches 150 years or so, while
polymer science is about half that old. There are still direct living memories of many
focal events in the evolution of polymer science and technology. Today, on the global
scale, the polymer industry is one of the dominant, most progressive economic
forces. It suffices to note that the production of plastics is nearly two and a half
times larger than that of steel. Thus, the almost universal lack of knowledge of the
history of polymer science and technology is, to put it mildly, surprising.
Most reviews and evaluations of polymer evolution have been written by people
from academe, from the perspective of the scientific literature. As an exception, in
1985 Morawetz published a book tra\;ing back to their origin the basic concepts of
polymer science, namely the molecular structure, polymerization mechanisms and
polymer characterization, as well as describing the beginnings of the polymer
industry.
For an industry to grow, it must form a flexible partnership with academia. As the
history of the polymer industry demonstrates, progress has been made by a series of
loop interactions. At first, the development was market driven, attempting to
produce waterproof clothing, to imitate expensive natural materials (e.g., ivory or
amber), to provide materials for new industries (e.g., cable insulation) etc. The
inventions provided a strong motivation for research on fundamental mechanisms,
for the formulation of a scientific basis. This, in turn, led to new materials, as well as
to refinements of technology. Often the discovery of the basic principles resulted in a
quantum jump in evolution, such as Carothers' synthesis of thousands of polyesters
and polyamides based on the clear concept of linear chain macromolecules. The
production and the use of new materials always open a new Pandora's box of
xiv Preamble
problems, namely a need for better control of the reaction kinetics, demands for
better processing equipment, for better performing materials, and so on, which in
tum require new analysis and fundamental re-evaluation. As history teaches, the
most rapid progress in science and technology has been observed when there was a
coordinated effort within a country or a company to set up bidirectional interactions
between long-term research and industrial production. Unfortunately, the polymer
literature is strongly biased toward the academic - the second vital arm, the techno-
logy, is undervalued.
This book complements Polymer Alloys and Blends - Thermodynamics and Rheology
(1989). It originated in pure curiosity - I was not writing a book, but rather collecting
information on how the principles described in the former book on fundamentals
have been used by the industry, trying to learn when polymer blends technology
started and how it evolved. At a certain point in the process, it became apparent that
the information provides a new perspective on polymer blends technology, as seen
through the eyes of industrial inventors, and as such it may be of interest to many
researchers and engineers. Thus the information was reorganized (several times) to
provide a coherent view of the evolution of blends technology, from its beginning in
1846 to 1995/6. Furthermore, in many cases the fundamental mechanisms were
described in an attempt to generalize about the patented inventions as well as to
explain 'why it should work.'
The history clearly shows that it is impossible to separate the evolution of polymer
science and technology from that of polymer blends - in many cases, blends were
commercialized before the component resins. From the very beginning of the poly-
mer (that is rubber, plastics or fibers) industry, blending offered the flexibility and
economy most appreciated in modem times. For these reasons, Part One provides a
short history of polymer science and technology. Part Two summarizes the reasons
for, and the fundamental principles of, blending. The chronological evolution of
blends technology is presented in Parts Three (commodity resin blends) and Four
(engineering and specialty resin blends).
The text was in preparation for several years. Great effort was made to provide a
factual description of the technological evolution of more important blends, starting
with the initial binary mixtures to the modem complex alloys. Owing to the great
diversity of the patented blends, this required a subjective selection of the blends as
well as of the events that shaped their evolution. In the later stage of the preparation,
the book has been carefully re-examined for logical presentation of the information,
as well as for elimination of repetitions and errors.
The final text is organized in the sequence of the commodity, engineering and
specialty blends, initially listed by the major polymeric component in the blend.
However, since a great number of the patents specify a wide range of compositions,
such as from 5 to 95 wt % of each component, it was found more logical not to
classify blends by the major component, but rather by the presence of a specific
type of resin. Thus, the blends comprising a commodity resin (with another com-
modity resin, then with engineering, and finally with specialty resins) are described
first, then all the blends of engineering resins (with either engineering or specialty
resins), and finally the specialty/specialty resin blends are presented. To provide
a total image of the engineering blends technology, in Part Four the blends with
the commodity (already discussed in Part Three) and with the specialty resins, are
summarized.
Polymer technology barely stretches 150 years or so, whereas polymer science is
about half that old. There are still living pioneers who helped to formulate the basic
concept of macromolecular configuration. However, the evolution of polymer tech-
Preamble xv
nology has been extremely rapid. In 1990 the world production was about 30kt,
while in 1994 it reached 114000kt. In 1983 the plastics' production caught up with
that of steel - today it is twice as large in volume and about thrice in value. It is
important to recognize that most modem commercial plastics are multicomponent.
They frequently comprise resins having different performance characteristics, rein-
forcements, modifiers and other additives. Blends and blending technology are vital
parts of the industry. Parallel with the growing size of the polymer market there has
been unprecedented expansion of the technical publications on the topic. On poly-
mer blends alone, annually there are 4500 patents and more than 50000 articles.
To proVide credit where credit is due, most inventions are dated by the year of the
patent deposition. This means that in most cases two different dates are quoted - in
the text the date of invention is used, while (as is accepted in the literature) in the
bracketed reference the date of the patent publication is given, namely in 1937
Badum invented PVC/NBR blends (Badum, 1942). Obviously, since the two dates
may vary by more than ten years, it may not be fair to blame the inventor for the slow
pace of the patenting procedure.
In spite of all efforts, undoubtedly there are errors and omissions in the offered
text. Furthermore, some parts may be controversial or unclear. All criticism, com-
ments and additional information pertaining to the evolution of blends technology,
will be gratefully appreciated.
Montreal, November 1996

Abbreviations in Appendices
In the Appendices, the following abbreviations will be used:
A.-G. AktiengeseUschaft
Adv. Advanced
ASTM American Society for Testing Materials
Chem. Chemical
Co. Company
Corp. Corporation
DIN Deutsches Institut fUr Normung
Div. Division
DuPont E. I. du Pont de Nemourns & Co.
Eng. Engineering
G.m.b.H. GesseUschaft mit beschrankter Haftung
GECo. General Electric Company
ICI Imperial Chemical Industries
I. G. Farben. I.G. Farbenindustrie AktiengeseUschaft
Inc. Incorporated
Ind. Industries
Int. International
ISO International Organization for Standardization
IUPAC International Union for Pure and Applied Chemistry,
JSR Japan Synthetic Rubber Co., Ltd
JSW Japan Steel Works
K.K. Kabushiki Kaisha
Komb. Kombinat
Mfg. Manufacturing
Petrochem. Petrochemical
Petrol. Petroleum
Plast. Plastics
Res. Research
SA Societe Anonyme
Thermoplast. Thermoplastics
W. With
Part One
Polymer science and technology
1
Introduction
In 1992 the annual world production of plastics reached 102 x 1()6 m 3 at a value of
over US$ 300 billion, while that of steel was 50 x 1()6 m 3 at a value of US$l25 billion
(Table 1.1). Furthermore, from 1980 to 1990, plastics production increased by 62%,
while that of steel decreased by 21%. Considering the uneven polymer consumption
around the world, polymer production will have to increase by a factor of ten before
currently recorded levels of plastics sales in developed countries will be universally
reached. Polymers are the fastest growing structural materials. In addition, the
polymer blend segment of the plastics industry increases at a rate about three
times higher than the whole. The aim of this book is to trace the historical evolution
of the polymer blends industry.
Table 1.1 World production of steel and plastics for 1992

Production Steel Plastics
Production volume (Mt/year) 410 102·
Production volume (M(m3 )/year) 51 102
Production value (billion US$/year) 125 310
Growth from 1980 to 1990 (%) -21 -1;62
,. 121 Mt/year in 1996
A polymer (from the Greek poly = many and meros = units) is a substance composed
of macromolecules built by covalently joining at least 50 molecular segments, called
mel'S. The word polymer was introduced in 1832 by Jons Jacob Berzelius for sub-
stances that may have identical chemical composition but differ in molecular weight
(e.g., acetylene, benzene and styrene, having the formula CnHn with n == 2,6 and 8,
respectively). During the years 1859-1863, Louren~o reported that condensation of
ethylene glycol with ethylene dibromide resulted in a mixture of ethers, whose
members, separated by distillation, were identified as HD-(C2l4D-)n-H with
n == 2 to 6 (Stahl, 1981).
When the units are all identical and each is able to link with two, and only two,
other divalent mers, a linear homopolymeric macromolecule is formed, and its
structure may be expressed as (mer]n' with n being the degree of polymerization.
When the divalent mers are not identical, the joining process (polymerization) leads
to a linear copolymer. Conversely, when at least some mers are able to join with more
than two units, the polymerization leads to branched or crosslinked structures.
4 Introduction
Polymers can be divided into two major groups: natural or biopolymers that
result from natural biosynthesis, and synthetic or man-made. The biopolymers
(polysaccharides, proteins, nucleic acids, natural rubbers, cellulose, lignin, etc.) are
nature's building blocks. Although some of them, such as natural rubber, are homo-
polymers, in most cases they are copolymers with complex structures and high
molecular weights (Flory, 1953; Batzer and Lohse, 1979; Mark, 1982; Morawetz,
1985).
The use of polymers is as old as humanity itself (Table 1.2). Woods, leather, natural
resins and rubbers accompanied man in his gradual progress from a nomadic to a
modern lifestyle. The first spinning and weaving dates from about 35000 BC. As
long as 10 000 years ago, the Swiss lake dwellers knew how to cultivate flax and
weave it into fine linens. In Egypt, musical string instruments, papyrus for writing
and styrene (in the balsam from Liquidambar orientalis) for embalming were already
used in 3000 BC.
Table 1.2 Early use of natural polymers
Thousand years BC Polymer use

50-30 Homo Sapiens Neandertalis: skins, fibers, wood
35 on Homo Sapiens Cromagnon: first spinning and weaving
12 on Homo Urbanis: cultivation of flax, use of mortar and bitumen
4 on Harappan culture: use of bitumen, cultivation of cotton
3 on Documented cultivation of cotton, use of shellac, papyrus,
strings for musical instruments, styrene
lon Use of rubber and gutta-percha
Shellac has been used in Indian turnery for millennia, not only as hot wood varnish
(even today it makes the Ghujarati furniture not only sturdy and long lasting, but
beautiful as well), but also as a binder for molding everyday objects, such as cups
and knife handles. The Harappan culture along the Indus river flourished 6000 years
ago. Multi-storied, wooden buildings with carved porticos and decorated balconies
were built according to a plan in Harappa, Mohenjo Daro and other cities along the
river. Each house was connected to an underground sewer system. Large, communal
water pools were waterproofed by means of bitumen sealants. Wealth was based on
agriculture and trade, with cotton cultivation playing a major role (Chattopadhyaya,
1986).
Natural rubber was used by the Olmecs (Aztec language for The Rubber People) at
least 3000 years ago (Stuart, 1993). The long use of natural polymers was not
hindered by lack of understanding of their chemical structure and their polymeric
nature.
While recognizing the primordial importance of biopolymers, the object of interest
for this book is mainly the second group, the synthetic polymers, especially their
blends. However, in Part 3, while discussing biodegradable polymer blends,
their pertinence will be evident even in the narrow aspect of this book. The term
'synthetic polymer' refers equally well to linear, saturated macromolecules (i.e.,
thermoplastics), unsaturated polymers (Le., rubbers), and to any substance based
on crosslinkable monomers, macromers or pre-polymers (i.e., thermosets). Again,
the focus of this volume will be narrowed mainly to blends of thermoplastics having
predominantly saturated, linear macromolecules.
Introduction 5
It is convenient to discuss polymer history, considering first the early period from
1800 to 1945, and then the modern one from 1945 to the present day. The early period
is characterized by a number of accidental discoveries, use of modified biopolymers,
domination of the thermosets, pragmatic 'quick-and-dirty' evolution of technology,
and an emerging science and technology of polymers. Most polymer processing
equipment was either adopted or invented during this period. The commercial
production of several types of mixers, extruders and molding machines had
begun. Before 1945 such resins as low density polyethylene (LDPE), polyamide-6
(PA-6), polyamide-66 (PA-66), polyvinylch1oride (PVC), and polyethyleneterephtha-
late (PEn, were already known. However, their commercial production was used
mainly to support the military effort during World War II, with little spillover to
civilian use.
In 1900, the world production of plastics was about 30000 tons. By 1937, this
amount had increased by a factor of eight, by 1944 by a factor of 42, and by 1960
by a factor of 333. The world production of plastics in 1990 was reported to be
94 million tons (Mt), projected to increase to 151 Mt in 2000. This is illustrated in
Figure 1.1.
The second, or modern (for the lack of a better term) period, is characterized by
the rapid expansion of polymer consumption. In the 1940s the annual growth rate
(AGR) reached its maximum of 30-40%. In 1945, the US production of plastics was
about 1.3 Mt, and in 1992 it was 35 Mt, giving an average AGR for the period of about
7.25%. During these years several new polymerization methods were either invented
or developed to the level of industrial production, namely, anionic, coordination,
oxidative coupling, single-site metallocene catalysis, etc.
WORLD PLASTICS PRODUCTION 1990 - 1990
...........................:. : .
. ..
poirits - data; lin~ - population growth eq.

10-2 - 1 . ---" ---' "-- -'-- -'--
1900 1920 1940 1960 1980 2000

YEAR
Figure 1.1 World plastics production 1~2000. The data are taken from business literature.
The solid line was computed from the log-population growth equation log(Production) =
-1.7653+3.769/[1+1.566 expHJ.0904 (x-1942)}); R=O.9955.
6 Introduction
These methods resulted, on the one hand, in polymers having better control of
macromolecular structure and performance and, on the other hand, in the prepara-
tion of new polymers inaccessible by way of other, more traditional, routes. Thus, for
example, the Ziegler-Natta and, more recently, single-site catalysts, have made it
possible to commercially produce, respectively, isotactic and, since 1992, syndiotac-
tic polypropylenes (Schut, 1992), whereas oxidative coupling led to the preparation
of polyphenyleneether (PPE).
In the 19905, the AGR of plastics production in the developed countries started to
show a leveling trend, while that in the developing countries accounts for a con-
tinuous expansion. The disparities and potential for growth are enormous: in 1991,
the per capita consumption of plastics in Belgium was reported by different sources
as 150 or 180 kg, whereas in the most populated countries, China, India and Pakistan,
it was below 1 kg. This is illustrated in Figure 1.2.
Historical developments in the field of polymers will be discussed in three parts
dealing with developments in technology, processing and science. Furthermore,
discussion of polymer technology and science is further divided into the two afore-
mentioned periods, early and modem.
More detailed discussion on polymer history can be found in several books: Han-
cock, 1857; Meyer and Mark, 1930; Staudinger, 1932; Mark and Whitby, 1940; Mark,
1940; Mark and Raff, 1941; Meyer, 1942; Ott, 1943; DeBell et al., 1946; Staudinger,
1947; Mark and Tobolsky, 1950; Boundy and Boyer, 1952; Winding and Hiat, 1%1;
Dingley, 1963; Kaufman, M., 1963, 1969; Staudinger, 1969, 1970; Warrington and
Newbold, 1970; Dubois, 1972; Mason, 1972; Elias, 1973; Batzer and Lohse, 1976;
Proskauer, 1978; Olabisi et al., 1979; Priesner, 1980; McMillan, 1981; Stahl, 1981;
Boyer, 1982; Carra et al., 1982; Cassidy, 1982; Deanin, 1982; Lank and Williams,
1982; Schwartz and Goodman, 1982; Seymour, 1982; Seymour and Cheng, 1985;
170
C 150 PLASTICS CONSUMPTION IN 1991
~
1
~
133
127
z 102
0 101
i= 97 94
ll. 89
::!: 79
~ 85 74
C/)
z 70696966 64
0 59
() 5552
~ 40
0: 36
~ " 27
Q:
W
10
ll.
0
Figure 1.2 Plastics consumption in indicated countries in 1%1 [data: plast europe, 1992].
Introduction 7
Morawetz, 1985; McAdams and Gamon, 1985; Ballard, 1986; Kennedy, 1986; Sey-
mour and Kirshenbaum, 1986; Martuscelli et al., 1987; Seymour and Cheng, 1987;
Yogi and Immergut, 1987; Alper and Nelson, 1989; Morris, 1989; Seymour, 1989;
Sperling, 1992; Mark, 1993; Sparke, 1993.
2
Polymer industry
The first hall of the 18th century, the age of enlightenment, was a period of collection,
segregation and reflection on all the knowledge accumulated over the ages. This was
the last time that boundaries between different intellectual activities were not
apparent. Art, science and craft could equally be parts of the same individual's
activities. The 17 volume Encyclopidii au Dictionaire Raisonni des Sciences, des Arts et
des Metiers was published by Diderot from 1751 to 1766, with an additional 11
volumes of illustrations distributed during the period 1762-72. The preparation of
this monumental publication had a dominant effect on the classification and
systematization of knowledge. The 4000 copies of the encyclopaedia, published
despite condemnation by church and state, seriously affected the social fabric of
the society. It accelerated the tendency to question all the accepted truths and axioms
of the past.
Probably the most significant result of this movement was the emergence of the
'natural laws' that implied equality of right and wealth. This led to revolutions - an
industrial one in England, but quite bloody ones in North America and subsequently
in France (that emerged financially ruined from the American conflict).
2.1 EARLY PERIOD: 1800-1945

The great French revolution of 1789 resulted in general chaos and a quarter of a
century of wars raging in most European countries. Napoleon took power in 1799,
starting a cycle of wars that finally ended in his defeat at Waterloo in 1815. The
rebellion in 1830 deposed France's king Charles in favor of his cousin, Louis Philippe.
Bad harvests in Europe from 1845 onward resulted in peasants' uprisings. In
1848-49, there was a revolutionary wave of social discontent throughout Europe -
The Spring of the Nations - that started in France and spread East to the Ottoman
empire. In 1854-56, there were the Crimean wars. This was also a period for estab-
lishing unified, central governments in Italy (1861-70) and in Prussia (which, after
unification, became part of Germany).
The Franco-Prussian war of 1870 culminated in the defeat of France and the
occupation of Paris. On 18 January 1871, William I of Prussia was crowned at
Versailles as the first emperor of the newly united imperial German Reich. As a
result of the war, France transferred Alsace and Lorraine to Germany, and paid 5
billion francs in indemnities. The Paris Commune was suppressed by the provisional
government with the help of the Prussian army - the 'pacification' resulted in
execution of 30000 Communards.
Early period: 1800-1945 9
1873 saw the beginnings of the first world-wide financial crash that lasted 17 years.
During this period there were labor struggles, draconian laws, militarization, finan-
cial bankruptcies and unchecked international monopolization of capital and mar-
kets. As a result of these upheavals, in the second half of the 19th century, Germany
emerged as the most dynamic country. Its industrialization was directed towards the
chemical, steel and electrical industries. In collaboration between the German gov-
ernment and private industry several research centers were created (e.g., in 1887
the Physikalische-Technische Reichsanstalt for research in science and technology).
Thus, the industrialization of Germany (similarly to the more recent growth of
industrial potential in Japan) was not an accident, but rather the result of well
planned and executed efforts.
The polymer industry traces its beginning to the early modifications, usually by
trial and error, of shellac, natural rubber (NR; an amorphous cis-l,4-polyisoprene),
gutta-percha (GP; a semi-crystalline trans-l,4-polyisoprene), and cellulose (whose
elemental composition was published by Payen, 1839). Columbus, returning from
his second transatlantic voyage in 1496, brought from Hispaniola (Haiti) bouncing
balls of a substance known today as rubber. The word 'rubber' was introduced in
1774 by John Priestley, who found the substance useful for rubbing out unwanted
pencil marks. Gutta-percha was introduced to Western civilization by John Trades-
cant in the second half of the 17th century. However, little use was found for either of
these materials until the mid-18th century. The activity was precipitated by an
unlikely chain of events (Brydson, 1975).
In 1731, the Paris Academy of Sciences sent Charles Marie de la Condamine on
a voyage to measure the shape of the Globe. In 14 weeks, he crossed South America
from Quito (Ecuador) to Para, now Belem (Brazil), then to Cayenne (French
Guyana). He returned to France, carrying not only natural rubber balls, but also
rubber-waterproofed cloth and bottles of Amerindian manufacture. This started the
race for development of cloth-waterproofing technology in Europe. In 1763 the
French chemist Macquer reported that turpentine was a good solvent for natural
rubber. The first patent for cloth waterproofing by means of treatment with
turpentine solution was granted to Samuel Peel in 1791. The first rubber plant
was built in 1811 by J. N. Reithoferin. in Vienna. In 1820, Thomas Hancock
invented the rubber mill, and reported that mastication makes rubber more
formable - it was made to flow without solvent. In 1820-23, Macintosh developed
a method of cloth waterproofing with solutions of rubber, sandwiching the sticky
rubber between two layers of cloth. These events mark the beginning of today's
plastics industry.
The development of polymer technology was market driven; only after the useful-
ness of natural rubber was learned from examples brought from South America was
attention focused on the material, which had been known in Europe for a good 300
years. The pioneers of the new industry were mainly entrepreneurs and inventors
with little scientific training.
The early natural rubber products were soft and sticky in hot weather, and stiff
and brittle in the cold. In spite of these disadvantages, the rubber industry grew
rapidly in all industrialized countries (Hurley, 1982). Rubber vulcanization by sulfur
was discovered by Lundersdorf in Germany. However, the accidental rediscovery of
vulcanization by Charles Goodyear in 1836 provided the major breakthrough (Good-
year, 1844).
The first patent on natural rubber vulcanization by sulfur was granted to Thomas
Hancock in Britain in 1843, a year before Charles Goodyear received his patent.
Hancock wrote:
10 Polymer industry
, ... my experiments had shown that the rubber and sulfur must first be blen-
ded.... Sulfur could be blended by rollers and masticators; the blended material
could be reduced to a state of solution by any of the usual solvents, or to a state
of dough, and spread on cloth by machinery of my own previous patents for
waterproofing.... Blocks of the masticated compound could be pressed in
moulds and cut into sheets, and into every variety of form and size.'
Hancock also gave the origin of the term vulcanization as being suggested by his
friend, Mr. Brockedon, after the Roman god Vulcanus, who worked with sulfur and
heat (Hancock, 1844, 1857). Vulcanized rubber was used to manufacture tires, as well
as for a variety of items, such as match boxes, dentures and jewelry.
In 1851, Nelson Goodyear was granted a patent on Ebonite, a hard, thermosetting
material obtained by heating 100 parts of natural rubber with at least 50 parts of
sulfur. The same year, articles made of Ebonite were shown at the Great Exhibition.
In 1846, Alexander Parkes (an artist by his own description) received a patent for
the dynamic covulcanization of natural rubber (NR) with gutta-percha (GP) in the
presence of C~. This is the first known patent on polymer blends; it marks the
beginning of the polymer blending industry. These blends were, one may say today,
quite obvious, since products made from natural rubber were soft and sticky,
whereas those from gutta-percha (obtained from latex of the tree Palaquium oblongi-
folium in Malaysia) were brittle, cracking with time. Blending these two isomers of
polyisoprene resulted in materials with significantly improved properties, whose
rigidity was controllable by the composition. The blends had many applications,
ranging from picture frames, tableware and ear-trumpets to sheathing the first
submarine cable in 1850. In 1881, GP-containing crosslinked NR was introduced as
a dielectric. In 1859, chlorination was used to harden natural rubber. The same year,
Thomas Taylor in Britain invented vulcanized fibers.
On the following pages the beginnings of the synthetic polymer industry will be
summarized. The order of presentation will follow the commercialization dates
listed in Table 2.1, namely, cellulosics, phenolics, styrenics, acrylates, vinyls, poly-
ethylene and other resins.
2.1.1 Modified natural polymers

Cellulosics
The first man-made polymer was nitrocellulose (NC) discovered by Braconnot
(1833); thus he may be considered the father of the synthetic polymer industry. In
1845-47, the nitration process was improved by Schonbein (1847), who used sulfuric
acid as a catalyst and dehydrating agent. This made it possible to produce NC for
either gunpowders or Celluloid thermoplastics. Owing to the growing demand for
these materials, NC production soon expanded: Collodion (lacquers based on
alcohol--ether solution of cellulose nitrate); Parkesine (introduced in 1862, the first
thermoplastic material that could be hot rolled into NC sheets, to be hot formed into
different shapes, patented in 1865, named by the inventor after himself, successfully
presented at the Great International Exhibition of 1862, but later a commercial fail-
ure); lvorite (used as a substitute for ivory billiard balls - there are several reports on
their flammable and explosive character!); Celluloid (cellulose nitrate manufactured
according to A. Parkes' invention, plasticized with camphor, manufactured since
1868 by John W. Hyatt in Albany, NY (Hyatt and Hyatt 1870), trademarked in 1872,
introduced to Britain in 1877, and a year later to Germany by Rhein Gummi- und
Celluloidfabrik); Xylonite (plasticized NC, introduced by Daniel Spill in 1877, used
Table 2.1 Commercialization dates of selected polymers
Year Acronym Polymer Producer

1868 NC cellulose nitrate; Nixon Hyatt Bros.
1900 CS casein; Galalith Kritsche (France)
1909 PF phenol formaldehyde; Bakelit Bakelit Gesellschaft
1915 PS polystyrene; Trolitul I. G. Farbenindustrie
1926 AK alkyd resins; Glyptal General Electric Company
1927 CA cellulose acetate fibers; Lumarith Canadian Celanese/Eastman
1927 PMA polymethylacrylate O.R6hm
1928 PVAc polyvinylacetate; Elvacet Shawinigan Chemical Ltd
1928 PVC/Ac polyvinylchloride-co-vinylacetate I. G. Farbenindustrie
1928 PMMA polymethylmethacrylate; Plexiglas R6hm and Haas
1929 GRS/SBR styrene-butadiene rubber; Styrolux I. G. Farbenindustrie
1929 UF urea/ formaldehyde resins; Pollopas Stein Hall Mfg. Company
1930 PAN polyacrylonitrile I. G. Farbenindustrie
1930 CR chloropren rubber; Neoprene E. I. du Pont de Nemours &
Co.
1930 TR polysulfide rubbers; Thiokol Thiokol Chemical
Corporation
1931 PVC polyvinylchloride; Trovidur, I. G. Farbenindustrie
Vestolit
1931 PEG polyethylene glycol I. G. Farbenindustrie
1931 PVAI polyvinyl alcohol!formaldehyde I. G. Farbenindustrie
fibers
1932 Buna-S styrene-butadiene rubber I. G. Farbenindustrie
1932 Buna-N acrylonitrile-butadiene rubber I. G. Farbenindustrie
1932 UM urea/melamine American Cyanamid Co.
1933 PEMA polyethylmethacrylate R6hm and Haas
1933 EC ethyl cellulose; Methocel ICI
1933 AF aniline/ formaldehyde resins; Ciba
Cibanite
1934 PCTFE polychlorotrifluoroethylene; I. G. Hoechst
Hostajlon
1934 PVFO polyvinylformal Shawinigan Chemical Ltd
1935 PVBO polyvinylbutyral Shawinigan Chemical Ltd
1936 AB5-A acrylonitrile-butadiene-styrene; Naugatuck Chemical
Royalite Company
1936 MF melamine/formaldehyde resins Ciba
1937 PA-66 polyamide-66; Nylon E. I. du Pont de Nemours &
Co.
1937 SAN styrene-acrylonitrile copolymer; I. G. Farbenindustrie
Luran
1937 TPU thermoplastic polyurethane O. Bayer
elastomers
1937 1'5 thermoset polyesters Marco Chemical Company
1937 PVK poly-N-vinylcarbazole; Luvican I. G. Farbenindustrie (BASP)
1938 MF melamine-formaldehyde resin; Henkel A.-G.
Resart
1938 CAB cellulose acetate-butyrate; Tenite Eastman Kodak Company
12 Polymer industry
Table 2.1 Continued

1938 PA-6 poly-e-eaprolactam; Perlon I. G. Farbenindustrie
1938 PA-66 polyhexamethyleneadipamide; E. I. du Pont de Nemours &
Nylon Co.
1939 LOPE low density polyethylene; Alketh ICI
1939 PVDC polyvinylidenechloride; Saran Dow Chemical Company
1939 PVP poly-N-vinylpyrrolidone I. G. Farbenindustrie
1939 PU polyurethane fibers, Perlon U I. G. Farbenindustrie, Wolfen
1940 OAC diallyl glycol carbonate; CR-38 PPGCo.
1942 UP unsaturated polyester; Vestopal United States Rubber Co.
1942 PTFE polytetrafluoroethylene; E. I. du Pont de Nemours &
Teflon TFE Co.
1943 EP epoxy; Araldite Ciba-Geigy
1943 BR butyl rubber St. Claire Processing
Corporation
1943 HOPE high density polyethylene; BASF A-G.
Vestolen
1943 POMS polydimethylsiloxane; Dow Corning Corporation
Dow-Corning
1943 PVAI polyvinyl alcohol; Vinaviol Shawinigan Chemical
1943 PVCAc vinyl copolymers; Vinidur Shawinigan Chemical
1945 CP cellulose propionate; Forticel Celanese
1947 PU polyurethanes; Perlon U Bayer A-G.
1948 ABS-G acrylonitrile-butadiene-styrene Rohm & Haas
latex
1948 ACM acrylic elastomer; Hycar PA B. F. Goodrich Chemical Co.
1950 EVAc ethylene-vinylacetate copolymer ICI
1950 CSR chlorosulfonated PE; Hypalon E. I. du Pont de Nemours &
Co.
1950 PCTFE polychlorotrifluoroethylene Hoechst A-G.
1952 OPET oriented polyethyleneterephthalate E. I. du Pont de Nemours &
film Co.
1953 PET polyethyleneterephthalate; ICI
Melinite
1954 PVAc/Ph polyvinylacetate phthalate C. E. Frosst & Company
1955 PA-ll polyamide-II; Risilan Thann & Mulhouse
1956 PC bisphenol-A polycarbonate; Bayer A-G./General Electric
Macrolon Co.
1956 PCME polydichloromethyltrimethylene Hercules
ether; Penton
1957 PEG polyethylene glycol; Carbowax Union Carbide Canada Ltd
1957 PP isotactic polypropylene; Pro-Fax Hoechst/Montecatini/
Hercules
1958 DAP/ allyl unsaturated polyester; Dapon FMC Corporation
OAIP
1958 SMM poly(styrene-co- Rohm & Haas A-G.
methylmethacrylate); Kamax
Table 2.1 Continued
1958 UHMWPE ultra high molecular weight Hoechst A-G./Himont

polyethylene; Hostalen CUR
1959 CPE chlorinated polyethylene; Hoechst A-G.
Hostapren
1959 POM polyoxymethylene (acetal); Delrin E. 1. du Pont de Nemours &
Co.
1959 POM poly(oxymethylene ethylene); Celanese
Celcon
1959 TPU thermoplastic polyurethane; Estane B. F. Goodrich
1960 EVAc ethylene-vinylacetate; Elvacet E. I. du Pont de Nemours &
Co.
1960 CAP cellulose acetate propionate; Tenite Eastman Kodak
1960 CBR chlorobutyl rubber; Exxon Butyl Exxon
1960 EPR ethylene-propylene elastomer; Exxon
Vistalon
1960 LLDPE linear low density polyethylene; DuPont-eanada
Sclair
1960 - chlorinated polyether; Penton Hercules Inc.
1%1 - polyamide epichlorohydrin; Hercules Powder Company
Hydrin
1961 Aramid poly(m-phenyleneisophthalamide); E. 1. du Pont de Nemours &
Nomex Co.
1961 FEP fluorinated-ethylene propylene; E. I. du Pont de Nemours &
Teflon FEP Co.
1961 PVOF polyvinylidenefluoride; Kynar Pennwalt Chemical
Company
1962 SB styrene-butadiene block copolymer Phillips
1962 ACM acrylate rubber Polymer Corp. Ltd (Polysar)
1962 Phenoxy polyhydroxyether of bisphenol-A; Union Carbide
Phenoxy
1962 PI polyimides; Kapton E. 1. du Pont de Nemours &
Co.
1963 EPDM ethylene-propylene-diene; Nordel E. I. du Pont de Nemours &
Co.
1963 SMA styrene-maleic anhydride; Dylark Sinclair Petrochemicals Co.
1963 10 ethylene copolymer ionomers; E. I. du Pont de Nemours &
Surlyn Co.
1964 EVAc ethylene-vinylacetate copolymer; E. I. du Pont de Nemours &
Elvax Co.
1964 EVAc ethylene-vinylacetate copolymer; U. S. Industrial Chemicals
Ultrathene
1964 PIAN isoprene-acrylonitrile rubber Polymer Corp. Ltd (Polysar)
1964 PPE polyphenylene ether; PPE General Electric Company
1964 PB polybutylene; Vestolen BT Hills A-G.
1965 PAl polyamide-imide; Torion Amoco Chemical
Corporation
1965 PBIA polybenzimidazole Naramco, Materials Div.
1965 PSF polysulfone of bisphenol-A; Udel Union Carbide Corp./
Amoco
14 Polymer industry
Table 2.1 Continued

1965 SBS poly(styrene-b-butadiene); Kraton D Shell Chemical Company
1965 EP poly(ethylene-b-propylene); Eastman Chemical Products
Polyallomer
1965 (blend) PU/polyester; Corfam E.I.du Pont de Nemours &
Co.
1965 PPX polyparaxylene; Parylene Union Carbide Co.
1965 PMP poly-4-methyl pentene-1; TPX ICI/Mitsui Petrochemical
Ind.
1966 PPE blend polyphenylene ether; Noryl General Electric Company
1966 PA-12 polyamide-12; Vestamid Hills A-G./Emser Werke
1969 - amorphous, aromatic PARA; Dynamit Nobel
Trogamid
1%9 PB polybutene-1; Duraflex Hills A-G.
1969 PBT polybutyleneterephthalate; Celanex Celanese
1%9 PBT polybutyleneterephthalate; Hostadur Hoechst A-G.
1970 PO Unipol process Union Carbide Co.
1970 LCP poly(p-oxybenzoyl); Ekonol Carborundum
1970 BIIR bromobutyl rubber Polysar
1970 PA-612 polyamide-6,12; Zyrel 150 E. I. du Pont de Nemours &
Co.
1970 Aramid poly(p-phenyleneisophthalamide); E. I. du Pont de Nemours &
Kevlar Co.
1971 PASU polyarylsulfone; Astrel 3M Company
1971 PPS polyphenylene sulfide; Rayton R Phillips Petroleum Company
1971 PAE polyarylether; Arylon T Uniroyal
1972 EVAl ethylene-vinyl alcohol; Elvanol Kuraray Company Ltd
1972 LCP liquid crystal polymers; Carborundum
Ekkcel 1-2000
1972 PES polyethersulfone; Victrex ICI Ltd.
1972 PFA perfluoro alkoxy polymer; E. I. du Pont de Nemours &
Teflon PFA Co.
1972 ETFE poly(ethylene-co- E.I.du Pont de Nemours &
tetrafluoroethylene); Tefzel Co.
1972 SB styrene-butadiene blocks; K-resin Phillips Petroleum Company
1972 SEBS poly(styrene-b-ethylene butylene); Shell Chemical Company
Kraton G
1973 PVOF polyvinylidenefluoride; Dyflon Dynamit Nobel
1973 PAr polyarylate (mixture of isophthalic- Unitika
and terephthalic acid with
bisphenol-A); U-polymer
1976 PPSU polyphenylsulfone; BXL, Radel R Union Carbide/Amoco
1978 PEEK polyetheretherketone; Victrex ICI
1980 APEC aromatic polyestercarbonate; Apec Chemical Werke Albert
Bayer
1981 PEBA polyether block amide; Pebax Atochem
1981 TPO dynamically vulcanized PO blend; Monsanto Company
Santoprene
Table 2.1 Continued
1982 PEl polyetherimide; Ultem General Electric Company
1983 PAS polyarylsulfone; Radel Amoco
1983 PBI polybenzimidazole; PBI Celanese Corporation
1985 PAE polyarylether; Parylen Union Carbide
1985 MPR melt-processable rubber; Acrylyn E. I. du Pont de Nemours &
Co.
1986 PISO polyimidesulfone Celanese
1987 PTES polythioethersulfone; Amoroon Dainippon Ink & Chemicals
1987 PA-46 polyamide-4,6; Stanyl DSM
1987 PPMB poly-p-methylenebenzoate Amoco
1989 sPS syndiotactic polystyrene Idemitsu/Dow
1991 PPA polyphthalamide; Amodel Amoco
1992 sPP syndiotactic polypropylene Surnitomo Chemical
1994 PENi polyethernitrile Idemitsu Materials Company
1995 capo linear, alternating ethylene-CO Shell Chemical Company
copolymer: Canlon
for manufacture of hand mirrors, combs, knife handles, dolls, dental plates, letter
openers, hatpins, tape measures, brushes, toothpicks, spectacles, baby rattles, per-
fume bottles, ping-pong balls, etc.) were the principal products and, for gunpowder,
a tri-nitrocellulose was manufactured.
The main use of the nitrocellulose plastics was as a replacement for natural and
expensive materials, such as ivory, tortoise-shell, amber, ebony, onyx or alabaster.
The new resins were treated as raw materials for imitation of the finer things in life,
giving the growing bourgeoisie a feeling of self-worth. NC products were designed
to look like something more expensive and more difficult to manufacture. In 1883,
Chardonnet patented the use of NC fibers as an imitation of silk for women's
stockings. The first non-imitative role for CN to play was its use for thin, transparent,
flexible film. In the late 1880s, Hannibal Goodwin and, independently, Henry Reich-
enbach, discovered casting NC films. These films were introduced in 1889 by the
George Eastman Company, to be used in the newest Kodak cameras.
The main inventors and producers of these materials (Alexander Parkes, Daniel
Spill and John Wesley Hyatt) had no scientific training. They were entrepreneurs,
who tried to develop a product and immediately place it on the market. The average
lifetime of their companies was about two years - their ephemeral character was
related to an untrained labor force, poor quality control, emerging international
competition, as well as to the rapid growth of empirical knowledge and the resulting
improvements in formulations and manufacturing methods. Of the three pioneers of
the cellulose nitrite plastics, only the Hyatt brothers, John and Isaiah, eventually
achieved commercial success. This was due to the brothers' preoccupation with the
parallel development of new resins and plastics manufacturing machinery, namely
injection molding (see further in the text).
Alkali cellulose
Also known as mercerized cellulose, this material was discovered by John Mercer in
1844. However, only after the discovery of xanthation (obtained by treating alkali
cellulose with CS:z), giving viscose solution (Cross et al., 1893), did new materials-
regenerated cellulose or viscose - start to be explored. In 1891, Chardonnet
16 Polymer industry
introduced viscose fibers (initially known as artificial silk then, after 1924, as
Rayon™), and a year later he introduced Cellophane™ films in Britain. Viscose film
casting was invented by a Swiss chemist, Jacques Edwin Brandenberger, in 1907. In
Europe, Cellophane became commercially available in 1911. In North America, the
first Cellophane production facility was built by du Pont de Nemours in 1924. The
second plant was build 7 years later in Canada at Shawinigan Falls, by Canadian
Industries Limited, CIL (Lank and Williams, 1982).
Cellulose acetate
Cellulose acetate (CA) was introduced in 1869 by Schutzenberger (Ott, 1943). In 1894,
Cross and Bevan in Britain developed an industrial process for manufacturing CA.
In 1907, the first CA fibers were produced by Eichengrun in Germany. The same
year, Lane and Legere in the USA founded the Standard Pyroxyloid Company for
the manufacture of CA. The following year, George Eastman introduced CA safety
film. In 1919, CA became commercially available. CA fibers arrived in the USA in
1924 (as Lumarith™ from the Celluloid Corporation), and in Canada 3 years later
(from Canadian Celanese). The use of CA as a thermoplastic material began in 1926,
when the Celluloid Corporation started manufacturing CA sheets, rods and tubes. In
the USA, thermoforming of CA started in 1938 (by the Plax Corporation) and
molding a year later (by Hercules) (Warrington and Newbold, 1970). In 1939,
Eichengrun patented the injection molding of plasticized CA in his new machine,
specifically designed for thermoplastic materials.
Cellulose ethers and esters

These were patented by Bayer in 1912 (Bayer, 1912, 1913). The company was founded
as Friedrich Bayer in 1861. In 1881, it moved to Leverkusen and went public as Bayer
Aktiengesellschaft. In 1925, it became a part of the concern I. G. Farbenindustrie that,
in 1952, was dissolved back to individual companies (e.g., Bayer, BASF and Hiils).
Cellulose acetate (CA) and cellulose butyrate (CB) became commercially available in
1927. These have been used to produce sheets, fibers and moldings. Ethylcellulose
(EC) was commercialized by Traill in 1933 (Traill, 1934), cellulose acetate-butyrate
(CAB) in 1938, and cellulose propionate (CP) in 1944.
Proteins
The modification of proteins came later. The discovery in 1885 by Kritsche and
Spitteler that casein can be crosslinked by formaldehyde, to give formable horn-
like materials, was a basis for a French patent of 1897. In 1899, the two inventors
started manufacturing the new materials named Galalith™ and Erinoid™, respect-
ively, in Germany and Britain. The material could be formed into a great variety of
shapes. However, the principal advantage of the modified casein was its dyeability -
it could be mixed with pigments or surface dyed into a rainbow of colors. These
resins were used to manufacture jewelry and decorative boxes, but primarily
buttons. In 1904, the production facility was established in Germany. The same
year Todtenhaupt prepared the first casein-based artificial silk fiber. Galalith™ has
been quite successful as an imitation of ivory and porcelain (Pontio, 1919; Bassett,
1921). It is still being used for the production of buttons.
Thus, the polymer industry traces its history to the first modifications of biopoly-
mers: natural rubber, gutta-percha and cellulose in the 183Os. However, it should be
remembered that these modifications, for example of rubber by vulcanization or
cellulose by nitration, are but recent steps in a process that started thousands of years
ago (namely the use of UV-crosslinkable resins for embalming or molding of every-
day objects, or of crosslinkable albumin in mortar).
2.1.2. Synthetic rubbers

The chemical composition of NR was established in 1826 by Michael Faraday as
(CsHg)w but only in 1860 was the basic unit identified as isoprene, CHz=C(CH3)-
CH=CHz, by Greville Williams, who not only obtained (by destructive distillation
of NR) and purified isoprene, but also showed that it can be polymerized in the
presence of air into 'white, spongy elastic mass that when burnt it exhales a peculiar
odor hitherto considered to be characteristic of caoutchouc itself' (Williams, 1860,
1861). Bouchardat managed to conduct the first synthesis of isoprene into rubber by
treating isoprene with HCl (Bouchardat, 1875, 1879). Spontaneous polymerization of
isoprene in sealed bottles was reported in 1884 by Tilden, and in 1887 by Wallach. It
seems that Tilden was the first to realize the commercial significance of the process.
In consequence, most early efforts towards preparation of synthetic rubber involved
polymerization of isoprene. However, the more successful attempts were with its
homologues, butadiene and 2,3-dimethylbutadiene.
At the beginning of the 20th century, the emerging automobile industry created
greater interest in synthetic rubber. The first polymerization of isobutylene into
liquid polymers was reported by Butlerov (Butlerov and Gorianov, 1873; Butlerov,
1877). In 1900, Kondakov in Russia polymerized 2,3- dimethylbutadiene by heating it
with alcoholic potash, and a year later by spontaneous polymerization in sealed
tubes. Lebedev (1910) managed to polymerize butadiene.
Buna
In Germany, the systematic studies of polymerization of isoprene were initiated in
1906 by Fritz Hoffmann at the Friedr. Bayer Aktiengesellschaft. In the 1909 patents,
synthetic rubber was obtained by heating isoprene in closed tubes to 200 °C for 8
days. Four years later, Hoffmann developed a methyl rubber by thermal polymer-
ization of 2,3-dimethylbutadiene. In 1912, two patents were granted to I. G. Farben-
industrie for polymerization of isoprene.
As a result of naval blockades during World War I, Germany was forced to
accelerate this synthetic rubber development program. Profiting from Hoffmann's
experience (but using dimethylbutadiene instead of isoprene), the production of
methyl rubber began in 1914. The polymerization at 70°C required ~ months.
The material was of such a poor quality that production was discontinued when
the war ended. It took 12 more years to get a respectable synthetic elastomer.
In England, Matthews and Strange patented (1910) a sodium-initiated polymer-
ization of isoprene. Three years later, Holt at Badische Anilin und Soda Fabrik,
BASF Aktiengesellschaft, modified the process by conducting the polymerization
under a blanket of C~. The process was used commercially for production of cable
insulating material during World War I. The discovery of sodium-initiated polymer-
ization of dienes was a major step in the development of the first generation of
commercial synthetic rubber. In 1926, Konrad developed a sodium-initiated poly-
merization of butadiene known as Buna™ for BUtadiene + NAtrium. However, the
material was crosslinked and difficult to form. In the Soviet Union, the sodium-
initiated commercial polymerization of butadiene was continued well into the 1940s.
The next major step in the development of the synthetic rubber industry was the
discovery (patented in 1912 and 1913) by Friedr. Bayer Aktiengesellschaft
18 Polymer industry
laboratories of emulsion polymerization. The patents described polymerization
of both isoprene and butadiene. However, the method started to be fully
explored only when the benefits of copolymerization were discovered (Bock
and Tschunkur, 1927, 1928, 1933). In 1933, Tschunkur and Bock patented copolymer-
ization of butadiene and styrene, named Buna-5, and a year later Konrad
and Tschunkur (1934) patented copolymerization of butadiene and acrylonitrile,
named Buna-N. Buna-5 was the first synthetic general purpose rubber. By 1942,
the German production of each elastomer, Trolitul™ and Buna-S™, was about
6Okt/year.
Chlorinated rubber
Chlorinated rubber (CR) was introduced in 1928 by Hamburger Gummiwaren
Aktiengesellschaft. In 1931 Carothers and his colleagues described synthesis of
2-chlorobutadiene chloroprene that when polymerized gave rubbers a uni~e set
of properties. The same year, du Pont de Nemours introduced Duprene (the
name soon changed to Neoprene™). In 1932, about 250 tons of this material was
produced.
Polyureas and polysulfides

In 1923, Pollak introduced polyureas to the Austrian market.
In the USA there was little interest in development of synthetic rubber until the
1920s, when 1. 1. Ostromislensky from Naugatuck Chemical Company in Connecti-
cut started copolymerization of butadiene and styrene (see below). The first
American synthetic elastomer was based on polysulfides. It was discovered by
Patrick (Patrick, 1932, 1942; Patrick and Mnookin, 1927; Thiokol Chemical Corpora-
tion, 1932; Patrick and Ferguson, 1949), and was commercialized by Thiokol
Chemical Corporation as Thiokol™. In 1937, Buna N and Buna S were introduced
in the USA. The same year, butyl rubber (a copolymer of isobutylene with isoprene)
was invented by Thomas and Sparks at Standard Oil Company. In 1939, the
company started manufacturing Buna N, simultaneously licensing Firestone Tire
& Rubber Company and the US Rubber Company to manufacture the Buna™
rubbers.
The research and development of synthetic rubber took a big leap in 1940, when
the Rubber Reserve Company of the US government was established (with head-
quarters located at the University of Akron). The program was integrated with the
similar Canadian Synthetic-Rubber Program. From 1941 to 1944, USA rubber pro-
duction increased every year from 0.23, to 3.7, 182 and 670 kt, respectively. The
Rubber Reserve Company was dissolved in June 1945 (Whitby et al., 1954; Morton,
1982).
In the mid-1980s, Monsanto Chemical Company developed an interesting blend of
NBR with thermoplastic elastomer, ethylene-propylene-diene copolymer (EPDM),
characterized by cocontinuous morphology. These blends are still available from
Advanced Elastomer System as Geolast™, or from Japan Synthetic Rubbers as 15R
NE™. They were formulated for extrusion, injection and blow molding. The appli-
cations included boots, insulating sheet membranes, bushings, covers, casters, coup-
lings, gaskets, hoses and tubings, anti-vibration mountings, etc. Products made from
these alloys showed good processability, oil and heat resistance, low compression
set, low-temperature fleXibility, nearly total elastic recovery and excellent weather
resistance.
2.1.3 Synthetic thermosetting polymers
Phenolics
The first fully synthetic commercial polymer was phenol-formaldehyde (PF), first
described in 1872 by A. V. Baeyer, and patented by Smith in 1899. Eight years later,
the Tech-Art Company molded the first phenolic plastic compounds. In Germany,
Raschig started manufacturing PF in 1909. However, it was the PF commercializa-
tion genius of Leo Hendrik Baekeland, who, after several years of research in his
Yonkers, NY, laboratory, formed in 1909 the General Bakelit Company, that intro-
duced Bakelite™ to the world. He totally dominated the international PF market, and
was instrumental in developing PF production to 175 kt/year. The company was
highly profitable, and in 1939 it became part of Union Carbide and Carbon Chemi-
cals. From 1907 to 1944, the year of his death, Baekeland received 119 patents on PF
resin compositions and methods of manufacture. Amongst other discoveries, he
patented reactive molding of PF resins (Baekeland, 1909). Since the reaction gener-
ates water, it was necessary to prereact the ingredients into resoles, then continue
with the final cure. The products from the Bakelit Company were manufactured
in any color the customer wanted - provided it was black or dark brown. The
claimed reasons were the need to hide the heterogeneity of the material
(mainly fillers), as well as the process imperfectiOns leading to darkening of the
original PF resin. Thus, the name Bakelite is associated even today with these somber
colors.
The original patent on PF expired in 1927. Ta~ advantage, the American Catalin
Corporation introduced rainbow-eolored Catalin resins without fillers, in the form
of rods, tubes and sheets, to be easily machined into a variety of products, such as
costume jewelry, toys, chessmen and decorative panels.
PF resins found many uses, and caused the formation of numerous specialist
companies. For example, to produce phonograph records, J. A. Aylsworth in 1910
created the Condensite Company of America. Four years later, the Redmol Chemical
Products Company was formed to manufacture phenolics furniture. In 1916, the
Terklson Machine Corporation started to mold PF parts for the electrical industry.
Eight years later, the General Electric Company went into production of phenol-
formaldehyde breakers, radio tube bases and switches.
Urea-formaldehyde
In addition to PF, there are several thermoset resins of commercial interest
that employ formaldehyde as a co-reactor. The urea-formaldehyde resins (UF)
were discovered by Holzer in 1884. The first patent was granted to John in 1918,
and commercial production of UF started ten years later as Beetle™ moldable resin.
UF was easy to mold into a variety of shapes and sizes, in all colors, including
white, without loss of performance. Its use further expanded in 1931, when
Formica™ (phenolic paper covered with a decorative layer protected by UF) was
introduced. The same year, the Toledo Scale Company developed grocery-store
scales with Plascon™ UF light-color housings, weighing one-fifth and occupying
63% less space than the cast-iron housings previously used. The housings were
injection molded by the General Electric Company using the largest (then 45 t)
molding press. In 1937 the use of UF as a hot glue for wood was introduced by
Aero Research, then in 1956 as insulating foams, recently notorious for their envir-
onmental effects.
20 Polymer industry
Production of thiourea-formaldehyde molding powders was established in 1920,
and that of urea-formaldehyde (patented by I.G. Farbenindustrie (1925» by Stein
Hall Manufacturing Company in 1929 (also by lCI in the 193Os) (Dingley, 1963;
Kennedy, 1986).
Formaldehyde has also been used as a crosslinking agent in the preparation
of Vinylon™ fibers. These, discovered by Herman and Haehnel in 1927, were spun
from an aqueous solution of polyvinyl alcohol (PVAI) hardened by formaldehyde.
In 1933, the Ciba Company introduced Cibanite™ molding materials based on
aniline-formaldehyde (AF) and, two years later, melamine-formaldehyde (MF)
thermosetting resins. In the USA, MF sheets became commercial in 1938.
Alkyds
Alkyd resins (the term alkyd was introduced by Kienle in 1927) are prepared by
reacting glycerol with a difunctional acid, such as phthalic anhydride. Frequently, a
natural oil containing triglyceride is used, such as linseed, safflower, soy bean, castor
or tung oil. Discovery of these resins is credited to Smith in 1901. General Electric
started commercial production of alkyd resins in 1912, and their coating variety
Glyptal™, in 1926.
Epoxy
Synthesis of the epoxy (EP) compounds was discovered by Prileschaiev in 1909, and
the epoxy resins were invented 29 years later by Paul Schlack at Berlin laboratories
of I. G. Farbenindustrie (Schlack, 1942). The same year, I.G. Wolfen introduced
epoxy-polyamine resins. Realization of the importance of epoxy resins only came
after further work in 1938 by Castan (1940, 1941) that resulted in denture
applications (patented in 1940-44, and licensed to Ciba for manufacture under
the trade name of Araldite™), as well as by Theodore Evans and his colleagues in
the San Francisco Shell laboratories. The latter group developed a new, economic
method of synthesis of glycidyl ether (Evans et al., 1943). The Shell Chemical
Company introduced epoxy surface coatings in 1941. During World War II
epoxy resins were used as adhesives in the manufacture of DeHaviliand Hornet
twin engine airplanes. Commercialization of epoxy plastics occurred in 1950 and,
6 years later, epoxy-glass fiber reinforced plastics were commercialized for pro-
duction of printed circuit boards. Today, entire railroad passenger cars are being
manufactured by glass fiber-epoxy filament winding - a process invented in 1946
by R. E. Young.
Thermoset polyesters
The thermoset (TS) polyesters were developed by Carleton Ellis in 1933. These
materials were used in 1935 by the Marco Chemical Company to mold parts for
the US Wright-Patterson Air Force Base. In 1936-41, Carleton Ellis received several
patents on TS polyesters, induding the currently used formulations with vinyl
monomers. In the USA, commercial production of TS polyesters started in 1937.
The first use of glass-reinforced TS polyesters dates from 1938. Since 1950, the resins
have been used to build large parts: furniture, boats, storage tanks, containers, large
diameter pipes, etc.
Allylic plastics were discovered in the late 1930s at the Pittsburgh Plate Glass
Company (later PPG Ind.), and commercialized in 1943 (Pollak et al., 1942). These
clear, glass-like abrasion-resistant resins were initially used exclusively for surface
coatings, and later also as molding powders.
2.1.4 Synthetic thermoplastic polymers
Styrenics
The discovery of styrene is credited to Neuman, a chemist of the 18th century. Simon
in 1839 named the distillate of Storax officinalis, a natural balsam from the Liquidambar
orientalis tree (used as embalming oil for Egyptian mummies) a styrol. By 1845, the
thermal polymerization of styrene as well as the thermal depolymerization of poly-
styrene were both reported. Stobbe and Posnjak (1909) published the first kinetic
studies of styrene polymerization.
The commercial production of styrene began around 1915 by I. G. Farbenindustrie
for the manufacture of neat polystyrene, Trolitul™. The basic patent to I. G. Farbe-
nindustrie (today's BASF Aktiengesellschaft in Ludwigshafen was created as
Badische Anilin- und Soda-Fabrik, and from 1925 to 1952 was a part of the I. G.
Farbenindustrie concern) was granted in 1936, the year when full-scale production
started. Polybutadiene rubber toughened high impact polystyrene (HIPS) was first
manufactured in 1946. However, up to the 1950s, PS was produced in relatively
small quantities - the resin was brittle, thermally unstable, with poor solvent and
scratch resistance. Its main use was in the manufacture of Buna-S, SBR, and ABS
(Table 1.2).
The first injection molding of PS dates from 1930. The Norddeutsche Seekabel-
werke Aktiengesellschaft developed and patented the technology for PS sheet extru-
sion in 1933. Two years later, bi-axial orientation was introduced. Blow molding of
PS was introduced by the Plax Corporation in 1938.
The first blends of a copolymer of acrylonitrile with butadiene, known as nitrile
rubber (NBR), with glassy styrenics, such as styrene-acrylonitrile copolymer (SAN,
developed in 1932), date from 1936. These were the first mechanical blends that
produced acrylonitrile-butadiene-styrene, ABS type-A. NBR was also found to be an
excellent solid plasticizer, toughener and processing-aid for PVc. In 1942, E. Badum
received a patent for ozone resistant cable insulation made by blending NBR with 10
to 50wt% PVc.
In the United States, I. I. Ostromislensky (1924,1926,1927,1928) from the Nauga-
tuck Chemical Company in Connecticut patented the co-polymerization of styrene
with 'rubber, balata or other elastic and plastic gum'. This was the first patent on
high impact polystyrene (HIPS). Naugatuck Chemical started production of styrene
in 1925. For a few years the company marketed PS under the name Victron™, but
owing to many difficulties production was discontinued. In the early 1930s, the Dow
Chemical Company became interested in styrene for the manufacture of SBR rubber.
In 1938, Dreisbach, with the engineering assistance of Grebe, made the first PS
batches (Dreisbach, 1941; Dreisbach and Stoesser, 1942). In 1942, to improve its
flexibility for radar cable insulation, Dow introduced Styralloy 22. The material was
prepared by sequential emulsion polymerization of styrene and butadiene, which
resulted in interpenetrated polymer network morphology, E-IPN. Modem HIPS was
introduced by Dow in 1945 (Amos et al., 1954), and the emulsion polymerized and
blended, grafted ABS type-G soon followed (Boyer, 1982). By 1944, styrene produc-
tion in the USA. was 90kt/year (Boundy and Boyer, 1952). Today's volume is about
35 times larger. The AB5-type A resins were commercialized in 1950 by Borg-
Warner. At present, the annual production of ABS in the USA exceeds 900kt.
22 Polymer industry
Acrylates
In the late 1870s experimentation on ethyl methacrylate and methacrylic acids led to
water-insoluble polymeric materials. Attempting to distil these materials resulted in
the precipitation of white flakes that showed 'great stability' (Fittig, 1876; Fittig and
Engelhorn, 1880).
Polymethylacrylate (PMA) was first obtained by Kahlbaum (1880) then, along
with a host of other acrylates, three years later by Weger (1883). After being awarded
his doctorate at Tiibingen in 1901, Otto Rohm was persuaded by F. Hofmann to
investigate the possibilities of development elastomers based on acrylates.
However, Rohm had strong business ambitions. By 1907, in partnership with
businessman Otto Haas, he developed Oropon, the first standardized, sanitary repla-
cement for the bates of fermenting dog dung long-used in tanneries. The partners
spent the next two years establishing Oropon in European tanneries. They visited
potential customers, and worked with them in their plants to demonstrate how the
new product could solve their problems. The Rohm & Haas Company first opened its
doors in the United States in Philadelphia on 1 September 1909. Rohm developed
'polyacrylates as substitutes for natural resins (Rohm, 1914). In 1917, America entered
WWI; thus, Haas incorporated the American branch of Rohm & Haas as the inde-
pendent company it has been ever since. Rohm ran the independent Rohm & Haas
Aktiengesellschaft of Darmstadt. In 1912, he obtained a patent on sulfur vulcaniza-
tion of acrylic rubber and, three years later, on acrylic substitutes for drying oils.
For years the main problem had been to find an inexpensive method of synthesis
for acrylic monomers. Rohm's breakthrough came in 1927 - accidentally he discov-
ered that if methacrylate is polymerized between two sheets of glass, the glass will
cleave cleanly, leaving a transparent plastic polymethyl acrylate (PMA) sheet. The
following year, the Rohm & Haas Company of Darmstadt commercialized his first
commercial acrylic product, an interlayer for automotive safety glass. Haas, who had
acquired American rights to his friend's work, set up his own acrylic research group
and in 1931 introduced Plexigum™, his own interlayer, and Oroglas™ PMA sheets
(Utracki, 1989a; Ulrich, 1982; Stinson, 1992). The drawback of PMA was that it was
too soft, and to be useful it had to be copolymerized with ethylmethacrylate (Salkind
et al., 1959), or with other acrylates (Rohm and Haas, 1929). Furthermore, the low
glass transition temperature of PMA, Tg = 110°C, and high moisture absorption
makes it unsuitable as a thermoplastic. In later years PMA, produced by free radical
polymerization in a solution or emulsion, and sold under the trade names of
Acryloid™ or Plexigum™, found uses in textile and leather-finishing operations.
For the discovery in 1930 of rigid polymethylmethacrylate (PMMA) credit must
be given to Hill and Crawford. Furthermore, in 1933 John Crawford developed a
simple and most economic method of methylmethacrylate manufacture. The dis-
covery made it possible for lCI to start successful production of PMMA sheets,
Perspex™, in 1936.
In 1932, Rohm discovered that polymerization of methylmethacrylate between
two sheets of glass leads to a superior product, Plexiglas™. The product was clear,
like glass, but superior in other properties, including formability, shatter resistance
and weight. It took three years' hard work on both sides of the Atlantic to turn the
laboratory curiosity into a commercial product. Darmstadt introduced Plexiglas™ in
Germany in late 1935, and the American company followed the next year. Because of
its superior qualities, Plexiglas™ soon found a market in the transparent portions of
military aircraft, such as cockpit canopies and gunners' turrets. At first, this market
was a small one, but within a few years America began rearming in preparation for
WWII, and military aircraft production boomed, carrying Rohm & Haas with it. By
the end of the war, sales had increased ninefold and the work force sevenfold
(Riddle, 1954).
By the late 1930s, du Pont de Nemours started manufacturing Lucite™ PMMA
sheets. Four years later, the material found its first large-scale application in thermo-
formed bomber nose-cones to be used during WW-II operations (Kennedy, 1986).
To the automotive industry, PMMA was first introduced in 1946, when Chrysler
engineers used it as replacement material for automobile taillight glass lenses.
The quest for acrylic elastomers, (ACM or ANM; the latter containing acrylo-
nitrile), was inaugurated in 1901 by Otto Rohm, but it reached its first commercial
success 43 years later, when Mast and his colleagues at the US Department of
Agriculture's laboratory emulsion-copolymerized ethyl acrylate, allyl maleate lac-
tones, chloroethyl vinyl ether, butadiene, isoprene and acrylonitrile. (Mast et al.,
1944; Mast and Fischer, 1946, 1948, 1949, 1950). The acrylic elastomers could be
vulcanized with PbOz, Sz or sulfides. In 1947, B. F. Goodrich introduced experimen-
tal polyacrylic ester rubber, and a year later Hycar™ PAll (B. F. Goodrich, 1948).
ACMs, having a saturated backbone chain and polar side groups, showed good
resistance to heat, sunlight, ozone and oil. Over the years, several reactive cure-site
comonomers (unsaturated, chlorine, acidic, epoxy, etc.) have been used to improve
storage, vulcanizability and properties of finished materials (Whitby et aI., 1954;
DeMarco, 1979). In 1975, du Pont de Nemours introduced ethylene-acrylic elasto-
mer, Vamac™, curable with diamines.
Polyacrylonitrile (PAN) was introduced commercially in 1930 by I. G. Farben-
industrie. Note that the thermal decomposition temperature of PAN is below its
melting point. Thus, only when, in 1938, H. Rein found solvents for PAN (e.g.,
dimethylformamide (DMF), aqueous solutions of quaternary benzylpyridinium
chloride, ZnCl2, LiBr, NaCNS, etc.), did its fiber spinning begin to be feasible
(Rein, 1936, 1938). Eight years later, R. C. Houtz at du Pont de Nemours obtained a
patent on reacting PAN with PVAl in alkaline medium to obtain products soluble in
acetone, MeOAc or dioxane (Houtz, 1944, 1950). The first fibers made of these
coreactants were produced for military use; then, in 1950, du Pont commercialized
the fibers on the open market as Orlon™ and, two years later, PAN-fiber staple. In
1952, the Chemstrand Corporation (now Monsanto) introduced Acrilan™ acrylic
fibers.
By definition, acrylic fiber must contain ~ 85wt% PAN; fibers containing
35 :s wt % PAN :s 85 (the rest being either vinyl chloride, vinylidene chloride, or
vinylidene cyanide) are known as modacrylic. The first modacrylic fiber, Vinyon™
N (copolymer of acrylonitrile with 60wt% vinyl chloride) was commercialized by
the Union Carbide Corporation in 1948.
Vinyl and Vinylidene Halides

Polyvinylchloride (PVC) was first obtained by Regnault (1835), who exposed vinyl
chloride to sunlight in a sealed tube, obtaining a solid white powder. The experiment
was repeated by Baumann (1872), follOWing Hofmann's polymerization of vinyl
bromide by the same method (Kaufman, 1969). Details of vinyl halides polymeriza-
tion have been discussed by Ostromislensky (then in Moscow) in several patents and
publications (1911, 1915, 1916). The first patent on polymerization of PVC was
granted to him in 1912. The same year, PVC was polymerized in Germany by
Klatte, who a year later applied for a patent for manufacture of PVC fibers. In
1914, Klatte and Rollet disclosed the use of peroxides as accelerators in the thermal
24 Polymer industry
polymerization of PVc. However, to make commercially viable articles, PVC had to
be stabilized and either plasticized or blended.
The benefits of plasticization have been known since Comides, in 1855, modified
cellulose nitrate (NC) by addition of a copal gum. In 1869, plasticization of NC by
camphor brought Hyatt brothers a commercial success (Celluloid). However, owing
to the low molecular weights of plasticizers, they tend to migrate to the surface and
evaporate, causing premature brittleness. Thus, the main industrial efforts were
directed towards development of either compositions that would minimize the use
of plasticizers (so-<:alled rigid formulations), or blends with other polymers.
B. F. Goodrich started production of PVC (Vinylite™) in 1927. In the same year
was developed a PVC plasticization method for molding applications (Semon, 1933).
The following year, the material was introduced by the B. F. Goodrich Company.
PVC usa~ for high-voltage cable insulation started in 1932, for floor tiles a year later
(Vinylite of Carbon Chemicals Corporation), for pipelines in 1936 and 1937. The
general-purpose plasticized PVC was commercialized in late 1936 (Mipolam™). By
1936, vinyl records became the choice of the recording industry. In 1940, B.F. Good-
rich ~tented the NBR/PVC blends, and 7 years later introduced it commercially as
Geon Polyblends. From these beginnings, PVC production increased to 0.22, 6.1 and
22Mt in 1950, 1970 and 1991, respectively (Semon and Stahl, 1982).
I. G. Farbenindustrie commercialized plasticized (by tritolyl phosphate and
dibutyl phthalate) and stabilized PVC in 1931, and started full-scale production 6
years later. The initial use was for fabric coatings and shoe soles. Rigid PVC for-
mulations were patented in the 1930s (Fikentscher and Heuce, 1930; Fikentscher and
Wolff, 1931; Fikentscher and Schmidt, 1936). PVC was extruder blended with poly-
ac~c ester impact modifier and sold under the names of Troluloid™ and Astra-
Ion (later Trovidur™ and Vestolit™) - these two were the first commercial
thermoplastic polymer blends (Fisher, 1958). PVC blends with Buna-N (introduced
in 1932) resulted in excellent thermoplastic materials (Badum, 1937). Rigid PVC not
only has a higher heat deflection temperature (HDT), but in addition it is perma-
nently plasticized. During WWII, rigid-PVC piping allowed the Germans to restore
their fresh water supply within hours after Allied bombing raids (Lutz, 1936, 1937).
Emulsion polymerization (used since 1912 for polymerization of isoprene) of PVC
was developed only in 1929. The use of a redox system was introduced eleven years
later at ICI (Bacon, 1946). In 1934, I.G. Rheinfelden introduced post-chlorination of
PVC, and I. G. Wolfen started to manufacture post-ehlorinated PVC fibers.
Polyvinylidenechloride (PVDC) bi-axially oriented film Saran™, was developed
in 1939 at Dow Chemical by Reilly and Wiley, who also invented methods of
molding PVDC (Wiley, 1946). Polyvinylidenefluoride (PVDF) was introduced com-
mercially by Kureha Chemical Industries, and by Dynamit Nobel, respectively, in
1971 and 1973.
Polyvinylacetate (PVAc) was developed by Klatte at Chemische Fabriken
Greisheim-Electron in 1912 (Klatte, 1912), but no commercial application was
found until 1924 when, independently, Wacker and Herrmann & Haehnel (1927)
discovered its hydrolysis to polyvinyl alcohol (PVAI), useful for textile sizing. Two
years later, I. G. Farbenindustrie patented the use of PVAc as an adhesive. However,
before these events, the vinyl acetate monomer was frequently copolymerized by I.G.
Farbenindustrie and du Pont de Nemours with other vinylic and acrylic monomers.
Shawinigan Chemicals, Limited started the first commercial production of PVAc
(Elvacet™) in 1928 at Shawinigan Falls, Canada (Blaikie, 1930). The following year,
large scale production of PVAc began in Germany. The resin was commercially
introduced to the USA in 1936.
In 1928, Reid, from the Carbide & Carbon Chemicals Corporation of New York,
and Voss and Dickhauser from I. G. Farbenindustrie in Frankfurt a. M., independ-
ently applied for patents on peroxide-initiated copolymerization of vinyl chloride
with vinyl acetate, PVCAc. The resin, after mixing with NC or CA, was to be used in
lacquers or plastics (Reid, 1933; Voss and Dickhauser, 1933). The latter patent also
included copolymerization of vinyl chloride or vinyl bromide with styrene. The
copolymers were used in blends with cellulose-derivatives, resins and elastomers.
Three years later, the same authors obtained patent rights for copolymerization of
styrene with maleic anhydride, to be used in a variety of applications, including
lacquers, such as impregnating materials, electrical insulating materials, adhesives,
thermoplastics, etc. (Voss and Dickhauser, 1936).
In 1929, Morrison et al. at Shawinigan Chemicals developed polyvinyl formal
(PVFO) and polyvinyl butyral (PVBO). The company started manufacturing these
resins (primarily for safety glass applications) in 1934 and 1935, respectively (Morri-
son et aI., 1936).
Ethylene-vinyl acetate copolymer (EVAc) was introduced by du Pont de
Nemours in 1960.
Polyethylenes
The first crystalline polymethylenes (with melting point, Tm = 137°C) were obtained
by thermal decomposition of diazomethane (Hinderman, 1897; von Pechman, 1898;
Bamberger and Tschirner, 1890). The first attempts to polymerize ethylene were
unsuccessful (Gorianov and Butlerov, 1873), but in 1913 Ipatiev reported oligomer-
ization of ethylene in the presence of ZnCh and AICh. In 1930, Carothers and his
colleagues at du Pont de Nemours produced polydisperse polymethylenes by con-
densation of decamethylene bromide: (CH2)lOBr2 + Na = H(CH2)nH. After fractio-
nation, the polymerization degrees were determined as n = 40,50,60,70, . ... At
about the same time, at I. G. Farbenindustrie the polymerization of ethylene in the
presence of BF was carried out under high pressure (Hofmann and Otto, 1931).
In 1931, ICI initiated the fundamental studies of high pressure reactions (up to 300
MPa). On 24 March Fawcet and Gibson (1933), left overnight an autoclave filled with
ethylene and benzaldehyde at a temperature of 170°C, at a pressure of 190 MPa - in
the morning the pressure was near zero. The vessel was repressurized and left at
170°C for the weekend, but on Monday the pressure again was zero. Inside the
dismantled reactor there was about half a gram of a waxy, white powder, later
identified as polyethylene. Unfortunately, the reaction was highly irreproducible.
During the 1935 meeting of the Faraday Society, Fawcet announced the discovery.
Luckily for ICI and Britain, the participants (including Hermann Staudinger,
Herman Mark, Kurt Meyer and other luminaries) dismissed the information as
implausible. Mark authoritatively stated: 'ethylene does not polymerize' (Kennedy,
1986).
By 1935, M. Perrin and J. Swallow established that polymerization of ethylene was
radical in nature, and that it was initiated by traces of oxygen or a peroxide. Under
the conditions used by Fawcet and Gibson (without benzaldehyde, but with con-
trolled amounts of oxygen), the new team was able to achieve reproducibility. In
February 1936, a provisional British patent was filed. It described polymerization of
ethylene at 100-300 °C and 50-300 MPa, into polymers with density of 910-920 kg/m3
and melting point of 115°C. A year later Telcothene™, a blend of polyethylene
(PE) and polyisobutylene (PIB), was manufactured for submarine cables. On
1 September 1939, the first high pressure, low density polyethylene (HPPE or
LDPE; Alketh™) plant with 100 tons/year capacity went into operation (Seymour
26 Polymer industry
and Cheng, 1985; Ballard, 1986). A year later a 1Q-fold larger plant was commis-
sioned (Kennedy, 1986).
In the USA, the first PE was produced by Union Carbide in a tubular reactor using
its own technology in 1940. Two years later, on license from lCI, Union Carbide and
du Pont de Nemours started production of LDPE in plants with SOO ktons/year
capacity. The third PE manufacturer, Eastman Chemical Products, started produc-
tion in 1954.
Polyamides
Polyamide-6 (PA-6 or poly-€-eaprolactam) was first obtained by J. Von Brown and
his collaborators at G6ttingen University during 1905-10. In 1930, Carothers
and Berchett reported conversion of w-aminocaproic acid to lactam and a gray
waxy polyamide with a molecular weight below 3 kg/mol (Carothers and Hill,
1932). Schlack (1938) applied for several patents on the catalytic polymerization of
€-eaprolactam to PA-6. The patents specified that heating acylated aminoacids or
lactams produced polyamides with fiber-spinning characteristics. The following
year, I. G. Farbenindustrie introduced the polymer, Perlon™. In spite of the patent
claim that 'the product can be continuously spun from melt into uniform threads',
I. G. Farbenindustrie used PA-6 for moldings. Thus, Schlack may be considered the
inventor of commercial PA-6. In 1941 the invention was patented in the USA, and by
mesne assigned to du Pont de Nemours. In France, production of PA-6 started in
1942. During the years 1937-42, du Pont de Nemours obtained several patents on
polymerization of €-eaprolactam into PA-6, suitable for making synthetic fibers
(Hanford, 1941; Greenewalt, 1941; Martin, 1942).
In a series of four patents Carothers (1937) disclosed the invention of polyamide-
66 (PA-66). This resin was one of the more than 3000 polyamides he and his
colleagues at du Pont managed to synthesize. The patents described several other
important aliphatic and semi-aromatic polyamides, e.g., PA-6 and PA-610. Two
years later, on an experimental basis, du Pont introduced PA-66 fibers. In 1938, the
company started its commercial production under the trade name Nylon™, an
aggregate of New York and LONdon. The first applications were as a replacement
for silk in women's stockings, and for paint brush bristles. The Nylon TM success was
a fit crowning of the 10th anniversary of the fundamental research program on
polymers established at du Pont.
Also in 1938, on a license from du Pont, lCI commercialized the PA-66 fiber in
Britain. A year later, the BASF division of I. G. Farbenindustrie and Societa Rhodia-
toce introduced PA-66 in Germany and Italy, respectively. Unfortunately, the public
sale of Nylon TM was short-lived. Owing to the cut-off of the importation of silk from
Asia, PA was used as a replacement. For the duration of WWll, PA production was
dedicated to military use for fabrics, tow ropes, parachutes, tire cords, etc. After
1941, molding grades of PA-66 were introduced by du Pont. The second production
facility was built in 1941 by the Canadian Industries, Limited (ClL) at a specially
selected site in Kingston, Ontario. In 1954, as a result of the great divorce of ClL from
du Pont, the ownership of the Kingston plant was transferred from ClL to Du Pont
Canada (Kohan, 1973; Nelson, 1976; Lank and Williams, 1982).
Thermoplastic polyesters (PEST)

Linear polyesters from diacids and dia1cohols were described by Carothers and
Arvin (1929). The condensation of ethylene succinate that resulted in oligomers
with molecular weight ranging from 265 to 321 g/mol was discovered much earlier
(Vorliinder, 1894). However, even the next generation of polyesters, having molecu-
lar weights near 5 kg/mol, was not fiber-forming. Three years later, Carothers, with
Hill, published several papers describing new superpolyesters having molecular
weights above 10 kg/mol. These new materials were prepared using a molecular
still, that made it possible to carry out polycondensation at pressures below
10-5 mm Hg. Polyesters from acids (w-hydroxydecanoic, w-hydroxypentadecanoic
or from hexadecamethylene dicarboxylic acid and trimethylene glycol) could be
'drawn out into very strong, pliable and highly oriented fibers'. However, at that
stage, after studying large number of polyesters, neither Carothers nor, apparently,
du Pont expected them to be useful as fiber-spinning polymers - the melting point of
these polyesters was too low. Furthermore, since in the meantime superpolyamides
with better fiber-formability and higher tenacity were discovered, the work on
aliphatic polyesters was discontinued.
In 1941, J. R. (Rex) Whinfield and J. T. Dickson of the Calico Printers' Association
approached lCI with a few grams of polyethylenete~hthalate(PET) proposing a
licensing agreement for commercialization of Terylene fibers. Their patent applica-
tions of 1941 described condensations of terephthalic acid with ethylene glycol that
resulted in crystalline, aromatic polyesters with good fiber-spinning properties.
Catalytic transesterification of dirnethylterephthalate with di-, tetra- and hexamethy-
lene glycols (thus leading to PET, PBT and PHMT) was described as well (Whinfield
and Dickson, 1941). These aromatic polyesters, with a melting point of 256 °C,
showed superior properties over those of the aliphatic analogs. In 1990, the world
production of PET was 1.3 Mtons, with expected growth to 2.3 Mtons by the year
2000.
Polyurethilnes (PU)
In 1937, Otto Bayer and his colleagues at the Leverkusen laboratories of I. G.
Farbenindustrie, invented the diisocyanate addition process, leading to production
of polyurethanes for fibers and rigid foams (Bayer, 1939, 1942, 1947). The discovery
also resulted in the first production of thermoplastic PU elastomers, Igamid U™. In
1939, the Wollen division of IG. Farbenindustrie started production of PU fibers and
bristles, Perlon™ type U. Polyester-type PU was commercialized in Germany in
1942, and a year later in Britain. Otto Bayer was also one of the team members that
in 1952 announced discovery of the thermoplastic linear polyurethanes (TPU; Milller
et al., 1952). Two years later, Bayer-Mobay (later to become Miles Inc.) introduced PU
to the USA. In 1961, the company commercialized Texin™ PU elastomeric resins for
extrusion and injection molding (Texin™ 300 and Texin™ 4000 are blends of poly-
ester urethane with bisphenol-A polycarbonate, with either TPU or PC being the
major phase).
In 1959, B. F. Goodrich introduced thermoplastic polyurethanes (TPU), Estane™
TP. In 1965, du Pont de Nemours announced the Corfam™ technology (based on
polyester-reinforced PU) for the production of shoes. Six years later, this US$1OO mil-
lion investment was abandoned - sold to a Polish government company. Polyether
polyurethanes were introduced in 1971 by Uniroyal under the trade name Roylar™
A863.
Silicones
The beginning of organosilicone chemistry goes back to Friedel and Crafts's synthesis
of tetraethylsilane (Friedel and Crafts, 1863). However, it was the four decades of
Kipping's work (starting in 1899) that provided the basic information (Kipping, 1912,
1937; Kipping and Murray, 1928). In 1931, the work toward development of
28 Polymer industry
organosilicone polymers started at Corning Glass Works - it was based on Kipping's
method of monomer synthesis (SiC4 treated with Grignard reagents). However, the
first silicones were introduced by Dow Chemicals only in 1938, and full scale com-
mercialization 4 years later (by the newly formed Dow Corning Corporation; Free-
man, 1962).
The process based on Kipping's chemistry was expensive. An alternative method
of monomer synthesis was developed by Rochow at the General Electric Company
(Rochow, 1941, 1945). The author found that treating Si + Cu alloy with CH3Clied to
(CH3hSiC!z. In 1946, General Electric started production of silicone polymers based
on Rochow's method (Liebhafsky, 1978).
2.2 GROWTH PERIOD: POST 1945
2.2.1 Commodity resins

Five large-volume polymeric groups belong to this category: low and high density
polyethylenes, polypropylene, styrenics and polyvinylchloride. Their world market
share (Table 2.2) remains relatively stable; the commodity resins represent 71 % of all
consumed plastics.
Polyethylenes (PE)
In 1991, the world production of LDPE, HDPE and LLDPE was 16.3, 15.4 and 7.8 Mt/
year, respectively, amounting to 39 wt % of all thermoplastic resins' market.
During WWTI, the ICI high pressure radical polymerization of ethylene to LDPE,
was licensed in 1942 to du Pont de Nemours and Union Carbide, then to Arco,
Eastman and several other companies. (It should be noted that both du Pont
and Union Carbide modified the ICI process, e.g., tubular reactors were used
instead of stirred autoclaves. The modifications evolved into new, proprietary
technologies). After WWTI, other production methods of LDPE were developed by
BASF, Dart Industries, Dow Chemical, du Pont de Nemours, Gulf Oil and Union
Carbide.
In 1951, the first patent for low pressure (1-10 MPa) catalytic polymerization of
ethylene into HDPE (density 920-980 kg/m3) was deposited by Zietz of Standard Oil
of Indiana (ZIetz, 1954). The document described formation of a rubbery polymer
with high molecular weight. It was soon followed by similar application by Hogan
and Banks of Phillips Petroleum Company (Hogan and Banks, 1955), and by Ziegler
et al. (1960, 1966). Thus, three catalytic systems were disclosed: ZIetz used molyb-
Table 2.2 World market share by resin type in 1992
No. Resin type Market share (%)

1. Low density polyethylene, LDPE + LLDPE 20
2. High density polyethylene, HDPE 12
3. Polypropylene, iPP 12
4. Polystyrene homopolymers and copolymers, PS + ABS 10
5. Polyvinylchloride, PVC 17
6. Other thermoplastics, TP 13
7. Thermosets, TS 16
Growth period: post 1945 29
dena-alumina, Hogan and Banks claimed hexavalent CrQ3 on silica, while Ziegler et
ai. employed aluminum trialkyl (e.g., AIEt3) with TiClt. Hoechst (in 1954) was the
first large-scale manufacturer of HDPE by means of the Ziegler process. Commer-
cialization by Hiils, Riihrchemie, Montecatini, Shell, Mitsui, Dow, Esso, Gulf, Her-
cules/ Koppers, Monsanto and Union Carbide soon followed. In the USA, production
of HDPE was initiated in 1956 by Phillips. By that date, the company already
licensed the process to nine companies in seven countries. In 1957/ Hercules was
the first to introduce the ultra-high molecular weight HOPE (UHMWPE), also
produced using the Ziegler-Natta-type catalyst. In 1960, the production of HDPE
in the US reached 120 kt, of which 90 kt were produced by the Phillips process
(Sailors and Hogan, 1982). In 1957/ at the peak of the hula hoop craze, consumption
of PE in the USA climbed to 500 tons/week.
In 1953, Karl Ziegler at the Max Planck Institute in Mulheim, using a catalyst based
on transition metals suspended in organic solvent, polymerized ethylene at pres-
sures slightly above the ambient to linear, high density polyethylene (HDPE), as well
as propylene and butylene to isotactic polymers, PP and iPB. Similar discoveries
were published by Giulio Natta, who focused on the ability of the new catalyst to
produce stereospecific poly-Q-alkenes. (In 1924/ at the age of 21, Natta graduated
from the Milan Polytechnic. During the years 1933-37, he lectured at the Universities
at Pavia, Rome and Turin, before returning to Milan as Professor and Director of the
Industrial Chemical Institute - the post he held until his death in 1979. In 1963/ Zieg-
ler and Natta shared the Nobel Prize in chemistry). From then on, these organome-
tallic compounds (usually of aluminum trialkyl with a transition metal compound)
have been known as the Z-N catalysts. Soon thereafter, similar catalysts (based on Cr
and Mo) for polymerization of ethylene were developed in Amoco and Phillips
laboratories.
The typical Ziegler-Natta catalysts (or Z-Ns) are based either on TiClt, VCls or
CoCh mixed with either AI(CzHsh or Al(CzHs}zCl in an inert solvent. Both the
crystalline solid and highly colored supernatant solution can initiate polymerization,
but only the former leads to stereospecific polymers. The crystalline catalyst has
many active sites catalyzing different reactions - for example, four types were
postulated by Floyd et ai. (1987/ 1990). Thus/ the Z-N catalysts lead to polymers
with a wide range of polydispersity, composition and limited stereospecificity.
To improve selectivity of the catalyst, two routes were taken: (i) additives have
been used to 'poison' some of the sites, and (ii) ligands have been incorporated to
force the monomer to unique molecular orientation when approaching the active
site. For example, the new Dow Chemical Company Insite™ metallocene catalyst
contains [CsMe4(SiMezN-Bu)]TiMez (where CsMer is a tetramethylcyclopenta-
dienyl group)/ with two cocatalysts, tris(pentafluorophenyl)borane and modified
methyl aluminooxanes (ratios B:Ti = 2:1/ Al:Ti = 4:1), all dissolved in saturated
hydrocarbons, CS-lO.
In 1962/ Vanderberg patented polymerization of alkenes to polymers having
controlled molecular weight by injecting controlled amounts of hydrogen into the
reactor. The molecular weight control was described as useful in combination with a
hydrocarbon insoluble catalyst system comprising the reaction product of
a compound of a metal of Groups IVB, VB, VlB and VIll, with an organometallic
compound of an alkali metal, alkaline earth metal, zinc, earth metal or rare earth
metal.
In 1956/ B. F. Goodrich started production of cis-1/4-polyisoprene, soon to be
followed by Firestone Tire & Rubber Company. Both manufacturers used the Z-N-
type stereospecific catalyst system (Home et al., 1954; Stavely, 1956).
30 Polymer industry
LLDPE
In 1957/ in Du Pont Canada research laboratories in Kingston, Ontario/ the work on
Z-N-type catalysts led to a low-pressure solution technology, Sclairtech™, based on a
new coordination catalyst. The process made it possible to copolymerize ethylene
with 10-20 mol % of higher alkenes (butene, hexene or octene), which prOVided
greater variety of polyethylenes than the standard Z-N-type process. The Sclair-
tech™ technology made it pOSSible to produce a variety of resins from HDPE to
new linear low density polyethylenes (LLDPE). The density and crystallinity (that
control the performance) of the new resins depended on the type, amount and
sequence of placement of a comonomer. These LLDPEs had been used to manufac-
ture films and fibers. However, owing to excellent performance parameters, the
resins were also used at a premium in more critical applications, such as for
natural-gas pipelines. A full scale production facility, the St. Claire River Works
near Sarnia, Ontario, Canada, began in 1959 (Lank and Williams, 1982).
For about 20 years, the importance of LLDPE remained unrecognized, until in 1968
Union Carbide introduced the gas phase, fluidized bed, low pressure UnipolTM
process for large-volume production of the resin. The first production unit with
UnipolTM technology started in 1970 in Sweden. In the USA, the first UnipolTM reactor
was on stream in 1975. The Unipol-LLDPE resins became darlings of the polyalkene
industry - within the first 10 years, 28 manufacturers in 15 countries were licensed.
By 1991/ production of LLDPE had grown to about 25% of the world demand for PE.
From 1945 to 1991/ the annual volume of PE world production increased from 5 to
39.5 kt. Since the new resins were difficult to process on the processing lines
designed for the low density (high pressure) polyethylenes (LDPE), a number of
patents were issued for the LLDPE blends with other polyalkenes, e.g., LDPE or EPR.
In 1982 alone, hundreds of patent applications for blends of LLDPE with other
polyalkenes, copolyalkenes and alkenic elastomers have been filed. For example,
ethylene copolymers, thermoplastic elastomers, TPO/ EPDM, EPR, EVAc, maleated
polypropylene, PP-MA, etc., have been used (Haas and Raviola 1982; Hughes, 1982;
Cowan, 1983; Janac et al., 1983; Turtle, 1983; Fukui et al., 1983; Haas, 1983; Hert, 1983).
In the 198Os, new catalysts further extended the range of PE properties to those of
very low density polyethylenes (VLDPE, density = 900-915 kgjm3 ) and ultralow
density polyethylenes, (ULDPE, density =855-900 kgjm3 ). The latter, a copolymer of
ethylene with n-butene, n-pentene or 4-methyl pentene-l, was polymerized using
MgTAlsTit(OR)uClv (where the subscripts are positive integers) catalyst in either a
gas phase reactor or in a hexane solution at 70-11 °C and 0.5-2 MPa (Cady, 1987).
ULDPE, commercialized by Mitsui Toatsu Chemicals in 1986, has low crystallinity
and a low melting point of 4G-85°C. As a result, it shows properties intermediate
between those of PE and an elastomer (Kim et al., 1992).
With development of VLDPEs and ULDPEs, the distinction between thermo-
plastic polyethylenes and elastomeric ethylene-propylene rubbers (EPR)
became increasingly difficult to make (PEs with density ::; 900 kg/m3 are basically
elastomeric). By 1992 Exact™ PE, a VLDPE made using metallocene or single-site
catalyst, was introduced by Exxon Chemical. The 1992 world production of
VLDPE was 110 kt, increasing about 20%/year toward the expected market satura-
tion at 1.8Mt/year. The prime use of ULDPE is in blends of LDPE, HDPE or PP
(Utracki, 1989b; Kohyama and Yamada, 1991; Leaversuch, 1992; Utracki and
Dumoulin, 1995).
As shown in Figure 2.1, the density of PE determines stiffness of the resin. The
relationship indicates that it is not the molecular weight but crystallinity that deter-
mines the value of the modulus of commercial polymers.
10"
-e:.
( II
(/)
:h~
::>
Cl
0
~
....J
~102
::>
><
w
....J
U.
10'
860 900 940 980
3
DENSITY (kg/m )
Figure 2.1 Flexural modulus versus density of polyethylenes.
Multi-site catalyzed LLDPE
~~ ------- -----
120 - - - -- - - 120
--~
I-
Z 100 100
~
C>
z
5w 80 80
~
Single-site catalyzed LLDPE
60 '---80----'----9--'0-0----'-----9-'-2-0------' 60
8
DENSITY (kg/nr)
Figure 2.2 Comparison of the melting point versus density relationship for linear low density
polyethylenes synthesized using older Ziegler-Natta multisite catalysts and newer metallocene
single-site catalysts. (adapted from Todo et al., 1994).
The newest, single-site metallocene catalysts (e.g., the constrained geometry

catalyst technology (CGCT) using Insite™ catalyst from Dow Plastics) open new
vistas for production of high quality polyalkenes, with controlled molecular weights,
molecular weight distribution, comonomer placement and density, i.e., crystallinity.
As shown in Figure 2.2, there is a significant difference in the melting point versus
composition dependence for polyethylenes prepared using the classical Z-N cat-
32 Polymer industry
alysts (older LLDPE technology) and the metallocene ones. The difference originates
in the regularity of the comonomers' placement, which controls the size of the
crystallizing chain segments. Such regularity can be obtained using metallocene
but not Z-N catalysts.
In 1975, Mitsui Petrochemicals introduced metallocene-made Tafmer™ linear low
density polyalkene with strictly controlled comonomer placement in the chain. The
resins had rather low molecular weights. Eight years later, Polysar disclosed bi-
metallic metallocene alumoxane catalyst used in polymerization of alkenes into
elastomeric ethylene-a-alkene copolymer or ethylene-a-alkene nonconjugated di-
alkenes (Davis, 1994). Unfortunately, reengineering of the company prevented it
from pursuing this invention.
Also in 1983, Exxon Chemical deposited a patent application (that was granted 11
years later!) for polymerization of ethylene in the presence or absence of comono-
mers to polyethylenes of controlled molecular weight and density. The molecular
weight was controlled by selecting appropriate substituents on the cyclopentadienyl
ring as well as ligands for the metallocenes. Selecting the catalyst components made
it possible to control the (co)polymer molecular weight and density. The metallo-
cenes were cyclopentadienyl derivatives of the general formula ~(Cp hMpQm when
M is a metal from Group IVb, Vb or VIb (preferably Zr), Cp is a cyclopentadienyl or
substituted cyclopentadienyl, R' is a Cj -e4 alkylene radical, a dialkyl germanium
or silicone, Q is an alkylidene radical having from 1 to about 20 carbon atoms,
s = 0-1, P = 0-2 and m = 4-5]. The catalyst was used in combination with
alumoxanes (Welborn and Ewen, 1994).
Four years later, Exxon jointed Mitsui Petrochemicals to further development of
metallocene technology. The collaboration resulted in development of the single-site
metallocene catalysts, ExxpolTM.
In a patent disclosure, originally deposited in 1991, a method of ethylene (co)po-
lymerization in a solution, gas or slurry phase, into polymers with broader mole-
cular weight distribution was described. The metallocene catalyst had at least one
substituted cyclopentadienyl ring. The possibility of using a single cyclopentadienyl
ring is important, since it opens up possibilities of producing PEs with less regular
structure, beneficial for the processability. The catalyst also comprised a transition
metal salt, selected from the group consisting of Ti, Zr, Hf and their combinations.
Furthermore, the patent described catalyst support, as well as a methylalumoxane
cocatalyst. Disclosed PE resins had a unimodal molecular weight distribution with a
molecular weight distribution index Mw/M n = 4-20 Gejelowo, 1994).
Both single-site metallocene catalysts, ExxpolTM from Exxon-Mitsui and Insite™
from Dow, have been evaluated on a pilot-plant scale since 1991 (Leaversuch, 1991;
Lai et al., 1993, 1994). The new polymers show betterprocessability, clarity and mechan-
ical properties than those obtained using older Ziegler-Natta catalysts. The first com-
mercial metallocene-made PE was introduced by Exxon in 1991 as a Plastomer™.
In 1991-2, Dow Plastics produced developmental quantities of ethylene copoly-
mers with up to 25 mol % of butene, hexene or octene. The material had low density
of 855-970 kg/m3 , narrow molecular weight distribution, and precisely controlled
comonomer sequencing. As a result, it showed good flexibility, clarity, gloss, punc-
ture resistance, dart impact, toughness and strength.
The 1tnityTM resins were introduced in 1993. The polyalkene plastomers (POP;
Affinity , density 885-895 kg/m3 ) and the polyalkene elastomers (POE; Engage™
density 864-880 kg/m3 ) from Dow Chemical Company, are copolymers of ethylene
with 0-20 wt % of octene, pol-hTerized using the single-site, and single cyclopenta-
diene ring catalyst, the [nsite technology. The resins showed narrow molecular
weight distribution and long chain branching, similar to LOPE. They have excellent
processability, clarity, impact strength and oxidative stability.
In 1993, also using the metallocene catalyst technology, Mitsui Petrochemicals
started production of HOPE, LLOPE, LOPE and VLOPE in a pilot plant with
capacity 100kt/year (Martino, 1992). Several other companies in Europe and Japan
are active in this field (SPSJ, 1992). Mitsui, Mitsubishi, Dow, Union Carbide and
Exxon forecast production capacity of metallocene-catalyzed polyethylenes of
650kt/year by the year 1995. By 1995, several companies (BP Chemicals, Chiso,
Dow, Exxon, Hoechst, Mitsui, Mitsui Toatsu, Mitsubishi, Sumitomo, Tosoh and
Union Carbide) developed production capacity for polymerizing the new type of
PE and PP resins of about 750 and 350 kt, respectively.
To summarize:
• 1939 (ICI - Alketh): radical polymerization to LOPE, characterized by broad dis-
tribution of molecular weight (MWD), long-ehain branching (LCB), and short-
chain branching (SCB).
• 1955 (Phillips, Hoechst - Marlex, Hostalen): Ziegler-Natta slurry polymerization of
HOPE, characterized by linearity of macromolecules, moderate MWD and high
crystallinity.
• 1957 (Du Pont Canada - Sclaire): Ziegler-Natta slurry polymerization of LLOPE,
characterized by broad MWD, absence of LCB and random placement of SCB.
• 1968 (Union Carbide - Unipol): Ziegler-Natta (multi-site catalyst) gas-phase poly-
merization of LLOPE, characterized by moderate molecular weight, broad MWD,
absence of LCB and uneven placement of SCB on short and long macromolecules.
• 1975 (Mitsui Petrochemical- Tafmer): metallocene, single-site catalyst polymeriza-
tion of LLOPE, characterized by narrow MWD, absence of LCB and regular
placement of SCB. Owing to possibilities of incorporation of diverse comonomers,
even at high concentration, LLOPEs having a wide range of densities may be
obtained.
• 1991 (Exxon - Exact): metallocene, single-site catalyst polymerization of LLOPE,
characterized by narrow MWD, absence of LCB and regular placement of SCB.
• 1993 (Dow - Affinity): metallocene, single-site, single ring catalyst polymerization
of LLOPE, characterized by narrow MWD, presence of LCB (engendered by the
monocyclopentadienyl metallocene catalyst that offers easier access), and regular
placement of SCB. Good processability and excellent melt strength.
• 1993 (BP): metallocene/Ziegler-Natta, polymerization of LLOPE aimed at achiev-
ing good balance between economy, processability and performance.
The LLOPE, VLOPE and ULOPE have been extensively used in polymer blends.
Although the extent of blending varies from one country to the next, the general
advantages of blending are widely recognized. Blends with PP have attracted much
commercial interest (Utracki and Dumoulin, 1995). Since these polymers are immis-
cible, copolymers such as EPR or EPOM are frequently employed. Compatibilization
can also be achieved by reactive blending, dynamic vulcanization, or post-blending
crosslinking using peroxides, electron beam or 'Y irradiation. Both factors, the react-
ive compatibilization and irradiation, lower the crystallinity. Thus, the micromor-
phological character of PP-PE blends can be controlled by composition, presence of
the nucleating agents, type of compatibilizer and thermal or radiative treatment
(Nadkarni and Jog, 1991). The new polyalkenes with narrow molecular weight,
controlled comonomer placement and high stereospecificity, that can be obtained
by means of the single-site catalytic systems introduced new challenges to blending
science and technology.
34 Polymer industry
Polypropylene
In 1991, world production of polypropylene (PP) was 17.2Mt, and constituted 16.9%
of the thermoplastic resin market. Extensive scientific research, as well as 22-year-
long litigations, made it an expensive polymer to develop. Several companies, du
Pont de Nemours, Hercules Powder, Montecatini, Phillips Petroleum and Standard
Oil of Indiana, all had claimed priority. In 1980, a District Court awarded the priority
to Phillips (Hogan and Banks, 1985). The PP technology has been mainly based on
the Ziegler-Natta process developed for HDPE. The required pressure was kept only
at the level sufficient to maintain up to 20% propylene in a solvent at 90 0c. The final
slurry contained 2Q-40 wt % of PP.
There are three types of polypropylene on the market: amorphous (aPP), isotactic
(iPP) and syndiotactic (sPP). The tacticity refers to stereospecific structures that may
be derived from the monomer. Stereospecific propagation may be applied in the
polymerization of ethylenically unsaturated monomers such as C3-a-alkenes,
1-diene, or substituted vinyls such as styrene, vinyl chloride, vinyl ethers or vinyl
esters, Stereospecific polymer propagation is probably most important in the pro-
duction of isotactic or syndiotactic polypropylene.
The iPP structure is usually described as having the methyl groups attached to the
tertiary carbon atoms of successive monomeric units on the same side of a hypothet-
ical plane, passing through the main chain of the polymer, e.g., the methyl groups
are all above or below the plane. Alternatively, using Bovey's NMR nomenclature,
an isotactic pentad is described as ... mmmm ... where each 'm' represents a meso
dyad, or successive methyl groups on the same side in the plane.
Syndiotactic polypropylene was first obtained in the Natta laboratory, using a
catalyst prepared from TiCh and AlCI(Eth. Syndiotactic polymers have a unique
stereochemical structure in which monomeric units having enantiomorphic config-
uration of the asymmetrical carbon atoms follow each other alternately and regularly
in the main polymer chain. In other words, the sPP structure is that in which the
methyl groups attached to the tertiary carbon atoms of successive monomeric units
in the chain lie on alternate sides of the plane of the polymer. In NMR nomenclature,
this pentad is described as ... rrrrrr ... in which each 'r' represents a racemic dyad,
Le., successive methyl groups on alternate sides of the plane. The percentage of
racemic dyads in the chain determines the degree of syndiotacticity of the polymer.
The tactic polypropylenes are crystalline and insoluble in xylene, whereas an
atactic polymer is amorphous and soluble in xylene. An atactic PP exhibits no
regular order of repeating unit configurations in the polymer chain and forms
essentially a waxy product.
Although it is possible for a catalyst to produce all three types of polymers, it is
desirable to produce predominantly either isotactic or syndiotactic polymer with
very little aPP. Since the mid-1980s, stereorigid metallocene catalysts are more
frequently used for this task. The catalysts may have the structure:
R"(CpR,.)(CpR;")MeQ,, where Cp represents a cyclopentadienyl or substituted
cyclopentadienyl ring, R and R' hydrocarbyl radicals having 1-20 carbon atoms, R"
is a structural bridge between the rings imparting stereorigidity to the catalyst, Me
represents a transition metal (zirconium, titanium or hafnium) and Q a hydrocarbyl
radical or halogen, n, m = 0-4, and k = 0-3. Note that CpR;" may be sterically
different from CpR,.. The sterically different cyclopentadienyl rings produce predo-
minantly syndiotactic polymer, rather than an isotactic polymer.
Commercial production of isotactic polypropylene (PP) started in 1957 by
Hoechst, then within a year by Montecatini (Moplen TM developed in collaboration
with Natta) and Hercules. The slurry process in hexane requires a Phillips (Cr-
doped NiO on aluminosilicate) or Ziegler-Natta (AIEt2Cl + TiAlC~) catalyst. Later,
other catalysts became available. In the early 19808, new high-surface-area catalysts,
showing fourfold higher chemical activity, were developed in Solvay and Shell
laboratories (Sailors and Hogan, 1982).
In 1954, the first metallocene - a ferrocene or iron sandwich - was developed and
characterized by Wilkinson and Fischer. A recent member in the isotactic polypro-
pylene family is high melt strength PP, the material showing large stress hardening
in extensional flow, similar to that reported for LOPE (Phillips et al., 1992).
In 1985, Hoechst patented metallocene polymerization of isotactic PP, based on
Britzinger and Kaminsky zirconocene catalyst. The following year, Fina obtained
patent protection for metallocene polymerization of syndiotactic polypropylene. In
1989, Dow and Idemitsu started collaborative work on commercialization of sPP.
Progress in catalysis led in 1992 to small scale commercialization of sPP by Sumi-
tomo Chemical. Exxon Chemicals, Hoechst, Mitsui Petrochemicals and Petrofina,
also have pilot plant production capabilities for manufacture of sPP.
In 1991, Hoechst Aktiengesellschaft disclosed a new polymerization method that
led to production of isotactic PP with high steric regularity (isotactic index: II ?: 96%),
controlled molecular weight and a narrow molecular weight distribution. The
method applies a metallocene catalyst, rac-dimethylsilyl(2-methyl-4,6-diisopropyl-
1-indenylh·ZrCI2, and methylaluminoxane cocatalyst (Winter et al., 1993). The
following year, the company announced development of a modified catalyst that
made it possible to polymerize or copolymerize polyaIkenes (e.g., PP or EPR) having
either a monomodal, bimodal or multimodal molecular weight distribution, with the
polydispersity index Mw/Mn ?: 3.0 (Winter et al., 1994).
The advantage of sPP over isotactic PP is that even the specimens with 50% lower
modulus have 200% higher impact strength, and that the tensile modulus of sPP is
fivefold higher than that of PP (Kaminsky, 1992). These differences originate in the
molecular configurations of PP and that ofsPP. Isotactic PP has a planar zig-zag helical
structure, and melting point of 165 °C, sPP has a three-dimensional structure that
leads to lower crystallinity and a significantly lower melting point of about 133°C.
lt is expected that the manufacturing process of sPP in a single reactor is capable of
generating materials with performance similar to PP copolymers requiring expen-
sive, multireactor capabilities (Schut, 1992, 1993, 1995). Mitsui Toatsu, Chiso,
Hoechst and Exxon forecast production capacity of metallocene-eatalyzed PPs of
320 kt/year by the year 1996. In 1994, Exxon and Hoechst announced R&D collabora-
tion on the development of metallocene catalysts for isotactic PP.
Thermoplastic olefin elastomers (TPO)

Ziegler and Natta's greatest contribution to polymer science and technology rests
with the idea of controlled polymerization of a-alkenes to stereospecific products.
The new family of catalysts made it possible to polymerize ethylene-propylene-
diene into copolymers having a controlled degree of crystallinity and crosslinkability.
Natta and his collaborators reported that vanadium-based catalysts gave better
products then those based on titanium (Natta et al., 1955, 1957). Unfortunately,
vanadium-based LLOPEs were found to be more susceptible to mechanical degrada-
tion than those based on titanium and/or chromium (Schlund and Utracki, 1987).
Commercially, the first ethylene-propylene rubbers (EPR) were manufactured in
1960 by Esso, and the ethylene-propylene-1,4-hexadiene copolymer (EPOM) in 1963
by du Pont de Nemours. The aim was to produce a thermoplastic elastomer
36 Polymer industry
characterized by a block copolymer structure, with PP being the rigid and PE the
elastic block. Thus, in a manner similar to the styrene-butadiene-styrene three-block
copolymers (SBS, see below), the elastomeric behavior of the new type of thermo-
plastic elastomers would be secured by physical rather than chemical crosslinking.
The materials showed high tensile strength of 8-27 MPa, with maximum strain at
break of € = 500%. EPR could also be crosslinked by addition of peroxides. However,
vulcanization of EPDM could lead to highly crosslinked products. In 1990, the world
consumption of TPO was 177kt, projected to increase at a rate of 7.2% per annum to
356kt by the year 2000 (Shih and Su, 1987; Reisch, 1992). The popularity of TPOs
originates from excellent low temperature impact strength, good stiffness, flowabil-
ity, low shrinkage, wide range of modulus, low density, and good moisture, chemi-
cal, solvent and electrical resistance, as well as recyclability (Gallagher, 1992). TPOs
can be reinforced by addition of glass fibers and/or mica flakes (Bhardwaj, 1990;
Xavier et al., 1994).
EPR and EPDM are mainly used in blends (ca. 68%) with other resins, mainly PP.
First blends of EPR or EPDM with PP date from 1950. The main goal was improve-
ment-of PP low temperature impact strength (Coran et al., 1985; Coran, 1987, 1988).
Gessler and Haslett (1962), in the presence of a curative, blended PP with 5-50 parts
of chlorinated butyl rubber. They named the process dynamic curing. The term has
been adopted for vulcanization of an elastomer during melt mixing. At concentra-
tions exceeding 25wt% of elastomer, PP blends are known as olefinic thermoplastic
elastomers, TPO.
Coran et al. (1978) dynamically vulcanized EPDM in PP to high crosslink density
Santoprene™. By varying the composition and process variables, a wide range of
properties was obtained. Blends of PP and EPR (30:70) showed an excellent set of
properties originating from the dual phase co-continuity; the term 'thermoplastic
interpenetrating polymer network system (T-IPN),' has frequently been used to
describe these systems (Kresge, 1978). For additional enhancement of properties
(e.g., high notched Izod impact strength), the materials can be compatibilized by
grafting PP onto EPR backbone, or by partial crosslinking (Kresge et al., 1992). TPOs
are manufactured not only by large resin producers but also by compounding
houses. The resins can be fireproofed with tetrabromobisphenol-A-dibromopropyl
ether (Lo and Khatab, 1991).
For a broad range of applications (e.g., in automobiles, consumer products,
construction, geomembranes and medical applications), TPOs range from flexible
to rigid and tough (Utracki and Dumoulin, 1995). Most TPOs are prepared by
mechanical mixing, with morphology dependent on the compounding and
processing steps (Fukui et al., 1982). More recently, direct sequential polymerization
of propylene and ethylene-propylene mixture was used to generate the reactor-
made EPR/PP blends, RTPO (Cecchin and Guglielmi, 1990). However, up to date,
RTPOs do not have the same range of properties as the compounded TPOs (Chu,
1992; Reisch, 1992). Furthermore, the elastomer forms large particles ("fish eyes")
that require mechanical homogenization, preferably in an extensional flow field
(Luciani and Utracki, 1996).
Polystyrene
In 1991, world production of polystyrene (PS) was 14.6 Mt, which constituted 14.3%
of the thermoplastic resin market. An additional 3.4Mt (Le., 3.3%) of styrene was
used in styrenics - copolymers with acrylonitrile (SAN), acrylonitrile and butadiene
(ABS), acrylonitrile and acrylic elastomers (ASA), etc.
PS was first commercialized by I. G. Farbenindustrie in 1915, but up to the 195Os,
its production was rather low. High-impact PS (HIPS), was introduced by Dow
Chemical Company in 1945 (Amos et ai., 1954), and the emulsion-polymerized,
grafted ABS type-G followed three years later (Boyer, 1982). Since the 193Os, PS and
HIPS have been extruded as sheets (including biaxial orientation) or profiles,
and the resins were also injection or blow molded. Extra-thin PS films (O.8-lOmil,
or 0.02-o.25mm) were introduced by Dow in 1957. Foaming of PS, or expandable
polystyrene EPS, was developed by F. H. Lambert in 1963.
The common type of PS is amorphous and atactic. Ten years ago, using the
Ziegler-Natta catalyst, isotactic polystyrene (iPS) was obtained (Ishihara et ai.,
1986; Guerra et ai., 1989, 1990, 1992). Syndiotactic polystyrene (sPS) is more recent.
Both isomers are crystalline with the principal melting points of 230°C and 272 °C,
respectively. Evolution of their technology is closely related to metallocene catalysis.
In 1985, Idemitsu Kosan Company, Limited obtained a patent for the pro-
duction of syndiotactic polystyrene, sPS, using a single-site metallocene catalyst
(TiRlaR2bR3c~-(a+b+c), where R; groups are either H, alkyl, alkoxy, aryl, alkylaryl,
acyloxy, cyclopentadienyl or a substituted cyclopentadienyl group). Two years later, a
patent application from the company specified that titanium-based catalyst and
an organoaluminum cocatalyst (e.g., trimethylaluminum, with a small amount of
H 20) should be used. The reaction between trimethylaluminum and water can be
violent and difficult to control. Furthermore, an excessively large amount of expensive
methyl aluminoxane was required, making it an expensive catalyst with poor activity.
In 1989 the company deposited a patent describing that addition of a third component
(e.g., an aliphatic polyhydric alcohol, such as glycol, 1,4-butanediol, l,2-pentanediol,
hexanediol, pinacol, glycerin, etc.) increases the catalyst activity (Tomotsu and Mae-
zawa, 1994). Also in 1989, the company deposited several patents describing the use of
sPS, such as in the production of electric or electronic parts that require heat resistance
to a soldering temperature of 260°C. Thus sPS is an inexpensive replacement for more
traditional resins, such as polyimides and polyphenylene sulfides. Another use of sPS
is for the production of plastic bottles. The containers produced by injection blow
molding of PET are difficult to use at T:::: Tg(PET) = 69°C. The sPS has a glass
transition temperature of 100 °C, a melting point of 260-270°C, and can readily be
partially crosslinked by irradiating with electron rays (Funaki and Yamasaki, 1994).
At the next stage of evolution of the technology, in 1991, Idemitsu Kosan deposited
a patent describing a new catalyst for the polymerization of sPS. The system com-
prised: (1) TiCpXYZ (Cp = cyclopentadienyl or substituted cyclopentadienyl group,
and X, Y and Z are independently either H, alkyl, alkoxy, aryl or halogen), e.g.,
pentamethylcyclopentadienyltrimethyltitanium; (2) a coordination complex com-
pound comprising an anion in which several radicals are bonded to a metal and a
nitrogen-containing cation, e.g., N,N-dimethylanilinium tetra(pentafluorophenyl)
borate; and (3) a metal-alkyl compound, e.g., triisobutylaluminum. The new catalyst
was found to be efficient for polymerizing sPS having a high degree of syndiotactic
configuration, without the use of expensive aluminoxane (Watanabe et al., 1994).
In 1991, another team from Idemitsu Petrochemical disclosed a process for con-
tinuously and efficiently producing sPS using fluidized bed technology. The polymer-
ization temperature was controlled by vaporizing part of the styrene, maintaining
the reactor under reduced pressure. Such problems as reactor scale-up, adhesion of
polymer to the reactor walls and polymer particle aggregation have been eliminated
(Imabayashi et ai., 1994).
Even at the early stage, it was realized that sPS could profit from modifications.
For example, in 1987, Idemitsu Kosan deposited a patent aimed at increasing the
38 Polymer industry
crystallization rate and crystallinity of sPS by adding 0.01-10wt% of either talc or
mica (Yamasaki et al., 1994). Two years later, the company disclosed a method of
thermal treatment of molded sPS parts that efficiently improved total crystallinity
with moderate spherulite size of 5-10 J-Lm (Uchida et al., 1994). In 1992, Idemitsu
Kosan disclosed sPS composition comprising functionalized sPS, functionalized
hydrogenated styrene-butadiene-styrene thermoplastic elastomer and filler. The
system showed remarkably improved impact resistance and elongation without
detriment to heat resistance and modulus of elasticity. These blends have been
favorably used for molding industrial materials including electric and electronic
connectors and printed circuit boards, industrial construction materials, automobile
parts (wheel caps and cylinder head covers), domestic electrical appliances and
various machine parts (Okada, 1994).
In 1989, Idemitsu Kosan Company Limited signed an agreement with Dow
Chemical for joint development of sPS. Currently, sPS is being produced using a
single-site metallocene catalyst at a rate 50 kt/year (Moore, 1992; Schut, 1995). The
construction work has begun on a production facility in Chiba that is expected
to come on stream in 1996. The resin is primarily targeted for injection molding
to replace more expensive engineering resins, e.g., PA and PET. The potential
applications include injection molding of electronic parts and business
equipment. Since 1992, pilot-plant quantities of sPS have been manufactured by
Montedison.
Metallocene technology also makes it possible to polymerize substituted styrenes.
For example, in 1991, Idemitsu Kosan disclosed polymerization of styrene with para-
substituted styrenes that resulted in syndiotactic homo- or copolymers. In particular,
polymerization of p-phenylstyrene and p-trimethylsilylstyrene was described. The
metallocene catalyst comprised a transition metal compound (derived from a Group
!VB metal, e.g., a pentamethylcyclopentadienyltrimethyltitanium), a compound pro-
ducing an ionic complex by the reaction with the transition metal compound (e.g., a
tri(n-butyl)ammoniumtetra(pentafluorophenyl) borate), and an organoaluminum
compound, e.g., a triisobutylaluminum, TIBA (Watanabe and Machida, 1995). Syn-
diotactic poly(p-phenylene styrene) has a melting point of 352°C, and is fully
miscible with sPS. The melting point of the blend was reported to be a linear function
of composition (Watanabe et al., 1992)
Polystyrene copolymers
A large part of styrenics production is consumed in blends with elastomers, poly-
olefins (polyalkenes), PVC, PMMA, polycarbonate, polysulfone, polyphenyleneether
and polyurethane. In most cases, instead of neat crystalline PS, its copolymers are
used. Of these, ABS, SAN and HIPS have already been mentioned.
In 1961, using a lithium catalyst, a series of styrene-isoprene and styrene-buta-
diene block copolymers were synthesized in the Shell Rubber Research Laboratory
(Legge et al., 1987). Full-scale production of Kraton™ started in 1965. The importance
of these materials goes beyond their utility. Here, for the first time, a model of
thermoplastic elastomers could be directly examined. Thus, it was postulated that
the elastomeric materials can be formulated by a judicious combination of soft and
rigid segments. Owing to the nature of anionic polymerization, the block copolymer
macromolecules could be precisely tailored. The first observations of this type of
reactions were made by Ziegler and his coworkers in the context of the search for the
synthetic "sodium rubbers" (Ziegler and Bahr, 1928). By independently changing
the size and the number of blocks, the fundamental principles responsible for the
elasticity were investigated (Holden et al., 1969; Holden and Legge, 1987). These
principles were crucial for development of the new family of thermoplastic elasto-
mers, namely: TPO, PS-PDMS, polysulfone-PDMS, polyester-polyether, polycarbon-
ate-PDMS, polyester-polyamide, polyurethane ether-ester type, etc. At present,
TPEs constitute about 5% of the global elastomeric market.
Over the years, the technology of styrene-butadiene-styrene (SBS) three-block
copolymers have evolved, following the needs of the plastics industry. Two- and
three-block copolymers, hydrogenated then later also maleated (for improved inter-
actions with engineering polymers), have been produced (see Appendix IV). Cur-
rently, with the world-wide consumption of 330 kt/year, the styrenic block
copolymers constitute the largest part of the commercial TPE market. A major part
of this goes into blends with PS, PE, PP, PDMS, polybutyleneterephthalate (PBT),
polyphenyleneether (PPE) and polycarbonate (PC) (Utracki, 1989a).
Polyvinylchloride
In 1991, world production of polyvinylchloride (PVC) was 22.0Mt, or 21.6wt% of
the thermoplaStic resin market. The resin was commercialized in 1927 after the
discovery of plasticization and/or blending that made processing possible. Whereas
the first PVC formulations were heavily plasticized (known as flexible formula-
tions), attention soon shifted toward the use of blending technology with elastomers
and acrylics, which in tum led to rigid formulations.
Rigid PVC technology was brought to the USA after wwn by the Army
Quartermaster Corporation, and commercialized in 1950. In 1946, Union Carbide
introduced the plastisols and organosols for forming and coating (Rubin, 1990). During
the following years, the technology was perfected in parallel with the development
of twin-screw extruders and other more technologically advanced processing
methods.
The first acrylic processing aid for PVC was marketed by R6hm & Haas in 1957. In
1960 flexible PVC dominated the market (consuming 97% of PVC), but by 1990 its
share had decreased to 38%. New forms of PVC and its copolymers have been
developed to fit specific uses, such as latex, plastisol, organosol, as well as flexible,
and mostly the rigid PVC formulations (Semon and Stahl, 1982). From 1950 to 1979,
the number of companies manufacturing PVC in the USA increased from 5 to 20.
PVC has been extensively used in blends with elastomers and thermoplastics, such
as acrylic rubber, EPDM, ABS, chlorinated PE, acrylics, ethylene vinylacetate, poly-
vinylfluoride, polyurethanes and acrylonitrile-styrene-acrylate terpolymer. Owing
to environmental concerns, since the early 1990s the production of PVC in Scan-
dinavian countries has been temporarily reduced.
2.2.2 Engineering resins

The term engineering polymer is applied to processable polymeric materials that (1)
are capable of being formed to precise and stable dimensions, (2) exhibit continuous
high performance at temperatures exceeding 100 °C, and (3) have tensile strengths of
over 40 MPa (Utracki, 1989a). Five polymer families belong to this category: poly-
amides (PA), thermoplastic polyesters (PEST), polycarbonates (PC), polyoxymethy-
lenes (POM) and polyphenylene ethers (PPE). Although the relative size of the
engineering resin market varies from country to country, these polymers constitute
about 13% by volume and 34% by value of total plastics consumption (see Tables 2.2
and 2.3).
40 Polymer industry
Table 2.3 Plastics production for 1988 (kilotons, kt)
Resin Canada USA Europe Japan

Commodity
Low density polyethylene 1120 4725 4958 1363
High density polyethylene 710 3818 2556 955
Polypropylene and copolymers 305 3307 2947 1637
Polystyrene and other styrenics 287 3523 2116 1523
Polyvinylchloride and copolymers 465 3895 4914 1750
Engineering
Polyamides 95 257 320 144
Polycarbonates 13 196 130 84
Thermoplastic polyesters (PET, PBT) 45 912 35 493
Polyoxymethylene (Acetal) 58 105 109
Modified polyphenyleneether, PPE 82 65 59
Specialty
Polyphenylenesulfide 14.52 4.68 4.9
Amorphous polyarylate 0.92 1.2
Polyphenylenesulfone 6.74 1.26 0.79
Polyethersulfone 2.23 1.01 0.40
Polyetheretherketone 0.47 0.18 0.05
Liquid crystal polymers 0.48 0.16
Polyetherimide 2.29 0.47 0.09
Polyamideimide 0.48 0.09
Polyimides 0.11 0.03
Polyamides
In 1938, Paul Schlack demonstrated homopolymerization of t:-eaprolactam into poly-
t:-eaprolactam (polyamide-6 (PA-6); Schlack, 1941). The same year, for fiber produc-
tion, polyamide-66 (PA-66 or Nylon TM) was commercialized by du Pont de Nemours.
Poly-t:-eaprolactam was commercialized by I. G. Farbenindustrie in 1939 under the
trade name Perlon™. Although the initial production of PA in the USA evolved
toward fine fibers, in Germany it was used mainly for molding applications. During
wwn, PA production was dedicated to military use. After the war, the civilian
consumption of PA exploded from l.5kt in 1940 to 71 and 4140kt in 1950 and
1980, respectively. The use of PA for moldings and extrudates gradually increased
to the present level of about 29%. In 1991, consumption of the thermoplastic PAs
(PA-6, -46, -66, -612, -69, -11, -12, -610, -41, -6T, -6T61, etc.) was estimated at 1.2Mt.
In 1955, Allied Chemical started production of PA-6 in the USA. At this time, Than
& Mulhouse introduced PA-11 in France. PA-12 was commercialized by Hiils in
1966, PA-612 by du Pont de Nemours in 1970, and PA-46 byOOM in 1987. Glass fiber
reinforcing of PA dates from 1960 (e.g., Fiberfil from ICI), while that with mineral
dates from 1972 (Monsanto). In 1976, du Pont de Nemours started production of
super tough polyamide blends (Damm and Matthies, 1990).
In 1955, du Pont de Nemours patented the interfacial polymerization technique
that later was used to produce several high performance resins, including the liquid
crystal aromatic polyamides, with a melting point of 455°C (Magat and Strachan,
1955; Shashoua and Eareckson, 1959). The first patent was issued in 1958, and three
years later du Pont de Nemours started production of poly(meta-phenylene
isophthalamide), later sold under the tradename of Nomex™. Similar polymers
have been·manufactured in Japan and the former USSR under the names of Conex™
and Fenilon™, respectively. The lyotropic poly(p-phenylene terephthalamide),
Kevlar™-49, was invented in 1965 and introduced commercially in 1970 (Cassidy,
1982). A similar resin was introduced in 1986 by AKZO as Twaron™, and a year later
by Teijin as HMO-50.
Amorphous aromatic polyamides (PARAs) were marketed by Dynamit Nobel
(Trogamid™) in 1969. In 1980, du Pont de Nemours also disclosed transparent
PARA. The latter resins were prepared by reacting 60-90% isophthalic and 40-10%
terephthalic acid with 92-8% hexamethylenediamine and 8-92% bis(p-amino-
cycloexyl)methane (Pagilagan, 1982, 1983). In 1988, Mitsui Petrochemical Industries
introduced another amorphous PARA - a copolyamide from caprolactam, hexam-
ethylenediamine and isophthalic and terephthalic acids (PA-6IT6). A more recent
addition to the family is polyphthalamide (AmodeI™), commercialized in 1991 by
Amoco Company, used mainly for the automotive applications.
In the early 198Os, Monsanto developed a method of reactive injection molding
(RIM) of caprolactams - in later years, the technology was sold to DSM (Iobst, 1985).
Thermoplastic polyesters
Thermoplastic polyesters (PESTs) are the preferable choice when developing high
performance polymer alloys. They are being blended with elastomers, polyalkenes,
SAN, ABS, all engineering resins, as well as many of the newest, high performance
specialty polymers.
The first liqUid crystal polyester, polyoxybenzoate, was developed by Carborun-
dum in 1970 and two years later was commercialized as Ekkcel™. Thus, the first two
liquid crystal polymers (LCPs), polyester Ekkcel and polyamide Kevlar™, were
commercialized the same year.
Polyethyleneterephthalate
Polyethyleneterephthalate (PET) was invented in 1941 by Whinfield and Dickson of
Calico Printers' Association and licensed to ICI. Because of WWll, it was only in 1946
that the first Terylene™ fabric was woven, and two years later it was commercially
introduced in Britain. The resin was so successful that in 1956 ICI decided to form a
Fibers Division to take care of this part of the business. In 1952, du Pont de Nemours
introduced oriented PET films. By 1954, both ICI and du Pont de Nemours (who bought
the Whinfield and Dickson patent and in the late 1940s started manufacturing PET
fibers as Dacron™) offered PET as fibers or biaxially oriented films (Kennedy, 1986).
1970 marks the beginning of biaxially oriented PET bottles for carbonated beverages -
the main patent for the technology was granted to du Pont de Nemours 3 years later.
PET has high strength and stiffness, good dimensional stability, slip and wear
properties, low creep, good electrical characteristics and high chemical resistance.
Many of these performance characteristics critically depend on the level of crystal-
linity, which may vary from zero to 30-40% - the maximum rate of crystallization is
high, at about 175°C. Since the glass transition temperature of PET is 98°C, and the
melting point is 255°C, the recommended mold temperature is 140-160 0c.
Polybutyleneterephthalate
Polybutyleneterephthalate (PBT) (also known as polytetramethyleneterephthalate
(PTMT) was commercialized in 1969 by Celanese (Celanex™), two ~ars later by
Eastman Chemicals (Tenite™ 6PRO), and by General Electric (Valox ). The main
42 Polymer industry
advantage over PET rests in better processability, as well as lower melting and
crystallization temperatures.
PBT is a semicrystalline polyester with many characteristic features similar to
those of PET - it has high strength, stiffness and hardness, has a high heat distortion
temperature (HDT), good toughness at low temperature, favourable slip and wear
characteristics, low water absorption, low thermal expansion coefficient (thus good
dimensional stability) and good resistance to chemicals, fuels, oils, solvents, etc. The
glass transition temperature of PBT is 60 DC, and the melting point is 223 DC, thus the
maximum rate of crystallization occurs at about 140 dc. Good crystallization rates
can be obtained with the mold temperature at 3Q-60°C. However, the low I g of the
resin requires reinforcement either by blending (e.g., with PET) or by incorporation
of fibers or mineral fillers.
Polyarylates
Polybisphenol-A-terephthalate (PAr, [-4>-C (CH3}z-4>-C0l-4>-C0d n)' is an amor-
phous polyester of bisphenol-A with isophthalic and terephthalic acids. It was
commercialized by Unitika in 1973 under the trade name U-Polymer™. Since that
time, several other varieties of PAr have been marketed, such as Ardel™ from
Amoco Chemicals, ArylonTM from du Pont de Nemours, and Carodel™ from ICI.
PAr has performance characteristics that place it somewhere between the amor-
phous PC and semicrystalline PEST. PAr has high strength, stiffness and hardness,
excellent impact strength, HDT and good dimensional stability and electrical char-
acteristics. It is transparent, flame-resistant and has excellent weathering and UV-
resistance behavior. However, its resistance to organic solvents, strong acid and
alkaline solutions is poor.
Poly(ethylene-Z,6-naphthalene dicarboxylate)
Poly(ethylene-2,6-naphthalene dicarboxylate), also known as polyethylenenaphthate
(PEN), was discovered in 1948 by Whinfield and Dickson and licensed to ICI. In
1973, Teijin, Ltd commercialized PEN under the name Q-film™. PEN has excellent
stiffness, strength, heat resistance, high glass transition temperature and excellent
barrier properties, making it an ideal component for blow molding transparent, rigid
bottles for hot-fill applications. However, the resin shows a hazy and bluish fluor-
escence. Furthermore, owing to its high melting point and viscosity, the best proces-
sability/performance ratio is obtained from its blends with PET. Today, besides
Teijin, several other companies manufacture PEN, such as ICI (Kaladex™) and East-
man Kodak.
Polycarbonates
The term polycarbonate refers to a whole class of polyhydric phenols linked through
carbonate groups. Polycarbonates (PC) are polyesters of carboxylic acid, and in
many cases their behavior resembles that of PEST (namely transesterification). In
general usage, polycarbonate refers to PC derived from bisphenol-A. In specific
cases, a small amount of other polyhydric phenols can also be added, halogenated
phenol for example to improve flame retardancy, or trifunctional phenol to improve
the melt strength. World consumption of PC in 1991 was 650kt.
It is ironic that, while condensation of hydroquinone and resorcinol to practically
insoluble, high-molecular-weight polycarbonates was reported by Einhorn (1898),
the new class of high-molecular-weight polycarbonates and intention to start com-
mercial scale production of PC was announced simultaneously in 1956 by General
Electric and Farbenfabriken Bayer. PC was prepared in two-step interfacial phosge-
nation of bisphenol-A. The reaction was catalyzed by tertiary amines. At present, a
small quantity of PC is also manufactured by transesterification at 300 °C of bisphe-
nol-A and diphenylcarbonate (Soder, 1976; Deanin, 1982; Rubin, 1990). In 1982, Bayer
introduced high-purity PC grades for manufacturing compact disks.
By the end of the 198Os, General Electric disclosed a polymerization method
involving formation of a cyclomer, a cyclic oligomer, as an intermediary step. The
process that seems to be particularly suitable for PC, was developed for manufactur-
ing high-fill composites with high-molecular-weight polymeric matrix (Salem, 1991).
The polymerization occurs in two steps: (1) preparation of a cyclomer (having up to
20 structural units), and (2) at 200-250 °C a catalytic ring-opening reaction, leading to
PC with the degree of polymerization up to 1000. The oligomer is a powder that
melts at 150°C. At higher temperatures it turns into a low viscosity liquid, with the
ability to penetrate and wet solid beds of glass fibers before being polymerized to Pc.
At room temperature, PC has good impact strength, it is tough, transparent, self-
extinguished, dimensionally stable, resistant to salts and oxidation, but susceptible
to abrasion, stress cracking and attacks by solvents, acids and alkali. Its ductile--
brittle transition depends on the temperature, specimen thickness, notch sharpness
and thermal aging. Unmodified PC has a sharp ductile--brittle transition at 0-10 °C
(Carhart, 1985), thus the resin is brittle below O°c. Another deficiency of PC is the
sensitivity of its notched impact strength to specimen thickness - the notched !zod
impact strength is reduced by a factor of nine when the thickness is increased from
3.2 to 6.4mm Oones, 1985). In consequence, owing to low impact strength at low
temperatures and of thicker parts, PC is often impact modified, for example, by
addition of acrylic rubber interpolymer, as KM 330 (Witman, 1981).
PC is one of the principal engineering polymers with a broad range of applica-
tions. Its annual consumption and growth rate are 700 kt and 5 % respectively, with
70 % of the production still controlled by the two original manufacturers (Anony-
mous, 1992). It is estimated that about 50% of PC is used in glazing and 40% as a
component in blends for structural materials, in transportation, electrical and appli-
ance applications.
Poiyoxymethyiene
Polycondensation of formaldehyde was reported by Butlerov in 1859. Trautz and
Ufer (1926) also described its polymerization. In 1927, Staudinger prepared the first
man-made fiber from polyoxymethylene (POM), but the discovery had no practical
consequence - the polymer was unstable, oxidizing and depolymerizing upon heat-
ing. In 1937, Staudinger et ai. studied the structure of POM single crystal (Staudinger
et ai., 1929, 1937).
In 1950, du Pont de Nemours developed technology for end-capping the POM
chain with acetic anhydride, thus preventing the thermal unzipping. An addition of
anti-oxidizing and acid-accepting agents further im~ved POM stability, making it
possible to start commercial production of Delrin acetais in 1959. In Celanese
laboratories was developed poly(oxymethylene-co-oxyethylene) offering (at a cost
of a slightly lower modulus) good stability without end-capping (Walling et ai., 1962;
Berardinelli et ai., 1965). Three years later, the copolymer was commercialized as
Celcon™ (Deanin, 1982; Sinker, 1990). The world consumption of POM and its
copolymers in 1991 was 468kt, and the annual growth rate is about 5%. It is
estimated that 35 wt % of POM is used in transportation, and 18 % in the construction
industry (Anonymous, 1992).
44 Polymer industry
POMs have good processability, rigidity, ductility, lubricity, strength, dumping
properties, resistance to fatigue, solvents and chemicals. For many applications,
semicrystalline POM offers a better set of performance parameters than Pc. How-
ever, owing to its simple chain structure, POM is not easy to compatibilize - only
about 10 wt% of POM is sold as blends (mainly with thermoplastic polyurethanes),
compared with 30 wt % of PC. This situation may soon change, since chain-end
functionalization and/or reactive processing make it possible to compatibilize POM
with a wide variety of other polymers.
Polyphenyleneether
Commercialization of poly(2,6-dimethylphenylether) (PPE) by General Electric in
1965 constituted a major step in polymer blend technology. Prior to this event, there
were many attempts to produce a macromolecular analog to diphenylether, well
known for excellent thermal and oxidative stability. In 1956, Allan Stuart Hay, using
catalyzed oxidative coupling of 2,6-dimethyl phenol, produced the first PPE.
PPE is an amorphous resin, with a glass transition temperature of 210 0c. Upon
annealing or slow evaporation from solution, the resin can be crystallized, and the
crystals melt at 257°C. PPE is thermally stable up to about 150 °C; thus, to process
PPE, it should be stabilized, and plasticized by blending. Since oxidation of the
methyl groups starts at 125 °C, the continuous use temperature is usually limited to
this level. The polymer has good rigidity, creep resistance, dimensional stability,
high melting point, as well as electrical, chemical, moisture and flame resistance,
but its melts (not far from Tg ) are highly viscous, requiring processing temperatures
well above the decomposition level. It is said that only a lucky incident (attempt
to extrude PPE in an extruder contaminated with polystyrene) saved PPE from
obscurity.
PPE blends with PS were sold by GE under the name of NorylTM. In 1982,
Borg-Warner Chemicals introduced its blends of poly(2,6-dimethylphenol-co-2,3,6-
trimethylphenol), Prevex™. Both the PPE homo- and copolymer are sold as blends.
The original Noryl underwent several modifications. PPE has been blended with
high-impact polystyrene, styrene-butadiene di- and tri-block copolymers, and other
styrenics. Modified PPE grades are available with glass fibers, self-extinguishing, for
structural foams, etc. Their major application is in transportation, office/hospital
furniture, electrical and electronic parts (Deanin, 1982; Bartges, 1990; Feth, 1990).
PPE is also blended with all other engineering resins, namely PAs, PEST, PC and
POM.
In 1979, Xyron™ resins were introduced by Asahi-Dow, Limited. The resins were
based on styrene-grafted poly(2,6-xylenol), PPE. Glass fiber reinforced resins, with
5-35 wt % filler were also made available. The materials were rigid, with HOT =80-
140 °C and good flame, moisture, solvent, chemical and impact resistance. They were
used for industrial and automobile parts, home appliances, etc. (Izawa, 1979, 1992):
Today, PPE is being manufactured by numerous companies all over the globe.
Its current annual production and growth rate are 300 kt and 9 %. Considering its
moderate price, one can hardly imagine the arduous times while developing the resin
and turning such an unyielding material into an international success story.
2.2.3 Specialty polymers

Table 2.2 provides a partial list of commercialized polymers: thermosets, rubbers, as
well as commodity, engineering and specialty thermoplastics. By contrast with the
commodity and engineering polymers, the specialty polymers are more difficult to
define. These are expensive, small-volume resins, either used in specific applications
or awaiting market acceptance.
Fluorocarbon polymers
The fluorocarbon industry traces its origin to the synthesis of C2H2F4 and C2F6 (Ruff
and Bretschneider, 1933). Polychlorotrifluoroethylene, as HostaflonTM, was first com-
mercialized by Hoechst in 1934 (production, suspended during WWII, was resumed
in 1950). Polytetrafluoroethylene (PTFE, known in Germany since 1933), was accid-
entally rediscovered in 1938 by Plunkett and Rebok at the Wilmington laboratories of
du Pont de Nemours. Experimental quantities of Teflon™-TFE were introduced in
1942, and full-scale production started in 1950. Auorinated ethylene-propylene
Teflon™-FEP), perfluoro alk~ polymer (Teflon™-PFA), and ethylene-tetrafluor-
oethylene copolymer, Tefzel ,were commercialized by du Pont de Nemours
respectively in 1961, 1972 and 1972.
Polyvinylidenefluoride (PVDF) was discovered at du Pont de Nemours laborat-
ories and patented in 1948. The resin was experimentally introduced in 1960, and
commercialized two years later, by Pennsalt (later Pennwalt) Corporation, then by
Kureha Chemical Industries in 1971, and by Dynamit Nobel in 1973. Poly(ethylene-
co-ehloro-trifluoroethylene) (ECTFE) was introduced in 1971 by Allied Chemical
Corporation as Hylar™. The world consumption of fluoropolymers in 1991 was
72kt. To expand the range of properties, either vinylidene fluoride has been co-
polymerized with other fluorinated monomers, e.g., hexafluoropropylene, or its
polymer (PVDF) has been blended with other resins. PVDF is a semicrystalline
polymer with about 50 % crystallinity, a melting point of 160-180°C and a glass
transition temperature varying from -56 to -35°C.
The fluorine-eontaining polymers are characterized by stability at high tem-
peratures, toughness and fleXibility at low temperatures, non-adhesive and low
friction properties, insolubility and inertness to chemicals, as well as low dielectric
losses and high dielectric strength. For example, commercial PTFE is a
crystalline polymer with an exceptionally high degree of crystallinity X = 92-98 %,
and a melting point of 342 °C. However, since its number average molecular weight is
high, Mn = 500-9000 kg/mol, the melt has a viscosity TJ of 10 GPas - the materials
resemble a gel. To improve processability, the tetrafluoroethylene was copolymer-
ized into FEP, ETFE and PFE. These resins, with Tm of 260, 260 and 304 °C, respect-
ively, can be melt processed at 315-400, 300-350 and 315-425 °C, respectively. The
degradation temperature Tdeg of all these resins is 425-440°C.
Besides the linear fluoropolymers, there is a large family of copolymeric fluoro-
elastomers. The first of these, a copolymer of vinylidenefluoride and chlorotrifluoro-
ethylene (Kel-F™) was commercialized by MW Kellog Comp~ in 1955.
Copolymers of vinylidenefluoride and hexafluoropropylene, Fluorel from 3M
and Viton™ from du Pont de Nemours, were commercialized in the late 1950s. A
copolymer of vinylidenefluoride and propylene, Aflas™ from Asahi Glass, soon
followed. These resins have the brittle point at -50 to -20°C and a thermal degrada-
tion temperature of 400-550°C. Similar to linear fluoropolymers, the fluoroelasto-
mers are insoluble and have high resistance to chemical attack. In consequence, these
resins are difficult to compatibilize, thus fluoropolymers are habitually used in
relatively small quantities, to reduce frictional properties, i.e., to produce the self-
lubricating resins. SUPEC™ W331 is a blend of crystalline PPS with PTFE and 30
wt % of glass fibers, available from General Electric Co. The material is characterized
46 Polymer industry
by extra wear resistance, lubricity, high heat and chemical resistance, making it
suitable for the manufacture of pumps, gears, valves, etc.
Silicone resins
Silicones, with the general formula [-RnSi-0(4_n)/2-] (where R is either H or not
necessarily identical aliphatic or aromatic groups, and n = 1-3) belong to a large
family of organosilicon compounds, out of which linear polymers, polysiloxanes of
general formula [-O-Si(RR')-], constitute the largest group. Polysiloxanes were
invented in 1937 by Kipping. The resins can easily be branched or crosslinked
into elastomers. Owing to a low energy barrier for rotation around the siloxane
bond (-Si-O-) and the large free volume fraction at room temperature, polysiloxanes
are known for their high compressibility, high permeability to gases, low glass
transition temperature,low viscosity and low surface tension coefficient. For example,
polydimethylsiloxane (PDMS) has Tg of -127°C, electrical volume resistivity
1014_1015 0cm, and a surface tension coefficient v of 21 mN/m. Substituting one
-CH3 group by phenyl (-¢) increases Tg to -86°C and improves the thermal and
oxidative stability. Whereas PDMS starts oxidizing at 290°C and undergoes structural
rearrangement at 435°C, for a polymethylphenylsiloxane these temperatures are
375°C and 410 °C, respectively. The polysiloxanes show an exceptional weatherability.
Polydimethylsiloxane was first introduced by Dow Corning Corporation as an
experimental resin in 1938, Dow-Corning PDMS, and on a full scale in 1943. Three
years later, General Electric Company started production of silicone polymers based
on Rochow's method (Liebhafsky, 1978).
High-temperature polymers
Polyarylene sulfide
The first patent describing preparation of polyarylene sulfide (PPS; [4>-&-]n)
was deposited by Phillips Petroleum Company in 1963. The resin was prepared by
reacting Na2S with halogen-substituted aromatics: for example p-e6~Ch was reacted
with Na2S at 231°C for 44 h in N-methyl pyrrolidone. The resin was molded at 290°C to
give rigid, heat resistant parts (Edmonds and Hill, 1967). PPS was commercialized by
the company in 1971 as Rayton R. The resin is semicrystalline with a melting point of
288°C, and a glass transition temperature of 194 0c. As a linear polymer, it can be
formed from melt or from solution, but it can also be vulcanized by heat and/or sulfur.
PPS has relatively poor impact resistance. The resin has been primarily injection
molded, but it has a tendency to adhere to the mold surface and flash, Le., it flows
into crevices in the mold. Blends have been developed to alleviate all these problems.
To improve the impact strength, PPS has been blended with elastomers, namely
EPR, EPDM, ethylene-acrylate or butyl acrylate. Owing to immiscibility with these
materials, it was difficult to improve its impact strength without affecting the heat
resistance and mechanical properties. Under pressure in a wet and hot environment,
the impact strength of these blends rapidly deteriorated. Furthermore, the molded
parts showed poor surface appearance. The molding temperature of PPS must be
above its melting point, i.e., Tprocess ~ 290°C, but at these temperatures these elasto-
mers tend to degrade. Clearly, blending of PPS with commodity resins did not solve
the basic problems. In consequence, there is strong tendency to blend PPS with high
performance resins. The first PPS blends with 25 wt % of either polysulfone (PSF),
polyphenyleneether (PPE), or polycarbonate (PC) were deposited by Phillips in 1975
(Bailey, 1977).
Several commercial PPS blends are available, such as those with PPE, PARA or
PTFE. The first commercial PPS-PPE blend, DIC PPS from Dainippon Ink & Chemi-
cals, was commercialized in 1982. A similar blend, NorylTM APS-440, is available
from the General Electric Company. These materials have been designed for injec-
tion moldin~ but extrusion, compression moldin~ or thermoforming grades can
also be used. The blends show reduced flash in injection moldin~ good processa-
bility, toughness, and high heat and chemical resistance. They find application in
electrical and electronic industry (parts and multiconnectors), as well as in mechan-
ical engineering for pump impellers. Blends of PPS with polyaramid fibers and/or
PTFE, are available from RTP Company as RTP 1300. Blends of PPS with 13-20 wt %
PTFE are also manufactured by LNP Engineering Plastics (a business unit of ICI
America) as LUbricompTM PPS. The materials are reported to show excellent wear, as
well as solution, chemical and oxidation resistance.
Polysulfones
There is a great diversity of commercial polysulfones (PSF), having different
molecular structure and properties. Since there is also confusion of abbreviations,
whenever possible, the molecular structure should be used.
Polyarylsulfone (PAS, also abbreviated as PSU or PSO), or more exactly, poly-
arylethersulfone (PAES), is a polymer of the general formula [+SOz-ln' where if>
stands for an arylic group that mostly includes a phenyl ether moiety, -efr-O-. The
first PSF was introduced by Union Carbide in 1965. The resin having the structure
[+CCCH3h--</rO-<l>-SOz-efr-O-]n was initially sold as Bakelite Polysulfone, then as
Udel™, with a Tg of 196°C, and a continuous use temperature (CUT) of 160°C.
It is a condensation product of the bisphenol-A disodium salt and 4,4'-dichloro-
diphenylsulfone.
In 1971, Astrel™ PAES, with Tg of 288 °C and structure [+4>-SOz--</rO-<l>-SOz-ln'
was introduced by 3M Company. The follOWing year, Imperial Chemical Industries
commercialized polyethersulfone, PES as Victrex™ (see below). In 1976 Union
Carbide introduced polyphenylethersulfone, PPSF Radel™ R, with the structure [-
</r--O---ifr-SOz-efr-O-l n, with a glass transition temperature of 220°C. Another
PAES with the structure [~SOz+ln - [~lm' was introduced as Radel™
A. Its glass transition temperature was 217°C. The resins were developed by Union
Carbide and are now available from Amoco Performance Products.
Examples of other commerci~olysulfonesare: Astrel™ [-efr-O-ifr-SOz+4>-SOd
from Carborundum; Ultrason E from BASF; Talpa™ 1000 from Mitsui Toatsu; and
Sumilite™ FS-1300 from Sumitomo Chemicals. In 1986, Celanese commercialized
polyimidesulfone, PISO, and the following year Dainippon Ink & Chemicals came
up with the polythioethersulfone (PIES) AmoroonTM.
Polyarylethersulfone
Polyethersulfone (PES) belongs to the family of polyarylethersulfone (PAES) having
the general formula -[ifr-SOzl n-, where </> stands for an arylic group that in most
cases includes a phenyl ether moiety, -efr-O-. Polyethersulfone, Victrex™ with Tg of
228-232°C, was introduced by Imperial Chemical Industries in 1972. It is a conden-
sation product of the dipotassium salt of 4,4'-dihydroxydiphenyl sulfone and 4,4'-
dichlorodiphenyl sulfone, with structure [+SOz-4>-Oln'
Polyarylates
Polyarylates (PAr) with the structure [-0-¢r-C(CHhh-¢r-C02+CQ-ln are linear
polyesters, usually of biphenol-A and phthalic acids that, depending on the ratio of
48 Polymer industry
isophthalic to terephthalic acids, are either amorphous or semicrystalline. The PAr
resins were first introduced in 1974 by Unitika as U-polymer™, then in 1978 as Ardel
D- lOOTM by Union Carbide, a year later as Durel™ by Hooker Chemical Company,
and in 1986, as Arylon™ NOO by du Pont de Nemours. Their glass transition
temperature is T g ::::: 188°C and, depending on the molecular structure, their heat
deflection temperature varies between 120 and 175 0c. These resins have been
frequent components of blends.
Polyaryletherketone
Polyaryletherketones (PAEK) are aromatic polymers having ether and ketone lin-
kages in the main chain to enhance processability. A choice of these resins, with
different ratios of ether to ketone linkages, is available, such as PEK, PEEK, PEEKK,
etc. For example PEEK, having the structure [-<P-CQ-<P--CHt>-O--ln' was synthesized
by Imperial Chemical Industries in 1977, test marketed in 1978, and commercialized
in 1980 as Victrex™. It is a tough, semicrystalline thermoplastic with a glass transi-
tion temperature of 143°C, and a melting point of 334 0c. The resin is usually
processed at 370-380 °C and, to encourage crystallization, is annealed at 185°C. At
high temperature (~4OO 0c) in the presence of oxygen, the resin degrades and
crosslinks (Domininghaus, 1993).
Aromatic polyamides
The aromatic, semicrystalline polyamides (PARA) were developed at du Pont de
Nemours' laboratories (Kwolek et al., 1962). The first patent was issued in 1958 and,
three years later, du Pont started production of poly(m-phenylene isophthalamide),
sold as Nomex™. The lyotropic poly(p-phenylene terephthalamide), Kevlar™-49,
was invented in 1965 and introduced commercially in 1970 (Cassidy, 1982). These
polyamides can be fiber-spun from concentrated sulfuric acid, but cannot be formed
by the standard processing methods. There was a need for development of aromatic
polyamides with higher chain mobility - the amorphous-type aromatic polyamides.
There is a great diversity of amorphous, aromatic or semi-aroma~olyamides.
The first PARA was introduced in 1969 by Dynamit Nobel as Trogamid . In 1980, du
Pont de Nemours disclosed transparent, amorphous, aromatic polyamides, prepared
by reacting 60-90% of isophthalic and 40-10% of terephthalic acid with 92-8% of
hexamethylenediamine and ~92% of bis(p-aminocycloexyl)methane (Pagilagan,
1982, 1983). In 1988, Mitsui Petrochemical Industries introduced a copolyamide
from caprolactam, hexamethylenediamine and isophthalic and terephthalic acids
(PA-6IT6). More recently polyphthalamide, as Amodel™, was commercialized in
1991 by Amoco.
Liquid crystal polymers

The liquid crystalline state was recognized by Reinitzer (1888) - low molecular
weight substances, such as chloresterylbenzoate, may show this behavior. In princi-
ple, the molecules of these substances, or mesogens, are highly anisometric, rigid or
adopting rigid configurations ordered over large distances, which imparts some
solid-like properties. For these reasons they show anisotropic optical and electrical
behavior. One of the characteristic properties of these substances is a drastic change
of viscosity within certain ranges of temperature and pressure, which makes them
particularly useful in specific applications for high performance lubricants.
The natural liquid crystal polymers (LCP), such as tobacco mosaic virus, collagen,
cellulose derivatives (such as hydroxypropyl cellulose), polypeptides (such as poly-
r-benzyl-L-glutamate), and many others, have been studied since the 194Os. The
LCPs may have the mesogenic groups either as side chains, or forming the main
chain, with either rigid or flexible linkages between them. In the latter case, the LCP
behavior originates from formation of rigid helices. Thus, a LCP shows a high degree
of order in three-dimensional orientation and positioning of mesogens in its crystal-
line region and high disorder in the liquid region.
In 1958, du Pont de Nemours applied for patent protection for aromatic poly-
arnides (having at least 90wt % aromatic repeating units) with a melting point above
300 0c. The resins were prepared by condensation of isophthaloyl chloride with
Et3N x HCl in CH2Cl2. The liquid crystal poly(m-phenylene isophthalarnide), used
for fiber spinning, was characterized by high tenacity and self-extinguishing proper-
ties (Kwolek et al., 1962). It was soon discovered that solutions of these resins showed
liquid crystalline behavior. In the later patents, other aromatic LCP polyamides were
described, such as poly(m-phenylene isophthalamide) (PPA) commercialized as
Nomex™, poly(p-phenylene-2,6-naphthalamide) (PPN) and poly(p-phenylene
terephthalarnide) (PPf) commercialized in 1965 as Kevlar™ (Kwolek, 1970). These
LCP resins were fiber-spun from sulfuric acid, but they were not processable in
the molten state.
In the early 1970s the wholly aromatic polyesters were also synthesized. The
intermolecular interactions in polyesters are not as strong as in polyarnides; never-
theless, several LCP polyesters (e.g., poly-p-oxybenzoate or poly-p-phenylenetere-
phthalate), had such a high melting point that they could not be melt-processed.
The first melt-processable LCP was a copolyester obtained by condensation of
p-hydroxybenzoic acid, terephthalic acid and 4,4'-bisphenol, introduced in 1972 by
Carborundum as Elliel™ 1-2000. At the processing temperature of about 400 °C the
resin was not entirely thermally stable, causing serious difficulties for either fiber
spinning or injection molding. Clearly, lower melting point material was needed.
Attempts to "soften" the LCP polyester molecules were the introduction of
flexible links (aliphatic chain segments), and blending. In 1974, Eastman Kodak
developed a thermotropic copolymer comprised of polyethyleneterephthalate and
polyhydroxybenzoate segments (PETIlB). In 1978, poly(bis(4-methoxyphenyl)
terephthalate) was blended with polyethyleneterephthalate (PET) to give alloys
with good processability. The blends were biaxially stretched. They showed excellent
mechanical properties (Toray Industries Inc., 1980a). It should be noted that proces-
sing of LCP polyester blends leads to transesterification that results in formation of
copolymers having a random sequence of homopolymeric blocks, and as a conse-
quence, depressed crystallinity. A review of processing and properties of LCPs and
their blends was recently published (Acierno and La Mantia, 1993).
Several LCP resins have been commercialized: Xydar™ by Amoco in 1984;
Vectra™ by Celanese in 1985; E-konol™ in 1985 by Sumitomo; X-7G by Mitsubishi
Chemical in 1985; Ultrax™ by BASF; KU 1-90 by Bayer; Granlar™ by Montedison;
Novoaccurate™ by Mitsubishi Chemical Ind; Rodron™ by Unitika; and Victrex™
byICI.
Polyimides
A polyimide (PI) is a polymer having in the chain an imide group -R-N=(COh=R'-.
If a PI is to be incorporated into a blend, it must be melt-processable. Owing to the
variety of the R and R' groups, there is a great diversity of thermoset and thermo-
plastic polyimides with glass transition temperatures of 180-420 0c. When R and R'
groups are aliphatic, the PI has a softening point below 150 0c. However, a fully
aromatic PI, in spite of its linear macromolecular structure, has such a high softening
point that it must be considered a thermoset resin. To make PIs more amenable to
50 Polymer industry
processing, they are often modified by incorporation of flexible linkages, such as
ether or amide.
The early PIs were produced in reactions between aromatic dianhydrides and
aromatic diamines. In 1962, du Pont de Nemours introduced Kapton™, that did not
behave as a thermoplastic in spite of linear chain structure. XU-2IB with Tg of 320°C
from Ciba-Geigy, is a condensation product of 3,3',4,4'-benzophenone, tetra-
carboxylic dianhydride (BIDA), and 5(6)-amino-l-(4'-aminophenyl)-I,3,3-trimethyl-
indane. PI-20BO, with a Tg of 310°C from Dow Chemical, is a condensation product
of BIDA and a 4:1 molar mixture of 2,4-toluene diisocyanate and 4,4'-diphenyl-
methane diisocyanate. In 1985, Raychem Corporation developed polyimides having
in the backbone phenylindane amines and/or dianhydride moieties. These resins
can be blended with other polymers and cured, to provide rigid and stable matrix
materials for manufacturing fiber reinforced composites.
To improve the processability of PI, several modifications have been tried,
aimed at increasing main-chain flexibility, either by introducing aliphatic-aromatic
segments, or chemical groups with higher degree of mobility, such as ether, amide
or sulfone. Polyamide-imide (PAl) with a Tg of 275°C was commercialized in
1965 by Amoco Chemical Corporation as Torlon™. Polyetherimide (PEl), with a
Tg of 217°C, was commercialized by General Electric Company in 1982 as
Ultem™. Polyimidesulfone (PISO) with a Tg = 273°C, was introduced by Celanese
in 1986.
Polyetherimides
Polyetherimide (PEl), Ultem™, was commercialized in 1982, as a result of 10 years of
research and development at General Electric Company at an estimated cost of
U5$12 million. The poly[2,2'-bis(3,4-dicarboxyphenoxy phenylpropane)-2-phenyl-
ene-bisimidel, has the structure [-N(COh-</>-O-4>-C(CH3h-¢-O-t!>(COhCN-</>]n'
Its glass transition temperature is 215-220°C, it has exceptionally high mechanical
properties, a high heat deflection temperature of 217°C, and no weight loss below
400 0c. PEl, being amorphous, exhibits predictable shrink rates - isotropic for
unreinforced and anisotropic for reinforced grades. In 1990, General Electric intro-
duced PEl blends with bisphenol-A polycarbonate as Ultem TM LTX. The blends were
formulated to balance heat and impact properties (Utracki, 1994b).
PEl has exceptional strength and moduli at elevated temperatures, high long-term
heat resistance, inherent flame resistance with low smoke evolution, high dielectric
strength, stable dielectric constant and dissipation factor over a wide range of
temperatures and frequencies, good chemical resistance, transparency, good proces-
sability on conventional molding equipment, and excellent machinability and finish-
ing characteristics. The unreinforced grades have a continuous use temperature of
170°C. The glass-reinforced grades proVide greater rigidity and improved dimen-
sional stability, whereas the glass and mineral reinforced resins have good balance of
low wa%::ge, dimensional stability and low CUT.
Ultem has high tensile (E = 3309 MPa) and flexural moduli, approaching that of
many glass reinforced resins, even at elevated temperatures. Reinforced grades have
E = 11 721 MPa at room temperature. The resin shows excellent creep resistance,
even at temperatures and stress levels that would prohibit the use of many other
thermoplastics and excellent impact resistance, but the resins display notch sensitiv-
ity when subjected to high strain rates. It also has excellent property retention and
resistance to environmental stress cracking when exposed to most commercial auto-
motive and aircraft fluids, fully halogenated hydrocarbons, alcohols and weak
aqueous solutions, but exposure to partially halogenated hydrocarbons and strong
alkaline environments should be avoided. It displays excellent retention of tensile
properties following long-tenn exposure to hot water. The resin is inherently
resistant to UV radiation without the addition of stabilizers, as well as to gamma
radiation.
Polyamideimides
Aromatic polyamideimide (PAl) is obtained by polycondensation of imide chains
with aromatic diamines. The first PAl was manufactured at room temperature, by
phosgenation of trimellitic anhydride in pyridine, and reaction of acid chloride with
4,4'-diaminiphenylmethane. The resulting amorphous polymer, with a unit structure
-[-N=(COh=4>-C0-NH-R-NH-Co--¢l=(COh=N-]-, was commercialized by
Amoco under the trade name Torlon™. The resin has a glass transition temperature
of 275°C, HDT of 265-280 0c, shows high strength and impact strength at -190
to +260 DC, excellent dimensional stability, very good dielectric properties,
solvent and chemical resistance, flame retardance, good UV stability and low
outgassing in high vacuum. TorIan TM polymerizes further at above 246 dc. Since
the resin has high viscosity and is usually processed at above 350 DC, post-
polymerization does occur. To improve processability, PAl has been blended
with polyamides, polysulfones or aromatic polyesters (Toray Industries Inc., 1979,
198Ob). The first blends of PAl with PPS and PEEK, were announced by Upjohn
in 1984.
Aliphatic polyketone
The radically polymerized copolymers of alkenes with carbon monoxide
(CaPO) have been known since the early 1940s (Ballauf et al., 1941). Depending
on composition, the melting point may vary from about 110 to 242 DC. At com-
positions approaching 50 mol % the copolymer behaves as high perfonnance
engineering resins. Owing to sensitivity of the keto groups to ultraviolet light,
capOs are prone to photodegradation. The UV degradation can potentially be
used to produce packaging materials with a calibrated lifetime when exposed to
sunlight.
Since the radical polymerization of ethylene with CO makes it possible to incor-
porate other monomers (such as vinyl acetate, vinyl chloride, acrylonitrile, alkyl
acrylates or tetrafluoroethylene), from the 19605 these resins have been used as
pennanent plasticizers - impact modifiers for PVC.
In 1995, Shell Chemicals announced the introduction of Carilon™ resin. The linear
copolymer of carbon monoxide and an alkenic monomer (ethylene-propylene-
carbon monoxide xyz copolymer, where y : x = (}.-().1) is obtained in a coordination
polymerization using a palladium-based metallocene catalyst. The strictly alternat-
ing copolymer [-CO-C2~-ln is an engineering resin with molecular weight 2~
90kg/mol, glass transition temperature 15-20°C, melting point Tm ::::: 220°C, tensile
strength 80 MPa and elongation f of 25%. The resin shows a unique balance of
properties: easy thin-wall moldability without a need for pre-drying, moldings
have good definition, glossy or mat surface. The moldings have outstanding
wear and friction resistance, high resilience over a wide temperature range, low
sensitivity to water and organic solvents and good barrier properties. Blends of
capo with a-methylstyrene-co-acrylonitrile, (SAN; AN content 55-80 wt%) were
found to be miscible (Machado, 1992). Starting in 1991, Shell applied for patent
protection for capo blends with PA-6 and SEB5-MA (Machado, 1993), with poly-
urethane, TPU (George, 1992), with 2~5wt% paM and 0.5-10wt% PVPh
(Machado, 1993), etc.
52 Polymer industry
Other specialty resins
Several other high performance polymers have been commercialized since 1965:
poly-p-methylenebenzoate (PMB), polybenzirnidazoles (PBI), polyoxadiazobenzirni-
dazole (POBI), polyirnidesulfones (PISU), polyirnidazipyrolone (PIPO), poly-
cycloenes (PCE), polybismaleirnide (PBMI), polyacrylic ester imide (PAEI),
polyphthalamide (PPhA), polythioethersulfone (PPSS), etc. For most of these resins
the glass transition temperature exceeds 200°C and modulus 3 GPa (Rubin, 1990;
Kroschwitz 1991).
The consumption of specialty resins is small. For example, in 1991 the total world
consumption of PSF and PES was 8.5 kt. The relative volumes of production of the
three principal categories of thermoplastics are best judged from the 1988 production
data in industrialized countries listed in Table 2.3.
3
Development of polymer
.
processmg
To convert the diverse polymeric materials into marketable products, an entirely

new polymer processing industry had to be created. As late as at least 1915, polymer
processing was not recognized as having anything to do with engineering activities.
Davis (1901), in his highly recognized Handbook of Chemical Engineering, does not
even mention anything polymeric in nature, rubber or plastic. A review of recent
developments in polymer processing has been published (Utracki, 1991a).
McKelvey (1962) proposed to group polymer conversion operations into three
categories:
• modifications, such as mixing, surface activation and chemical modification of
polymers;
• forming, such as extrusion, molding and calendering;
• bonding, such as heat sealing, laminating, coating and printing.
3.1 MIXING
The oldest processing operation is mixing. The first annular container with a spiked
rotor for rubber compounding was developed in 1820 and patented 3 years later
(Hancock, 1823, 1857). A more efficient, counter-rotating twin shaft internal mixer
with elliptical rotating discs was patented by Freyburger (1876, 1877), while its
sigma-blade versions were patented by Pfleiderer (1880, 1882, 1895), and by Banbury
(1916,1917, 1924, 1927, 1928, 1929, 1933). The latter two inventors initiated the well-
known modern mixers manufacturing companies, Werner & Pfleiderer (created in
1870) and Farrel Corporation, respectively.
The first calender/ two roll mill was patented by Chaffe, and manufactured by the
Farrel Foundry and Machine Company (Chaffe, 1836). These machines became the
basic processing units of the rubber industry (Farrel, 1956). A short summary of
the evolution of mixing technology is given in Table 3.1.
3.2 EXTRUSION
Extrusion is the most important processing method in the plastics industry. The first
recorded commercial use of a ram extruder was in 1797 by Bramah to produce
seamless lead pipes. At the same time, screw extruders were used in Italy for
54 Development of polymer processing
Table 3.1 Development of mixing and extrusion technology
Technology Year Event

Mixing 1823 Spiked internal mixer for rubbers & blends (Hancock)
1836 Two-roll mill (Chaffe)
1876 Counter-rotating twin-shaft mixer (Freyburger)
1916 Banbury mixer
Extrusion 1800 Piston extrusion of macaroni in Italy
1845 Adapted by Bewley to rubbers
1879 Screw extrusion of rubber (Gray)
1892 Steam heated screw extrusion (Troester)
1932 Pin-barrel extruders (Anderson)
1939 First modern extruder (Leistritz); L/D = 10
1939 Corotating twin-screw extruder (Colombo)
manufacturing macaroni (Dubois, 1972). The first British patent on an extruder with
·an archimedian screw was granted to Gray (1879). The same year, Francis Shaw
Limited produced the first commercial screw extruder. However, by the early 1870s,
screw extruders for soaps were commercially produced by Messrs E. Forshaw and
Son, Engineers of Warrington under the descriptive name of plodding machines
(Davis, 1901). These belt-driven units had a set of speed-eontrolling gears, a hopper,
screw and pressure chamber. They were supplied with a set of dies to form the
extrudate strands with cross-sections of different sizes and shapes.
In Britain, Francis Shaw Limited started manufacturing commercial extruders in
1879. In the USA, extruder manufacture was started a year later by John Royle &
Sons, and by Francis Shaw Ltd. In 1880, Royle introduced the first screw extruder,
and ten years later started manufacturing machines designed for wire and cable
rubber insulation (Kaufman, 1969; Rosato, 1993).
The first patent on extrusion of gutta-percha was granted to Brooman (1845), and
later modifications to Bewley (1845). The submarine cable that was laid across the
English Channel in 1851 was a product of extrusion-wire coating using a shellac
gutta-percha blend in a Bewley extruder. By 1858, extrusion was also used for wire
coating in the USA.
The first extruders were hand-operated, discontinuous ram presses, initially used
for forming natural rubber or gutta-percha, then later, cellulose nitrate (NC); (Fisher,
1958; Dubois, 1972). Ram presses are still used for extrusion of NC-based gun
propellants.
In Hannover, Paul Troester Maschinenfabrik (PTM) started manufacturing screw
extruders in 1892. A great number and variety of these machines have been pro-
duced. In 1935, PTM introduced the first extruder designed for thermoplastics.
Initially, the extruders had small diameter, short auger screws. Later, multi-screw
designs (with as many as eight concentrically located screws), and finally the mod-
ern computer-eontrolled extruders for rubbers and thermoplastics were designed
(Colombo, 1939; White, 1992). The latest type of extruder, the pin barrel type for
rubber extrusion, was introduced about half a century ago (Anderson, 1937).
The early steam heated extruding machines, with screw length to diameter ratio,
LID = 4, were used to extrude either rubbers or cellulosics. Extrusion of cellulose-
derivative solutions was used by Cohoe (1915) and Henderson (1926) to produce
films by film-blowing techniques. Commercial extrusion and film blowing of cellu-
lose acetate (CA) date back to 1939. The method was extended to synthetic polymer
Extrusion 55
melts by Wiley in 1946. The bi-axial orientation process was invented in Germany
in 1935.
It was the introduction of thermoplastics in the 1930s that spurred the develop-
ment of extrusion technology. Electrically heated extruders for thermoplastics
appeared in the early 1930s. They were produced in close cooperation between
resin (e.g., I. G. Farbenindustrie) and machine (e.g., Paul Leistritz Maschinenfabrik)
manufacturers. By 1935, several companies in Europe and the USA were selling
thermoplastics extruders on the open market. In 1939, PLM built an electrically
heated, air-cooled extruder, having LID = 10, with automatic temperature control,
variable screw speed and a nitrided barrel. This machine is a precursor of modem,
automated extrusion technology (Decker and Troester, 1939). Paul Leistritz is cred-
ited with the design and manufacture of intermeshing, counter-rotating twin-screw
extruders and kneading machines, mainly for polyvinyl chloride and synthetic
rubbers. Also in 1939, the Industrial Research Laboratory introduced the first bime-
tallic barrels, as XaioyTM 100, for extrusion or injection molding machines, and Fred
M. Reddy designed the first knife-type granulator that became an industrial stan-
dard for many years to come.
During WWlI, breaker plates, screen packs, crosshead dies, coextrusion, mono-
filament extrusion, film blowing and biaxial sheet orientation (Plax Corporation,
1941) were introduced. In the 195Os, Lavorazione Materie Plastische, (LMP), in
Italy developed a coextrusion process to coat steel pipes. Extruder venting and
two-stage screws became available, the extruder length-to-diameter ratio increased
to LID = 15 (by 1965 to LID = 30). The first film production line (25 kg/h capacity)
was built in Germany by Reifenhauser in 1948. In 1951, Howald and Meyer received
the first patent on pultrusion of fishing rods (Howald and Meyer, 1951).
In 1959, an elastic melt extruder was invented. The machine consisted of two
vertical circular plates, one stationary with a die hole in the middle, and the second
rotating. The polymer was melted by the shearing action and forced out from the gap
by the so-called Weissenberg (or normal stress) effect. The melt residence time was
short and its distribution relatively narrow (Maxwell and Scalora, 1959). In 1975, this
design was incorporated into an extruder designed for compounding thermally
unstable PVC formulations or waste plastics (Patfoort, 1976).
In 1961, corrugated vinyl sheet extrusion was developed in Europe and Japan.
Three-layer, coextruded PP/LOPE/PP blown film started to be manufactured in
1962. By mid-196O, the external and internal air cooling systems for film blowing
were developed by Japan Steel Works Ltd. At the same time, extrusion of crosslinked
HOPE pipe was introduced by the Cabot Corporation. By the end of the 196Os, a
bimetallic barrel liner was developed by Xaloy Inc. In the 1970s, the continuous screen
changer, microprocessor control and foam extrusion were introduced (Chabot, 1992).
In 1979, Zehev Tadmor invented the screwless rotating disks extruder, Diskpack™.
The shearing action of the disks melted, mixed and pumped the polymer. However,
since the three functions were performed by different ~metry disks, the machine
provided greater flexibility. The main use of Diskpack has been for mixing and
compounding color masterbatches and blends, as well as for preparation of rein-
forced and filled engineering resins (Tadmor et ai., 1983).
In the 198Os, microprocessor control evolved into computer integrated manufac-
turing (CIM) technology. During the decade, helical grooved feed barrels, high
pressure gear pumps generating 40-80 MPa pressure on the die, air lubricated die
flow, biaxial orientation of blown film and other advances were introduced. Today,
CIM automated extruder lines, equipped with closed-loop product quality control,
generate output of more than 20ton/h (Utracki, 1991a).
In polymer blend technology, twin-screw extruders play an increasingly impor-
tant role. The first patent for a fully intermeshing, corotating twin-screw extruder
was granted to Coignet (1869). The first modular counter-rotating machine was
patented by Paul Pfleiderer in 1882. Kneading pump, positive displacement, twin-
screw machines were designed by Kiesskalt for suspensions and rubbers (Kiesskalt
et ai., 1937). Wiinsche (1901), Easton (1917), Pease (1936), Colombo (1939), Fuller
(1948, 1952), Meskat and Erdmenger (1953) and Meskat and Pawlowski (1956)
contributed to development of this technology.
The direct predecessor of the modem twin-screw extruders was a machine
designed by Colombo and Pasquetti in 1938 for extrusion of CA, and manufactured
by LMP (the US patent was granted in 1947). This intermeshing, corotating twin-
screw extruder was used in the early 1940s by I. G. Farbenindustrie for continuous
reactive extrusion (I. G. Farbenindustrie, 1953). After WWII, the extruders (with
90mm screw diameter) were build in the UK. In 1950, Mapre of Luxemburg intro-
duced an intermeshing counter-rotating twin-screw extruder.
The development of twin-screw technology was mainly carried out in Germany,
first in collaboration between I. G. Farbenindustrie and Paul Leistritz Machinenfab-
rik, and later between Bayer Aktiengesellschaft and Werner & Pfleiderer. The latter
company introduced, in 1959, what became the industry workhorse - the ZSK twin-
screw extruders. These machines are vented, intermeshing and corotating, with
segmented screw and barrel. Here the material is conveyed in a figure-eight pattern,
alternating between moderate shear stress in the overflight zone (between screw and
barrel) and high shear stress in the apex zone. Owing to the segmented design, both
screw and barrel can be custom assembled to optimize the machine's performance
for specific needs. The screw is usually made of at least six different types of screw
and kneading-mixing elements, able to convey the material forward or (for en-
hanced mixing) backward. These extruders are self-wiping, provide a good balance
between dispersive and distributive mixing, and can be operated at a relatively high
output rate.
In 1970, Moi of Italy and a year later Mapre, built a counter-rotating twin-screw
extruder. The first of these was specifically designed for styrofoam extrusion. The
counter-rotating, non-intermeshing twin-screw extruders mainly provide distribu-
tive mixing. The material undergoes a moderate shearing in the overflight zone and
in specially added high shear stress elements, making them suitable for processing
shear-sensitive materials. Owing to the non-intermeshing nature, they offer an
advantage in the venting capability, distributive mixing at low screw speed, and
high output rate per screw diameter.
In the USA, several companies continued development of multi-screw extruders,
such as American Leistritz, Welding Engineers, Cincinnati Milacron and APV Che-
mical Machinery. Welding Engineers manufactured multi-screw extruders with
three distinct zones: feeding, mixing and extruding. In 1972, Cincinnati Milacron,
and a year later, Egan Machinery, developed, respectively, conical and counterrotat-
ing, fully intermeshing twin-screw extruders. American Leistritz has been active in
designing kneading elements for improved mixing capabilities by means of an
induced extensional flow field.
Since early 1980, a new class of twin-screw extruders, specifically designed for
reactive processing, has become available from major equipment manufacturers
(Chabot, 1992). In 1979, Japan Steel Works developed the TEX-series of twin-screw
extruders, permitting an easy change of the screw direction from co- to
counter-rotation. In collaboration with Sumitomo Chemicals, the barrel elements
with sampling ports for TEX were designed. These permit ready access to
Transfer molding 57
the processed material for determining reaction progress and morphology (Nishio et
aI.,I990).
Excellent reviews of the early developments of twin-screw extrusion technology
have been published by White (1990, 1992, 1993), as well as by White and Wang
(1991). The twin screw extruders for compounding available on North American
market were reviewed by de Gasparich (1992). A short summary of extrusion
developments is presented in Table 3.1. Modem twin-screw extruders with deep
screw profile and screw speeds up to 1500 rpm are characterized by excellent mixing
capabilities and high throughputs.
3.3 COMPRESSION MOLDING

Compression molding is one of the oldest processes. It has been used by man for
thousands of years to form clay, papier mache, animal horns (e.g., for combs) or
natural resins. Thomas Hancock in Britain is credited with the first application of
compression molding to rubbers in 1840. At present, compression molding is mainly
used for forming highly filled composites.
In the USA, the first patent on the use of a hydraulic press to compression mold
NC was issued in 1870 to the Hyatt brothers. From 1907, Leo Hendrik Baekeland
used this technology to mold phenol formaldehyde (PF) based compounds. Starting
in 1916, special compression molding machines for PF were designed and manufac-
tured by Terklson Machine Corporation of Boston. Around 1910, Burroughs
invented a semiautomatic press for compression molding of CA, and later, a series
of process or equipment modifications, such as resin preforming, flash molding,
tilting-head press, heating and cooling molds, etc. (Anderson, 1937).
In 1916, Novotny developed a method of molding cylindrical printing plates - the
patent is considered to be the precursor of transfer molding technology. Since
compression molding is not suitable for the manufacture of articles having either
intricate sections, thin walls or inserts, the transfer molding process was patented in
1926 (Shaw, 1928). By about 1927, compression molding began to lose ground to
rapidly developing injection molding.
Automation of the thermoset compression and transfer molding processes was
patented by Zelov in 1937 for the Stokes Machine Company (Hull, 1990). The first
fully automatic multistation compression molding unit was introduced by the New
England Butt Company of Boston in 1937. In 1940, the dielectric preheating of molding
powders was developed by Monsanto with help from the collaborating companies:
Westinghouse, Baldwin Locomotive Works and Bryant Electric Company. In the 1950s,
automatic presses with 2.5 kt capacity were manufactured (Anonymous, 1956).
In the 1970s, close-loop control, screw feeding and preforming plastication were
developed. To eliminate waste and to speed up the process, Pennwalt provided a short
screw extruder attachment for generating preforms with well-controlled length and
weight. The most recent tendency is to combine the injection and compression mold-
ing processes into one, to produce large, fiber reinforced thermoset or thermoplastiC
parts, such as horizontal body panels for the automotive industry (Wright, 1984).
3.4 TRANSFER MOLDING

This technology stands between the compression and injection molding methods. It
was developed mainly for thermosets. The material is heated up to the flowing (but
below the crosslinking) temperature, then it is forced into a mold where, under
pressure, it is cured.
The first commercial application of transfer molding dates from 1926, when the
Shaw Insulator Company molded firing pins in phenolics for the US Navy. The
machine used had a single vertical piston to transfer the preplasticated resin down to
the mold. By 1929, the company developed a 24-cavity automatic unscrewing mold
with pinpointing gates, for molding thermoset pencil bodies. The first automatic unit
was built in 1935 by J. D. McDonald (Dubois, 1972).
Development of dielectric preheating made it possible for J. Krause to build Hyjeta
Die™ in 1938. The machine had a horizontally dividing mold, with the material
transferring ram located below, and the mold closing hydraulic press located above.
It also had an electrically heated nozzle to start the curing reaction before resin
entered the mold. The unit was an intermediary between the transfer and injection
molding machines. The first machine of the later type was a Reed-Prentice thermo-
plastic injection molding unit. In 1940, United Plastics Corporation modified the
machine for thermosetting materials by providing it with a smaller ram and a water-
cooled nozzle (Morse, 1942).
The further developments of the transfer molding technology progressed in par-
allel with those of compression or injection molding. In 1949, screw preplastication
was introduced by Keaton Bros. The screw was non-reciprocating, thus transfer was
still performed by a plunger operating in a material-accumulating cylinder. Only in
1961 did Stokes incorporate a reciprocating screw into the Injectoset™ transfer
molding machines. In the 1960s, automation and microprocessor controls were
introduced. With these, the technology developed into a high-speed commercial
process (Fredricks, 1935; Norris, 1943; Simons, 1975). A short summary of the
evolution of molding technology is given in Table 3.2.
Table 3.2 Development of molding technology

Molding Year Event
Compression 1840 Compression molding of rubbers (Hancock)
1862 Baldwin's patent compression molding
1916 Terklson Machine Corporation molds for
L. Baekeland
Transfer 1926 Transfer molding of phenolics (L. E. Shaw)
Injection 1870-72 Injection molding of NC (Hyatt brothers)
1878 Multi-mold invented by Hyatt
1921 Modern 1M machine for thermoplastics (Eichengrun)
1926 Horizontal 1M patented by Eckert and Ziegler
1932 Automatic injection molding (Gastrow)
1946 Screw injection molding (Henry)
1975 Computer controlled injection molding
Blow 1881 Blow molding of NC (W. B. Carpenter)
1930 Blow molding of CA rattles (Hyatt), and bottles (Plax)
1935 Hot melt machine (Ferngren and Kopitke)
1940 Blow molding of polyethylene bottles
Roto 1820 Splash molding of chocolate menagerie in Holland
1850 Adapted to cellulosics (Dodge)
1940 Tri-axial rotomolding of plastisols (Union Carbide
Corporation)
Injection molding 59
3.5 INJECTION MOLDING

In 1872, the Hyatt brothers adopted the injection molding process (used since 1838 to
die-cast metals) to form NC (Halbach, 1946). The machine contained a steam-heated
cylinder, hydraulically operated plunger, a nozzle and a vertically closing mold.
Near the end of the injection cylinder there was a restrictive core (a precursor of the
later torpedo designs) to help the plastication of the polymer and improve heat
conduction. In 1910, Baekeland injection-molded phenolics. In 1916, Dr Hesse, a
German dentist, manually injection-molded dentures and other articles out of CA.
The work was continued by Eihengrun, as well as by Eckert and the Ziegler Com-
pany in Cologne, who respectively patented and built the first commercial injection
molding machines. In the 19308, the technology started to be used to mold synthetic
thermoplastics (Thomas, 1947; Sonntag, 1980).
Devolatilization, and the use of an axially movable screw, date back to 1905. Early
machines were hand-operated, plunger-type units (Buchholz, 1923). In 1926, Eckert
& Ziegler, in close cooperation with I. G. Farbenindustrie, started commercial pro-
duction of horizontal, electrically heated, 60 ml capacity machines, equipped with a
pneumatically operated ram (also patented in 1926). Commercial-scale injection
molding of PS began in 1931. In 1932, Hans Gastrow (working for Franz Braun
Aktiengesellschaft) developed the first automatic injection molding machine, the
Isoma-Automat (30 g capacity per shot), with torpedo-type heating chamber. These
machines found immediate acceptance by the international plastics industry. By
1945, about 1000 units had been sold world-wide (Sonntag, 1985; Chabot, 1992).
These developments stimulated interest in the USA (Boundy and Boyer, 1952). In
1919 Sam Foster and William Grant started a company in Leominster dedicated to
the manufacture of injection molding machines based on the hand-powered units
imported from Eckert & Ziegler. In 1923, the Grotelite Company built the first hand-
operated injection molding unit for CA in the USA, based on Buchholz's patent. In
1929, the company started production of automatic injection molding units and, five
years later, hydraulic-operated machines based on the German design. In the 1930s,
new polymers - PVC, acrylics and PS - required upgrading of the technology. By
1931, du Pont de Nemours started injection molding.
In 1934, Palmer and Simpson of the Tennessee Eastman Corporation designed the
first injection molding unit (constructed by the E. W. Bliss Company) able to mold
230 g of a polymer per shot. In 1931, the Hydraulic Press Manufacturing Company
(HPM) introduced hand-operated ram injection molding machines and, five years
later, one-liter-capacity four-injection-cylinder units that could be operated with a
single mold or with four molds. The machines used hydraulics (with oil as the
hydraulic fluid) for injection and clamping. By 1939, numerous companies manu-
factured injection molding machines in Europe and the United States, such as Eckert
& Ziegler, Franz Braun, Francis Shaw, HPM and Van Dorn. The machines (up to
750 ml injection capacity) were all plunger type, with a heating chamber equipped
with a torpedo and, frequently, several concentrically mounted injection rams (Cha-
bot, 1992).
World War Two slowed the international development program. It is estimated
that by 1939 about 3000 injection molding units were operating world-wide, 574 in
the USA. After the war, in the late 194Os, the modernization of the injection molding
process recommenced. Some of the changes involved replacement of mechanical by
hydraulic systems - plunger by screw, single by multiple mold cavity, the introduc-
tion of electronic process controls, etc. In 1946, J. Hendry built a screw preplasticator
and piston injection molding machine - the screw eliminated the need for a torpedo,
reducing the pressure required to inject. By 1951, 81 capacity injection molding
machines, with reciprocating screw plastication and non-return valves, were used
to mold refrigerator parts, battery cases or kitchen cabinets. A decade later, the shot
size again doubled and the clamping pressures reached 5kt. In 1951, William H.
Willert invented an in-line reciprocating screw plastication (patented in 1956) that
revolutionized the injection molding industry.
Following the Battenfeld Company example, most of the injection molding
machines built after 1959 had a reciprocating single-screw plasticating unit. By the
late 19605 the hydromechanical system of clamping doubled the mold closing and
releasing rates. Units with vented barrels were offered by Japan Steel Works Ltd. The
increase of shot-size resulted in longer cooling time for thick wall parts, which in
turn caused the development of rotary-table molding.
The first automated injection molding plant was developed by Eastman Kodak in
1950, well before the microprocessor revolution that started in the 196Os. The first
microprocessor control unit was installed on an injection molding machine in 1964
by Biihler Brothers in Switzerland. Ten years later, Eagle Signal Industrial Controls
provided a microprocessor control system, built around an Intel 8080 chip, to control
a Fellows 150 ton injection machine - computerization and automation of the process
have been increasing ever since. The closed-loop control made the process more
reliable, resulting in better quality, reject free parts. Since 1975, the computer-aided
mold design and computer numerically controlled machining have been gaining
increasing acceptance by the industry. In 1978, Kobe Steel developed the Quick Mold
Changing system. In 1976, the Barber-Colman Company introduced a truly inte-
grated control system for injection molding that later became commercially available
as the MACa microprocessor control with a central minicomputer able to control up
to 100 machines (Chabot, 1992). Today, injection molding is the most computerized,
automated and robotized process of all polymer processing operations. Numerous
totally automated production facilities are in operation around the globe (Utracki,
1991a).
The reactive injection molding (RIM) or reinforced RIM (RRIM) technologies were
developed in the 196Os, primarily to form large automobile panels from reinforced
polyurethanes. RIM of epoxy, thermoset polyester and dicyclopentadiene resins
soon followed (Gum et al., 1992).
3.6 BLOW MOLDING

Blow molding is another polymer processing method developed in the 193Os. How-
ever, by 1880 (patented a year later) it was used at Hayatt's Celluloid Corporation to
mold baby rattles out of CA tubes or sheets Oones and Mullen, 1961). In 1930, Plax
Corporation started to develop blow molding machines for flexible CA bottles -
patented 6 years later. The first hot-melt blow molding machine was invented in
1935 by Femgren and Kopitke.
In 1938, Plax Corporation patented a hot-melt intermittent extrusion machine with
crosshead die, that formed a parison, clamped it in a mold, and air blew it to the
desired shape. Initially, the machine adopted the glass-blowing method, where the
melt was intermittently extruded into a cavity. Later, injection molding units have
been incorporated into the design. Blow molding of cellulosics and styrenics made
rapid progress in the 194Os. However, only after WWII, when LDPE became avail-
able, did high-volume production start. In 1942, Owens-lllinois patented an injec-
tion-blow molding technology. The same year, Plax Corporation started
manufacturing soft squeezable LDPE bottles. By 1951, the company (since 1950, a
Rotational molding 61
part of Monsanto) manufactured 1 and 2 gallon LOPE bottles Gones and Mullen,
1961). The first commercial blow molding machines became available in 1950 from
Kautex Werke.
Blow molding of thermosets soon followed. In 1952, Pirelli developed a machine
for blow molding 14 gallon containers (Crosio, 1952). The unit (a predecessor of the
modem blow molding technology) used a continuously running horizontal extruder,
an accumulator, vertical ram (to form parisons) and a blow molding unit. Develop-
ment of continuous extrusion blow molding and multilayer blow molding (in 1955)
resulted in rapid expansion of the technology. By the end of the 1950s, blow molding
was the most rapidly developing polymer processing method. In 1957, blow molding
of high density polyethylene bottles for bleaches, detergents and milk greatly
expanded the market. In 1958, Monsanto blow molded experimental Coca-Cola
bottles, using the biaxially stretched method developed by du Pont de Nemours.
In 1961, two-color blow molding was introduced. A year later, Stokes developed
reciprocating screw blow molding machines, while the following year, LMP
offered a blow molding plant based on a twin-screw extruder, capable of manufac-
turing 1800 PVC bottles per hour. During the 196Os, the size of blow molded
containers increased to 150 gallon drums (manufactured by Kautex Werke).
In 1968, Owens-illinois introduced hollow-handle blow molded PVC bottles for
edible oils.
In 1965, Wyeth, of du Pont de Nemours, using the stretch-blow molding tech-
nique, produced carbonated beverage bottles from polyethyleneterephthalate (PET).
By the end of the 1970s, these bottles captured nearly the total market previously
held by glass containers. In 1975, Cincinnati Milacron and Gildamister Corpoplast-
Krupp offered commercial equipment (with separate machines for preforming and
blowing) for two-stage blow molding of biaxially oriented PET bottles. A year later,
Nissei ASB introduced machines capable of accomplishing this task in a single step.
In 1980, two-and-a-half billion PET bottles were produced in the USA. By 1985, hot-
filled PET beverage bottles were introduced.
In 1972, for food applications, Toyo Seikan introduced a multilayered blow
molded bottle from polypropylene (PP) and ethylene-vinyl alcohol copolymer
(EVAI). In 1983, American Can Company adopted this technology to manufacture
280z squeezable ketchup bottles. Eight years later, PP was replaced by PET. In 1976,
Ishikawajirna-Harima Industries introduced an intermittent coextrusion blow mold-
ing system for large parts (Anonymous, 1976). During the following years, the
technology evolved into blow molding of multilayer containers on multimold rotat-
ing wheel machines. In the early 1980s, microprocessor-eontrolled automatization
was introduced. By 1984, Quakes State Oil started to use HOPE blow molded bottles
for its entire motor-oilline.
Today, blow molding is used to manufacture a range of products, such as fuel
tanks, automotive air spoilers, seat backs, toy tricycles, typewriter cases, etc. (Fritz,
1981; Chabot, 1992).
3.7 ROTATIONAL MOLDING

The history of the rotational molding (or rotomolding) of polymers can be divided
into two periods, with 1950 being the dividing date. Before 1950, the molding was
done either by splashing the liquid inside a mold or by rotating the mold about one
axis. In both cases, the liquid slowly solidified on the inside wall of the mold, and its
excess was poured out. Initially, the molds were either custom-made by, or for, a
specific molder. After 1950, the situation changed - molding was done using
commercial molds rotating about two axes. The amount of material was detennined
before molding and entirely used up during the process.
The rotational molding of polymers has its origin in the splash molding technique
developed by the Dutch around the 18205 to mold a hollow chocolate menagerie
such as rabbits, roosters, bears, etc. The method was introduced to the plastics
industry in the 1850s (Dodge, 1990). Its use grew along the expanding line of
available materials - initially cellulosics, rubbers, and thermosets, then in the 19405
PVC-plastisols (introduced by Union Carbide) and in the 19605 polyethylene. In the
later part of the 196Os, the process started to be automated for large-scale production.
At that time, parts as large as 0.8 x 0.8 x 4 m containers were rotomolded.
Microprocessing controls and robotization were introduced to rotomolding in the
early and mid-1980s, respectively. However, even today, most molders consider
rotomolding an art form, not an engineering process (Shearer, 1970, 1971; Leaver-
such, 1986).
3.8 THERMOFORMING
Thermofonning is a method of fonning a preheated plastic sheet into a desired shape
by pressing or sucking onto a mold surface. The technology has been known for
thousands of years - softened tortoise shells were thermoformed in ancient Egypt.
Later, the vacuum-fonning method was used for papier mache (Estevez, 1963;
Frados, 1976).
In the 19305, thermofonning was used for CA. In 1932, the first automatic
machines (e.g., for automatization of heating, fonning and part removal) were
developed in Germany by Claus B. Stauch, and widely exported. In 1938, Plax
Corporation in the USA purchased several units to mold Christmas-tree ornaments,
cigarette package premiums and ice cube trays. In 1942, blister packaging was
invented. During WWll, several aircraft parts (turrets, cockpit closures, astrodomes,
windows, etc.) were produced by thermofonning (Dubois, 1972).
The first commercial vacuum-fonning unit was developed in 1951; 4 years later, it
was followed by a two-stage machine. By 1957, thermofonning units able to simul-
taneously form 240 drinking cups were offered by Welding Engineers Inc. Roll-
feeding also began to make inroads during this period. Stimulated by the demands
of the packaging industry, the technology expanded during the 196Os. Large units
able to form 4 x 10 m sheets were introduced. By 1969, infrared sensors for control of
the molding cycle became available. In the 1970s, thermofonning of large ABS parts
(up to few square meters) was developed. The material was used to manufacture
parts for the automotive, furniture and construction industries, as well as luggage
and recreational items. By the end of the decade, thermofonning of PP sheets became
possible. Machines for the thermofonning of oriented PET containers were devel-
oped in 1985 by Thermofonning USA (Chabot, 1992).
4
Development of polymer science
The history of polymer science and technology is amazingly short, but so is that of
modern physics and chemistry. The idea that heat flows from a high to a low energy
reservoir was introduced by Carnot in 1824. This led to fonnulation of the second
law of thennodynamics by Joule and Kelvin in the 18508. The concept of entropy was
introduced by Clausius in 1865, who in 1879 wrote, 'Die Energie der Welt ist
Konstant. Die Entropie der Welt strebt einem Maximum zu.'
The concept of chemical valency was introduced by Edward Franklan as late as in
1852. The tetravalency of carbon atoms was demonstrated in 1858 by Kekule (later,
von Stradonitz), who 7 years later proposed the ring structure of the benzene
molecule. The liquid crystalline state (of cholesterol) was first reported by Reinitzer
in 1888.
4.1 BEGINNINGS
To develop polymer science and industry it was necessary not only to concoct the
polymeric species but also to analyze their composition, structure, molecular weight
(MW) and molecular weight distribution (MWD). The analysis should be perfonned
in three stages:
1. First the chemical composition of the material must be established, using the
standard methods of organic chemistry, such as elementary analysis, spectro-
scopy, mass spectrometry, etc. Next, the structure of the statistical segment unit,
the mer, is to be determined, then confirnled by synthesis.
2. The polymeric nature must be established. Thus, determine the molecular
weight and molecular weight distribution, demonstrating that these do not change
upon dissolution in one solvent or another, but do change in a predictable
manner upon a chemical modification, such as hydrolysis, esterification, halo-
genation, etc. This may be a relatively simple task today, but Raoult's theory for
cryoscopy was developed in 1882-5, while van't Hoff's solution theories (on which
the vapor pressure method was based) came in 1886--8. These first methods of MW
determination were applicable only to low-molecular-weight substances with
MW ::; 30 kg/mol (Brown and Heron, 1879; Brown and Morris, 1888, 1889).
3. Once the polymeric nature is established, then whether the macromolecules are
linear, branched or cross-linked, composition of chain ends, confonnation of the
macromolecular chain in the solid and liquid state, tacticity, sequence of trans and
gauche configurations, parameters of the macromolecular helix, etc., should be
64 Development of polymer science
determined. Note that X-ray diffraction was discovered by Max von Laue in 1912,
and started to be used for natural polymers in the early 1920s. The theory of
oriented crystallites in cellulose based on the X-ray diffraction pattern was pro-
posed by Polanyi (1921). In the 1920s, the studies were extended to other natural
macromolecular species, namely rubber (Katz, 1925), fibrin, chitin and Hevea
(Mayer and Mark, 1928). Studies on polyalkenes and polyvinylchloride followed
ten years later.
Thus, development of polymer science required the creation of a new branch of
science, involving complex interrelations between macromolecular chemistry, phy-
sics and engineering.
The elementary analysis and chemical constitution of several natural polymers
were determined relatively early. The composition of natural rubber was proposed
in 1826 by Faraday as [CsHs]n' and by Williams, who in 1862 obtained isoprene by
pyrolytic distillation of rubber. For cellulose and starch, the formula [C6HIOOS]n was
deduced early (Gay-Lussac and Thenard, 1811; Kirchhoff, 1815) but, due to their
hygroscopicity, the nature of polysaccharides was not identified until a hundred
years later (Willstatter and Zechmeister, 1913).
The beginning of polymer technology (mostly based on natural rubber) can be
traced to the 1830s. The first reports on synthetic polymers were also published
during this period. In 1838, Regnault reported photopolymerization of vinylidene
chloride. A year later, Simon observed that heating styrene in the presence of air
generates a tough gelatinous material - polystyrene (PS). The observation was
confirmed by Hoffmann (1860). In 1872, several new polymeric species were
announced, such as polyvinyl chloride (PVC) by Baumann, polyvinyl bromide
(PVB) by Hoffmann, and phenol-formaldehyde (PF) by Baeyer. A summary of
early polymer discoveries is given in Table 4.1.
Table 4.1 Early polymer disCoveries
Polymer Inventor Year

Cellulose nitrate Braconnot 1833
Polyvinyl chloride Regnault 1835
Polyvinylidene chloride Regnault 1838
Polystyrene Simon 1839
Polyacrolein Redtenbacher 1843
Polyoxymethylene Butlerov 1859
Polyethyleneglycol Lourenc;o 1860
Polyvinylidene bromide Sawitsch 1861
Cellulose acetate Schutzenberger 1865
Polysalicylic acid ester Kraut 1869
Polyvinyl bromide Hoffmann 1872
Polyisobutene Butlerov and Gorianov 1873
Polyvinyl methyl ether Wislicenus 1878
Polyisoprene Bouchardat 1879
Phenol-formaldehyde resin Baeyer 1880
Polymethacrylates Kahlbaum 1880
Polymethacrylic acid Fitting and Engelhorn 1880
Polyacrylates Weger 1883
Urea-formaldehyde resins Holzer 1884
Casein-formaldehyde resins Krische and Spitteler 1885
Polymethylene Hinderman 1897
Beginnings 6S
Table 4.1 Continued

Polycarbonate Einhorn 1898
Alkyds (glycol + phthalic anhydride) Smith 1901
Poly-f-eaprolactam (polyamide-6) J. von Braun 1907
Polybutadiene Lebedev 1910
Poly(methyl isoprene) Hoffmann 1910
Polyvinyl acetate Klatte 1912
Cellulose ethers (acetate, butyrate, etc.) Farbenfabrik Bayer 1912
PF/NR simultaneous IPN Aylsworth 1914
Urea-melamine resin Ripper and Pollac 1922
Polysulfide Patrick and Mnookin 1923
Polyurea Pollak 1923
Polyvinyl alcohol Herrmann and Haehnel 1924
Polyoxymethylene Trautz and Ufer 1926
Poly(vinylacetate-co-vinylchloride) Reed 1928
Styrene-maleic anhydride copolymer Voss and Dickhauser 1928
Polyvinylformal Morrison et ai. 1929
Polyvinylbutyral Morrison et ai. 1929
Polymethylmethacrylate Hill and Crawford 1930
Polyacetylene Nieuwland 1931
Styrene-acrylonitrile copolymer (I. G. Farbenindustrie) 1932
w-Polyesters: glycol + 1,16-hexadecane
dicarboxylic acid Carothers and Hill 1932
Polyethylene Fawcet and Gibson 1933
polyvinylidene chloride Wiley and Reilly 1933
polychlorotrifluoroethylene (Hoechst) 1934
Epoxy-polyamine resins (I. G. Wolfen) 1934
Poly(N-vinylcarbazole) (I. G. Farbenindustrie) 1934
Epoxy resins Schlack 1934
Polyamide-6,6; -6,10; -10,6 Carothers 1935
Melamine-formaldehyde resins Henkel 1935
Unsaturated polyesters Ellis 1936
Polyurethane (rigid or thermoplastic) Otto Bayer 1937
Allyl resins (DAP/DAIP) Ellis 1937
Butyl rubber Thomas and Sparks 1937
Polysiloxanes Kipping 1937
Polyamide-6 Schlacka 1938
Polytetrafluoroethylene Plunkett and Rebok 1938
Polybutyleneterephthalate Whinfield and Dickson 1940
Polydimethylsiloxane Rochow and Gilam 1941
Polyethyleneterephthalate Whinfield and Dickson 1941
ABS - mechanical blend Daly 1948
Fluorocarbon polymers, PEP Sauer 1951
thermoplastic polyurethane Bayer et ai. 1952
i-Polypropylene Natta et ai. b 1954
a The first condensation of f-eaprolactam was obtained by J. von Brown in 1907.

In 1930, from w-aminocaproic acid, Carothers and Berchett obtained waxy poly-f-
caprolactam, PA-6. In 1938, Schlack catalytically polymerized f-eaprolactam
into fiber-forming PA-6, and thus is considered the inventor of the resin.
b The coordination polymerization was discovered by Ziegler and his students in
the late 1940s (Ziegler and Gellert, 1950, 1952; Ziegler, 1964).
4.2 EARLY POLYMERS AND POLYMERIZAnON REACTIONS

Development of polymer science as a special discipline has its beginnings in Thomas
Graham's research that started in 1861. He classified the substances into crystalloids
and colloids. The former were made of small fast-diffusin~ crystallizable particles,
where the latter materials were made of large particles that did not crystallize. Their
solutions had low diffusion rates and high viscosity. Graham considered colloids to
be a new state of matter, comparable to gases, liquids or solids. The origin of the
new state was the molecular associations by special forces without covalent
bonding. This concept was reinforced by other recognized authorities of the day
(Ostwald, 1907). Herzog and Jancke (1920) using X-ray diffraction data demon-
strated partial crystallinity of cellulosic fibers with small unit cells. These data
were accepted as evidence of cellulose low molecular weight (from 1922 to 1927
one of Herzog's assistants was Herman Mark). However, the cellulose solutions
behaved like Graham's colloids.
Graham's idea (1861) that association of small molecules is responsible for the
colloidal nature (colloids are aggregate particles, not chemical molecules) slowed the
progress of polymer science. Many observations that could not be explained within
the framework of the association led to a search for new, mysterious forces suppo-
sedly responsible for the behavior (Stahl, 1981).
However, parallel with the association concept, the idea of long linear
macromolecules was developed. In 1860, Louren<;o synthesized polyethylene glycol
Ho-(C2~O)n-H, postulating a linear structure for the product. He considered that
the colloidal behavior originated from the structure of large, covalently bonded
linear- macromolecules (Louren<;o, 1859, 1860, 1863). Hlasiwetz and Habermann
(1871) also interpreted the characteristic behavior of the natural polymers (e.g.,
cellulose) as well as synthetic ones (e.g., polystyrene) by this mechanism. In 1910,
Hermann Staudinger had undertaken systematic studies of the polymerization reac-
tions. After a decade of work on the.synthesis and properties of several polymers he
became convinced that the idea of association theory was wrong (Staudinger, 1920).
During the next two decades, Staudinger was the main proponent of the large,
covalently bonded, linear, rod-like polymer molecules. For his lifetime achieve-
ments, in 1953 he obtained the Nobel prize. According to friends of the family,
Hermann StaUdinger's obsessive idea of the rigid-rod nature of the polymeric
molecules came from his wife, a noted biochemist, Dr Magda Staudinger. It has
been demonstrated that a great number of biopolymers indeed possess the rigid
structure.
The early analysis of large molecules did not reveal the chain-end effects. This led
to the third model of colloidal substances, that of ring molecules, either separated or
catenating. Kraut (1869) assumed that his product of salicylic acid polycondensation
had interlocked ring structures, each having relatively low molecular weight, but
forming large physically locked colloidal aggregates with an effective MW ranging
from a few to hundreds of kg/mol. Also Staudinger, as late as 1929, visualized
polystyrene macromolecule as closed-loop, bifilar structures with two strands
parallel to each other (Staudinger and Breusch, 1929). Only systematic, step-wise
polymerization studies with careful titration of chain-ends resolved this misconcep-
tion (Lycan and Adams, 1929).
Thus, in the second half of the 19th century, there were three schools of thought for
interpreting the polymeric behavior by: (1) association of low molecular species by
way of secondary bonds, (2) linear macromolecules and (3) the presence of catenates.
Bitter disputes took place, not only between proponents of different concepts, but
Early polymers and polymerization reactions 67
even between believers from the same school. On the occasion of Staudinger's Nobel
prize in 1953, it was noted that 'The development of macromolecular science does
not present a picture of peaceful idylls' (Fredga, 1954). The intensity of these discus-
sions, particularly in the early stage, is particularly noteworthy, for at that time
methods for determination of high molecular weights did not exist (science has
been known to give rise to strong 'religious' beliefs).
The first methods of MW determination were applicable to what today would be
considered oligomers and low-molecular-weight polymers. Cryoscopy was pro-
posed by Raoult (1882, 1885). The method was used to determine the molecular
weight of amylodextrin (Brown and Morris, 1888) and natural rubber (Gladstone
and Hibbert, 1888). Osmosis has been known since at least 1748, when Nollet studied
the phenomenon using animal membranes. However, only van't Hoff's solution
theory (1887) made it possible to relate the vapor or osmotic pressure to the mole-
cular weight; only in 1900 did Rodewald and Kattei for the first time use an
osmometer to determine the molecular weight of starch.
4.2.1 Molecular weight determination

In 1930, Staudinger and Heuer proposed that solution viscosity be used to measure
the polymer molecular weight M. Assuming rigid-rod macromolecules, the authors
postulated that the specific viscosity should be proportional to concentration c and
molecular weight:
11sp == (11- 110)/110 = cK'M (4.1)
where 110 is the solvent viscosity, and K' is the equation constant. The dependence
contained two gross simplifications: neglect of the hydrodynamic interactions
between molecules (thus implying that final concentration solution viscosity is a
measure of macromolecular size) and the assumption that macromolecules are rigid.
A year earlier, Mark and Fikentscher (1929) reported that intrinsic viscosity 11
(defined as the value of the inherent viscosity factor 11sp/C at infinite dilution),
prOVides information on the volume of individual colloidal particles, and thus on
MW. In analogy to the virial expression of osmotic pressure, the authors extended
Einstein's viscosity relation for diluted hard spheres to higher concentration (Simha,
1981, 1993). During the years 1932-38, the solution viscosity of suspensions and
solutions was investigated in Mark's laboratory in Vienna by Fred R. Eirich, Eugene
Guth and Robert Simha. For freely rotating chain molecules, the dependence, nowa-
days known as the Mark-Houwink-Sakurada equation, was obtained (Guth and Mark,
1934):
(4.2)
where M v is the viscosity-average molecular weight, and K and a ;:::: 0.5--{).7, are the
equation parameters. Kraemer in 1938 and Huggins in 1942 proposed their comple-
mentary methods of plotting the solution viscosity data to obtain reliable values of
[11] with Kraemer's, kK , and Huggins', kH = 0.5 - kK constants, being measures of the
hydrodynamic interactions.
In 1911, Svedberg and Esrup used ultracentrifugation to estimate the size of
colloidal particles. By 1927, the technique was sufficiently refined to measure the
MW of hemoglobin {Svedberg and Nichols, 1927) and, by 1933, that of synthetic
polymers (Kraemer and Lansing, 1933). The light scattering method takes its origin
from a suggestion by John William Strutt (Lord Rayleigh) that light scattering is
proportional to the volume of scattering particles (Strutt, 1899). However, develop-
ment of the method was slow - only in 1944 did Debye demonstrate its utility for
determination of the molecular weights of polymers (Debye, 1944, 1946).
Thus, even in the 1920s only the cryogenic, ebulliometric and osmotic pressure
methods were available for determination of MW. Owing to limits of resolution, the
measurable values of MW were only within a few kg per mol. Furthermore, since the
number average molecular weight, Mn , is sensitive to the presence of solvents and
other contaminants (the concept of polydispersity was introduced by Lansing and
Kraemer (1935», the arguments of believers in colloidal association were not based
on solid experimental evidence. Poor reproducibility, suspicions that test conditions
did not provide an adequate environment for the associations to break, as well as the
authority of Thomas Graham continued to keep the linear macromolecule concept
unpopular. As Mark (1982) recounted, two events were primarily responsible for the
turn: the 1926 meeting of the Deutscher Naturforscher und Arzte GeseUschaft, and
the 1935 meeting of the Faraday Society.
In 1920, Hennann Staudinger, then professor at the Eigenossische Technische
Hochschule in ZUrich, ETH-Z, postulated that cellulose and its derivatives, natural
rubbers, as well as synthetic polymers, such as polystyrene, are covalently bonded
linear macromolecules with a molecular weight in the hundred thousands.
During the 1926 meeting, Staudinger proposed a new classification of colloids,
dividing all substances into three categories (Staudinger 1932, 1947, 1950, 1969, 1970):
• suspensions - polydisperse particles consisting of more than 109 atoms, that are
filterable and can be seen under (optical) microscope;
• colloids - polydisperse particles consisting of Hf-109 atoms, that are not filterable,
do not dialyze, and are not resolvable under microscope;
• solutions - particles consisting of about 10" atom, that diffuse and dialyze easily,
and are not resolvable under microscope.
Furthermore, the second category, colloids, was divided into four subcategories:
• Dispersoids - these dissolve without swelling, prodUCing lyophobiC, electrically
charged, stable solutions with low Newtonian viscosity.
• Micellar colloids - aggregates of small molecules that dissolve after swelling.
• Molecular colloids - high molecular weight materials that dissolve after swelling
into polydisperse, lyophilic solutions. This group was further subdivided into
sphaerocolloids (low viscosity, e.g., glycogen) and linear macromolecular colloids
(high viscosity, non-Newtonian solutions, that tend to age on storage, e.g., starch,
rubber, cellulose, gelatin).
• Macromolecular associations - formed by dissolution without swelling, producing
lyophilic, stable solutions with Newtonian behavior (e.g., biocolloids such as
globulin).
Thus, what we now call linear polymers were labeled by Staudinger as linear
macromolecular colloids. Since the classification was based on dilute solution beha-
vior, insoluble substances were not classifiable. The classification had many oppon-
ents, who even in the 1930s kept calling Staudinger's work 'Schmierenchemie',
implying inadequate purification procedures. During the 1926 meeting, Mark
reported that X-ray crystallographic data of cellulose were consistent with the linear
macromolecules concept, thus declaring himself on the side of the linear macro-
molecule camp. Two years later, the concept of crystalline micelles made of
long molecules interacting by hydrogen bonds was introduced (Meyer and Mark,
1928).
Wallace Hume Carothers recognized the macromolecular nature of polymeric
materials. On the basis of the covalent macromolecule model he successfully synthes-
ized a series of aliphatic polyesters, polyamides and polyamide-esters, thus demon-
strating unity between organic and polymer chemistry. From 1929 to 1936, he and his
colleagues published 53 scientific papers and had 22 patents granted. After Caro-
thers' suicide in 1937 (at the age of 41), du Pont obtained 30 additional patents,
most with only Carothers' name. During the last seven years of his life, Carothers'
output was staggering in concept as well as in volume (Bolton, 1942; Mark and
Whitby, 1940).
Five years after the Deutscher Naturforscher und Arzte Gesellschaft meeting,
Carothers published a 73-page review entitled Polymerization. The article was widely
accepted as the basic text, unifying different observations and outlining the chemical
principles responsible for synthesis of the new category of organic macromolecules
(Carothers, 1929, 1931; Carothers and Berchet, 1930). Polymerization was defined
'as any chemical combination of a number of similar molecules to form a single
molecule'. Depending on the reaction mechanism, the polymers were named
either addition or condensation type (A or C polymers). Carothers considered poly-
merization to be a specific type of chemical reaction, capable of proceeding
indefinitely. Accordingly, only three types of molecules were supposed to undergo
such a transformation: unsaturated, cyclic and polyfunctional of the type (x-R-y) or
(x-R-x + y-R'-y). Carothers and Hill (1933) announced that their synthetic
superpolymers (polyesters or polyamides) could be spun and drawn into silk-like
fibers. Thus, in the early 1930s, Carothers not only formulated the principles of
polymerization, but also showed the utility of the method.
During the Faraday Society meeting from 26 to 28 September 1935 on 'Phenomena
of Polymerization and Polycondensation' Carothers reported on the polymerization
of bivalent and trivalent monomers, demonstrating general validity of the principles
(Carothers, 1936). He ended the lecture by presenting a theory for calculating MW
and MWD from the probability of a condensation reaction. The theory, developed by
Carothers' younger colleague at du Pont de Nemours, Paul J. Flory, was published
the following year (Flory, 1936, 1939). It provided the basis for verification of the
newly formulated principles of the polycondensation reaction. By the end of the 1936
meeting the discussion was not about the existence of macromolecules, but the
methods of polymerization and characterization. Polymer science came into being.
4.2.2 Free volume

The free volume theory of liquids dates from the beginning of the 20th century. The
original idea was to simulate a pseudocrystalline structure of liquids by placing each
rigid molecule of diameter a in a cell of diameter b made of the surrounding
molecules. Thus, the observed specific volume of a given liquid, V = (1r/6)EIJ3,
was seen as a sum of the occupied volume, Voce = (1r/6)Ea3, and free volume Vt.
Instead of these specific volumes it is more convenient to use a relative measure, the
free volume fraction f. Two expressions for f have been used:
f = (V - Vocc)/V
(more frequent) and
f = (V - Vocc)/Voce
The model has been found particularly useful in developing rheological and thermo-
dynamic theories of liquids and their mixtures.
To confirm the validity of the free volume model, the temperature and pressure
dependencies of liquid viscosity were measured (Batschinski, 1913). Experimentally,
Vocc was defined as the specific volume at which the liquid viscosity was immea-
surably high, ." -+ 00. The observed value of Vocc was found to be slightly larger than
the specific volume of the crystallized substance. Furthermore, good correlation was
found between Voce and either the critical volume or the van der Waals constant:
Vocc/(Vcritf3) = Voce/b = 0.921 ± 0.018
Thus Batschinski was the first to correlate liquid viscosity and free volume fraction,
the latter expressed in terms of the specific volume:
." = ao + atll = ao + Vatl(V - Voce) (4.3)
where ai are equation parameters. The dependence was found to adequately
describe observed dependencies of the liquid's viscosity on pressure and temp-
erature.
Nearly 40 years later, analysis of more accurate data of viscosity and specific
volume for a series of paraffins with molecular weights of 72-1000g/mol resulted
in derivation of a logarithmic dependence (Doolittle, 1951):
In." = ao + Vatl(V - Vo) (4.4)
where Vo is the value of V extrapolated to 0 Kelvin. It should be noted that Equation
(4.4) provides a basis for derivation of the well-known WLF time-temperature shift
factor aT (Williams et al., 1955).
The free volume concept was found equally important for the thermodynamic
description of the glassy and liquid states. Eyring developed the cell theories of
glasses and liquids, postulating that molecular motion is feasible by presence of
holes in the regular lattice (Eyring, 1936). The basic assumptions of the theory were
confirmed by a rigorous derivation by Kirkwood (1950). In the language of statistical
mechanics, the free volume fraction is determined by the difference in potential
energy:
1= (l/V) Jexp{ -[E(r) - E(O)]/kT}dr ~ (1 - a/b)3 (4.5)
The free volume model was also incorporated into the molecular theory of solu-
tions (Prigogine et aI., 1957) and it constitutes an integral part of several theories used
for interpretation of the thermodynamic properties of polymer blends (Utracki,
1989a). In particular, it is a part of the most successful equation of state derived for
liquids and glasses (Simha and Somcynsky, 1969), which recently was critically
examined using data for 56 principal polymers (Rodgers, 1993).
The thermodynamics of polymer solution has its origin in the work carried out in
the Kurt H. Meyer laboratory in Geneva on the entropy of mixing (Meyer, 1942).
These developments were continued in the 1930s by Guggenheim and by Rush-
brooke, in the 1940s by Huggins and by Flory, in the 1950s by Prigogine, then by
Simha, and their collaborators (Flory, 1953; Tompa, 1956; Huggins et al., 1966, 1968;
Prigogine et al., 1957; Simha and Somcynsky, 1969). The thermodynamic fundamen-
tals of rubber elasticity were developed in the 1930s (Meyer et al., 1932; Guth and
Mark, 1934). The first studies of polymer-polymer miscibility were published in the
late 19405 (Dobry and Boyer-Kawenoki, 1947).
Simha and Somcynsky assumed that free volume exists in two forms: (1) as larger
lattice cell volume, in comparison with the occupied volume of the statistical seg-
ment (the solid-like contribution), and (2) as a fraction of unoccupied lattice holes
(the gas-like contribution that makes it possible to correctly describe the system
entropy). During the following 30 years the theory was extended to polymer solu-
tions and blends (Xie et al., 1992).
Over the years the free volume model had numerous opponents who questioned
the physical reality of the hollow solids. Since the mid-1960s the positron annihila-
tion technique has been used to study polymers. It was reported that the lifetime of
ortho-positronium increases with temperature, interpreted as evidence of an increas-
ing free volume. More detailed analysis indicated that free volume should be
discussed in terms of the number and size of the holes; thus, in terms of a distribu-
tion. The measurements showed that above the glass transition temperature the
number of holes does not increase, but their volume does (Kobayashi et al., 1989).
'This, in turn, provides an interesting opportunity for interpretation of the coordi-
nated motion of molecules, where only a fraction of the free volume, having suffi-
ciently large holes to accommodate statistical segments of a macromolecule, can
participate (Utracki, 1985a).
4.2.3 Viscoelasticity
In 1874, Boltzman presented his theory of viscoelasticity to the Kaiserlich Akademie
der Wissenschaft, thus beginning rheology as we know it. The concept of the
relaxation spectrum was introduced by Thompson in 1888. The spring-and-dashpot
analogy of viscoelastic behavior (Maxwell and Voigt models) appeared in 1906.
The first theory of suspension viscosity was published by Einstein (1906, 1911). The
statistical approach to polymer problems was introduced by Kuhn (1930).
In 1932, Busse noted that green (not vulcanized) rubber, under stress, shows a
dual behavior - when stretched for a short time it recovers its original shape as an
elastic solid, whereas when stretched for a long time it flows like a viscous
liquid (Busse, 1932). To explain this, he postulated the presence of two types of
interaction: a few widely separated strong ones acting as physical crosslinks, and
many weak ones of the van der Waals type, that make it possible for one macro-
molecule to slip by the others. The former postulate was the first connotation of
chain entanglement, an idea pursued by many others (Treolar, 1940; Hory, 1944;
Green and Tobolsky, 1946).
The model of the shear-rate-dependent chain entanglements was introduced by
Buchdahl (1948) to explain the pseudoplastic behavior of polymer melts. Two years
later he used this model to calculate the molecular weight between entanglements.
Me from creep and stress relaxation data (Nielsen and Buchdahl, 1950). However, it
was Bueche (1952, 1956, 1962) who developed the model of frictional drag engend-
ered by the entanglements. Defining the molecular friction constant per statistical
segment as the unit force needed to pull the undeformed macromolecule through the
surrounding medium at unit speed, fo = FIN (with N being the number of statistical
segments per macromolecule), he derived the relations listed in Equation (4.6)
between the diffusion constant D or zero-shear viscosity 1'/0, and such molecular
parameters as density p, molecular weight M, and radius of gyration Rg :
DTJo = (pNA/36)(R~/M)kT
TJo == (pNA/36)(R~/M)N*fo
(4.6)
N* == (MIMo); for M::s 2Me
N* == (MIMo)(pNA/48)(MIMe)2Ml/2(R~/M)3/2{3; for M> 2Me
where {3 is a numerical constant approximately equal to 0.6. Thus, Bueche predicted
that for low-molecular-weight liquids (M below the value of the critical molecular
weight for entanglement, Me = 2Me, where Me is the molecular weight between
entanglements), 110 should be proportional to M, whereas for high-molecular-weight
macromolecules (above Me) 110 should be proportional to M3.5. Thus, predictions of
the entanglement-based theory were in good agreement with observations: 11OooM3·4.
Bueche also introduced chain entanglements into the theory of rubber elasticity as
one of the contributions to the effective number of network chains.
The correlation between the plateau modulus and entanglement concentration
soon followed (Ferry, Landel and Williams, 1955). The long and sometimes bitter
discussions on the nature of entanglement led to defining it as 'a special type
of interactions, affecting mainly the large-scale motions of the chains, and
through them, the long time end of the viscoelastic relaxation time spectrum'
(Graessley, 1974).
4.2.4 Radical polymerization

The early thermoplastic polymers (e.g., polyvinylidenechloride in 1838, polystyrene
in 1839) were obtained by radical polymerization initiated either by heat or by
sunlight. In 1993, Herman Mark reminisced 'The concept of free radicals was not
known in 1920 - well, perhaps in politics, but not in chemistry.' Mark's papers with
Wilhelm Schlenk (Schlenk and Mark 1922) were the first reports on systematic
studies of free radical chemistry. Later, at I. G. Farbenindustrie, Mark contributed
to the development of peroxide-initiated, emulsion copolymerization of butadiene
with styrene (Buna-S, GSR, or SBR - the first synthetic, general purpose rubber) or
with acrylonitrile (Buna-N, or NBR) into vulcanizable rubbers. During 1910-30, the
radical polymerization of vinyl chloride and styrene was also studied by Ostromi-
slensky, first in Moscow, then after the Bolshevik revolution, at Naugatuck Chemical
Company in Connecticut.
Radical copolymerization has been commercially explored since the beginning of
this century. The systematic studies of radical copolymerization started in the late
1920s at I. G. Farbenindustrie's laboratories, where Hans Fikentscher empirically
determined which one of the 30 or so monomers liked or disliked to copolymerize
with other monomers from the list. During this period the company was granted
nearly a hundred patents on various emulsion-polymerized vinyl and/or acrylic
polymers and copolymers. At that time also, the advantage of latex-blending
was established. The theory of copolymerization was developed in the 1940s (Alfrey
et al., 1952).
As already mentioned, the work that began in 1927 in du Pont de Nemours'
laboratories by Carothers and his colleagues prOVided the basis for understanding
the polycondensation reactions, especially those leading to polyesters and poly-
amides. Good agreement between Flory's theoretical predictions and the experi-
mental observations provided a convincing argument for the acceptance of the
linear macromolecule model. However, polycondensation reactions had been
known for 70 years (LourenlOo, 1859; Wurtz, 1859, 1860). Oligomeric polyethers and
polyesters have been produced over the years in several laboratories by diverse
methods, such as by condensation of ethylene glycol with ethylene bromide, by
reacting ethylene oxide with H 20 (and separating the products by distillation), by
reacting a, w-dibromoalkanes with magnesium, ethylene glycol with succinic acid,
etc. The achieved degree of polymerization was up to 30 which, combined with an
inability to detect chain-end groups, seemingly supported the cyclic macromolecular
structure. Until the discoveries of Carothers et al., there was little understanding of
the nature of the reaction (Morawetz, 1985).
A partial list of the early polymers is given in Tables 2.1 and 4.1. More detailed
information can be found in the source publications listed at the end of Chapter 1.
4.2.5 Anionic polymerization

In 1928/ Ziegler used alkyllithium to initiate living, anionic polymerization of elas-
tomers. In 1955/ Firestone reported Li-initiated polymerization of isoprene. The work
led to examination of the reaction by several research groups. Szwarc et al. (1956)
reported on the use of sodium naphthalene in tetrahydrofurane as an anion-radical
di-initiator for polymerization of styrene-isoprene block copolymers. For the same
application, an organolithium initiator was used by Holden and his colleagues at
Shell Chemical (Legge et al., 1987). The mechanism of anionic polymerization
initiated by this catalyst was described by Bywater (1965). Szwarc is credited with
rediscovery of the living anionic polymerization and elucidation of details of its
mechanism (Szwarc, 1968).
4.2.6 Ziegler-Natta catalysis

Ziegler's experiments with Li-eatalyzed polymerization revealed that to avoid ins0-
lubility of LiH, its cohydride with aluminum, LiAll-J4, should be used. Later, he
noted that a-alkene polymerization proceeded quite well without LiH, and that
impurities of transition metal complexes increased the reaction rate. Thus/ in early
1950/ low temperature and pressure polymerization of ethylene into linear, high
density polyethylene (HOPE) was carried out using ZrC4 + AlR3 . Subsequently,
Natta discovered that these types of catalysts polymerize a-alkenes to stereoregular
polymers.
The catalysts developed in Ziegler's and Natta/s laboratories became known as
Ziegler-Natta (Z-N) catalysts. These can be defined as polymerization initiators
created from (1) a catalyst and (2) a co-eatalyst, where (1) is the halide or oxyhalide
of a transition metal from Groups IV to vn, mostly Ti, V, Cr, Mo, Zr, Fe, Ni and Co,
and (2) is an organometallic compound of a metal from Groups I to ID, primarily
alkyls, aryls or hydrides of AI, Li, Zn/ Sn, Cd, Be and Mg. The Z-N catalyst is
prepared by mixing ingredients (1) and (2) in a dry, oxygen-free solvent. They are
used mainly for heterogeneous polymerization, although soluble forms are also
known (Natta and Oanusso, 1967; Keii, 1973).
Recently, Z-N catalysis has experienced a renaissance, with new advances in
heterogeneous and homogeneous polymerization. The new MgCh-supported cata-
lysts have 100-fold more active sites per mole of Ti and about 10 times higher
propagation rate. They are able to generate polypropylene with an isotactic content
R-CH-X
I
R CH 2
\ /
/ ,,
/ \ ,, ,,
/
Ti AI CH 2=CHX Ti AI
,, ,
\ ,,
\
~
/ /
/
/
R /
R
Structure 4.1 Ziegler-Natta catalyst: (.5-TiChhAlCI3AlEt2Cl

of 99%, as compared to 92% by the older riCh catalyst (Galli et al., 1981; Barbe et al.,
1986; Rieger et al. 1990).
4.2.7 Single-site metallocene catalysts

The newest, single-site metallocene catalysts have opened a new vista for the pro-
duction of high quality polymers. The catalyst makes it possible to control molecular
weights, molecular weight distribution, comonomer placement, stereoregularity,
lifetime of the reactive chain-ends, etc.
Hhas been known that stereospecificity of the catalyst depends on the morphology
of its complex. In the presence of methyl aluminooxanes (MAO), the stereorigid
chiral compounds belonging to the Group IVA metallocenes lead to highly stereo-
specific (> 98%) polymerization of a-alkenes (Ewen, 1984). Depending of the nature
of the aromatic ligand, high purity iso- or syndio-isomers can be produced
(Kaminsky et al., 1985, 1992).
Single-site metallocene catalysis leads to materials with superior physical proper-
ties. For example, syndiotactic PP was reported to have a modulus nearly five times
larger than isotactic PP (Kaminsky, 1992). When used for copolymerization of
ethylene (either in a gas phase at a pressure of 0.2 MPa and a temperature of 30 °C,
or in solution), the new catalysts make it possible to obtain polyethylenes with a high
control of comonomer placement (up to 25% can be incorporated without losing the
free-flowing character of pellets), an average molecular weight of 2200 kg/mol, and a
polydispersity Mw/Mn ~ 2.4 (usually 1.9). The catalyst activity is reported to be
high, more than 61 t PE/mol. The new PEs show uniform properties, and higher
strength and elasticity. Owing to the absence of low MW fractions, the materials do
not fume during processing and do not have taste or odor. However, the narrow
MWD of the new resins leads to a different rheology than the traditional, requiring
blending and/or process modification.
The first metallocene, a ferrocene, was discovered in 1954 by Geoffrey Wilkinson
at Harvard and Ernst Otto Fischer at Munich University. In 1975, Mitsui Petrochem-
icals introduced metallocene-made Tafrner™, linear low density polyethylene with
strictly controlled comonomer placement in the chain, but rather low molecular
weight. In 1976, Hansjoergen Sinn at the University of Hamburg discovered a
catalyst system for the polymerization of ethylene, consisting of bis(cydopentadie-
nyl)titanium dialkyl, aluminum trialkyl and water. A few years later, Walter
Kaminsky polymerized ethylene - using a catalyst system consisting of zirconium
metallocenes of the general formula (CP)nZrY4-n (where Cp represents cydopenta-
dienyl, n = 1-4, Y = alkyl or metallo-alkyl), an aluminum trialkyl cocatalyst, and
water. It has been reported that relatively low molecular weight polymers were
obtained at higher polymerization temperatures and relatively high molecular
@ CH 3
I
Zr + -( -AI-O -) -
"CI
n
@
Structure 4.2 Mettalocene catalyst
weight polymers at low polymerization temperatures (Sinn and Kaminsky, 1980).
However, to achieve high polymerization activity and reduce operating costs, it is
desirable to maximize polymerization temperatures. In 1987, Walter Kaminsky
authored the Hoechst patent on the Kaminsky catalyst - zirconocene with methyl-
aluminooxane, MAO, The same year, Exxon joined with Mitsui Petrochemicals to
develop metallocene technology for polyethylene polymerization. One of the earliest
patents (deposited in 1983) from Polysar disclosed a bimetallic metallocene alumox-
ane catalyst used in polymerization of alkenes into elastomeric ethylene-a-alkene
copolymer or ethylene-a-alkene non-eonjugated di-alkene (Davis, 1994).
An advantage of the cyclopentadienylmetal-alumoxane catalyst system is its high
activity for ethylene polymerization. Unlike alkene polymers produced in the pres-
ence of a heterogeneous Z-N catalyst, terminal unsaturation is present in polymers
produced in the presence of these homogeneous metallocene catalysts. The use of
hydrogen for molecular weight control for these new catalysts is disadvantageous,
since the terminal unsaturation would become saturated and result in a loss of
available sites for building functionality into the alkene polymers.
One of the earlier patents on the technology provides a detailed description of
the metallocene catalytic system. In 1983, Exxon Chemical deposited a patent
application for polymerization of ethylene with or without other comonomer(s).
The catalyst employed was a cyclopentadienyl derivative of general formula
(Cp) R's(Cp)MQ3_p' or ~(CphMQ'. Here, M is a metal from Group IVb, Vb or
VIb (preferably Zr), Cp is a cyclopentadienyl or substituted cyclopentadienyl, R' can
be hydrogen or an hydrocarbyl radical such as alkyl, alkenyl, aryl, alkylaryl or
arylalkyl radical, R" is a CrC4 alkylene radical, a dialkyl germanium or silicone
(e.g., a dimethylsilyl radical) or an alkyl phosphine or amine radical bridging two Cp
rings, Q is a hydrocarbon radical such as aryl, alkyl, alkenyl, alkylaryl or
arylalkyl radical, Q' is an alkylidene radical having from 1 to about 20 carbon
atoms,s = 0-1, P = 0-2, m = 4-5). The molecular weight was controlled by selecting
an appropriate substituent on the cyclopentadienyl ring as well as ligands for the
metallocenes. The comonomer placement (thus density) was found to depend on the
metallocenes. Hence, selection of the catalyst components made it possible to inde-
pendently control the (co)polymer molecular weight and density. The catalyst was
used in combination with a large amount of alumoxanes (Welborn and Ewen, 1994).
The first commercial metallocene-made PE in the USA was introduced by Exxon in
1991 as a PIastomer™. The same year, Dow Plastics produced developmental quan-
tities of AffinityTM resins - ethylene copolymers with up to 25 mol % of butene,
hexene or octene. Insite™ technology was based on a metallocene catalyst with a
single cyclopentadiene ring, thus providing for a certain randomization of the poly-
merization process. The resins had narrow molecular weight distribution and long
chain branching, similar to LDPE.
The metallocene catalysts also produce high melting point polymers out of com-
modity monomers, e.g., syndiotactic polystyrene with a glass transition temperature
of 100 °c, and a melting point of 266 0c. The sPS has good dimensional stability, heat,
chemical, solvent, water and steam resistance, transparency, as well as excellent
electrical properties. It can be used in blends with other polymers (e.g., polypheny-
leneether) to enhance blend properties (Guerra et al., 1992). Syndiotactic poly(p-
phenyl styrene) (sPhPS), with Tg = 196°C Tm = 352°C and a decomposition temper-
ature, Tdecomp of 380°C was also synthesized. Since sPhPS is miscible with sPS over
the whole range of concentration, the copolymer or blend of these two polymers can
be processed at any temperature above 266 °c (Ishirara et al., 1986, 1988; Watanabe et
aI.,1992).
Using a metallocene catalyst, an isotactic or syndiotactic poly(ethylene-alt-eydo-
pentene), or polynorbomene with Tm = 400-60Q°C was obtained (Fu and Grubbs,
1992; Grubbs et al., 1995). The authors also reported that, under ambient conditions
of temperature and humidity, Ru(P3hCh catalyst leads to living telechelic poly-
mers that can be used for block copolymerization and diverse end-eapping.
4.2.8 New polymerization methods and new polymers

In the final years of this century, the polymer industry is being increasingly oriented
toward high technology and high value-added materials. This tendency is evident in
improved polymerization methods of old polymers, in new processing methods, and
in new high performance polymers. For example, new syndiotactic polypropylenes
or polystyrenes far surpass the performance of their predecessors. Gel-spun
polyethylene fibers have 200 times higher tensile strength than polyethylene pre-
pared under normal processing conditions. A new aromatic polyester, EKF from
Sumitomo Chemical Company, shows a tensile strength of 4.1 GPa, compared with
70MPa for standard polyesters (Table 4.2).
New types of polymer are also being introduced. For example, dendritic-structure
polymers have been disclosed by Frechet and co-workers (Hawker and Frechet,
1990; Wooley et al., 1991; Frechet et al., 1992). By comparison with linear polymers,
dendritic polymers with similar molecular weight are highly soluble and have low
intrinsic viscosity. At the time of writing, these materials have not left the labora-
tories, and full characterization of their properties as well as evaluation of their
potential is still awaited (Tomalia et al., 1993). By the end of 1989, new carbosilane
dendritic macromolecules had been introduced (Roovers et al., 1989, 1993). The new
technology makes it possible to synthesize a full spectrum of macromolecules from
linear to 2"-branched (data for polymers with n = 2-7 have been published), and to
fully dendritic.
Other new polymeric materials, specifically designed for nanotechnological high
performance applications, have the hairy rod molecular structure, where rigid-rod
chain macromolecules are provided with short and flexible side branches. The
Langmuir-Blodgett monolayers prepared from these polymers can be assembled
Table 4.2 High performance materials - a comparison

Material Strength (CPa) Modulus (CPa)
Theoretical Obseroed Theoretical Observed
Polyethylene standard 21 :S 0.03 316 0.2
Polyethylene gel-spun 21 6 316 220
Polyester standard 24 0.07 124 2.2
Polyester oriented 24 1.2 124 21
Aromatic polyamide 21 3.6 190 125
Aromatic polyester 4.1 139
Poly(phenylene 4.2 371 365
benzothiazol)
Polyazomethin 4.7 125
Carbon fiber 3.1 235
Steel 29 2.1-3.5 210
into a nanometer-thick composite multilayer with high optical, electrochemical or
electrical properties (Wegner, 1992).
At the same time, the technology moves away from single phase materials to
diverse combinations of polymers, additives and reinforcements. Although syner-
gistic effects are often found and frequently cited, the principal reason for the use of
multicomponent and multiphase systems is a need for widening the range of proper-
ties, for developing materials showing combinations of properties not obtainable
in chemically pure polymers; hence, there is growing need for evolution of blend
technology.
5
Nomenclature of polymeric systems
A polymer is a substance composed of large molecules, the macromolecules, built by

covalently joining at least 50 molecular mers, segments or recurring constitutional
repeating units, (CRU). The longest sequence of CRU defines the main chain of the
macromolecule. The main chain may be composed of a series of subchains, identi-
fied by some chemical or physical characteristic (e.g., tactic placement). The
main chain may also contain long or short side chains or branches, attached to it
at branch points. A small region in a macromolecule from which at least four
chains emanate constitutes a crosslinking point. A macromolecule that has
only one crosslink point is the star macromolecule. A macromolecule consisting
of several crosslinked chains, but haVing a finite molecular weight, is a micronet-
work. A highly ramified macromolecule in which each CRU is connected to every
other CRU is a polymer network. When the main chain of a macromolecule has
numerous branch points from which linear side chains emanate, it is a comb
macromolecule.
Within the International Union of Pure and Applied Chemistry (IUPAC), the early
work on nomenclature of polymers (1962-8) was coordinated by Huggins, Natta,
Desreux and Mark. In 1974, the IUPAC Commission on Macromolecular Nomencla-
ture defined 52 terms related to polymer structure, including: polymer, constitu-
tional units, monomer, polymerization, regular polymer, tactic polymer, block
polymer, graft polymer, monomeric unit, degree of polymerization, addition poly-
merization, condensation polymerization, homopolymer, copolymer, bipolymer,
terpolymer, copolymerization (IUPAC, 1974). These terms found general acceptance
in polymer literature. Table 5.1 lists the sources for information on the nomenclature
of polymeric materials.
5.1 TRADmONAL
Examples of traditional polymer names (reluctantly permitted by the IUPAC) are
listed in Table 5.2. These are compared to the systematic names derived by applica-
tion of the structure-based set of IUPAC rules.
5.2 COPOLYMERS
When the mers are not identical, polymerization leads to a copolymer. For divalent
mers, a linear copolymer is obtained, but when at least some mers are
Copolymers 79
Table 5.1 Polymer nomenclature as proposed by the IUPAC commission on macro-

molecular nomenclature
Title Reference
Report on nomenclature dealing with Huggins, M. L./ et al., 1966
steric regularity in high polymers
Basic definitions of terms relating to Pure Appl. Chern./ 40/ 479 (1974)
polymers
Nomenclature of regular single-strand Pure Appl. Chern./ 48/ 373 (1976)
organic polymers
Stereochemical definitions and notations Pure Appl. Chern./ 53/ 733 (1981)
relating to polymers
Note on the terminology for molar masses J. Polym. Sci. Polym. Lett. Ed., 22/ 57
in polymer science (1984)
Nomenclature for regular Single-strand Pure Appl. Chern./ 57/ 149 (1985)
and quasi-single-strand inorganic and
coordination polymers
Source-based nomenclature for Pure Appl. Chern./ 57/1427 (1985)
copolymers
Use of abbreviations for names of Pure Appl. Chern., 59, 691 (1987)
polymeric substances
Definitions of terms relating to individual Pure Appl. Chern., 61, 1769 (1989)
macromolecules, their assemblies, and
dilute polymer solutions
Definitions of terms relating to crystalline Pure Appl. Chern./ 61, 769 (1989)
polymers
A classification of linear Single-strand Pure Appl. Chern., 61, 234 (1989)
polymers
Compendium of macromolecular Metanomski, V., 1991
nomenclature
Source-based nomenclature for non-linear Jenkins, A. D., et al., 1993
macromolecules and macromolecular
assemblies
able to join more than two units, then polymerization leads to branched or cross-
linked copolymers.
When the polymerization starts on a polymer chain of different chemical character
than the one that is subsequently forming, the resulting structure is known
as grafted copolymer. Thus, the arrangement of the different types of
monomeric units must be Specified. Various classes of copolymers are listed in
Table 5.3. Note that polymers having monomeric units differing in constitutional or
configurational features, but derived from a single monomer, are not
regarded as copolymers (e.g., polybutadiene with mixed sequences of 1,2 and 1,4
units). The nomenclature system can, however, also be applied to such pseudo-
copolymers.
80 Nomenclature of polymeric systems
Table 5.2 Traditional and systematic names of common polymers
TraditionJll nJlme Systematic nJlme

Polyethylene poly(methylene)
Polypropylene poly(propylene)
Polyisobutylene poly(l,l-dimethyl ethylene)
Polybutadiene poly(l-butenylene)
Polyisoprene poly(l-methyl-l-butenylene)
Polystyrene poly(l-phenyl ethylene)
Polyacrylonitrile poly(l-cyano ethylene)
Polyvinyl alcohol poly(l-hydroxy ethylene)
Polyvinylacetate poly(l-acetoxy ethylene)
Polyvinylchloride poly(l-chloro ethylene)
Polyvinylidenefluoride poly(l,l-difluoro ethylene)
Polytetrafluoroethylene poly(difluoro methylene)
Polyvinylbutyral poly[(2-propyl-l,3-dioxane-4,6-diyl) methylene1
Polymethylacrylate poly[l-(methoxycarbonyl) ethylene1
Polymethylmethacrylate poly[l-(methoxycarbonyl)-l-methyl ethylene1
Polyformaldehyde poly(oxy methylene)
Polyethylene oxide poly(oxyethylene)
Polyphenylene ether poly(oxy-l,4-phenylene)
Polyethyleneterephthalate poly(oxy ethylene oxy terephthaloyl)
Poly-EO-caprolactam poly[imino(l-oxohexa methylene)1
Polyamide-66; or poly[imino (l,6-dioxohexa methylene)
polyhexamethyleneadipamide iminohexa methylene1or
poly(iminoadipoyliminohexa methylene)
Table 5.3 Nomenclature of copolymers
Type Connective Example

Short sequences
Unknown or unspecified -copoly(A-co-B)
Statistical -stat- poly(A-stat-B)
Random (Bernoullian statistics) -ran- poly(A-ran-B)
Alternating -alt- poly(A-alt-B); (AB)n
Periodic with respect to at least -per- poly(A-per-B-per-C); (ABC)n; (ABAC)n;
three monomeric units (AABB)n' etc.
Long sequences
Block -block-, poly A-black-poly B; poly(A-b-B)
or -b-
Graft (polymeric side chain -graft- poly A-graft-poly B; poly(A-g-B);
different) or -g- AAAAA(g-BBB)AAAAAAA
Star -star- star-poly A
Star-block -star- ... star-poly A-black-poly B
-block-
Networks
Crosslinked -cross- cross-poly A
Interpenetrating -inter- cross-poly A-inter-cross-poly B
Conterminous -cross- poly A-crass-poly B
Polymer blend terminology 81
5.3 NON-LINEAR MACROMOLECULES AND MACROMOLECULAR
ASSEMBLIES
To describe non-linear polymers or polymer blends with greater precision, a set of
qualifying descriptors was recently suggested Oenkins et al., 1993). These are sum-
marized in Table 5.4.
Table 5.4 Proposed descriptors for non-linear macromolecules and macromolecu-

lar assemblies
Polymer structure Descriptor
Cyclic cyclo
Branched (unspecified) branch
short-chain sh-branch
long-ehain I-branch
with f (give numerical value) branch points f-branch
Comb comb
Star (unspecified) star
withf(give numerical value) arms f-star
Network net
Micronetwork m-net
Polymer blend blend
Interpenetrating polymer network ipn
Semi-interpenetrating polymer network sipn
Macromolecule-macromolecule complex compl
5.4 POLYMER BLEND TERMINOLOGY

The polymer blend terminology is provided in Table 5.5. Two terms are controver-
sial: miscible blend and compatible blend.
Table 5.5 Terminology of Polymer Blends

Term Definition
Polymer A substance composed of large molecules, the
macromolecules, built by covalently joining at least 50
molecular mers, segments or recurring constitutional
repeating units, CRU. Commercial polymers may
contain up to 2 wt % of another polymeric modifier.
Copolymer Polymeric material synthesized from more than a single
monomer.
Engineering polymer Processable polymeric material, capable of being formed
to precise and stable dimensions, exhibiting high
performance at the continuous use temperature above
100 °C, and having tensile strength in excess of 40 MPa.
Polymer blend Mixture of at least two macromolecular substances,
polymers or copolymers, in which the ingredient
content is higher than 2 wt %.
82 Nomenclature of polymeric systems
Table 5.5 Continued
Term Definition
Homologous polymer Mixture of two homologous polymers, usually narrow
blend molecular weight distribution fractions of the same
polymer.
Miscible polymer blend Polymer blend, homogenous down to the molecular
level, in which the domain size is comparable to the
macromolecular dimension, associated with a negative
value of the free energy and heat of mixing,
~Gm:::::: ~m::; 0, and &~Gm/fJqJ > o. Operationally,
it is a blend whose domain size is comparable to the
dimension of the macromolecular statistical segment.
Immiscible polymer blend Polymer blend whose free energy of mixing
~Gm::::::~m>O.
Compatible polymer blend Term to be avoided! At best a utilitarian, non-specific
term indicating a marketable, visibly homogeneous
polymer mixture, with enhanced performance over the
constituent polymers.
Polymer alloy Immiscible, compatibilized polymer blend with modified
interface and morphology.
Compatibilization Process of modification of the interfacial properties in an
immiscible polymer blend, resulting in formation of
the interphase and stabilization of the desired morpho-
logy, thus leading to the creation of a polymer alloy.
Interphase Third phase in binary polymer alloys, engendered by
interdiffusion or compatibilization. Thickness of this
layer varies with the type of polymers and
compatibilization method from 2 to 60 nm.
Compatibilizer Polymer or copolymer that added to a polymer blend
modifies its interfacial character and stabilizes the
morphology.
Chemical Compatibilization by addition of a compatibilizer, in
compatibilization most cases either a copolymer or multipolymer.
Physical compatibilization Compatibilization by physical means: high stress field,
thermal treatment, irradiation, etc.
Reactive compatibilization Compatibilization during reactive processing, extrusion

or injection molding.
Engineering polymer Polymer blend or polymer alloy either containing or
blend having properties of an engineering polymer.
Interpenetrating polymer Polymer alloy, containing two or more polymers in
network (IPN) network form, each chemically crosslinked. Sequential,
simultaneous (SIN) and latex type IPNs are known.
Thermoplastic IPN Polymer alloy, containing two or more polymers in a
cocontinous network form, each physically
crosslinked. The crosslinking originates in crystallinity,
ion cluster formation, presence of hard blocks in
copolymers, etc.
Part Two
Technical and economic rationality
for polymer blending
6
Reasons for, benefits and problems
of blending
Today, polymer blends constitute over 30wt% of polymer consumption, and with
the annual growth rate of 9% (constant for the last 12 years) their role can only
increase. Benefits of blending can be discussed from the perspective of material
properties and economies it can bring to the manufacturer. There are a number of
good reasons for blending; however, these tend to change with time and geographic
location.
In the 1960s, the principal reason for blending was modification of a specific resin
for a specific type of behavior - in most cases, improvement of impact strength.
During the next decade, blending was used to gain direct economy by diluting
expensive engineering resins with commodity ones. During the 198Os, the impor-
tance of the high temperature specialty resins required improvement of processa-
bility. Currently, blending aims at securing sets of specific properties required for an
envisaged application. For example, the blend formulated for use in automotive
body panels must be easy to mold to precise dimensions, must retain its shape at
temperatures up to 85°C, be impact resistant down to -40 °C, resistant to gasoline,
motor oil, and soap solution, must be paintable, recyclable, economic, etc. The only
way such a dream-list of properties can be met is by combining characteristic
properties of several polymers into a multicomponent system. To achieve reliability
and reproducibility, both the compounding and processing require sophisticated
control of compatibilization and morphology. Thus, with time, alloying demands
greater knowledge from resin manufacturers, compounders and processors. How-
ever, the historical shift of emphasis from one goal of blending to the next does not
mean that the previous one is abandoned.
The reasons for blending can be separated between those that are related to
products, and those related to the producers. The following material-related reasons
are often given:
• Developing materials with a full set of desired properties.

• Extending engineering resins' performance by diluting them with low-cost com-
modity polymers.
• Improving a specific property, e.g., impact strength, rigidity, ductility, chemical-
cum-solvent resistance, barrier properties, abrasion resistance, flammability,
gloss, etc.
• Adjusting the material performance to fit customers' specifications at the lowest
price.
• Recycling industrial and/or municipal plastics waste.
86 Reasons for, benefits and problems of blending
As far as the producer is concerned, the following advantages of the blending
technology have been identified:
• Better processability, thus improved product uniformity and scrap reduction.

• Product tailorability to specific customer needs, thus better customer satisfaction.
• Quick formulation changes, thus plant flexibility and high productivity.
• Blending reduces the number of grades that need to be manufactured and stored,
thus savings in space and capital investment.
• Recyclability of blends achieved by control of morphology, thus improved
economy.
About 65 % of polymer alloys and blends are produced by polymer manufac-

turers, about 25 % by compounding companies, and the remainder by the transfor-
mers.
6.1 COMPATIBILIZATION
There are several hundred reports of polymer-polymer miscibility (Krause, 1972,
1989,1991; Krause and Goh, 1998). However, it should be stressed that miscibility is
limited to a specific set of conditions (such as configuration of polymeric molecules,
molecular weight and molecular weight distribution, temperature, pressure, stress
field, additives, etc.) while immiscibility dominates - most blends are immiscible,
requiring compatibilization. Alloying polymer blends involves several operations
that are to result in alloys characterized by stable and reproducible properties. Since
the material performance depends not only on the ingredients and their concentra-
tion, but also on morphology, the requirement for such properties means that the
morphology must either be stable, unchanged by the processing conditions, or the
changes must be reprodUcible and well predicted.
To achieve reproducibility of immiscible blends' performance involves compati-
bilization. There are three functions of the process: (1) to reduce the interfacial
tension, thus engendering finer dispersion; (2) to make certain that the morphology
generated during the alloying stage will not be destroyed during high stress and
strain forming; and (3) to enhance adhesion between the phases in the solid state,
facilitating the stress transfer, hence improving the mechanical properties of
products.
Several strategies of compatibilization have been proposed: (1) addition of a small
quantity of a third component that is miscible with both phases (cosolvent); (2)
addition of a copolymer whose one part is miscible with one phase and another
with another phase (e.g., 0.5-2 wt %, usually block copolymer, less frequently a graft
copolymer); (3) addition of a large amount, usually 25-35wt%, of a core-shell
copolymer that behaves like a multipurpose compatibilizer-cum-impact modifier;
(4) compounding blends in the presence of chemical reactants that lead to modifica-
tion of at least one macromolecular species (reactive compatibilization), resulting in
generation of an in-situ desired quantity of a compatibilizer (block and/or graft
copolymer); and (5) mechano-chemical blending that may lead to chains' breakup
and recombination, thus generation of copolymers (even at liquid nitrogen temper-
atures).
Different strategies lead to blends with different sets of properties. For example,
addition of a small amount of copolymer (block-, graft-, random copolymer or
cosolvent) mainly affects the interfacial tension coefficient, hence the size of disper-
sion, but under normal circumstances it has little effect on the shear sensitivity of the
Compatibilization 87
blends' morphology, or on their solid-state behavior. In most studies on blends'
compatibilization, di- or tri-block copolymers have been used - the first type seems
to be more efficient in reducing the interfacial tension coefficient v, but the second
type is often found better in improving the mechanical behavior.
Addition of large quantities of core-shell copolymer (e.g., ethylene-acrylate-maleic
anhydride, glycidyl methacrylate-ethylene-vinyl acetate, ethylene-glycidyl metha-
crylate-methylmethacrylate, etc.) has been found particularly useful in blends of
two brittle, immiscible polymers that not only must be compatibilized, but also
toughened. An example is polyamide blended with either a thermoplastic polyester
or polyphenylene ether.
The reactive blending was found to engender a thick interphase that resulted in
excellent stability of morphology under high stress and strain, such as exists
during injection molding. In some cases, as for example in polycarbonate/polybu-
tyleneterephthalate (PC/PBT) blends, transesterification seems to be the easiest
compatibilization method. Unfortunately, since PBT crystallinity is of utmost import-
ance, the method is neither easy to control nor of apparent advantage. Reactive
processing can also be used as a method of functionalization of a polymer, which
upon addition of the other resin forms an alloy, e.g., acidification of PPE that
enhances its interactions with PA. Alternatively, a preblend of polymer A with
functionalized interphase polymer is prepared, then polymer B is added, e.g., pre-
blending PPE with oxazoline-modified PS, then adding PA, PEST or PC.
Solid-state compounding requires an efficient, intensive mechanical mixing of
immiscible blend components, then stabilizing the obtained morphology. The stabi-
lization can be achieved either by chemical (e.g., recombination of free radicals,
crosslinking by electron beam irradiation) or physical means (e.g., by controlled
crystallization). These alloys have a higher modulus and a different fracture mechan-
ism than that observed for melt-mixed ones.
The early polymer blends usually comprised two principal polymeric ingredients
that, depending on composition, were compatibilized or not. With the continuous
evolution of the technology the systems are becoming progressively complex.
Today's commercial alloys may comprise up to six polymeric ingredients. Develop-
ment of these alloys is complex, involving broad knowledge of thermodynamics,
rheology, processing and their influence on morphology and thus performance. The
increased number of components n is not trivial, since the number of interfaces
between them grows as N = n(n -1}/2. Thus, compatibilization of multicomponent
polymer blends may pose serious problems - an improperly designed interface may
became a source of fracture initiation. One of the adopted strategies involves
addition of at least one ingredient with highly reactive groups that can interact
with several polymeric components of the blend; for example, a multicomponent
copolymer that plays the dual role of compatibilizer and impact modifier, or a low
molecular weight additive that at different stages of reactive blending binds to
different components, e.g., ethylene-glycidyl methacrylate, triglycidylisocyanurate,
etc. In consequence, the preferred method of compatibilization of such complex
systems is reactive processing. Several of these multicomponent systems can be
prepared and treated as blends of blends. In such a case, not only the ingredients
but also the order and method of incorporation are critical.
Although the first function of compatibilization, reduction of the interfacial ten-
sion, is relatively simple and can be accomplished by the methods mentioned above,
the two other functions, stabilization of morphology and improvement of inter-
phasial adhesion in solid state, mayor may not be simultaneously achieved. For
this reason, it is appropriate to consider these three aspects separately and use either
one compatibilizer that can fulfill all three roles (e.g., a multicomponent core-shell
universal compatibilizer), a combination of compatibilizers, each playing one or two
different roles, or use another, more direct method. For example, stabilization of
morphology can be accomplished by partially crosslinking any of the three phases:
matrix, dispersed and the interphase. The crosslinking can be chemical, thermal or
radiochemical.
The stabilization mechanism in polymer blends is based on copolymer migrating
to the interface between two polymer domains and forming a barrier against coales-
cence. Better stabilization is obtained when the interphase is thicker and more rigid.
Thus, even if addition of specially tailored block copolymer is more elegant and
leads to efficient reduction of the interfacial tension coefficient, frequently graft or
even random copolymers have been preferred - the latter provide better stabiliza-
tion.
Another method of morphology stabilization that is becoming increasingly popu-
lar involves addition of a small quantity of third polymer-e to a binary A/B blend.
The added polymer should have limited miscibility with either principal component
of the blend. The spreading coefficient (in the ternary system A-matrix B-dispersed
C-interphase) is defined as
5 == VAB - VCA - VCB (6.1)
where Vij are the interphasial tension coefficients, proportional to the square-root of
the thermodynamic binary interaction parameter, v ~ )(1/2. When 5> 0, i.e.,
when VAB > VCA + VCB, the interphase is rich in C, which results in stabilization
(Yeung et al., 1994). Thus, the basic requirement of the method is to add to a binary
blend a third resin that has better miscibility (i.e., it has a smaller thermodynamic
binary interaction coefficient) with both principal blend components than that exist-
ing between the two of them.
The third function of compatibilization, enhancement of adhesion in the solid
state, can be accomplished either by ascertaining that an appropriate concentration
of covalent bonds crosses the interface, by introducing a compatibilizer that can act
as an adhesive between two polymers, and/or by control of morphology, especially
of semicrystalline blends.
Several reviews on compatibilization have been published. For example, Casale
and Porter (1975, 1978) reviewed mechano-chemical compatibilization in a high
shear stress field capable of causing the chain scission that, after recombination,
results in formation of block and graft copolymers. The transesterification reactions
of polyesters have also been used to generate compatibilizing copolymers (Kotliar,
1981; Porter et al., 1989; Porter and Wang, 1992). The review by Brown (1992) gives
more details on the different types of compatibilization reactions. A review on
compatibilization provides the most recent information in the field (Ajji and Utracki,
1996).
Recyclability should be of major concern while designing new blends. As the
automobile industry moves closer to an all-plastics car, it is inconceivable that the
volume of polymer used in millions of vehicles per year can be buried or turned into
smoke. In 1984 only 1% of the total 133 million tons of plastics waste was recycled
(Franklin Associates Ltd, 1988). At the moment, recycling is limited to but a few
polymers: high density polyethylene, HDPE, polyethylene terephthalate, PET, and in
some cases, industrial or municipal plastics waste. The bright sign on the horizon is a
serious effort by General Electric's marketing division toward an integrated flow of
engineering materials. It is proposed that polymers or their blends will be reused
sequentially in less critical applications. General Electric also demonstrated that such
Interplulse 89
engineering materials as alloys comprising PPE, PC or PHT can successfully be
recycled after 10 years of use in an automobile.
6.2 INTERPHASE
In polymer blends technology, the interface/interphase is of key interest. Compati-
bilization can be regarded as a modification of the interphasial properties. To discuss
performance of the blend product is to discuss dispersion, morphology and adhesion
between the phases, which are all related to properties of the region between phases.
Helfand and Tagami's (1971, 1972) theory predicts that the density profile across
the interface follows the exponential decay function (see Figure 6.1). The intercepts of
the steepest tangential line (at the place of the steepest decline or incline for the other
component) with the horizontal lines defining the volume fraction of either one of the
two polymeric ingredients, <p = 0 and 1, defines the thickness of the interphase, Lll.
Experimentally (Table 6.1), it has been found that Lll varies from 2 to 6Onm, the
first value being valid for antagonistically immiscible polymer pairs, while the
second is valid for reactively compatibilized polymer alloys. Ellipsometric studies
of reactively compatibilized immiscible blends demonstrated that Lll increased with
annealing time up to a constant plateau. Its value was found to depend on the
system, concentration of reactive sites and temperature. The equilibrium interface
thickness ranged from 10 to 50 nm, thus being several times larger than the radius of
gyration of component polymers (Yukioka and Inoue, 1993, 1994). Not surprisingly,
addition of block copolymers only slightly increased the interphasial thickness, to 6-
8nm (Inoue, 1993).
-a
o
~ 0.8
Ci5
Z
W
Cl 0.6 [Helfand and Tagami, 1971]
I-
Z
W plpo =ll(1 + i) x '" 0.01; b(PS) '" 0.65 nm
~ 112
C)
w 0.4 Y = exp[(6x) (x/b»)
C/)
Cl
W
(,)
:::> 0.2
Cl
w
a:
o . .' .
-10 -6 -2 2 6 10
REDUCED DISTANCE ACROSS THE INTERFACE, xl b
Figure 6.1 Density profile across the interface, defining the thickness of the interphase (after
Helfand and Tagami, 1971).
Table 6.1 Interphase Thickness
Type of Blend Thickness (nm)
Immiscible 2
Block copolymer 4--6
Polymer/ copolymer 30
Reactive compatibilization 30-60
Radius of gyration, (Ri)1 / 2 5-35
According to Helfand and Tagami, the interfacial thickness tll oo and the interfacial
tension coefficient 1100 can be expressed as
tlloo =2b/(6X)1 /2 }
2 -> tlloolloo = kB Tpll/3 (6.2)
1100 =bpkBT(X/6)1 1
where b is a lattice parameter, kB is the Boltzman constant, and T is the absolute
temperature. The Helfand-Tagami lattice theory was based on the mean-field
approach: (1) the two homopolymers were assumed to have the same degree of
polymerization; (2) the complex set of equations derived for the segmental density
profile, Pi where i = A or B, was solved for infinitely long macromolecules M w -> 00;
(3) the isothermal compressibility was assumed to be negligibly low; and (4) there
was no volume change upon blending (i.e., the attractive or repulsive forces between
two polymers were assumed weak). The theory predicts that (1) the product tlloolloo
is independent of the thermodynamic binary interaction parameter x; (2) the surface
free energy is proportional to X1/2 ; (3) the chain-ends of both polymers concentrate at
the interface; (4) any low-molecular-weight third component is repulsed to the
interface; and (5) the interfacial tension coefficient increases with molecular weight
to an asymptotic value; II = 1100 - aoM- 2/ 3 • Later, the theory was generalized to
polymers with different molecular weights and mobility (Helfand and Sapse, 1975;
Helfand and Frederickson, 1989).
Recently, it was shown that the interfacial tension coefficient, 1IJ.2, can be calculated
from the molecular structure of two polymers. First, the three contributions of the
solubility parameters (dispersive, polar and hydrogen bonding) of each component
are computed using the Hoy's group contribution method. Then, the sum of squared
differences between these contributions is calculated. The interfacial tension coeffi-
cient was found to be proportional to the sum. The computed and experimental
values of 1112 for 46 polymer pairs showed good correlation with an average error of
±36% (Luciani et al., 1996).
When A-B block copolymer is added to an immiscible blend of homopolymers A
and B, the reduction of the interfacial tension follows the relation (Leibler, 1988)
tlll = 110 -II = (3/4)1 /3(kT/a 2)(E/a2rS/3(ZCAZA -2/3 + ZCBZ;2 /3) (6.3)
where ZCA and ZCB are respectively the number of A and B structural units in
the copolymer (having Zc = ZCA + ZCB total number of segments), ZA and ZB are
the degree of polymerization for the homopolymers A and B respectively, a is the
monomer length, E the interfacial area per copolymer chain that crosses the inter-
face. Equation (6.3) predicts that when the adsorption density E/a 2 is high, the
interfacial tension is low. For the same E/a2 value, higher molecular weight copoly-
mer is more efficient (Leibler, 1988). The theory also predicts that the more asym-
metric is the copolymer composition, the less efficient as an interfacial agent it
Interphase 91
becomes. Since there is no distinction between polymers A and B, the most efficient
diblock copolymer is the one with an equal amount of both components, fopt = 1/2.
When the interface becomes saturated with copolymer, II reaches its lower plateau,
II = IICMC, and the copolymer macromolecules start forming micelles, i.e., the critical
micelle concentration CMC has been reached, ¢> = ¢>&c-
Concentration dependence of the interfacial tension coefficient, also know as the
copolymer titration curve, is described by two semi-empirical relationships. The first
was obtained assuming an analogy between addition of a block copolymer to a
polymer blend, and titration of an emulsion with a surfactant (Utracki, 1992; Utracki
and Shi, 1992):
II = (¢>IICMC + ¢>mean/l())/(¢> + ¢>mean) (6.4)
where:
IICMC = II(¢> = CMC), ¢>mean = (c/>cMc + r/>o)/2
The second dependence, derived by Tang and Huang (1994)/ was rewritten as (Ajji
and Utracki, 1996)
II = IICMC + (/I() - IICMc) exp {-axZc¢>}
(6.5)
d = dCMC + (do - dCMc) exp {-atXZc¢>}
where a and at are adjustable parameters, and Zc is the copolymer's degree of
polymerization. Tang and Huang noted that diameter of the dispersed drop d
follows the same titration curve as II. These dependencies were found useful in
describing the experimental data (see Figure 6.2).
Addition of X-b- Y block copolymer to blends of polymers A and B may also result
in reduction of the interfacial tension coefficient, provided that the binary interaction
parameters Xii are appropriately balanced. The competitive interactions between the
blocks and the two polymers were shown to promote interfacial interactions.
0.65
PS/PB/SB
\
\
..
0.55 \
\
\
\
" ,
~.§. 0.45 ,
;>
.... .
0.35
-- .
1.. . . . . . . . . _
-------------1
1 2 3
58 concentration (wt % on dispersed phase)
Figure 6.2 Interfacial tension coefficient versus 58 concentration. Data from Anastasiadis
(1988); dotted line Utracki-Shi equation.
The reduction of II was expressed as (Vilgis and Noolandi, 1988)
li.1I = - (1/Ze) exp {Zc[(Xl/2) + X2)}
for Xl =Xsy = XAX = Xxy = XAB (6.6)
and X2 =X AY = XSX > Xl
The theory suggests possibilities of designing a universal compatibilizer operating
on the principle of competitive repulsive interactions.
Assuming that all the compatibilizer's molecules cross the interface once, the
amount Wcr required to saturate the interface can be expressed as a function of
the copolymer molecular weight M, the total surface area of the interface, and the
specific cross-sectional area of the copolymer macromolecule, a ~ 50m2 :
Wcr = M(3/aNAv )(</>/R) (6.7)
where </> is the volume fraction of the dispersed phase, R is the radius of the
dispersed drop, NAv is the Avogadro number and a is the area occupied by a
copolymer molecule. However, for randomly oriented diblock copolymer macro-
molecules at the interface, the following dependence was derived (Mathos, 1993):
Wcr = 3</>M/[RNAv (,z)/9] = (27/K)(</>/R) (6.8)
where (,2) = KM is the square of the end-to-end distance of the copolymer and K is
the characteristic parameter of the polymeric chain. Equations (6.7) and (6.8) both
predict that the amount of copolymer required to saturate the interface is propor-
tional to the total interfacial area, expressed as </>/R. The assumption that all copoly-
mer molecules cross the interface only once results in proportionality between Wcr
and M, whereas the assumption that copolymer macromolecules are coiled in the
interphase removes this proportionality. The reality is somewhere in between these
two ideal cases. Equations (6.7) and (6.8) are identical if a = (r 2 ) /9.
The interfacial tension coefficient of low-viscosity liquids can be determined using
any of the follOWing methods: liquid thread break-up, rotating drop, pendant or
sessile drop, du Nuouy ring or diffraction. However, for high-viscosity polymeric
melts, the choice is quite limited. Deformed drop retraction, liquid thread break-up,
PMMAI SAN-5.7
30 g.-- - - - & - -
--a
E
.s-
PMMAI SAN-38.7 --
VI
VI
Gl
c: 20
...:
<.l
:c
I-
Gl
VI
til
e- 10
~
~
.: PMMAlPS
0
120 140 160
T('C)
Figure 6.3 Interphase thickness versus temperature for polymethylmethacrylate blends with
(from top) styrene-acrylonitrile copolymers and polystyrene (Kressler et a/., 1993).
Compatibilization by addition of a copolymer 93
rotating drop and pendant or sessile drop can be used with a decreasing order of
probable success. Even fewer methods are available to measure the interphase thick-
ness, namely ellipsometry, microscopy or diffraction. So far, the interfacial tension
coefficient and the interphase thickness have not been measured for the same blends.
The first of these methods, the retraction of deformed (by :'S 15%) drop, is the only
one that makes it possible to repeatedly measure the interfacial tension coefficient V12
of the same specimen. The experiments conducted on commercial resin blends
showed that VJ.2 changes with time - in most cases it decreases, owing to the migration
of low molecular weight components towards the interphase. An opposite effect was
also observed for a PA-PO system to which a stabilizer was added. These time-effects
must be incorporated when predicting the blends' morphology (Luciani et al., 1996).
A summary of the measured til is provided in Table 6.1. The temperature depend-
ence of til for blends comprising polymethylmethacrylate, (PMMA) with either
styrene-acrylonitrile copolymer, (SAN) or with polystyrene (PS) is presented in
Figure 6.3.
6.3 CaMPATIBILIZATION BY ADDmON OF A COPOLYMER

Historically, the most popular method of compatibilization has been addition of a
third polymeric component to the two immiscible polymers. In most cases, it was
either a block or graft copolymer. Since the key-word is miscibility, it was not
necessary for the copolymer to have identical chain segments to those of the main
polymers, but this approach has been frequently used. The copolymer may be
composed of segments having specific interactions with the main polymers, such
as hydrogen bonding, dipole--dipole, dipole-ionic, Lewis acid-base, etc. The compat-
ibilizer should be designed to migrate to the interface, broadening the segmental
concentration profile, experimentally expressed as til. Addition of a block or graft
copolymer reduces the interfacial tension and alters the molecular structure at the
interface. Thus, compatibilization changes the interfacial properties of the blend, as
well as its rheological behavior.
One of the disadvantages of this method is the tendency of the copolymer to form
micelles in the bulk phases, thus on the one hand reducing its effectiveness as a
modifier of the interfacial tension and, on the other hand, increasing the blend
viscosity, thus reducing its processability. For these reasons, the copolymer must
be designed in such a way as to (1) maximize miscibility of the appropriate part of its
macromolecule with the specific polymeric component of the blends; (2) minimize its
molecular weight to just about the entanglement molecular weight for each interact-
ing segment; and (3) minimize its concentration in the blend. Addition of 0.5--2 wt %
of well-designed block copolymer has been found sufficient. A significant penetra-
tion of properly designed copolymer into the homopolymer phases has been
reported (Brown, H. R., 1989; Cho et al., 1990).
Effective compatibilization of binary polymer blends by addition of block copoly-
mer reduces the dispersed particles' size and the interfacial tension coefficient
(Anastasiadis et al., 1987, 1989; Wu, 1987, 1989; Patterson et al., 1971). The process
is characterized by the emulsification or titration curves, VAB versus r/> (compatibi-
lizer), that characterizes the additive's efficiency (Figure 6.2). The curve depends on
the type of emulsifier and the emulsification process. However, the amount of
emulsifier required to saturate the interface depends on the mixing time and equip-
ment, the affinity of the emulsifier to the dispersed phase, the size of the dispersion,
the orientation of the emulsifier at the interface, and its ability to stabilize the inter-
face against flocculation and coalescence.
In industrial practice, the time effects are quite important - the higher the viscosity
of blend components, the longer the diffusion time. The efficiency of a copolymer
is limited by the formation of micelles in bulk phases and by kinetic factors. The
morphology of commercial blends is usually far from equilibrium. Compounding
must take thermodynamic and kinetic parameters into account if the desired
effects are to be achieved. For melt compatibilization of the high-molecular-
weight blends, the non-equilibrium morphology must always be considered and
planned for.
In several publications, the effect of copolymer addition on particle size was
studied (Hobbs et al., 1983; Fayt et al., 1986; Annat and Moet, 1993). In particular,
the effects of the hydrogenated butadiene-b-styrene (SEB) and hydrogenated buta-
diene-b-isoprene-b-styrene (SEP) copolymers on the interfacial activity in polyethyl-
ene/polystyrene (PE/PS) blends were investigated (Fayt et al., 1986, 1989; Hobbs et
al., 1983). It was demonstrated that the copolymer was located at the interface,
forming a continuous layer around dispersed particles, either of PE in PS or PS in
PE. Its thickness was similar to the radius of gyration, ~I = 10-12nm. A competition
between the microdomain formation and migration to the interface was observed. It
was found that 2-5wt% of SEB was sufficient to reduce the interfacial tension
coefficient, the particle's size and coalescence, as well as to enhance the mechanical
properties (Fayt et al., 1986).
The interfacial thickness is less frequently measured than the interfacial tension,
but PS/PMMA blends are exceptions. For the uncompatibilized blends, the values
~I = 2nm (Foster et al., 1990; Russel et al., 1990, 1991), ~I = 6nm (Foster and Wool,
1991) and ~I = 5nm (Fernandez et al., 1988; Anastasiadis et al., 1989) were reported.
Upon addition of a PS-b-PMMA copolymer, the interface thickness ~I was found to
increase from 2 to 6nm (Perrin and Prod'homme, 1994). Polypropylene/polycarbon-
ate (PPfPC) blends were compatibilized by addition of hydrogenated styrene-buta-
diene-styrene triblock copolymer (SEBS). In blends comprising 10-20 wt % PC with a
PP:SEBS ratio of 95:5 to 90:10, SEBS was found to envelop PC drops embedded in PP,
indicating better interfacial affinity of SEBS to PP than that existing between PC and
PP (Srinivasan and Gupta, 1994).
6.4 REACTIVE COMPATIBILIZATION

The second method of compatibilization consists of creating specific chemical reac-
tions between two polymeric components during processing - the interfacial agent is
produced in situ, with segments from the two homopolymers. From the economic as
well as the performance points of view, the technique is more interesting than
addition of a well-tailored copolymer.
Reactive processing is an integration of fine polymer chemistry with precisely
executed polymer processing (melting, compounding, extruding and forming). It
combines chemical kinetics with the flow and thermal properties of the reaction
ingredients and products, integrating them into a mathematical model of reactive
extrusion or molding. The conditions for reactive processing require that there is:
(1) sufficient dispersive and distributive mixing to ensure the required renewal of
the interface; (2) presence of a reactive functionality, suitable to react across the
interphase, and; (3) sufficient reaction rate making it possible to produce sufficient
quantity of the compatibilizing copolymer within the residence time of the proces-
sing unit. During reactive processing, in extrusion or injection molding, block or
graft copolymers are usually formed. The chemical reaction leads to covalent or, less
frequently, ionic bonds.
Reactive compatibilization 95
The patent literature demonstrates that from the very beginning of the polymer
industry, blending involved both chemical and physical aspects. The very first
patent on polymer blends (Parkes, 1846) described mixing two polyisoprene is0-
mers, natural rubber (NR) and gutta-percha (GP) in the presence of SCh that
partially covulcanized the ingredients. Production of nitrile rubber (NBR), high
impact polystyrene (HIPS), or acrylonitrile-butadiene-styrene terpolymer (ABS), all
involved well-eontrolled physical and chemical activities required to generate the
desired behavior.
In 1939, I. G. Farbenindustrie patented blends of polyvinyl alcohol (PVAI) with a
multicomponent acrylic copolymer containing maleic anhydride, thus formally
introducing what is know today as reactive blending. In the early 19405, the com-
pany used the newly developed intermeshing, corotating twin-screw extruders for
reactive extrusion of PA-6.
In the 1948 patent from du Pont de Nemours, reactive blending of polyamide-66
(PA-66) was described - PA-66 was first maleated, then blended with polyvinyl-
acetate. Starting in the mid-1960s, reactive extrusion began to be used for toughening
and general modification of such engineering resins as PA, PET, PC or PBT. For
example, in the 1966 Bayer patent, PA-6-PVAI blends were obtained by polymeriz-
ing €-eaprolactam in the presence of PVAI. In 1969, the first reactive grafting of PPE
was patented.
In 1971, Tokyo-Shibaura patented a two-step reactive extrusion leading to PC/
SAN-grafted chlorinated polyethylene, CPE blends. The same year, Exxon patented
reactive modification of polyalkenes, PO (e.g., maleation of PP) by reacting PE or PP
with alkenic monomer in the presence of peroxides. A year later, styrene-grafted PE,
obtained in reactive extrusion, was blended with PPE for improved processability
and an excellent set of desired properties. In 1973, Dow introduced oxazoline-grafted
polymers to be used as compatibilizers in reactive blending, for example in PC/PA
systems. In 1975, du Pont de Nemours started to manufacture super-tough PA Zytel-
STTM, by reactive blending of PA-66 with maleated ethylene-propylene-diene elas-
tomer, EPDM-MA. The basic patent on reactive compatibilization of PPE/PA was
deposited in 1977 by Veno and Maruyama (1979).
During the 19708, Patfoort developed an extruder with residence time T greater
than 7 (Patfoort, 1976). The machine generated such a high shear stress that
extruded, immiscible polymers (e.g., PS and PE) showed good mechanical proper-
ties. Apparently, during the extrusion there was enough chain scission and recom-
bination of the free radicals to generate a sufficient amount of copolymer for
compatibilization of the systems.
During reactive blending, the hydroxy-terminated PPE was end-eapped in solu-
tion with trimellitic anhydride acid chloride, then extruded at 290°C with 41 wt % of
PA-66 to give PPE-PA copolymer that was subsequently used as compatibilizer for
the PPE/PA blends. Furthermore, to improve impact strength of the blends, 10 parts
of SEBS was also added. Molded parts showed higher impact and tensile strength
than those containing only non-functionalized PPE or PPE grafted with MA (Aycock
and Ting, 1986, 1987).
In many systems, the first step of the reactive processing involves modification of a
polyaikene resin, usually by grafting it with either maleic anhydride or glycidyl-
methacrylate. Both reactions are facilitated by addition of styrene into the reacting
medium (Lambla et al., 1989; Sun et al., 1995; Chen et al., 1995).
Maleation of polypropylene followed by compounding the product, PP-MA
(O-O.14wt% MA), with PA-6 was carried out in a specially designed JSW twin-screw
extruder. The number average diameter of PA-6 drops decreased with the amount of
generated di-block, PP-PA-6, copolymer from dn = 20 to 0.14j.Lm (at 20wt% co-
polymer content). The concentration dependence of the shear viscosity, ", versus
PP content, changed with the degree of compatibilization from the negative
deviation from the log-additivity rule (NDB) to the positive one (PDB) (Nishio
et al., 1992a).
As the cited examples indicate, many blends exist today only because of reactive
processing. Super-tough PA (introduced in 1975), PO/PA and PPE/PA blends (both
introduced in 1979), or PC/PA (commercialized in 1988) are all being produced by
reactive compounding. This powerful technology makes it possible not only to
develop new blends, but also to generate old blends with new sets of properties,
namely, blends with specialty resins, or new PVC/acrylics compositions. The tech-
nology also makes it possible to intelligently combine properties of several polymers
into complex, multicomponent alloys. In 1985, Toray introduced PPE/PET/PC/
EGMA blends for high performance automotive applications. In 1987, GEC patented
PPE/PBT/PC/SEBS blends (Campbell et al., 1990). These commercial activities find
a broad base of support in the open literature.
The basic method for generation of well-structured copolymer is through inter-
polymer reactions. The process may be defined as a reaction between two or more
polymers to form a copolymer. The five basic chemical processes by which inter-
chain copolymer formation has been achieved in an extruder are summarized in
Table 6.2 (Brown, 1992). Interchain block copolymer formation by reactive extrusion
is particularly useful.
As indicated in Table 6.2, block copolymers can be preferentially formed in reac-
tions involving functionalized end groups of two polymers. Since the probability of
two end groups reacting within a typical residence time in an extruder is low, highly
reactive functionalities, and high concentration of end group (i.e., low-molecular-
weight polymers) may have to be to be employed. The majority of polymers mod-
ified by reactive processing have nucleophilic end groups, such as carboxylic acid,
anhydride, amine or hydroxy group. These groups readily form covalent bonds with
suitable electrophilic functionalities, such as epoxide, oxazoline, isocyanate or
Table 6.2 Chemical processes for interchain copolymer formation during reactive
blending
Type of chemical reaction Type of copolymer obtained

Chain cleavage and recombination block and/or random copolymers:
AAAAABBBBB + AABBBBBAAA +
AABBAAABBB, etc.
End group of first polymer reacting block copolymer: AAAAABBBBB
with end group of second polymer
End group of first polymer reacting graft copolymer: I
with pendant functionality of A-BBBBB
second polymer I
A-BBBBB
I
Covalent crosslinking between graft copolymer or a crosslinked network
reactive groups of two polymers
that are parts of either main or side
polymer chains
Ionic bond formation Usually graft, A B, often crosslinked, A-B
Reactive compatibilization 97
carbodiimide, generating the desired copolymer. Many examples of this type of

reactions are given in Parts 3 and 4 of this book. Here, as an illustration, two blends
will be mentioned.
It has been reported that reactive blends have a thicker and more rigid interphase
than blends with added copolymer. The interfacial thickness in blends of amorphous
polyamide (PARA) with a styrenic copolymer, either SMA or SAN, was measured by
a time-resolved ellipsometric method during annealing (Yukioka and Inoue, 1993,
1994). The interphase thickness increased with time, then attained a plateau, whose
value depended on the temperature and net concentration of the reactive sites
(Kressler et al., 1993). The interface was thick (Ill = 1G-60nm) being larger than the
radius of gyration of the copolymer. The heterogeneous nature of the reactively
formed copolymeric species was suggested as a possible explanation for large III
values.
Another method of block copolymer generation is by trans reactions. However,
here the control of copolymer structure is quite difficult. Transesterification during
blending or processing of polyesters (PEST) is common. Owing to changes in the
molecular weight distribution as well as a decrease of the crystallinity, the reaction is
often associated with deterioration of blend properties. Hence, most studies have
sought to prevent transesterification rather than promote it. Several reviews of the
reaction have been published (Porter et al., 1989; Porter and Wang, 1992).
However, transesterification can be beneficial for reactive compatibilization and
toughening of engineering resins. For example, either PET or polyethyleneterephtha-
late glycol (PETG, a copolymer with 66 mol % ethylene glycol and 34 mol % cyda-
hexylene dimethanol), with ethylene-vinyl acetate, can be compatibilized and
toughened by a trans reaction (catalyzed by dibutyl tin oxide) with EVAc copolymer.
trans-esterification diminished the size of the dispersed phase, enhanced its adhesion
to the matrix (what resulted in increase of the elongation at break, e.g., from 20% to
140%) and augmented the dynamic shear storage modulus G' (Legros et al., 1994).
Ester-amide exchange reactions are also known. Block copolymer formation dur-
ing extrusion of PET/PA-6 blends was reported. The reaction was catalyzed by
addition of p-tolueno sulfonic acid (Pillon and Utracki, 1984, 1986). Similarly, block
copolymers of PA with carboxylic acid-terminated PET or PBT were obtained in an
exchange reaction, catalyzed by tertiary phosphite esters, above 200 0c. A trans
reaction was also found suitable for making graft copolymers of PA with ethylene-
acrylic acid (EAA) copolymers (Aharoni and Largman, 1983; Aharoni et al., 1984).
Copolymer formation by trans-amidation of PA-6 with either PA-66, PA-ll or PA-12
is known as well.
It is more difficult to reactively compatibilize blends of PC with PA. To ascertain
proper reactivity of the polymeric components, first, a hydroxy-terminated PC was
end capped with trimellitic anhydride acid chloride, then 40 wt % of functionalized
PC was extruder blended at 277°C with 4Owt% of PA-6 and 20wt% of an acrylate
styrene core/shell impact modifier. Molded parts showed high notched!zod impact
strength, and 192% tensile elongation. The presence of PC-PA copolymers was
determined by selective extraction (Hathaway and Pyles, 1988, 1989).
7
Morphology
7.1 EQUILmRIUM MORPHOLOGY AND PHASE INVERSION
Before discussing the performance of polymer blends, it is important to review the

basic elements of blend morphology. When concentration of the dispersed phase is
increased, the morphology changes from dispersion of nearly spherical drops to
progressively interconnected drops, then rods, fibers and sheets. At the phase
inversion concentration, </Ji, the distinction between the disperse and matrix phases
vanishes - the morphology becomes cocontinuous. It is important to recognize that
the phase cocontinuity is one of many aspects of blend morphology. Since the
morphology is strongly affected by large strains' flow, it is natural to expected that
the method of specimen preparation influences the cocontinuity. Both the phase
inversion concentration and the stability of the cocontinuous phase structure depend
on the strain and thermal history.
For a three-dimensional (3D) case, percolation theory predicts that ¢>perc = 0.156,
while for 10 ePperc = 0.019. In accord with this theory, the transition from drop
dispersion to cocontinuous structures occurs at an average volume fraction,
ePonset = 0.19 ± 0.09 (Lyngaae-Jergensen and Utracki, 1991). In Figure 7.1, variation
of phase cocontinuity in blends of high density polyethylene with polystyrene,
HDPE/PS, is shown. The data (obtained by selective extraction of the matrix
phase) indicate that the onset of phase cocontinuity occurred at ePIc = 0.16 and
rhc = 0.15 whereas </Ji = 0.64.
The cocontinuity contributes to synergism of properties, e.g., advantageous com-
bination of high modulus and high impact strength in commercial blends. Recently,
assuming validity of an emulsion model, the following relation was derived
(Utracki, 1991c):
(7.1)
where ePm = 1 - ePc, and "h and Tf2 represent the viscosity of the dispersed and matrix
phase at the same deformational stress. For most polymer blends the following
values of Equation (7.1) parameters prOVide a good approximation:
[17] ~ 1.9; ePm ~ 1 - ePc = 0.84. In Figure 7.2, the theoretically predicted phase inver-
sion concentration, <hI is plotted versus the viscosity ratio >.. The experimental data,
obtained for the mechanically prepared thermoplastics blends, are also shown
(Utracki,1991c).
Flow-imposed morphology 99
1.2
Degree of Phase cocontinuity versus composition
.....................
Z
0
~
~O.8
a:
u.
~
5
z
~
ZO.4
0
0
0
0
0
0 +2c +lC 1.0
+2
Figure 7.1 In immiscible blends the onset of phase cocontinuity coincides with the percolation
threshold [<Pc = 0.156 and 0.019, respectively, for shear (3D) and extension, (lD)]; experiment-
ally, <h: = 0.19 ± 0.09 (Lyngaae-Jergensen and Utracki, 1991).
Phase inversion concentration versus viscosity ratio.

Literature data (Utracki. 1991c).
0.8
0
N
.e-
o
0
0
0.4
Figure 7.2 Experimental invesion concentration <P2I versus viscosity ratio A dependence for
mechanically prepared thermoplastics blends. The solid line represents Equation 7.1; the
values: [11] = 1.9 and <Pm = 0.84 were used (Utracki, 1991c).
7.2 FLOW-IMPOSED MORPHOLOGY

The flow affects morphology in two ways - it changes the degree and type of
dispersion on a local level, and it imposes global changes of morphology in formed
parts. The latter effects originate from flOW-imposed migration of the dispersed
phase, such as skin-core structures, weld lines, etc. The flow-imposed morphologies
can be classified as: (1) dispersion (mechanical compatibilization), (2) fibrillation or
100 Morphology
generation of anisometric structures, (3) shear coalescence, (4) interlayer slip and
(5) encapsulation. These are discussed below (Utracki, 1995). A fundamental study
of morphology development was published recently (Kozlowski, 1994, 1995).
Flow may also cause mechano-chemical degradation that generates reactive com-
ponents, e.g., radicals, peroXides, acids, etc. trans-esterification and ester-amide
exchange reactions are well documented (their rates depend on the total interphasial
area that in turn depends on flow). The reactions are responsible for generation of
compatibilizers that tend to increase the interphasial area, may affect the phase
equilibrium and the regularity of the main chain, and thus the extent of dispersion
and blend crystallinity. The miscibility of polymer blends is another area of indus-
trial importance. There is also evidence that during processing, the imposed hydro-
static and shear stresses can change the lower critical solubility temperature (LCST)
by at least 60 0c. This may result in formation (inside the processing unit) of a single-
phase polymer blend that, emerging into a low pressure and stress domain, decom-
poses by the spinodal decomposition mechanism into two-phase blends having a
cocontinuous morphology whose degree of dispersion can be controlled by quench-
ing (Inoue, 1993).
It should be stressed that the relationship between morphology and flow behavior
is reciprocal - flow affects the structure, but variation in the structure engenders
changes in the rheological response of the blend. Plochocki (1978, 1982, 1983) defined
the particular rheological composition (PRe) most frequently reported for polyalk-
ene blends. At PRC, the TJ = TJ( 4» function reaches a local maximum or minimum.
The existence of the maximum is related to a change of the dispersed phase, either
from spherical to fibrillar, or passes through the phase cocontinuity (phase inversion
concentration), whereas that of the minimum is related to a reciprocal change and/
or to variation of the specific volume.
7.2.1 Flow-induced dispersion

The drop diameter usually decreases with the increase of shear rate (Figure 7.3).
However, one must be careful with data analysis. As the microrheology indicates,
there are different mechanisms operating in different flow types (e.g., shear or
elongation) or different field intensity. Furthermore, there is usually a difference in
PA-6 drop size in HOPE at 25o"C
0
0.9
J:>0
~
--,
.--
0.6
o wall
• center
0.3
1 10 100 1000
Shear rate (1Is)
Figure 7.3 Reduced drop diameter versus rate of shear at 250°C. The blend, comprising 10
wt % PA-6 in HDPE, was extruded through a capillary die with IjD = 40 (Utracki et al., 1986).
the quench time between the outer layer and the core of a specimen. Figure 7.3
illustrates variations of drop diameter with the rate of shear that occur during
capillary flows. The morphology was mainly affected by the extensional flow field
upstream from the die, shear flow (and flow-induced encapsulation) inside the die,
and slower cooling of the center, then of the extrudate skin.
7.2.2 Fibrillation
Stress-induced fibrillation occurs in steady-state shearing or elongation when the
capillarity ratio K- is greater than 2. Under these conditions, flow of the dispersed
phase is codeformational with that of the matrix. Since the capillarity parameter is
proportional to diameter, it is easier to fibrillate coarser dispersions (</> = aAb ) where
the numerical values of the parameters a and b depend on the composition of the
blend, and A is the viscosity ratio (Krasnikova et al., 1984).
Tsebrenko et al. [1976, 1982] studied fibrillation of polyoxymethylene (POM) in a
copolyamide (CPA) matrix, resulting from flow through a capillary. Fine fibrils with
diameters of about 20/-Lm and length 3.2 mm were obtained during extrusion at
T = Tm (POM) + 6°C. The low extrusion temperature facilitated stress-induced crys-
tallization of the POM fibers, preserving the morphology engendered at the entrance
to the die. Fibrillation of POM in poly(ethylene-co-vinyl acetate), EVAc, was found to
strongly depend on A. The finest dispersion of microfibers was obtained for A == 1; at
other viscosity ratios the morphology was either coarser or complicated by the
presence of drops or plates (Tsebrenko et aI., 1982).
As illustrated in Figure 7.4, fibrillation is affected by the compatibilizer. Evidently,
addition of a surface tension modifier has two effects: it lowers the interfacial tension
coefficient (increasing K-) and it decreases the diameter of the drop to be elongated
(increasing K-) - the net result is difficult to predict. However, compatibilization
frequently involves formation of an interphase whose viscosity is higher than that
of the main phases. For example, reactive compatibilization that involves coupling of
A and B polymers result in a high-molecular-weight copolymer that rigidifies the
50-,-----,-------------,--------,
PA-6/PP = 80/20 (0)
PA-6/PP/AA = 80/16/4 (0)
E 40
~ L
1:)
..1 30 o
o o o
20
o
10 d
....................~
..I::
..:::
..:::
..:::
..:::..:::..::;.....-I..I--.- _ . . - - - _ _ _ .
......•.............•
O...l.---L--------L-------~
10 100
Figure 7.4 The orthogonal axis of deformed polypropylene drops in shear at 250 0c. The
blend comprised PP/PA-6=1:5 with and without acrylic compatibilizer, AA (S0ndergaard
et al., 1992).
102 Morphology
interphase. In such cases, deformability of the dispersed domains is reduced by
compatibilization.
7.2.3 Flow-induced coalescence

Under normal circumstances, there is a dynamic equilibrium between the dispersion
and coalescence processes, making it difficult to assign a particular effect to coales-
cence. However, during flow at temperatures near the melting point, the effects of
coalescence dominate the final morphology. For example, blends of HDPE contain-
ing up to 30 wt% of PA-6 were extruded through a capillary die at 150, 200 and
250 0c. Fibrillation of the PA-6 phase was observed at all temperatures, below
and above the melting point of 219°C (Utracki et al., 1986). Judging by the diameter
of PA-6 domains before and after the capillary flow, formation of the fibrillar
structures at 150°C mainly originated in a shear-induced coalescence. Calculations
showed that the extensional stresses existing at the entrance to a capillary were more
than sufficient to deform the amorphous part of PA-6. The elongated structures, once
created, could neither disintegrate nor elastically retract to spherical shapes.
Recently it was reported that coalescence of fibers also takes place during the
complex flow in the mixing blocks of a twin-screw extruder (Huneault et al. 1995b)
At temperatures slightly above the melting point, coalescence of semicrystalline
dispersed domains combined with stress-induced crystallization, was found to
result in formation of long fibers. The effect has been explored for performance
improvement of blends comprising liquid crystal polymers (La Mantia, 1993).
7.2.4 Interlayer slip

Shear-induced interlayer slip was theoretically predicted by Lin [1979], who derived
a relationship for immiscible blends with interlayer slip factor, {3 = (3(a12), respon-
sible for engendering a telescopic-type flow:
(7.2)
The relationship predicts a negative deviation from the log-additivity rule. It was
reported that the interlayer slip creates a tree-ring structure in extrusion, observed
for example in samples containing 30 wt % PA-6 in HDPE matrix, extruded at
250 0c. The HDPE-PA-6 capillary viscosities at 250 °C followed Lin's prediction
quite well (Utracki et al., 1986). For {3 -+ 0, the fluidity additivity equation is recov-
ered (Heitrniller et al., 1964). The fluidity equation may be useful in describing the
steady-state viscosity of antagonistically immiscible polymer blends, such as
polypropylene/liquid crystal polymers (PP/LCP) shown in Figure 7.5.
7.2.5 Flow-induced encapsulation

Shear-induced segregation of polymer domains is related to differences in rheological
properties between blend components. The segregation takes place not only in
immiscible blends, where the viscosities and elasticity of the two phases differ, but
also in miscible blends comprising components of different chain lengths. In the
latter case, it is the difference in chain lengths that causes an imbalance of stresses
and relative motion of the components (Doi and Onuki, 1992).
Migration of the low viscosity component toward the high stress regions results in
flow-induced encapsulation of one phase by another. The effect has been well
PP/LCP BLENDS
5 ............ ~~
0.7 ....
~
1/(109 T1('/
S
..
:+ ///'/ ~
0.5
3 :.
/
//// --
•
"
0.3
'ir~
II ~.
··········1/T1 ......................................... 1
10l-----'------'-:------'-----,.L------' 0.1
40 80
w (wt % LCP)
Figure 7.5 Concentration dependence of shear viscosity of PP/LCP blends; dotted line
represents the fluidity equation (Ye et al., 1991).
documented and successfully explored in polymer processing (Utracki, 1987, 1988,

1989a, 1991b, 1995). For example, a high viscosity engineering resin that has poor
resistance to solvents, such as polycarbonate PC, polyesters PEST, or polyetherether-
ketone, PEEK, can be blended with a low melt viscosity liquid crystal polymer, LCP.
Extruding such a blend through a die with a long enough land forces the LCP to
migrate toward the high stress surface, thus lubricating the die flow. Furthermore,
the process provides a protective layer of LCP on the surface of an engineering resin.
The reduction of polymer melt viscosity upon addition of LCP was originally
described in 1979, in a patent deposition from ICI (Cogswell et al., 1981, 1983,
1984). The rheological behavior of LCP blends with polyether imide was studied
by Nobile et al. (1990) in steady-state capillary and dynamic mechanical modes of
deformation. The flow of LCP was reported to be sensitive to pressure, thus the flow
of blends was carried out using a short capillary.
A more common commercial exploitation of the phenomenon is the addition of
fluoropolymers to polyalefins. In this case, a small amount of fluoropolymer progres-
sively migrates to the die surface, reducing the die pressure drop and making it
possible to extrude the PO resins at high throughput without melt fracture. It has
been shown that this approach also works for other polymers, such as PEEK. Thus
blends of PEEK with polytetrafluoroethylene (1-5 wt% PTFE), were extruded. The
pressure drop across the die was reported to decrease with time to an equilibrium
value Plim. The value of Plim depended on PTFE content, whereas the time to reach it
on the rate of extrusion - the higher the rate, the shorter the saturation time
(Chan et al., 1992).
8
Rheology
8.1 INTRODUCTION
The rheology of polymer blends is complex, caused by viscoelasticity of the phases,
the viscosity ratio A that varies over a wide range, as well as diverse and variable
(during the test) morphology. For this reason, it is useful to refer to simpler systems
or models that can offer an insight. The systems listed below are frequently used
(Utracki, 1989a, 1995; Lyngaae-J0rgensen, 1983, 1985, 1989; Lyngaae-J0rgensen et al.,
1993):
• miscible blends - solutions and homologous polymer blends;
• immiscible blends - suspensions, emulsions and block copolymers.
8.2 SINGLE-PHASE MIXTURES

For miscible blends, theory predicts a positive deviation (PDB) from the log-
additivity rule (Arrhenius, 1887):
In~ = LX; In 1AJi + In rl (8.1)
with the excess viscosity term, In r{- -+ O. As a rule, in rheology of polymer blends,
the viscosities in Equation (8.1) are to be determined at the constant stress, not the
deformation rate.
However, there is mounting evidence that the PDB is not a rule for miscible
polymer blends. Depending on the system and method of preparation, polymer
blends can show either a positive deviation, negative deviation or additivity. Note
that miscibility in polymeric systems requires strong specific interactions, which in
turn affect the free volume, thus the rheological behavior (Utracki, 1987, 1989a).
In miscible blends, the flow behavior depends on free volume, entanglements and
specific interactions. From Doolittle's equation, assuming additivity of the occupied
volume and non-additivity of the free volume, Steller and Zuchowska [1990] derived
In '7/b=ttPi In 1'/; + { t wj[(hi -1)/(15; + l)]Vj }/{2tW ;V;/(hi + 1) }-(1/2) t tPi(h; -1)
15 == [1- 4(8In1'//OT)/(8ln V/8T)/Bjl/2 = (2Vo + Vt}/Vf (8.2)

Two-phase systems 105
where Wi and Vi are, respectively, weight fraction and specific volume of ith com-
ponent, and Vo and Vf are the occupied and free volumes, respectively. Parameter 8
can be experimentally determined from the temperature gradient of the viscosity
and specific volume.
8.3 TWO-PHASE SYSTEMS

For immiscible blends, the rheological behavior of at least three phases must be taken
into account: those of two polymers and the interphase. The simplest model is that of
a suspension. The following assumptions are usually used: (1) the size of a rigid
particle is large in comparison to the suspending medium molecules, but small
compared to the smallest characteristic diameter of the flow channel, so the con-
tinuum theories are applicable; (2) the flow is steady state, without inertia or
sedimentation effects; and (3) the suspending medium perfectly adheres to the
particles. Depending on the system (as well as the author), additional assumptions
may be made, such as those regarding interparticle interactions, orientation, etc.
Simha (1952) adopted a cage model, placing each spherical particle of radius a
inside a spherical enclosure of radius b. For distances x < b, the presence of other
particles does not influence flow around the central sphere and the Stokes relation is
satisfied. This assumption led to a modified Einstein (1906, 1911) relation:
11r(~) = 1 + (5/2)>.(y)tP
4(1 _ y7) (8.3)
>'(y) = 4(1 + ylO) - 25y3(1 + y4) + 42y5
with y(~) = 1/[2(¢>m1tP)1/3 -1]

where >.(y) is the modifying (or shielding) function of the relative cage size,
~ == tPltPm is the reduced volume fraction of the suspended particles, tPm is the
maximum packin& volume fraction. Thus, !.he magnitude of the shielding function
depends only on tP. At low concentration, tP -+ 0, the shielding factor vanishes and
Einstein's relation is recovered. However, at high concentration (~ -+ 1), the shield-
ing function and relative viscosity both go to infinity, >'(y), 11r -+ 00. The dependence
was successfully used for emulsions as well as polymer blends under two condi-
tions: the equation parameters, tPm and [17] are determined independently, and the
data are taken at the same stress.
The fundamental assumption of classical rheolOgical theories is that liquid
structure is either stable (Newtonian behavior) or changes in a well-defined manner
(non-Newtonian behavior). This is not always the case for flow of suspensions.
For example, orientation effects in sheared layers may be responsible for either
dilatant or pseudoplastic behavior, while strong interparticle interactions may
lead to yield stress or to transient behaviors. Aggregation, agglomeration and
flocculation range from transient rotating doublets (observed within dilute regions)
to a solid-like behavior of flocculated suspensions with yield stress originating either
in thermodynamic interparticle interactions, chemical bonding or geometric
crowding.
There are several methods for determining the yield stress u y . Among these is the
modified Casson equation (Utracki and Kamal, 1982):
(8.4)
106 Rheology
where F may be any rheological function (such as shear stress 0"12, elongational stress
O"n, shear loss modulus Gil, etc.), Fy indicates the yield value of F, Fm is the F-value of
the matrix liquid at the same deformation rate as F, and a is a measure of the
relative value of F. It has been observed that in many systems the value of
yield stress depends on the time-scale of the measurements. Setting all controversies
aside, pragmatically it is advantageous to consider that in these systems there
are aggregates of different size, characterized by dynamic interparticle
interactions. For a given system these interactions, have specific strength, a'f, and
the aggregates have a characteristic relaxation time T y . This model leads to the
relationship
O"y(w) = O"~ [1 - exp (-TyW)t (8.5)

where u = 0.2-1.0 characterizes polydispersity of the aggregates. Equation (8.5) was
found to be easy to use, and the parameters computed from curve fitting of the
experimental data, 0" apparent = O"y + O"true, agreed well with the independently
determined values. Recently, Leonov (1994) introduced kinetics of interactions into
his rheological equation of state. The new relationship can describe systems with a
dynamic yield stress, without resorting a priori to introducing the yield stress as a
model parameter, as has been done in the earlier models.
Liquids having yield stress show a plug flow behavior. As a result, these liquids
have drastically reduced extrudate swell, B == d/ do (d is diameter of the extrudate, do
that of the die) (Utracki et al., 1984), and significantly increased the entrance-exit
pressure drop P e (also known as the Bagley correction; Bagley, 1957). For single-
phase fluids, these parameters have been related by molecular mechanisms to
elasticity (Tanner, 1970; Cogswell, 1972; Laun and Schuch, 1989), but in multiphase
systems, both B and Pe mainly depend on the interdomain interactions and mor-
phology. Thus, in multiphase systems only the direct measures of elasticity, such as
that of normal stresses or storage modulus, N 1 , N2 or G' should be used.
It is customary to plot the measure of the elastic component versus that of
the shear components, such as N1 versus 0"12 or G' versus Gil. For rheologically
simple systems, the relationships are independent of temperature but, for the
multiphasial ones, they are not - the viscoelastic time-temperature principle does
not hold.
8.4 MICRORHEOLOGY
The term microrheology means '... prediction of the macroscopic rheological proper-
ties of a material from a detailed description of the behavior of the elements of which
it is composed' (Goldsmith and Mason, 1967). When a neutrally buoyant, initially
spherical droplet is suspended in another liquid and subjected to shear or
extensional stress, it deforms and then breaks up into smaller droplets. At low stress
in a steady, uniform shearing flow, the deformation can be expressed by means of
three dimensionless parameters: the viscosity ratio, the capillarity number and the
reduced time:
(8.6)
where 0" = 11mi' is the local shear stress, 1Jd and 11m are the dispersed phase and
matrix viscosity, respectively, i' is the shear rate, d is the droplet diameter and 1/12
is the interfacial tension coefficient. The deformability D is defined as the difference
of the major and minor prolate ellipsoid diameters divided by their sum.
Microrheology 107
For small stresses, D and the orientation angle a of a sheared droplet was
expressed as (Cox, 1969)
D = (d1 - d2 )/(d1 + d2 )
D = (1I:/2)[(19A + 16)/(16A + 16)lI[1 + (19AII:/40»)l/2 (8.7)
a = 7r/4 + (1/2) arctan{19AII:/20}
The above relationships are valid for Newtonian systems undergoing small, linear
deformation, smaller than that which would lead to breakup. The equilibrium
deformation is reached at the reduced time td ~ 25 (Elemans, 1989).
It is convenient to express the capillarity number in its reduced form 11:. = 11:/ K-cr,
where the critical capillary number K-cr, is defined as the minimum capillarity
number sufficient to cause breakup of the deformed drop. There are four regions
of the reduced capillarity numbers 11:. (both in shear and elongation) for drop
deformation and break up:
0.1 > 11:. droplets do not deform
0.1 < 11:. < 1 droplets deform, but they do not break
1 < 11:. < 2 droplets deform then split into two primary droplets
11:. > 2 droplets deform into stable filaments
Similar to 11:0 , the critical time for drop breakup, tj" also varies with A- in shear flows
the reduced time is tj, ~ 100.
When values of the capillarity number and the reduced time are within the region
of drop breakup, the mechanism of breakup depends on the viscosity ratio, A. In
shear, four regions have been identified (Goldsmith and Mason, 1967):
0.1 » A small droplets are shed from sigmoidal drops - tip spinning,
0.1 < A < 1 drop breaks into two principal and odd number of satellite droplets
1 < A < 3.8 drop deforms into fiber, which then disintegrate into small droplets
A > 3.8 drops may deform, but they do not break
For 11:. > 2, drops deform affinely with the matrix into long fibers. When the
deforming stress subsequently decreases, causing the reduced capillarity number
to fall below two, 11:. < 2, the fibers disintegrate under the influence of the interfacial
tension. The problem was theoretically treated by Tomotika (1935, 1936), who
described the thread instability by the growth rate parameter of a sinusoidal distor-
tion:
q = !lt2 fl (t\, A)/2T/mRo (8.8)
where t\ is the distortion wavelength, fl(t\, A) is a function tabulated by Tomotika,
and Ro is the initial fiber radius.
During mixing, the dispersed phase progressively breaks down until a minimum
drop diameter is reached. This minimum is a result of dynamic balance between the
dispersion and coalescence processes. There is evidence that coalescence may be
present even at low concentration of the dispersed phase, ¢o ~ 0.005 (Utracki and
Shi, 1992). Two types of coalescence must be recognized, the first being determined
by equilibrium thermodynamics (e.g., Ostwald ripening), the second, dynamic one,
being strongly affected by flow.
Recently, a new theory for drop breakup and coalescence in steady-state shearing
was proposed (Huneault et al., 1995a). The rate of drop generation by the break-up
mechanism was calculated from microrheological principles. The rate of coalescence
was derived from the theory of shear coalescence of emulsions (Utracki, 1973b). At
dynamic equilibrium, the rate of generation of new drops is equal to the rate of
108 Rheology
their consumption by coalescence; thus the equilibrium drop diameter can be
calculated as:
• 8/3) 1/2
deq = ~ + ( 6C"'crtb¢i (8.9)
where C is a coalescence constant, deq is the equilibrium drop diameter, reached by
the blend with the volume fraction of the dispersed phase ¢i mixed under a given set
of processing conditions, while ~ is its value extrapolated to zero concentration.
The only unknown in Equation (8.7) is the coalescence constant C. Its value can be
determined from a plot of deq versus ¢i4/3.
A greatly Simplified constitutive equation for immiscible 1:1 mixture of two New-
tonian fluids having the same viscosity and density was recently derived (Doi and
Ohta, 1992). The derivation considered time evolution of the area and orientation of
the interface in flow, and the interfacial tension effects.
8.5 CONCENTRAnON DEPENDENCE OF VISCOSITY

There is a correlation between the thermodynamic and rheological functions. In
miscible blends where the free energy of mixing is negative, ~Gm < 0, the experi-
mental data indicate that in most systems, either the log-additivity rule or small
positive deviations from it have been observed. Near the phase separation, where
~Gm ~ 0, the rheological response is complex because the free energy of mixing is
precariously balanced by the term describing the energy input by the flow. Finally,
in immiscible systems, where ~Gm > 0, five different types of behavior have been
identified. In Figure 8.1 the curves represent: (1) positively deviating blends (PDB);
(2) negatively deviating blends (NDB); (3) log-additivity; (4) PNDB; and (5) NPDB
(Utracki, 1991c). To understand the origins of these behaviors, it is first necessary to
evaluate morphology and flOW-imposed morphology in polymer blends. In the
following discussion, the constant stress (not the constant rate) viscosity, corrected
for the yield and time effects, will be considered. The emulsion model of polymer
blends predicts a positive deviation (PDB) from the log-additivity rule,
In 1/ = E¢ij In 1/j. While PDB has been found in about 60% of blends, the remaining
four types (see Figure 5.2) must also be accounted for. This means that at least one
other mechanism must be assumed when modeling the viscosity-eoncentration
2 SChematic representation of the five types

of PAB vlscoslty-concentratlon dependence
1.5
,.. ..........5.... - ...... , "

l' ..-
,;.;;..-::.::- 4 --_~.:::",,,,,,-
0.5 ......:.~ ...-<'" ..,
,,;.-
~., .............
../" 3
----- --------
2 ----
-0.5 L..-_ _--I. --'- ...I...-_ _---'L....-_ _--'
o 0.2 0.6 0.8
Figure 8.1 Five types of relationship between shear viscosity and concentration for immiscible
polymer blends: (I) PDB, (2) NOB, (3) log-additivity, (4) PNOB, and (5) NPDB [Utracki, 1991c].
Dynamic flow 109
1.6 ,-------,"""-----,,-------,,------,-----,
1.4
er rbars=±2%
i 1.2
a..
"'"
:; 1 .. _ _.'l.: at :.~ :.10_KPa
~ 0.8 PC/LLDPE at 24SoC . - . ' - . .......
~
~ 0.6 1]'
_.•._._.-._.1----..-,-'
at G" = 100 KPa
0.4 _.. _.. - .. -t'-

0.2 '. ._._.._.._.._._.•-._.._.._.._._.- • -
- -~-
1] at "'2= 100 KPa
0.2 0.4 0.6 0.8

$PC
Figure 8.2 Concentration dependence of dynamic, rf, and steady state, 11, shear viscosity of
linear low density polyethylene/polycarbonate blends at 245°C and at constant stresses
Gil =1, 10 and 100 kPa and 0"12 =100 kPa. Points are experimental, with the error bars indicating
the error of measurements ± 2% (Utracki and Sammut, 1990).
dependence of polymer blends. This second mechanism should lead to the opposite
effect, that is, to negative deviation from the log-additivity rule, NDB. Interlayer slip
provides such a mechanism (Utracki, 1991c):
log TJ = log TJL + A log TJE
logTJL = -log[l +,a(¢1¢i/2 )] -log(¢tlTJI + rhlTJ2) (8.10)
A 10gTJE = Tfmax{ 1 - [(¢l - ¢ld I(¢l¢~ + rh¢il)]}

where TJL indicates Lin's fluidity relation, and A log ~ is an excess term derived from
the concept of the emulsion-like behavior of blends.
Equation (8.10) was found to describe the observed dependencies well. As an
illustration, Figure 8.2 presents the viscosity-eoncentration dependence for uncom-
patibilized blends of polycarbonate with a linear low density polyethylene. The data
were determined at different dynamic and steady-state stress levels. Evidently, as
the stress and/or strain increases the PDB progressively turn into NOB, or in other
words, the flow initially being dominated by the emulsion-like behavior, shows an
increasing amount of interlayer slip.
8.6 DYNAMIC FLOW

Owing to the variability of blend structure with flow, the rheological responses are
sensitive to the way they are measured. Since modification of structure is related to
strain, the responses measured at high and low values of strain are different. For this
reason, the selected test procedure should reflect the final use of the data. When
simulation of flow through a die is attempted, the large strain capillary flow is
useful, but if the material characterization is important, low strain dynamic testing
should be preferred. As shown in Table 8.1, there is serious disagreement between
predictions of continuum-based theories and experiments for multiphase systems.
The dynamic testing of polymer blends at small amplitude is simple and reliable.
The storage and loss shear moduli, G' and Gil, respectively, should be first corrected
for yield stress, then the loss data can be fitted to
110 Rheology
Table 8.1 Comparison of continuum-based predictions for simple fluid with

experimental observations for polymer blends
Rheological function Simple fluid Polymer blend

Viscosity at vanishing 7J(i) = rf(w) = Tk(i)/3 7J(i) # rf(w) # TfE(i)/3
deformation rates
Extensional viscosity (from TfE = TfE(Cogswell) TfE # TfE(Cogswell)
entrance effects)
First normal stress difference N l = Nl(B-swell); Nl # Nl{B-swell)
(from extrudate swell) (Tanner, 1970)
(8.11)
to determine the value of the four parameters~, r, m\ and m2. Once these are known,
the Gross frequency relaxation spectrum HG can be calculated:
HG == HG/~ = (2/,rr)r- m2 sin(m28)
r= [1 + 2(wr)m cos(ml7r/2) + (wr)2m1t

l
2
(8.12)
8 == arc sin{(wr)m1r-l sin(ml7r/2)}
From the spectrum, any linear viscoelastic function can in turn be computed. For
example, the experimental data of the dynamic storage and loss shear moduli G' and
G", respectively, or the linear viscoelastic stress growth function in shear or uniaxial
elongation can be computed from the dependencies (Utracki and Schlund, 1987):
G'(w) = [: {sHG(s)/[l + (s/w)2]}dIns

G"(w) = [:00 {wHG(S)[l + (w/S)2] }dIns (8.13)
11t(t) = 3 [:00 HG(w)[l- exp(-wt)]dInw
Owing to definition of the reduced relaxation spectrum,

+00
1 HG(s)d Ins == 1
-00 (8.14)
Thus, the coordinates of the maximum (HG, max; wmax ) are related, respectively, to the
system polydispersity and molecular weight. However, if the system is miscible,
these functions are fully predictable from the composition, polydispersity and mole-
cular weight of the components. Note that in miscible blends the general relation
between the relaxation spectrum of a mixture and its component follows the third-
order blending rule:
H(r) = EWijkHijk(t/rijk) (8.15)
The dependence can be Simplified when all fractions are either entangled or not:
Hc(w) = EWiHGi(W) (8.16)
Thus, for miscible polymer blends, the relaxation spectrum should be a weight-
average combination of the components' relaxation spectra.
Dynamic flow 111
Two types of rheological phenomena can be used for detection of a blend's misci-
bility, influence of polydispersity on rheological functions and inherent nature of the
two-phase flows. The first principle makes it possible to draw conclusions about
miscibility from, for example,
• coordinates of the relaxation spectrum maximum (see Figure 8.3; Utracki and
Schlund, 1987);
• cross-point coordinates (Gx,wx) (Zeichner and Patel, 1981);
• free volume gradient of viscosity: a = d(In TJ}jdf;
• initial slope of the stress growth function: 5 == din r¥. jd In t, (Schlund and Utracki,
1987);
• the power-law exponent n == din O"l2/d In l' ~ 5, etc.
)
POLYETHYLENE BLENDS
-0.7
-- ... -- MISCIBLE
~ --.........-IMMISCIBLE
E
d
'.
:I: -0.9
Cll
.Q -., ,
,,
,,
----- -
-1.1 -... '.
---------------
_.
•
-1.
3 5 7 9
Mw/M n
, POLYETHYLENE BLENDS
o
~,:,""""
-2 "" """""
.' ,,
'.
--- ... -_. MISCIBLE ,,
" IMMISCIBLE
-4-+----r----r----r----r-----,
0.5 1.5 log 1]0 2.5
Figure 8.3 Coordinates of the maximum of the Gross frequency relaxation function (a) HG,m4X
and (b) wm4X , plotted as functions of, respectively, the polydispersity index M w IMn and the zero
shear Viscosity 1/0, a measure of the mlecular weight (Utracki and Schlund, 1987).
112 Rheology
The second principle involves evaluation of, for example,
• extrudate swell parameter, B = DIDo;
• strain (form) recovery;
• yield stress, etc.
Over the years, there has been an effort to describe the rheological functions of
liquid mixtures from those of neat ingredients and their content. Recent theory
is based on the assumptions that: (1) the system consists of two viscoelastic
liquids; (2) the concentration of the dispersed phase is moderate; (3) the drops are
spherical, polydisperse and deformable; (4) the drop deformation is small, so the
blend behavior is linear viscoelastic; and (5) the interfacial tension coefficient V12 is
constant, independent of stress and interfacial area. The analysis leads to
(Palieme,199O):
C*(w) = CM(w) [1 + 3~ !/>H;(W)] I [1 -2~ !/>iHi(W)]

(8.17)
H(w) = 4(vIR;) [2C:n + sCd] + (Cd - c:n) [16C:n + 19Cd]
J 40(vIRi) [C~ + Cd] + (2Cd + 3C~) [16C~ + 19cd]
where v the interfacial tension coefficient, !/>i and Ri are the volume fraction and the
drop radius respectively, C7(w) is the complex modulus, and subscripts i = m or d
indicate matrix and disperse phase, respectively. The main feature of this model is
the inclusion of a contribution from the interfacial tension to the viscoelastic propert-
ies and the inclusion of the effect of particle size polydispersity. Knowing C7(w) of
the two main components of the blend, one can predict the dynamic moduli of dilute
polymer blends from a knowledge of the interfacial tension coefficient and dis-
tribution of drop size - the ratio viR is the only parameter of the equation. Note
that the theory is applicable to low strains, and to the concentration range in which
the yield stress is absent. The model was found to well describe the dynamic
behavior for several blends, supporting the idea that the long relaxation times in
blends originate from geometrical relaxation of droplets (Graebling and Muller,
1990, 1991; Graebling et al., 1993, 1994). Replacing the sums in Equation (8.17) by
integrals, writing the appropriate expressions for the storage (real part) and loss
(imaginary part) contributions to the complex shear modulus, then applying the
Tikhonov regularization method made it possible to determine a fine structure of the
relaxation spectra, as well as the distribution of dispersed polystyrene drops
(Riemann et al., 1995; Friedrich et al., 1995).
8.7 COMPATIBILIZATION EFFECTS

Compatibilization enhances the dispersion, increases the total apparent volume of
the dispersed phase, rigidifies the interface, and increases interaction, not only
between the two phases, but also between the dispersed drops. The reactive com-
patibilization may involve chemical bonding between the two polymers' macro-
molecules, resulting in significant increase of molecular weight at the interface.
The rheological consequences of these changes are easy to foresee from the
perspective of the emulsion model of polymer blends. Making the interface more
rigid causes the intrinsic viscosity of the emulsion to increase. Similarly, an increase
of the apparent volume of the dispersed phase causes the relative viscosity to
increase. Furthermore, increased interactions between the phases reduce the poss-
ibility of interlayer slip and increase the formation of an associative network, result-
Compatibilization effects 113
ing in systems with increased yield stress. In short, compatibilization is expected to
increase melt viscosity, elasticity and the yield stress. The compatibilizer effects are
especially evident at low frequencies, but may have little effect on the flow at high
deformation rates.
There are two mechanisms that may invalidate this prediction. First, in spite of the
best efforts, the added copolymer may prefer to form micelles inside one of the
polymeric phases rather than to migrate to the interphase. This has frequently been
observed in blends with block copolymers, such as for PE/PS blends compatibilized
by addition of a hydrogenated styrene-butadiene block copolymer (SEBSi Utracki
and Sammut, 1988, 1990). Second, addition of compatibilizer may affect the total free
volume of the blend. This change originates in specific interactions and is difficult to
predict. An increase of the free volume (thus reduction of melt density) will result in
decreased viscosity.
Steady state and dynamic shear, as well as extensional flow behaviors of PP, PA-6,
and their compatibilized blend were studied at 225-250°C (Utracki and Sammut,
1992). The dynamic flow curves for the blend were significantly higher than could be
predicted from the components' flow behavior, but were quite regular, pseudo-
plastic and without apparent yield stress. However, the capillary flow was found
to be insensitive to temperature, suggesting a major modification of morphology
during these large strain tests. Similarly, the extensional viscosity of the blends was
significantly higher than could be expected from the component polymers' behavior.
Furthermore, the blends showed strain-hardening effects, absent in PP and PA-6.
Molecular weight increased by compatibilization could provide an explanation. The
measured elongational viscosity 'fJE for two homopolymers agreed quite well with
the value calculated from the entrance pressure drop in capillary flow Pe (Laun and
Schuch, 1989):
(8.18)
where n is the power-law exponent. However, for the blend, the calculated value of
'fJE was one order of magnitude higher than measured (see Figure 8.4).
In another report, compatibilization of PP/PA-6 blends resulted in change of the
viscosity--<:oncentration dependence from negative deviation (NDB) to positive
deviation (PDBi Nishio et al., 1992b).
Capillary entrance/exit correction

T = 230°C
o
o
o
:
o
D~ Orgalloy
~. PP
PA
0 ..
- - Laun and Schuch
Figure 8.4 Entrance-exit pressure drop in capillary flow of polypropylene, polyamide-6, and a
commercial PP/PA-6 blend at 230 0c. The line was computed from the Laun & Schuch relation-
ship, Equation 8.16. Points are experimental from Utracki and Schlund, 1987.
114 Rheology
8.8 TIME-TEMPERATURE SUPERPOSmON
The time-temperature superposition principle t-T used to be a cornerstone of vis-
coelastometry. It has been invariably used to determine the viscoelastic properties of
materials over the required 10-15 decades of reduced frequency waT (Ferry, 1980).
Measuring the rheological properties at several temperatures over the experiment-
ally accessible frequencies (usually two to four decades), then using the t-Tshifting,
made it possible to construct the complete isothermal function. The principle implies
that, upon change of temperature, all the relaxation times are modified by the same
factor.
In single-phase homologous polymer blends, the relaxations are mainly controlled
by the segmental mobility; thus, the t-T superposition has been observed. Similarly,
for polymers filled with high modulus particles, the filler is responsible for enhance-
ment of modulus without affecting the relaxation spectrum and, as a consequence,
the t-T superposition principle may still hold. However, in rheologically complex
heterogeneous systems, individual polymeric components contribute to the relaxa-
tion, and since their activation energies are usually different, a change of tempera-
ture affects them differently -lack of t-T is a result.
There is growing evidence that t-T superposition is not valid even in miscible
blends well above the glass transition temperature. For example, Cavaille et al. (1987)
reported lack of superposition for the classical miscible blends - PS with PVME. The
deviation was particularly evident in the loss tangent versus frequency plot. More
interesting, thermodynamically miscible blends of anionically prepared narrow
molecular weight 1,2-polybutadiene and 1,4-polyisoprene (PB/PI) were found to
be thermorheologically complex, not follOWing the time-temperature superposition
principle (Roovers and Toporowski, 1992). The explanation proposed by Ngai
and Plazek (1990) was based on the postulate that the number of couplings
between the macromolecules varies with concentration and temperature of the
blend. Thus, in miscible, single-phase blends, as either the concentration or
temperature changes, the chain mobility changes and relaxation spectra of
polymeric components in the blends show different temperature dependence,
i.e., the t-T principle cannot be obeyed. Chung et al. (1994) demonstrated, by two-
dimensional deuteron NMR, that the broad glass transition in miscible PB/PI
blends arises from a wide distribution of segmental motion rates for each
species, local composition variations, as well as from intrinsic differences in chain
mobilities.
In immiscible blends, the t-T principle does not hold. For immiscible amorphous
blends, it was postulated that two processes must be taken into account: the t-T
superposition, and the aging time - at test temperatures, the polymeric components
are at different distances from their respective glass transition temperatures,
T - Tg1 =1= T - Tg2 (Maurer et al., 1985). In blends of semicrystaUine polymers, such
as PE/PP, at best the superposition is limited to the molten state, within a narrow,
high temperature range (Dumoulin, 1988).
8.9 STEADY-STATE VERSUS DYNAMIC VISCOSITIES

For most blends, the morphology changes with the imposed strain. Thus, it is
expected that the dynamic low strain data will not follow the pattern observed for
the steady-state flow. One may formulate it more strongly - in polymer blends, the
material morphology and the flow behavior depend on the deformation field; thus,
under different flow conditions, different materials are being tested. Even if low
Elongational flows 115
strain dynamic data could be generalized using the t-T principle, those determined
in the steady state will not follow the pattern.
Chuang and Han (1984) reported that for miscible and immiscible blends at con-
stant composition, the plots of N1 versus 0'12 and G' versus Gil are independent of T.
However, whereas for single-phase systems the two dependencies are approximately
parallel, for immiscible blends, such as PS/PMMA, the steady state relation may be
quite different from the dynamic one. The agreement can be improved by means of
Sprigg's theory (1965). For a series of PMMA/ABS blends, the plot of the Sprigg's
structural parameter c versus composition was non-linear, with c = 1 found only for
PMMA homopolymer. The variation seemed to be related to differences of the
morphology existing in dynamic and steady-state flow fields (Utracki, 1989a, 1989b).
8.10 BLEND ELASTICITY

Four measures of melt elasticity have been used: the first normal stress difference N 1,
the storage modulus G', and the two indirect ones, namely the entrance-exit pressure
drop Fe or Bagley correction, and the extrudate swell B. In homogeneous melts, the
four measures are in qualitative agreement. In the blends where the dispersed phase
is difficult to deform, the extrudate swell and Pe should be small. Deformation-and-
recovery of the dispersed phase form provides a potent mechanism for energy
storage, leading to large elastic response. Neither Bagley's entrance-exit pressure
drop correction nor the extrudate swell can be used as a measure of blend elasticity.
In both cases the form recovery dominates the observed dependence.
Direct measurements of N1 and 0'12 indicate a parallel dependence of these func-
tions plotted versus rj>, even when these have a sigmoidal form. Considering the
steady shear flow of a two-phase system, it is generally accepted that the rate of
deformation may be discontinuous at the interface, and it is more appropriate to
consider variation of the rheological functions at constant stress than at constant rate,
Le., Nl = N 1 (0'12). Using a similar argument for the dynamic functions, it should be
concluded that G' = G'(G") should be used. Note that, as discussed above, the
steady-state and dynamic data for polymer blends rarely superimpose.
8.11 ELONGATIONAL FLOWS

Owing to experimental difficulties, there are few publications on extensional flow of
blends. It is convenient to distinguish two contributions to the tensile stress growth
function .,g - one due to the linear viscoelastic response .,gL and the other originating
in the structural change of the specimen during deformation .,gs' The first can be
calculated from any linear viscoelastic function, while the second depends on the
intermolecular interactions or entanglements, and its value depends on both the total
strain l' = it, and either strain rate f. or straining time t. Owing to the industrial
importance of strain hardening (SH), a large body of literature focuses on the
optimization of blend composition to maximize SH. Since SH depends on the
entanglement, blending branched polymers usually affects SH even in the low
concentration range.
Most of the work on uniaxial extensional flow of immiscible polymer blends has
focused on the behavior of systems containing polyethylene. The main reason is the
need for better, easier-to-process resins. Film blOWing conceptually involves two
different engineering operations, extrusion and blOWing. For most production lines,
the latter operation limits the productivity. For the low density resins (LDPE) strain
hardening prOVides a self-healing mechanism. For high density HDPE, and the
116 Rheology
linear low density LLDPE, resins only small SH has been observed for the high
molecular weight resins. As a result, most LLDPEs on the market are blends with
LOPE, rubbers, copolymers or another type of LLDPE resin. SH was also found to be
an important resin characteristic for wire coating. Here the surface finish and uni-
formity of the deposited layer were superior for blends with high strain hardening
and low shear viscosity (Utracki, 1988, 1989a, 1989b).
Recently, Dalby et al. (1994) attempted to experimentally examine the relation
between droplet deformability and the extensional viscosity ratio, DE = DE(AE). As
the authors demonstrated, the theories proposed by Taylor (1932, 1934) and Palieme
(1990) predict the same dependence:
h'd - 1)/h'm - 1) = 5/(2AE + 3) (8.19)
where rd and rm are, respectively, strain of the dispersed phase (defined as a ratio of
the long axis to the original drop diameter) and the matrix. Only for AE = 1 is
codeformation of the drop to be expected.
The convergent flow at the die entrance provides strong elongational flow. In 1989,
Laun and Schuch, discussing the approximate methods of TIE determination, derived
Equation 8.18. For Newtonian liquids the relationship predicts that Pe ~ 1.64a12' This
proportionality was shown in Figure 8.4, along with the experimental values deter-
mined for PP, PA-6 and PP/PA-6 commercial blend OrgalloyTM R-6000. Evidently,
the relationship is satisfactory for homopolymers, but for the blend the prediction is
about one decade too low. Similarly, as for shear flows, the elongational properties of
blends show different behavior under different extensional flow field conditions.
8.12 CONCLUSIONS
In multiphase systems, there is a reciprocal relation between morphology and
rheology. During flow, strains change the morphology, engendering diverse rheolo-
gical responses, such as normal stress in emulsions of Newtonian liquids. The most
efficient method of structure modification is extensional flow, but large strains in
Couette or Poiseuille flow also affect the morphology. To study material behavior
with a well-defined structure, only low strain dynamic methods should be used. For
generating data to be used in process modeling, or interpretation of die flow, one
must simulate not only flow conditions but also the system history, as well as the
geometry to scale. Since miscibility depends on temperature and pressure, flow of
some blends may be more sensitive to these variables than expected from the
properties of its components.
9
Development of polymer blends
9.1 ECONOMY OF BLENDING

There are several methods of blending, namely mechanical, solution, latex, fine
powder, as well as several variations known in the interpenetrating polymer net-
work (IPN) technology. For economic reasons, mechanical blending predominates. It
is important that the size of the dispersed phase be optimized, considering the final
performance of the blend. To avoid streaking and delamination during injection
molding, the size of the dispersed phase should be reduced to submicron. To
optimize impact strength of brittle resin requires that the diameter of the elastomeric
drops will be well within the material-specific range; for example, d = 1 to 3l1Ill for
PS, whereas smaller particles are required for PMMA, PVC, etc. However, for
generating lamellar or fibrillar structures, relatively large drops are needed.
Before discussing methods of compounding, the compatibilization process must
be considered. As discussed before, the role of compatibilizer is similar to that of
emulsifier in classical emulsion technology. The compatibilizer should migrate to the
interface, reducing the interfacial tension coefficient (thus, reducing the dispersed
phase dimensions), stabilizing the blend morphology and improving the adhesion
between phases in the solid state. Different morphologies and properties can be
obtained from a blend compatibilized by different means.
The cost of a polymer blend is given as a weight-average material cost, augmented
by the compounding cost per unit mass, e.g., Cb = ~WiC + K. Another approach is to
calculate the cost-to-performance ratios for diverse materials and/or compositions.
For example, one may ask how much a unit of the tensile modulus or the strength at
yield will cost, and optimize the composition accordingly.
Usually one pays more for a resin showing better performance characteristics. For
example, there is an approximately linear relation between, for example, tensile
strength or heat deflection temperature and cost per unit volume of resin (Figure
9.1). However, in practice, not one resin property but a set of six to ten dictates the
choice of material. This practice makes blends technology more attractive, and more
interesting.
Most frequently, the decision as to whether to use a particular blend is based on
replacement calculations. These involve not only the simple material cost, but the
total comparable costs of the materials, their forming and assembling, customer
satisfaction, esthetics, service We-spans, ease of disposal or recycling, etc. In this
approach, one of the most serious problems is to find reliable data on long-term
blend performance, i.e., on the mechanisms and rates of physical and chemical
aging, or weatherability.
118 Development of polymer blends
• PMMA •PA
POM·
.PP
PE·
• PS - - Y = 30.739 + 6.504 x R = 0.66833
2 4 6
Cost per unit volume ($/L)
.POM
.PBT
6'
o 140 PC.
.....
o
:I:
• SAN
.PA
100 PP • • PS • ABS
• PMMA
PE .CPVC
• PVC
--Y= 70.093 + 12.717x R=0.71479
60 L......L..J.......J---'---..L....J.---'-J.......L-'-L.L..J.......J---'---..L....J.---'-J.......L-'-L.L..J.......J---'---..L....J.--'--J
o 2 4 6
Cost per unit volume ($/L)
Figure 9.1 (a) Tensile strength and (b) heat deflection temperature versus cost per unit volume,
for commodity and engineering resins. The least-square line equations are also shown.
9.2 DEVELOPING COMMERCIAL BLENDS

Polymer blend performance depends on three factors: properties of ingredients, their
content and morphology. Since the cost is virtually fixed by the material and the
compounding costs, the economy depends on the blend's morphology, tailored to
the principal application.
The blends have been developed for economic reasons that can be translated into
several types of uses, such as improvement of either a specific property (e.g., impact
strength) or engendering a set of properties, extending engineering resin perform-
ance, improving processability, recycling, etc.
Developing commercial blends 119
Different philosophies and strategies for development of blends have been used
by the resin manufacturers and users. For the major resin manufacturer, blending
provides means to improve and broaden the resin performance and therefore
enhance its demand and sale. By contrast, the resin user starts with a set of
performance parameters that the material must possess. In both cases, the basic
preposition is the same - to have a blend with desired characteristics, one must
use a component that already shows this characteristic, or in other words, one cannot
create something out of nothing.
Although extension of engineering resin performance constitutes the largest part
of the high performance blends' production, the most difficult and interesting task is
the development of blends with a full set of desired properties. To achieve this goal,
a systematic flowchart has been developed. The procedure starts with selection of
blend components possessing at least one of the desired properties for the blend.
This task can be facilitated by making a tabulated list of resins and their principal
contribution in the blend (see Table 9.1). Half a century of experience indicates that
addition of one polymer to another can induce a specific response. Thus, the strategy
for modification of a polymer is to select a polymeric modifier known to cause the
desired effect. For example, to improve impact strength one should add an elasto-
mer; to induce flame retardancy a non-inflammable polymer should be used; to
improve modulus a stiff polymeric modifier should be incorporated, etc.
As is evident from Table 9.1, for each property there are several modifiers to select
from. The selection from between the possible candidates is based on the principle of
the compensation of properties. The selected polymers should compensate for defi-
ciencies of one polymer by advantages of the other, and vice versa. For example, in
Table 9.2 the disadvantages of PPE (processability and impact strength) are compen-
sated by advantageous ~perties of either PA or HIPS. Owing to PPE/PS misci-
bility/ the original Noryl was formulated around the PPE/HIPS pair. Only the
more recent reactive methods of compatibilization made it possible to develop the
second generation NorylTM GTX (based on PA/PPE pair).
Table 9.2 also lists advantageous and disadvantageous properties of other resins,
such as PC, ABS or ASA and PET or PBT. The best blends are obtained when
advantageous properties of one polymer compensate for the disadvantageous
Table 9.1 How to modify polymer properties by blending
Property Matrix Modifier

Impact strength PVC, PP, PE, PC, ABS, ASA, SBS, SAN, SMA,
PA, PPE, PEST MBA, HIPS, EPR, EPDM, PO
HDT, stiffness PC,PA, PEST, PEl, PPE
ABS/SAN PC,PSO
Flame retardancy ABS,PMMA PVC,CPE
PA,PC aromatic PA, PSO/ siloxanes,
phosphazenes
Chemical!solvent resistance PC, PA, PPE PEST, siloxanes, polyphosphates
Barrier properties PO PA, EVOH, PVDC
Processability PPE Styrenics (SBS, ABS, etc.)
Eng. resins LCP, TPU
PET, PA, PC PO, PBR, MBS, EVOH
PVC CPE, acrylics
PSO PA
PO PTFE; siloxanes
Table 9.2 Compensation of properties

Polymer Disadvantage Advantage Commercial Blend Advantage Disadvantage Polymer
1 2
PPE Processability HOT Noryl, Processability HOT HIPS

Impact Modulus Lauranyl Impact
strength Flame Xyron strength
retardance Arilocs etc.
PPE Processability HOT Ultranyl Processability Water PA
Impact Modulus GTX etc. Impact absorption
strength Flame strength,
retardance Crystallinity
PC Stress LowT PC/ABS: Impact HOT ABS,
cracking toughness Bayblend, Triax; strength ASA
Chemical HOT PC/ASA: Weatherability
resistance Terblend, Geloy Processability
PC Stress LowT PC/PBT: Chemical LowT PBT,
cracking toughness Xenoy, R2, etc.; resistance toughness PET
Chemical HOT PC/PET: Crystallinity Processability
resistance Makroblend,
Defsan
properties or the other, as for PPE and HIPS, or PC and PBI. In the tabulated
examples, the compatibilization was either not necessary (PPE/HIPS) or it occurred
by controlled transesterification during compounding and forming (PC/PBT). How-
ever, for PPE blends with PA, compatibilization is required. Only when the reactive
modification of either PPE or PA was developed could blends of these polymers be
introduced. The central column in Table 9.2 provides examples of commercial blends
based on these systems.
In the third and final step, the method of compatibilization, compounding and
processing must be chosen. The whole procedure is schematically illustrated in
Figure 9.2. Since polymer blend performance depends not only on the ingredients'
properties and composition, but also on morphology, the principal goal of the third
stage is to achieve the desired morphology. The desired morphology must be
identified, recognizing its influence on the expected performance of the blend, and
considering the selected polymeric ingredients (e.g., those that determine the frac-
ture mechanism). Thus, the method of compatibilization must be proposed, the
method of compounding established, the molecular weight (rheology!) of the com-
ponents must be selected, stability of morphology verified, etc.
An ideal blend compounder should have: (1) uniform shear and elongational
stress field; (2) flexible control of temperature, pressure and residence time; (3)
capability for homogenization of liquids having widely different rheological propert-
ies; (4) efficient homogenization before onset of degradation; and (5) flexibility for
change of mixing parameters in a controllable manner. Unfortunately, although the
requirements are simple, designing a mixer to fulfill them is difficult.
Most of the patented work on blends was done using either an internal mixer or a
single-screw extruder (SSE). In standard configuration, an SSE is a poor mixer,
inadequate for preparation of blends with controlled morphology. The run-to-run
reproducibility of blends extruders may be poor and, due to presence of dead spaces,
an SSE should not be used for reactive blending. However, there are several designs
for mixing screws, profiled barrel elements, and add-on mixing devices that ame-
Developing commercial blends 121
How to Develop PAS
no
no
Select processing
methods
yes
Figure 9.2 Schematic representation of the steps to be taken when developing polymer alloys
and blends with a specified set of desired performance characteristics.
liorate the mixing capacity of an SSE. From the latter devices, RAPRA's cavity
transfer mixer (CTM) or the newly patented extensional flow mixer (EFM) should
be mentioned. The first of these is a sort of dynamic motionless mixer, where
material is transferred from the cavities in the barrel to those on the screw, enhancing
the distributive mixing. Since the flow is complex, comprising elements of shear and
extension, dispersive forces also are at work (Gale, 1980).
The extensional flow mixer (EFM) is also a motionless device, in which the
extensional forces are generated by the convergent and divergent flow profile. The
crossection of an EFM is shown in Figure 9.3. The device provides excellent mixing
for multicomponent polymer systems, i.e., for blends with components having
widely different viscosities, such as PE with UHMWPE, PP with high elasticity
EPR, PC with PTFE (Nguyen and Utracki, 1995; Utracki and Luciani, 1996; Luciani
and Utracki, 1996).
More expensive but easier to control is the twin-screw extruder (TSE). Owing to
modular design its, with many types of element fulfilling different functions, the TSE
can be optimized for specific tasks. The ratio of dispersive to distributive mixing can
be adjusted, and the width of the residence time can be controlled. As a result, the
blend quality and run-to-run reproducibility are satisfactory. Computer models have
been developed to predict variation of blend morphology along the screw length in
these machines (Utracki and Shi, 1992; Shi and Utracki, 1992, 1993; Shi et al., 1992;
Bordereau et al., 1992; Huneault et al., 1995a, 1995b).
The quality of the compounded blend affects processing and performance. Layer-
ing, poor weld lines in injection molded parts and skin-core extrudate structure with
low notched Izod impact strength, indicate poor blend quality. Compounding of
blends requires exacting control of process variables. It also creates new problems
apart from those encountered in standard operations. For example, mixing batches
to match specifications is a common practice in the plastics industry. At present, a
large number of alloys are prepared by reactive processing; attempting to blend two
1
4
5
6
7
Figure 9.3 Cross-section of the extensional flow mixer (EFM). Molten polymers enter from an
extruder through adapter plate 1. The melt is distributed by plate 3 to slits, located between the
cone and the mounting ring. Next, the melt enters the annular space inside the EFM body 5
where it is directed to the space limited by the upper (4) and lower (6) convergent-divergent
plates. There it flows from the rim towards the center, undergoing convergent and divergent
deformations before sorting out through the central passage in the plate 6 and the central bore
in the plate holder 7. The gap is adjusted by rotating plate 8.
batches of the same blends, but having different degrees of reactive compatibiliza-
tion, may lead to disaster. Even a small variation in the extent of reaction may make
them immiscible, resulting in poor impact strength, especially at weld lines. The
mixed lot may pass standard tests and still yield unacceptable products.
9.3 BLEND PERFORMANCE

Blends are mainly used as structural materials; hence, the mechanical properties,
especially the impact strength, stiffness and elongation, are of principal concern.
However, recently and more frequently, blends are being developed for functional
purposes. To illustrate blend performance, two aspects will be discussed - mechan-
ical properties and electrical conductivity.
9.3.1 Mechanical properties

For structural blends, the mechanical behavior, including the impact strength, is the
most important. Historically, blending technology was developed to improve the
latter properties in the early resins, namely toughening of PS, PVC, PMMA, PET, PA,
etc. With time, blending involved mixing several polymers, thus impact modification
has progressively encompassed compatibilization. Even today, many blends profit
from the simultaneous compatibilization and impact modification accomplished by
addition of a multicomponent modifier.
Blend performance 123
The structure-property relationships constitute an ocean of mostly uncharted
information with only a few islands of knowledge. The maximum toughening effect
of brittle polymers has been obtained dispersing ~ 10 vol % of a ductile resin with
domain diameter d ~ 0.1-1.0~. The lower value is for resins that fracture by shear-
banding, whereas the higher is for those that fracture by crazing-and-eracking (Riew,
1976; Bucknall, 1977; Bucknall et al., 1984). Phase cocontinuity provides the best
balance of properties, e.g., maximum ductility and high rigidity in the presence of
large deformability (or elongation). As in the case of impact strength, properties
depend on the thickness of the interpenetrating strands, thus the interface. For
maximization of barrier properties, a lamellar structure is desired. To create it, the
blend should comprise large but stable drops (d ~ 5-15~) that easily deform into
lamellae during the forming step, as in blow molding.
Two types of mechanical behavior are important: at low rates of deformation
(tensile, compressive or bending), and at high speed impact. Poor compatibilization
affects both. For example, in tensile tests the maximum strain at break (or the
maximum elongation) and the yield stress (or the maximum strength) can be dra-
matically decreased by poor adhesion between domains. Similarly, this lack of
adhesion is responsible for low values of impact strength - the specimens are brittle.
Several toughening mechanisms have been proposed: enhanced (or multiple)
crazing and cracking, particle debonding, elastic deformation of the toughening
particles and cavitation. Under the triaxial stresses in the region ahead of the sharp
crack, a particle may cavitate at a certain strain, changing the stress field of the matrix
from the dilatation to the distortion dominated. Thus, the matrix may deform plas-
tically, consuming energy. In many systems the cavitation mechanism dominates. It
has been observed that the mechanism depends on two principal parameters: the size
of the dispersed toughening particles and the inherent plastic deformation capability
of the matrix (Yee, 1977, 1985; Borggreve et al., 1988; Borggreve and Gaymans, 1989;
Ramsteiner and Heckmann, 1985; Lazzeri and Bucknall, 1993; Cruz and Havriliak,
1995; Vee and Shi, 1995; Groeninckx et al., 1995). In polycarbonate, cavitation occurs
well before shear yielding takes place (Parker et al., 1992).
Polymeric systems are classified as either brittle or pseudoductile. The first type
tends to fail by the crazing mechanism, and it has low crack initiation as well as
propagation energy. Typical examples are PS, PMMA and SAN. The second type
tends to fail by yielding or shear-banding, has high crack initiation energy, and low
crack propagation energy. Typical examples are PA, PEST and Pc. As usual, there
are some polymers, such as POM and PVC, that show intermediate behaviors. The
transition from brittle to ductile mode of fracture depends on the intrinsic properties
of the material and external variables such as geometry, temperature, loading mode
and rate, etc.
For the set of data where the external variables are kept constant, Wu (1985, 1990)
postulated that toughness of the neat amorphous polymers, the craze-or-yield (or
brittle/ductile) behavior, is controlled by two intrinsic molecular parameters,
namely the entanglement density Ve and the chain stiffness expressed by the char-
acteristic chain ratio, Coo:
V e == Pa/Me = pRT /G'N
Coo == lim [(~)/n/21
,,~oo
= N,,/3 (9.1)
so that Ve = Pa/[3M"C~1
where Pa is the density, Me = pRT/G'N is the entanglement molecular weight (in-
versely proportional to plateau modulus), (~) is mean square end-to-end distance, n
is the number of statistical skeletal segments, each with [2 mean-square length, N" is
the number of statistical units, and M" is the average molecular weight of statistical
segment. Since crazing involves chain scission, the crazing stress U z should be pro-
portional to v~/2 and the yield stress should be proportional to Coo. In consequence,
uzlu y ex v~/2 ICoo
(9.2)
therefore uz/uy ex (Pa/3M,,)1/2C~2; or ex (3M"IPa)1/2 I1e
In Figure 9.4, the values of Coo are plotted against lie for 30 common polymers. The
polymers located left and up from the cross with coordinates (0.15, 7.5) tend to be
brittle, whereas the others are ductile. The slope of the least-squares line is s ::::: -0.4,
instead of -0.5 predicted by Equation 9.2. The approach formulated for glasses
seems to be applicable to semicrystalline polymers as well.
The formalism presented above for single-phase polymers is also helpful for their
impact modification and blending. It is a common practice to toughen brittle resins
by addition of elastomeric particles. The effectiveness of the process depends on the
diameter of the elastomeric particles and on their concentration. It has been found
that at constant concentration of the toughening agent its effectiveness (i.e., the plot
of toughness versus particle diameter) follows a bell-shape curve, defining the
optimum particle diameter. As shown in Figure 9.5, the optimum does not change
with concentration. The optimum particle size dopt was found to depend on the
entanglement density of the matrix resin (Figure 9.5). However, the dependence can
be used only as a general guide. Both the fracturing and toughening mechanisms
change from one resin to the next. Determination of dopt is also ambiguous, owing to
the polydispersity of sizes as well as to the presence of other macromolecular chains.
For example, it has been accepted that to toughen PS into HIPS, the optimum
diameter is defined as a diameter of the elastomeric particles expanded by occlusion
of the PS matrix. In PVC, the diameter of the elastomer was defined as the diameter
Chain stiffness versus entanglement

density (Wu. 1990)
•... ... ...
MO = 3.5215
Ml = -0.37818
100 L....:R--=----=----=.;0.~9.:..11:....:4.=.3 ..L_ ...J
-1
10-3 10
Figure 9.4 Plot of Coo versus lie for 30 common polymers. The cross indicates the limiting
position - points left and up from it represent brittle polymers, those right and down the ductile
ones (Wu, 1990).
Blend performance 125
Izad Impact Strength of PVC/MBS Blend
150 .----,.---..-----..,..----.---...,
-6-15 phr
-a--10 phr
0.2 0.4
Elastomer particle size in MBS (11m)
Figure 9.5 Izod impact strength at room temperature as a function of diameter of elastomeric
particles in methylmethacrylate-butadiene-styrene copolymer used for toughening poly-
vinylchloride resin (adaption from Bertelo and Mori, 1994).
of the original butadiene latex before grafting it with styrene and methylrnethacry-
late. In PC, the optimum diameter was defined from the point of view of availability
of the core-shell toughening agent. It is becoming increasingly difficult to find
tougheners with elastomeric particles having a diameter less than 100 nm. Further-
more, the strategy of preparation of polymer blends with stable morphology
demands that blends have a thick interphase, tll :S 60 nm. Frequently it is impossible
to decide how far the toughening by rubber core extends into the interphase. Many
impact-resistant engineering resin blends have been formulated using a core-shell
multicomponent with a rigid core and elastomeric shell whose thickness and affinity
to the matrix resin can be adjusted.
By contrast with brittle resins, where dopt is independent of concentration, in
pseudoductile ones these two variables are interrelated - when the concentration
of the toughening agent decreases the elastomeric particle size must be reduced. In
other words, in the latter systems it is the distance between the elastomeric particles
that controls the fracture mechanism. Again, there are resins showing intermediate
behavior between these two types.
The above discussion focused on the addition of discrete elastomeric particles.
However, there have been reports that formation of cocontinuous structures of either
a brittle or a pseudo-ductile resin with an elastomeric one can produce a quantum
jump in toughness, without greatly affecting the key engineering properties of the
high performance resin. Commercial blends of this type, e.g., of polyoxymethylene,
polyamides, polycarbonate or polyesters, are available. Blends formulated with a
relatively large content of two engineering resins may require toughening of both
phases. Usually this has been done using a sequential reactive blending.
Recently the impact-toughening mechanism in PPE/HIPS alloys (where the elas-
tomeric particles of HIPS were responsible for toughening) was investigated, con-
sidering the characteristic ratio Coo and the rubber particle size d (Okamoto, Y. et al.,
1993). Since PPE and PS are miscible, the values of Coo for the blends were calculated
from an arithmetic mean of composition. It was found that for HIPS having the
elastomeric particles with diameter 0.2 J.1lll, NIRT was relatively high, decreasing
with increasing Coo values, i.e., with increasing PS content. For HIPS haVing a
diameter of 4.9j1ffi, NIRT was low, slowly increasing with PS content. The different
impact behavior was related to the different fracture mechanism in the presence of
smaller and larger elastomeric particles. Shear yielding was enhanced when the Coo
value of the matrix polymer was relatively low and the rubber particles were small.
Large elastomeric particles rarely introduced yielding - in consequence the material
fractured by unstable crazing-and-eracking. The data indicate that the mechanism of
impact energy absorption is governed by two factors, Coo and d.
Polystyrene/polyalkene, PS/PO, blends were compatibilized by addition of
hydrogenated styrene-butadiene block copolymers (SEBS) having different molecu-
lar weights and structures (Appleby et al., 1994). The impact properties of 1:1 PS/PO
blends have been studied to establish the structure-property relationships. The most
effective compatibilizer was found to be a low molecular weight triblock SEBS,
Kraton™ G1652. Addition of only 5wt% of this copolymer to a PP:PS = 1:1 blend
resulted in a threefold increase of the impact strength, while the same amount added
to a LDPE:PS = 1:1 blend resulted in alloys having an impact strength similar to that
of HIPS. Kraton™ G1652 was found to be as effective as a high-molecular-weight
tapered diblock copolymer, and substantially more effective than either a low-
molecular-weight diblock or a high-molecular-weight triblock copolymer.
9.3.2 Electrically conductive blends

Polymer blends have often been used as electrical insulating materials. However, in
some applications, owing to the accumulation of surface charge that may discharge
rapidly and cause damage to electronic components, cause fires or explosions, too
much insulation may create problems. A need has existed for electrostatic dissipat-
ing polymeric compositions (ESD). These materials must have sufficient resistivity to
cause slow dissipation of static charge, but not too low as to allow the charge to move
too quickly through the material. A surface resistivity of lOS ::; R ::; 1012 n em is
considered desirable.
Several methods have been tried to develop ESD, namely to coat an electrostatic
dissipative material onto plastic, add solid conductive particles, incorporate organic
semiconducting materials or other low-molecular-weight antistatic agents, etc. How-
ever, coating can easily be wiped off, additives are expensive, make processing
difficult and often lower the mechanical performance, while the low-MW additives
must migrate to the surface and pose similar problems as coatings.
These problems can be minimized by addition of an antistatic agent that becomes a
part of the general formulation of the polymer blend. In 1968, Asahi Chemical
Industries disclosed PO blends with polyvinyl alcohol, 2 wt % PVAI. In this case,
incorporation of PVAl into polyethylene resulted in materials that showed good
mechanical, hygroscopic and antistatic properties. The blends were suitable for the
manufacture of films, fibers, tubes and coatings (Minekawa et al., 1969). Obviously
PVAI, that played the role of an ESD agent, did not require compatibilization.
In 1987, Borg-Warner Chemicals applied for world-wide protection for three-
component blends comprising a styrenic resin ID-96 wt %, an epihalohydrin
copolymer and a sufficient amount of a compatibilizing acrylate (co)polymer. The
styrenic resin that had to provide impact strength and hardness was selected from
ABS, HIPS, MBS, SAN, SMA, PS/PPE blends, etc. For example, 55-90wt% ABS
was blended with ethylene oxide-epich1orohydrin copolymer, 5-25wt% EO-CHR
and 5-25wt% polymethylmethacrylate. The blends showed good antistatic proper-
ties with rapid dissipation of static electrical charges, reduced delamination and
good ductility (Gaggar et al., 1988, 1989, 1993).
Outline of polymer alloys and blends evolution 127
Five years later, General Electric disclosed similar blends comprising styrenic
(co)polymer, 4O-96wt% PS, with an epihalohydrin-oxirane copolymer, 2-SOwt%
ED-CHR and 2-50 wt % of a polyalkylenelactone, selected from alkylenelactone
(co)polymers with ~ 50wt% acrylate. For example, blends containing 55-92wt%
PS, 5-25wt% ED-CHR and 3-25wt% polycaprolactone (PCL) were used to mold
parts having excellent static dissipative properties and good tensile elongation (Giles
and Vilasagar, 1994).
As these examples indicate, to obtain ESD performance it is desirable to incorp-
orate a sufficient concentration of -DH groups by blending the principal resin or
polymer blend with polymers haVing these groups, e.g., PVAI, ED-CHR, polyvinyl
phenol (PVPh) Phenoxy, etc.
In addition to the ESD formulations, blends with high electrical conductivity
(comparable to those of Cu or Ag) are being developed (some of these formulations
may also be used as ESD materials). The term electrically conductive polymer (ECP)
is used to mean a resin capable of electrical conductivity, regardless of whether it is
intrinsically electrically conductive or has been rendered conductive by doping. ECP
is expected to be used as a replacement for metallic conductors and semiconductors
in such applications as batteries, photoelectric components, printed-eircuit boards,
antistatic packaging and electromagnetic interference suppression materials. Their
potential advantages are light weight, mechanical properties, stability in corrosive
environments and lower costs in preparation and processing.
ECPs have been studied since the 1970s. Blends of ECP with thermoplastics have
been known since the early 1980s. For example, polyacetylene was polymerized into
PE film impregnated with a catalyst (Galvin and Wnek, 1982). Similarly, using
electrochemical methods, polypyrrole (PPy) can be polymerized in a resin matrix,
thus providing an electrically conducting material with improved mechanical prop-
erties over those of pure PPy (Lindsey and Street, 1985). There are several excellent
reviews on the topic (Cao et al., 1992; Yang et al., 1993). During the last decade there
has been intensive activity to transform the ECPs from laboratories into commercial
production. Electrically conductive polymer blends are discussed with specialty
polymer blends.
9.4 OUTLINE OF POLYMER ALLOYS AND BLENDS EVOLUTION

Since time immemorial, mixing has been the preferred method for widening the
range of materials' performance. No sooner do two materials become available than
someone starts experimenting with them. This is evident in the history of any type of
material, including polymer blends. For example, when in 1846 only natural rubber
(NR) and gutta-percha (GP) were available, these were blended. Once nitrocellulose
(NC) was invented, it was mixed with NR. Blends of NC with NR were patented in
1865, 3 years before commercialization of NC. Then, cellulose acetate became avail-
able and was soon blended with NC. Furthermore, comparing dates of commercial-
ization of new polymers (Table 2.1) and their incorporation into blends (Table 9.3),
one notices the surprising closeness of these events. Polyvinylchloride was commer-
cialized in 1931 and its blends with nitrile rubber (NBR) were patented in 1936, 2
years after the NBR patent was issued.
Some polymers require less modification than others. To the first category belong
the semi-erystalline polymers - since they already possess two phases an additional
modification is less urgent. To the second category belong the amorphous resins,
such as PVC, PS, PC, PPE, etc. These resins are brittle; hence, to improve their
ductility and impact strength, they have been more frequently blended. Rubber
Table 9.3 Historical milestones for polymer blends
Year Blend type

Commodity Engineering Specialty
1846 NR/GP
1865 NC/NR
1902 NC/CA
1910 NR/PF as IPN
1911 Solution grafted SBR
1925 HIPS (solution grafting)
1928 CA/PVAc; PVC/PVAc
(latex blending)
1929 PMA/PVAc
1934 Nitrile rubber, NBR
1936 PVC/PMA; AB5-type A
(mechanical blend)
1937 PO/Rubber (two-roll
mill blending)
1938 PVC/NBR
1939 PVAl/VC-MA
1941 PVC/CR (Neoprene)
1948 PVAc/PVA; PVC/TM PA-66/PVAc/MA
1950 AB5-type G(grafted) PVC/NBR/P-amine
1951 PVC/ABS; PVDC/NBR/CR
1953 PA/PEG
1956 PVC/MBS, CPE or TPU;
PVC/SAN/ABS;
PS/PB/SBR
1957 PVC/PE or CSR
1958 PE/PE; PP/PIB; PE/PP or PA/PO (PA-6 or PA-66 PCTFE/PVDF
PSIB; LLOPE/PIB or LOPE with PE or PP); PA/PA
1959 PVC/EVAc, CA or TPU PA/PVC
1960 PVC/PMMA or COPO; PP/ PPE/PS; PET/PBT;
EPR or EVAc; LLOPE/PC; PC/PO; PC/ABS;
PE/PE-PA;AMMA/SBR/ PA/PVAI
NBR
1961 PE/EPOM or SAN; PE/PP/ PAlABS; PC/POMS
EPR; PP/LLOPE
1962 PVDC/EVAc; PP/EPR PET/PMP
1963 PP/sPP; PE/EPOM/PB; PA/PMMA-Ac, or
PVC/PE/MBS; lonomer;
LOPE or PP/POM
1964 PE/lonomer; PVC/APC Phenoxy /EEA; PBT/PAr; PSF/ABS
PPE/PE
1965 PS/PPE;PP/PPG;CPE/ABS POM/PVAc; POM/ PAES/PC;
POM; PET/PE, or PAE/Phenoxy
lonomer PU/MPS;
PA/EMAc
Table 9.3 Continued
1966 PMMA/PVDF; PP/ aPP; PC/PET; PA/EVAI; PAES/PO

PVC/SBR-BA
1967 PVC/MABS, C-SBR or C- PET/EMM, EVAc, or PTFE/PHFP;
EPDM; PP/SBS; PEA; POM/PA; POM/ FPM/FEP;
PVDC/PU; ABS/EVA; PEG/PTHF; PA/PVP; PAES/AES
PPE/PS/PB
1968 PVC/PTHF/SAN; PVC/MM- PET/PA-6; PA/EVP; PA/PARA;
SB; PO/PVAI; PO/EVAc/ PET/ ABS/PDMS; PAl PAES/PAE-
POM, PP/PVC/PMMA or POM/PET; PC/POM; siloxane
PC; CA/PP/PMMA PPE/SAN; PPE/PS/
Elastom.; PBT or
PET/PB
1969 PVC/PVAc/Acryl; MMVAc/ PC/PAES/MBS or ABS; PSF/MBR;
MMEA; PP/EVAc/EVAc- PA/Acrylic; PBT/ PSF/EPRor
VC/PE; ABS/SMA; SIS/PS; EVAc-AA; POM/TPU; SBR;
PMMA/SAN PET/PC;PC/PSF/ PAES/
ABS; PPE/SBR or MBS EVAc;
PAES/MBS
orABS
1970 PS/PB/SBR; ABS/PES/PC; PPE/HIPS, (SB)n, FKM or PES/PA or PO
PP/SEBS Phenoxy; PET/Phenoxy;
POM/PE, EVAc or
PEG
1971 PVC/PET/PBG;PVC/COPO; PC/PMMA/ABS;PC/ PAr/ABS, PO,
PP/PS or HIPS Acryl; PPE/PA; PBT/ PC, PET,
PC; PBT/PET or PHI; EVAc or
acrylic
rubber;
PAr/PC/
PET
1972 LLDPE/aPP;PP/CSR PPE/PBT or PS-PE; PPE/ PAES/CHR;
EPR/PMMA;PBT/ PAES/MMS
PC/MBS; PC/MMBA;
PET/PE-COOH; PAl
PP/PP-MA;POM/PPE
orPSF
1973 ABS/PCL;PE/PP/PDMS PA-610/PVDF; PC/
ETFE; PPE/PS/SEP;
PPE/SEBS; PC/PA;
PPE/PC/SBR;
PPE/EPR or PIB
1974 PVC/PC/ABS; SB/PE or PP PBT/PO, PCL or Acry!.; PPS/PC;
PC/PA/PSF, PPE or PPS/PS
PET; PC/PCL or
EVAc; PC/PE/PTFE;
POM/SAN or PARA;
PA/ Phenoxy;
Table 9.3 Continued
Year Blend type

Commodity Engineering Specialty
1975 PE/PS; PVC/POM PA/m-EPDM; PBT/TPU; PPS/PSF;
PA/EEA, or EVAc; PPS/PPE
PBT/ Acryl-siloxane
1976 Suuch/PVAl;PVC/CPE/ PBT/TPU/PC;PC/PS; PI/PPS; PPS/
MMBA; PVC/PCN; PA/PO-MA or NBR; PAr; PAri
PU/m-ABS SEBS/PE, PA, PBT, PET/PA or
PES, POM, TPU:PMP, PPS;PAr/
or fluoro polyrn.; Ionomer
1977 LLDPE/LLDPE; ABS/SBR- PC/PE/SEB5-CSR; PC/ PSF/PC;
MA; LDPE/HDPE/aPP or PET/MBS; PC/PA/ PSF/PA;
EPDM SEBS; PBT/SEBS/ABS; SMI/PC;
PET/PBT/ Acrylics; PAr/PH-
PA/PA-eopol./TPU; SMA
PPE/PBT/SBS
1978 PVC/PECO; PS/PP/SEBS; PC/PBT/PEC;PBT/PC- PET/LCP;
PpMS/PE; ABS/TPU PDMS; PC/PET/SAN; PAr/EPDM;
PET/mPEG;PA/EPR/ PAI/PA,
EPR-MA; PA/SMA; PARA or
PC/PBT/PET/SEBS; PSF;PAr/
PPE/PS-PDMS PET or PBT
1979 R-TPO; PpMS/SBS; TPU/ PBT/EPR/ Ionomer; PAr/ PAl/PEl; PGI/
Ionomer; EVAl/EVAc PET/MBA or Phenoxy; ABSM/PC;
PC/PARA;PC/SBCL; LCP/Eng.
PPE/PA/SBR; PA/ Polymers;
PE/Ionomer; PAl PEC/PDMS,
CTBN;PBT/PET/PC/ or PTFE;
MBS; PC/SMA/ABS; PEC/PSF;
PET/EGMA PAr/PEl or
PCT;Co-
PI/CO-PAl
1980 ABM/PA; PVC/PI/MBS; PBT/PC/MBA or LCP/PC or
PVC/PS/C-SBR; SMA/ EGMA; PA/SBMA; PET; PEA/
PCN; PS/PP/SBR; PMMA/ PA/SMA/PPE;PPE/ SBA;PAI/
SAN; EPR/EVAc SBMI;PPE/PPS;PPE/ PE;PAr/
PPE-S/SBR; PET/ PPS;PPS/
SMA, SAA or Ionomer; PAS/SBR;
PC/ASA; TPU/SMI; LCP/PPS;
Phenoxy /PEG; PARA/PPS
POM/PA/PEG;
1981 CPVC/SMA; PC/SMA/PCL; PPA/PE; PSF/
EVAl/NBR; POM/PEG/PA; PEl;
SMI/ABS/SAN; PC/LLDPE/ABS; PPS/PEEK;
PVC/PVP or COPO; PPE/ABS/PA/SMA; PSF/PEA;
AAS/EGMA PARA/PE; PEA/PET
PET/PC/PCT; orPA;
Table 9.3 Continued
PBT/POM or PA PAr/PMBor
PA; PPBA/PES;
PEe/pc, PEI,
PA, PI or PAl
1982 PP/CPE; PA/PU; PEI/PC, PBT,
PE/PEOX; PBT/PAr; PA, PP or
PVC/EV Ac-CO/MBS PC/PET/EPR; PAr, or
PPE/EGMA; MBS/ABS,
PPE/ABS, SMA or EPDM,
SEBS; PAr/PS/
PET/PAr/PA PAr-PS;
PET or PBT/PAr; PEA/PI;
PET/EVAl/TPU/ PSF/PTFE;
Ionomer PPS/EGMA
orPTFE;
PAE/ABS/
Phenoxy;
1983 PVC/PBT-L PA/PET; PEI/PTFE;
PBT/ Phenoxy; PPS/SEBS;
PEBA/PBT/EVA; PEA/PBT
PEBA/PA/ Elastom.
1984 ASA/PMMA/PC; POM/EPR; POM/MBS; PAl/PEEK;
PVC/PC-PSF PPE/PS/PTO; PARA/PES;
PPE/PTO/PA PES/PEEK;
PPS/PA;
PPS/EPDM;
PEI/PET/
PEC
1985 ASA/PC; PP/PTO PPE/PS/PEC/PAr; PEEK/PEI/
POM/PEEK/PEI; PES;PPS/
PPE/SBS-MA/PA or PDMS/PE;
PET; PC/PVDF PES/EEA-
MA;PSF/
PPS/PPS-
PSF
1986 PC/PDMS/SEBS; PAEK or
mPPE/mPP; PAl PAE/LCP,
PEST/Phenoxy; PC/ PI, PAES or
PMMA; PPE/LCP, PI, PEST
PAES or PEST;
PA/ABS-MA
1987 PP/POD PA/PBT; PAr/PBI; PPE/ PI/PAI/ PPS/
PVDF/P(SMMA)/ PEI, PPE,
SEBS;PPE/PBT/PC/ PES or PSF;
SEBS PBI/PAr;
PEl/PC;
PEI/mPPE;
PEKS/PES
Table 9.3 Continued
Year Blend type

Commodity Engineering Speciality
1988 COPO/PVDF/EPR; PC/PA/PEA;PPE/PPS/ PEEK/PAl;
PO/POCA/ECMA SGMA; PPE/PP; PPS/PARA;
PA/PAr/PA-eo-PAr LCPs/
Phenoxy;
PPS/PPE/
SGMA
1989 PA/PPS/PSGMA;PC/ PARA/PO;
TPU; PC/POM/TPU; PPSS/PA;
PC/ABS/ASA; POM/ PPS, PES,
PP;PPE/PP/PPS/ PPSSor
SEPS; PKS/PA or
PARA
1990 CPVC/PC/mEPDM; EVAl/ POM/TPU/PEST, PE or PES/PTFE or
HBV; PE/Starch; PVC/PCI; PA; PA/PES; PEA/ Phenoxy;
PP/EVAI PPE;PC/COPO/PET/ PPS/PBT;
SEBS; POM/PVPH; PEl/PES or
PC/PAr/LCP; POM/ PAE;PPSS/
EVAl/PTFE PA or PEST;
LCP/PBTor
PEl; PPS/
PDMS;
PHZ/PVPH
1991 PP/LCP;PLA/PEC;PPCA/ PC/PEC; PC/PARS; PBI/PARA;
EPDM; COPO/TPU; PMP/ Inorg. LT-glass/Eng. PAr/PARA;
PPS; COPO/PA/SEBS-MA Polym.; PC/PA/PEI/ PPS/PC/
EPR-MA; POM/PVDF; PPE/ABS/
PET/PP SMA; LCP/
PEK; PSF/
PET;PEKs/
PAr; PEEl/
PA
1992 Starch-MA/PO/EMMA PC/PARA LCP/PPS
1993 PP/LLDPE-LMW/LLDPE PA/PVPh-PS/PPE/PS LCP/PAI;
FEP/PFA/
PTFE
blending predates that of thermoplastics by nearly a century. Thus, the 'father' of the
polymer blend industry is Alexander Parkes (an Artist by his own description,
Figure 9.6), who mixed two isomers of polyisoprene, amorphous cis natural rubber
and semicrystalline trans gutta-percha. Owing to the different stiffness of the two
isomers and their relative miscibility, this immediately offered a range of materials
with different performance. The blend solution was used for waterproofing 'leather,
silk or other textures: Furthermore, the two polyisoprenes were softened in sulfur-
containing C~ + SCh solution, then masticated on rollers or in a kneading machine,
which generated a chemical reaction resulting in lightly co-vulcanized polyiso-
A.D. I!Wj N" 11,I4i.
Treating Caoutchouc and Gutta Percha.
PARKES' SPECIFICATION AI'D DISCLAIMER.
TO .iLL TO WHO. TlIllSE PlLESE1M'S 81U.LL con I. ALUA••EI

PAUn. of Birmingham, Artist. aeod greeting.
Wll£1t.IaS Uer proseDt lDost Excellent Majesty Queen Victorio, by Her
Roy.1 Letters P , under the G.... Se.l or Great Britai•• beariog dale at
$ W..tmi.. ler. tile T ty-orth day or M.",b, io tbe ointlr year or H.. roip.
did, (or Herself, Her heirs and succeuors., gi". and ,nat unto me, tlte
-.id Alexander Pukes. Her .peeial licence. full power, sole priYiI~ ad
,authority. that J. the said Atexander Parkes., m1 eio Milo aad uaigas.
onoob oth... Ill. the aaid AIuu<Ier P.rI.... my .i adill or UIipo,
lO IboaId at any dme 'I1W will>, and DO otbers, f""" dme to dme and at all
d_ dori., tile term or j ' ' ' ' theroio ezpresaed. ab..lcI and ..wfuO, might
make. .... ue",ise, aDd vend. withio Engl.od, Wales, and tile To"" or
.Benrick-upoo-'r,,'eed. my IayeatiOD 01 .. b,IOYlIIUTI U ru Puuu,1'tQ or
eA1:WI VnftdU .t.n .A.auIu 8vwu..cu. UD 0 CDTAD' CoaiDj,flOU or f'D
U .... Soaat....ca &loOn 01 .tTI: O!U& Stmt&ftU;" ita which'lAid Leuen
Patent is contained a proviso. that J. the said AI.uoder Parkes. shall Quae
a pllrtic:ular deseril)tion of the nature of my said Ia..,tion. and in .hal
mauDer the Ame is to be I~rformed. to be inrolled in Her said ~1ajtsty'.
High Court or Ch;ulcer1 within six t'tllent1ar months next and ilnmedia~11
gO after the dale of the sa.id in l'tlrt recitel! letlel'$ Pattnt. 1\5 in and by the $,'\!liC.
~ference being thereuoto hart. will mflte fnll~ :m" at 1.,.. appear.
j;~~~
Figure 9.6 Alexander Parkes' Patent
prenes. The blends were also combined with fillers and molded into a variety of
articles, or vulcanized (as Parkes stated in his patent 'by methods similar to those
granted in an earlier patent to Thomas Hancock'), to be used for production of rigid
moldings (Parkes, 1846).
The first synthetic polymer was phenol-formaldehyde (PF). Among the
119 patents granted to Leo Baekeland for PF compositions, most dealt with modifica-
tions by mixing with solids or blending with liquids. In 1910, Jonas W. Aylsworth
(who for years was chief chemist in Thomas Edison's laboratory) set up his own
company to produce PF resins, under the name Condensite. These materials were
based in part on a license from Leo Baekeland and in part on Aylsworth's own 21
patents. One of these, deposited in 1910 and granted in 1914 (Figure 9.7), described a
'material obtained by simultaneous vulcanization of natural rubber and con-
densation of the phenol with formaldehyde', making it the first disclosure of a
simultaneous interpenetrating polymer network (SIN) (Aylsworth, 1914;
Sperling, 1987).
Many early blends were prepared from natural elastomers. In the beginning of the
20th century the thermoset resins and their mixtures dominated. However, this book
UNI'l'ED STATES PATENT OFFICE.
1000Aa .... .A.Tr,awOI.'J'll, o.....ft e1&Jfo., . 8 . J'UUT. ASSIONO.. TO COIfDJUlSl'U
OOID.urT or .IJO:II.IO.&. or ....f t OU"O" Jl'SW ~IT.... C:OB.OIIAT10:r 0. . . . . .
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fillc!n III1ed in the art. Jt. has •
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as r"Illidl, u tho welllmn\\'n ,....ietiu. and .. 11\
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~:r~~~, l~:~: t~~~:II~n~~~;tl~t.Jl)i~~~~
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milS t,cl r"nm rind become pan'lll&- B, &hill Iii
IIlfllH'O(l tilt" mUll rna)' n,nro rt:IlJilv .>ti lat.....
trll,IMt! tn lb, Ilcsirefl IM,lwdf't'ed' (lima for
in<1tl'!",ontiou willi lhe I'llld.lf.... 0, thl! 1'!f)Il'
drnl:lti"o pnxlllf't mill be III'tp:U1!tl by (lther
If\t"thod. kIlO'"1 ill the t1tL to
I prer~r to -:nml,leUlJ hn ...lftl !.he eon-
tlf'Mation product &on infut>ihilitT entl iQ-
tnIulJility befrore in~rl'nratiOTl "'iih the nIb-
~~':;II~'tt~!tr":lIin4g;;\~e~~~1;"::·F~ ..
runo,'. lilly free' ('Ihtnlll, moisture, nrllmnnifl.,
01' f\tIMr \nh\liIe 1l1l1!'C:I!lrO whieh 1H'l nillY in
~I~,:\~~'~:::~r i~'l~:~~ l~:~~infr ~t:~ 1:I~i::~ ~~
ill :l \':ICUllnt, • 11"\'~1' ll'lnperllllll'l! "ball "hut 100
IlIlLe.lll\)f."t<is""Ricir.ul.
TM IUll'dtmcd C\ln,It:Ub"ivn pt'(l(hld In:t.y
Figure 9.7 J. W. Aylsworth's patent.
focuses on thermoplastic polymer blends, thus the historical developments in the

fields of rubbers and thermosets will be very brief. Some of these blends were
already described in Part One.
In the following text, the historical evolution of blend technology is discussed in
the order of commercialization within a specific polymer category. The following
three categories have been used:
• commodity resins (styrenics, PVC, acrylics, PEs, PP);

• engineering resins (PA, PEST, PC, POM, PPE);
• specialty resins (PSF, PAE, PARA, PAr, PPS, LCP, PEl, PEA, etc.).
The commodity resins are discussed in Part Three, the other resins in Part Four.
Many patented blends of a polymer A with polymer B, and vice-versa, contain only
a small, modifying quantity of the second component. For example, polycarbonate of
bisphenol-A (PC) has been toughened by addition of 7wt% of linear low density
polyethylene (LLDPE). On the opposite end of the concentration scale, stiffer grades
of LLDPE have been prepared by incorporating about 5wt% of Pc. Initially, when
planning this book, it was attempted to clearly distinguish these two blend types by
writing either AlB, or BI A, for the systems in which, respectively, A or B forms the
dispersed phase. However, this attempt was soon found impractical. There is a
Conclusions and outlook 135
growing tendency to ask for patent protection for blends within nearly the whole
(e.g., from 0.5 to 99.5wt%) concentration range. It would be illogical to discuss the
same patent under two different headings.
There is also a more pertinent reason for abandoning the systematic discussion of
AlB and BI A blends. Owing to synergism of the physical behavior at the phase
inversion concentration, many patents describe blends with phase cocontinuity. This
morphology can be achieved even when the concentration of the minor phase is
below 20 vol %. The phase cocontinuity can be generated by rheological means. This,
on the one hand, involves selecting ingredients with appropriate molecular weights,
that translates into desirable viscosity ratio and, on the other hand, selecting the
appropriate flow field. Phase cocontinuity can also be generated by the spinodal
decomposition mechanism evoked by judiciously varying a blend's temperature,
pressure, solvent concentration, or combining these effects. Since in this case both
ingredients play roles of the matrix and dispersed phase, they would equally well
belong to either AlB or BI A type of blend.
Thus, a pragmatic approach was adopted (with humble apologies to readers
with well-organized, logical minds): (1) the symbol AlB is used to identify
any mixture of polymer A with B, independently of the concentration range or
morphology, and (2) the AlB blends are discussed under the name of polymer
that was blended earlier. This means that blends of the engineering or specialty
polymers with commodity resins are mainly discussed in the category of commodity
resin blends, that blends of specialty polymers with engineering resins are
discussed in the category of engineering resins, and that in the part entitled
'specialty resin blends' only mixtures of two (or more) specialty resins are con-
sidered.
Table 9.3 provides a coded synopsis of key events in the history of commercial
polymer blends. Explanations for the code, a list of internationally accepted acro-
nyms of polymers, is presented in Appendix I. An abbreviated list of the commercial
blends available on the market is given in Appendix ll. In Appendix ill, the major
types of polymer blends are presented. Finally, in Appendix IV, there is a chron-
ological description of patented inventions in the domain of polymer blends
arranged by the date of invention, not of patent granting. In essence, the text
presented in Parts Three and Four of this book is an interpretation of the events
summarized in these tables and appendices.
9.5 CONCLUSIONS AND OUTLOOK

The global blends market is estimated at US$100 billion. EVidently, the plastics
industry has been quite successful in exploring this technology. Polymer blends
must provide a variety of performance characteristics. Usually it is not a single
performance criterion but a set of criteria that determines if the material is accepted
or not. For specific application more weight can be given to one or another material
property. The advantage of blending is to provide materials with the desired set of
performance parameters at the lowest cost.
As has been demonstrated, blending requires a wide spectrum of information,
from the thermodynamic principles of miscibility and compatibilization, to the
interphasial characteristics, morphology, rheology, processing and performance. It
is important to recognize the relationships between these elements. For example,
flow effects on the interfacial energy, miscibility, morphology, thus performance. It is
often forgotten that commercial blends are more often than not in a non-equilibrium
state. Product performance will depend on the selected forming method, the set of
processing conditions as well as annealing conditions. In many cases such a
variability is purposely incorporated into the blend formulation; in other cases, the
blends' manufacturer may attempt to provide well-stabilized alloys that can be
similarly processed as neat resins.
During the 160-year-Iong history of the rubber and plastics industry, blending has
been an intrinsic part of the technology. On the one hand, as the fundamental
knowledge of blending improves, and on the other hand the demand for higher
material's performance grows, the role of blending can only increase. New polymers,
such as syndiotactic polystyrene, are being introduced into the market, offering new
challenges for blending technology. The reactor blending of poly alkenes is getting
more sophisticated and preponderant, as in the reactor blending of Ziegler-Natta
and metallocene-type polyethylenes. The high performance resins require blending
for improved processability. The blends are getting increasingly complex, compris-
ing numerous ingredients, diverse polymers and reinforcing solids.
Computational methods are being developed in the science and technology of
polymer blends. Molecular dynamics provides a means of computation of the
specific interactions and miscibility (Coleman et ai., 1991) or the interfacial energy
in a polymer blend (Yao and Kamei, 1995). Commercial computer programs are
available for designing blends with specific sets of properties. A mathematical model
of reactive blending is being developed. It combines three subroutines for flow
mechanics inside an extruder, the kinetics of reactive compatibilization, and micro-
rheological description of the dispersed phase size evolution. With the exception of
the first, the other subroutines are in a preliminary stage. Integration of all three into
a single program will provide a proper tool for examination of diverse effects
imposed by varying the composition and flow profile on the compatibilization
efficiency.
Noting all the progress in the science and technology of polymer blends, one must
not forget the scope for future development. There is a lack of information in all
areas. For example, the microrheology of viscoelastic systems is virtually unex-
plored, as are the interphasial properties. Even the crucially important domain of
fracture mechanics in multiphase systems is in its infancy.
Part Three
Commodity Resin Blends
10
Styrenics: polystyrene and styrene
copolymers
The first modification of rubber by incorporation of polystyrene (PS) is credited to

Francis Edward Matthews, who during the years 1911-1913 (Figure 10.1) received
several international patents for the manufacture of lacquers and 'articles that are
normally made of hard rubber, celluloid, vulcanite, ebonite, glass, wood and similar
materials'. He further specified that 'expecting finer dispersion and better control',
100 parts of rubber were mixed with 50 parts of styrene, then the polymerization was
initiated to obtain either a thermoplastic blend or a vulcanizable rubber (Matthews,
1911, 1913).
Polys,m-ene was commercialized initially in 1915 by I. G. Farbenindustrie as
Trolitur . The material was clear, brittle, thermally unstable and had poor solvent
resistance. The early attempts to improve the impact properties of PS without loss of
transparency failed. As a result its production was temporarily suspended. The
company also tried to use styrene to improve and control rigidity of synthetic rubbers.
At that time, several other groups conducted research on styrene, its derivatives and
polymers. In Germany, Staudinger was interested not only in colloid chemistry, in the
use of polystyrene polymerization and qepolymerization 'as a model for natural
rubber' (Staudinger et al., 1929), but also in the technological aspects (Staudinger,
1926). During the 1920s and 1930s, numerous patents on PS technology were granted
to I. G. Farbenindustrie and Naugatuck Chemical Co. (in Naugatuck, CT).
After the First World War (WWI) I. G. Farbenindustrie received the first patent on
styrene rubber (Buna-S or SBR), and started its production in 1929. The company also
developed blends of PS with polyisobutylene (pm; MW > 100 kg/mol), and small
quantities of a lubricant and/or a plasticizer (I. G. Farbenindustrie, 1939). The
impact-modified PS was commercialized in 1946 by the Badische Anilin- und
Soda-Fabrik (BASF A.-G.) in Ludwigshafen (between 1925 and 1952 BASF was part
of the I. G. Farbenindustrie concern).
In the USA, grafting of styrene onto polybutadiene rubber to get what is known
today as high impact polystyrene (HIPS) began after wwn in Dow Chemical
laboratories in Midland, MI (Amos et al., 1954; Boyer, 1982).
The most recent commercial styrenic entry is syndiotactic, semicrystalline poly-
styrene (sPS), having a glass transition temperature of 100 °C, and a melting point of
260-270°C. In 1985, Idemitsu Kosan obtained a patent on the use of a single-site
metallocene catalyst for its production. The need for optimization and modification
of sPS performance led to several early patents from the company. Thus, to increase
the crystallization rate and the total crystallinity of sPS moldings, the company
140 Styrenics: polystyrene and styrene copolymers
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applied nucleation (Yamasaki et al., 1994) and/or annealing (Uchida et al., 1994). To
improve its toughness, the company developed four components of reinforced
blends comprising sPS, functionalized sPS, functionalized SEBS and filler. The
system showed remarkably improved impact resistance and elongation without
detriment to heat resistance and rigidity. These blends have been used for molding,
such as electric and electronic connectors and printed-circuit boards, industrial
construction materials, automobile parts (wheel caps and cylinder head covers),
domestic electrical appliances and various machine parts (Okada, 1994).
10.1 HIGH IMPACT POLYSTYRENE AND ITS BLENDS

In the early 1920s, several patents on polymerization of acrylics or vinyls were
granted to Ivan I. Ostromislensky, and assigned to Naugatuck Chemical Company.
High impact polystyrene and its blends 141
In 1925, he deposited the first patent on the manufacture of what is known today as
high impact polystyrene (HIPS) where he wrote that '1-10wt% of rubber, balata or
other elastic and plastic gum [should be] dissolved directly in substantially pure
styrol, the solution is then polymerized to tough meta styrol' ('styrol' and 'meta
styrol' mean, respectively, styrene and polystyrene). The patent described grafting in
bulle 'as the heating is continued the solution, which first resembles any rubber
solution in its transparency, gradually becomes cloudy and by the time polymeriza-
tion is complete, the solution has converted into white or whitish solid product'. In
the second example polymerization in xylene was described (at 135-140°C in 48h).
The reaction products gave opaque materials with a pearl-like color effect that
showed 'a decreased sensitivity to shock, greater moldability and flexibility,
enhanced machining, and nacreous color effects' (Ostromislensky, 1924, 1926, 1927,
1928). The Naugatuck Chemical Company commercialized PS but, after the 1929
stock market crash, production was discontinued.
Ostromislensky's discovery predated the accepted invention of HIPS at Dow
(Amos et al.'s patent of 1954) by 27 years. In 1942, Dow started manufacturing
Styralloy 22. The material was prepared through sequential emulsion polymerization
of styrene and butadiene, which led to an interpenetrated structure, E-IPN. In 1944,
Boyer polymerized styrene in the presence of rubber dissolved in it, providing an
impetus for development of the HIPS (Amos et al., 1954; Briggs and Price, 1963;
Boyer, 1982).
Polymerization of styrene in the presence of soluble elastomer led to modem
HIPS, comprising 94wt% PS and 6wt% of styrene-butadiene graft copolymer
(SBR), containing 3Owt% of styrene. For example, as described in the Montecatini
patent, 4 wt % PB was dissolved in styrene, then bulk was polymerized for 22 h at
80 0c. The reaction resulted in high impact strength, transparent HIPS (Natta et al.,
1958). In an ICI patent, both PB and NR were used (Lee, 1959). An application of 1961
from Koppers Company described preparation of HIPS using 16 parts of SBR dis-
solved in 84 parts of styrene. The solution was polymerized while mixing, using a
gear pump (Fryling, 1964). In a 1967 patent application from Zaklady Chemiczne
Oswiecim, it was disclosed that HIPS can be obtained by bulk polymerization of
styrene to 20% conversion, followed by addition of polybutadiene (6% in total)
dissolved in styrene and completing the reaction. The PB phase had drop diameters
in the range 2-10 J.tm (Mitoraj et al., 1970). However, a patent from the Japanese
polystyrene industry specified that, initially, if styrene is to be polymerized in bulk
in the presence of PB or SBR, then the reaction should be completed in emulsion
(Osuga et al., 1968).
HIPS technology continuously evolves. For example, in 1992, Sumitomo Chemical
Company announced a new HIPS having high gloss, impact strength and transpar-
ency. The resin was prepared by blending two different types of high impact poly-
styrenes and a methyl-phenyl silicone oil (added before polymerization!). Thus,
HIPS-I was prepared with 24 wt % of elastomeric particles by polymerizing SBS
dissolved in styrene, whereas HIPS-2 was obtained by polymerizing 13-16wt%
butadiene in styrene. The first resin had small core-shell type elastomeric particles
with diameter 0.1-Q.3Ilm, whereas the second had salami-type (or cell-type) elasto-
meric particles O.l-I.5llm in diameter. The preferred composition had the ratio of
HIPS-l to HIPS-2 within the range 95:5 to 98:2, and 0.05-0.2 wt % methyl-phenyl
silicone oil (Okamoto et al., 1993).
The same year, Mitsui Toatsu Chemicals disclosed another method for preparation
of HIPS. Polystyrene, 30-99wt% PS, was blended with 70-1 wt% SBR. The SBR was
prepared from styrene-butadiene block copolymer (25-50wt% styrene) mixed with
another SBR copolymer, polybutadiene (BR), giving a SBR/BR mixture that con-
tained 5-20 wt % styrene. The elastomeric particles had a volume-average diameter
of 0.2-o.81lffi. In these materials, the styrenic resin can be derived either from styrene,
a-methyl styrene, p-methyl styrene or their mixtures. The alloys showed excellent
processability. They were molded into large-size articles, with thin walls and com-
plex shapes, with high gloss and good impact strength. Examples of applications
included parts for domestic appliances and electronic equipment (Ando et al., 1993).
HIPS has been frequently used in blends with commodity and engineering resins,
such as PP, PPE, PC, PA, etc. To avoid repetition, these materials are discussed
together with other blends of these resins. Here, only those blends that can be
considered modifications of HIPS are summarized.
10.1.1 HIPS with EPR

One problem with HIPS toughened by the presence of polybutadiene, is its lack of
resistance to the weathering factors, UV and oxidation, precluding their outdoor
use. The photochemical degradation occurs when the macromolecules absorb UV
radiation with a wavelength of less than 350 nm. Since the C = C bond energy is
384kJ/mol, the energy of this wavelength suffices to split them. In several new
grades of HIPS, PB has been replaced by ethylene-prof~lene or ethylene-propy-
lene-diene elastomer (EPR or EPDM), e.g., in Hostyren XS from Hoechst. The
replacement resulted in improvement of weatherability, stress cracking and notched
impact strength. Depending on composition, the hardness, stiffness and the heat
distortion temperature (HOT) of these new materials may be somewhat lower. The
temperature dependence of the impact and notched impact strengths, the electrical
properties and chemical resistance may differ from those recorded for HIPS. Mold-
ings may have a matte surface.
10.1.2 HIPS with block copolymers

The triblock styrene-diene thermoplastic elastomers, Le., SB, SBS or SIS, were
announced and patented in 1965. Since then, they have been frequently used to
improve transparency and impact strength of HIPS. In a 1969 disclosure from
General Tire and Rubber Company, HIPS properties were enhanced by blending it
with styrene-butadiene block copolymers (Durst, 1970).
In 1980, several patents pertaining to these compositions were deposited. In the
BASF document, high performance, glossy, PS composition was obtained by blend-
ing HIPS with 10% butadiene-styrene star block copolymer (SB)n; (Gausepohl et al.,
1982). In Asahi patents, HIPS also was blended with a SB block copolymer. The
document specified ranges of the rubber content and size of the rubber particles in
both components. Good transparency, as well as flexural, tensile and impact strength
was announced (Asahi Chemical Industry Co., 1982a). In the Montefina patent, HIPS
was blended with 45wt% HOPE and 10wt% hydrogenated styrene-butadiene-
styrene block copolymer to give materials with high impact strength. The following
year, Mobil Oil Corporation announced PS blends with poly(p-methylstyrene) (PMS)
and p-methylstyrene-diene-styrene block copolymer in the ratio 10:2:10-10:10:2. The
transparent blends (in spite of PS/PMS immiscibility) had good impact and stress
cracking resistance (Murray, 1982).
In 1984, Asahi Chemical Industry disclosed styrene-butadiene block copolymers of
the type, BS (B'S')n' terminated with 2,4-di-t-butyl-p-eresol and tris(nonyl-phenyl)
phosphite. These materials showed especially good adhesiveness. The copolymer
SBR and blends 143
could be blended with HIPS to increase its adhesive strength with other resins, e.g.,
methylacrylate-acrylonitrile copolymer (Shiraki et al., 1986).
Blends of HIPS with SB5-type block copolymers were frequently used as a base for
more complex systems. For example, in 1991 Dow Chemical disclosed thermoform-
able alloys that comprised three components, HIPS, SBS and polyethylene. Thus, 45-
70 wt % HIPS (having three-modal distribution of rubber particles with diameter 0.1-
0.8, 1.2-3.0 and 3-10 lUll), was blended with high density polyethylene, 15-40wt%
HDPE, and 5-25 wt % compatibilizing styrene-butadiene-styrene or styrene-iso-
prene-styrene (SBS or SIS). The blends were easy to process into parts with good
impact strength and resistance to solvents. The materials were used for refrigerator
or freezer liners (Swartzmiller et al., 1993).
10.2 SBR AND BLENDS

In 1951, Monsanto Chemical Company patented PS blends with 5O-4Owt% styrene-
butadiene or styrene-isoprene copolymer (SBR). The blends, with high tensile
strength and elongation, were useful as insulating, dielectric and packaging materi-
als (Seymour, 1951). The follOWing year Standard Oil disclosed compositions com-
prising 27wt% PS, 18wt% PIB, and 55wt% PSIB (Sparks and Turner, 1952).
Firestone Tire & Rubber Company patent applications from 1953 described blends
of PS with styrene-a-methylstyrene copolymer, 85 wt % SMS, and polystyrene-
grafted polybutadiene, 10 wt % SBR. The blends had good impact strength and
hardness. Blending of PS with 5-80 wt % PB was facilitated by addition of 20-95%
SBR. The blends containing 55-85 wt % PS were used for sheeting, and those contain-
ing 85-95wt% PS for molding (Hayes, 1956, 1967). In the early 196Os, the company
patented ternary blends of 6D-85wt% acrylonitrile-methylmethacrylate copolymer
(AMMA), 5-15% SBR and 10-20% NBR. The alloys had good processability and
solvent resistance. By varying the composition, a wide range of properties were
obtained (Reid and Conrad, 1960). In a later patent, 80-95% PS was blended with
SBR, and a crosslinked SBR. Latex blending, coagulation and milling produced blends
suitable for extrusion, injection molding or embossing (Conrad and Reid, 1963).
In a 1958 patent application, the Dow Chemical Company disclosed blends of PS,
with 3-15wt% SBR, and 1-15wt% PEG. The materials showed improved notched
impact strength and elongation at break (Briggs and Price, 1963).
In 1960, Bayer announced that blending of either SBR or NBR, with PS or SAN may
be significantly shortened when the elastomeric component contains carboxylic,
hydroxy-methyl or ureido moiety. For example, NBR containing 8 wt % methacrylic
acid was efficiently blended with SAN to give materials with excellent impact and
tensile strength properties (Schneider et al., 1960).
In the early 1980s, Sweetheart Plastics developed thermoformable blends of PS
with either styrene-butadiene rubber, or block copolymer and polypropylene (Gran-
do et al., 1981, 1983). In 1989 Johnson & Johnson announced that blends of SBR with
styrene-methyl methacrylate copolymer (SMM) were suitable for injection molding
of toothbrush handles (Kent et al., 1991).
Goodyear Tire and Rubber Company, in patents dating from 1990-1992, disclosed
sulfur-eured compositions that comprised (based on 100 parts by weight of rubber,
i.e., in parts per hundred parts of resin, phr) a terpolymer of styrene/isoprene/
butadiene (SIBR) 20-90 phr, l,3-polyisoprene rubber 5-35 Phr' and cis-1,4-polybuta-
diene, having 95% or more cis-1,4 structure or at least 90% cis and trans-1,4 structure,
5-50 Phr' The SIBR terpolymer contained 5-70 wt % styrene, 20-70 wt % isoprene and
10-60wt% butadiene, and had a glass transition temperature of -70 to - 5°C. In its
uncured state BR was characterized by a Tg of -15 to - 20°C, and Mooney (ML
1 + 4) value in the range 70 to 90. The blends of the three basic elastomers when
compounded and sulfur-cured into a polymer network gave at 0 °C high loss tangent
(tan 8) values (higher than those of previous materials) associated with good wet
traction, and low tan 8 values at 60°C, indicating low rolling resistance (DiRossi et al.,
1994).
Elastomeric blends that comprised high-styrene rubber 35-55 wt %, natural rubber
30-50 wt %, halogenated butyl rubber 10-20 wt %, and 30-45 phr plasticizer were
found particularly suitable for manufacturing hockey pucks. The blends showed a
low coefficient of restitution (low bounce) at -40 to + 40 °C (Douglas, 1994).
10.3 PS/PE AND PS/MODIFIED PE BLENDS

In 1959, Monsanto announced that PS with improved impact, elongation and
strength can be obtained by blending it with polyethylene (1-10wt% PE) and
chlorosulfonated-polyethylene (Herbing and Salyer, 1963). The patent is one of
several in which the addition of a small amount of non-compatibilized polymer to
'a brittle resin was found to Significantly improve toughness and elongation. This
blending strategy was successfully used to enhance performance of nearly all poly-
mers, including polyalkenes (e.g., low temperature toughness of polypropylene or
polyethylene), engineering resins (e.g., polycarbonate, polyamides, polyesters, poly-
phenyleneether or polyoxymethylene), and specialty resins (e.g., polysulfones, poly-
sulfides, liquid crystal polymers, aromatic polyamides, polyetheramides, etc.).
Many examples of the application of this strategy have been given, especially
when discussing PE or engineering polymers blends. Toughening a brittle polymer
requires optimization of the size and concentration of introduced heterogeneity
(another polymer, solid particles or gas bubbles). For most thermoplastics, the
optimum diameter of the dispersed drops is below 311m, and its volume fraction is
0.05 < <jJ < 0.10. For thermosets, elastomers with diameter ~ 20 11m have been used.
The accepted mechanism of toughening considers the heterogeneity as a stress
concentrator, generating excessive crazing and/or shear banding of the matrix,
thus requiring a higher amount of energy to cause fracture. The stress concentration
factor 1 <X 1/(1 - a<jJ2/3) where a depends on the matrix (Bucknall, 1977; Vollenberg et
al., 1988; Partridge, 1992).
Developing fine dispersion without degrading the polymers has always been a
serious problem. In the early 1970s Patfoort at the University of Liege designed a
new extruder for PVC. The machine had a short screw with LID = 5, a residence
time of about 10 s, and an adjustable gap between the screw and the die plate that
worked on the principle of the Weissenberg normal stress effect, Le., similar to the
Maxwell normal stress extruder. Owing to short residence time and controlled stress
field, the machine was soon found to be useful for blending. The patent application
was deposited in 1975, and the license was given to Fabrique Nationale Herstal, S. A.
The application described homogenous blends of immiscible polymers prepared at
high stresses and low residence time in the Patfoort extruder. For example, LLDPE
was blended with PS to give blends with good mechanical properties (Patfoort, 1976;
Fabrique Nationale Herstal, S. A., 1977).
In 1960 Union Carbide blended PS with 4Q-90wt% styrene-ethylene bulk copoly-
mer (SER). In the follOWing patent, PE instead of PS was blended with SER (Gorham
and Farnham, 1964). A few years later, Sekisui Chemical developed blends compris-
ing 2Q-80wt% PS with polyalkenes and with ethylene-Vinyl acetate copolymer,
EVAc. These opaque materials could also contain inorganic fillers. They have been
PS/PE and PS/modijied PE blends 145
used to extrude films with paper-like qualities (Yamamoto et al., 1971). Similar PSI
PO blends were disclosed in 1983 by Mobil Oil Corporation. Thus, blends compris-
ing 70wt% LLDPE, and either PS or poly-p-methylstyrene (30wt% PS) were found
useful for manufacturing films with dead-fold and paper-tear characteristics for food
wrapping (Canterino and Freudemann, 1985; Canterino et al., 1986).
In 1971, Sumitomo Chemical developed PS/PO blends for another application.
Thus, 3-30 wt % of either PS or HIPS, was blended with either PP or PE. The blends
were extruded into soda-straw tubes with pearly luster (Ogawa et aI., 1973). In 1978,
Shell International Research developed blends comprising 10D-45wt% PS or HIPS
with polyalkene, 2-30 wt % PP, and hydrogenated butadiene-styrene block copoly-
mer, 5-20 wt % SEBS, for good impact and flexural strength, as well as tensile yield
retention in cottonseed oil-oleic acid test (Holden and Gouw, 1979). Two years later,
Sweetheart Plastics disclosed thermoformable blends of PS, an alkene polymer, PP,
and either SBR or a block copolymer, (SB)n (Grancio et al., 1983). Similar compositions
were also disclosed by BASF. Thus, 10-90wt% PS was blended with a polyalkene,
e.g., 10-90wt% LLDPE and 5-40 wt% SE8S (comprising at least 50wt% styrene). The
system showed good resistance to impact and yellowing (Seelert et al., 1993).
Also at that time, high impact, transparent resins were obtained by blending PS
with (S8)n' and styrene-modified polybutadiene. It was mentioned that better
improvement of properties was obtained using two different grades of block copol-
ymers having different MW and composition (Asahi Chemical Industry Co., 1982b).
In 1992, Rohm and Haas disclosed an interesting method for preparation of PS-PO
segmented copolymers, free from non-grafted PS. (These resins were subsequently
used as compatibilizers, melt strength, and impact improvers of POS, reported to be
particularly useful for blow molding of polypropylene). The copolymers were pre-
pared by mixing PO with styrene (and with 0-20wt% of another monomer) in the
presence of an initiator that had a half-life at 110-125 °C of about 30 min. The mixture
was heated at ~ I°C/min to a temperature at which PO swells but does not melt,
then kept at this temperature until grafting was completed. Blends of PP with 0.2-
10 wt % of this copolymer showed improved sag resistance, making them suitable for
blow molding of bottles and containers for packaging of foodstuffs. The blends can
also be foamed, and molded articles may be used as substitutes for wood. Films may
be used in many protective or wrapping applications, e.g., for food packaging. The
creep resistance of the modified-PP fibers was also improved (Hamilton and
McCarthy, 1994). The same year, Mobil Oil Corporation deposited a patent docu-
ment for ternary blends contain 87-96wt% LLDPE (with either butene-I, hexene-l
or octene-l), l-lOwt% isotactic polybutene, and l-lOwt% PS. The blends may also
contain 0.01-10wt% additives, such as pigments, processing, anti-blocking agents,
etc. The blends were used to blow films that showed improved process efficiency in
terms of extruder power consumption, while retaining the inherent strength of the
LLDPE. The compositions were used for the manufacture of waste bags (Evans and
Shirodkar, 1993).
In 1989, Shell Oil disclosed that elasticity, tensile strength and die build-up of
blends comprising S8 and ethylene-vinyl acetate copolymers can be greatly
improved by addition of a small amount of PS, (viz. 40-80 wt % SBS; containing up
to about one-third oil), 15-40wt% EVAc (having 12-33wt% VAc), and ID-45wt%
PS. In a later patent it was disclosed that blends containing SB, EVAc and PS can be
further improved by replacing part of EVAc with polyalkene having low
crystallinity. Alloys useful for manufacturing elastomeric films were prepared
from ID-45wt% PS, 5-20wt% of either LLDPE or ULDPE with crystallinity below
60%, 4D-80wt% SBS Kraton™ D (having a molecular weight of 170kg/mol, a PS
content of about 32%, and comprising about 33wt% oil), and 5-20wt% EVAc
(containing 12-32%, preferably 28%, VAc). Addition of PO was found to increase
the tensile strength by 5-20%, without reducing elasticity (Djiauw and Mitchell,
1990; Djiauw, 1994).
In 1991, Dow Chemical Co. disclosed thermoformable polymer blends comprising
45-70 wt % HIPS (having three-modal distribution of rubber particles; with diameter
of 0.1-0.8, 1.2-3, and ~10J.1m), 15-40wt% HDPE, and 5-25wt% compatibilizing
styrene-butadiene-styrene, or styrene-isoprene-styrene, SBS or SIS block copolymers.
The alloys had good interfacial properties, were easy to process into refrigerator or
freezer liners with good impact strength and high resistance to solvents (Swartzmil-
ler et al., 1993). The same year, BASF disclosed blends of 10-90wt% PS with 10-
90 wt % PO (e.g., LLDPE), and 5-40 wt % styrene-hydrogenated butadiene star-block
copolymer, with at least 50% styrene. The system showed good resistance to impact
and yellowing (Seelert et al., 1993).
10.3.1 Recycling
There is a growing concern with polymer recycling. By design, blends are recyclable,
but ever popular coformed plastics are rarely so. Mixed post-eonsumer plaStiC waste
poses even more difficult problems. In 1990, a patent described how laminated trays
of foamed polystyrene with such a barrier polymer as ethylene vinyl alcohol can be
regranulated and re-extruded with virgin PS at least 20 times. The re-extrusion
generated PS/EVAc blends that, after foaming, produced articles with good
mechanical properties (Gusavage et al., 1994).
Post-eonsumer plastics scrap incorporates many different types of plastics; thus is
not suitable for recycling by the conventional techniques used for neat resins.
Techniques have been developed for reclaiming the most valuable and most readily
identifiable constituents of such a mixed waste stream, namely soft drink and milk
containers made principally of polyethyleneterephthalate or high density polyethy-
lene. These containers constitute an appreciable fraction of the post-eonsumer scrap
and can be identified by their size and shape so that it is feasible to segregate them
manually. After segregation of the PET and HDPE containers, there are tailings,
which consists of many different types of plastics, formed into films, laminates, or
composites. Polyalkenes, in particular polyethylenes, constitute 50-75 wt % of these
materials, and styrenics about 25 wt %. These tailings can be cleaned, comminuted,
melted and melt-formed into various articles that have relatively poor physical
properties, such as low compressive modulus and yield stress. It was reported that
mixing tailings with high melt strength polystyrene resulted in materials having
good modulus and impact strength.
In 1990, Rutgers State University patented recycling PO/PS, without a need for
compatibilization. The claimed compositions comprised 30-40 wt % PS having a
storage modulus of E' ~ 106 Pa and PO (high density polyethylene, low density
polyethylene, polypropylene or their mixtures). The high melt strength PS, having
relatively high melt viscosity at 200-220°C (required for compounding the PO
tailings), was capable of forming relatively stable cocontinuous structures that chan-
ged little during the solidification processes. The PS and PO formed interspersed
phases, one consisting predominantly of PS and the other of PO, with the PS phase
providing reinforcement to the PO phase. Within the specified composition range
(Figure 10.2), the process yielded particularly good physical properties such as high
compression modulus, yield stress and compression strength. The extraordinary
properties achieved in this range resulted from the cocontinuous structure, as well
PS/pE and PS/modifted PE blends 147
1.8,..---..,-----,.---,....----r-----,
o
v--....."e._o 35
l 1.4
~
m
r-
!. o
en
ilm
(/J
3
;:) en
Q 25 en
i 1.0 -::u
.!.
o Modulus
X Yield
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o 20 40
POLYSTYRENE CONTENT (wtGk)
Figure 10.2 Composition dependence of modulus and yield stress for recycled polystyrene/
polyalkene blends (Morrow et al., 1994).
as from a depressed crystallinity of PO. The performance was found unaffected by

contaminants present in the PO phase, namely pigments, additives and other plas-
tics. Advantages can also be achieved by uniaxially stretching the PS fibrils having
the mean length to diameter ratio 2: 8, and a mean diameter::; 151-£m. At 200 °C and a
frequency of 10 Hz, the storage shear modulus of PS should be G' 2: 10 MPa, and its
concentration about 35wt%. The blends can also be recycled (Morrow et al., 1994).
Since most polymers are immiscible, as is PS with PO, compatibilizers have been
used to facilitate dispersing the minority resins, and to improve mechanical perform-
ance. Addition of 5-B copolymers may homogenize these mixtures, making them
suitable for high-quality applications. However, it is important to recognize that
recycled plastics need to be re-stabilized. Although stabilizers for inhibiting thermal
oxidative and photo-oxidative degradation were originally incorporated in the neat
resins, some have been lost through migration, extraction or degradation during the
usage of the plastics, or storage of the waste. Moreover, recycled plastics need a
higher concentration of stabilizers than neat polymer, as sites of attack for oxidative
degradation have already formed (Sadrmohaghegh et al., 1985). Since each type of
polymer makes specific demands of the stabilizers, stabilization of post-consumer
scrap would require addition of a combination of different stabilizers. This is a
complicated and costly proposition. Experience indicates that in many cases, addit-
ives in one type of resin have detrimental effects on other resins and/or on their
additives. Such a mutual contamination may affect the interfacial properties as well
as increase vulnerability of the recycled material to weathering and aging.
In 1991, Ciba-Geigy Corporation disclosed that recycled thermoplastics recovered
from domestic and commercial waste, comprising 55-75wt% PO, 5-25wt% PS, 5-
15 wt % PVC and 0-10 wt % of other thermoplastics, can be stabilized against thermal
oxidative degradation by adding a combination of two stabilizers. The blends were
stabilized against light and thermo-oxidative degradation by adding O.I-o.swt% of
sterically hindered phenol(s) (e.g., pentaerythritol ester) and phosphite(s) (e.g., tris
(2,4-di-t-butylphenyl) phosphite), at ratios of 5:1 to 1:5, and when necessary other
stabilizers, namely thiopropionic acid, benzophenones, oxalides, benzotriazoles or
sterically hindered amines. To facilitate blending, and to improve performance of
these scrap materials, 3-20 wt % SB compatibilizer was also added. Stabilized
recycled scrap showed good long-term performance, such as lifetime to embrittle-
ment exceeding 270 days at 110°C, or retention of over 62% of the original impact
strength after exposure to 6000 h of artificial weathering at 63 °C and 60% relative
humidity (Pauquet et al., 1994).
10.4 PSI ACRYLICS BLENDS

In 1960, Canadian Industries Limited applied for a patent comprising styrene-
methacrylic acid copolymer (SAA) with 35% butadiene-methylmethacrylate-vinyl
pyridine terpolymer. The alloys had high impact strength and heat deflection tem-
perature, HDT. In the following patent, PS or styrene-methylmethacrylate copoly-
mer (SMM) was blended with SAA for good chemical, thermal and electrical
performance (Murdock et al., 1960, 1962). Styrenics' blends with (meth)acrylic acid
copolymers have been found to have good adhesion to metals, most polymers and
pigments. In 1967, Shell Oil Co. deposited a patent document for blends comprising
HIPS and polyalkylmethacrylates. The alloys showed Significant improvement of
performance over neat HIPS (Ward, 1970).
In 1969, Hercules announced that impact resistance of styrene-acrylonitrile (SAN)
can be improved by blending it with ethylene-propylene copolymer grafted with
styrene and acrylonitrile. The blends constituted a new type of ABS, having a
saturated elastomeric core for reduced weatherability, also known as acrylonitrile-
ethylenic elastomer-styrene, AES (Foglesong and Jabloner, 1972). In a patent applica-
tion depOSited in 1973, Japan Synthetic Rubber Co. disclosed blends comprising PS,
PMMA, SAN and poly(methyl norbomene-2-carboxylate). These toughened alloys
gave moldings with high impact strength (Ikeda et al., 1976).
10.4.1 Miscible blends

Miscible blends have rarely been a commercial success, the principal reason being
their single-phase morphology that frequently leads to brittle failure. The polymers
fail due to rapid crack propagation, without Significant deformation of the material;
thus they use little energy during fracturing. Several methods have been developed
for toughening, Le., reduction of the brittleness of thermoplastics. These include
incorporation of an elastomeric phase by copolymerizing or grafting the thermo-
plastic polymer onto an elastomer (d. discussions on HIPS and SBR), by incorpora-
tion of an impact modifier, or by addition of immiscible liquid rubber. Thus,
independently of the interpretation of the fracture mechanics, toughening involves
incorporation of an additional phase.
Polymer morphology is extremely important if the reduction in brittleness is to be
achieved. The form of the dispersed phase, its concentration, as well as the size of the
dispersed phase, are all important. Depending on the mode of failure, the required
particle size may vary from 0.01 to 1.0 11m. In most cases, impact modification is
carried out using a compounding extruder.
There is another method for controlling morphology of the minor phase within a
matrix. The method, known as spinodal decomposition, originates from fundamen-
tal studies of liquid-liquid miscibility, and has been mentioned in this text (Utracki,
1989a, 1994a). Its applicability is limited to systems that can be made thermodyna-
mically miscible. Modification of such independent variables as temperature,
PS/acrylics blends 149
pressure, stress, solvent concentration, or molecular weight may introduce con-
trolled phase separation. Since the rate of spinodal decomposition is controlled by
molecular diffusion, the type and coarseness of phase separation can be dynamically
controlled.
Another reason for basic studies of miscibility is the need for compatibilization of
commercial polymer blends (Utracki, 1994b). The process involves three different
aspects: (1) reduction of the interfacial tension coefficient, thus amelioration of the
degree of dispersion, (2) prevention of coalescence, and (3) formation of adhesive
layers between the separated phases during processing as well as in the solid state.
Knowledge of miscibility is crucial in all three aspects.
It is known that PS is miscible with either poly(2,6-dimethyl-1,4-phenylene ether)
or polyvinyl methyl ether (Olabisi et al., 1979). A more extensive list of polymers that
may also form miscible blends with PS includes: poly-2-chlorostyrene (PCS),
polymethylstyrenes (PMS), polycarbonate of tetramethyl bisphenol-A (TMPC), co-
polycarbonate of bisphenol-A and tetramethyl bisphenol-A, polycyclohexyl acrylate
(PCHA), polyethylmethacrylate (PEMA), poly-n-propyl methacrylate (PPMA),
polycyclohexyl methacrylate (PCHMA), copolymer of cyclohexyl methacrylate and
methyl methacrylate, bromobenzylated- or sulfonated-PPE, or copolymer of 2,6-
dimethyl-1,4-phenylene ether and 2,3,6-trimethyl-1,4-phenylene ether (Krause and
Goh,1998).
Miscibility of PS with polyalkyl(meth)acrylates has been studied at Roehm GmbH
Chemische Fabrik. In a series of patent applications that started in 1986, blends of PS
with several (co)poly(meth)acrylates have been disclosed. Thus, PS was reported
miscible with polycyclohexylmethacrylate up to the decomposition point T=2S0 0c.
Later the claim was broadened to include blends of PS or polymethylstyrene (0.1-
99.9wt% PMS) and a copolymer containing 5-40 parts of cyclohexylmethacrylate,
3~70 parts of ethyl- or methyl-methacrylate, l~SO parts of methacrylates with C3-24
in the ester group, and ~1O parts of a third, copolymerizable monomer. Preferably,
PS formed a core and the copolymethacrylate the skin. The blends showed
good performance. Miscibility was also found in blends comprising 1-99.9wt%
of a poly-a-methylstyrene (~20wt% a-methylstyrene, ~Owt% of a
methyl, ethyl, propyl or n-butylmethacrylate, and < 0.1 wt% of a polar monomer)
and 99--0.1 wt % of a (meth)acrylic copolymer containing ~ 2 wt % of a cyclohexyl-
(meth)acrylate. Particularly good miscibility was found when the copolymer con-
tained small amounts of cyclohexyl methacrylate (Siol and Terbrack, 1987, 1989,
1990a).
Similarly, poly-a-methylstyrene showed miscibility at room temperature with
PMMA, PEMA, polybutyl methacrylate and polycyclohexyl (meth)acrylates. Also,
poly-p-methylstyrene, and poly-p-t-butylstyrene showed some miscibility with poly-
alkyl (meth)acrylates, when the side chains of the poly(alkylstyrenes) and the side
chains of the polyalkyl (meth)acrylates show comparable van der Waals volumes.
However, as reported earlier, PS is immiscible with PMMA, PMA, PEA, PBA, or Pn-
BMA (Somani and Shaw, 1981).
In 1990, Novacor Chemicals (International) sought protection for a method that
provides a broad range of blends with the following characteristics: (1) the alloy is
miscible and it has either a lower critical solution temperature (LCST), upper CST
(VCST) or both; (2) the components are miscible over a broad composition range at
temperatures above the melting point of the polymer having the higher glass
transition temperature; and (3) upon subjecting the blend to phase separation and
quenching, the quenched alloy will have a yield of at least 10% when subjected to a
stress of 30MN/m2. Thus, the blends comprised 95-S0wt% of a brittle polymer (e.g.,
polyesters, polycarbonates, vinyl aromatic polymers, polyamides, polyimides, poly-
phenylene ethers and polyphenylene sulfides) and 5-SOwt% of rubbery coherent
polymer (e.g., polyvinyl alkyl ethers, natural rubber, cis-polybutadiene, block
copolymers) The process for preparing such a composition involves preparation of
a miscible blend, heating it to a temperature at which it becomes immiscible, then
cooling within 2-5 min to a temperature below the Tg of the brittle polymer to obtain
the phase separated alloy. Preparation of such a system may involve mixing a
solution of a brittle polymer with a solution of an elastomer, heating the resulting
solution to above the LCST, then evaporation of the solvent that causes the
phase separation. The claims, however, are less general, focusing on the
mixtures of PS with PVME: 9Q--60wt% PS having a molecular weight of 100kg/
mol, and 10-40 wt % isotactic PVME haVing a molecular weight of 2Q--60 kg/mol,
Mw/Mn = 5, T g ::; -20°C, and a degree of crystallinity X ~ 3%. The PVME was
miscible with PS at temperatures above its melting point/ and the blend had either
a LCST or a VCST, or both. Homogeneous blends were prepared by extrusion at a
temperature at which the ingredients were miscible, then causing a phase separation
either without shearing or a minimum of thereof, by altering the temperature of the
blend to cause spinodal phase separation and, finally/ quenching the phase sepa-
rated blends to below Tg(PS). The blends, containing a least 10wt% isotactic PVME,
were tough and transparent (Beaucage and Stein, 1994).
In 1992/ Roehm GmbH Chemische Fabrik disclosed miscible blends that com-
prised: 0.1-99.9 wt % PS and 99.9-0.1 wt % PEMA (M w = 20-200 kg/mol). The blends
showed a single Tg intermediate between those of the polymer components and
LCST ~ 75°C. To improve miSCibility PEMA may contain up to 10wt% of cyclo-
hexylmethacrylate. The blends were first prepared by dry blending solid granules,
followed by melt compounding at 150-300 °C in single-screw extruders, multi-screw
extruders or kneaders. The PS/PEMA blends are glass-clear (in contrast to immisci-
ble PS/PMMA blends), and show moderate water absorption. Furthermore, in these
blends the double refraction of ps/ as well as its high refractive index no is reduced.
The possibility of matching no of PS/PEMA blends with another immiscible ingredi-
ent/ such as elastomeric (co)polymer, is important for amelioration of the impact
behavior of transparent plastics. Mixing 70-95wt% of PS/PEMA blend with
30-5 wt % of a polymer whose refractive index does not differ from that of the
blend by more than 0.01/ such as polybutadiene or polyisoprene, results in three-
component alloys with high impact strength, improved chemical resistance and
transparency (better than that of PS by at least 2%). Blends that may also containing
customary additives, such as stabilizers and UV absorbers, have been found useful
for optical· gradient fibers and multiframe panels for glazing greenhouses, having
improved transparency and weatherability (Siol et al., 1994a).
Evidently, the miscibility is not limited to PS systems. For example, the following
systems comprising a commodity resin were reported miscible: polypropylacrylate
with polyvinylbutyrate; sulfonated-EPDM with amine-terminated polycaprolactone;
SAN (containing 20-35wt% AN) with rubber-modified N-phenylmaleimide-styrene
copolymer; styrene-maleic anhydride with styrene-N-phenylmaleimide; chlori-
nated-PVC with PMMA; PMMA with either poly(p-hydroxy styrene) and EVAI, or
with polyglutarimide; PGI with PVAl and poly-€-eaprolactam; PGI with EVAI; PVC
with MBA; poly(acrylate-N-eyclohexyl maleimide) with PMMA and three-layered
core-shell impact modifier (e.g., PMMA center bead, crosslinked butyl acrylate-
styrene middle layer and PMMA shell); PMMA with fluorinated bisphenol-A
polycarbonates; PVC with a copolycarbonate of bisphenol-A and bishydroxy-
phenyl-hexafluoropropane; polypropylene, poly-2-ethyl oxazoline and EVAc;
PS/acrylics blends 151
poly(ethylene-co-vinyl acetate), with poly(styrene-co-acrylic acid); ethylene-propy-
lene-earbon monoxide xyz-eopolymer with SAN (based on a-methylstyrene with
55-80wt% AN); block copolymers of p-(hexafluoro-2-hydroxyisopropyl)-a-methyl-
styrene with polymers containing carbonyl groups (e.g., PC, PEST, PA, acrylates,
methacrylates, etc.).
Several blends of engineering and specialty resins have been reported miscible:
PPE with styrene-dibromostyrene copolymers; polyethersulfones with poly
(p-phenyleneether-co-p-phenylene sulfonyl); mixtures of different polyarylethersul-
fones; polyethersulfone with aromatic polyimide; polyetherimides with aromatic
alkyl methacrylates (e.g., polybenzylmethacrylate); PEl with PC and a polyaromatic
alkyl methacrylate; polycarbonate of tetramethylene-bis-sulfone and bisphenol-A
with PVC; amorphous, aromatic polyamide (having low concentration of -NH2
end groups) with PC; PC with polyester of neopentyl glycol; PC with poly
(oxetanylalkyl methacrylate); PC with either PMMA or syndiotactic PMMA; poly-
benzimidazole with polyarylates; PBI with PARA, aromatic polyamide-hydrazides
or aromatic polyamides containing heterocyclic linkages; aromatic polyesters
containing t-butyl-substituted aromatic nuclei with aliphatic-aromatic polyamides
having a ratio of aliphatic to aromatic carbons 1.4 to 2.5; polyoxymethylene with
PVPh; PVPh with thermoplastic polyesters (e.g., PETG, PCTG, PET, PBT or PEN),
and polymers miscible with polystyrene (such as PPE, HIPS or TMPC), and styrene-
vinyl phenol either block, graft or random copolymer; bis-aminophenyl hexafluoro
propane polyimides with structurally identical dianhydride moieties and
structurally different diamine moieties; polyphosphazenes with sufficiently acidic
polymers (e.g., PVPh, poly(styrene-co-vinyl phenol), poly(styrene-co-styrene-sulfo-
nic acid).
These miscible blends are discussed later, under the appropriate headings.
10.4.2 Blends with static dissipative properties

In this part, only the electrostatic dissipating polymeric materials (ESD) containing a
commodity resin are discussed. More detailed information can be found in Part
Four.
Polymers do not conduct electricity, are inexpensive in comparison to other
known insulating materials, and are sufficiently durable and heat resistant. How-
ever, they may pose problems due to the accumulation of surface charge that may
discharge rapidly, and thus cause damage to electronic components, cause fires or
explosions, be an annoyance to the users, attract dust, interfere with sensitive
electronic components, etc. Consequently, a need has existed for ESD compositions.
The ESD compositions must have sufficient surface and volume resistivity to
cause slow dissipation of a static charge, but not too low as to allow the charge to
move too quickly through the material, thereby causing an arc or spark. The
accepted surface resistivity of ESD materials should be lOS ~ R ~ 1012 n em. Accept-
able charge dissipation is 90% decay time above 3 s and a 99% decay time above 5 s.
Attempts have been made to coat an electrostatic dissipative ingredient but, owing to
wear and interference with surface properties, this method can be impractical. Other
methods involve addition of graphite, or metal fibers, flakes or particles. However,
such additives are expensive, make processing difficult, and often lower the mechan-
ical performance of the plastic part. Incorporation of organic semiconducting mater-
ials, or other low molecular weight antistatic agents, also has its disadvantages.
These additives must migrate to the surface and the above listed arguments against
the surface coating method are pertinent.
The problems associated with development of ESD plastics resemble those
encountered with plasticization; thus the simplest and most satisfactory solution is
similar. To create an intrinsically ESD polymeric system, the selected polymer
should be blended with another polymer having the ESD properties. The method
has been primarily used with polymers having high Tg , such as PVC, styrenics (such
as SAN or ABS, PC), etc.
For example, in the 1942 document from Thiokol Corporation, blends comprising
aliphatic polysulfides with polybutadienes were found to be suitable for molding
static charge-free rolls and guides for the textile industry (Patrick, 1942). In these
blends, TM not only was a vital part of the formulation providing for the long-term
mechanical performance of the elastomeric blend, but it also engendered the ESD
properties.
In 1968, Asahi Chemical Industries disclosed polyalkene blends with polyvinyl
alcohol (2 wt % PVAI). In this case, incorporation of PVAl into polyethylene resulted
in materials that showed good mechanical, hygroscopiC and antistatic properties,
and were suitable for the manufacture of films, fibers, tubes and coatings (Minekawa
et al., 1969). Here, PVAl played the role of the ESD agent. By contrast with TM in the
Thiokol patent, PVAl did not significantly contribute to the other performance
characteristics of the blend, thus it must be considered an additive, a polymeric
electrostatic dissipating agent.
Incorporation of a polymeric ESD agent into plastics is the best method for
controlling the static charge problems. It offers better control of the surface and
volume resistivity, as well as of long-term performance. The method has been
described in several patents. Besides PVAI, other polymers with polar groups that
result in increased hygroscopicity and/or electronic mobility have been used. To this
group belong polymers and copolymers of epihalohydrin, especially those with
oxirane, polyethyleneglycol (PEG) with ~ 80 wt % EG and molecular weight 200-
10 000 kg/mol, etc. These materials show high ESD performance, especially in a
humid environment.
In 1985, B. F. Goodrich asked for patent protection for a broad range of thermo-
plastic or thermoset polymeric compositions having antistatic properties. According
to the patent claims, compositions comprising such polymers as CPVC, PC, PEST,
epoxy, EP, phenolics, PF, or their mixtures, can have electrostatic dissipating char-
acter when blended with either homopolymers or copolymers of an epihalohydrin
(Barnhouse and Yu, 1988). Two years later, the company disclosed ESD blends
comprising 65-97 wt % of a polymeric matrix, and 3-35 wt % of a semicrystalline,
antistatic copolymer of ethylene oxide and epihalohydrin (ED-ECH) having not
more than 40 wt % epihalohydrin. In this case, the matrix polymers were specified
as either chlorine- or styrene-eontaining polymers, such as PVC, CPVC, PVDC, PS,
SAN, ABS, PaMS, etc. The blends showed good antistatic properties, while the
mechanical properties and thermal stability of the material were not affected. The
blends may also include an impact modifier. ESD properties were also obtained
using a copolymer of ethylene oxide and a comonomer selected from the group
consisting of cyclic ethers, cyclic acetals and cyclic esters (Yu, 1988).
In 1986, Borg-Warner Chemicals disclosed antistatic thermoplastic compositions
that comprised at least 80wt% ABS (containing not more than 6Owt% elastomer),
and a copolymer of epihalohydrin and an oxirane, ED-ECH. The required ratio of
epihalohydrin to oxirane is defined as being between about 1:19 to about 7:13 by
weight (Federl and Kipouras, 1986; Kipouras and Feder!, 1988). The following year
the company applied for world-wide protection for three-eomponent blends com-
prising styrenic polymer 40-96 wt %, EO-ECH and a sufficient amount of compati-
ABS and its blends 153
bilizing acrylic copolymer. The styrenic polymer that had to provide impact strength
and hardness was selected from between HIPS (containing 5-S0wt% elastomer
selected from polybutadiene, styrene-diene copolymers, acrylic rubbers, EPDM,
etc.), ABS, polymethylmethacrylate-butadiene-acrylonitrile styrene, MBS, blends of
(co)polystyrene and polyphenylene ether, PS/PPE, copolymers of styrene-acrylon-
itrile or styrene-maleic anhydride, SAN or SMA, etc. For example, S5-90wt% ABS
was blended with 5-25wt% ED-ECH and 5-2Swt% of polymethylmethacrylate,
PMMA. The blends showed good antistatic properties with rapid dissipation of
static electrical charges, reduced delamination and improved ductility (Gaggar et
al., 1988, 1989,1993).
In 1991, B. F. Goodrich asked for patent protection of a wide range of blends
comprising three ingredients: (1) matrix polymer (polyalkenes, urethane, condensa-
tion, vinylic or styrenic polymer, e.g., HOPE, LOPE, VLDPE, LLDPE, PP, PB, pco,
EPR, EPDM, TPU, PA, PC, PET, CPVC, acrylates, methacrylates, polymeric derivat-
ives of 2-ethylhexyl hydroxyl, epoxy or halogen acrylate, PVAc, PVC, ABS, SAN,
SMA, HIPS, or SMMA); (2) an electrostatic dissipating agent (e.g., an oxirane copoly-
mer of ethylene oxide and epichlorohydrin in a weight ratio of about 80:20); and (3) a
non-electrostatic dissipating non-conductive promoter for the ESD agent, that by
acting synergistically with the agent makes it possible to reduce the amount of ESD
agent. Thus, for applications where rigidity may be significant, the inclusion of the
third constituent and the reduction of the ESD agent could be used to maintain the
rigidity or toughness of the composition while also imparting the ESD properties to
the composition. Depending on the other components, this third component can be a
plasticizer, stabilizer, antioxidant, antiozonant, filler, fiber, impact modifier and/or
the like. Blending was carried out in at least two steps. First the ESD agent and the
promoter were compounded, then in a subsequent step the matrix polymer was
added. For example, 6O-7Swt% of a matrix polymer (e.g., styrene-butadiene-styr-
ene, styrene-ethylene/-butylene-styrene, or chloroprene), was blended with 10-
4Owt% ED-ECH, and 5-30wt% of glass fiber. The reinforced alloy showed good
mechanical and electrostatic dissipative characteristic (Lee, 1993).
In 1992, General Electric asked for patent protection for blends of a styrenic
(co)polymer, 4O-96wt% PS, with 2-SOwt% EO-ECH and 2-S0wt% of a polyalk-
ylenelactone, selected from alkylenelactone (co)polymers with 2 SOwt% acrylate.
For example, blends containing S5-92wt% PS, 5-25wt% ED-CHR and 3-25wt%
PCL, were used to mold parts having excellent static dissipative properties and good
tensile elongation (Giles and Vilasagar, 1994).
There is growing interest in developing blends with a controlled degree of elec-
trical conductivity. Here the aim is not ESD but rather electrical conduction; thus
attempts are made to reduce the resistance to values comparable to those of Cu or
Ag. EVidently, these systems must combine a matrix polymer, not with an ESD but a
highly conductive resin, such as polyaniline, polypyrrole, etc. Some of these fonnu-
lations can be also used in ESD applications (Shacklette et al., 1993).
10.5 ABS AND ITS BLENDS

In 1946, Naugatuck Chemical Company (later a part of US Rubber Co.) introduced
Royalite, a mechanical blend of styrene-acrylonitrile copolymer (SAN) and NBR,
known as ABS-type A (Daly, 1948). The second version, ABS-type G, was developed
in 1950 (e.g., in the laboratories of Standard Oil, U. S. Rubber and B. F. Goodrich), by
first emulsion-polymerizing butadiene into the desired size particles, then grafting
them with styrene and acrylOnitrile. Next, the latex containing the graft copolymer
was mixed with similarly prepared SAN latex and the mixture coagulated, dried and
flaxed (Vanderbilt and Bascom, 1950; US Rubber, 1951; Wheelock and Ferrini, 1957).
In a later patent from Union Carbide, latex of SAN (comprising 65-75 wt% styrene)
was premixed with latex of PB in a ratio 7:6. To the mixture, styrene and acrylonitrile
at a ratio 11:10, as well as an initiator, was added, and the system was polymerized at
90 °C (Schroeder, 1959).
In 1961, Monsanto disclosed another method of ABS preparation. Thus, suspen-
sion and emulsion-type SAN (containing 25-40wt% AN) was blended with poly-
butadiene grafted with less than 15wt% of styrene and acrylonitrile. The blends
showed improved impact performance. In contrast to the melt-mixed AB5-type A,
the emulsion polymerization made it possible to incorporate up to 50 wt % of rubber,
and to improve the control of morphology by means of the reaction parameters and
process variables (Calvert, 1962, 1963, 1966).
ABS technology continuously evolves. There is a great variety of ABS and AB5-
type resins on the market. These may differ in composition, morphology and con-
centration. The transparent ABS grades are offered with submicron elastomeric
particles. The impact performance also is strongly affected by the concentration,
size, and size distribution of rubber particles. One of the first patents on these blends
was deposited by Cosden. Inexpensive blends with good elongation, flexibility and
impact strength were obtained by blending two ABS copolymers, one having rubber
particles with diameter 0.08-0.4 Jlm and the other ~7 Jlm (Morris et al., 1980).
More drastic modifications of ABS have also been known. For example, replacing
acrylonitrile with methacrylonitrile led to a modified version, MABS, advantageous
when blending with PVC (Wilsher, 1979). When polybutadiene (PB) was replaced
with saturated acrylate elastomer and acrylic acid, a new and technologically import-
ant class of acrylonitrile-styrene-acrylate (ASA; e.g., Centrex™ from Monsanto Che-
mical, GeloyTM from General Electric, Luran™S from BASF) was discovered.
Replacing PB by chlorinated polyethylene led to acrylonitrile-chlorinated polyethyl-
ene-styrene (ACS) terpolymer. Replacing PB by EPDM led to acrylonitrile-ethylene
rubber-styrene (AES) weatherable copolymers (e.g., Hostyren™XS, Novodur™AES
and RoveI™). These resins were described in the 1969 patent application from
Hercules (Foglesong and Jabloner, 1972). The terpolymers ASA, ACS and AES
have systematically shown better oxidative degradation resistance and weatherabil-
ity than ABS. These developments are briefly summarized below.
ABS resins are available from many suppliers: AbsafilTM from Fiberfil/DSM,
Abstrene™ from Distillers, AfcorylTM from Pechiney-Saint-Gobain, Arradur™ from
Elf-Atochem, Bapolan™ 8445 from Bamberg Polymers, Blendex™ and Cycolac™ from
General Electric, Magnum™ from Dow, Diarex™ from Mitsubishi-Monsanto,
Epolan TM from Industrial Resistol, Forsan TM from Chemapol, Lastiflex™ and Lastiiac™
from Lati Engineering Thermoplastics, Lustran™ABS from Monsanto, Novodur™
from Bayer/Miles, PolylacTM from Polychemical, Ravikral™ from Enichem, Restiran TM
from Montedison, Ronfalin™ from DSM, Sconatex™ from Buna, Shinko-Lac™
GH from Mitsubishi Rayon, Sicoflex™ from Sic Plastics, Snissan™ from Snia Tecno-
polimeri, Starglas™ from Ferro Eurostar, Sternite™ from Atochem, Stylac™ from
Asahi Chemical, SunlojdTM from Tsutsunaka Plastic Ind., Taitalac™ from Taita Chem-
ical, Teluran™ from BASF, Toyarac™ from Toyo, UrtaITM from EniChem, etc. The
material gained worldwide acceptance to a tune of about 2 Mt/year, or 2wt% of all
polymers. Nowadays, ABS blends dominate the blend market; in 1986, they amounted
to 74 wt % of all blends sold in Europe, 77 wt % in Japan and 69 wt % in North America.
Typical applications of ABS include transport containers, textile spools, parts for
office equipment and domestic appliances, housings for television, radio and stereo
equipment, door and luggage handles, hair drier hoods, safety helmets and fittings
for cars and aircraft, as well as toys. Extruded foil and sheet are cold- and thermo-
formed into transport containers, suitcase shells, cladding, covers, food trays, etc. For
joining, heated tools and spin-welding methods are recommended. Ultrasonic and
high frequency weldings have been less successful, but they can be used to join ASA
to such resins as SAN, ABS, PVC or PMMA. Suitable solvents for bonding are
methylethylketone, dichloroethylene and cyclohexane. Electroplated moldings are
used as fittings for furniture and building, knobs for radio and television sets,
fittings, spectacle frames, toys and typewriter keys. Foamable ABS molding com-
pounds are made into wall panels, picture frames, handles, ice buckets, drawers,
table tops and furniture frames by injection molding.
10.5.1 High heat ADS

In 1958, Borg-Warner disclosed that blends of ABS with interpolymers of a-methyl-
styrene and acrylonitrile (containing 6O-90wt% a-methylstyrene and 4{}-lOwt%
acrylonitrile), showed a good set of mechanical properties. This formulation was
an early version of the high heat ABS, introduced 4 years later by Borg-Warner
Chemicals (Irving, 1961). One year later, Rhone-Poulenc patented another version of
the high heat ABS, replacing styrene by a-methylstyrene. Blending it with PB grafted
with either acrylates or methacrylates, Le., with NBR, resulted in resins having a
good set of mechanical properties and higher heat deflection temperature (Societe
des usines chimiques, 1959).
Kanegafuchi Chemical Industry announced in 1965 new high heat ABS, impact
modifiers. These were obtained by mixing methylmethacrylate-a-methylstyrene
either with styrene-grafted polybutadiene or with an ABS (Kanegafuchi Chemical
Industry Co., 1967).
Four years later, Dow Chemical introduced another method for improving the
heat performance of ABS. It was found that incorporation of styrene-maleic anhy-
dride copolymer to ABS resulted in alloys that had high heat deflection temperature
and excellent impact strength (Stafford and Adams, 1972). Similar effects were
claimed by Daicel for the blends of ABS with either polycaprolactone and/or adipic
acid-1,3-butylene glycol copolymer (Kudo et al., 1975).
In 1981, Starnicarbon disclosed that blending 62.5-75.0wt% of ABS with a-methyl
styrene-acrylonitrile copolymer (MeSAN) resulted in alloys showing good impact
strength and heat resistance (Hoen, 1983). The following year, BASF deposited a
patent for SAN blends with a-methyl styrene-acrylonitrile-butadiene copolymer (or
a copolymer of styrene, maleic anhydride and acrylic acid), and ethoxylated octyl
phenol, to produce alloys with good processability, high HDT, antistatic properties
and good appearance (Brandstetter et aI., 1983a).
Monsanto Chemical has been working on another method of improvement of ABS
performance. It was reported that styrene-maleic anhydride-methyl methacrylate
copolymers, SMA-MMA, is miscible with SAN (Hall et al., 1982; Mendelson, 1985).
In consequence, incorporation of the terpolymer into ABS made it possible to
produce ABS/SMA-MMA blends, such as Cadon™. These resins showed higher
heat deflection temperature, impact strength and weatherability as compared to
ADS, as well as good processability and cost advantages over PPE/HIPS and ADS/
PC blends for the use in automotive interior, appliance, business machine housing
and other applications (Kosoff, 1987). Cadon™ also provided proper means for
chemical interactions with polyarnides and polyesters that led to formulation of
the new family of successful Triax™ blends.
ABS can also be produced by first dissolving polybutadiene (or styrene-butadiene
copolymer) in a mixture of styrene and acrylonitrile, which are subsequently poly-
merized. During the polymerization, the styrene-acrylonitrile radicals graft onto the
rubber-phase, causing it to precipitate. The size and size distribution of the rubber
particles are controlled by the rate of reaction and the agitation speed. The resins
produced by this process have fewer contaminants, thus they show better stability,
toughness and color, but lower gloss than ABS-type G.
In 1992, General Electric Co. disclosed new method of ABS manufacture. Thus,
impact-resistant SAN/ ABS materials were obtained by blending a bi-Iobed graft
copolymer (ABS) and a rigid matrix polymer (SAN). The bi-Iobed copolymer was
prepared in two-step emulsion polymerization, first preparing rigid seed particles of
a vinyl monomer(s) (St and AN), butadiene, and a grafting agent, then grafting
butadiene onto the seeds to form rubbery particles attached to the rigid ones. In
blends with SAN, the rubbery part of the dumbbells agglomerated, providing
excellent impact resistance (Kidder, 1993).
10.5.2 Weatherable ABS

The main drawback of standard ABS grades is the lack of resistance to weathering,
Le., to UV and oxidation, which limits their use outdoors. Photochemical degradation
occurs when the macromolecules absorb UV radiation with a wavelength of less than
350nm. Since the C=C bond energy is 384kJ/mol, the energy of this wavelength
suffices to split the bonds.
Aging of the two-phase ABS consists of three processes. (1) Oxidation and decom-
position of the elastomeric phase, i.e., photolytic oxidation of cis-I, 4-polybutadiene,
transforming methylene groups to carbonyl, carboxyl and hydroxyl groups followed
by decomposition and crosslinking. As a result, the rubber phase becomes brittle and
susceptible to cracking. (2) The interphasial bonding, obtained by SAN grafting onto
PB, is reduced, which in tum decreases adhesion between the two phases. (3) In the
presence of abundant free radicals, the SAN matrix degrades, and the molecular
weight of SAN decreases, which may lead to brittle failure.
Since the weathering processes are initiated by susceptibility of PB to degradation,
it was reasonable to investigate ABS terpolymers in which PB was replaced with a
more stable elastomer. Successful materials based on this concept comprise
thermoplastic polyalkene elastomers, EPR or EPDM. Here, the degree of unsatura-
tion in the elastomeric phase can be controlled during polymerization by adjusting
the diene, e.g., ethylidene norbornene, content. Only the number of double bonds
necessary for adequate grafting by SAN and for crosslinking could be incorporated.
The material, known as either AES or AXS, was found to have good weather
resistance.
In a 1967 patent application, Japan Synthetic Chemical Industry announced mod-
ification of ABS to improve its weatherability and electrostatic dissipative properties.
For this purpose ABS was latex-blended with 5-25 wt % ethylene-vinyl acetate
copolymer, EVAc (Fukushima and Mitarai, 1971). Owing to the hygroscopic char-
acter of EVAc, the modification resulted in better surface adhesion and electrostatic
discharging properties. Similar effects have also been obtained by incorporation of
either styrene-maleic anhydride copolymer, polycaprolactone or adipic acid-l,3-
butylene glycol copolymer (Kudo et al., 1975). In a 1979 patent application from
Borg-Warner Chemicals, to produce flame-retarded ABS without loss of other prop-
erties, the copolymer was prepared using styrene and brominated styrene (Arthur
and Turner, 1983).
The AES developed in 1982 by Uniroyal was found to be a particularly successful
compatibilizer-eurn-impact modifier for engineering resins blends, e.g., in PBTfPC
alloys (Wefer, 1984, 1985, 1988). Also developed in 1982 was another AB5-type
copolymer, AB5-MA. The material, comprising di-alkenes, vinyl aromatics, unsatu-
rated carboxylic acid and acrylonitriles, was obtained by dissolving SBR in the
monomer mixture, then polymerizing it (Daicel Chemical Industries, 1984). The
same year, Surnitomo Naugatuck and Denki Kagaku Kogyo also announced new
AES resins with good processability, weatherability, high coloring yield, interlarni-
nar and low-temperature mechanical strength, and HDT. In the first case, styrene
and acrylonitrile-grafted EPDM (AES) was blended with methylmethacrylate-buta-
diene-styrene copolymer (MBS), whereas in the second case ABS was blended with
styrene-butadiene-maleimide and tristearyl phosphite (Surnitomo Naugatuck Co.,
1984; Denki Kagaku Kogyo K. K., 1983a).
In 1990, Surnitomo Dow Limited disclosed thermoplastic resin compositions com-
prising 100 parts of a mixture comprising 9(}-lQwt% PC, either PET or PBT, and 1-
300phr of AES. The latter copolymer was obtained by polymerizing 0.1-400 parts of
glycidyl methacrylate and (}-1Q00 parts of other copolymerizable monomers (e.g.,
acrylonitrile, styrene (meth)acrylates) in the presence of 100 parts of an ethylene-Q-
alkene-based elastomer, such as EPDM. Moldings showed improved balance of heat,
chemical and impact resistance, as well as shrinkage, weld strength and appearance
(Nishikubo et al., 1994).
In 1994, Sarnsung Cheil Industries introduced interesting blends of 5(}-70wt%
SAN with maleated EPDM and chlorinated polyethylene, CPE. The presence of CPE
provided enhanced compatibility between SAN and EPDM. The blends showed
dispersed core-shell morphology, with EPDM forming the core, and CPE the shell.
The dispersion was binary - single particles of EPDM with a skin of CPE had an
average diameter of 100nrn, whereas their aggregates had an average diameter of
500 nrn. The maleation was used to control of the degree of aggregation, in order to
optimize the mechanical behavior of the blends. The alloys showed excellent
weatherability, and good mechanical performance, as well as high impact and
chemical resistance. They have been used for road signs, outdoor pool floors, air
conditioner housing, window frames, antennas, portable chairs, helmets, golf cart
panels, etc. (Kim et al., 1996).
10.5.3 Reactive acidified ADS

Another important class of the AB5-type of resins involves incorporation of acrylic
ester elastomers. These acrylonitrile-styrene-acrylate terpolymers, known as either
ASA or AAS, are available as Centrex™ from Monsanto, Luran™S from BASF,
Richform™ from Richmond Technology, etc. Before processing, ASA should be
dried for 3-4 h at 85 DC. The recommended temperatures are: for injection molding,
the melt 23(}-280 DC and the mold 4(}-80 DC (resulting shrinkage is 0.4 to 0.7%); for
extrusion, the melt 230 DC and the water bath 7(}-80 DC; for thermoforming 14(}-170 dc.
ASA terpolymers are prepared by grafting styrene and acrylonitrile onto acrylic
ester copolymer. The domains of the latter resin should be small and uniformly
distributed. ASA is characterized by outstanding weatherability, high resistance to
aging and yellowing, high toughness, stiffness, thermal stability and chemical resist-
ance, as well as high gloss and good electrostatic performance. It can be painted,
coated, or plated without pretreatment. These resins have been used wherever the
mechanical properties and superior UV and thermal stability are required. Examples
include road signs, warning lights, boats and caravans. Other proven applications
are housings for vending machines, cases, covers for tractors and motorbikes, screen
aerials, fittings, telephone housings, garden furniture, sprinklers, hose carriers and
watering systems.
Owing to the acrylic ester and/or acid content, these resins also have superior
compatibilizing capabilities. For example, in 1987 Nippon Petrochemicals disclosed
modification of ABS by incorporation of either maleic anhydride or glycidyl meth-
acrylate. These ABs-GMA copolymers blended with polybutyleneterephthalate gave
alloys with outstanding heat, chemical and impact resistance (Orikasa et al., 1989).
Owing to the presence of carboxylic or epoxy groups, the ABS-MA or ABs-GMA
copolymers have been particularly suitable for reactive blending in systems com-
prising PC, PA, PPE or PEST, either as impact modifiers or compatibilizers.
10.5.4 Methacrylate-Butadiene-Styrene copolymers

In 1962, the first non-weatherable copolymers to gain world-wide popularity as
impact modifiers (e.g., ZylailM from Novacor) were disclosed by the Dow Chemical
and Cyanamid Companies. The preparation steps were similar to those used for
manufacture of ABS; they were prepared by dissolving stereospecific polybutadiene
or its copolymer in methyl methacrylate and styrene or a-methylstyrene, then poly-
merizing. The resulting methyl methacrylate-butadiene-styrene graft copolymers
(MBS) had good tensile and tear strength on their own (Ruffing et al., 1964). The
same year, Cyanamid disclosed resins composed of PB grafted with methyl metha-
crylate, styrene and acrylonitrile. The graft copolymer (AN:PB:St:MM = 1: 64: 7: 28)
was blended with 94wt% of a St:MM:N = 19:71:10 terpolymer, to give transparent
resins with good impact strength and HOT (Schmitt et al., 1967).
Owing to the variety of monomers that can readily be used in preparation of these
materials, a great diversity of MBS copolymers is available on the market, lately also
with acidic or epoxy groups. For example, in a series of patents deposited in 1977-79,
Monsanto disclosed blends containing lo-90wt% ABS (comprising 5-70wt% elas-
tomer) with 9O-10wt% copolymer prepared by grafting 2-30wt% polybutadiene
with maleic anhydride-methyl methacrylate-styrene (at ratios 15-35:2-20:40-80),
ABS-MA. The blends showed improved HOT and impact strength (Lee and Tre-
mentozzi, 1979, 1980, 1981, 1982). In 1981 MBS blends from BASF and Dow were
announced. In the first case, SBR was grafted with butyl acrylate, styrene and methyl
methacrylate, then blended with ABS and a butyl acrylate-methyl methacrylate
copolymer (McKee et al., 1982). In a Dow patent, ABS blended with polybutadiene
emulsion-grafted with methyl methacrylate gave tough and impact resistant plastics
(Keskkula et al., 1984).
Resume
To summarize this introduction to the wonderful world of ABS blends, it must be
stressed that especially in today's market there is a wide variety of materials with
diverse compositions and properties hidden behind this simple acronym. The ABS
resins are characterized by excellent processability, good mechanical properties,
rigidity, impact strength, scratch resistance, dimensional stability, paintability and
plateability, moderate solvent, chemical and heat resistance. Usually the surface has
high gloss, but for anti-glare applications (e.g., in the automotive industry) MABS
may contain partially crosslinked acrylic microgel particles that give a matte surface
(Niessner et al., 1994). These materials can be processed using all known methods of
thermoplastics shaping. Specific grades have been developed for extrusion, thermo-
or vacuum-forming, injection and blow molding. ABS may also be calendered and
compression molded.
The polar nature of the -C == N groups in the acrylonitrile component of ABS,
along with the relatively low viscosity of the SAN phase, favor the use of ABS in
blends with other thermoplastics. The most important commercial blends of ABS are
those with PVC, PC, PA, PEST and TPU (Utracki, 1994b). However, as is evident
from data in Table 9.3, ABS has been successfully compounded with most polymers.
Patents were issued for its blends with: PVC in 1951; PMMA in 1956; PC in 1960;
poly-l'-eaprolactam in 1961; polysulfone in 1964; chlorinated polyethylene in 1965;
polyesters in 1968; polyarylether sulfone and styrene-maleic anhydride in 1969 (so
called high heat ABS); polyethersulfone in 1970; polyarylates in 1971; polyurethane
in 1976; polyarylether in 1982; polyphenylene sulfide in 1991.
ABS terpolymers have been frequent ingredients in commercial polymer blends.
Of 175 trade-name blends listed in the Encyclopaedic Dictionary of Commercial Polymer
Blends, 42 contain either ABS, AES or MABS. The popularity of these materials is also
evident from the list of commercial blends given in Appendix n - well over 25% of
them contain ABS. The alloys that comprise ABS constitute a large part of blend
tonnage, especially when the engineering polymer blends are considered.
10.5.5 ABS!PVC blends

ABS blends with PVC (as well as those with PC) are of great commercial importance.
Good properties of these systems originate from the miscibility between PVC and
SAN-part of ABS, containing at least 20wt% of acrylonitrile. The blends also show
the most interesting complementarity of properties of the two principal polymeric
ingredients. In spite of the limited miscibility, the control of morphology may require
use of acrylic compatibilizers. For example in GeloyTM from General Electric, ABS
was replaced by ASA. These blends show improved miscibility and superior
weatherability in comparison to PVC/ABS alloys. For enhancement of the heat
deflection temperature, styrene-maleic anhydride (SMA) may also be used.
Owing to the simplicity of compounding, the PVC/ABS blends are frequently
made by the processors. Pre-eompounded blends are also available from major resin
producers (e.g., Cycovin™ K-29 from Goon Co., Denka Taimel™ from Denki Kagaku,
GeloyTM XP2003 from GE Plastics, Kaneka Enplex™ from Kanegafuchi Corp.,
Kralastic™ from Uniroyal, Nipeon™ AL from Zeon Kasei, Lastiflex™ from LATI,
RonfaloyTM V from DSM, Tufrex™ VB from Mitsubishi Chemical, or Triax™ CBE
from Monsanto).
The PVC/ABS blends are available in grades formulated for injection molding,
extrusion, thermo- or vacuumforming and calendering. The blends offer excellent
processability (e.g., no plate-out or bloom, although the thermal instability of PVC
requires careful control of processing), high impact strength, UV stability, flame
resistance (self-extinguishing, with V-O ratings described in UL94 "Vertical Burns
Test Method"), weatherability at a low cost, and excellent cost-to-performance ratio.
These blends have often been used as low cost alternatives to flame retarded grades
of ABS or of PPE/HIPS. As is the case for other blends, the properties and long-term
performance of PVC/ABS blends depend on morphology - commercial blends with
either a dispersed or cocontinuous morphology are available.
The blends exhibit good dimensional stability at high temperature, and high
impact strength, both properties absent in rigid PVC formulations. The blends
comprising more than 30wt% PVC are difficult to process, but they are self-
extinguishing. The main use of PVC/ABS blends is in housings for electrical tools,
electrical and electronic equipment housings, moldings for domestic appliances,
aircraft, computers, business machines, impact resistant blow moldings, diverse
automotive, pipes and profiles, industrial tools, plugs and receptacle covers.
The first AB5-type G blends with PVC for the manufacture of phonographic
records were patented by the Radio Corporation of America (Parker, 1951). The
following year, Firestone Tire & Rubber disclosed ABS/PVC blends for the produc-
tion of artificial leathers (Schule, 1952; Humphrey and Reid, 1953). PVC blends with
isobutylene-butadiene-acrylonitrile were patented by Standard Oil (Banes et aI.,
1953).
In several early patents from Monsanto Chemicals, PVC was blended with 10phr
of styrene-acrylonitrile copolymer (SAN) and 10 phr of AB5-type G, to give resins
with 'low sensitivity to mechanical working'. For vacuum forming the blend per-
formance was improved by addition of less than 20 wt % of vinyl chloride-vinyl
acetate copolymer (Parks and Jennings, 1956). Later, the company patented PVC
blends with acrylonitrile-butadiene-a-methylstyrene copolymer (ABmS) (Slocombe
and Salyer, 1961).
In 1959, Borg-Warner Corporation disclosed PVC blends with AB5-type G show-
ing high tensile strength, hardness, impact strength, and heat distortion temperature
(Grabowski and Irvin, 1962). In the 1963 patent application, Mitsubishi Monsanto
Chemicals disclosed that blends comprising 5-5Owt% PVC with 1-50% ABS, and
post-ehlorinated PVC, showed improved processability, impact strength and ther-
mal stability (Kojima et aI., 1970). The same year Kanegafuchi applied for a patent on
high impact strength PVC blends containing a mixture of PVC with 5-30 wt % of
acrylonitrile-butadiene-styrene-methylmethacrylate, MABS (Himei et al., 1967).
In 1966, Japanese Geon applied for a patent on PVC blends with a core-sheIl-type
copolymer, consisting of AB5-core and grafted on it acrylOnitrile-ethyl acrylate-
styrene. This was an excellent idea, since the acrylic shell had better miscibility
with amorphous PVC than SAN, enhancing its compatibility with ABS, while the
elastic core proVided good impact strength. The resulting alloys displayed excellent
mechanical properties, high impact strength, transparency, surface smoothness and
whitening resistance (Tanaka et al., 1971). Two years later, Pechiney-Saint Gobain
developed similar blends with core-sheIl-type copolymer (ABS-eore and grafted on it
methylmethacrylate). Since PMMA enhanced compatibilization of PVC/ABS mix-
tures, the concept worked here as well. These alloys displayed excellent mechanical
properties and impact strength (Michel, 1969). In a contemporary Asahi patent
application, PVC was blended with ABS and SBS for improvement of impact
strength and toughness (Minekawa et aI., 1971a).
In JSR's patent application of 1971, PVC blends with 5-30wt% of either MBS or
MABS were described. The alloys showed good transparency and impact strength
(Kumabe et al., 1973). Similarly, a year later Kureha disclosed that blends of 7~
99 wt % PVC with a multilayer butadiene-styrene-divinylbenzene-butylacrylate-
methYlmethacrylate copolymer, were found to give transparent, craze and impact
resistant resins (Usarni and Ochiai, 1976).
Blends of PVC with 1~100phr of poly(2-eyano-5-norbornene) (PCN) and 5-50phr
ABS were developed in 1976 by the Nippon Telegraph & Telephone Public Corpora-
tion. The alloys showed high HOT and impact strength (Matsuura et al., 1978).
Blends of 2~O% PVC with polybutadiene grafted with styrene, methylmethacrylate
and maleic anhydride (ABSM-MA), or with a mixture of ABS and styrene-methyl-
methacrylate-maleic anhydride copolymer (SMM-MA), were disclosed in 1981 by
Monsanto. The blends showed good flame retardance, HOT and impact strength
(Dufour 1982).
In 1985, Borg-Warner Chemicals, and a year later Monsanto, described clear PVC
blends prepared by compounding it, respectively, with either 14phr modified
methylstyrene-styrene-acrylonitrile-grafted polybutadiene or with maleated styr-
ene-methylmethacrylate-butadiene, ABS-MA (Meredith and Ferguson, 1988;
Dufour, 1988). Four years later, B. F. Goodrich disclosed PVC blends with ABS and
vinylchloride-ethylhexyl acrylate copolymer for improved abrasion resistance
(Greenlee et al., 1992).
In a du Pont patent application of 1991, 10-95 parts PVC was blended with a
complementary amount of a mixture consisting of 30-85 wt % imidized acrylic
copolymer, having the glass transition temperature above 130°C (e.g., ParaloiJIM),
and a third polymer processable at temperatures of 150-300 °C that was free of
functional groups capable of causing degradation of PVC (e.g., SMA, Dylark™
232) to give co-processable blends with high heat deflection temperature (Gia, 1992).
The same year Roehm applied for patent protection for a broad range of materials
comprising tough and hard phases, at least partly covalently bonded. The glass
transition temperature of the tough phase was below 10 °C, whereas that of the
hard phase was above 30 0c. The patents comprised PVC blends with AES. The
latter resin was a core-shell graft copolymer prepared from EPDM, styrene-buta-
diene methacrylate or allyl cyanurate grafted copolymers. The blends, showing high
notched impact strength, could be molded or extruded to form instrument housings,
car bumpers and other auto parts (Siol, Fischer, Tebrack and Koralewski, 1993, 1995).
Also in 1991, B. F. Goodrich disclosed ternary alloys for molding or extrusion that
comprised PVC, CPVC and an acrylic polymer, such as PMMA, methylstyrene-
acrylonitrile-methylmethacrylate, methylstyrene-acrylonitrile-styrene, imidized
PMMA, imidized SMA and SAN. The binary blends of PVC/CPVC and PVC/
MABS showed HDT higher than predicted by the linear-additivity rule. Thus sub-
stantial amount of alloying acrylic copolymer could be replaced with CPVC without
changing the HDT or the melt viscosity (Soby et al., 1994).
In 1992, Kanegafuchi Kagaku Kogyo announced PVC blends with a graft copoly-
mer (containing 5O-85wt% polybutadiene with particle diameters below O.lllm,
grafted with methacrylate, styrene and divinylbenzene). These moldable alloys
showed high impact resistance and good transparency (Takaki et al., 1992, 1993,
1994).
In summary, incorporation of IG-40wt% ABS (high rubber, low modulus emul-
sion resin) to PVC improves processability and impact strength. The ABS/PVC
systems are immiscible, forming three phases, PVC, SAN and elastomer. For many
applications the interactions between SAN and PVC provide sufficient compatibility.
However, as cited above, there are many applications where enhanced miscibility
offered by incorporation of acrylics is advantageous. The elastomeric component is
responsible for enhanced toughness. The particle size of the elastomer is critical to
the transparency of the system.
10.5.6 ABSIPC blends

Bisphenol-A polycarbonate (PC), was invented in 1958, whereas the first, easily
moldable ABS/PC blends were developed in the 1960s. The materials were prepared
by compounding PC with 5-49wt% ABS (Dow Chemical Co., 1960a). Shortly after,
Borg-Warner patent described blending 30-90wt% PC with AB5-type G. The blends
were mixed on a two-roll mill, granulated and injection molded, to give materials
with good thermoplasticity, impact strength and hardness (Grabowski, 1964a, 1964c,
1966,1970,1971,1972). In a sense, this basic technology has been used to produce the
highly successful PC/ABS commercial blends BayblendfM from Bayer or Mobay,
CycoloyTM from General Electric, Idemitsu™ PC/ABS from Idemitsu Petrochemical
Company, Iupilon™ from Mitsubishi Gas Company, Lastilac™ from Lati Engineer-
ing, LupoyTM from Lucky Company (now LG Chemical Limited), Multilon TM from
Teijun Chemicals, NovaloyTM-S from Daicel Chemical Industries, Pulse™ from Dow
Chemical, Ryulex™ from Dainippon, TerblendfM B from BASF, Techniace™ TC from
Sumitomo Dow Limited or Triax™ 2000 from Monsanto Chemical Company. The
first ABS/PC blends entered the market in 1967. Ten years later Borg-Warner
introduced CycoloyTM and, simultaneously, on the license from Borg-Warner,
Mobay-Bayer introduced Bayblend (Gasparich, 1981). In 1980 Daicel Chemical Indus-
tries commercialized their NovaloyTM-S blends; 4 years later Lucky Company intro-
duced LUpoyTM. Pulse blends were commercialized by the Dow Chemical Company
in 1987; Techniace in 1992 by Sumitomo Dow Limited.
The ABS/PC blends are becoming increasingly important, as their properties are
nearly additive, and their cost-to-performance ratio is low. The alloys have the
processability of ABS together with the excellent mechanical properties, impact
and heat resistance of Pc. By varying the composition and morphology it is possible
to tailor performance to requirements. For example, varying the PC content results in
changes of the Vicat-B softening point from 112 to 134 0c. The blends show high
dimensional stability, low shrinkage, low moisture absorption, high stiffness and
hardness, good electrical properties in the low voltage and low power range and
good impact resistance at temperatures from -50°C, thus extending the impact
range of Pc. The ABS/PC blends show excellent flow characteristics, especially at
the high shear rates of injection molding, which makes them suitable for molding
thin-wall complex parts.
Commercial ABS/PC blends (similarly to those of ABS/PVC) are being manufac-
tured with either a dispersed or a cocontinuous morphology. The ABS/PC blends
with dispersed morphology show high tensile strength and high flexural modulus at
room temperature. The modulus. gradually decreases until the temperature
approaches the lower glass transition temperature, i.e., that of ABS (85-100 0C),
and then decreases rapidly. The blends maintain a high tensile strength at modulus
up to a temperature of HDT-I0°C. By contrast, the blends with cocontinuous
morphology show a particularly attractive set of mechanical parameters. Since in
this case both phases form a matrix and dispersed phase, the mechanical perfor-
mance only slightly decreases at the Tg of ABS, then continues nearly independently
of the temperature up to the vicinity of Tg (PC), about 150°C. These blends have been
offered by, for example, Dow, Monsanto and Sumitomo Naugatuck. The cocontinu-
ity has been observed for nearly equal volume fractions of the two principal compo-
nents, PC and ABS, such as for PC contents between 35 and 65 vol %.
The key characteristics of commercial ABS/PC alloys include good impact
strength, excellent UV stability, processability, mechanical properties, heat resist-
ance, flame retardance and blow moldable grades. The creep behavior of ABS/PC
blends, with values between those for PC and ABS, depends on temperature, stress
and time. The Poisson's ratio for most ABS/PC grades is 0.35. The ABS/PC alloys are
resistant to a variety of household and commercial chemicals. They show good
resistance to acids, diluted alkaline solutions, vegetable oils and mineral oils, but
poor resistance to gasoline, aromatic hydrocarbons, esters, ketones and some
chlorinated hydrocarbons. They may suffer loss of properties when highly stressed
parts are exposed to hot water or moist high-temperature environments. The resins
were found well suited for computer and business machine housings and structural
components, electrical applications, cellular phones, lawn and garden equipment
and automotive components including instrument panels, interior trim and wheel
covers.
Similarly to ABS/PVC blends, the ABS/PC ones are immiscible having three
distinct phases of PC, SAN and elastomer (Echte, 1989; Suarez et al., 1984; Kim and
Burns, 1988). The blends are compatibilized by the presence of dipole-dipole inter-
actions between PC and SAN. The miscibility between the PC and SAN is particu-
larly evident at high AN content, e.g., AN ~ 25wt% in SAN (Keitz et al., 1984;
Morbitzer et al., 1985; Kim and Burns, 1988). However, for some applications the
PC-SAN interactions may be insufficient. In this case, modification of ABS
by incorporation of acrylic, acidic or epoxy groups is known to provide a solution.
Com~sitions of ABS/PC blends vary broadly, from modified-ABS resins such as
Cycoloy EHA or Techniace™ (improved OTUL and tensile strength, but not the
notched impact strength), to the impact-modified PC, such as Puise™. As the PC
content increases, the impact strength also increases, but the ductile-brittle transition
shifts to lower temperatures (Weber and Paige, 1986).
The multicomponent PC/ABS blends started to be patented in the mid 196Os, such
Borg-Warner blended PC with 10-70wt% ABS and a grafted butadiene-acrylate
elastomer, in a Banbury mixer at 210°C (Grabowski, 1964a). In the following patent,
10-80wt% PC was blended with 10-50% ABS and with 80-10% styrene-a-methyl-
styrene-acrylonitrile (MSAN) copolymer, for use as metal replacement in automobile
body parts - these alloys had high impact strength HOT and hardness. To further
increase HOT without losing high impact and tensile strength, polysulfone (PSF)
was added to ABS/PC blends. Thus, PC was pre-blended with PSF at a ratio of 1:1,
then 10-90 wt % ABS was incorporated to give materials with an excellent set of
properties (Grabowski, 1970, 1971, 1972). Similarly, in the 1969 patent application
from Surnitomo Chemical, PC was blended with 1-99 parts of poly(aryl ether
sulfone) (PAES) and 1-90 parts of either ABS or butadiene-methylmethacrylate-
styrene (MBS) to give alloys with good heat and impact resistance (Yamauchi et al.,
1974). A year later, Uniroyal announced blends of ABS with 10-50wt% PC and 10-
45wt% aromatic polyethersulfone (PES). The alloys had good processability, high
HOT and impact strength (Weaver, 1972). As is evident from this resume, PC/ABS
blends frequently comprise another polymer or copolymer that improves miscibility
and/or toughness, or provides a special characteristic property.
In a 1972 patent application, Teijin Chemicals disclosed PC blends with ABS and
ethylene-vinyl acetate copolymer (EVAc). The material was reported to show good
flow, thermal and mechanical properties (Hasegawa et al., 1974). By contrast, blends
containing 20-80wt% PC, 10-80% ABS and 10-80% PMMA, were melt-blended into
resins with good processability, a reasonable impact resistance, pearl-like irides-
cence, dyeability and solvent resistance (Ikura et al., 1974). These blends were
commercialized as Meta-marbie™. In the 1974 patent disclosure from Bayer, high
heat resistant, dimensionally stable molding compositions were prepared by blend-
ing PC with PVC and ABS (Hardt et al., 1975; Mietzsch et al., 1975).
In a Tokyo Shibaura Electric Company patent, PC was blended with CPE grafted
with SAN, ACS. Preparation of these blends involved two steps, first grafting, then
compounding with Pc. The resulting materials showed excellent mechanical
properties (Kabuki et al., 1973). Easily moldable, impact resistant PC alloys were
disclosed in 1976 by Surnitomo Naugatuck Company. Thus, PC was blended with a
variety of skin-core copolymers, prepared by grafting styrene and acrylonitrile on
particles of an elastomeric latex (Sakano et al., 1978). Two years later new PC/PEST/
ABS blends were proposed. Accordingly, PC was blended with less than 6Owt% of
an aromatic polyester, less than 6Owt% of SAN, and with methylmethacrylate-
butadiene-styrene copolymer (MBS). The blends showed excellent impact strength
and thermal stability (Teijin Chemicals, 1980).
In the beginning of the 1980s the reactive blending of PCI ABS began to dominate
the patent literature. It became recognized that to obtain good mechanical behavior
of these blends the interface must be modified. As will be evident from the examples
listed later in the text, two methods have been used in parallel: (1) introduction of an
acid or acid anhydride units into ABS, and (2) preparation of multicomponent (at
least three components) blends comprising PC, ABS and an acid-groups containing
copolymer, such as SMA.
Initially, the PC blends with ABS modified by incorporation of the maleic anhy-
dride moieties were developed. These groups, capable of reacting with the hydroxyl
groups of PC, improved blend compatibility, making it possible to generate finer
dispersions (thus higher impact strength), better adhesion between the phases, as
well as higher HOT. Later patents described compositions comprising ABS modified
by incorporation of acrylic acid groups, AB5-AA. These moieties are less reactive
than maleic anhydride, but at the same time they provide more stable reaction
products that are easier to reprocess. In the third generation of this type of blends,
ABS modified by copolymerization with glycidylmethacrylate, AB5-GMA, was
used. The latter materials, Originally developed in Germany then widely used in
Japan, offered particularly interesting possibilities, as the epoxy group is reactive
with a number of moieties having labile hydrogen, such as -DH, -COOH, -NH2, etc.
AB5-GMA became a preferred compatibilizer and impact modifier for a variety of
engineering and specialty resins.
The multicomponent PCI ABS blends were developed in parallel, but there is less
clear evidence of progressive modification of composition. For example, in the late
1970s Dow Chemical developed blends containing 3O-4Owt% PC, 2-25wt% ABS
and 45-55 wt % rubber-modified SMA. However, at the same time, blends of PC with
styrene-acrylic acid copolymer (SAA) and ethylacrylate-methylmethacrylate
(EAMM) were also proposed. Both these systems were reported to have high impact
strength and HOT. Addition of organosilanes or perfluoroborate salts served as
ignition depressants. The blends showed improved melt flow properties, heat resist-
ance and impact strength (Henton, 1980, 1982; Thomas, 1982; Weber and Paige,
1986). In a patent deposition of 1981, blends of PC with ethyl acrylate-methyl-
methacrylate grafted-rubber (ACM) and styrene-acrylic acid copolymer (SAA)
were reported to show improved impact strength and HOT (Henton, 1984). In
1985, Dow disclosed flame resistant blends of PC obtained by incorporating
bromostyrene-grafted ABS into PC (Henton, 1986).
Similarly, in a Sumitomo Naugatuck disclosure of 1980, 50 parts PC was blended
with 50 parts ABS, and an acid or anhydride (Sakano et ai., 1978, 1981a). In later
patents, PC blended with ASA was found to have superior weatherability over PCI
ABS blends (Sakano et ai., 1981b, 1984). The same year, Stamicarbon disclosed blends
of PC with a-methylstyrene-grafted ABS. The alloys showed good stickiness, heat
stability and impact strength (Van Asperen, 1982). Similarly, in a Mobay patent
application, 5-95wt% PC was blended with 95-5wt% ABS, and 0.1-15 phr ethy-
lene-acrylic acid (EAA) acidic compatibilizer. Blending was reported to improve
processability and impact strength (Grigo et ai., 1984). In a series of patents deposited
in 1981 BASF announced that PC was extruder blended with 90wt% ABS for
materials with high HOT, good mechanical, tensile and impact properties. In the
following document, 4Owt% PC (linear or branched) was impact modified by
blending with ABS, SAN and 1 wt% styrene-maleic anhydride-acrylic acid (SMA-
AA) copolymer. Alternatively, branched PC was blended with ABS and SAN. The
blends showed high HOT and impact strength (Brandstetter and Haaf, 1982; Brand-
stetter et al., 1982, 1983).
The same year, Oaicel Chemical blended PC with styrene-methylmethacrylate-
glycidylmethacrylate copolymer (SMM-GMA) than styrene and acrylonitrile
were added and polymerized in situ. The material had excellent processability,
HOT and impact strength. In a later patent, PC was blended with SMM, and a
three-stage copolymer (styrene-diallyl maleate-butadiene-methylmethacrylate). The
blend with good appearance, showed high notched Izod impact strength, and
HOT. The company also developed new types of ABS containing maleic anhydride.
These resins were produced by dissolving SBR in styrene, maleic anhydride and
acrylonitrile, then polymerizing the solution. Blends of PC with ABS-MA were
particularly suitable for injection molding. Molded parts showed significant
improvement of HOT and impact strength over the twcrcomponent PC/ABS blends.
Similar perfonnance was also obtained from alloys comprising 10-60 wt % PC and a
mixture of styrene-butadiene-styrene block copolymer with SMA (Oaicel Chemical
Industries, 1982a, 1983, 1984). In a document deposited in 1984 the company
revealed that PC blended with styrene-maleic anhydride-grafted elastomer, SBR-
MA, showed excellent processability and low thennal expansion (Tanaka, and Mori,
1985).
Also in 1982, PC blends with lOwt% ABS and/or MBS graft copolymers were
disclosed. The injection molded and chrome-plated blends showed high notched
Izod impact strength (Japan Synthetic Rubber Co., 1983).
In the 198Os, several patents described three-eomponent alloys of great commer-
cial interest: PC/PEST/ ABS. For example, in the early 1980s Bayer disclosed a family
of blends containing PEST, PC and an impact modifier, e.g., ABS or an ACM. Thus
polybutyleneterephthalate (PBT) was blended with PC and either ABS or a graft
copolymer of polybutadiene and (meth)acrylate esters and possibly acrylonitrile,
acrylate rubber, ACM (Bier and Indner, 1982; Neuray et al., 1982; Nouverte et al.,
1982; Serini et al., 1982). At about the same time Uniroyal developed AES, based on
styrene-acrylonitrile grafted EPOM. Addition of 1(}-30wt% of these copolymers to
PC blends with PBT, engendered lO-fold higher impact strength over the PC/AES or
PBT/ AES systems (Wefer, 1984, 1985, 1988). In a Mobay patent application of 1983,
43wt% of PET was blended with the same amount of PC and 14% ABS (comprising
7(}-80wt% of PB core), to give blends with good impact strength at low temperature
(Chung et a/., 1985). These impact modified PC/PEST blends will be discussed later
in the text under the appropriate subtitles.
In 1983, Monsanto disclosed blends of ~70 wt % PC, with ~70% ABS (comprising
a-methylstyrene and styrene) and with ~70% of styrene-methylmethacrylate-maleic
anhydride (SMMA-MA). The blends with cocontinuous morphology showed
excellent impact properties (Jones and Mendelson, 1985). They proVided the base
for development of the highly successful PC/ABS commercial blend, Triax™ 2000.
In Apri11993 the company also commercialized Triax™XP40 containing ABS, PC
and PET. The blends showed similar properties to Triax™ 2000. However, owing to
the presence of the semicrystalline PET resin, they show improved melt strength, as
well as solvent, chemical and heat resistance. These blends can be extruded, injection
molded or blow molded into a variety of parts for internal and external use in
automobiles.
In a Bayer patent application of 1984, 1(}-80% PC was reactively blended with 1(}-
60% ABS, styrene-acrylonitrile-glycidylmethacrylate, 10-60% SAN-GMA and 1-20%
NBR, to give alloys with good HOT and toughness (Lindner et al., 1985). The
following year PC was blended with graft copolymer from acrylonitrile-butadiene-
a-methylstyrene-methylmethacrylate (lG-60 parts MeABS), and acrylonitrile-a-
methylstyrene-methylmethacrylate copolymer (1-70 parts MeSAN). Moldings
showed good compatibility, toughness and thermal stability (Kress et al., 1986).
These patents form a basis for Baybientf'M resins.
In 1984, blends of 6Owt% ASA with 30wt% PC and lOwt% PMMA were
described in General Electric's patent disclosure as haVing excellent weatherability,
impact and mechanical properties (Giles and Sasserath, 1986). The same year, Teijin
Chemicals announced several PC blends, including the ones comprising 100 parts of
PC, with 20-200 parts ABS and 0.5-7 parts of acrylic rubber. These systems were
characterized by good solvent and low temperature impact resistance (Ohara and
Kishimoto, 1985). Later the same year, the company disclosed a new family of PC/
ABS blends, for example comprising 3D-90wt% PC, with 10-70wt% methyl-
methacrylate-butadiene-styrene copolymer (MBS) - Kane™ Ace B-28, 0.5-10% PO,
and 1-20% acrylic elastomer, HIA-15. These alloys gave good processability, HDT,
interlayer adhesion and impact resistance (Kitamura, 1986).
According to a General Electric patent application of 1987, the properties of PC/
ABS blends were improved by addition of acid-modified ABS or SEBS, vinyl alcohol
copolymer and polypropylene or its copolymers (Gallucci and Bookbinder, 1989;
Gallucci, 1989). A simultaneous Borg-Warner Chemicals' patent described blends of
15-65wt% PC with styrene-acrylonitrile-maleic anhydride copolymer, 25-75wt%
SAN-MA and 4-19wt% ABS (having 2 4Owt% BR). The blend showed good HDT,
impact strength and modulus (Parsons, 1989).
In 1989, Dow Chemical disclosed PC blends with ABS (AN 2 18%) and ASA, at a
ratio of 1:1:1. The alloys showed high melt elasticity and impact resistance as well as
good weatherability (Laughner, 1991). Bayer patented blends of PC with ABS, PTFE,
and cresol novolak phosphate oligomers. The material showed non-dripping pro-
cessability, and fireproofed behavior (Fuhr et al., 1992).
In 1990, to improve the impact and weld line strength of PC, General Electric
developed its blends with 5-25wt% ABS (containing 4Owt% BR) and 1-20wt%
PMMA (Kambour, 1992; Gaggar and Ziegelmeyer, 1992, 1994). Flame resistance
was improved by addition of 5-15 wt % resorcinol diphosphate. The following
year Nippon Petrochemicals applied for patent protection for blends containing 1-
99% polyphenylenesulfide (PPS) Fortron™, PC, PPE and ABS. To this mixture 0.1-
loophr compatibilizing graft copolymer [multiphase copolymers of styrene-glycidyl
methacrylate (SGMA) or ethylene-glycidylmethacrylate (EGMA)] was added.
The principal alloys, comprising ABS/PC/PPE/SGMM, showed good processabil-
ity, impact strength, heat resistance and appearance, and have been used
to manufacture automobile, electrical or electronic parts (Orikasa and Sakazume,
1992).
In 1992, General Electric Company deposited several patents for low-gloss, mold-
able blends of PC with ABS. The gloss-reducing components (usually 5-35wt%)
were either a graft copolymer of styrene, hydroxyethylmethacrylate and acrylonitrile
bonded onto a 1,3-butadiene rubber (Rawlings and Vilasagar, 1993), styrene-acrylo-
nitrile-methacrylic acid copolymer (Vilasagar, 1993), styrene-acrylonitrile-hydro-
xyethylmethacrylate (Vilasagar, 1994) or an acrylonitrile polymer containing gels
(Wildi et al., 1994). For example, low-gloss blends comprising 5D-75wt% PC, 10-
25wt% ABS and 5-35wt% AB5-HEMA were developed for injection molding.
Addition of 10-15phr of resorcinol diphosphate was found to reduce flammability
to V-O rating as defined in the UL94 test method. (Vilasagar and Rawlings, 1994).
The blends comprising hydroxethyl methacrylate (HEMA) also had electrostatic
discharge properties.
Resume
PC/ABS blends are amorphous and show good dimensional accuracy, low distor-
tion and shrinkage, low moisture absorption, high softening point (Vicat B = 112-
134 °C, increasing with PC content), stiffness and hardness comparable to that of PC,
good notched impact strength down to -50°C, and good electrical properties in
the low voltage/low power range. However, owing to the PC content, the blends
have limited resistance to hydrolysis (extended contact with water at temperatures
above 50°C should be avoided), and because of the ABS presence they are opaque.
Since their toughness decreases with weathering, special stabilization systems,
additional varnishing or metallization are frequently used. Alternatively, in view
of the exceptional weathering resistance of ASA and AES, these copolymers may be
used to replace part of ABS in specialty blends.
Blending ABS with PC leads to materials characterized by good processability,
high weldline strength, high impact strength even at low-temperature, high heat
distortion temperature (HDT), good rigidity and strength, good dimensional
stability, toughness, delamination resistance, creep, solvent and chemical resistance,
and excellent plating. The blends are available as flame retardant, suitable for electro-
plating and glass fiber reinforced grades. Addition of glass spheres and mineral
fillers opens the way to numerous possibilities for modification. Injection molding,
extrusion, and thermo- or vacuum-forming are the usual processing methods. They
can also be compression or transfer molded. The surface of injection-molded
parts usually has high gloss, except for specially formulated blends comprising gel
particles.
Moldings and semifinished PC/ABS blends are easy to fabricate both by hand and
by machine. Joining can be effected by ultrasonic, vibration, friction and hot plate
welding or by bonding with one- or two-pack adhesives. Suitable products for
printing and coating are available. Electroplating can be carried out by the same
process as for ABS (grades with high ABS content give the best results). Their most
important properties are superior HDT and toughness. There is increasing demand
for improved weathering resistance - the ASA/PC blends are an obvious solution.
Comparing ASA to ABS it is noteworthy that the first resin has a higher glass
transition temperature, that results in somewhat poorer toughness at low tempera-
tures. However, the lack of unsaturation in ASA increases its resistance to photo-
oxidative decomposition - ASA/PC resistance to weathering is outstanding. In
comparison to ABS/PC blends those with ASA have better stress crack resistance
and similar room temperature impact strength, Vicat softening temperature, heat
distortion temperature and toughness. The solvent resistance of both blend types is
poor.
PC/ABS blends are available from numerous suppliers. Owing to good processa-
bility and performance, ABS/PC blends find many applications. They have been used
in the automotive and electrical industries, lighting, domestic appliances and leisure.
Examples include automotive interior instrument panels, dashboards, mirrors, vent-
ilation systems, roof linings, badges, profile strips, side strips, grills, glove-box lids,
parcel shelves, loudspeaker grills, consoles, wheel trims, column cladding, spoilers, in
exterior body panels, wheel covers, protective side trims, first aid boxes, typewriter
shells, connector boxes, fuse boxes, plugs, sockets, switches, timer housings, lighting,
vacuum cleaners, iron handles, humidifiers, enclosures of business machines and
electrical appliances (flame retardant blends), electrical and electronic parts, connec-
tors, carriages, switches, fans, power and agricultural tools, cameras, optical instru-
ments, electronic or telecommunication parts, snow throwers, snowmobiles etc.
10.5.7 ABSIPA blends

Blends of ABS with PA are antagonistically immiscible, hence the standard three
strategies for blending: (1) addition of small amount of ABS can act as an impact
modifier to improve PA toughness without a need for compatibilization; (2) genera-
tion of cocontinuous morphology may produce materials with attractive perform-
ance without a need for compatibilization; (3) Compositions comprising a large
amount of either component, ABS or PA, must be compatibilized. Several compat-
ibilization strategies for PAlABS systems have been developed.
Since linear polyamides, such as poly-~-caprolactam (PA-6) or poly(hexamethyle-
nediamine-adipic acid) (PA-66) are crystalline with a high melting point, it is pre-
ferable to have these resins as the continuous phase (these systems have better heat
and solvent resistance than the ones with reversed morphology). However, to pre-
serve the ABS-generated toughness in a wide range of conditions, the ABS phase
should also be continuous. Thus, cocontinuity of phases has been the preferred
morphology of these blends. As stated in Part 2, such a morphology can be achieved
by adjusting concentration and the viscosity ratio of the individual components
(Utracki, 1991c). Although cocontinuity of phases results in materials having advant-
ageous properties, for optimization of the performance usually requires compatib-
ilization. In these systems compatibilization must stabilize the cocontinuity of
morphology, and provide an appropriate degree of dispersion. The key to high
performance of ABS/PA alloys has been optimization of the amount and the type
of compatibilizer to generate stable cocontinuous morphology with an appropriate
degree of dispersion. Just as in the case of blends with dispersed-drop morphology,
so also in systems with cocontinuous structures it is the degree of finesse that
determines the performance.
In alternative systems, ABS with its lower softening temperature (Tg ::::: 85-100°C)
is incorporated as a dispersed phase impact modifier. Since the amount of ABS
required for adequate impact modification exceeds 10 wt %, ABS should be acidified
by incorporation of either acrylic acid, maleic anhydride or poly(p-hydroxy styrene),
(PVPh) (Lavengood et aI., 1986, 1987; Howe and Wolkowicz, 1987). Owing to high
processing temperatures of PA, it is also desirable to use high temperature ABS,
comprising EPR elastomer, p-methyl styrene, and/or SMA. The advantages of
blending ABS with PA are primarily to reduce moisture sensitivity, improve tough-
ness and reduce shrinkage and warpage of the latter resin.
The ABS/PA compatibilized alloys (with either PA as a matrix or with cocontinu-
ity of both phases) combine the intrinsic properties of the semi-crystalline PA with
those of the amorphous ABS. In many cases the resulting blends show synergistic
enhancement of properties. The materials have good processability and flow, good
surface finish (gloss or matte as required), high heat, chemical, oil, wear and abrasion
resistance, dimensional stability, low temperature impact strength, reduced moist-
ure sensitivity and economy. The blends are formulated for injection molding,
extrusion and thermoforming, but they can also be formed by blow and compression
molding.
Several commercial alloys of this type are available on the market, such as N5 from
Thermofil, Stapron™ N from DSM and UltramicJTM from BASF. NovalloyTM-A from
Daicel Chemical Industries was commercialized in 1988, Techniace™ TA from Sumi-
tomo Dow Limited was introduced in 1992 and Triax™ 1120 was placed on the
market in 1987 by Monsanto. Properties of these materials as well as the processing
requirements are described in the recent Encyclopaedic Dictionary (Utracki, 1994b). In
1995 Japan Synthetic Rubber Corporation introduced ABS/PA alloys under the trade
name MacslloyTM. Several grades of MacslloyTM were developed, each for specific
applications: MacslloyTM A has high moldability and chemical resistance, MacslloyTM
H has permanent antistatic properties and MacslloyTM K, comprising ABS, PA and
AES, has good weatherability and resistance to heat and chemicals.
The main uses of ABS/PA alloys are in the automotive, chemical, electrical,
electronics, consumer and sport industries, such as large components for recreational
vehicles, snow-mobiles, tractors, lawn and garden equipment, power tool housings,
impellers, wheel covers, gears, mirror housings and automobile interior compo-
nents. The material has also been used in antivibration damping structures.
The first ABS blends with polyamide (PA) were developed in 1961, in Borg-
Warner laboratories (Grabowski, 1964b, 1966). Blending PA-6 with l0-60wt% ABS
produced materials having good tensile strength, elongation, hardness and stability
during molding. Twenty years later the company introduced the ABS/PA blend
ElemitJTM for use in automobile body panels.
One of the most successful PAlABS blends has been Triax™-1000, introduced by
Monsanto in 1987. The material is an alloy of PA with maleated-ABS, having a
cocontinuous morphology. In the early Monsanto patents (priority date 1980) 55-
99wt% PA-66 was blended with core-shell copolymer, AB5-MA, specifically
developed for toughening PA. The copolymer comprised crosslinked butadiene
rubber core (particle diameter 0.3-D.8 J.Lm) and was emulsion-grafted with styrene,
acrylonitrile and ethyl maleate or fumarate as rigid polymer shell with thicknesses
from 0.25 ~m. The PA-66/AB5-MA alloys show excellent impact strength (Baer,
1981, 1982, 1986, 1987). Further developments in these alloys were disclosed by
Monsanto in 1985 (Lavengood et al., 1986; Lavengood, 1987; Lavengood et al.,
1988). The maleic anhydride group was incorporated into the SAN chain, providing
the controlled amounts of acidic functionality of ABS, which reacted during com-
pounding with a PA to form a graft copolymer of SAN and PA, able to compatibilize
the blend. The compatibilizer reduced the interfacial tension and improved the
adhesion between phases in the solid state. The blends showed stable, dispersed
morphology with high delamination resistance and excellent toughness. It was
found that extrusion-blending of PA-6, PA-6,66 or PA-66 with the copolymers,
each having Tg < O°C, provided materia,Is with excellent mechanical properties.
For example, PA was alloyed at a ratio from 1:9 to 9:1 with emulsion-grade of either
ABS, AES, AAS or MBS. To 100 parts of this blend less than 40 parts of a mixture of
acid-containing acrylic rubber and maleic anhydride-grafted SAN was added. The
resulting alloy was reported suitable for extrusion or injection molding of articles
with good mechanical performance and impact strength. In the 1988 patent, 50wt%
ABS (containing 4Owt% PB) was blended with 6wt% maleated SAN and 44wt%
PA to give alloys with excellent impact strength.
The patent application of 1980 described PA-6 blends with polybutadiene grafted
with styrene and maleic anhydride (SBMA). The resins compounded at a ratio 1:1
produced an alloy having a set of properties superior to those shown by PA-6/ABS
blends (Asahi-Dow Ltd., 1981). In 1981 Borg-Warner disclosed that PA-6 blended
with ABS containing 0.5-15% carbon-amide, (e.g., acrylamide) with partially
maleated SAN or carboxylated EPDM, gives alloys with high HDT and impact
strength (Grant and Meyers, 1983; Grant, 1985; Grant and Howe, 1988; Howe et al.,
1989).
In patent applications from General Electric of 1987, blends of amorphous co-
polyamide(s), PA, and AB5, at a ratio 1:9 to 9:1 showed improved impact properties
over those of PA. The latter resin(s) was transparent, without a melting point, with
the heat of fusion ~ 1 cal/g. It was composed of either aromatic diamines and
diacids, or be a copolymer of polyamides chosen from PA-6, -66, -11, -12, -63, -46,
-64, -610 or -612. Compared to crystalline blends, these had improved thermal
stability and barrier properties, as well as lower water absorption, hence better
dimensional stability (Fox et al., 1989).
The same year, in an AlliedSignal patent application, maleated acrylonitrile-buta-
diene-styrene, (AB5-MA) or maleated ethylene-propylene copolymer (EPR-MA)
were described as suitable impact modifiers for either amine-terminated polya-
mides, (e.g., PA-6) or thermoplastic polyesters (e.g., PET). Here, the commercial
grades of ABS with high rubber content (although standard grades with about
20 wt % PB can also be used) were modified by reactive extrusion with either maleic
anhydride or fumaric acid, then melt-blended with PA-6 and optionally a small
amount of functionalized EPR. In these blends, PA was the matrix with ABS forming
a fine dispersion (Akkapeddi et al., 1990, 1992a). A small amount of maleated EPR,
pre-blended with the maleated-ABS then compounded with PA, significantly
improved the notched !zod impact strength (Akkapeddi et al., 1993).
Also in 1987, Nippon Petrochemicals and Stamicarbon used acidified ABS, either
ethylene-glycidylmethacrylate graft copolymer or ABS modified by incorporation of
maleic anhydride or glycidyl moieties, (respectively, AB5-MA and AB5-GMA) to
compatibilize and toughen PA blends with other resins, such as PC, PEST or PAr
(Yuichi and Suehiro, 1989; Yasue et al., 1989).
Recently, new mechanical alloying technology has been used to blend ABS with
PA-66. First, the pellets of these two resins were separately ball-milled in a specially
designed shaker ball-mill at acceleration of 12.3 g, a frequency of 29 Hz and tem-
perature of -150°C. The milling times for ABS and PA-66 were, respectively, 8 and
24 h. Next, the resulting fine powders were combined at a ratio of 35:65 wt % and
milled together for another 24 h. The final powder had an average particle diameter
of ::::: 21lm. This powder was then placed under vacuum for 24 h, then consolidated
for 28 h at 69 MPa and 162°C. These mechanically alloyed blends fractured by a
different mechanism than for the melt-blended, compatibilized ABS/PA alloys (Pan
and Shaw, 1993, 1994; Shaw, 1993; Shaw et al., 1993).
10.5.8 ABSIPEST blends

The thermoplastic polyesters (PEST) are dominated by two resins, polyethylenetere-
phthalate, (PET), and polybutyleneterephthalate (PBT). There are similarities
between the ABS/PA blends discussed above and ABS/PEST. In both cases, the
principal blend components are immiscible and require compatibilization: ABS is an
amorphous resin, whereas PAs and PESTs (e.g., PA-6, PA-66, PET or PBT) are
semicrystalline polymers. Thus, it is preferable to formulate the ABS/PEST blends
as either a dispersed system with the latter resins being a matrix, or a cocontinuous
one. Care must be taken to avoid extensive reduction of the crystallinity during the
reactive blending and subsequent processing. Addition of a semicrystalline polymer
to ABS increases its post-processing shrinkage. For this reason addition of mineral
filler or glass fiber to ABS/PA or ABS/PEST blends is advantageous. Compatibiliza-
tion of PA/ABS blends is simpler than that of PEST/ ABS at the same time, higher
hygroscopicity and resistivity to oxidation of PA than of PEST makes the latter
blends more attractive, especially for automotive application.
In these blends a compatibilizer frequently plays the additional role of an
impact modifier. The morphology (thus, final blend properties) depends on the
ingredients' concentration, their rheological properties as well as the compounding
and processing conditions. In most commercial blends PEST forms the matrix in
which ABS and an impact modifier are dispersed. For improvement of weatherabil-
ity at least a part of ABS may be replaced by ASA, such as UltrablencfIM S from
BASF.
In many recent blends, part of the PEST is replaced by polycarbonate, Pc. Most
commercial PBTfPC and PET/PC blends contain 10-20 wt % of an impact modifier,
for example core-shell rubbers such as poly(methylmethacrylate-g-butadiene-co-
styrene) elastomer, MBS, poly(MMA-g-n-BuA), ABS (with PB content ~ 50 %) or
ASA (with acrylate rubber content ~ 50 %), etc. The commercial grades frequently
contain up to 30 wt % glass fiber which significantly reduces shrinkage and warpage
of the molded products.
There are many commercial ABS/PEST blends available on the market. In most
cases, the letter A after the blend trade name indicates that the blend contains PET,
whereas the letter B indicates PBT. Examples of ABS/PBT blends are AlphaloyTM
MPB from Kanegafuchi Chemical, Cycolin™ from General Electric, DiaaloyTM B from
Mitsubishi Rayon, Malecca™ B from Denka Kagaku, MaxloyTM B from JSR and
Triax™ 4000 from Monsanto. Lumax™ was introduced in 1989 by Lucky Company
(now LG Chemicals), NovaloyTM B from Daicel Chemical was commercialized in 1988
and Techniace™TB in 1990 by Sumitomo Dow. In some blends at least some ABS is
substituted by ASA, as in BaitaloyTM VL from Hitachi Chemical or UltrablencfIM S
from BASF. Blends of ABS/PETfPC are also available, such as Makroblend from
Miles and Bayer. In 1995 Japan Synthetic Rubber Corporation introduced new ABS/
PBT alloys under the trade-name MacslloyTM B, having chemical resistance and
superior fatigue performance characteristics.
The ABS/PEST blends have been primarily formulated for injection molding,
although they may also be extruded, compression molded, thermo- or vacuum-
formed, as well as roto-, compression- or transfer-molded. The formed parts can be
assembled using ordinary methods, such as snap-fit, self-tapping, ultrasonic weld-
ing, glUing, etc. They may be painted without primer treatment.
The ABS/PEST alloys show excellent moldability, k>w post-molding shrinkage
and warpage, stress-crack resistance, high gloss, high temperature stiffness, tough-
ness and mechanical strength, high heat resistance at temperatures below 140 °C, low
shrinkage, good dimensional stability, impact strength, good wear and abrasion
resistance, good thermal and weathering resistance, as well as solvent (e.g., to gaso-
line and motor oils) and chemical resistance. Their applications include parts for
electronics, automotive and electrical industry, as well as business and household
equipment manufacturers, namely, automotive exterior or interior parts, chassis,
carriages, fans and castings, connectors, switches, bobbins, parts for videotape
recorders, housings for printers and facsimiles. The reinforced ABS/PBT blends
are frequently used as replacements for metallic parts.
The first ABS blends with PET or PBT were disclosed by Union Carbide in 1968
(Sauers and Barth, 1970). PET was blended with rubber-modified polyacrylates or
methacrylates (5-95wt% ABS and optionally polydimethylsiloxane (1-20wt%
PDMS) to improve its notched impact and embrittlement resistance.
In 1971, Unitika Co. announced that polyarylphthalates (PAr) produced by poly-
condensation of iso- and terephthalic acids with bisphenol-A, when blended with
30wt% ABS, showed improved processability and impact strength (Koshimo, 1973).
Later, in a patent application of 1977, Shell Oil disclosed that the presence of
hydrogenated styrene-butadiene-styrene three-block copolymer (SEBS) stabilized
the morphology of the PBT/ ABS blends, reducing their tendency for phase separa-
tion during processing (Gergen and Davison, 1977, 1978, 1979, 1984; Davison and
Gergen 1977, 1980).
The first reactive blending of ABS with PBT was described in a Toray patent
application, also dated 1977. In this case the blend performance was improved
when PBT was blended with 5-50phr carboxyl-modified ABS (Tanaka et al., 1979).
In a 1987 patent application Nippon Petrochemicals described blends of PBT with
ABS modified by incorporation of maleic anhydride or glycidyl moieties. The alloys
had good heat, chemical and impact resistant properties (Orikasa et al., 1989).
In 1981, Bayer applied for a series of patents on PET/PBT and/or PBTfPC blends
toughened by addition of either ABS or ACM (a graft copolymer of polybutadiene
with acrylate esters, acrylonitrile and acrylate rubber). When ABS with rubber
particle diameters of :::::: O.4llm was used, the blend showed especially high impact
strength and a good balance of mechanical properties. These alloys were found
commercially interesting (Bier and Indner, 1982; Neuray et al., 1982; Serini et al.,
1982; Binsack et al., 1982). To provide lubricating properties, PBT was blended
with ABS and a polytetrafluoroethylene, PTFE. The blends also showed high
impact resistance even at low temperature, and high tensile strength (Koehler et al.,
1986).
Also in 1981, Stauffer Chemical Co. announced that blends of PET with 50wt% of
their three-step interpolymer (obtained from crosslinked acrylate elastomer, cross-
linked styrene-acrylonitrile and uncrosslinked styrene-acrylonitrile copolymer)
showed good toughness, and impact strength (Silberberg, 1982a).
In a Mitsubishi Rayon patent application of 1982, PBT was impact modified by
blending it with thermoplastic polyester elastomer and ABS (Mitsubishi Rayon Co.,
1984). The following year General Electric applied for a patent on blends containing
5-95wt% PET or PBT, and either ABS, MBS or other suitable copolymer. These
alloys showed high gloss and solvent resistance (Michel, 1985). In 1983 Mobay
disclosed blends containing 43wt% PET, 43wt% PC and 14wt% ABS. The alloys
had high impact strength at low temperature (Chung et al., 1985). Two years later, in
the patent applications from Celanese and du Pont, PBT was blended respectively
with either 20-30 wt % of a butadiene-based multipolymer, as AcryloiQfM KM 653, or
with 3-40 wt % ethylene-butylacrylate-glycidylmethacrylate (EBA-GMA). The alloys
showed improved impact performance even at low temperature (McNally and
LaNieve, 1986; Deyrup, 1985).
In 1987, Sumitomo Naugatuck deposited the first patent application on molding
blends comprising PEST and ABS. The document is one of the basic patents for the
PBT/ ABS alloys, as Iechniace™ IB, commercialized in 1990. Thus, PET or PBT was
blended with a graft copolymer of unsaturated epoxide and at least one of vinyl,
nitrile or acrylic monomers, prepared in the presence of EPR or EPDM elastomer,
such as acrylonitrile-styrene-EPDM-glycidylmethacrylate graft copolymer (AE5-
GMA). The specified ratio of PBT to AE5-GMA could vary from 95:5 to 5:95. The
alloys were found suitable for molding electrical or automobile parts (Hirai et al.,
1988, 1989, 1992, 1994). Two years later, the company disclosed blends comprising
2D-40wt% PEST (preferably PBT with M v = 18-88kg/mol), 15-55wt% ABS (PB
content of 5-30wt%, with particle diameter 0.05-5Ilm), 25-45wt% of an a-methyl-
styrene-acrylonitrile copolymer, MeSAN with 15-25 wt % AN. The alloys gave mold-
ings with good impact resistance, flexural modulus, chemical and heat resistance,
and dimensional stability (Kodama et ai., 1992, 1990).
Also in 1989, Sumitomo Naugatuck announced blends of polyphenylene ether,
10-90wt% PPE, 8-88wt% ABS and 1-30wt% of an AB5-type graft copolymer
having vinyl groups at molecular end(s). The materials showed good processability,
giving moldings with improved impact resistance (Minematsu and Nagai, 1992,
1993).
10.5.9 ABSrrpU blends
ABS/TPU blends have been formulated to profit from a combination of the inherent
advantageous properties of the two main ingredients, namely TPU's toughness and
paintability, and ABS's low temperature impact strength and adequate HDT. The
main performance characteristic of these alloys is their excellent impact behavior
down to -40 0c. Furthermore, TPU improves antifriction properties, abrasion resist-
ance, low temperature impact strength and chemical resistance. Stiffness is also
increased and the flowability of injection molding compounds is good. The blends
show low modulus.
In most ABS/TPU blends, ABS is uniformly dispersed in TPU matrix. Depending
on the type of TPU compatibilization may not be necessary. It is TPU that makes it
possible for the blends to be painted without a primer, while the ABS component
imparts adequate heat resistance for paint ovens. Thus, the blends are particularly
well suited for use in exterior automotive parts, that after painting must go through
the paint curing oven.
The two commercial alloys Prevaii™ and Techniace™ TU have been available,
respectively, since 1990 from Dow Chemical and 1992 from Sumitomo Dow. The
blends have been designed for injection molding or extrusion. However, they may
also be formed by blow, transfer or compression molding, by calendering or thermo-
forming and by solid state forming methods. The ABS/TPU blends have good
processability, intermediate hardness (between that of TPU and ABS), outstanding
fleXibility, superb low temperature toughness, excellent chemical resistance, good
appearance and paintability. Fabricated parts can readily be finished and decorated
by a variety of conventional methods, including hot stamping, metalizing or plating.
These blends are primarily used for automotive markets as paintable, soft bumper
fascias, and trim, but find many applications in consumer goods as well.
The first blends of ABS with thermoplastic polyurethane (TPU) were developed in
1964 at Borg-Warner. In 1976 Sumitomo Naugatuck disclosed blends of TPU with
styrene-butadiene rubber (SBR), grafted with acrylonitrile, acrylate or methacrylate
esters (MABS). The resulting materials had good processability and elongation (Abe
et ai., 1977). Two years later, in a patent application from ICI, blends comprising 1-
99 wt % TPU with ABS were described. These uncompatibilized alloys were char-
acterized by high moldability and low temperature impact strength (Aitken and
Lord, 1979; Aitken et ai., 1979).
In 1991, Monsanto and Dow disclosed new types of TPU/ ABS blend. In the
first case, ester-type polyurethane (2D-89 wt % TPU) was blended with acrylic copo-
lymer (1D-70wt% SMM-MA), diamino- or dihydroxy-terminated polydimethylsi-
loxane (1-2Swt% mPDMS) and D-SOwt% ABS or MBS. Extruded or molded articles
showed reduced fogging and enhanced low temperature fleXibility (Gomez, 1992). In
the second case, high modulus polyurethane, 35-9Swt% TPU, was blended with
bulk-polymerized ABS to give high impact strength materials for automotive body
parts, and housings for electrical appliances (Henton et ai., 1992).
10.5.10 ABSIPSF blends

In the ABS blends with polysulfone (PSF), it is the role of ABS to improve flowability
and reduce cost, while that of PSF is to improve the shape retention at high tempera-
tures similarly to, but more effectively than, Pc. Thus, ABS/PSF blends have good
processability, toughness (particularly the notched lzod impact strength), plateabil-
ity, hydrolytic stability and economy. However, they may show poor surface and
weld-line strength. They need to be compatibilized, for example with Phenoxy,
ethylene-vinylacetate-glycidylmethacrylate (EVA-GMA) or SMA copolymers.
Arylon™, the first commercial ABS/PSF blend originally introduced in 1964 by
Uniroyal, and Mindel™ A from Amoco are examples of these alloys available on the
market. In the early 19705, Union Carbide acquired from Uniroyal the rights to
manufacture these alloys, then transferred them to Amoco. The unfilled, mineral-
filled and glass fiber-reinforced materials may also incorporate other engineering
thermoplastics as modifying components. Ucardel™ is an example of PSF blends
with SAN. The latter blend is composed of PSF, high heat ABS based on a-methyl-
styrene, Phenoxy as compatibilizer and MBS core-shell rubber as impact modifier. It
shows good processability, toughness, plateability, heat and water resistance. The
blends have been used in plumbing, sterilizable equipment, electrical and electronic
parts, circuit boards, connectors, etc.
The first commercial ABS/PSF blend was Arylon.™ The patent deposited by
Uniroyal in 1967 specifies blending PSF with 4O-52wt% ABS (Ingulli and Alter,
1969, 1970). The materials were reported to have excellent flow properties, HOT =
145°C, good impact resistance and self-extinguishing character. To improve proces-
sability, a copolymer of a-methylstyrene with acrylonitrile (MSAN) could also be
added. About the same time, Borg-Warner patented three-component blends com-
prising 10-90 wt % ABS with equal amount of PSF and Pc. These blends were also
reported to have good processability, rigidity, impact and tensile strength, as well as
high HOT. In the following patent from the company, addition of 5-40 wt % halogen-
ated norbornene methano-naphthalene compound to the previously disclosed for-
mulations was found to further increase HOT (Grabowski, 1971, 1972).
In 1967, Union Carbide disclosed development of polyarylether sulfone (PAES)
blends with acrylonitrile-ethylene copolymers, 2-30 wt % AES. These systems, when
partially crosslinked by irradiation, showed high toughness and impact strength
(Barth, 1970). Two years later, Uniroyal applied for patents on PAES blends with
ethylene-vinylacetate copolymer (1-25wt% EVAc) or with methylmethacrylate-
butadiene-styrene copolymer (1-5Owt% MBS). Good tensile, flexural and impact
strength, as well as HOT were announced (Lauchlan, 1971). In a later patent, ABS
was blended with lQ-45wt% PAES and 10-50wt% PC to give alloys with good
processability, HOT and impact strength (Weaver, 1972).
At the same time, Sumitomo Chemical disclosed similar blends, containing 1-99
parts of PAES, and 1-90 parts of either MBS or ABS, and Pc. These alloys showed
good heat stability and impact resistance (Yamauchi et al., 1974). In a following
patent, PAES was blended with 5-95 wt % a-methylstyrene-methylmethacrylate
copolymer (MMS) to give alloys with good moldability and high HOT (Kawakubo
et al., 1974).
In 1978, Toray Industries applied for patent protection for blends comprising PSF
(Udel™ P-1700), with 10% of an anhydride-terminated PSF and 5-55wt% of buta-
diene rubber grafted with styrene, acrylonitrile and methylmethacrylate (MABS).
The blend showed excellent HOT, and impact resistance (Aya et al., 1979). In another
invention, styrene-acrylonitrile-grafted EPOM (AES) was used in blends with
70 wt % PSF. The materials were reported thermally stable, with good impact proper-
ties (Sumitomo Naugatuck Co., 1982).
In a Stauffer Chemical patent application of 1981, PSF was blended with 5-50 wt %
three-stage interpolymer comprising crosslinked acrylate copolymer, crosslinked
styrene-acrylonitrile copolymer (SAN) and uncrosslinked SAN (Silberberg, 1982b).
The injection molded blends had good tensile modulus and yield strength, excellent
impact resistance, and respectable HOT at 106 °C (Robeson, 1985a).
In more recent patents (applications in 1988) better processability of PSF was
claimed after blending it with ABS and ethylene-vinylacetate-glycidylmethacrylate
copolymer (EVA-GMA) as compatibilizer. The blends having high impact strength
and heat resistance were reported to be particularly well suited for electric or
electronic applications (Gaafar, 1990a; Orikasa and Sakazume, 1990). The 1992 patent
application from Ford describes blends containing 45-60wt% amorphous PSF, 25-
45wt% semicrystalline polyphenylene sulfide (PPS) and 0-10wt% methacrylate-
butadiene-styrene (MBS) (ParaloiJIM EXL). These materials were prepared by first
compounding PPS with MBS to form toughened matrix preblend, then melt-blend-
ing it with PSF. Molded articles showed good resistance to impact, high temperature
and other adverse environmental conditions. Applications include car body panels
(Golovoy and Cheung, 1994).
10.5.11 ADS/SMA blends

Two types of styrene-maleic anhydride copolymers (SMA) are available. The first,
the regular SMA, usually contains 5-12wt% of maleic anhydride (MA) and is
produced by bulk polymerization. The second, impact resistant type, contains 4-
16wt% MA, and is produced by grafting polybutadiene with styrene and MA.
Blending can also be used to impact-modify SMA. SMA/ABS blends and modified
SMA (terpolymer) show partial miscibility with PC and modified PPE.
The ABS/SMA blends show excellent processability, high heat resistance, HDT,
low warpage, stiffness at high temperature, good impact strength, as well as solvent
(e.g., to gasoline and motor oils) and chemical resistance. For numerous applications
they successfully compete with PPE or PC alloys. The main consumption includes
automotive (interior and exterior trim, instrument panels, thermoformable auto-
mobile roof linings, hubcaps, headlight housings), electronics and electrical industry,
houseware, custom sheets, appliances, power tools, industrial machinery, plumbing
products, parts for washing machines and vacuum cleaners, etc.
Several commercial ABS/SMA blends are available. For example, in 1981 Cadon™
was introduced by Monsanto. Simultaneously a blend of impact modified SMA with
PC, ArloyTM, was commercialized by Arco. Some grades are reinforced with glass
fibers. These ASS/SMA alloys have been formulated mainly for injection molding
and extrusion, although they can be thermoformed as well. Of particular interest are
the high temperature resistant, electroplatable terpolymers. Glass fiber reinforced
and antistatic grades are also available. Before processing, the ABS/SMA blends
should be pre-dried for 2-3 h at 95°C. Recommended temperatures for injection
molding are 230-250 °C and for extrusion 220-250 0C. The melt temperature should
not exceed 265 0c.
In 1969, to provide materials with high heat deflection temperature, HOT and high
impact strength, the first blends of ABS with SMA were developed by Dow Chemical
as so call high heat ABS (Stafford and Adams, 1972). They also showed high strength,
stiffness and impact strength (also at low temperatures), and as good chemical
resistance (especially to alkalis) as that of ABS.
In 1980, blends of SMA with a mixture of suspension and emulsion-type ABS were
claimed to show high impact strength and HDT. In the following patent, SMA was
blended with ASS and methylmethacrylate-butadiene-styrene-copolymer (MBS) as
Aeryloid KM 653, to give materials with high impact strength, HOT, gloss and no
surface defects (Oaicel Chemical Industries, 1982b, 1983; Tatuhiko and Akira, 1982).
In the Monsanto patent application of 1982, styrene-methylmethacrylate-maleic
anhydride (SMM-MA) was blended with ABS, polyacrylate (PAC) as Hyear™ 1034,
and with 1,4-butanediol-polybutyleneglycol-terephthalic acid co-polymer (TPE) as
Hytrel™ 4056 (Holtrop and Dufour, 1984).
10.6 SBS BLOCK COPOLYMER BLENDS

In a sense, the styrene-butadiene (or isoprene) di-, tri- or multiblock copolymers (first
reported in 1956), SB or SBS, constitute the next stage of PS modification (Porter,
1964; Holden and Milkovich, 1963, 1966). The key to this technology was on one
hand the rediscovery of anionic polymerization, and on the other hand realization of
the importance of thennoplastic crosslinking - in SB or SBS copolymers the latter
property is provided by small, hard domains of polystyrene.
The block copolymer technology offers a precise control of the size and number of
blocks, thus the size and concentration of the elastomeric domains in the resin or its
blends. Once fracture mechanics has determined the optimal conditions for tough-
ening of a specific polymer, the chemist is able to synthesize the required copolymer.
Since the elastomeric domain size is controlled on the molecular level, the resulting
blends containing these copolymers are relatively insensitive to the compounding
and processing conditions, offering good reproducibility and stability of morphol-
ogy and perfonnance.
The triblock styrene-diene thennoplastic elastomers were announced and
patented in 1965. The domain theory of elasticity was presented in 1967 (Legge et
aI., 1987). By 1967 several patents had been deposited for SBS with commodity resins,
vinyls, styrenics and polyalkenes. Soon these elastomers were also incorporated into
engineering resins, such as PPE, PET, PBT or Pc, either as impact modifiers or
compatibilizers (Bull and Holden, 1977).
Several commercial SB5-type resins are available, such as Clarijlex™ TR and
Elexar™ from Shell Chemicals, Collimate™ from Mitsubishi Monsanto Chemical,
Europrene™ Sol T from Enichem, Finaclear™ from Fina Oil & Chemicals, Kraton™
from Shell Oil, SolTM T from Enarco Elastomers, Stereon™ from Firestone Company,
Thermolastic from Gumiwerke Kraiburg, Tufprene from Asahi, Vector™ 6000 from
Dexco Polymers and Vitacom™ TPE from British Vita. The resins have two distinct
glass transition temperatures, at -90 and +90°C. Their tensile strength is 300-
350 MPa, i.e., nearly twice than that of vulcanized BR. They found applications in
hot melt adhesives and shoe soles, but mainly as additives and blend components.
In 1977 and 1978 patents from Shell Oil (filed in 1976) it was disclosed that
selective hydrogenation of SB or SBS copolymers leads to materials with properties
particularly attractive for blending. For example, blends of hydrogenated styrene-
butadiene-styrene triblock copolymer (SEBS) with such resins as PP, PA, PC, PBT or
PES, showed phase cocontinuity and excellent overall perfonnance. A dispersed
phase size as small as 200nm was obtained (Gergen et al., 1987).
More recent modifications of SBS or SEBS involve incorporation of acidic or acid-
anhydride moieties. For example, a patent disclosure from Shell Oil of 1985
described grafting SEBS with maleic anhydride. The adduct, SEB5-MA, was then
used as an impact modifier for polyamides or polyesters such as PBT. Thus, blends
comprising 50-97 wt % PA and SEB5-MA showed high notched Izod impact strength
(Gelles et al., 1987).
During the intervening years, these grafted copolymers, usually of low molecular
weight, have been used as compatibilizers and/or impact modifiers in blends with
most commodity and engineering resins as well as with some specialty polymers,
such as: PVC or PS with either PE, PP or PPE; PET with PE; PC with PP; PA with PP,
PPS and others (Lindsey et al., 1981; Traugott et al., 1983; Traugott, 1985).
SBS block copolymer blends 177
In the following text a brief review of SBS/SEBS blends will be divided into three
groups comprising blends of these copolymers with either commodity, engineering
or specialty resins.
10.6.1 SBS/SEBS blends with commodity resins
Vinyls
In most blends with vinyl polymers, the role of SBS is mainly that of an impact
modifier. However, its addition is known to impose a stable internal morphology -
one of the attributes of a compatibilizer. For example, in Asahi patent applications of
1967, polyvinylchloride (PVC) was blended with ABS and SBS to improve proces-
sability and impact strength (Minekawa et al., 1971a). In the 1982 patent application,
blends of PVC with ethylene-vinylacetate (EVAc) and SBS were found to have
excellent processability, transparency, thermal stability, weather resistance, low-
temperature flexibility and blocking resistance (Sekisui Chemical Co., 1984). In
1980 blends comprising ABS with PP and SBS at a ratio 100:10:5 were developed.
The materials showed good impact strength, and resistance to chemicals (TDK
Electronics Co., 1982).
Blends of SBS with PS and ethylene-vinylacetate copolymers have a long and
interesting history. In 1971, BASF applied for a patent on polymer mixtures compris-
ing 7~wt% PS with 13-20wt% EVAc and 5-lOwt% SBS. The alloys were
reported to have good impact and tensile strength (Hinselmann et al., 1973). In
1983 Procter & Gamble patented blends comprising ~Owt% SBS and 15-
60 wt % EVAc (with vinyl acetate content 22-33% and melt index < 0.6). The
materials were found particularly useful for manufacturing films (30-150 11m thick-
ness) having both good tensile strength and elasticity (Wnuk, 1984). Later, in a 1989
deposition from Shell Oil it was disclosed that such properties as elasticity, tensile
strength, and reduction of die build-up, of these blends can be improved by the
addition of small amounts of polystyrene, ID-45wt% PS (Djiauw and Mitchell,
1990). Next, in 1992 it was disclosed that the tensile strength of polymer films
containing SB, EVAc and PS can be further increased by replacing a part of the
EVAc with a polyalkene having low crystallinity. Thus, alloys useful for manu-
facturing elastomeric films were prepared from ID-45wt% PS, 5-20wt% of either
LLDPE or ULDPE with crystallinity below 60%, 40-80 wt % SBS Kraton 1M D (having
a molecular weight of 170kg/mol, styrene content of about 32%, and comprising
about 33 wt % of oil), and 5-20 wt %, EVAc (containing 12-32 % preferably 28%,
VAc). Addition of PO was found to increase the tensile strength by 5-20%, without
reducing elasticity (Djiauw, 1994). Thus, in a span of 9 years the blends formulated
for production of elastic films had the number of components doubled.
Styrenics
The role of SBS or SEBS in styrenic blends is twofold - they can be incorporated
either to introduce the desired quantity of well-dispersed elastomeric phase, i.e., as
impact modifiers, or they can serve as compatibilizers, especially effective between
styrenic and alkenic parts in a blend. Several examples of these applications can be
found below.
In 1969, The General Tire and Rubber Company disclosed that blending HIPS with
12.5 wt % SBS resulted in a substantial enhancement of mechanical properties (Durst,
1970). The following year, the company disclosed blends comprising PS with
12.5wt% polybutadiene, compatibilized by addition of 12.5wt% SBS block copoly-
mer. According to the patent the PS/PB/SBS alloys showed better impact strength
than HIPS (Durst, 1975).
Also in 1969, the Japanese Institute for Production and Development of Science
disclosed blends comprising styrene-isoprene block copolymer (SIS) with polysty-
rene (PS) and/or polyisoprene (IR). Depending on composition, the cast films
showed spherical, rod-like or lamellar morphology, resulting in a range of optical
and mechanical properties (Kawai et al., 1978).
In 1978, Shell International Research disclosed blends comprising PS and/or 100-
45 parts HIPS, 2-30 parts PO (preferably polypropylene, PP) and 5-20 parts hydro-
genated styrene-butadiene-styrene block copolymer (SEBS). The blends showed
good impact and flexural strength, as well as tensile yield retention in cottonseed
oil-oleic acid tests (Holden and Gouw, 1979). Three years later, Montefina similarly
disclosed blends of HIPS with high density polyethylene, 45 wt % HDPE and 10 wt %
SEBS to obtain materials with high impact strength (Castelein, 1982).
In 1979, Mobil Oil disclosed poly-p-methylstyrene (PpMS) blends with SBS as
suitable for the use in the packaging industry. These alloys had good mechanical
properties and optical clarity (Sherman, 1981, 1983). The following year, Uniroyal
developed a new type of ABS, mislabeled high impact styrene-acrylonitrile co-
polymer SAN, by grafting acrylonitrile onto SEBS and then blending it with SAN
(Paddock, 1981).
The same year, a deposition from Lehigh University described an interesting
use of the intrinsic properties of SEBS. Thermoplastic interpenetrating polymer net-
works (IPN) with superior mechanical properties, were obtained by dissolving
50 wt % SEBS with 44.5 wt % styrene, 5 wt % methacrylic acid and 0.5 wt % isoprene,
then polymerizing the solution (Siegfried et al., 1984). In 1982 Allied Corporation
explored the IPN technology to produce electrically conductive blends comprising
ethylene-vinylacetate copolymer (EVAc) and carbon black (CB) (Sorensen, 1984).
In 1980, high impact, transparent alloys were obtained by blending PS with (SB)",
and styrene-grafted polybutadiene (SBR). Better improvement of properties was
obtained using two different grades of block copolymers, with different MW and
composition. Similarly, HIPS was blended with a S8-block copolymer. Later patents
published the same year specified the rubber content and size of the particles of both
blend components. Good transparency, flexural, tensile and impact strength were
obtained (Asahi Chemical Industry Co., 1982a, 1982b).
In 1984, Japan Synthetic Rubber Company disclosed that replacing styrene-
butadiene-styrene tri-block copolymer (SBS) by copolymers containing tapered
styrene-butadiene random sequence, results in blends with improved mechanical
performance. Thus, blends of 5-95wt% PS with AXBXA or (AXB)n block copoly-
mers (where A = styrene block, B = butadiene block and X = AB tapered sequence),
were found to give moldings with excellent impact strength, and transparency
(Toyama et al., 1985).
In 1985, Asahi developed terminally modified styrene-butadiene-styrene block
copolymers that when blended with other resins provided interesting sets of proper-
ties. The method involved attachment of a variety of groups, such as acidic, amino,
imido, etc. For example, 2-98wt% of such SBS was blended with 98-2wt% of a
mixture comprising water-absorbing crosslinking resin (e.g., a copolymer of
methacrylic acid and a vinyl monomer with an alkali metal group) and a polar
polymer (e.g., PA, PEST, TPU, POM, PVA!, PC, PSF, PPE, PPS or PVC). These blends
are useful as water-swelling materials, such as water-stopping materials, in civil
engineering and construction because they absorb water and expand. The blends
could easily be adopted for adhesive applications, or as a base for electroconductive
materials. Similarly, SBS with amino or imido terminal groups, was blended with 5-
9S wt % styrene, Mn = 5-1000 kg/mol, to give materials with excellent tackiness,
adhesiveness and creep resistance (Shiraki and Hattori, 1986, 1994).
In 1987, 5hell International Research announced transparent, impact and blush
resistant blends. These were obtained by compounding LLDPE with 5EBS (Holden
and Hansen, 1989). Two years later, Polysar disclosed tough, transparent blends
comprising 10099wt% styrene-butadiene block copolymer, 0.1-1.0wt% (SB)n' cis-
polybutadiene having preferred particle diameter of O.5-1.S ~m and either PS or
SAN. The blends may contain other miscible components, such as PPE, HIPS,
styrene-acrylates, PPS, PSF, etc. They have been used for packaging, containers,
snap-top lids and protective covering (Thompson et al., 1994).
In 1991, the Dow Chemical Company applied for patent protection for thermo-
formable, chemically resistant blends, useful in the preparation of refrigerator and
freezer liners. The blends containing 45-70 wt % HIPS (1-25 wt % of rubber, Mw PS of
S0-4ookg/mol, and having a three-modal distribution of rubber particles: 0.1~.8,
1.2-3 and 3-10 ~), 15-40 wt % HOPE and 5-2S wt % of either SB5 or 5IS (Mw = 20-
100 kg/mol and 35-4Swt% 5T) had a cocontinuous morphology. They were easy to
process into parts with good impact strength and resistance to solvents (Swartzmil-
ler et al., 1994). The same year BA5F announced that blends of S0-80 wt % of either PS
or HIPS, with 20-S0 wt % of either PE or PP, were compatibilized by addition of 0.05-
50phr non-symmetrical linear triblock, 51-D-S2 (containing S0-8Swt% styrene),
where 51 and 52 were polystyrene blocks, 0 was a polydiene block and 51 ~ 52.
The moldable blends had good processability, stress cracking resistance, imperme-
ability to water vapor, and improved impact resistance (Hoenl et al., 1993). In the
following patent from the company, 10-90 wt % PS was blended with 10-90 wt % PO
(e.g., LLDPE) and 5-40 wt % 5EB5 (with at least 50 wt % styrene). The system showed
good resistance to impact and yellOWing (Seelert et al., 1993).
In a series of patents deposited in 1991 and 1992 by Novacor Chemicals (the
company that absorbed a major part of Polysar), new transparent, the high impact
strength alloys Zylar™ were described. The materials were prepared using 30-
82wt% of a brittle styrene-methylmethacrylate copolymer, NAS 30, 3-S0wt% rub-
bery tapered 5B copolymer (43wt% styrene), and 15-67wt% of ductile 5BS triblock
copolymer (7Swt% styrene). The alloys showed extremely low haze and good
impact resistance, making them suitable as replacement for crystal (or lead) glass,
e.g., in patio tumblers (Blasius, 1992). In a following patent, Zylar™ was reported to
retain more than 80% tensile elongation and not to yellow after exposure to either
SMrad ,-radiation or sterilizing ethylene oxide (Blasius, 1994). Later patents
described transparent alloys comprising 85-98wt% NAS (75-80wt% styrene), and
either a mixture of 5B5 and a tapered B5B triblock copolymer, or 4-lOwt% poly-
butadiene grafted with 96-90wt% styrene (having matched refractive index to that
of NAS). The blends showed improved crazing, haze, and impact resistance (Hauser
et al., 1993; Colella, 1993; Colella and Marcoulier, 1993).
In 1992, Sumitomo Chemical invented high gloss alloys with good impact
strength and transparency obtained by blending two different types of HIPS
(and methyl-phenyl silicone oil). Thus, HIPS-I was prepared by polymerizing SBS
solution in styrene, whereas HIPS-2 was obtained by polymerizing butadiene
in styrene solution. The first resin had small core-shell type elastomeric particles
of diameter 0.1~.3~, whereas the second had salami (or cell) type
elastomeric particles of diameters 1.0-1.5 ~m. The preferred composition had a
ratio of HIPS-I to HIPS-2 within the range 95:5 to 98:2. The blends should also
contain 0.05-0.2 wt % methyl-phenyl silicone oil (added before polymerization!;
Okamoto et al., 1993).
The same year, Roehm disclosed blends comprising 1-99wt% of either HIPS or
SBS, and 99-1 wt% acrylic copolymer. The blends were found useful for manufac-
ture of either heat-sealable synthetic films or tight sealing plastic containers for
foodstuffs. The materials were readily processable and easy to manufacture. Further-
more, they exhibited good mechanical stability, and were recyclable (Maul et al.,
1994).
Polyalkenes
In a 1967 disclosure, blends of polypropylene (PP) with 20% of either SBS or SIS
were reported to show high impact strength, without adversely affecting other
physical properties Oapan Synthetic Chemical Industry Co., 1971). In a 1974 patent
deposition from Sumitomo Chemical styrene-butadiene block copolymer (SB) was
blended with either 30wt% PP or 20wt% HDPE. The blends were reported to have
good mechanical properties (Tabana and Maki, 1976).
It was disclosed in 1977 and 1978 patents from Shell Oil (filed in 1976) that
selective hydrogenation of SB or SBS copolymers leads to materials with properties
particularly attractive for blending. For example, blends of hydrogenated styrene-
butadiene-styrene triblock copolymer (SEBS) with such resins as PP, PA, PC, PBT or
PES were reported to have the phase cocontinuity that resulted in excellent overall
performance. Furthermore, addition of SEBS was found to result in dispersions with
particle diameter as small as 200nm (Gergen et al., 1987).
In a 1982 application, styrene-isoprene-styrene block copolymer, 5-30wt% SIS,
was blended with crystalline ethylene-propylene block copolymer (EPR) and 3-
5 wt % PS, to give materials suitable for manufacturing articles with good paint-
ability (Mitsubishi Petrochemical Co., 1983a).
In 1991, Johnson Service Company developed a method of recycling PP and PET
by blended these two waste products at a ratio between 1:4 and 4:1, then adding 15-
20 wt % maleated SEBS as a reactive compatibilizer. The resulting materials had high
modulus and good mechanical properties, making them suitable for use as batteries
and fuel cell containers (Tekkanat et al., 1993). The following year maleated hydro-
genated styrene-butadiene block copolymer (SEB5-MA) was used by Globe-Union as
a compatibilizer I impact modifier in PET IPP blends. The ratio of the latter polymers
was varied from 2:3 to 3:2, Le., covering the most probable range of cocontinuous
structures. Presence of SEB5-MA (15-20 phr) was responsible for improved degree of
dispersion, stabilization of morphology and amelioration of adhesion in the solid
state. As a result, the blends showed improved impact strength while maintaining
tensile strength, elongation and flexural modulus. Furthermore, recycled PP and
PET at a ratio between 1:4 and 4:1 blended with SEB5-MA provided stiff blends with
good mechanical properties, suitable for molding battery containers, fuel cells and
other automotive components (Tekkanat et al., 1994).
Also in 1991, BP Chemicals disclosed that SEBS was used in blends with liquid
polybutadiene, PB as Opanol™. Blends with O.I-lOwt% SEBS, Kraton™, were
prepared at 20°C using cyclohexane as co-solvent that was later evaporated at
75°C under vacuum (Iamurri, 1992). The following year, Phillips Petroleum asked
for patent protection for reversed compositions: 85-97wt% SB (e.g., K-Resin™ from
Phillips), 3-15wt% PB (e.g., Amoco RTM PB with Mn = 320kg/mol), hydrogenated
polybutene (e.g., Amoco's Panalane with Mn = 320), and/or an epoxy-terminated
polybutene. The blends were extruded into sheets, formed into films, or injection
molded into articles characterized by good impact strength, flexural modulus, and
economic feasibility without compromising clarity (Hasselbring, 1994).
One year later, Ferro Corporation disclosed PA/PO blends compatibilized by
addition of acidified alkenic. copolymer. Thus, blends comprised 70-90wt% PE or
PP, 5-25wt% PA, 5-25wt% SMA, and 1-25wt% of at least two compatibilizers
selected from SEBS (Kraton G 1652), maleated-SEBS or copolymer of ethylene, pro-
pylene, acrylic ester, with either maleic anhydride or glycidyl acrylate. The moldable
alloys showed improved impact strength. They could also be reinforced by mineral
fillers and/or glass fibers (Chundury, 1994).
Also in 1992, BASF announced that recycled polyalkenes, 5-95wt% PO, and
recycled styrenics, 5-95 wt % of, for example, an ABS, can be compatibilized by
blending these (at 220-290 °C for 0.2-30 min) with 0.5-30 wt % of a mixture compris-
ing an inexpensive coupling agent, such as 5-95wt% ethylene with minor amounts
of polar and/or acidic comonomers and 5-95wt% SEBS. Furthermore, 0.1-40wt%
of other thermoplastic recycled polymers could also be added. The blends were used
to manufacture fibers, films or moldings. The compatibilized alloys showed
improved rigidity, impact strength and reduced molding shrinkage (Weber et al.,
1994). The same year Shell Oil disclosed blends for manufacturing elastomeric films,
composed of 4O--8Owt% SBS Kraton™ D (MW = 170kg/mol, 32wt% styrene and
about 1/3 oil), 5-20wt% EVAc (28% VAc), 10-45wt% PS, and 5-20wt% of either
LLDPE or ULDPE with crystallinity not greater than 60% (Djiauw, 1994).
10.6.2 SBS/SEBS blends with engineering resins

Since the anionically polymerized block copolymers are relatively expensive they
have been more frequently used in blends with engineering than commodity resins.
However, as in the above cited exemplary blends of commodity resins, the role of
block copolymers in blends with engineering resins remains the same - to comp-
atibilize and/or to toughen.
For blends with polyesters (PEST), polycarbonates (PC) or polyamides (PA), the
block copolymers should be modified by incorporation of acidic, acid anhydride or
epoxy moieties. These groups can either interact with these macromolecules or
chemically react with their terminal groups. Thus, reactive blending dominates the
technology. By contrast, owing to the miscibility of styrene blocks with polypheny-
lene ether (PPE), SBS and SEBS are natural ingredients in PPE blends, and do not
require modification. The obvious exceptions are the PPE blends with PA and/or
PEST, where the reactive blending is again advantageous.
Since styrenic block copolymers are the topic of this part, only selected blends that
exemplify the use of these materials will be discussed. More detailed discussion of
the engineering resin blends with (or without) SBS can be find under the appropriate
headings in Part Four.
Polyphenylene ether
The use of styrenic block copolymers in blends with polyphenylene ether (PPE) was
pioneered by General Electric. By 1969, PPE was blended with 10-90wt% SBS for
high impact strength and good surface appearance (Kambour, 1970). Four years
later, for the first time SEBS was used in PPE blends. Thus, PPE was blended with
40wt% PS, 20wt% SEBS (Kraton™ GXn, and 1.5wt% PE (to improve solvent!
chemical resistance). The blends had good impact strength and aging characteristics
(Haaf, 1979). The follOWing year, 35wt% PPE, was blended with either SBS or
EPOM-modified polystyrene, and 15wt% SEBS. The alloys showed good flow,
impact and thermal properties - synergistic effects were reported. In the later patent,
80 parts of PPE were blended with 20 parts of HIPS, 5 parts of SEBS and 3 parts of PE.
The blends showed excellent impact behavior (Lee, 1977, 1979, 198Oa, 1982, 1983a,
1985; Haaf and Lee, 1978; Haaf 1983). The first PPE/PEST blends compatibilized by
addition of SBS were disclosed by General Electric in 1977. These alloys comprised
PPE, PBT, SBS and (PhOhPO - a plasticizer and fire retardant. The materials had
low viscosity, good impact, fire-resistance and tensile strength (Lee 1978).
When the validity of the General Electric basic patents for PPE expired other
companies became increasingly active in the field. In 1980 and 1981 BASF issued a
series of patent applications for PPE blends comprising a mixture of HIPS and SB
block copolymer (having controlled elastomeric particle diameters range 0.1-10 J.lID)
with 25-35 wt % PPE. The resulting alloys showed good processability, high gloss,
excellent impact and solvent resistance (Brandstetter et al., 1982). Asahi-Dow
disclosed PPE blends with 5-95 wt % styrene-phenyl-maleimide copolymer and
o-90wt% of either SB, SBS or SEBS. The blends were reported to show high HOT,
as well as good impact and solvent resistance (Fukuda and Kasahara, 1982).
'Similarly, Sumitomo Chemical asked for patent protection for PPE blends with
HIPS, styrene-grafted EPOM, and/or SB with ethylene-glycidylmethacrylate
(EGMA) (Ueno et al., 1982). For good processability and impact strength, PPE was
also blended with SBR, SBS and EPR (Mitsubishi Gas Chemical Co., 1982). In 1982,
the company described blends comprising 60 parts PPE, 37 parts HIPS, 2 parts SBS,
37 parts SBR, 1 part EPR and 0.4 part hdrogenated poly(bisphenol-A-phosphite). The
materials showed good processability, impact strength, high HOT and flame
retardance (Sugio et al., 1984).
In 1980, Asahi-Dow announced an important step in the PPE blending technology
- the styrene grafting of the resin. The grafts, PPE-S, were either used alone in blends
with SBR and SB or they were combined at a ratio 1:1 with unmodified PPE, then
compounded with styrenics. These alloys were reported to show good process-
ability, high gloss and good toughness, as well as high impact and tensile strength
(Izawa et al., 1983).
One of the early patents on PPE blends with styrenics and polyamide was depo-
sited in 1981. Blends comprising PA-66 (dispersed as 0.5-5 lim particles), PPE, PS,
maleated PP and SEBS showed excellent impact strength (Mitsubishi Petrochemical
Co., 1982, 1983b). Improvements to PPE/PA blends were discussed in several patents
deposited by General Electric in 19~. For example, it was found that incorporation
of SEBS resulted in low temperature ductility (Fujii et al., 1987; Lee et al., 1987). In
another invention, PPE was reactively blended with SBS and maleic anhydride. The
maleated resin, PPE-MA, was in turn mixed with either PA or PEST giving alloys with
high impact strength and good chemical resistance (van der Meer and Yates, 1987).
In 1985, Borg-Warner disclosed reactive blends of carboxylated PPE with PA-66
and SEBS Kraton™ G, reactively extruded with maleic anhydride, without peroxide.
Also, PPE blends with PA-66 were compatibilized by reactively extruding PPE with
1 wt% tetracarboxyl cyclopentane, then combining it at a ratio 1:1 with PA-66 and 5
phr SEBS, Kraton™ G. The alloys were smooth, non-delaminating, ductile, with good
impact strength, elongation and tensile strength, showing high solvent resistance
(Grant and Jalbert, 1987, 1989; Grant et al., 1987, 1990). Similarly, in 1986 the Japan
Synthetic Rubber Company announced blends comprising 4-95 wt % PPE, 4-95 wt %
PA and 1-50wt% SBS, as well as a reactive mixture of styrene-glycidylmethacrylate,
an unsaturated monomer (preferably styrene) and a perOXide. Excellent melt flow,
moldability, heat and impact resistance were reported (Mawatari et al., 1987).
In 1982, Asahi Chemical Industry announced blends comprising PPE, ABS and
SEBS. These materials were reported to have good moldability, impact strength and
mechanical properties (Veda and Fukuda, 1983; Veda and Sasame, 1986). In a
contemporary patent, blends of PPE with 1-20wt% SB di-block copolymer were
also reported to show good moldability and impact strength (Denki Kagaku Kogyo
K. K., 1983a). In a patent deposited in 1983, PPE blends with PS, SBR and SBS were
found to have good plateability and mechanical properties (Mitsubishi Gas Chem.
Co., 1985). Two years later it was discovered that further incorporation of lOwt% of
a radial SB copolymer improved processability and mechanical properties (Sugio et
al., 1987).
In 1984, BASF announced that materials with high HDT and impact strength
were obtained by blending PPE with HIPS, SEBS and 1 wt % LLDPE (Hambrecht
et al., 1986). The same year General Electric disclosed PPE blends with HIPS and
a styrene-butadiene block copolymer, SB, SBS or (SB)n' The alloys showed
good impact strength and stress cracking resistance (DeMunck and Lohmeijer,
1986).
In 1985, General Electric Company deposited a most interesting patent describing
blends that comprised 10-45wt% PPE, 10-45wt% PBT, 8-25wt% SEBS, and
3-40wt% Pc. The alloys showed good processability, high impact strength, and
solvent resistance (Brown et al., 1987). It has been found that here the morphology is
complex - PBT was the matrix, SEBS was absorbed by the PPE phase (forming
rubbery islands in the PPE/PS drops), and PC was located at the boundary between
the PBT and PPE phases, forming protective layers against the shear coalescence
(Hobbs et al., 1992). The following year the company disclosed blends composed of
1Q--65wt% PPE, 1Q-75wt% HIPS, 2-10wt% polyester(s), 1-25wt% polystyrene
with reactive (2-oxazoline) groups, and optionally polycarbonate and SBS. The
blends showed improved impact strength over those of prior art, with favorable
combination of properties, such as mechanical strength, resistance to chemical
solvents and flow properties in the melt (Avakian et al., 1988). These blends were
further improved in a document deposited in 1987, describing blends of 2Q-40wt%
PPE with 25-75wt% PBT (or PET), 8-25wt% SEBS, 5-40wt% PC and, if
needed, mica (Yates, 1987, 1989). The same year PPE grafted with fumaric
acid was reactively blended either with PC and SEBS (Ishihara, 1989), or with
PC, PBT, dimethylsiloxanes and SEBS. The blends had good mechanical
properties with enhanced solvent and impact resistance (Brown et al., 1992). In a
1988 disclosure it was reported that addition of SEBS and/or acrylate copolymer to
these blends has further beneficial effects on impact strength (Yates and Lee, 1990).
The commercial blends based on these patents, Gemax™, show good impact and
solvent resistance, excellent surface finish and a low coefficient of thermal
expansion.
Also in 1985, General Electric announced PPE blends with HIPS, an ethylene-
methacrylic acid copolymer, 1-40wt% EMAA, 1-20wt% SEBS, and O.1-10wt%
styrene-glycidylmethacrylate copolymer (SGMA). The alloys had good process-
ability, thermal and chemical resistance, as well as high tensile and impact strength
(Fuji and Ting, 1987). Here the ionic interactions provided the additional, reinforcing
mechanism.
In 1986, blends with excellent solvent resistance, moldability, impact and mechan-
ical properties were described in a patent document from Mitsubishi Petrochemical.
The reactively blended materials comprised PPE, SEBS grafted with glycidylmeth-
acrylate (SEB5-GMA) and PET. The alloys showed excellent solvent resistance,
moldability, impact and mechanical properties (Mayumi and Omori, 1988).
Similarly, in a patent document of 1988 from Shell, PA/PPE blends were compati-
bilized and impact modified by incorporating maleated hydrogenated styrene-buta-
diene block copolymer (SEB5-MA; Modic and Gelles, 1988).
In another inventive document from General Electric, in 1987 blends of PPE with
polyvinylidenefluoride, PVDF, and two styrenic block copolymers: SEBS and poly
(styrene-co-methylmethacrylate) (P(5-co-MM)) were described. The former copoly-
mer was responsible for improved impact strength and elongation while SMMA for
compatibilization of PPE with PVDF (Van der Meer et al., 1989). The following year,
PPE blends with HIPS and PE were compatibilized by addition of SEBS, giving
materials with high flexural modulus and HOT, as well as good weatherability
(Ting, 1990). Similarly, PPE blends with 2 5Owt% PP and::; 20wt% SEBS showed
high HOT and stiffness (Lee, 1990).
In 1988, Sumitomo applied for a patent for PPE/PBT blends toughened by addi-
tion of urea-butylated resin and SEBS (Mizuno and Maruyama, 1990).
In 1990, Mitsubishi Gas Chemical deposited a patent application for HIPS blends
with 3Owt% PPE. To toughen these materials, they were sequentially compounded
with oligo(ethylene-co-a-alkene), and either SBS or SEBS. Good mechanical perform-
ance and high chemical resistance were reported (Uno et al., 1992). The same year,
General Electric deposited patent applications for PPE blends with either SBS
Kraton™, and an effective amount of antioxidant/metal deactivators (Richards
and Kelly, 1992), or with 2G-60wt% PBT, and 15-3Owt% of a block copolymer of
the A-B-A type (where A = PC and B = PS block, preferably PCPS = 1). The
compositions could also contain less than 25 wt % impact modifier, such as SEBS
Kraton™G, D, RlM, or a core-shell type, and not more than lOwt% PC (Brown and
Fewkes, 1992, 1994).
An important deposition in 1991 from Idemitsu Kosan Company concerned
blends of syndiotactic polystyrene, 100 parts sPS, an inorganic filler (e.g., 1-350
parts arninosilane-treated glass fibers), polyphenylene ether modified with either
maleic anhydride or glycidyl methacrylate, 0.1-3.5 parts PPE-MA or PPE-GMA, and
5-100 parts SEBS Kraton™G. The alloys showed markedly improved dynamic prop-
erties, rigidity and heat resistance (Okada and Masuyama, 1994). Note that to profit
from the crystalline character of sPS, the processing and compounding steps must
promote its crystallization.
The same year, General Electric deposited further improvements to the blends of
PPE/SEBS and either PEST or PA. Thus, 3Owt% epoxy- or phosphate-functionalized
PPE, was blended with 46wt% of either PBT or PET, palrnitamide, 1-3Owt% SEBS
and 1-30wt% PC - improved processability, and enhanced low-temperature ducti-
lity were claimed (Yates, 1993). Similarly, a mixture of 30-70wt% PPE with 70-
30wt% PA-66, 1-2 phr of either citric acid or chloro-epoxy triazine, and 9-15 phr
styrene-butadiene radial copolymer, K-Resin™, was added. The Izod impact
strength was improved (in comparison to blends with HIPS) by a factor of three.
In the following patent excellent impact strength was achieved by using a tapered
instead of a radial block copolymer. Thus, blends of PPE with PA at ratios of 70:30 to
30:70 were impact modified by addition of 5-15 phr linear-SB copolymer, citric acid
and SEBS (Gianchandai et al., 1993). The following year, a mixture of 5-95wt% PPE
with 95-5 wt % PA-6 or PA-66 was compatibilized by addition of maleic anhydride
and toughened with 5-25 phr of a selectively hydrogenated diblock copolymer of the
SB type (St = 2G-40wt%), Kraton™ ex. When the PA content was above 35wt%, it
formed a continuous phase. The saturated diblocks provided excellent heat aging
characteristics, unexpected since previous work with saturated SEBS triblock had
shown no improvement in this regard (Lee, 1994).
Polyamides
SEBS were incorporated into commercial polymer blends immediately after their
introduction. For example, as a Celanese application from 1974 specified, to improve
tensile and impact strength of PA-66 it was blended with 1-29 wt % SEBS (bisphenol-
A-epichlorohydrin) and 0.5-3wt% Phenoxy (Freed, 1975).
During the years 1976-9, Shell Oil deposited a series of basic patents for blends
comprising SEBS. For example, to improve the impact properties, PA-6 was blended
with 5 wt % SEBS (Davison and Gergen, 1977). In later patents, to improve toughness
of PA-66, PE, PBT or pc, the resins were compounded with SEBS (Gergen and
Davison, 1978). The 1:1 blends usually had a cocontinuous morphology, good
dimensional stability and mechanical behavior varying from rubber-like to flexible.
Good resistance to shrinkage and distortion was also reported (Davison and Gergen,
1980). Blends of SEBS with PES, POM, TPU, PMP, fluoropolymers and acrylonitrile
copolymers were also disclosed (Bull and Holden, 1977; Davison and Gergen, 1980).
Alloys comprising maleated SEBS were developed at Shell by the mid-1980s. Thus,
blends composed of 70 wt % PA-66 with maleated and unmodified resins - either a
polyalkene or an elastomer (e.g., maleated SEBS, SEB5-MA, PO, etc.) were reported
to give moldable alloys with high impact strength (Gelles et al., 1988).
Probably the earliest patent application for the use of SEB5-MA as an impact
improver for PA was deposited in 1979 by the Firestone Tire & Rubber Company.
Blends comprising 90-50 wt % PA-6 and 10-50 wt % SEB5-MA were reported to show
excellent impact strength (Hergenrother et al., 1984). The following year 40-99wt%
PA-6 was blended with ethylene-a-alkene copolymer grafted with a, jJ-unsaturated
carboxylic acid or its anhydride, or maleic anhydride-grafted hydrogenated SBS or
LLDPE (Mitsubishi Chemical Industries Co., 1982a). The same year, Rhone-Poulenc
Industries disclosed blends of PA-6 or PA-66 with SBS as having improved impact
strength and reduced modulus (Cerny and Troncy, 1981).
In 1981, acid-modified styrene-elastomer block copolymers (SB, SBS, SEBS) were
introduced as a general class of compatibilizers for polar polymers - polyamides or
polyesters (Asahi Chemical Ind. Co., 1983, 1984, 1987). In particular, maleated
styrene-butadiene block copolymers (SB5-MA) were discovered to be excellent
impact modifiers for PA. For example, 80 wt % PA-6 was blended with SB5-MA to
give alloys with Significantly improved impact strength and elongation (Shiraki et al.,
1983; Kahata and Koyama, 1987).
As discussed in the preceding part, SBS or SEBS have been frequently used as
impact modifiers in PPE/PA blends. These blends, with PA being the matrix and
PPE the organic (hence low density) rigid filler, were first developed in the early
1970s by Asahi Chemical. By the end of the decade the first reactive blends were
announced by Sumitomo Chemical (Ueno and Maruyama, 1981). During the same
period several other companies worked on PA/PPE blends. The well-known
NoryITM GTX was developed in the European laboratories of the General Electric
Company and commercialized in 1983 (Van der Mer, 1989). In 1981, blends compris-
ing PA-66 (dispersed as 0.5-5jl,ffi particles), PPE, PS, maleated-PP and SEBS were
disclosed by Mitsubishi Petrochemical Company. This seems to be the first time
when SEBS was used to toughen PA/PPE blends. During the follOWing years, the
company continued to improve the formulations. For example, in 1990 blends of PA
with 45 wt % of a mixture comprising low and high MW fractions of PPE, maleated
polystyrenes (P5-MA) and SBS were disclosed. The blends showed good process-
ability and mechanical properties as well as heat and impact resistance (Nishida
et al., 1991).
In 1985, Shell Oil Company deposited a series of patents describing super-tough
blends of PA with hydrogenated styrene-butadiene block copolymer, at least in part
grafted with maleic anhydride. The adduct, SEB5-MA, was then used as impact
modifier for polyamides or polyesters such as PBT. Thus, blends comprising 50-
97 wt % PA and SEB5-MA showed very high notched Izod impact strength (Gelles et
al., 1987). Another patent described blends comprising 80wt% PA-66 (with
M n = 5 kg/mol and Tm > 200°C) and 20wt% of a 1:1 blend of SEBS (with 29wt%
styrene) and a modified SEBS (with 1.6wt% maleic anhydride). The blends showed
super-toughness and could be readily fonned by using any conventional molding -
injection molding, blow molding, pressure forming, rotational molding and the like.
For example, sheets, films and foamed products, as well as injection-molded, blow-
molded, pressure-fonned or rotational-molded articles in various shapes were pro-
duced. These articles were used in the automobile, building, electrical or mechanical
industries, as well as for packaging and other applications (Gelles et al., 1994).
In 1988, Sumitomo Chemical deposited another patent for impact resistant PA
alloys, prepared in sequential blending. First, PA was compounded with acidified
elastomer, SEBS, EPR or EPDM, then the adduct was incorporated into PA, along
with other customary additives. Good processability, mechanical properties and low
temperature impact strength were reported (Ohmae et al., 1991, 1992).
In 1991, Shell Oil described blends comprising a linear, alternating terpolymer:
ethylene-co-propylene-co-earbon monoxide, poly(carbon monoxide-co-polyalkene)
(CaPO), with 2-20 wt % PA-6, and with 0.5-20 wt % maleated, hydrogenated sty-
rene-butadiene-styrene (SEB5-MA). The blends showed a good balance of strength
and toughness (Machado, 1992).
Thermoplastic polyesters
In 1976, Shell Oil disclosed selective hydrogenation of SB or SBS copolymers to SEBS.
One year later the company deposited patent application for blends comprising
polybutyleneterephthalate (PBT) and ABS - the presence of SEBS was found to
stabilize the morphology, reducing the polymer separation during processing (Ger-
gen and Davison, 1978). Four years later the reactive compatibilization was discov-
ered. Thus, PBT was blended with 57 wt % SEBS, 19 wt % SMA and 5 wt % extending
oil. The alloys were reported to have a good set of properties required in automotive
applications (Durbin et al., 1983).
In 1978 and 1979, General Electric Company announced blends comprising,
39.8wt% PBT, 30wt% polyethyleneterephthalate (PET), 15wt% SEBS and 15wt%
of bisphenol-A polycarbonate (PC). The alloys showed good impact, heat and tensile
strength. In later patents, PBT and PET were blended with PC, (SB)n and butadiene-
caprolactone-styrene, or butadiene-caprolactone block copolymer (Wambach and
Dieck, 1980; Dieck, 1980; Wambach, 1991).
Reactive compatibilization of PEST/SEBS was developed by Mitsubishi Petro-
chemical Industries. In a patent application of 1984 it was reported that PBT blends
with SEBS, and maleic anhydride showed good moldability, improved low tempera-
ture impact strength, HDT and mechanical properties (Shiraishi and Goto, 1986). The
method was general enough, extending to other polyesters.
Polycarbonates
The first use of SEBS with bisphenol-A polycarbonate (PC) was described in a
document dated 1976 from the Shell Oil Company. It was found that blends of PC
with 30 wt % SEBS formed cocontinuous structures with a high modulus up to 140 °C
(Gergen and Davison, 1977). The importance of the cocontinuity of phases in PC/
SEBS blends is illustrated in Figure 10.3, which shows tensile storage modulus
versus temperature for a series of polycarbonate blends with hydrogenated sty-
rene-butadiene-styrene tri-block copolymer. The blends had cocontinuous morpho-
logy. Isothermal moduli could be fitted to the relationships.
n
(E~1r= L</>i(E;)m (10.1)
;=1
where <Pi is the volume fraction of ingredient i having tensile modulus E;. The
exponent m = 0.5 was found experimentally (Gergen et al., 1987).
In 1990, Dow Chemical disclosed blends with enhanced impact and solvent
resistance, comprising pc, a carbon monoxide-polyalkene copolymer (COPO), a
polyester, SEBS, and butylacrylate-methylmethacrylate grafted rubber (Laughner et
al., 1992). The following year Shell Oil deposited the already mentioned patent
application for COPO blends with PA-6 and SEB5-MA (Machado, 1992).
General Electric's interest in PC technology is reflected in the patent liter-
ature concerning PC/SBS systems. In 1977 it was disclosed that PC, blended with
1-40wt% PE and selectively hydrogenated and chlorosulfonated SBS copolymer,
showed improved processability and high impact properties (Bussink et al., 1978). As
mentioned earlier parts, SBS or SEBS have been used to toughen binary blends of
engineering polymers, such as PPE/PBT, PPE/PA or PET/PBT. The same effects
were also reported by General Electric in 1978 for blends comprising PBT (and
optionally PET), 15wt% PC, 7.5wt% SEBS Kraton™, and mineral fillers (Dieck
<is
Q. 2
~ 10
o
SEBS/PC =7/3
~
-50 o 100 150 200
Figure 10.3 Storage modulus versus temperature for polycarbonate (PC) hydrogenated
styrene-butadiene-styrene triblock copolymer (SEBS) and two SEBC/PC =713 blends with the
blends had cocontinuous and dispersed morphology (adapted from Gergen, Lutz and Davison,
1987).
and Wambach, 1980), as well as for PC/ABS blends toughened by addition of SEB5-
MA and PP (Gallucci and Bookbinder, 1989; Gallucci, 1989). In depositions from
1981, PC blends with either SB teleblock and SEBS (Lee, 1983), or with 3-25 wt % SBS
and 2-20wt% acrylate polymer, AkryloicffM, were described (Liu, 1982, 1984a). Two
years later, PC was blended with 10 wt % SEBS, 6 wt % of ethylene-ethylacrylate
copolymer (EEA), and 2 wt % LLOPE, for improved resistance to environmental
stress crazing and cracking (Liu, 1983, 1984b). In these as well as the following
patents from General Electric, SEBS has been used to improve the impact resistance
of the LexanTM polycarbonates.
Similar PC/SEBS blends have been developed in other parts of the world. In a
1981 patent application, 80-97% PC was blended with 1-10% PE, and 1-5% SEBS.
The alloys were found to have excellent processability and appearance, and good
resistance to solvents, heat and impact (Idemitsu Kosan Co., 1983). The same year,
PC blends with 1-20 parts of either SBS, EGMA or MBS were reported to show
improved impact resistance (Sumitomo Chemical Co., 1982, 1983). The following
year, to improve heat and impact resistance, PC was blended with 40-90 wt % of a
mixture comprising SMA and SBS (Oaicel Chemical Industries, 1984).
In 1992, BASF announced blends comprising 50-90wt% PC, 3-25wt% PPE,
3-25 wt % elastomeric polybutylacrylate grafted with styrene and acrylonitrile
(ASA), 3-40wt% SAN, 1-20wt% PS, 0-20wt% phosphate esters, 0-2wt% PTFE,
and 0-25 wt % SEBS. The blends were compounded at 260 DC in a twin-screw extru-
der, then injection molded. The moldings were found to be fire resistant, and to have
a good set of mechanical properties, impact strength and HOT (Niessner et al., 1993).
Also in 1992, Shell Oil Company disclosed blends comprising polycarbonates and
modified hydrogenated styrene-butadiene block copolymer (mSEBS; comprising
about 2 wt % of a hydroxyethyl acrylate terminated E-caprolactone oligomer), such
as 90 wt % PC and 10 wt % mSEBS. The alloys showed general improvement of
mechanical properties, particularly the low temperature notched Izod impact
strength (Wilkey, 1994).
10.6.3 SBS/SEBS blends with specialty resins

Following the disclosure of the hydrogenation of SB or SBS into SEBS made in 1976,
these resins were soon incorporated into commercial blends comprising commodity
or engineering resins, either as impact modifiers or compatibilizers. However, owing
to thermal stability requirements for processing temperatures below 280 DC, the use
of SEBS with specialty resins has been sparse, limited to polyphenylenesulfide (PPS).
The latter resin has good heat stability and rigidity as well heat and chemical
resistance but, owing to poor impact resistance, it must be toughened.
In 1974, Mitsui Petrochemical Industries disclosed blends comprising polyaryle-
nesulfide (PPS) and 30wt% of either polystyrene or a styrene-copolymer. The blends
showed improved processability and impact strength (Miyanishi, 1976; Miyanishi
and Manabe, 1976).
In a 1983 patent application, Phillips Petroleum disclosed that blending PPS
Ryton TM with SEBS, improved moldability, impact performance and crystallinity of
the former polymer (Garcia and Martinovich, 1984). Similar blends were described
6 years later in a patent application from Hoechst Celanese Corporation
(Auerbach, 1991).
In 1991, multicomponent blends were announced by GE Plastics, Japan. The
alloys, compounded in a twin-screw extruder at 300 DC, comprised: (1) 35-59 wt %
PPS Topren™, (2) 6-19wt% PPE, (3) 11-29wt% PA-6 or PA-12, (4) 11-24wt% SEBS
PS/PC blends 189
Kraton™G, (5) 1-14wt% acidified polyalkene (e.g., maleated EPR, ethylene/GMA
or ethylene/vinyl acetate/GMA), (6) 0.01-10 phr of a reactive compatibilizer
(citric, maleic or agaricic acid), and (7) 0.1-5 phr of talc. The blends had PPS as
a matrix, with the dispersed phase comprising PA containing PPE/SEBS and the
filler particles. The blends showed excellent dimensional stability and impact
resistance, as well as good heat resistance and surface appearance (Ishida and
Kabaya, 1994).
10.7 PS/PA BLENDS

These two polymers are antagonistically immiscible, thus to achieve a reasonable
performance they require compatibilization. In 1985 Isover Saint Gobain announced
blends comprising 5G-75wt% PS, 25-SOwt% PA-6 and 2-lOwt% SMM. The com-
pression molded specimens had a PS matrix and PA as dispersed particles of
diameter 5-20/lom (Fayt et al., 1986).
Recently, enhancement of adhesion between amorphous, transparent, aromatic
polyamide, poly(trimethylhexamethyleneterephthalamide) (TrogamicfIM T, from
Dynarnit Nobel), PARA and PS by the addition of styrene-maleic anhydride random
copolymer (SMA) was studied. Reactive blending was responsible for formation at
the interface of an in situ copolymer. Surprisingly, the fracture toughness of the
binary PA/SMA was low at all temperatures and annealing times. However, when a
thin layer of SMA was introduced between PA and PS, the fracture toughness was
remarkably increased. A qualitative model was proposed that took into account two
effects, namely the reaction at the interface and the diffusion process. In con-
sequence, the experimental results were segregated into two groups, the first
where diffusion dominated the process, and the second where both the diffusion
and the reaction at the interface contributed, engendering a strong interface (Lee and
Char, 1994).
10.8 PS/POM BLENDS

Owing to the molecular structure of polyoxymethylene (PaM) the resin is immis-
cible with nearly all polymers, and is one of the more difficult resins to blend with.
Progress in polymer chemistry has recently yielded paM grades with functionalized
chain-ends, specifically prepared for blending (see Part Four).
In the Polyplastics patent application of 1990, paM was blended with 5-50wt% of
either PS, poly(o-methyl styrene) (MPS) or SAN, and particulate fillers with particle
diameter 0.1-10/lom. The blends had cocontinuous structure, good surface appear-
ance and low molding shrinkage (Tajima et aI., 1991).
10.9 PS/PC BLENDS

The blends of PS with polycarbonate of bisphenol-A (PC) are immiscible, but since
many copolymers show good affinity with both these resins, blends of PC with
styrenics were developed relatively early.
In 1976, several patents were filed for blends of PC with copolymers containing
styrene. Thus, Mitsubishi Rayon disclosed that PC blends with 20 wt % SAN and
10 wt % styrene-allylmethacrylate-butylacrylate-methylmethacrylate copolymer, had
good HDT and impact strength. In the following patent, PC was blended with
20wt% multilayered copolymer from styrene, allyl methacrylate, benzyl acrylate
or divinylbenzene (Kishida et aI., 1978).
The first modified blend of PC with PS was also developed in Mitsubishi Rayon
laboratories. In the 1977 disclosure, PC was blended with 4O-94wt% PS, then
compatibilized and toughened by addition of 5-45wt% SAN, and 1-30wt% of a
styrene-grafted acrylic rubber. The blends showed good mechanical properties, HDT
and excellent impact strength (Kamata et al., 1979).
About the same time Mitsubishi Petrochemical devised an ingenious method of
bypassing the immiscibility problem between PS and Pc. A patent deposition from
1976 described the process. First, PC was dispersed in water with vinyl monomer(s)
that subsequently were polymerized. The slurry was filtered out, washed, dried and
compounded. When styrene was used as the vinyl monomer, the resulting PC/PS
blends showed improved mechanical properties in comparison to neat PC (Kanai et
a/., 1978). It is highly probable that the reaction resulted in grafting some of the
polystyrene radicals onto the PC surface, virtually compatibilizing the PC/PS
blends. In 1978 a modification of this process was disclosed. Thus, PC pellets were
swollen with ::; 50% of styrene, dispersed in water and then the suspension was
polymerized. Next, the grafted PC was blended with PC, PS and/or other styrenics,
acrylics or PVC, to generate blends showing a good set of properties (Kakizaki et a/.,
1979). Note that both PS and PC are glassy and brittle polymers, thus their compa-
tibilized blends may profit from impact modification.
General Electric Company patented a number of blends comprising PC and
diverse styrenics, such as ABS, SAN; SB, SBS, MBS, etc. For example, in 1978 the
company announced PC blends with 7-80% PS and/or 0-25% butadiene-methyl-
methacrylate-styrene copolymer (MBS) (Lee, 1980b). The compatibilized PC/PSI
MBS blends seemed to be of main interest.
In 1992, BASF disclosed blends comprising 50-90wt% PC, 3-25wt% PPE,
3-25 wt % of a polybutylacrylate grafted with styrene and acrylonitrile (ASA),
3-40wt% SAN, 1-20wt% PS, 0-20wt% phosphate esters, 0-2wt% PTFE and
0-25 wt % SEBS. The blends were compounded at 260 °C in a twin-screw extruder,
then injection molded. The specimens were fire resistant, with a good set of mechan-
ical properties and HOT (Niessner et al., 1993).
The same year Dow Chemical announced a new family of multicomponent blends.
These were prepared in two parts: (1) PC, PEST and not more than 5 wt % of an AB5-
type resin comprising alkyl (meth)acrylates and glycidyl methacrylate, and (2) PPE
with either PS, HIPS or SEBS, and a polyalkyl(meth)acrylate. These two parts were
compounded together and molded. The blends had low gloss even when molded at
high temperature. They were used to manufacture instrument and appliance hous-
ings, car panels and radio components (Laughner, 1993, 1994).
10.10 POLYSTYRENE/POLYESTER BLENDS

Polystyrene (PS) is immiscible with thennoplastic polyesters (PEST). Blends of these
two polymers are mainly used for decorative applications or as the so-called plastic
paper. When good mechanical behavior is required they must be compatibilized and
toughened, in this case not a difficult task.
Mitsubishi Rayon was first to describe PS/PEST blends in 1978. Polyethylenetere-
phthalate, 4-96 wt % PET was blended with 2-94 wt % PS and 2-94 wt % PMMA. The
blends had good processability, excellent unifonn iridescence, and high impact
strength (Kamata et a/., 1980).
In 1982, both BASF and Unitika deposited patent applications for blends compris-
ing aromatic, amorphous polyesters of isophthalic and terephthalic esters (PAr) with
styrenics. In the BASF document, PAr was blended with 90 wt % SAN, giving materi-
PS/PPE blends 191
als with good processability, weld strength, and high HDT (Brandstetter et al., 1983b).
In the other patent, PAr was blended with 20 wt % PS and 10 wt % PAr-PS segmented
copolymer as a compatibilizer. The alloys had good moldability, resulting in semi-
transparent moldings with excellent mechanical properties (Unitika Ltd, 1983a).
In 1988, multicomponent blends were disclosed by General Electric Company.
High impact strength alloys comprised PPE, PEST, PS, PC, SEBS and/or acrylate
copolymer impact improvers (Yates and Lee, 1990). Similarly in Rohm & Haas's
application, the new blends comprised an engineering resin, such as PPE with PS,
and a high-molecular-weight copolymer of methylmethacrylate-ethylacrylate-butyl-
methacrylate of M w > 500kg/mol. The high-molecular-weight acrylic copolymer
improved the melt flow and increased the sag time, thus facilitated blow molding,
thermoforming or extrusion (Memon, 1994).
In 1991, Foster-Miller announced blends comprising thermotropic liquid-erystal-
line polyester (LCP; about lOwt% Xydar™ or Vectra™) with thermoplastic poly-
mers (e.g., PP, PS, PC or PI). To control the LCP molecular orientation the blends
were multiaxially oriented dUring processing. The resulting materials showed a
tailored coefficient of thermal expansion (Haghighat et al., 1992).
The following year, Kao Corporation described formulations and the method
of molding two-eomponent blends, that comprised 98-50wt% PEST (e.g., PET)
and 2-5Owt% of an immiscible resin (e.g., PO, PMMA, PS, PC or PA). The resulting
injection or blow-molded articles showed high anisotropic luster. When the viscosity
ratio TJA/1fB was greater than 2, and the storage moduli was: E:'" < EB, the dispersed
phase was in the form of prolate ellipsoids with an aspect ratio of 1-10 (Odajima et
al., 1993). When good mechanical performance is required the blends should be
compatibilized and preferably formed with cocontinuous morphology.
Also in 1993, General Electric applied for a patent protection for blends having
dissipative properties and good tensile elongation. The claimed compositions com-
prised 4O-96wt% of a styrenic (co)polymer, 2-50wt% of an epihalohydrin-oxirane
copolymer such as E0-ECH or CHR, and 2-50 wt % of a polyalkylene lactone poly-
mer selected from alkylene lactone (co)polymers with at least 50wt% acrylate. For
example, blends of 55-92wt% PS, 5-25wt% copolymer of epichlorohydrin and
ethylene oxide and 3-25 wt % polycaprolactone were found advantageous for mold-
ings with good static dissipative and mechanical properties (Giles and Vilasagar,
1994).
10.11 PS/PPE BLENDS

One of the major category of PS blends is that with polyphenylene ether (PPE). The
latter resin is considered miscible with PS in the full range of compositions. The glass
transition temperature of the PPE/PS blends is a continuous function of composition
varying from Tg(PS) ~ 100°C to Tg(PPE) ~ 20B°C. Diluting PPE with PS made it
possible to avoid the oxidative degradation of the former resin at the high tempera-
tures that would be required for its processing, while maintaining useful properties,
namely hydrolytic and dimensional stability, as well as excellent electrical proper-
ties. Since these blends of two amorphous and brittle polymers are miscible, the
binary blends can be treated as a continuous series of homopolymers, spanning the
full range of intermediate properties and prices. For these reasons the PS/PPE family
of blends is exceptionally large and diverse, comprising systems with as many as six
different polymeric components.
The discovery of PS miscibility with PPE led to a family of General Electric
NoryJTM blends, commercialized in 1965. In a series of Hay's patents the oxidative
polymerization of xylenols to PPE was described, as well as diverse methods of PPE
modification, such as by reacting it with butyl-Li (Hay et ai., 1959; Hay, 1964, 1967,
1968). In a 1960 patent application from GEC, for the first time blends comprising
PPE, PS and polysiloxanes were described (Boldebuck, 1962; Cizek, 1968). In 1965
Westlake Plastics Company introduced Aiphaiux™ 400, extruded rods, sheets and
tubing of PPE. For an obvious reason, during the early years the field was dominated
by General Electric. Only after expiration of the original patents other companies
started production of PPE and PPE-type resins. For example, in 1982 Borg-Warner
Chemicals introduced its blends of poly(2,6-dimethylphenol-eo-2,3,6-trimethylphe-
nol) Prevex™. This was also the time when a new series of PPE blends was disclosed
around the world.
In 1967 and 1978, Chemische Werke Hills and Uniroyal announced impact-modi-
fied blends of PPE/PS, the first company with 6.5wt% PB (Chemische Werke Hills,
A.-G., 1968), the second company with less than 50wt% of such elastomer as PB, SBR
or NBR (Lauchlan and Shaw, 1970). In both cases good processability, thermal
stability and impact strength were also reported.
In 1970 and 1971, Asahi-Dow issued a series of patents describing PPE blends with
PS. These were prepared in two-step polymerization: first, a solution of dimethyl
phenol was oxidatively polymerized in the presence of styrene, then the solution
was dispersed in water and styrene was polymerized by free radical reaction, to give
solid particles with diameters ~ 5/-Lm. The materials had improved mechanical
properties, HDT and impact strength (Nakanishi et ai., 1971, 1973). In a later patent
PPE was blended with 2G-80wt% PS or poly(methylmethacrylate-eo-styrene), then
0.1-lOwt% low molecular weight polyalkene was added (Izawa et ai., 1973). The
company also disclosed PPE alloys with 0.5-20 wt % PS, PMMA, PC, PEST, acrylates
or Phenoxy (Izawa and Nakanishi, 1973; Izawa, 1974).
In 1972, Japan Synthetic Rubber Company announced blends comprising 50wt%
PPE, 25wt% PS and 25wt% of either SBR or ABS (Nishioka et ai., 1973). The
following year, Kanegafuchi Chemical Industries disclosed blends of PPE with
45 wt % PS and 6 wt % vinyl-terminated ethylene-propylene-styrene terpolymer
(SEP). The reactive processing resulted in materials with excellent impact strength
(Shioji et ai., 1974). The same year General Electric applied for a patent for blends of
PPE with 4Owt% PS, hydrogenated styrene-butadiene-styrene copolymer (20wt%
SEBS, Kraton TM GXn and 1.5 wt % PE. (This was the first application of SEBS in PPE
blends.) The blend had good impact strength and aging characteristics (Haaf, 1979).
In 1981, Bayer and Mobil Oil disclosed flame resistant PPE/PS blends comprising
3.5wt% polyphosphonate (Schmidt and Reinking, 1981), while Mobile Oil de-
veloped high impact resistant PPE/PS blends by incorporation of butadiene-1-
methyl-4-ethyleneylbenzene graft copolymer (Russo, 1981).
The same year a series of invention documents was deposited by Mitsubishi
Petrochemical Company for PPE/PS type blends. Thus, PPE was blended with PS
and 1-15 phr PA-66 (dispersed as O.5-5/-Lm diameter particles). The resulting alloys
showed improved moldability and impact strength (Mitsubishi Petrochemical Co.,
1982). Next, PPE was blended with O.1-50wt% PPE-polyalkene graft copolymer and
PS, to give moldable blends with good impact and mechanical properties. Further-
more, it was shown that the impact resistance of PPE/PS/NBR blends nearly
doubled when part of the required PPE was solution blended with NBR, precipit-
ated, then compounded with the rest of the PPE and PS (Mitsubishi Petrochemical
Co., 1983b). Blending PPE and PS and epoxy-terminated liquid polybutadiene rub-
ber also gave high impact strength materials. In another patent of the series, PPE/PS
PS/PPS blends 193
blend compounded with maleated-PP, SEBS and CaC03 was reported to give excel-
lent impact strength resins (Mitsubishi Petrochemical Co., 1983c).
In 1983, PPE blends with PS, SBR and SBS were developed. The alloys were found
to have good plateability and mechanical properties (Mitsubishi Gas Chemical
Company, 1985a). Two years later the company announced new PPE/styrenics
blends - 60wt% PPE, with 25wt% PS, 5wt% SBS and 10wt% radial-SB copolymer.
The materials showed good flow rate and mechanical performance (Sugio et ai.,
1987).
Similarly, in 1983, PPE was blended with 40wt% ABS, 12.5wt% SAN and
12.5wt% PS, to give alloys with good processability, heat and solvent resistance,
impact and mechanical strength. The next series of patents described PPE blends
with either PS or a styrene-divinylbenzene copolymer and ABS. The alloys were
reported to have good processability, high HDT, and excellent impact strength
Uapan Synthetic Rubber Co., 1985a).
In a contemporary deposition from Mitsubishi Petrochemical Company it was
announced that moldability of PPE with high impact polystyrene (PPE/HIPS) was
ameliorated by incorporation of 5wt% hydroxynaphthoic acid (Tamura, 1985). Also
in 1984, to reduce PPE/PS blends' adhesion to metal during processing, Borg-
Warner Chemicals developed blends comprising: PPE, PS and ethylene glycol-pro-
pylene glycol copolymer (PEG-PPG, Vaughan, 1985).
The patent literature on polymer blends indicates a growing concern for safety and
environmental protection. There is an increasing number of patents for biodegrad-
able blends, for blends with waste plastics, and for a safer production environment.
For example, in 1992 Novacor Chemicals (International) disclosed a process that
makes it possible to reduce the amount of volatiles to less than 50 ppm. Thus PPE/PS
blends were heated to 20o-270°C, up to 10wt% water was injected at a pressure
ranging from 3.5 to 10 MPa, and the mixture was passed through a flash chamber,
kept at 200-270°C and a pressure of < 8 torr (Skilbeck, 1994).
10.12 PS/PPS BLENDS

In 1974, Mitsui Petrochemical Industries disclosed blends comprising polyarylene-
sulfide (PPS) and 30wt% of either polystyrene or a styrene-eopqlymer. The blends
showed improved processability and impact strength (Miyanishi, 1976).
11
Polyvinylchloride
Polyvinylchloride (PVC) has been known in research laboratories since 1835, but it
was commercially introduced nearly a century later, in the late 1920s, when its
plasticization was developed. However, owing to the low molecular weights of
plasticizers, these tend to migrate to the surface and evaporate. Their loss causes
premature brittleness, that shortens the useful life-span of the material. The oily
surface of the PVC moldings as well as the smell of plasticizers also made it less
appealing to customers. Permanent plasticization by blending PVC with polymeric
materials, was soon recognized as the best long-term solution.
The first PVC blends were introduced in the late 1920s. In 1928, the first patents
were deposited by I.G. Farbenindustrie and Carbide & Carbon Chemicals for the
latex blends of PVC with polyvinylacetate (PVAc) and poly(vinylchloride-co-
vinylacetate) (PVCAc) having 8O-95wt% Vc. These moisture-proof blends were
mainly used as leather substitutes (Voss and Dickhauser, 1930, 1933, 1935, 1936;
Reed, 1935). This was the first use of a copolymer as compatibilizer.
However, the preferred early blends of PVC were those with nitrile rubber (NBR).
These systems were prepared by using one of the three methods: (1) rubber-milling
technology, (2) latex blending, thus combining the aqueous suspensions of PVC with
that of an elastomer, and (3) dry powder blending using fine powders obtained from
drying the latices. After the discovery of ABS in 1946, this terpolymer became the
preferred impact modifier for PVc.
During the following years, PVC continued to be impact modified by blending - in
1956 with methylmethacrylate-butadiene-styrene (MBS) and chlorinated polyethyl-
ene (CPE), a year later with chIorosulfonated polyethylene (CSR), in 1959 with linear
polyurethane (TPU), in 1967 with chlorinated ethylene-propylene-diene terpolymer
(C-EPDM), then with polysiloxanes, acrylic impact modifiers, etc. In the early 1960s
high-shear dry-blending (also known as powder blending) begun to dominate the
PVC compounding technology.
Over the years, several types of polymeric modifiers have been specifically devel-
oped for PVC (Lutz and Dunkelberger, 1992; Asay et al., 1992). Since many of these
were polymerized in emulsions, latex-blending was initially the preferred method
(Harvey, 1950). During the early 1930s I. G. Farbenindustrie obtained a series of
patents on emulsion polymerization or copolymerization of vinyl and acrylic mono-
mers, such as: methyl and ethylacrylate with acrylonitrile; vinylacetate and chIoro-
acetate; acrylic acid, acrylic esters, acrylonitrile and styrene; or vinyl chloride, vinyl
acetate, styrene, acrylonitrile and acrylic esters. Blending these emulsions, then
spray-drying the mixture, and processing, was a natural method for widening the
PVC/NBR blends 195
range of resin properties and easy evaluation of their applicability. Latex blending is
still the preferred method for formulating paints, adhesives, plastisols, organosols,
etc. Developed at Shawinigan Chemicals, a highly efficient loop-reactor technology
for polymerization or copolymerization of vinyl, acrylic and alkenic monomers
extended the use of latex blending to our times (Lanthier, 1966).
In time, melt-mixing begin to dominate the PVC blending. However, this is a far
from simple technology. First, there is the well-known problem of thermal stability
that limits the compounding and processing temperature to :S 220°C (stabilized
formulations). Furthermore, PVC melt is non-homogenous. During suspension or
emulsion polymerization the PVC particles grow by multistage aggregation. The
primary grain structure, most likely helped by partial crystallinity of the syndiotactic
chains, tends to remain in the melt at temperatures at least up to 250°C. As a
result, the flow of PVC blends (especially the rigid formulations) has been interpreted
using a suspension model, with an apparent yield stress (Utracki, 1973b, 1974, 1985b).
Compounding and processing PVC blends requires fine control of temperature and
the stress field. Different operational conditions result in different levels of breakage
of the PVC grains, thus in different blend morphology and performance.
These observations suggest that the miscibility of PVC affects only a part of the
polymer. Even in such miscible systems as amorphous PVC with polymethylmethac-
rylate (PMMA), detailed NMR studies led to the conclusion that the system is
homogenous at a resolution of 20 om, but heterogeneous at 2 om (Albert et al.,
1985; McBrierty and Packer, 1993).
For the melt blending of two high polymers it is important to begin with the finest
degree of dispersion of the macromolecular ingredients. This suggests that emul-
sion-grade PVC would be preferred. However, the emulsion polymers are notori-
ously dirty, containing large amount of contaminants, residues from the emulsifiers,
initiators, buffers, etc. These impurities may be intolerable for certain applications
(e.g., electrical), or they may require extensive stabilization in others. Furthermore,
alimentation of fine powders of spin-dried PVC to processing machinery, extruder
or compounder, is troublesome. The high-shear dry- (pre-)blending may offer an
expensive but the only solution. Thus, depending on the application, a suspension of
PVC may be preferred.
Starting in 1971, the search was for improved PVC performan~e by incorporation
of engineering or specialty resins, namely PET, PC, POM, PI, PBT (PBT-L in Table 9.3
stands for the compatibilized PBT adduct with caprolactone), or PC-polysulfone
copolymer (PC-PSF). Sixty-five years after the first patent on a PVC blend was
granted new alloys are being invented - recent patents on compositions with car-
boxylated NBR, polyarnides, particulate-grafted crosslinked silicone and acrylic
rubbers, or with maleirnide-based block copolymers are but some of the latest
examples.
11.1 PVC/NBR BLENDS

Some of the earliest blends were prepared by methods adopted from the rubber
industry, such as milling and extruding. The mechanical blending of dry latex
powders was introduced in the early 193Os. In 1936 Fikentscher and Schmidt
patented a mixture of PVC with acrylic impact modifier to be used for cable cover-
ing. Soon after the invention of the nitrile rubber (NBR), Ernst Badum working for
Bergisch-Gladbach discovered that milling it with lQ-SOwt% PVC resulted in easily
processable materials for cable insulation, having excellent ozone resistance (Figure
11.1) (Badum, 1942). The blend was commercialized in 1936, whereas the patent to
196 Polyvinylchloride
Patented Sept. 29.1942 2,297,194
UNITED STATES PATENT OFFICE

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IO~ 01 arnlbeUc rubber to correspond. Tho mIx- II acrrUc add Illlrlie arnlbeUc rubber compoUDd
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ODd mar be vlU1ed be,oDel _ Umlla depend- 10 per cent b, wellbt 01 polJvlnrl chlorld. . . a
lila u _ addlUonol propetUea. oucb .. _blllJr ruler.
for eumple. ltlal mar be _red. 2. A ....terlal lor coverlnl InsUlated ....trl..1
The 1Illxln. iI efreeted In blown wile In • 10 conductors comprlalnc an tnUmate mechanical
rubber mblllI drum. In accordance I'IIb the mLllure of polJV\nrl chIorid. and polym.rI.....
Invention the po17Yln,rl chloride may hereby be of butadlenes and acl1'Uc acid nitrile, the pro·
added to the mlxlure I'Itb or without lI\e addl- potUono of polyvln,1 cblorlde belnl from ap-
Uon 01 softenora. MiXed polrmertxatoa 01 hula- proxlmatel, 10 to 10 per cenl of the .....ht 01
dl.... and acrylic add Illtm. bay. abo... them- tI the ..hole compoUDd.
aelYeS to be puUcularlJ' adapted to \lie . . a1O· 3. '!be Improvement In I7DUleUc rubber Insu·
lI\eUc rubber. laUon of the lJpe compaoed 01 mixed pol",..r-
The osone reslItant cable m., In the ftrst place latea of but..cUenea &Ild aer,Uc acid nitrile. tom·
be eaaed In tnown ..... In a rubber lnodlallon. prlalnl a mecbanl..1 mixture 01 such srnth.Uc
with • protecUve layer aecorcl11l1 to the Innn· JO rubber eompOundl with 10 to 50 parts b, wel.ht
lion a_e lhJo. ..horeb, the proJecUv. Ia,er .. 01 polJV\nr1 chloride to Import to SlId compOW\d
prelerabl1 united with the rubber InauI.Uon • hl.h and lonaevous reslltaDce to ozone.
I'Itbout a lIP. Inlermadlale la,.rs, ..blch are
made 01 mlxluiu 01 the lIlauJaUIlI subot&nce and ERNST BADUM.
Figure 11.1 Ernst Badum's patent for PVC/NBR blends.
Bergisch-Gladbach deposited in 1937 was issued in 1942. These PVC blends, one
with the acrylic impact modifier and the other with NBR, were the first commercial
thermoplastic blends in the modem sense of the word.
Nearly identical blends were patented by B.F. Goodrich seven years later. Thus,
PVC was mechanically blended with 50-90 wt % NBR to produce rubbery materials
used as ozone-resistant cable insulator (Henderson, 1943). In 1947 the company
introduced the ever popular Geon™ Polyblends (Pittenger and Cohan, 1947). The
alloys showed good processability and excellent ozone resistance.
The miscibility of PVC/NBR blends is controlled by the acrylonitrile content in
NBR. When the latter resin contains more than 25 wt % AN good miscibility with
PVC (evidenced by a single glass transition temperature) was reported (Matsuo et al.,
1969; Zakrzewski, 1973). However, high resolution transmission electron microscopy
(TEM) showed fine dispersion of the two polymers on the scale of about 10 om
(Matsuo, 1968). Thus, increasing the concentration of AN improves the blend misci-
bility, enhances the degree of dispersion, plasticization and processability. However,
PVC/NBR blends 197
as the AN content increases the low temperature flexibility and impact strength
decrease. The best compromise has been obtained using NBR with a medium AN
content of about 34 wt %. When the blends do not have sufficient flexibility, a small
amount of plasticizer, e.g., diethylhexyl phthalate (OOP), may be added. Once the
NBR component is optimized, the same must be done for PVC (see also the general
discussion on PVC blends). The molecular weight (MW) of PVC is the main para-
meter to optimize. Decreasing MW makes it easier to blend and process, but tends to
reduce the modulus, impact strength, abrasion and ozone resistance. The low MW
PVC resins are used in injection molding formulations. For general purpose alloys,
medium MW PVC with a K value of about 60 is usually selected.
Most commercial PVC blends contain 50-90 wt % NBR to produce easily process-
able rubbery thermoplastics. These blends have good adhesion to rubbers (provided
that the rubber is also preblended with cocompatibilizing NBR). The reversed
composition blends, with 50--90 wt % PVC, are also known. They belong to the family
of rigid PVC formulations with NBR playing a dual role, that of solid plasticizer and
processing aid.
Nowadays, PVC/NBR blends are prepared by either mixing NBR latex with
emulsion or suspension PVC (followed by coagulation, fluxing and drying), or
mechanical compounding in the molten state. Furthermore, the blends can either
be pre-eompounded, or (profiting from the above-mentioned miscibility of the main
ingredients) directly blended in the same extruder or molding machine that is used
to form the product. However, increasing the degree of fluxing produces tougher,
stiffer blends with higher melt viscosity, that are more difficult to process. Again, the
compounding and processing must be optimized, and once this is achieved these
processes must be controlled by closed-loop product monitoring in order to secure
good reproducibility.
Today, the PVC/NBR blends are still of major commercial interest around the
globe, namely GeonTM from B. F. Goodrich, /5R NV from Japan Synthetic Rubber,
Krynac™ NV from Polysar, NipolTM from Nippon Zeon, Paracril™ 020 from Uni-
royal Chemical Company or Vynite™ from Alpha Chemicals and Plastics. In most
cases the composition varies from 1:1 to 3:7. The PVC/NBR alloys are designed
primarily to be extruded and calendered, but injection, blow, compression and
transfer molding are feasible as well. Their impact and tear strength, oil, fuel,
chemical, abrasion, weathering, and ozone resistance, antistatic, flame and moisture
resistance are good. Some grades contain a plasticizer (mainly diethylhexylphtha-
late, OOP), some are filled or reinforced (e.g., with CaC03 or carbon black).
The blends are used in manufacture of hoses, rolls, wire and cable insulation,
footwear, sheets for expanded insulation, foamed extruded profiles for door and
window seals, automotive accessories, diaphragms, conveyor belts, protective cloth-
ing, shoe soles, jacketing, roll covers, cable and wire jackets, etc. The main advan-
tages are processability, long storage stability, excellent abrasion and tear resistance,
ozone, weathering, fuel, and oil resistance, antistatic and flame resistant properties,
low compression set, low temperature properties and low water absorption.
Several PVC/NBR alloys have been patented. In 1950 it was discovered that good
adhesion of PVC to a rubber can be achieved when both materials are pre-blended
with NBR - this was the first use of a common, co-soluble polymer as a co-
compatibilizer (Societe chimique de Gerland, 1950). The same year Firestone
patented NBR blends with PVC (or VC copolymers with vinyl or acrylic monomers)
using polyamines as coupling agents (Eberly, 1950). In 1951 B. F. Goodrich Company
patented a wide range of PVC/NBR compositions, Geon™, to produce easily
processable thermoplastic alloys (Wolf, 1951).
In the patent granted to Visking Corporation, 10-25 wt % NBR as Hycar™, was
used as a compatibilizer for either PVC or polyvinylidene chloride (PVOC as
SaranTM), blended with 70-20 wt % polychloroprene (CR as Neoprene™). The blends
were transparent, thermoplastic, heat-sealable, printable, odorless and tasteless,
suitable for a wide range of applications (Signer and Beal, 1951, 1953). Similarly,
PVC blends with 5-13 phr of SBR were compatibilized by addition of NBR - the
alloys showed improved impact strength at low temperature (Bataafse Petroleum
Maatschappij N. V., 1960).
In some patents the PVC/NBR blends were plasticized to further flexibility of the
mixtures. For example, 100 parts PVC was blended with ID-400 parts vulcanized
NBR and 25-300 parts plasticizer, to give alloys with good heat distortion resistance,
resilience and delustered effect (Sumitomo Bakelite Co., 1983). In 1959 a ternary
system, PVC with NBR and chloroprene rubber, was found to be superior to any
PVC/plasticizer system (Alekseenko and Mishustin, 1959).
In later patents, acidification of NBR made it possible to use it as a compatibilizer
in blends with polyamides, polycarbonates or polyesters. For example, in Tosoh
Corporation laboratories PVC blends with PA were efficiently compatibilized and
impact modified by incorporation of carboxylated NBR (Iwanaga et al., 1990).
In 1992, Uponor Innovation discovered that a PVC blend with carbon monoxide-
ethylene-vinylacetate copolymer, 25phr COPo-VAc, can be compatibilized by add-
ing 10 phr NBR. The blends could also comprise stabilizers, lubricants and fillers.
The final composition had a glass transition temperature of 45-75°C, the ratio of
tensile moduli measured at 20°C and 75 °C equal to 20, and elongation at break (at
20°C) 200%. The alloys were found suitable for production of expandable folded
pipes for realigning underground pipelines (Lund and Agren, 1993).
11.2 PVC/ACRYLICS BLENDS

The term acrylics describes a family of polymers or copolymers containing repeating
units that can be considered as derivatives of acrylic or of a substituted acrylic acid of
the type -CH2-C(Y)CX-, where X =-H (acrylic acid derivatives) or X =-CH3
(methacrylic acid derivatives), and Y = N, ONH2,OOCn H 2n +1, etc.
The origin of PVC-acrylic miscibility is the interaction between the -CHCl- group
of PVC and the carboxyl group of the acrylic. In principle, the mechanism is
analogous to that responsible for miscibility of PVC with linear aliphatic polyesters,
e.g., polycaprolactam Gager et al., 1983; Tremblay and Prud'homme, 1984; Riedl and
Prud'homme, 1984, 1986; Walsh and Cheng, 1984), or polypentamethylene-adipate
or polytetramethylene-adipate, -glutarate, -sebacate, etc. These resins have been
incorporated into blends, patented by Imperial Chemical Industries (ICI) (Small
and Small, 1951). In a later patent from ICI, penta- and hexadiols were condensed
with a mixture of glutaric and succinic acids. The resulting polyesters blended with
PVC at a ratio 1:1 gave clear, flexible sheets (Aitken et al., 1959). The same year, PVC
or PVCAc were blended with fumaric acid-butanediol polyester and CA, to give
gasoline-resistant coatings (Roser, G. m. b. H., 1959).
The principal member of the acrylics family is polymethylmethacrylate (PMMA),
also known as 'the acrylic'. In spite of PVC miscibility with PMMA, blends of these
two polymers are not commercially important (although addition of PVC is known
to reduce PMMA flammability). Both resins are amorphous with similar glass
transition temperatures and poor impact strength. To be useful they require tough-
ening. It is worth noting that PMMA also forms miscible blends with chlorinated
polyvinylchloride (CPVC). These blends (containing:::; 80% PMMA) are known for
PVC/acrylics blends 199
their good processability, HDT and toughness (Lehr, 1986). PVC miscibility with
imidized polymethacrylate (polyglutarimide) was discussed in a 1990 patent
application from R6hm & Haas - the alloys were reported to give special advantage
for high heat applications (Fromuth et al., 1992).
On numerous occasions, the miscibility of PVC with acrylics was explored for the
purpose of compatibilization. For example, in a du Pont de Nemours patent applica-
tion of 1991, 10-95 parts PVC was blended with a complementary amount of a
mixture consisting of 30-85 wt % imidized acrylic polymer (Tg = 130 ec, e.g., Para-
loiJfM) and a polymer, processable at 150-300 ec, that did not enhance degradation
of PVC. (e.g., ABS or SMA). The resulting blends showed good processability and
high HDT (Gia, 1992).
The acrylics that are currently used in PVC alloys are mainly elastomeric acrylic
type. Some of these blends are discussed with ABS or modified ABS blends in
Section 10.5.5. Here only additional patents will be mentioned.
The first patent on PVC/acrylics was issued to I.G. Farbenindustrie (Fikentscher
and Schmidt, 1936). In 1956 R6hm and Haas introduced butadiene-methylmethacry-
late-styrene copolymer, (MBS AcryloidfM, now ParaloidfM), as a PVC impact modifier
(Feuer, 1958). The PVC/MBS alloys have been prepared by latex blending (Fujii and
Ohtsuka, 1954; Mertz et al., 1956). ICI patented blends comprising 65-73wt% PVC,
with 10-15wt% PMMA and 17-20wt% poly(butadiene-g-methylmethacrylate)
copolymer (Jarrett and Williams, 1960).
Newer types of MBS, designed as impact modifiers for PVC, have controlled size
of the elastomeric particles that makes it possible to prepare transparent PVC/MBS
sheets for packaging. For example, MBS with cluster-like structures is being offered.
The individual particles fonning the clusters have a diameter of 50-70 nm. They are
held together by a styrene-methylmethacrylate graft copolymer or terpolymer (Saito,
1973). An alternative route to transparency is to use acrylic elastomers that match the
refractive index of PVc.
In 1959 and 1960 patent applications from Kureha Chemical Works, for rigid PVC
blends having high impact strength and heat deflection temperature, were obtained
by blending it with a copolymer of vinylchloride, alkyl acrylate and vinylidene
chloride or alkyl vinyl ether (Hoshi and Kaneko, 1962, 1963, 1965). In a later patent
PVC was blended with a copolymer of butadiene-styrene-methylacrylate-ethylacry-
late (Ichinoe, 1967). In 1959 Union Carbide Corporation applied for a patent for easy
to process, tough PVC blends with ethylene-ethylacrylate copolymer (Van Cleve and
Mullins, 1962). In a Dow patent application of 1965, for good processability, flame
resistance and strength, PVC was blended with butadiene-a-methylstyrene-methyl-
methacrylate copolymer and polysiloxane (Amos et a1., 1969).
In a series of patent applications dated from 1966, Mitsubishi Rayon Company
disclosed blends of PVC or poly(vinylchloride-eo-vinylacetate) copolymer (PVCAc)
with poly(butadiene-co-butylacrylate-co-styrene), 3-40 wt % SB-BA or with poly
(styrene-co-acrylonitrile -co-methylmethacrylate-g-butylacrylate-g-methylmethacryl-
ate) elastomer. The resulting alloys were transparent, with good weatherability and
high impact strength (Ide and Deguchi, 1971; Ide and Miura, 1971; Ide et al., 1972). As
a result of this work the company developed advanced technology for manufactur-
ing a variety of compatibilizers/impact modifiers, as Metablen™, originally desig-
ned for PVC, later expanded to such engineering resins as PC, PEST, PPS, etc.
As Figure 9.5 indicates, the highest impact strength was obtained for Metablen™
MBS impact modifier having particle size of about 300 nm. This maximum is best
explained by the mechanism of cavitation inside elastomeric particles that is gov-
erned by the total energy of deformation. The latter is composed of two terms that
show opposite trends with increase of particle diameter - the energy required for
deformation (or the strain energy) decreases, while the energy required for creation
of new surface (or surface energy) increases. Since by varying the chemical composi-
tion of MBS one can change the deformability of both MBS and PVC matrices, the
technology makes it possible to shift the maximum, thus accommodating other
desirable properties, such as transparency (Partridge, 1992).
In 1968, B. F. Goodrich Company blended PVC with polytetrahydrofuran (PTHF)
and styrene-acrylonitrile copolymer (SAN). The alloys were reported to show good
processability, chemical, solvent, and impact resistance (Dreyfuss and Dreyfuss,
1970).
In a Hitachi patent, PVC was blended with polybutadiene grafted with methyl
methacrylate, styrene and vinyl acetate, to give good processability, transparency,
impact and whitening resistance (Kakefuda and lto, 1971). In a Pechiney-Saint
Gobain patent, the impact and strength of PVC were improved by blending with a
core-shell copolymer core made of partially crosslinked ABS, and PMMA shell
grafted onto it (Michel, 1969).
In 1970, Japanese Geon applied for patents on PVC blends with a core-shell
copolymer, either poly(acrylonitrile-co-ethylacrylate-co-methylmethacrylate), poly
(acrylonitrile-co-methylmethacrylate), or poly(acrylonitrile-co-ethylhexylacrylate-co-
methylmethacrylate). Good processability, transparency and impact strength were
claimed (Tanaka, H. et a!., 1971; Tanaka, A. et al. 1971, 1972). Similarly, in a Kureha
patent, 70-99 wt % PVC was blended with butadiene-styrene-divinylbenzene-butyl-
acrylate-methylmethacrylate copolymer, to give transparent, craze and impact resist-
ant resins (Usami and Ochiai, 1976).
In a Mitsubishi Rayon patent application of 1976, PVC was blended with 10-90%
of a graft copolymer obtained by grafting methylmethacrylate and styrene onto an
acrylic elastomer. Good transparency, impact strength, and weathering character-
istics were disclosed (Kishida et al., 1977). Later, the company announced PVC
blends with acrylonitrile-methylmethacrylate block copolymer (AMMA) that was
compatibilized with acrylamide-acrylonitrile-vinylbromide. These blends showed
superior compatibility and mechanical properties, as well as good flame resistance
(Iwata et al., 1979). At the same time Mitsubishi Plastics Industries disclosed PVC
blends with chlorinated polyethylene (30-40 wt % CPE) and poly(methylmethacry-
late-co-butylacrylate) copolymer (3-10wt% MMBA). These alloys showed excellent
tensile and impact strength (Maruyama et al., 1977).
Interesting blends were described in a document from Politechnika Warszawska
of 1977. These materials comprised 70-90wt% PVC and ethylacrylate-grafted Pvc.
The alloys were reported to have high impact strength and good tensile properties
(Hibner and Laskawski, 1980).
In the early 1980s, Hiils developed poly(phenoxyethoxyethylacrylate) (PPOEA).
The resin blended with PVC and a graft copolymer of vinylchloride on PPOEA
resulted in transparent alloys with good impact resistance (Stuetzel et al., 1984).
Similar transparent blends were disclosed by Japan Synthetic Rubber Company.
PVC composition with good processability, transparency and impact resistance
comprised 5-40 wt % of a multistage graft copolymer of SBR with methylmethacryl-
ate and styrene (MBS) Oapan Synthetic Rubber Co., 1985b).
In 1982, blends of PVC with either EVAc, and styrene-butadiene block copolymer
(Sekisui Chemical Co., 1984), or with ethylene-vinylacetate-carbon monoxide copoly-
mer (EVAc-CO) and a methyl methacrylate graft copolymer (Kaneace™) (Mitsui
Petrochemical Co., 1983d) were described. In the first case the resulting alloys
showed excellent processability, transparency, thermal stability, weather resistance,
PVC/acrylics blends 201
low-T flexibility and blocking resistance, while in the second the transparent blends
had excellent impact properties.
In 1988 Bayer disclosed the use of three-layer, core shell impact modifier for PVc.
Thus, PVC-based molding blends, contained graft polymer particles, having cores of
crosslinked silicone rubber, inner shells of crosslinked acrylate elastomer (butyl
acrylate, tri-allylcyanurate) and outer shells made of styrene-acrylonitrile copoly-
mers. The alloys showed excellent low temperature impact behavior (Lindner et ai.,
1990).
In 1991, Sumitomo Chemical Company announced new blends comprising granu-
lar PVC powder 3-20 wt %, and fine granular vinylchloride-acrylate copolymers.
The material showed good excess-powder removability and adhesion to poly-
urethane layers in the mold. It was used for molding interior covers for automobiles
(Nakatsuji et al., 1993). The following year, Geon Company announced blends
comprising 100 parts of either PVC, or a copolymer of vinylchloride with
(meth)acrylic ester(s) (PVC-EA), polyethylene or polypropylene glycol (PEG or
PPG), and 12~5wt% poly(imide-co-methacrylate). The resulting alloys showed
high transparency with the light transmission exceeding 70%. The blends could
also contain conventional additives, such as lubricants, impact modifiers, fire retard-
ants (Rajagopalan, 1994).
The following year, Solvay announced impact-resistant blends of PVC that com-
prised 5-25 wt % of vinyl chloride grafted onto a lightly crosslinked polybutylacry-
late (containing 25-40wt% crosslinked PBA), 30-75wt% of a graft copolymer
of vinyl chloride onto an ethylene-vinylacetate (containing 1.5-5 wt % EVAc),
20-50 wt % PVC and, as a reinforcing filler, 5-8 phr coated CaC03 (particle size
< 1 jLm). The blends exhibited high notched impact strength. They were found
useful for the extrusion of profiles used in the construction of exterior window
frames (Gloesener, 1993, 1994).
There are many commercial PVC/acrylics blends on the market: Acrylivin™ from
General Tire & Rubber, Cladux™ from R. Daleman Company, DecoloyTM from GE
Plastics, Enplex™ from Kaneka Corporation, Haibulen™ from Nippon Zeon, Hos-
talit™ Hand HM from Hoechst, Kane-ace™ from Kanegafuchi Chemical, Kydex™
100 (introduced in 1964 by Kleerdex Company as blends of PVC and PMMA) and
Kydene™ from Rohm & Haas, Metabulen™ from Mitsubishi Rayon, Polycast™ from
Royalite, Sunloid™ KD from Tsusunaka or Vinidur™ (commercialized in 1960) from
BASF.
PVC/acrylics extruded sheets have been used for thermoforming applications.
Ease of thermoformability, toughness, resistance to cleaning solvents, and the flame
retardancy characteristics of the blends have been the primary features leading to its
use. The inherent flame retardancy and low smoke-generation characteristics of
PVC/PMMA blends meet the aircraft fire safety standards. These aspects, coupled
with the low cost, led to use in aircraft and mass-transport vehicles.
PVC/ acrylics blends have been used to form industrial, commercial and consumer
goods (e.g., as wall coverings, corner guards, column covers, shelving, counter
laminates, chairs, seats, trays, ceiling tiles, window frames, weather boards, roof
gutter systems, pipes, swimming pools, ladders, claddings), in medical, electrical
(cable ducts and conduits) and diverse chemical engineering equipment, for food or
beverage equipment, as aircraft or mass transit interior components, for power tool
housings, razor bodies, vacuum cleaner parts, protective helmets, steering wheels,
records, toys, sport articles, aircraft components such as toilet shrouds, floor pans,
air diffusers, emergency respirator enclosures, office equipment and computer parts,
and in other applications requiring good resistance to weathering.
11.3 PVC/ELASTOMER BLENDS

PVC blends with ABS and modified-ABS, as well as those with acrylic elastomers
were discussed in earlier sections. Here, only the evolution of commercial PVC
blends with non-acrylic elastomers is considered. Since PVC is immiscible with
alkeneic or alkanic macromolecules, hydrocarbon elastomers can be used as impact
modifiers either at low concentration (e.g., 5-lOwt%), or they must be chemically
modified to promote interactions with PVC macromolecules. Alternatively, the
blend has to be compatibilized by addition of a third ingredient.
In 1935, Carbide and Carbon Chemicals Corporation blended poly(vinylchloride-
co-vinylacetate) (PVCAc) with natural rubber to give materials suitable as leather
substitutes (Reed, 1935). The first impact modifications of PVC by addition of non-
acrylic elastomers (namely polyisobutylene (PIB) natural rubber (NR) or polyiso-
prene (IR), were patented in 1938, independently by Standard Oil and I. G. Farbe-
nindustrie (Bayer). However, a major improvement of PVC performance was
achieved by blending PVC with chlorinated rubber (8. F. Goodrich Co., 1941).
The first blends of PVC with thio-rubbers date from 1949 - to improve PVC
resistance to gasoline and oil, Socony Vacuum Oil Company compounded PVC
with 3D-40wt% polysulfide rubber (TM) (Rittershausen, 1949). A few years later
PVC blends with 7 wt % TM, and 7% chlorosulfonated polyethylene (CSR) were
patented. These easy-to-process resins had high impact strength and HOT (Allied
Chemicals Corp., 1965, 1966).
In a Visking patent, PVC was blended with 70-20% polychloroprene, (CR,
Neoprene™) and 10-25% NBR, Hycar™, as a compatibilizer. The blends were trans-
parent, thermoplastic, heatsealable, printable, odorless and tasteless, suitable for a
wide range of applications (Signer and Beat, 1953). PVC or PVCAc blends with 0.5-
50 % of chlorinated polybutadiene (CPB) were patented few years later. The material
showed high impact strength, good fleXibility and other mechanical properties (Esso
Research and Engineering Co., 1960).
In a 1959 patent application, blends of PVC with polyisobutylene (PIB) were
described. The materials were reported to show good processability and improved
impact strength (Lonza Ltd., 1964). The same year, Hills described toughening of
PVC by blending it with 0.5-2wt% dibutyl fumarate and butadiene copolymer.
Extruded pipes were found to be resistant to prolonged exposure to high pressures
(Koenig et al., 1963, 1964). Five years later, Asahi Chemicals disclosed PVC blends
with polybutadiene and/or a copolymer of ethylene (or butadiene) with vinyl and
acrylic monomers, e.g., EVAc. The blends showed improved impact resistance
(Kasuya et al., 1969).
In 1982, PVC blends with EPOM and ring-opened polynorbornene having car-
boxylic, and carboxylic ester groups were disclosed. The materials were molded into
sheets showing excellent impact resistance (Mitsubishi Petrochemical Co., 1983d).
Several PVC/elastomer blends are on the market, namely, CarloyTM from
Cary Chemicals Incorporated, OxyBlenJIM and OxyClear™ from OxyChem or
Vynaprene™ from Vista Chemical Company. Most commercial blends that comprise
3D-60wt% PVC have been primarily formulated for extrusion (e.g., for wire coat-
ing), but calendering, injection, blow, compression and transfer molding can also be
used. These materials have excellent processability, HOT, impact and tear strength,
as well as good oil, fuel, chemical, weathering, ozone, flame and moisture resistance.
Their applications include bottles for cosmetics, consumer goods or automotive
chemicals, sheets for exterior signs, window accessories, cables and hoses, printing
plates and rollers, shoe soles, profiles, military coax jacketing etc.
PVC/CPE and PVC/CSR blends 203
11.4 PVC/POLYALKENE BLENDS
Polyvinylchloride (PVC) is antagonistically immiscible with polyalkenes (PO). For
this reason four types of PVC/PO blends are possible: (1) with a small amount of PO
to facilitate processing and improving the impact strength; (2) with cocontinuous
structures, used mainly for decorative materials; (3) incorporation of PO as part of a
copolymer containing polymeric segments miscible with PVC; and (4) compatibi-
lized PVC/PO blends. illustrations for these strategies can be found on the following
pages.
To improve processability and impact strength of PVC it was blended in 1968 with
a small amount of PO (Hiils A.-G., 1971). The same year Sumitomo Bakelite
announced that the impact properties of calendered sheets from chlorinated PVC
(CPVC) were improved by incorporating 5-30 phr of vinylchloride-propylene
copolymer (Moritani et aI., 1972). In a contemporary document from Sanyo Kako,
blends comprising PVc, PP and either polymethylmethacrylate (PMMA) or
polycarbonate (PC) were described. These materials showed a layered, wood-like
structure. They had good processability and machinability (Yahata et al., 1971a).
In many cases polyalkenes were incorporated into a PVC matrix as parts of
copolymers aimed at improvement of processability and impact strength. In a du
Pont de Nemours patent application of 1970, PVC was blended with 20wt% ethy-
lene-sulfur dioxide-vinylacetate terpolymer. The blends with excellent processability
were found suitable for manufacturing films with good mechanical properties
(Hammer and Hickman, 1972). In 1971 blends with high impact strength, comprising
PVC and cyclopentene-vinylchloride copolymer, were developed by Montecatini
Edison (Severini et al., 1971).
In 1982, PVC was copolymerized with 1-40 wt % polypropylene (PP) to give alloys
with good moldability and high HDT (Unitika Ltd., 1984). The following year,
blends comprising 100 parts PVC, a polyethylene (1D-300 parts HDPE) and chlor-
inated polyethylene (0.1-5 parts CPE), were disclosed. These materials were found
suitable for manufacturing of weather-stripping gaskets for automobile windows
(Nippon Zeon Co., 1984).
In a broad patent deposited in 1992 by R6hm and Haas, blends that comprised 100
parts of a polar resin (e.g., PVC homo- 'or copolymers), 1-15 parts of segmented
polymer comprising non-polar, non-rubbery polyalkene (PP, PE or their copoly-
mers) with M w = 5D-1000kg/mol, and a polymer derived from at least SOwt% of
alkyl, aryl, alkaryl, or methyl methacrylate ester and not more than 20 wt % acrylic or
styrenic monomer, with M w = 2D-200kg/mol, were described. The blends were
mixed while heating until fluxed. The blending improved processability, decreasing
the time to flux, as well as the temperature and pressure required for injection
molding. The alloys were used for extrusion or injection molding of pipes and
pipe fittings, garden tools, electrical, automotive and business machines or appli-
ances parts, toys, sporting goods, footwear, battery cases, conduits, construction
profiles, wire coatings, garden hose, packaging film, and profiles for medical
applications, automotive or furniture seating, wall coverings and bottles (Williams
and llenda, 1993).
Owing to difficulties in compatibilizing PVC/PO blends, systems containing high
concentrations of the two major components are not commercially available.
11.5 PVC/CPE AND PVC/CSR BLENDS

The macromolecular structure of PVC is locally similar to that of chlorinated HDPE
(CPE). However, the higher concentration and greater regularity of the chlorine
atoms in the PVC chain results in greater rigidity. The chlorine atoms in the main
chain repel each other and the intermolecular dipole interactions further stiffen the
macromolecules. By contrast, the chlorine content in CPE can be adjusted, but since it
is lower than that in PVC, the chain mobility and toughness of HDPE is locally
retained. Depending on the mixing ratios, the blend toughness varies from that of
PVC to CPE, the heat resistance and heat distortion characteristics are nearly inde-
pendent of the CPE content and the outdoor weathering characteristics are similar to
PVc. However, the formulations must be stabilized against thermal degradation
(during processing) and/or weathering (during use). The electrical properties, chem-
ical and flame resistance of these blends are equivalent to those of Pvc. The systems
can easily be modified by additives and fillers (in particular, calcium carbonate is
frequently used). Extrusion and injection molding grades are available. Their range
of applicability has been extended to transparent grades by compounding with
acrylic modifiers.
This important new class of PVC blends was patented and commercially intro-
duced in 1956 by Hoechst. Hostalit™ Z is a blend of PVC with about lOwt% CPE,
haVing good impact resistance and a wide range of hardness. The well-known
disadvantages of extractability and migration of plasticizer and reduction of elec-
trical properties are non-existent. The patents protect a wide range of compositions
comprising polymers and copolymers of vinyl chloride or vinylidene chloride (e.g.,
PVC or PVOC) or vinylidenechloride-acrylonitrile copolymers (VOC/AN), blended
with 10-70wt% CPE, or chlorinated EPR, reported to give improved impact
strength, transparency and non-combustibility (Frey, 1958, 1960-1964).
Independent discoveries of PVC/CPE blends were announced at about the same
time by several other companies, e.g., Dainippon, Dow, du Pont de Nemours,
Hoechst, Kanegafuchi Chemical, and others (Dow Chemical Co., 196Ob). For ex-
ample, in a 1959 patent application from Monsanto Chemical, blends of PVC with
polyalkenes (5 wt % PO) were compatibilized either by introducing polar groups into
PO macromolecules or by using either CPE or MBS graft copolymer (Baer and
Hankey, 1963; Salyer and Holladay, 1964). The following year saw PVC blends
with 5-12wt% CPE, and 0.1-10wt% of a diamine, which behaved as an interfacial
agent. The blends had high impact strength (Hankey and Kianpour, 1964). In another
patent from Monsanto, PVC was solution blended with chlorinated or chlorosulfon-
ated polyalkenes, to give homogenous blends, with good clarity, physical properties
and solvent resistance (Beer, 1963).
In 1960, blends comprising PVC (or its copolymers with vinyl acetate), and
0.5-50wt% of chlorinated polybutadiene (CPB) were disclosed. Blending resulted
in high impact, flexible thermoplastic materials (Esso Research and Engineering
Company, 1960).
In 1963, Mitsubishi Monsanto Chemical, developed blends that comprised
5-50wt% PVC, postchlorinated polyvinylchloride (CPVC) and 1-50wt% ABS. The
blends showed improved processability, impact strength and thermal stability
(Kojima et al., 1970). In a contemporary patent, PVC was blended with polysulfide
rubber (7wt% TM) and chlorosulfonated polyethylene (7wt% CSR), to obtain easily
processed resins with high impact strength (Allied Chemicals Corp., 1965, 1966).
Similarly, to improve HDT, in a du Pont de Nemours patent, PVC was fluxed for 2: 3
min with an equal amount of CPE or CSR. Twenty years later the company
announced high performance blends comprising PVC with 1-50phr each of CPE
and CSR (Hedberg and Magner, 1965; Wallace, 1985).
However, the discovery of PVC blends with chlorosulfonated polyethylene, and
the advantages it offered should, be credited to Dainippon Celluloid who in 1957
PVC/CPE and PVC/CSR blends 205
made the first disclosure for this type of alloy. It specified that addition of 1-lOwt%
CPE or chlorosulfonated polyethylene (CSR) to PVC improved its moldability,
stability, impact strength and resistance against chemicals. The blends were found
to be particularly useful for molding applications (Matsuda, 1960; Matsuda et al.,
1960). In 1960 Goodyear Tire and Rubber Company introduced blends of PVC with a
chlorosulfonated polyethylene (CSR, Hypalon 1M) from du Pont de Nemours
designed specifically for blends with PVC (Law, 1960).
In a Toa Gosei patent deposited in 1963, PVC and PE powders (with particles
passing through 60 mesh screen) were blended at a ratio of 85:15, then chlorinated
and milled. Improvements of heat and impact resistance were claimed (Kato et al.,
1967).
In a 1964 patent application, PVC was blended with 2-40wt% EVAc, and
1-20wt% CPE (Dow Chemical Co., 1965). Two years later ICI disclosed that PVC
blended with two heterogenously chlorinated LDPEs having CI contents of 5-30 %
and 5-55 % resulted in alloys showing higher notched impact and tensile strength
(Willott, 1968). In 1967 Ruberoid applied for patent protection for PVC/CPE blends
containing coal tar pitch. These materials were used as weather resistant roofing
sheets (Moor, 1971).
It did not take long to realize that chlorination (or chlorosulfonation) of other
polymeric or elastomeric species may also offer similar advantages for blends with
PVC as these of CPE. In a Kanegafuchi Chemical Industry patent application of 1960,
PVC latex was blended with chloroprene latex (30 wt % CR) then acidified, washed,
dried and formed into moldings or extrudates of excellent impact strength and HDT
(Nyori et al., 1962). At the same time Monsanto disclosed PVC blends with 2-3Owt%
CSR and the same amount of SAN (Salyer and Holladay, 1964).
Patent applications of 1964 described PVC blends with either chlorinated SBR (C-
SBR) (Takkosha Co., 1967) or (Toyo Koatsu Industries) with chlorinated ethylene-
propylene-diene terpolymer (C-EPDM; prepared by emulsion grafting polybuta-
diene with ethylene and vinylchloride monomers) (Watanabe et ai., 1967). Similar
formulations were described by Asahi Chemical Industry in a patent application of
1967, where PVC blends with chlorinated and/or chlorosulfonated EPDM, were
prepared for applications requiring high impact strength (Aijima and Takashi,
1971).
Chlorinated rubbers have been also used as a compatibilizers, as in PVC blends
with polystyrene. For example, Borg-Warner Chemicals' patent application of 1980
described PVC:PS = 1:1 blends with 1-20wt% chlorinated styrene-butadiene
block copolymer (Falk, 1981). In 1983, blends comprising 100 parts PVC with 10-
300 parts HDPE and 0.1-5 parts CPE, were reported to give materials useful for
weather-stripping of automobile windows (Nippon Zeon Co., 1984).
The first use of a high speed powder mixer for fluxing PVC formulations (since
then the technology has been widely adopted by the industry) was described in a
series of patent applications dating from 1963. For example, high impact strength,
rigid PVC was manufactured by powder blending PVC powders with up to 10wt%
CPE in a high speed mixer, then immediately extruding. The material showed
significant improvement of the principal performance parameters. It was noted
that an earlier method of PVC/CPE blending in a Banbury-type mixer resulted in
inadequate blends (Allied Chemical Corp., 1965, 1966).
The possibilities of blending PVC with CPE and/or its homologues became
exhausted by the mid-1970s. At the same time the emphasis shifted toward blends
with acrylic elastomers. Alloys of PVC comprising both these components have also
been proposed. For example, in a Mitsubishi Plastics Industries patent application of
1976, PVC was blended with 3O-4Owt% CPE, and poly(methylmethacrylate-co-
butylacrylate) copolymer (3-10wt% MMBA), to give excellent tensile and impact
strength (Maruyama et al., 1977).
In 1980, Borg-Warner Chemicals disclosed a new class of PVC blends based on
chlorinated styrene-butadiene block copolymer (C-SBS). Thus, blends comprising
50wt% PVC and polystyrene were compatibilized with 1-20wt% C-SBS
(Falk, 1981). One year later Atlantic Richfield disclosed miscible blends comprising
1-99 wt % CPVC and SMA. The materials showed good flame retardance, HOT and a
single glass transition temperature. For example, a blend of CPVC with SMA = 80:20
had a Tg of 114°C (Bourland, 1983).
Fuso Kagaku Kogyo deposited in 1986 a patent on interesting PVC blends with
10phr chlorinated polyethylene and 1 phr of glycidyl p-t-butylbenzoate. The alloys
showed high impact strength and HOT (Sugiara and Takayama, 1988).
In 1991, ternary alloys for molding and extrusion were announced by the B. F.
Goodrich Company. These materials comprised 5-SOwt% PVC, 1Q-85wt% CPVC
and either an acrylic copolymer (MABS; methylstyrene-acrylonitrile-methylmetha-
crylate or methylstyrene-acrylonitrile-styrene) or a mixture of either PMMA, with an
imidized-PMMA, or imidized-SMA, and SAN. The blends showed higher heat
distortion temperatures than predicted from linear additivity of properties of the
PVC/CPVC and PVC/MABS blends. Thus in the alloys a substantial amount of
expensive acrylic copolymer was replaced with CPVC without changing HOT or
melt viscosity (Soby et al., 1994).
In 1992, Dow Chemical disclosed blends comprising CPE (30-42 wt% Cl) with a
copolymer of styrene and either methylmethacrylate or vinyl acetate. These mater-
ials were in turn uSed as impact modifiers of PVC, particularly effective for low-
molecular-weight PVC (e.g., formulated for injection molding). For example,
5-25wt% of the CPE blend was mixed with 95-75wt% PVC to give high-impact-
strength alloys (Liou and Sun, 1993). The same year blends of 50-95wt% PVC with
50-5 wt % CPE were announced by Mitsubishi Kasei Vinyl. The alloys were prepared
by kneading and mixing the formulation at 100-230 °C with 20-400 phr NBR contain-
ing a THF insoluble crosslinking component, and 10-300 phr plasticizer (OOP). The
mixture showed good compression set, creep resistance, low temperature flexibility,
and blocking resistance, making it useful for manufacture of automotive glass runs
and weather strips (Oshima and Yamamori, 1993).
The PVC/CPE blends should be processed after drying the pellets in a circulating
air oven for 2h at 135°C. The processing should be done at well-specified tempera-
tures. The recommended extrusion temperature is 170-175°C, but when extruding
window profiles the required impact strength is achieved only at 190-195°C. For
calendering and thermoforming temperatures of 165-190°C and 150-175°C (mold
temperature 6O-70°C) have been used respectively. Compression molding of blocks
and sheets should be carried out at 175°C and 120-130 °C, respectively. For injection
molding a melt temperature of 170-180°C and a mold temperature of 20-50°C are
recommended.
These blends are mainly used for outdoor applications, limited by the
climatic conditions. Performance has been satisfactory for more than 30 years in
countries where the mean annual temperature is not more than 17°C and the mean
temperature during the hottest month is not greater than 24 0C. Under these
conditions the blends show good impact resistance over the whole temperature
range encountered in the application, as well as being resistant to aging, UV
.and weathering over the intended duration of use. The upper service temperature
is 6Q-65°C.
PVC/EVAc and PVC/EVAc-VC blends 207
Applications include profiles for windows, gutterin~ street barriers, gas pipes,
bench slats, sheet for facades, balcony claddin~ chemical plant, refrigerators, traffic
signs, foil for identification and punch cards, flame retardant wall coverings, cases,
prams and automobile interiors. Injection molded components include extractor
hoods, gullies in sewage systems, guttering parts, caps for road reflector posts and
bench slats.
11.6 PVC/POLYURETHANE BLENDS

Another commercially important category of PVC/elastomer blends is that with
polyurethanes. In 1956 the first tw<reomponent PVC rigid blends with 8-12wt%
of non-erosslinked, elastomeric, ester-type polyurethane were announced. The alloys
had good processability and impact resistance (B. F. Goodrich Co., 1960).
One year later, du Pont de Nemours filed for patent protection for blends com-
prising 100 parts PVC, with 15-100 parts linear polyurethane (TPU) and 5-150 parts
plasticizer. The alloys were reported to give good low temperature pliability and
impact strength (Hochberg, 1966). Between 1957 and 1960 similar blends were also
patented by several other companies: Dayco, PVC/TPU/plasticizer blends for
vacuum hoses (Dayco Corp., 1963); General Tire & Rubber Company (now known
as Gencorp) PVC blended with styrene-acrylonitrile copolymer and a rubber mixture
(Greene and Maurer, 1966); B. F. Goodrich Company, binary blends comprising
5-80 wt % PVC with polyester-type TPU for materials having good abrasion
resistance, hardness and flexibility at low temperature (Waugaman et ai., 1963);
and Saint-Gobain-ehauny & Cirey, who patented PVC blends with up to 20 %
TPU, and/or polyamide for improved mechanical strength and impact resistance
(Kepes, 1959).
In a 1976 patent application from the Kao Soap Company, 120 parts PU elastomer
was blended with 100 parts PVC, to give alloys with good impact strength and small
variation of stiffness upon aging (Kazama et ai., 1977). Two years later, a Czechoslo-
vakian patent application described PVC blends with 2-45 wt % TPU. The alloy had
high impact strength and good toughness (Mokry et ai., 1982).
Reactive blending of PVC with TPU was invented in 1981. Thus, PVC was mixed
with polyols and isocyanates that were later polymerized. Owing to intimate mixing
of the ingredients, the alloys showed excellent processability, low temperature flex-
ibility, impact strength and a good set of mechanical properties (Dainichiseika Color
and Chemicals Manufacturing Company, 1983).
In 1991, Amtico Company announced PVC blends with polyester-type polyur-
ethane and a plasticizer. The materials, developed for floor coverings (linoleum),
were reported to be scratch- and abrasion-resistant (Wilson, 1993).
The commercial PVC/TPU blends may also comprise another impact modifier,
such as NBR as in Duraiex™ from Dexter. These materials are usually formulated for
extrusion. The barrel temperature should be set at 160--175 0c. It is important not to
overheat the material. The alloys have been used for wire and cable insulation, hoses
and packaging.
11.7 PVC/EVAc AND PVC/EVAc-VC BLENDS

Blends of PVC with polyvinylacetate (PVAc) are one of the oldest - they were
patented by Standard Oil Development Company in 1938. Besides the main compon-
ents, the blends may contain such elastomers as polyisobutylene (pm), polyether-
sulfide, polychloroprene (CR) or polyisoprene (PI). Ten years later PVC (or
poly(vinylchloride-co-acetate), PVCAc, was compounded at 160 °C with polyvinyla-

cetal (PVA). The blends showed improved moldability (Lonza Elektrizitats & Che-
mische Fabriken A.-G., 1948).
In later patents, PVC instead of being mechanically blended with PVAc was
copolymerized with vinyl acetate. However, the copolymer still required impact
modification. For example, in a Hoechst patent deposition of 1967, PVC was emul-
sion polymerized. The final 15-50 wt % polymerization was carried out in the pres-
ence of styrene-butadiene-vinylacetate latex. The internally impact-modified
materials also showed good optical properties (Farbwerke Hoechst, 1970a). Sim-
ilarly, in a series of patents from Mitsubishi Rayon deposited in 1968 and 1969 either
PVC, or its copolymers with vinylacetate (PVCAc) were blended with a variety of
butadiene-butylacrylate-styrene copolymers, e.g., 3-40wt% SB/BA. The blends
showed good overall performance, with particularly significant improvement in
transparency and impact strength (Ide and Deguchi, 1971; Ide and Miura, 1971; Ide
et al., 1972).
More recent PVC/elastomer blends have been prepared exploring specific inter-
actions between PVC and ester groups. For example, in a patent application of 1982,
.du Pont de Nemours described blends of PVC or PVDC with thermoplastic elasto-
mers, containing ethylene, unsaturated organic monomers, CO or C~, S02 and
75 wt % vinyl halide or vinylidene halide, compatible with the homopolymers. As
an example, 23wt% PVC was blended with poly(ethylene-co-earbon monoxide-co-
vinylchloride) copolymer, to give blends with good moldability, Shore hardness, and
high tensile strength at break (Loomis and Statz, 1984, 1986). The Alcryn™ blends
were introduced by du Pont in 1986.
In Europe, poly(ethylene-co-vinylacetate) (EVAc) has been used as the preferred
polymeric plasticizer for PVC in window profiles, cable jacketing and other outdoor
applications. In the early patents from I. G. Farbenindustrie (1929-32, 1938) EVAc
was emulsion polymerized, then latex-blended with PVc. The miscibility of PVC
with EVAc depends on the vinyl acetate content - on the one hand, for 65-75 wt %
VAc, the blends showed a single glass transition temperature (thus were judged
miscible, although pulsed NMR showed phase separation), but on the other hand,
for VAc contents below 45wt% the blends are phase separated (Hammer, 1971;
Ranby, 1975; Elmquist, 1977; Rellick and Runt, 1985; Runt et al., 1989).
At the same time, PVC blends with ethylene-vinylacetate-carbon monoxide
copolymer (EVAc-CO) and a methylmethacrylate graft copolymer, KaneAce™,
were disclosed. These alloys were reported to be transparent with excellent Izod
impact strength (Mitsui Petrochemicals Co., 1983a). Also in 1982 PVC blends
with EPDM and ring-opened polynorbornene with carboxy, and carboxylic ester
groups were introduced. The blends were molded into sheets' with excellent
impact resistance (Mitsubishi Petrochemicals Co., 1983d). Nippon Zeon's patent of
1989 described PVC blends with chlorothene-polyester elastomeric copolymer.
The thermoplastic alloy was found able to retain shape memory (Saito and Nagata,
1990).
To summarize, commercial PVC blends with either poly(ethylene-co-vinylacetate)
or poly(ethylene-co-vinylacetate-g-vinylchloride) copolymers have been offered
since the 1970s as high impact strength, rigid formulations. Addition of EVAc was
found to improve low temperature impact strength as well as processability. Mis-
cibility of EVAc with PVC depends on the ethylene:vinyl acetate ratio. PVC blends
with EVAc comprising less than 30 wt % VAc are highly immiscible, showing low
toughening effect and poor impact strength. Blends of PVC with EVAc comprising at
least 50 wt % VAc behave as miscible. The optimum VAc content seems to be about
PVC/ABS blends 209
45wt%. The best alloy performance is usually obtained for 7-10wt% of EVAc in the
blend.
Blending is usually done either by mechanical mixing, by suspension polymeriza-
tion of vinyl chloride in the presence of EVAc latex, or compounding EVAcVC graft
copolymer (comprising 50% EVAc) with PVC to give 4-lOwt% EVAc in the final
blend. These resins show high hardness, rigidity, and adequate heat, chemical and
flame resistance. However, the toughening effects can only be achieved if the
copolymer has low glass transition temperature, and its separate phase consists of
homogeneously distributed drops with optimized average diameter. The PVC/
EVAc blends are used for window profiles, roof gutters, drain pipes, profiles for
benches and fences, light panels, road sign posts, panels for facade cladding, ventila-
tion systems, for chemical, waste, gas, or drainage pipes, for cable conduits, thermo-
forming sheets, fittings, covers, bottles, containers, etc.
Several PVC/EVAc blends are on the market: DenkovinyI™ from Denki Kagaku
Kogyo, EthyITM from Ethyl Corporation, Hostaiit™ from Hoechst, Krene™ from
Union Carbide, Laroflex™ and Vinidur™ from BASF, Lutofan™ from BASF,
Organil™ and SoIvic™ from Solvay & Cie., Trosipiast™ from Dynamit Nobel,
Varien™ from DSM, VinnoITM from Wacker Chemie, etc.
11.8 PVC/ABS BLENDS

These blends are discussed under Section 10.5.5. 'ABS/PVC Blends'. Here an abbrev-
iated version summarizing the most important developments is presented.
The first blends of PVC toughened by addition of ABS, useful for manufacture of
phonographic records, were patented by Radio Corporation of America (Parker,
1951). The following year, similar blends were patented by the Firestone Tire &
Rubber Company for manufacturing of artificial leathers (Schule, 1952; Humphrey
and Reid, 1953). The General Tire & Rubber Company in 1955 applied for a patent
for blends comprising 44-70 wt % PVC, a copolymer containing 70 wt % of
vinylchloride and 30 wt % monoalkene monomer (VCE) and ABS (Urbanic and
Maurer, 1966). In the 1956 patent from Monsanto, PVC was blended with lOphr of
styrene-acrylonitrile copolymer (SAN) and 10 phr of ABS-type G, to give resins with
'low sensitivity to mechanical working'. When used for vacuum forming these
blends additionally comprised up to 20 wt % vinylchloride-vinylacetate copolymer
(Parks and Jennings, 1956). In a later patent, PVC was blended with a-methylstyr-
ene-acrylonitrile-styrene (Slocombe and Salyer, 1961).
In 1959, Borg-Warner Corporation developed PVC blends with a graft copolymer
of butadiene-ethylacrylate-styrene-acrylonitrile and vinylchloride (Calvert, 1961,
1962,1963, 1966). At the same time the Corporation deposited the principal patent
for PVC blends with ABS-type G. The blends had high tensile strength, hardness,
impact strength and heat distortion temperature (Grabowski and Irvin, 1962; Gra-
bowski et al., 1969). Two years later, blends of PVC with a copolymer of acrylonitrile-
butadiene-vinylchloride (ABVC) were developed for production of translucent
materials with good impact strength (B. X. Plastics Ltd., 1962).
In 1963, Kanegafuchi announced high impact strength formulations comprising
PVC and 5-30wt% of acrylonitrile-butadiene-styrene-methylmethacrylate copoly-
mer (Himei et al., 1967). In an application dated 1965 from Asahi Chemical, PVC was
blended with 5-40 wt % of a graft copolymer obtained by grafting an elastomeric
latex with methyl acrylate, styrene and/or acrylonitrile (MBS) (Suehiro et al., 1969).
The resulting alloys had good processability, and their moldings were transparent,
weather and impact resistant. Similarly in a disclosure of 1967 from Princeton
Chemical Research, PVC was blended with either methacrylonitrile-butadiene-styr-
ene, MABS, or methacrylonitrile-butylacrylate copolymer. The alloys showed optical
clarity, tensile strength and flexibility (Wilsher, 1979).
In 1967, Japanese Geon invented PVC blends with 10phr of a core-shell type ABS
(obtained by crosslinking polybutadiene latex with divinylbenzene, then grafting it
with styrene and acrylonitrile). The blends showed good processability and impact
strength (Tanaka et al., 1971). Pechiney-Saint Gobain's patent deposition of 1968
claimed improved impact strength of PVC after blending it with a core-shell copoly-
mer, comprising partially crosslinked ABS core and polymethylmethacrylate
(PMMA) shell (Michel, 1969). In a contemporary document from Hitachi, PVC was
blended with polybutadiene-grafted with methyl methacrylate, styrene and vinyl
acetate to give good processability, transparency, impact and whitening resistance
(Kakefuda and Ito, 1971).
Mitsubishi Rayon Company disclosed in 1969 PVC blends with styrene-acryloni-
trile-methylmethacrylate-grafted butylacrylate-methylmethacrylate elastomer
(MAES). The resulting alloys showed good weatherability and impact strength (Ide
and Miura, 1971). Similar blends of PVC with (meth)acrylate-butadiene-styrene
elastomer (5-30wt% MBS) or ABSM were disclosed in 1971 by Japan Synthetic
Rubber Co. The alloys showed good transparency and impact strength (Kitagawa
and Shiraishi, 1973). In a Kureha patent application of 1974, 70-99 wt% PVC was
blended with butadiene-styrene-divinylbenzene-butylacrylate-methylmethacrylate
core-shell copolymer. By controlling the particle size of the elastomeric domains
the alloys were transparent, as well as craze- and impact-resistant (Usami and
Ochiai,1976).
In a patent application of 1976 from Nippon Telegraph & Telephone Public
Corporation blends comprising PVC, 10-100 phr poly(2-eyano-5-norbomene)
(PCN) and 5-50 phr ABS were described. The alloys showed high HDT and impact
strength (Matsuura et aI., 1978). In a contemporary document from Mitsubishi
Rayon, PVC was blended with 10-90wt% methyl methacrylate and styrene grafted
on acrylic rubber (MBS). The blends had good transparency, impact strength, and
weathering characteristics (Kishida et al., 1977). PVC blends with excellent compat-
ibility were described in a 1978 document from Mitsubishi Rayon, in which PVC was
blended with acrylonitrile-methylmethacrylate block copolymer (AMMA) and
compatibilized with acrylamide-acrylonitrile-vinylbromide copolymer (Iwata
et al., 1979).
In 1981, Monsanto announced a new category of PVC blends having outstanding
performance. Thus, 20-80 wt % PVC, was blended with polybutadiene grafted either
with styrene-methylmethacrylate-maleic anhydride (ABSM-MA), or with ABS and
styrene-methylmethacrylate-maleic anhydride copolymer (SMM-MA). Good flame
retardance, HDT, impact strength and weatherability were obtained (Dufour, 1982).
In 1992, Vista Chemical Company announced that high-impact polyvinyl halide
(e.g., PVC) blends were obtained by compounding 45-75 wt % PVC with 12-50 wt %
ABS (containing 6Owt% PB), 5-30wt% copolymer of a-methyl styrene and acrylo-
nitrile and with 2-4wt% EVAc (comprising 45wt% VAc). The alloys showed
unexpectedly large improvement in impact strength at -40 and 25 °C (Asay and
Mok,1993).
In summary, to improve processability and impact strength PVC is usually
blended with l0-40wt% of an ABS having high rubber content. During the last 20
years or so there has been tendency to modify the ABS by optimizing the degree of
dispersion of the elastomeric phase, by controlling its deformability, by enhancing
ABS miscibility with PVC via copolymerization with acrylics, and by increasing its
PVC/engineering resin blends 211
high temperature capabilities. Owing to a wide variety of copolymers used in these

blends it is impossible to guess what is hidden behind the ABS acronym. In most
cases the ABS contains some acrylics, such MABS, MBS, MAES or AAS, in some
cases ABS was acidified by addition of acrylic acid or maleic anhydride (AAS or
AB5-MA). Addition of maleic anhydride is known to improve weatherability, but
this effect can also originate from replacement of polybutadiene by ethylene-propy-
lene elastomer (AES). In short, the simple ABS/PVC blends became quite diverse
materials, offering a wide range of compositions and performance parameters.
ABS/PVC blends are available from many resin manufacturers: Cycovin™ K-29
from Geon, Denka TairneI™ from Denki Kagaku, GeIoyTM XP2003 from GE Plastics,
Kaneka Enplex™ from Kanegafuchi, Kraiastic™ from Uniroyal, Nipeon™ AL from
Zeon Kasei, Lastiflex™ from Lati Engineering Thermoplastics, RonfaIoyTM V from
DSM, Tufrex™ VB from Mitsubishi Chemical, etc. These resins offer excellent pro-
cessability and are formable by all principal methods. They have been used to
produce housings for electrical tools, electrical and electronic equipment housings,
moldings for domestic appliances, aircraft, computers, business machines, impact
resistant blow moldings, diverse automotive items, pipes and profiles, industrial
tools, plugs and receptacle covers.
11.9 PVC/ENGINEERING RESIN BLENDS
11.9.1 Blends with PEST

The first blends of PVC with engineering resins date from the late 196Os. For
example, in 1969 Rohm & Haas disclosed blends comprising PVC and 5-25wt%
polypropylene-terephthalate (PPT). Addition of relatively small amount of this
thermoplastic polyester improved processability, thermal, irradiation and impact
resistance over that of neat PVC (Hurwitz and DeWitt, 1970). Two years later du
Pont de Nemours announced similar blends of PVC blended with a semi-aromatic
copolymer obtained by reacting PET with polybutyleneglycol (PBG) and 1,4-buta-
nediol. The homogenous blends had good low temperature impact properties
(Crawford and Witsiepe, 1972).
Air Products and Chemicals patent disclosure of 1978 described PVC blends with
polyethylene carbonate (40 wt% PECO). The alloys showed increased melt flow and
reduced oxygen permeability (Dixon and Ford, 1979). In 1985 B. F. Goodrich dis-
closed blends comprising PVC, 40 wt % semicrystalline polyester from butanediol,
dimethylterephthalate and butylene adipate, and 30wt% glass fiber. The materials
were reported suitable for injection or compression molding (Yang, 1987).
In 1991, Labinal deposited a patent document for plasticized PVC (Shore hardness
of 70-100) blended in a co-rotating twin-screw extruder with an aliphatic polyester-
aromatic polyester block copolymer (Peiprene™ 1002 from Toyobo Corp., haVing
Shore hardness of 80-100). The blends with physically crosslinked structures and
service temperature of 125°C, were found useful for manufacturing heat-resistant
insulation for electric cables (Jean and Devauchelle, 1993).
11.9.2 Blends with COPO

Copolymers of alkenes with carbon monoxide (COPO) have been known since the
early 1940s (Ballauf et al., 1941). In particular, radically polymerized copolymers of
CO with ethylene and/or propylene are of interest. Depending on composition, the
melting point varies non-linearly from about 110°C to 242 °C (Figure 11.2). At
Y _ 1.40 + M"X + M2'X' + M3'X3
1.40 141.1
1.41 1.4638
1.4 2 -0.22789
1.4 3 0.0048222
200 A 0.9962
o
100 L-_---'_ _----'-_ _---"-_ _---'--_ _--'
o 20 40 CO (mol%)
Figure 11.2 The melting point (Tm ) of ethylene-carbon monoxide copolymer as a function of
composition.
compositions approaching 50 mol % the copolymer behaves as high performance

engineering resins. At the same time, capo is prone to photo degradation by
ultraviolet light. Owing to sensitivity of the keto groups to UV degradation these
blends potentially can be used to produce packaging materials with calibrated life-
times when exposed to sunlight.
Since the radical polymerization of ethylene with CO permits incorporation of
other monomers (e.g., vinyl acetate, vinyl chloride, acrylonitrile, alkyl acrylates, or
tetrafluoroethylene) these resins have been used as permanent plasticizers/impact
modifiers for PVc.
The first blends of this type were described in a patent application of 1960 from
Union Carbide Corporation. Thus, PVC was blended with ethylene-earbon monox-
ide copolymer (1-30wt% CaPO) to give materials with good impact strength and
HDT (Mullins, 1964).
In 1971, du Pont de Nemours disclosed that PVC melt viscosity was reduced
(without affecting rigidity and transparency) by blending it either with 35-70wt%
capo, or with carbon monoxide-ethylene-vinyl acetate (comprising 40-80 % ethy-
lene, 1D-60% vinyl acetate and 3-30% CO), or ethylene-sulfur dioxide-vinylacetate
copolymer. The blends showed better processability, reduced rigidity and enhanced
toughness. They were found useful for heat-resistant wire coatings (Hammer and
Martens, 1973; Hammer, 1973). Modification of these compositions was disclosed by
du Pont de Nemours in 1981. Thus, PVC was blended with ethylene-carbon mon-
oxide-vinylacetate copolymer (COPO-VAc) and butylmethacrylate-methylmethacry-
late copolymer (BMMM). The alloys showed excellent processability and mechanical
performance (Reardon, 1982).
In 1995, Shell Chemicals introduced a new generation of the capo polymer as
Carilon 1M (see Section 2.2.3). These polymers are prepared using a proprietary
metallocene catalyst that enables copolymerization of an alkene and CO into linear,
alternating structures. The engineering resins are easy to process, semicrystalline,
resistant to chemicals, as well as to scratch.
11.9.3 Blends with PC

High heat resistant, dimensionally stable molding compositions of PVC with poly-
carbonate, PC, and in some cases ABS, were disclosed in 1974 by Bayer. The blends
PVC/engineering resin blends 213
showed good impact and tensile properties (Hardt et al., 1975; Mietzsch et al., 1975).
Four years later Mitsubishi Petrochemical invented a method of grafting polycarbo-
nates with vinyl monomers that opened the way to a new class of materials. For
example, PC pellets were swollen with not more than 50 wt % styrene, dispersed in
water and the suspension was polymerized. The styrene-grafted PC was in tum
blended with neat PC, PS and other styrenics, acrylics or PVC, to generate blends
showing a good set of properties (Kakizaki et al., 1979).
In 1992, Enichem announced new blends comprising 35-90wt% PVC (having a
number averaged molecular weight M n =20-300 kg/mol), bisphenol-A polycarbo-
nate (PC) and at least 15wt% of bishydroxyphenyl-hexafluoropropane (6F-PC). The
alloys were found miscible, with a single glass transition temperature. They were
flame-resistant, and resistant to acids, bases and many organic solvents. These
moldable, transparent and fireproof alloys had the stability and strength of PC
and the processability of PVc. They were used for packagings, bottles, parts in
medical and chemical instruments and for hot water pipes (Drzewinski, 1993a,
1994a).
11.9.4 Blends with POM

In 1975, self-extinguishing, acid resistant, low friction, moldable PVC blends with
10-90wt% polyoxymethylene (POM) were described in a patent application from
Dynarnit Nobel (Doerffurt and Waeteraere, 1977).
11.9.5 Blends with PI

In 1980, Rohm and Haas invented blends comprising 20wt% PVC, 5Owt% of a
methylmethacrylate-butadiene-styrene copolymer (MBS) and 30 wt % of polyimide
(PI) based on the monomer:
The new alloys showed high heat deflection temperature, excellent impact strength
and high clarity (Kopchik, 1981). Five years later the company announced that
polymerization of vinylchloride in the presence of polyimide (PI) resulted in alloys
with cocontinuous morphology, an IPN. The materials showed good processability,
impact resistance and HOT. Blending 10wt% of this IPN with 82wt% PVC and
butylacrylate-methylmethacrylate copolymer (8 wt % MBA), gave ductile alloys with
low sag at 185 DC (Clikeman et al., 1987).
In 1988, Tosoh Corporation announced impact resistant, rigid PVC blends. The
alloys comprised COOH-terminated acrylonitrile-butadiene copolymer (NBR) treat-
ed with diisocyanates in the presence of PVC and alkaline earth oxides, such as CaO
(Iwanaga et al., 1990). The same year, Nippon Oils & Fats disclosed heat resistant
blends composed of 4O-95wt% vinylchloride-co-maleimide-based copolymer (60-
95:40-5) and 6D-5wt% of maleimide-based block copolymer. For example, 80 parts
of vinylchloride-co-N-eyclohexylmaleimide and 20 parts of styrene-b-N-cyclohexyl-
maleimide were kneaded and pressed at 190°C, to give sheets with HDT of 90°C
Vicat T of 121°C and high impact strength (Kato et al., 1990).
In 1989, Mitsubishi Rayon announced blends comprising PVC, poly(methylmeth-
acrylate-co-maleimide-co-vinyl cyanide), and styrene-eyclohexylmaleimide-grafted
butadiene. High transparency, heat distortion temperature and impact strength
were obtained (Ito et ai., 1990). The following year to increase the heat resistance of
PVC, Rohm and Haas blended it with imidated polymethacrylate, polyglutarimide
(Fromuth et ai., 1992). In 1991 du Pont de Nemours disclosed blends comprising 1~
95 parts PVC and a complementary amount of a compound consisting of 3~5 wt %
imidized acrylic polymer (Tg > 130°C, e.g., Paraioid™) and a third polymer
(processable at 15~300 °C, free of groups capable of causing degradation of PVC,
such as ABS or SMA Dyiark™ 232) to give blends with high HDT (Gia, 1992).
11.9.6 Blends with PVP

In 1981, it was disclosed that PVC blended with polyvinylpyrrolidone (2-80wt%
PVP) gave materials with good transparency, as well as water and heat resistance
(Tokuyama Soda Co., ltd. 1982).
12
Polyvinylidene halide blends
12.1 POLYVINYLIDENE CHLORIDE BLENDS

Polyvinylidene chloride (PVOC) was discovered in 1838 by Regnault, but commer-
cially developed a hundred years later (in 1939) at Dow Chemical by Reilly and
Wiley as bi-axially oriented film for food wrapping, Saran TM. These researchers
also invented a method for molding PVOC (Wiley, 1946). The symmetrical structure
of vinylidene chloride results in highly crystalline polymer that is difficult to
process. Today, the commercially available PVOC is modified by incorporation of
either 15-20 % vinyl chloride, or 13 % vinyl chloride and 2 % acrylonitrile. PVOC is
known to possess extremely low permeability to nearly all gases and vapors.
The first commercialized PVOC blend was Saran F-120, developed by Visking
Corporation in the late 194Os. The invention document described blending PVOC
with acrylonitrile-butadiene rubber (lOwt% NBR, Hycar™) and polychloroprene
(25wt% CR, Neoprene™). The blends were used for production of films suitable for
packaging (Signer and Beal, 1951). In 1967 Goodyear Tire and Rubber announced
PVOC blends with polyurethanes. These resins had good tack to polyamide fibers
(McCready 1976).
In 1982, du Pont de Nemours deposited a patent describing blends of polyvinyl
halide (PVC or PVOC) with a thermoplastic elastomer, compatible with the homo-
polymers, prepared from ethylene, unsaturated organic monomers, CO or C~, SO:2
and 75% vinyl halide or vinylidene halide. For example, 23 wt % PVC was blended
with ethylene-earbon monoxide-vinylchloride copolymer to give blends with good
moldability, and high Shore hardness and tensile strength at break. Alcryn™ blends
were introduced by du Pont in 1986 (Loomis and Statz, 1984, 1986). Three years later
Dow Chemical applied for patent protection for blends comprising 75wt% PVOC
with 25% polyalkenes and 10 phr ethylene-methylacrylate compatibilizing copoly-
mer. The blends had good processability and toughness, and were impermeable to
oxygen (Burgert, 1987).
In 1991, du Pont de Nemours disclosed new blends comprising either polyvinyl
chloride or polyvinylidene chloride (40-60wt% PVC or PVOC) and polyamide (40-
6Owt% PA) processable at temperatures not exceeding 220°C (e.g., PA-6, PA-1212
or aromatic, amorphous PARA). The blends were compatibilized by addition of
1-20wt% copolymer comprising 50-70wt% ethylene, 24-40wt% of either alkyl
(meth)acrylate, Vinyl acetate, or (meth)acrylic acid, 5-15wt% CO and 0.1-5wt%
anhydride. To prevent degradation of the vinyl resins, PVC or PVOC, the blends
were processed at below 220°C. The formulations were found useful for recycling
216 Polyvinylidene halide blends
halide (co)polymers from the commingled polymer scrap into a variety of articles
formed by extrusion or injection molding (Hofmann, 1994).
In 1992, W. R. Grace and Company announced blends comprising vinylidene-
chloride-vinylchloride copolymer (75-65wt% PVOC-VC, having 2D-24wt%
vinyl chloride and a weight average molecular weight of 9D-14Okg/mol), and
vinylidenechloride-methylacrylate copolymer (25-35wt% PVOC-MeA, having 7.5-
8.5wt% methyl acrylate with M w = 1QO-120kg/mol). In the blend the total content
of the vinyl chloride segments was at least 12% while that of methyl acrylate did not
exceed 2.8 wt%. The blends also comprised 1-5 wt% plasticizer and epoxidized
soybean oil (stabilizer). It was discovered that these economic materials could be
extruded at temperatures lower than these required for forming neat PVOC-VC or
PVOC-MeA copolymers, thus reducing the likelihood of thermal degradation. The
alloys were found useful as barrier layers in packaging films (Paleari and Fornasiero,
1994).
Also in 1992 a method for recycling polyalkene films laminated with PVOC was
disclosed by Mobil Oil Corporation. For example, biaxially oriented PP/PE/EPR
films, laminated with PVOC and having an adhesive layer in between were recycled
by first soaking the films in caustic solution containing O.l-SOwt% NaOH and 0.05-
1.0 wt % wetting agent at 25-140 °c, then scrubbing and separating the laminas. After
separating PO from PVDF and washing, the resins were separately reprocessed (Su
and Lilly, 1994).
12.2 POLYVINYLIDENE FLUORIDE BLENDS

Polyvinylidene fluoride (PVDF) is a semicrystalline polymer with the glass transition
temperature varying from -56 to -35°C, about 50% crystallinity and a melting point
of 160-180 dc. Owing to its piezo- and pyro-electrical character (generation of electric
charge on deformation or heating) the resin and its blends have been used in
microphones, earphones, burglar alarms, fire detection systems or loudspeakers.
PVDF blends with acrylics are particularly suitable for usage as stable electrets,
with the 'frozen in' polarization being preserved for years.
PVDF was discovered at du Pont de Nemours laboratories and patented in
1948. The resin was experimentally introduced in 1960, and commercialized
two years later, by Pennsalt (later Pennwalt) Corporation. To expand the range
of properties, either vinylidene fluoride has been copolymerized with other
fluorinated monomers, viz. hexafluoropropylene, or its polymer PVDF, has been
blended with other resins. The first PVDF blends were disclosed in a patent
application dating from 1958 (Kaufman, H. 5., 1963). The document described blends
of polychlorotrifluoroethylene, PCTFE, with PVDF, as most suitable for wire
coating.
Owing to its crystallinity, the melt-blending of PVDF must be carried out at
relatively high temperatures, of 200 °c or above. Thus, only resins with relatively
good thermal stability can be used in its blends. Alternatively, latex or solution
blending may offer a viable method. For example, the solution method was used
to incorporate 25 wt% PVDF into polyamide-610 (PA-6lO) to reduce moisture
absorption of the latter resin (Saito, 1975).
Another method for improving PVDF processability was proposed in a patent
application deposited in 1987 by the Minnesota Mining and Manufacturing Com-
pany. It was discovered that addition of small amounts of a thermotropic liquid
crystalline polymer, at least 0.01 wt% LCP Vectra™, to several difficult to process
resins, including PVDF, facilitated production of oriented films having microprotru-
Polyvinylidene fluoride blends 217
sions that resulted in low coefficient of friction of less than about 0.8, more preferably
one of less than about 0.4. (Wong, 1994).
In 1992, University (of Calgary) Technologies International disclosed solid-state
formation of polymers and alloys. The process comprised heating the precursor
materials, having polymer particles with diameter < 1 nun, to a temperature below
either the melting or softening temperature at a pressure 2 5 MPa. PVDF was one of
the specifically mentioned blend components. The alloys exhibited superior physical
properties when compared to similar polymeric materials made using conventional
methods (Shaw, 1993).
Biodegradable polymer blends were announced in 1993 by the Industrial Techno-
logy Research Institute of Taiwan. The blends contained 5G-99wt% synthetic poly-
mer such as PVDF, starch and O.5-tO wt % peracid. The peracid contained at least
one peroxy carboxylic group, and another functional group, such as carboxyl,
aldehyde or cyanate - it increased the blend's bio- and photodegradability. The
mechanical properties of new blends were superior to those without peracid (Hsu
et ai., 1994).
The most frequent use of PVDF blends (responsible for nearly 25 wt % of PVDF
consumption) is in weather-resistant architectural coatings, able to withstand pro-
longed exposure to severe climatic conditions. PVDF/ acrylics blends at a ratio of 7:3
are usually applied by spray finishing or coil coating techniques to metals (alumi-
num or steel), roofing, curtain walls, wall panels, window frames, doors, hand rails,
fascias, awings, louvers and canopies (Lin, 1994).
12.2.1 PVDF/acrylics blends

The amorphous PVDF is thermodynamically miscible with polymethylmethacrylate
(PMMA). The blend exhibits a single glass transition temperature (Bernstein et ai.,
1977; Mijovic et aI., 1982). Owing to miscibility, several blends of these resins have
been patented. In the first disclosure (by Pennwalt Chemical Company) PVDF was
blended with PMMA for use as outdoor films with better chemical and UV stability
than that of PMMA alone, and better clarity than that of PVDF (Koblitz et ai., 1966). A
year later, for the same application, PMMA blends comprising 7-23% PVDF and
polyethylacrylate (PEA) were disclosed by American Cyanamid (Schmitt and Miller,
1970).
In a patent application of 1970, Kureha Chemical Industry described PVDF/
PMMA blends prepared by dissolving PVDF in methyl methacrylate than initiating
a radical polymerization. The resulting blends, containing about 40 wt % PMMA,
were homogenous. They were used for long-lived electrets. It was also reported that
PMMA could also be successfully replaced by 30 wt % poly(methylacrylate-co-
methylmethacrylate) copolymer (Murayama and Fukuda, 1972).
The scientific literature on PVDF/PMMA blends is quite extensive (Lin and
Burks, 1993). The important feature of these is that, if allowed to crystallize,
they show a glass transition temperature of ::::: 74°C, relatively constant for up to
about BOwt% PVDF - at higher PVDF loadings the T g drops sharply (Nishi
and Wang, 1975). Similarly, the high transparency (about 92% transparent), reaches
up to 75wt% PVDF. Owing to PVDF crystallinity, the heat deflection temp-
erature sharply increases in blends containing more than 50 wt % of this
resin. Furthermore, there is a large peak at about 70 wt % PVDF in plots of the
elongation at break versus composition (Tanaka et ai., 1990). Thus, the optimum set
of properties are expected for the blends comprising about 70wt% PVDF and
3Owt%PMMA.
218 Polyvinylidene halide blends
PMMA/PVDF blends are commercially available, such as Polycast™ from Royal-

ite. They are primarily used as outdoor film with good clarity, and excellent chemical
and UV stability.
12.2.2 PVDF/engineering resin blends

PVDFIPA blends have been mentioned in the introduction to PVDF blending
technology. In a patent deposited in 1973 by Showa Dernm, PVDF was solution-
blended with polyamide, 75 wt% PA-6lO. The blend, after immersion in water at
30°C for 100h, had significantly lower water absorption than PA-6lO alone (Saito,
1975).
Profiting from the miscibility of acrylics with both PVDF and polycarbonate, the
three-eomponent blends (PC with PVDF and an acrylic copolymer) were developed
by the Roehm G. m.b.H. The blends formed clear, yellowish film with a single Tg of
120°C (Leibler and Ringenberg, 1986).
In a 1987 patent application from General Electric, polyphenyleneether (PPE)
toughened by addition of a styrene-(ethylene-butylene)-styrene block copolymer
(SEBS Kraton™ G), was blended with PVDF and a poly(styrene-co-methylmethacry-
late) copolymer acting as a compatibilizer. Improved weatherability, impact
strength, elongation, chemical and solvent resistance were obtained (Van der Meer
et al., 1989). The following year, Kureha Chemical Industry described compatibilized
PVDF IP A blends. These alloys were used in applications requiring high impact
resistance and good gas barrier properties (Hizasurni et al., 1989). In a contemporary
series of patent applications from Shell Oil, alternating carbon monoxide-alkene
copolymers (CaPO) were blended with PVDF, polyester rubbers, polyvinylpyridine,
poly-2-oxazoline or polysulfone. Furthermore, the blends could be toughened by
incorporation of ethylene-propylene copolymers (EPR or EPDM; Gergen and Lutz,
1989).
In an application dating from 1991, Mitsubishi Gas Chemical announced the
development of blends of polyoxymethylene (80-99.9 % paM) with PVDF and
optionally a lubricant (e.g., silicone oil, polyalkene wax, etc.). Molded blends had
excellent resistance to frictional wear as well as good heat and UV stability (Shibata
et al., 1992).
13
Poly(methyl)methacrylate, PMA
and PMMA, blends
The first rigid acrylic polymer was polymethylacrylate (PMA) discovered in 1880 by
Kahlbaum. In 1928 R6hm & Haas Company of Darmstadt commercialized clear,
transparent sheets of PMA (Ulrich, 1982; Utracki, 1989a; Stinson, 1992). Since PMA is
rather soft (Tg = 6°C) it had to be copolymerized with ethylmethacrylate (Tg = 75°C)
(Salkind et al., 1959). However, the main obstacle to commercialization was the high
cost of acrylic monomers.
PMMA was discovered by Hill and Crawford in 1930 and the following year it
was commercialized by R6hm & Haas as Oroglas™ (Riddle, 1954). In 1933 John
Crawford of ICI developed a simple and economic method of methylmethacrylate
manufacture. The discovery made it Ktossible for ICI to successfully start in 1936
commercialization of PMMA, Perspex . The same year R6hm & Haas introduced
Plexiglass™ molding powders. During the intervening decades for people associated
with the plastics industry PMMA became synonymous with acrylic, whereas for the
public Plexiglass plays the same role.
Acrylics are used mainly in two forms, either as glazing materials with good
abrasion resistance, or as a part of variety of impact modifiers, forming either a
rigid core or vice versa, a compatibilizing shell. The following examples will illustrate
these applications.
13.1 PMA BLENDS

Blends of PMA with polyvinylacetate (PVAc) at ratios of 1:10 to 10:1 were described
in a Monsanto Chemical patent as homogenous, single-phase materials, suitable for
film casting. Blends of polypropylacrylate with polyvinylbutyrate were also found
miscible, whereas those of PVAc with polyethylacrylate or polymethylmethacrylate
(PMMA) are immiscible (Kern, 1957). Since PMA has been found to be unsuitable as
a thermoplastic only few blends with it were patented.
13.2 PMMA BLENDS
13.2.1 Copoly(meth)acrylate blends

Polymethylmethacrylate (PMMA) has been incorporated into a variety of multi-
component compatibilizers and impact modifiers. Owing to the relatively high (for
220 Poly(methyl)methacrylate, PMA and PMMA, blends
acrylic) glass transition temperature of common atactic PMMA (Tg values for iso-
tactic, atactic and syndiotactic PMMA are, respectively, 45, 105 and 115°C), and its
ability for free radical copolymerization as well as relatively frequent miscibility,
PMMA has often been incorporated into acrylic formulations wherever higher
rigidity was required. Since the 1930s either copolymerization and/or latex blending
has been used to produce paints, adhesives or modifiers.
In the 195Os, R6hm & Haas developed one of the first versions of the ever popular
impact modifier for polyviny1chloride (PVC) - a core-shell, emulsion type methtt
methacrylate-butadiene-styrene terpolymer (MBS) Acryloid™, now Paraloid
(Mertz et al., 1956; Feuer, 1958; Fujii and Ohtsuka, 1954). In 1962 Dow Chemical
disclosed non-weatherable, impact-modified acrylic resins, that comprised methyl-
methacrylate-butadiene-styrene graft copolymers. These were obtained by dissolv-
ing stereospecific polybutadiene (PB) or its copolymer in methyl methacrylate (MM),
and either styrene (S) or a-methylstyrene (MS), then polymerizing them into materi-
als with good tensile and tear strength (Ruffing et al., 1964). A year later, Kureha
Chemical Works developed another type of MBS, a copolymer of butadiene-styrene-
methylacrylate-ethylacrylate, also as an impact modifier for PVC (Ichinoe, 1967). A
few years later Pechiney-Saint Gobain introduced MABS - a partially crosslinked
ABS core and PMMA shell (Michel, 1969).
As it will be evident in Part Four, the MBS resins playa critical role in compat-
ibilizing and toughening engineering polymer blends. Furthermore, profiting from
miscibility of the PMMA chain with several thermoplastics, copolymers containing
methyl methacrylate and at least 50 wt % bis(2-ehloroethyl)vinyl phosphonate were
developed to reduce flammability of several engineering resins, such as PA, PEST,
PC, modified PPE or TPU (Beaman, 1958).
Neat, as well as blended copolymers of (meth)acrylates also have found use as
thermoplastic resins. In the late 1950s Rh6ne-Poulenc disclosed blends of a rigid
copolymer (containing 6O-90wt% a-methylstyrene and 4O-10wt% acrylonitrile), 0-
MeSAN, with polybutadiene grafted with (meth)acrylates (NBR). The blend was an
early version of the high heat ABS, introduced three years later by Borg-Warner
Chemicals (Rh6ne-Poulenc, 1959, 1961; Irving, 1961). Also at this time, Firestone
announced ternary blends comprising 60-85 wt % acrylonitrile-methylmethacrylate
copolymer (AMMA), 5-15wt% SBR and 1~20wt% NBR. The alloys showed good
processability and solvent resistance. By varying the composition a wide range of
properties were obtained (Reid and Conrad, 1960).
Similarly, blends comprising styrene-(meth)acrylic acid copolymer (SAA) and
35 wt % of a terpolymer from butadiene, methyl methacrylate, and vinyl pyridine
were developed by Canadian Industries Ltd. The blends showed high impact
strength and HDT (Murdock et al., 1960). In a later patent, polystyrene or styrene-
methylmethacrylate were blended with SAA for improved chemical, thermal and
electrical performance (Murdock et al., 1962).
In 1962, Cyanamid patented blends that comprised 9wt% of MABS copolymer
(PB grafted with MM, S and AN; MABS = 28:1:64:7) with 5-MM-AN = 19:71:10
terpolymer. The blends were transparent, and had good impact strength and HDT
(Schmitt et al., 1967). In 1965, high heat and impact resistant blends, high heat ABS,
were developed by mixing methylmethacrylate-a-methylstyrene copolymer with
styrene-g-polybutadiene (SBR) or with acrylonitrile-butadiene-styrene terpolymer
(ABS). The alloys have also been used as impact modifiers in high temperature
formulations (Kanegafuchi Chemical Industry Co., 1967).
In 1967, Shell announced that properties of the high impact polystyrene (HIPS)
were improved by blending it with polyalkylmethacrylates (Ward, 1970). Two years
PMMA blends 221
later, American Cyanamid disclosed blends of methylrnethacrylate-vinylacetate-
acrylic acid copolymer (MMVAc-AA) with methylrnethacrylate-ethylacrylate copo-
lymer (MMEA). The partially crosslinked alloys gave extrudates showing high
impact strength (Holland et ai., 1970).
In 1989, Du Pont-Mitsui Petrochemical deposited a patent application for blends
comprising 90-99.5wt% ethylene-methacrylic acid Zn salt, an ionomer, and 0.5-
10 wt % ethylene-glycidylrnethacrylate-vinylacetate copolymer (EVAc-GMA). The
alloys were found to be scratch and heat-resistant, flexible, matte and particularly
suitable for automotive moldings (Kawamoto et ai., 1990). A year later, Exxon
applied for a patent on binary ionomeric blends comprising a neutralized sulfonated
ethylene-propylene-diene copolymer (Zn-SEPDM) and 1-40wt% of a neutralized
copolymer of ethylene and methacrylic acid (Zn-EMA, an ionomer containing 80-
99.9wt% ethylene). The alloys showed reinforced elastomeric behavior with high
impact strength and fine dispersion of the polymeric phases, that originated in
ionomeric clustering in micro-separated domains (Peiffer, 1994). A contemporary
patent from Dow Chemical described SAN blends with methylrnethacrylate-glutar-
imide copolymer. The blend was transparent, with isotropic, low birefringence
(Maurer and Dibbs, 1992).
In 1991, Novacor Chemicals (International) patented transparent high impact
alloys, as Zyiar™. These were prepared using 30-82 wt % of a brittle styrene-methyl-
methacrylate copolymer, NAS 30, 3-50 wt % of a rubbery tapered styrene-butadiene
copolymer (43wt% St), and 15-67wt% of a ductile SBS triblock copolymer (75wt%
St). The blends showed extremely low haze and good impact resistance, making
them suitable for patio tumblers (Blasius, 1992). In following patents, 85-98wt%
NAS (75-80 wt % St), was alloyed with a mixture of SBS and a tapered butadiene-St-
butadiene triblock copolymer, or 4-lOwt% polybutadiene grafted with 96-90wt%
St (having matched the refractive index to that of NAS). The transparent alloys
showed improved crazing, haze, and impact resistance (Colella, 1993; Colella and
Marcoulier, 1993).
In 1992, BASF announced that transparent impact-resistant moldings can be
produced from blends containing: (1) 5-50wt% of a copolymer comprising
80-100% methylrnethacrylate and 0-20% Ct-a alkyl acrylate, (2) 5-50wt% of a
copolymer comprising 75-85 % styrene and 15-25 % acrylonitrile, (3) 0.02-3.0 %
polysiloxane, and (4) 5-60wt% of a graft copolymer with a particle diameter
~ 0.2 t-tm, comprising 30-80 % butadiene, isoprene or C4-8 alkylacrylate substrate
with Tg < O°C and 20-70% graft shell with 30-100% Ct-a alkyl (meth)acrylate(s)
and 0-70 (preferably 35) wt % of vinyl-aromatic monomer units. The difference
between the refractive indexes in the mixture was ~nD ~ 0.01. The alloys had as
high notched impact strength as toughened PMMA/SAN blends and was transpar-
ent (Guentherberg et ai., 1994a).
13.2.2 PMMAlpoly(meth)acrylates blends

To improve PMMA performance the resin has been blended with a variety of
copolymers. As early as in the early 1940s PMMA was mechanically blended with
polyvinylacetal (PVA) to give homogenous resins, suitable for molding or extrusion
(E. I. du Pont de Nemours & Co., 1942). In a patent application of 1958 Eastman
Kodak disclosed blending either PMA or PMMA with copolymers of methacrylo-
nitrile and another monoethylenically unsaturated polymerizable monomer, such as
ethylacrylate or a-methylstyrene. The moldable, tough blends showed relatively
high HDT (Coover and Wooten, 1962). In a patent application of 1968, Mitsubishi
Rayon described blends comprising 25-90 wt % PMMA and an elastomeric copoly-
mer of butadiene, butylacrylate and methyl methacrylate. The blends had excellent
impact strength (Kotama, 1972).
In 1970, Sumitomo Chemical blended PMMA with ethylene-vinylacetate-vinyl
chloride copolymer (EVAc-VC) to give alloys with improved transparency and
impact strength (Kishikawa et al., 1971). In a contemporary BASF patent, styrene-
maleic anhydride (SMA) was blended with methylmethacrylate-methylacrylate
copolymer, and/or PMMA. The blends had increased softening point, dimensional
stability and good mechanical properties (Bronstert et al., 1971). The following year
Teijin announced blending PMMA with styrene-acrylonitrile copolymer (2G-9Owt%
SAN) to obtain materials with good impact strength and either pearly or metallic
gloss (Sugimura et al., 1972). The next year, Japan Synthetic Rubber Company
claimed significant improvement of properties when to PMMA/SAN blends poly-
styrene and poly(methylnorbomene-2-carboxylate) were added. These easy-to-mold
alloys showed high impact strength (Ikeda et al., 1976).
In 1980, Stauffer Chemical blended 20 wt % PMMA with an interpolymer contain-
ing crosslinked polybutylacrylate, crosslinked styrene-acrylonitrile (SAN) and
uncrosslinked SAN. The blends had high impact strength (Silberberg, 1982).
In 1989, ICI announced interesting, miscible, heat-resistant three-component
blends comprising 1-99wt% PMMA, a poly(acrylate-N-cyclohexylmaleimide)
(1-99wt% PM!; S 3Owt% of N-cyclohexyl maleimide), and 1-99wt% of a three-
layered core-shell impact modifier (comprising PMMA as a center bead, crosslinked
butylacrylate-styrene copolymer forming the middle layer and a PMMA shell; the
average particle diameter was 200-300 nm). The blends retained the optical and
physical properties of PMMA, and had a single Tg that was higher than that of
PMMA. These alloys showed increased heat resistance, good weatherability and
high impact strength (Shen, 1994).
The same year, R6hm and Haas disclosed gas-barrier polymer blends that com-
prised: (1) 2G-95wt % of polymer having at least 50 mol % of (meth)acrylates or
glutarimides forming a matrix, (2) 2.5-40 wt % of another polymer having at least 50
mol % of vinyl alcohol, and (3) 2G-30wt% of a polymer(s) miscible with the matrix
polymer. Thus, PMMA was blended with poly(p-hydroxystyrene) and EVAI. The
blends (formed into films, sheets, moldings or containers) showed good gas-barrier,
physical and optical properties (La Fleur et al., 1992, 1994). Good mechanical
performance of these blends originated in the specific interactions between the
ester group of PMMA and -DH functionality of the poly(vinylphenol).
Two years later, BASF disclosed transparent, moldable blends with improved low
temperature impact strength. These alloys comprised IG-96 wt % of a PMMA-based
polymer and 4-90wt% of a core-shell, MMA-based, graft copolymer. The PMMA-
based polymer contained 68-99.49wt% MMA, 0.5-10wt% alkyl-acrylate, G-20wt%
other comonomer(s) and 0.01-2wt% chain transfer regulator. The core-shell graft
copolymer was obtained by emulsion polymerization of IG-30wt% MMA, with
dimethacrylate and unsaturated comonomer(s), followed by in situ emulsion poly-
merization of 40-75 wt % alkyl acrylate, phenyl-alkyl acrylate, vinyl aromatic mono-
mer(s), then that of IG-35wt% MMA, unsaturated comonomer(s) and chain transfer
regulator. The blends were useful for molding transparent, weather-resistant parts,
with good low temperature impact strength (Lauke et al., 1992, 1993).
Also in 1991, the company announced impact-resistant, high gloss blends pre-
pared in a twin-screw extruder. Thus, 62 wt% of either PMMA or SAN solid pellets
were compounded with coagulated acrylate rubber latices (e.g., allylmethacrylate-
butylacrylate-butanedioldimethacrylate-styrene-methylmethacrylate copolymer, or
PMMA blends 223
acrylonitrile-butylacrylate-tricyclodecenylacrylate-styrene copolymer) (Farwerck et
al., 1993). In the following patent, thermoplastic molding compositions were pre-
pared by blending PMMA or an acrylic core-shell copolymer with 30-94 wt % PBT or
PET. The blends were reinforced with 3-40 wt % glass fibers. The formulations
showed good mechanical and surface properties (Bright et al., 1993).
The capability of PMMA to form hydrogen bonding with linear polyesters was
explored in a contemporary patent from Camelot Technologies for biodegradable
blends of PMMA. The alloys comprised polylactic acid, polyglycolides, polybutyric
acid, or copolymers of butyric and valeric acid, blended with 25-50 wt % of polymers
having a T g of 75-200°C (e.g., PC, PMMA or imidized-PMMA). The alloys showed
improved thermal properties (e.g., heat distortion temperature, HOT) while still
remaining biodegradable (Nemphos and Kharas, 1993, 1994).
In 1992, Rohm and Haas announced reactive blends of PMMA with polyglutar-
imide and a copolymer prepared in three stages by (1) copolymerization of buta-
diene, (meth)acrylate and/or styrene (50-80 wt % MBS), (2) grafting the copolymer
with either styrene, a-methylstyrene and/or acrylonitrile/styrene (1Q-50wt%), and
(3) polymerizing methyl methacrylate (1Q-35wt%). The imidized impact modifier
could be prepared during imidization of the matrix polymer, providing an intimate
blend with stable morphology. The blends were used to manufacture automobile
parts, electrical or electronic devices, construction units, consumer products, non-
woven fabrics, clear drink containers, translucent or transparent medical ware and
food packaging, toys, sports goods etc. (Cohen and Freed, 1993, 1994).
13.2.3 PMMAlPVC blends

Polymethylmethacrylate (PMMA) is known to form miscible blends with chlorinated
hydrocarbons such as polyvinylidenechloride, polyvinylchloride, chlorinated-PVC
(Cpvq or even with highly chlorinated polyethylenes. The phase diagram has a
lower critical miscibility temperature (LCST) that depends on the type of chlorinated
polymer, tacticity of PMMA, and molecular weight of the polymer pair. The range of
melt miscibility, tlT, is determined by the gap between the binodal and the softening
temperature: either the melting point, Tm, or the glass transition temperature, Tg , of
the blend, (thus it is a function of composition). It is interesting that the effect of
PMMA tacticity on miscibility with PVDC is opposite to that with either PVC or
CPVc. It was reported that when isotactic PMMA (i-PMMA) was replaced by
syndiotactic PMMA (s-PMMA) in blends with PVDC, the LCST increased from
about 130 to 180°C, whereas in blends with. PVC it decreased from 180 to 100 °c,
and in blends with CPVC it decreased from lBO to 130 °c (Lemieux, 1988). The
practical consequences of these observations are numerous. It suffices to note that
since the Tg of i-PMMA is quite low (Tg values of i-PMMA, a-PMMA and s-PMMA
are, respectively, 45, 105 and 115°q, this polymer is particularly ill-suited for
blending with PVc. Much better results are to be expected for s-PMMA/PVC
blends for which not only is the Tg higher, but also tlT > BOOC for PVC content
~ 25wt%.
PMMA, and especially its elastomeric copolymers have been frequent components
of PVC formulations. The resin is incorporated to improve processability of PVC,
to increase its rigidity and to compatibilize the resin with acrylic-containing elasto-
mers. For example, the early alloys developed by ICI comprised lQ-15wt% PMMA,
65-73wt% PVC and 17-20wt% poly(butadiene-g-methylmethacrylate) copolymer
Garrett and Williams, 1960). In a Pechiney-Saint Gobain patent, the impact and
tensile strength of PVC was improved by blending with a core-shell copolymer,
comprising partially crosslinked ABS as a core and PMMA forming a shell (Michel,
1969).
Antagonistically immiscible, rigid blends of PVC with polyalkenes and either
PMMA or cellulose acetate (CA) were disclosed in 1968 by Sanyo Kako Co. These
materials were obtained by blending PMMA (or alternatively PC) with PVC and PP
at a ratio of 1:1:1. The injection molded or extruded blends gave layered, wood-like
materials with good machinability (Yahata et al., 1971b).
PMMA is also miscible with other chlorinated hydrocarbons, such as polyvinyli-
dene chloride (PVOC), chlorinated-PVC (CPVC) and chlorinated polyethylenes
having high degree of chlorination. Blends of PMMA with at least 20 wt %
CPVC were developed in 1985 by B. F. Goodrich Co. The alloys were found
miscible, with good processability, heat deflection temperature and toughness
(Lehr, 1986).
Additional information on PMMA/PVC blends can be found in Section 11.2.
13.2.4 PMMAIPO blends

PMMA is antagonistically immiscible with any polyalkene (PO), thus blends of these
two must be compatibilized. Early blends of this type were formulated for manu-
facturing either plastic paper or plastic wood.
In 1968, Sekisui Chemical blended either polypropylene or polyethylene (100 parts
PO) with up to 80 parts of PMMA and 5-100 parts ethylene-vinylacetate copolymer.
The materials were extruded into paper-like sheets (Yamamoto et al., 1971b). The
same year Sanyo Kako developed blends that comprised PP, PVC and PMMA (or
polycarbonate, PC), to give layered, wood-like materials with good machinability.
In the accompanying patents PVC was replaced by cellulose acetate, CA. The
three component blends, CA:PP:PMMA = 1:1:1, also produced layered, wood-like
materials with good machinability (Yahata et al., 1971).
In 1992, Mobil Oil applied for a patent on blends for easy to tear films. The
formulation comprised 90-99wt% LLDPE, 10-1 wt% PMMA and optionally an
elastomeric copolymer such as SEBS, EPR or ES. The blends were found to produce
blown films with improved tear in the machine direction, high modulus, and impact
strength (Dobreski and Donaldson, 1994).
13.2.5 PMMAIelastomer blends

In several patents the impact strength of PMMA was improved by blending it with
acrylic elastomers. For example, in 1968 Mitsubishi Rayon disclosed blends compris-
ing 25-90 wt % PMMA, with butadiene-butylacrylate-methylmethacrylate elasto-
meric copolymer (Kotama, 1972). In a Teijin patent application of 1971, PMMA
was blended with 20-90 wt % SAN to obtain materials with good mechanical proper-
ties, having pearly or metallic luster (Sugimura et al., 1972). In 1970 several patent
applications from Sumitomo Chemical described PMMA blends with ethylene-
vinylacetate-vinylchloride terpolymer (EVAc-VC). The alloys showed improved
transparency and impact strength (Kishikawa et al., 1971). In a contemporary BASF
patent application PMMA was blended with styrene-maleic anhydride (SMA), to
give materials with increased softening point, dimensional stability and good impact
and mechanical properties (Bronstert et al., 1971).
High-impact-resistant blends comprising PMMA with an interpolymer (contain-
ing crosslinked polybutylacrylate, crosslinked SAN and uncrosslinked SAN) were
disclosed in 1980 by Stauffer Chemical (Silberberg, 1982c).
PMMA blends 225
In a patent application of 1991, BASF described PMMA blending in a twin-screw
extruder with coagulated, acrylic rubber latices (e.g., poly(allylmethacrylate-
co-butylacrylate-co-butanedioldimethacrylate-co-styrene-co-methylmethacrylate) co-
polymer, or poly(acrylonitrile-co-butylacrylate-co-tricyclodecenylacrylate-co-styrene)
copolymer) containing 62wt% solid, to give impact-resistant thermoplastics with
high gloss (Farwerck et al., 1993).
13.2.6 PMMAIPC blends

PMMA has been frequently blended with bisphenol-A polycarbonate (PC). Initially,
these blends were not considered miscible, thus transparency was not an issue. For
example, in a Teijin Chemical patent application of 1971, PMMA was solution
blended with PC for better homogeneity and gloss than that obtained when the
alloys were melt mixed (Nawa et a/., 1973). The following year, melt-blended systems
comprising 20-80 wt % Pc, 10-80 % PMMA and 10-80 wt % ABS were patented. The
materials were reported to have good processability, impact strength, pearl-like
iridescence, dyeability and solvent resistance (the company later commercialized
the blends as Meta-marble™) (Ikura et a/., 1974; Sakai et al., 1975).
In 1984 General Eiectric disclosed blends comprising PMMA, PC and poly(acryl-
ate-co-styrene-co-acrylonitrile) terpolymer (ASA). The alloys were reported to have
excellent impact and mechanical properties (Giles and Sasserath, 1986).
Miscibility of PC/PMMA blends was described in one of the General Electric
patent applications deposited in 1986. It was discovered that mixtures of standard,
commercial PC and PMMA resins result in miscible PC/PMMA blends. The phase
diagram has a lower solubility temperature (LCST) of 2 140 0c. The range of mis-
cibility could be greatly increased by modifying the PC chain ends - LCST values up
to 300 °C were obtained. These miscible, transparent blends showed a combination
of PC toughness and PMMA clarity and abrasion resistance. They were mainly
designed for use either as glazing materials (e.g., for fighter planes), or optical
disks with improved performance (Kambour, 1988). In a patent disclosure of 1990
from the company, it was reported that PMMA acts as a weldline strength improver
for PC moldings (Gaggar and Ziegelmeyer, 1992).
In a patent application of 1989 (to Edison Polymer Innov. Corp.), demixing of
miscible blends by the spinodal decomposition mechanism provided means to
generate two-phase alloys with improved mechanical properties. For example, a
single-phase PC/PMMA blend (prepared below the lower critical solution tempera-
ture) was heated to the spinodal region, where it phase-separated. Once the desired
coarsening of morphology was reached, the blend was quenched to below 100°C,
i.e., to below the lower of the two glass transition temperatures. The alloys showed
high modulus, high yield stress and high elongation (Kyu, 1990; Kyu et al., 1991).
In 1992, Enichem disclosed other miscible blends. Thus, transparent, thermody-
namically miscible blends, with single Tg , comprised 35-90wt% PMMA (Mw = 2Q-
300kg/mol), and fluorinated bisphenol A-polycarbonates (9Q-10wt% F-PC). The
blends may also contain fillers, stabilizers, antioxidants, pigments, dyes, impact
modifiers, and PMMA-copolymers with PB, PI, C1-10 alkylacrylates, PVAc, PVAI,
PVDC, diethylfumarate and dimethylmaleate. They were found suitable for molding
or extruding a variety of articles, e.g., containers, glazings and aircraft windows
(Drzewinski, 1994b). In the accompanying patents, blends comprising 1-99wt% PC
and 1-99 wt % syndiotactic polymethylmethacrylate, were also reported miscible and
transparent in all ratios (Drzewinski, 1993b). In the follOWing patent, 35-70wt% PC
was blended with a block copolymer comprising s-PMMA as one block and another
block formed from PB, PI, NR, PS, polyalkylacrylate, polyalkylstyrene or siloxane
elastomer. These materials had good processability, transparency, and mechanical
properties, useful for production of improved optical disks, transparent housings,
medical containers, glazings, recreational equipment, food storage or water bottles
(Drzewinski, 1994c).
Also in 1992, Bayer announced thermoplastic molding blends that contained
polycarbonate and two acrylic copolymers: 5-95wt% PC, l-SOwt% of a copolymer
[~99wt% styrene, methylstyrene and/or (meth)acrylonitrile, MMA, with maleic
anhydride (MAH) and/or N-alkyl- or N-aryl-substituted maleimide], and 5-95wt%
of a graft copolymer(s) [5-95wt% styrene, methylstyrene, and/or C H alkyl
(meth)acrylate, and/or C1--4 alkyl- or phenyl-N-substituted maleimide with cross-
linked, elastomeric particles of diameter 0.05-5 JLm and Tg < 10 QC]. Stabilizers,
pigments, release agents, flow improvers, fire retardants, antistatic, fillers and/or
reinforcing agents could also be added. The blends showed good processability,
without detrimental effects on the advantageous properties of the PC/acrylics, such
as notched impact strength and HDT (Eckel et al., 1993).
13.2.7 PMMAlPEST blends

Polyethyleneterephthalate (PET) invented in 1941 has been mainly used for fiber
spinning. The first use of PET in injection molding dates from the 19608. This is also
the period for the first disclosures of PEST blends. Since the main disadvantages of
PEST are low melt viscosity, slow crystallization rates and relative brittleness,
incorporation of neat PMMA is not expected to be of major interest. However,
PEST blends with acrylic elastomers would be an obvious choice.
In 1967, ICI deposited a patent disclosure on blends comprising PET and lOwt%
of ethylene-methylmethacrylate copolymer (EMMA). According to claims, the
blends were found useful for both principal applications - fiber spinning and mold-
ing (Dijkstra and Jones, 1969). In a contemporary patent the company disclosed PET
blends with EMMA, EHEMA or EVAc. Blending was reported to result in crystalline
materials, suitable for molding thick-walled articles, with good impact strength
Gones et al., 1971). The following year Union Carbide patented PEST blends with
rubber-modified poly(meth)acrylates, 5-95wt% ABSM, and polydimethylsiloxane,
1-20wt% PDMS. The materials were used for molding parts that showed good
notched impact and embrittlement resistance (Sauers and Barth, 1970).
In 1973, Mitsubishi Rayon blended polybutyleneterephthalate (PBT) with methyl-
methacrylate-methylacrylate copolymer (S SOwt% MMMA). The material showed
good moldability, bending strength, and pearl-like luster (Kamata et al., 1974). The
following year, du Pont de Nemours announced PET blended with ethylene-vinyl-
acetate-methacrylic acid copolymer (3 wt % EVAc-MA). The moldable alloys showed
high toughness and low mold shrinkage (Gander et al., 1977).
The first patent on PEST blends with PMMA was deposited in 1977 by GAP Corp.
Thus, PBT was blended with PMMA, 1,4-butanediolterephthalate-polybutylene-
glycol copolymer (PBT-PBG) and fillers. The reinforced blends showed good resist-
ance to shrinkage, warpin~ as well as great improvement of impact strength
(Charles and Gasman, 1979).
Blends of PMMA with polyethyleneterephthalate (2-94wt% PMMA, 4-96wt%
PET and 2-94wt% PS) were disclosed in 1978 by Mitsubishi Rayon Co. The mater-
ials were reported to have good processability, excellent uniform iridescence and
high impact strength (Kamata et al., 1980). In a 1982 application a new type of blend
was described - PBT was blended with 20 wt % polyglutarimide, obtained in reactive
PMMA blends 227
extrusion of PMMA with CH3NH2. The alloys showed high moldability, mechanical
properties and HDT (Toray Industries, 1983a, 1984a).
In 1990, Rohm Chemische Fabrik discovered miscible blends comprising 0.1-
99.9wt% of a polyester (PBT or PET) and 99.~.1 wt% of either a poly-p-methoxy-
phenylmethacrylate, or polyphenylmethacrylate. The blends contained also other
additives, such as O.l-lOwt% of a UV protecting agent. Compared to immiscible
blends, these compositions had the advantages of better adhesion of the layers one to
another, and perfect recyclability at any composition (Siol et al., 1993a, 1994b).
In 1992, Kao Corporation asked for patent protection for formulations and the
methods of molding of a new broad class of alloys. These comprised 98-50 wt % of
part A (a thermoplastic polyester, e.g., PET, PBT, PCT, etc.) and 2-SOwt% part B (an
immiscible resin, e.g., PO, PMMA, PS, PC or PA). The resulting injection or blow-
molded articles showed high anisotropic luster. When the viscosity ratio TJA/TfB > 2
and the storage modulus ratio E~ < E~, the dispersed phase formed prolate ellips-
oids with the axial ratio 1-10, resulting in high mechanical performance (Odajima et
aI.,1993).
13.2.8 PMMAIPPE blends

PMMA has been infrequently used in blends with poly(2,6-dimethyl-p-phenylene
ether), PPE. Although interactions between the PMMA ester group and the ether
linkages of PPE do exist, they are not strong enough to cause miscibility. PMMA is
brittle, thus by itself it is unable to provide the required toughening. Furthermore,
PMMA is known to thermally degrade by the s<rcalled unzipping mechanism,
which at higher temperatures may lead to catastrophic depolymerization.
The use of acrylic elastomers is discussed later, with impact modifiers used with
PPE. The following blends comprising PPE and PMMA provide a few examples.
In a General Electric patent application of 1971, PPE was first modified by blend-
ing it with a methylmethacrylate-cis-polyisoprene ABS-type copolymer. The mixture
was then blended with PMMA to improve flowability. The final alloys were easy to
process. The moldings had high impact resistance (Abolins and Reinhardt, 1976). In
a contemporary patent from Asahi-Dow, similar PPE blends with 0.5-20wt%
PMMA were disclosed (lzawa and Nakanishi, 1973). In a patent application of
1972 from Sumitomo Chemical, PPE was first polymerized in the presence of EPR
(or EPDM), then the product was melt-blended with 3Owt% PMMA to give good
flowability, flexural and impact strength (Matsunaga et al., 1974).
13.2.9 PMMAIPA blends

In blends with polyamides (PA), PMMA is mainly used as an impact-modifying
copolymer. For example, in 1963 du Pont de Nemours used copolymer of methyl-
methacrylate-methacrylic acid-ethylacrylate (90:6:4) to improve tensile and impact
strength, as well as elongation (of PA-6, PA-66 or PA-610) (Halliwell, 1965, 1966).
Similar improvements were described in an ICI patent. Here, PA was blended with
an acrylic copolymer, e.g., ethylene-2-hydroxyethylmethacrylate-methylmethacry-
late (Hepworth et al., 1970). To improve toughness and impact strength of PA,
Bayer used ethylene-ethylacrylate-acrylic acid. The optimum of the ionomer content
was found to be less than 20. (Meyer and Tacke, 1978). During the following years
several other companies (e.g., Dart Industries, ICI, Asahi Dow, Bayer, BASF,
Mitsubishi, etc) similarly employed acidified, elastomeric (meth)acrylic copolymers
as impact modifiers for PA.
SurIyn™ Ionomers, ethylene-acrylate-acrylic acid copolymers with Na+ and/or
20++ counterions, were developed by du Pont de Nemours in the early 1960s.
Since then they have been frequent components in commodity or engineering blends
developed by several companies. In a 1968 patent Dart claimed PA (PA-6, PA-66 or
PA-610) compositions with SurIyn™. The blends showed improved toughness and
impact strength (Boyer et al., 1970).
13.2.10 PMMAIPOM blends

Considering the molecular structure of PMMA and paM one may expect the
existence of hydrogen bonding. Since both resins are brittle only addition of limited
quantity of PMMA may provide improvement of the impact stress. However, much
better effects can be obtained by using either a copolymer comprising methylmetha-
crylate segments or a three (or more) component blend in which PMMA serves as a
compatibilizer. Examples of both these approches are found in the patent literature.
In 1988, Polyplastics Company announced that POM blended with polythioiso-
cyanate (TPU) showed improved impact strength and flexural resistance (Sugiyama
and Mochizuki, 1990). In a contemporary disclosure by the company, it was reported
that addition of PMMA and benzotriazole improved POM weatherability (Endo et
al., 1990). Other parallel patents revealed that the POM/TPU blends can significantly
profit from addition of (co)polymethacrylates. Thus, addition of ethylene-methyl-
methacrylate (EMMA) was found to improve abrasion resistance, whereas addition
of PMMA with benzotriazole was reported to improve weatherability (Okuda, 1990;
Takayama et al., 1991). In 1991 BASF discovered that PMMA forms impact-resistant
blends with thermoplastic polyurethanes (Cramer et al., 1993).
In 1991, du Pont de Nemours disclosed POM blends with acrylic copolymers. For
example, paM was blended with O.Ol-lSwt% EGMA (glycidyl(meth)acrylate
copolymer with styrene, ethylene, ethylene-acrylate, etc.). The matte blends were
used for molding parts used in electrical!electronic applications. The moldings
showed excellent tensile properties (even after long term aging in grease) (Takahashi
and Kobayashi, 1992). In the accompanying patent, the weathering resistance of
POM was improved by incorporation of O.Ol-Swt% UV-absorber and/or light
stabilizers along with O.l-30wt% graft copolymer containing epoxy or oxazolyl
units, e.g., EGMA, EGMA/ AS, EGMA/PMMA or their mixtures (Kobayashi and
Shinohara,l993).
13.2.11 PMMAlPVDF blends

PMMA blends with polyvinylidene fluoride (PVOF) are used for electrets or as
outdoor films with good clarity as well as chemical and UV stability. There is
increasing commercial interest in PMMA/PVOF blends. These blends were also
discussed in Section 12.2.1 Commercial PMMA/PVOF blends are available, such
as PoIycast™ from Royalite.
In most of these single-phase blends (for outdoor applications as transparent,
protective coatings), PVOF constitutes about 70wt%. The technology continues to
evolve since 1966, when Pennwalt applied for patent protection for these materials
(Koblitz, 1966). The following year, American Cyanamid Company blended PMMA
with 7-23 wt % PVOF and polyethylacrylate (PEA) for the manufacture of transpar-
ent films with good weather resistance (Schmitt and Miller, 1970).
Exploration of the piezoelectric and pyroelectric properties demonstrated that
PVOF electret stability can be enhanced by incorporation of acrylics. In the patent
PMMA blends 229
application of 1970/ Kureha Chemical Industry described that for high homogeneity
and high stability PVDF should be dissolved either in methyl methacrylate or its
mixture with methylacrylate then polymerized. The resulting homogenous, single-
phase PVDF/acrylics = 3/2 blends were used for long-lived electrets (Murayama
and Fukuda, 1972).
14
Polyethylene blends
Fawcet and Gibson of ICI are credited with the discovery of low density polyethy-
lene (LDPE) in 1933. Today, various grades of PE constitute one-third of the total
thermoplastics resin market.
In a sense, the majority of PE resins are blends. Four types may be identified: (1)
resins prepared by batch blending to meet standard specifications for density and
melt flow rate; (2) PE blends with up to 15wt% of other polymeric resin(s) added to
enhance PE performance, but not identified as blends; (3) identified commercial PE
blends; and (4) reactor poxiders containing multimodal functions.
Type 1 resins are not considered blends because of frequently encountered varia-
tion in properties between grains. The materials should be processed using equip-
ment able to provide as good a mixing or homogenizing action as that required for
dispersing of any polymer blend. In fact, the linear low density polyethylenes,
prepared using the multisited Ziegler-Natta catalysts are blends of different poly-
ethylenes that are not always thermodynamically miscible.
Regarding the type 2 resins, in most countries it is not necessary to identify resins
as blends, provided that the polymeric additive content is below a certain limit -
frequently as high as 10 or 15 wt %. Thus, the second type of blends, undisclosed as
they may be, represents by volume an important part of the blend market. Here
blends of different PE types are the main concern. For example, blends of low density
PE, with linear low density PE, or with high density PE, belong to this type. Their
market share varies from one country to another. In Canada 70wt% LLDPE are
blended, whereas in the USA only about 30 wt % benefit from this technology.
Note that, with a few exceptions, polyalkene blends are immiscible (e.g., LDPE
with LLDPE), or even LLDPE with another LLDPE prepared using different
catalytic systems (Utracki and Schlund, 1987; Schlund and Utracki, 1987). These
heterogeneous two-phase systems may require compatibilization, chemical or
physical. In the latter case, blending may be done at high shear stresses. Since the
interfacial tension coefficient in these blends is vanishingly small, the coarsening
process is slow, and the blends may behave as a single phase material. However, the
same care of processing must be given to this type of blends as to the other,
disclosed ones.
To the third resin type belong blends that are clearly identified by producers as
such. These are mixtures of PE with other thermoplastics or thermoplastic elastomers.
To the fourth type belong newer multimodal POs obtained using metallocene
catalysts. These meterials have fractions with large difference in Mlt(e.g., 0.05 and
200) which makes them difficult to compound and process.
PE/Elastomer Blends 231
As mentioned above, owing to the chemical nature of the PE chain, these resins are
immiscible with nearly all polymers, including PEs differing in the chain configura-
tion. For this reason, three standard blending strategies can be applied: (1) prepare
uncompatibilized blends with low concentration of the dispersed phase, ca. 5 vol %
of either PE in another resin, or another resin in PE; (2) prepare uncompatibilized
blends either for use in non-eritical applications, or blends having cocontinuous
morphology, preferably with the second polymer being miscible at least with low
molecular weight fraction of PE: and (3) develop compatibilized blends. Historically,
the need for compatibilization became urgent since, as early as the 196Os, without it
even strategy (2) frequently failed.
In the following text on PE blends several examples are given for the use of each of
the three strategies. Here only one for each of them is provided.
• Type 1 In the 1968 disclosure from Asahi Chemical PP or PE was blended with
polyvinylalcohol (2 wt % PVAI). The resulting materials showed improved
mechanical, hygroscopic, and antistatic properties, useful for manufacturing
films, fibers, tubes or coatings (Minekawa et al., 1969).
• Type 2 In a patent application from Monsanto of 1981, PE was blended with
neoprene rubber at a ratio of 1:1. To stabilize the morphology of these immiscible
blends, they were irradiated by an electron beam. The resulting materials showed
high impact strength, and significantly improved other mechanical properties
(Coran and Patel, 1982a).
• Type 3 The first patent on compatibilization of PE blends dates from 1959. It was
disclosed that antagonistically immiscible PE blends with PVC, PIB or PS can be
compatibilized by addition of at least one PE-graft copolymer, such as styrene or
vinylacetate grafted on PE (Houillieres du Bassin-du-Nord et du Pas-de-Calais
and Ethylene-Plastique, 1959).
In the follOWing sections PE blends are discussed in order of historical appearance,
first PE/elastomer systems, then PE blends with commodity, engineering and speci-
alty resins.
14.1 PE/ELASTOMER BLENDS
14.1.1 Rubber blends

The first patent on impact modification of polyalkenes (by addition of elastomers)
was issued in 1937 (Standard Oil Development Co., 1937). The document described
addition of rubber 'as a softening agent' to 'saturated, linear hydrocarbons of the
linear type, the mean molecular weight of which is greater than that of paraffin, e.g.,
between 800 and 500,000'. Five years later LDPE was blended with cycla-rubber, to
give compounds useful for bonding polyethylene to metal (Child et al., 1942).
To improve extensional behavior PE was blended with polybutadiene (butyl
rubber BR) as described in a patent from General Electric (Cole, 1959). In 1964 W.
R. Grace & Company announced blends comprising 10-81 wt % LDPE with butyl
rubber, 15-50 wt % BR, and ethylene-vinylacetate copolymer, (4-40 wt % EVAc). The
blends were found useful for cold-molding of sealing gaskets (Ceresa et al., 1968). PE
blends with lOwt% BR were also patented in 1980 by Polysar. These formulations
were developed to improve low temperature impact strength of PE - blending was
carried out on a roll mill (Kent, 1983).
In 1979, National Distillers and Chemical Corporation developed blends compris-
ing ethylene-vinylacetate (EVAc) and partially hydrolyzed EVAI. The alloys were
232 Polyethylene blends
transparent with good impact strength (Pritchett, 1980). In a later patent, hydrolyzed
ethylene-co-vinylacetate (EVAI) was blended with diene-nitrile copolymer (NBR)
and acidic compatibilizer for improved impact resistance (Pritchett, 1981). Partially
saponified EVAc was also blended with ethylene-vinylacetate-maleic anhydride
graft copolymer (5(}-98 wt % EVAc-MA), to give alloys that could be formed into
films for agricultural use (Mitsubishi Petrochemical Company, 1980).
During the early 1960s, the Central Research Laboratory of Canadian Industries
Limited in McMasterville, Quebec, was a world-class center for polymer research.
The first constant stress reometers were build, the test methods established (such as
the Ed Bagley pressure correction (1957) and the first relations between flow and
molecular parameters were published. On this rich fundamental background the
company issued a number of patents pertaining to PE technology. For example, in
1962 it applied for a patent on blends comprising LDPE or its copolymers with poly-
1- butene (PB). These materials were reported to show improved processability and
resistance to environmental stress cracking (Rudin and Schreiber, 1964a).
In a patent application of 1981 from Monsanto, blends of PE with neoprene rubber
at a ratio 1:1 were described. After compounding, the blends were irradiated by
electron beam. The alloys showed improved tensile strength and other mechanical
properties (Coran and Patel, 1982a). In 1985 Daicel Huels deposited an invention
document for the use of polytransoctanamer (PTa) as a general impact modifier of
polyalkenes. Blends of 100 parts PO with 0.1-100 parts PTa showed good compat-
ibility and high impact strength at low temperatures down to -40°C (Kita and
Hashimoto, 1987).
•
14.1.2 Atactic PP blends
Sanyo Pulp Company developed LLDPE blends with atactic polypropylene,
(0.1-5wt% aPP). The material was found useful for production of blown or stretched
packaging films, with large anisotropy of tensile strength and elongation at break
(Nakamura et a/., 1973). Similar blends were described in a 1977 patent application
from Idemitsu Petrochemical. Thus, soft, thin films, with improved cuttability,
suitable for packaging, were prepared by blending PE (a mixture of LDPE and
HDPE) with either EPDM or aPP (Sakane et a/., 1979).
14.1.3 CSR blends

Chlorination of PE transforms it into elastomer. When the reaction is carried out in
the presence of 50:2, amorphous, elastomeric, chlorosulfonated polyethylene (CSR or
CSM) is obtained. The best elastomeric properties are obtained at about 27% CI and
1.5% S content. Commercial CSR, Hypa/on TM, is available from du Pont de Nemours.
The first blends comprising CSR date from the 1950s. Thus, in 1958 B. F. Goodrich
patented blends that comprised 5-120 parts of LDPE and 100 parts of CSR,
Hypa/on TM. It was reported that blending resulted in materials suitable for use as
smooth, tough, non blocking films or coatings of natural or synthetic elastomers
(Boger and Thomas, 1958).
One of the applications for CSR blends is for single-ply roofing membranes. How-
ever, microbial action causes cracking or alligatoring. The thermoplastic CSR is easily
processable in sheet form, but it tends to crack, whereas vulcanized CSR is more
resistant to microbial cracking, but it is difficult to process. Therefore, a blending of the
two may optimize the performance, marrying the advantageous features of both.
However, it is difficult to partially crosslink one part of CSR in the presence of another,
PE/Elastomer Blends 233
without also affecting the latter part. In 1990 Dow Chemical Company disclosed the
following method to solve this problem. First, either CSR or CPE was dispersed in a
polyalkene and dynamically vulcanized in a Banbury mixer (about 70% load), then
the vulcanizate was dispersed into fresh CSR (or CPE) to form a partially crosslinked
dispersed phase. For example, CSR was blended with ultra-low density polyethylene,
(ULDPE). After compounding, the blends were partially vulcanized, using a deriva-
tive of 2,5-dimercapto-1,3,4-thiadiazole. The product was then dispersed within a
thermoplastic CSR, and an inorganic filler (o-l00phr of MgO, CaO, CaC03 and/or
Ti(h) was added. It was found that these blends may be plasticized using 0-150 phr of
trioctyltrimellitate. The resulting materials showed good processability, hot-weld
strength, interplay adhesion and crack resistance (Ainsworth, 1990, 1994).
14.1.4 PIB blends

Polyethylenes have been frequently blended with polyisobutylene (PIB). In 1958
Esso Research and Engineering patented LDPE blends with 25-40 wt % PIB, for use
as transparent, impermeable, shrink-wrap packaging films (Briggs et aI., 1958). A
year later, a Phillips patent document disclosed LLDPE blends with PIB developed
for the manufacture of grocery bags (Martinovitch and March, 1963). The BASF
patent application of 1960 described a two-step blending method of LDPE with
PIB, resulting in uniform dispersion of the elastomeric phase, thus superior perfor-
mance. First, a pre-blend comprising LDPE with 60% PIB was prepared and granu-
lated. This master batch, with good flowability in the hopper feed lines, was blended
with LDPE to give 5-15wt% PIB in the final material (Dietrich, 1969).
In 1970, BASF developed the high shear rate blending process which was found
particularly useful to secure good dispersion in diluted, non-compatibilized blends.
For example, LDPE was blended with PIB in a single-screw extruder at the shear
rates 600000s- 1 . The residence time in the high stress zone was 34 J-Ls. The resulting
blends had finely dispersed PIB phases with a drop size of 2-5 J-Lm. There was no
evidence of thermal degradation (Urban et aI., 1971).
In 1973, Tokuyama Soda Company announced that polyalkenes, PP or PE, when
blended with 4.5 wt % CSR and filled with large amounts of CaS04, give materials
with good mechanical properties (Shikata et al., 1973).
14.1.5 Ionomer blends

The first PE/Ionomer blends date from 1966, when independently du Pont de
Nemours and Imperial Chemical Industries deposited invention documents. The
first of these documents described blends comprising 20-40 wt % PE with ethylene-
acrylic copolymer with Na+ and/or 20++ counterions, SurIyn™. The resulting
materials were used to manufacture films with good tear and yield strength
(Murch, 1974). In the ICI document, PE was blended with ethylene-methacrylic
acid copolymer, Ionomer, and ethylene-vinylacetate copolymer (EVAc) to give films
with high toughness, stiffness and impact resistance (Willott, 1968).
In 1985, Du Pont Canada announced PE blends with 10-40 wt% of either poly
(ethylene-co-vinylcarboxylate) or an acrylate copolymer. These materials exhibited
notched !zod impact strength more than three times higher that functional-group-
free PE (Broadhed, 1987).
In 1992, Solvay announced blends comprising LLDPE, starch and at least one ionic
compound (in such quantities that the concentration of anions and cations was from
0.002 to 5 mol/kg). The alloys were used for production of high frequency sealable
articles. The starch could contain up to 50 wt % of a plasticizer. The materials could
be calendered, extruded or molded, into multilayer films, sheets and parts that can
be welded or sealed by induction heating at high frequency. They were found useful
for packaging, paper making, etc. The presence of the starch improved the long-term
biodeterioration of the materials (Dehennau et al., 1994).
14.2 PE/EPR OR EPOM BLENDS

An alternative method of impact modification of PE explores its miscibility with
the PE sequences in elastomeric copolymers of ethylene-propylene type (EPR), ethy-
lene-propylene-diene type (EPOM), or ethylene-acrylic acid ionomers. The EPR
technology makes it possible to produce variety of structures from block copolymers
(having different number and size of blocks) to random - the higher the randomness
the lower the crystallinity.
The Ziegler and Natta's family of catalysts, Z-N, made it possible to polymerize
ethylene-propylene-diene copolymers with a controlled degree of crystallinity and
crosslikability (Natta et al., 1955, 1957). Commercially, the first ethylene-propylene
rubbers (EPR), were manufactured in 1960 by Esso, and ethylene-propylene-l,4-
hexadiene (EPOM), in 1963 by du Pont de Nemours. These thermoplastic elastomers
are characterized by a block copolymer structure, with PP being the rigid and PE the
elastic block. By controlling the degree of blockiness, one can obtain materials with a
range of crystallinity, Le., the elastomeric behavior and hardness. Thus, in these
resins the elastomeric character originates from physical rather then chemical cross-
linking. Furthermore, EPR may be lightly crosslinked by addition of peroxides,
whereas vulcanization of EPOM can result in highly crosslinked, rigid products.
It is noteworthy that the first patent on PE/EPR blends was deposited by Mon-
tecatini in 1959, before commercialization of EPR. Blending was reported to improve
processability and mechanical properties of all then known polyethylenes - HOPE,
LOPE or LLOPE. For further enhancement of properties, either polypropylene or
polybutene could be added (Corbellini, 1962). Two years later, several other compan-
ies deposited invention records describing similar compositions. Thus, Imperial
Chemical Industries disclosed HOPE blends with 3Q--60 wt % EPR for improved
processability and impact strength (Crawford and Oakes, 1963, 1966). Similarly,
HOPE was blended with 15 wt % EPR to improve impact resistance (Farbwerke
Hoeehst A.-G., 1962), and in an Esso disclosure the mechanical properties of PE
were improved by blending it with 5-25wt% EPOM (PriUieux et al., 1962).
In 1963, CIL patented PE/EPOM blends with further enhanced properties by
additional incorporation of PP or PB (Schreiber, 1966). Blends of PE with EPR and
ethylene-acetoxybicycloheptene copolymer were developed in 1968 by Sumitomo
Electric Industry. It was found that blending resulted in increased impact and
tensile strength, and brittle resistance (Shirayama and Iketa, 1971). One year later,
the company disclosed blends of PE with less than 15 wt % EPOM. The materials
were reported suitable for use as corona discharge-resistant insulation for high-
voltage cables (Matsubara, 1972).
To improve adhesion to polar materials, POS are frequently grafted with acidic or
acid anhydride moieties. This modification has been also used in PE blends. The
first patent disclosure of 1979 was from Neste Oy. Thus, PE was first grafted with
0.1-5 mol % of maleic anhydride and then blended with 1-50% EPOM. The resulting
material showed excellent adhesion to polar resins (Honkanen et aI., 1983). The 1980
patent application described blends of HOPE with 80-97 wt % EPR prepared with a
single catalyst and containing 70-95 wt % PP-block and 5-30 wt % EP-random copo-
PE/PE blends 235
lymer (Mitsubishi Chemical Industries Co. 1982b). In a 1991 patent document from
Mitsubishi Petrochemical, very low density polyethylene (VLDPE, density
885 kg/m3 melting point 6~90°C), was blended with EPR, EPDM or their mixtures
having T m = 3~55°C, EPR block copolymer, and 0-7phr talc. The blend showed
excellent moldability, surface appearance and hardness, as well as good impact
resistance (Nishio et al., 1992a).
There is a tendency to prepare PO blends directly in a reactor (Rifi et al., 1987; Galli
and Haylock, 1991). This technology makes it possible to produce materials ranging
from impact modified polyalkene (either PE or PP) to reactor-type thermoplastic
polyalkene (RTPOs). The first blends of this type comprising PE were disclosed in
1969 by Showa Denko. Using highly reactive catalyst in a fluidized-bed, gas
phase reactor the elastomeric particles can be grown to a desired size before the
major component polyethylene or polypropylene resin is synthesized. In that
patent ethylene-butene-type LLDPE was reactor-blended with PP or poly (pentene-
co-propylene), or poly(ethylene-co-pentene) copolymer. The product was then melt
blended with additional homopolymer to give materials with improved performance
(Yamazaki and Fujimaki, 1970, 1972). In 1974 Hoechst announced reactor blending of
PE with PP and EPR. The alloy was reported to have high impact strength at low
temperature (Strametz et al., 1975). The first patent on reactor-blended thermoplastic
olefinic elastomer (R-TPO) was disclosed in 1979 by Mitsui Petrochemical Industries.
Thus, PE was polymerized in the presence of an active catalyst and already poly-
merized alkenic copolymer (e.g., ethylene-I-butene copolymer) or the sequence was
reversed. The blends had superior resistance to environment stress cracking, and the
blown film showed fewer fish-eyes (Morita and Kashiwa, 1981).
In 1992, Bridgestone/Firestone announced polyalkene blends formulated for heat-
sealable roof sheeting. These comprised 2~95 wt % of an amorphous PO (having less
than one percent crystallinity; the copolymer comprised not more than 60 wt %
ethylene, with dicyclopentadiene, and/or ethylidene norbornene), ~75wt% of a
crystalline polymer, (i.e., PE, PP, poly(ethylene-co-propylene), poly(ethylene-b-
octene) or poly(ethylene-b-butene) having 2-65% crystallinity, 20-300phr of a (non)-
reinforcing filler, and 20-150 phr of either alkparaffinic oil, naphthenic oil and/or
wax. The materials exhibited good adhesion - neither an adhesive nor curing was
necessary (Davis and Valaitis, 1993, 1994).
The same year, Hoechst patented blends comprising polycycloalkene with
0-95wt% PCO, 0-95wt% PE and O.I-99wt% block copolymer(s). The alloys were
designed for injection molding. They showed outstanding properties, namely
low melt viscosity thus good processability, high elongation at break, impact strength,
toughness, hardness and modulus. The block copolymers preferably used in these
systems comprised ethylene (or propylene) and norbornene blocks. They were
obtained in the polymerization process carried out the presence of aluminoxane and
a metallocene catalyst, that resulted in copolymers having narrow molecular weight
distribution, with polydispersity ratios Mw/Mn S; 2 (Epple and Brekner, 1994).
14.3 PE/PE BLENDS

Two polyethylenes of different type chain structure are usually immiscible. The
immiscibility is not limited to the resins with different comonomers (alamo et al.,
1997). For example, two linear low density polyethylenes, both being copolymers of
ethylene with hexene, but polymerized using different catalyst systems (both Z-N
type, but one based on Ti the other on V) were reported immiscible (Utracki and
Schlund, 1987; Schlund and Utracki, 1987; Utracki, 1989b; Utracki and Dumoulin,
1995). By contrast, some LLOPEs, especially those containing a small amount of
butene comonomer, showed limited miscibility with high density polyethylene
(HOPE). The PE immiscibility refers to the molten and solid states. Note that the
small changes in molecular structure lead to difference in the melt temperature, that
in turn creates a sequence of crystallization of the ingredients. Thus, in most cases
the spherulites of one PE (having higher Tm) are encapsulated by those of the other
PE. Co-crystallization of two PEs into a single type of isomorphic cell has rarely been
observed (Utracki, 1989a).
Mixtures of different polyethylenes constitute an important category of PE blends.
The first PE/PE blends, either crosslinked in an electron accelerator or not, were
disclosed by Phillips Petroleum in 1958 (Canterino and Martinovich, 1963; Nelson,
1964). More recently, Mitsubishi Yuka Industrial Products disclosed interesting PO
blends comprising vinyltrimethoxysilane-grafted polyalkene (either PP, LOPE, EPR
or EVAc) and ethylene-acryloyloxytetramethylpiperidine copolymer. These water-
crosslinkable resins were found useful for the manufacture of weather-resistant
crosslinked PO pipes for outdoor applications (Ohnishi and Fukuda, 1993). Ther-
mally reversible crosslinks, by means of ionic interaction between maleated and
glycidylmethacrylate grafted polyalkenes, have also been used, e.g., by Idemitsu
Kosan (Okada, 1994).
14.3.1 LDPEILLDPE blends

The blends comprising LOPE with LLOPE were reported to have improved stiffness,
abrasion resistance and reduced water vapor permeability. In a Celanese patent
application of 1961, the improvement of LLOPE processability was stressed (Wiss-
brun et al., 1962, 1965). In a contemporary du Pont patent application, 1G-50wt%
LLOPE was blended with LOPE to obtain materials suitable for use as heat-
shrinkable films (Golike, 1962).
Since LLOPE differs from LOPE by the presence of short side groups introduced
as a part of the comonomer unit, and by the absence of long chain branching, there
have been several attempts to create the latter chain structure by addition of radicals
to molten LLOPE, expecting that generated macroradicals will graft on some LLOPE
macromolecules, thus converting part of the resin into LOPE-like polymer. These
long-branched molecules would be simultaneously blended with unmodified
LLOPE macromolecules creating an intimate PE/PE blend possessing all the super-
ior characteristics of the LLOPE/LOPE blend. The main problem associated with this
technology was the difficulty in controlling uniformity of product. The small quant-
ity of peroxides tended to form pockets of highly degraded resins that contaminated
the product. Thus, the idea was correct, but (so far!) polymer engineering has failed
to provide adequate support.
In 1971, Exxon Research and Engineering disclosed reactive grafting of either
polyethylenes or polypropylenes. The extruder was modified to make it possible to
separately feed the polymer, grafting monomer and a peroxide (Steinkamp and
Grail, 1976).
In a Societe Chimique des Charbonnages patent application of 1982, LLOPE was
blended with 2-25 wt % LOPE to give films with large difference of the tensile
strength in the machine and transverse directions (Hert, 1983). The reversed compo-
sitions were disclosed in Japan the following year. Thus, LOPE was blended with
LLOPE at ratios varying from 100:20 to 100:90. The alloys were reported useful for
production of packaging films (Asahi Chemical Industry Co., 1985a). Also in 1982,
Exxon Research & Engineering Company disclosed blends of high density polyethy-
PE/PE blends 237
lene, 75wt% HDPE, with ethylene-vinylacetate copolymer and EPDM. The compo-
sitions were found useful for manufacture of soft films, having high tensile, tear and
impact strength Oanac et ai., 1983).
A 1984 patent disclosure from Mobil Oil, described LLDPE blends with 10-45 wt %
LDPE, and polypropylene or ethylene-propylene copolymer (with a high propylene
content), 2-15 wt wt % EPR. The blends had high modulus and excellent clarity (Bah!
et ai., 1985).
In 1992, Euro-matic developed blends comprising LLDPE with LDPE at a ratio of
about 3:10. These resins were used for blow molding hollow balls containing pres-
surized air and consisting of two hemispheres welded to form a ball with a wall
thickness of 0.5-1.8mm (Moss and Modigh, 1994).
14.3.2 LLDPEILLDPE blends

Blends of two different types of LLDPE, were first disclosed in 1977 by Phillips
Petroleum Co. Thus two different types of LLDPE, one with butene, the other with
hexene co-monomers were blended. The blends were found suitable for pipe extru-
sion (Larsen, 1982).
In 1979 the Unipoi™ process for gas-phase production of LLDPE was introduced
by the Union Carbide Corporation. Since the new resins were difficult to process on
the lines designed for LDPE, by 1982 several patents were issued for improvement of
LLDPE processability by blending it with other polyalkenes such as LDPE, PP or
olefinic rubbers. Ethylene copolymers, rubbers, EPDM, EVAc, maleated polypropy-
lene, EPR, etc., have also been used (Haas and Raviola 1982; Hughes, 1982; Cowan,
1983; Turtle, 1983; Fukui et ai., 1983; Haas, 1983; Hert, 1983).
More recently, LLDPE was graft-modified by incorporation of basic groups from,
for example, dimethylamino ethylmethacrylate, t-butylamino ethylmethacrylate,
vinyl pyridine or allyl urea. These copolymers were then used as reactive compo-
nents for alloys with acidified polymers, such as maleated LLDPE or PP (Baker and
Simmons, 1991).
In 1992, Phillips Petroleum applied for patent protection for blends that comprised
melt blended high and low molecular weight ethylene polymers having melt vis-
cosities (at 100 S-1) of > 5 and < 0.3 kPa, respectively. The polymers were blended in
two stages: first the high-molecular-weight polymer was blended with a small
amount of the low-molecular-weight one: then an additional low-molecular-weight
polymer was incorporated in a second stage to form the final blend. The materials
had good processability and excellent physical properties. The process provided
improved resins for the production of films with low fish-eye content, for blow
molding, extrusion of pipes, wire coating, as well as for injection or rotational
molding (Coutant, 1994).
The same year, Mobil Oil announced reactor blends of polyethylenes (with butene
and/or hexene) for manufacturing blown films that exhibited improved MD/TD
tear balance. These materials were produced in a multistage gas phase, fluidized-bed
polymerization process wherein the blending occurred in situ. The resulted bimodal
molecular weight distribution resins had the weight fraction of a higher molecular
weight component from about 0.35 to about 0.75 (Ali et ai., 1994).
Also in 1992, Minnesota Mining and Manufacturing Company disclosed blends
that comprised very low density polyethylene: 100 parts VLDPE (80-95 mole %
ethylene and C4 -eS comonomer(s) and 15-600 parts LLDPE (ethylene copolymer
with 2-8 mol % octene). The blends showed excellent processability. Formed into
10-300 Jim thick films, they were used for transdermal drug delivery devices as
single layer backings. The films were clear, colorless and transparent to visible light,
and capable of being heat sealed at relatively low temperature. They are permeable
to oxygen, stable to various common components of transdermal delivery devices,
strong, comfortable and did not absorb sigtiificant amounts of common elements of
transdermal carriers (Godbey and Martin, 1993, 1994).
In a contemporary patent application from W. R. Grace, improved heat shrinkable
PE films were described. These comprised single site catalyzed copolymers of ethy-
lene and a C:Hj a-alkene, LLOPE with density ~ 9OOkg/m3 , blended with another
polymer of ethylene and a C:Hj a-alkene and a second comonomer (e.g., vinyl acetate,
alkyl acrylate, CO, butadiene, styrene, acrylic acid and a metal salt of an acrylic acid),
or an a-alkene homopolymer. These films had improved shrinkability, impact
resistance and optical properties as compared to homogenous copolymers. The
blends were found useful for manufacturing packaging films (Babrowicz et al., 1994).
In 1990, Exxon Chemical disclosed blends of linear ethylene interpolymer that
comprised linear low density polyethylene with very low density polyethylene. The
polymers prepared using metallocene catalyst had narrow molecular weight distri-
bution, Mw/Mn = 1-3, and a narrow composition distribution, as expressed by
COBI > 50%. COBI was defined as weight percentage of the copolymer molecules
having a comonomer content within 50% (that is, 25% on each side) of the median
total molar comonomer content. The COBI of a copolymer was determined using the
temperature rising elation fraction (TREF).
The components could have either the same molecular weight but different co-
monomer contents, the same comonomer content but different molecular weights, or
co-monomer contents that increase with molecular weight. The blends had either
M w / Mn > 3 or com < 50%, or both these inequalities being observed. They could
be multimodal in respect to molecular weight and/or comonomer content. They
were generally free of components having both a higher average molecular weight
and a lower average comonomer content than another blend component, and have
densities of 910-940kg/m3 . These blends can be coextruded or compounded with
other polymers to further enhance processability and physical characteristics.
Single or multilayer films having enhanced physical properties were produced.
The materials showed improved mechanical, physical and/or chemical properties
(Stehling et al., 1995).
Blends that included 70-90 wt % of a polymer derived from ethylene and at least
one higher a-alkene (e.g., LLOPE, VLOPE or LOPE, haVing melt index MI ofO.l-lO),
10030wt% of an auxiliary cocrystallizable polymer, derived from ethylene and at
least one alkenic comonomer (e.g., LLOPE, VLOPE or LOPE having MI 2: 80% lower
than that of the first polymer), and moisture crosslinking additives (e.g., silane, a
silanol condensation catalyst and a free radical initiator) were disclosed by Exxon
Chemical in 1992. The patent reported that crosslinking was rapid, thus the moisture
curing step subsequent to extrusion of electrical cable was short. The blends could
also contain processing aids, (e.g., fluorinated polymer and/or a polyethylene with
high MI) and 5-70wt% filler. The materials were developed for use as shaped
coatings or wire and cable insulation (Wong and Varrall, 1994).
14.3.3 LOPE or LLOPE blends with HOPE

The miscibility of two PE resins depends on the degree of difference of their chain
structures. As a rule, different type PEs are immiscible with each other (Utracki and
Schlund, 1987; Schlund and Utracki, 1987; Utracki, 1989a). However, so as to control
density, the high density polyethylene (HOPE) contains a small amount of propene
PEIPP blends 239
or butene comonomer, it was reported that some HDPE blends with LLDPE (that
contained a small amount of butene comonomer) have limited miscibility with
HDPE. These blends were first disclosed in the 198Os.
In 1977, Idemitsu Petrochemical announced that blends of LDPE with HDPE, and
either an EPDM or an atactic polypropylene (aPP) are particularly suitable for
production of soft, thin films, with improved cutting properties, suitable for packag-
ing (Sakane et al., 1979).
In 1981, it was disclosed that blends containing ~9Swt% HDPE with SD-5wt%
LLDPE gave blown films with improved strength and transparency over that of
HDPE (Showa Denko K K, 1983a). In the following patents the company disclosed
immiscible blends of LDPE with either HDPE or MDPE. These were well suited for
manufacturing films with uniform thickness and anisotropic tensile strength (Showa
Denko K K, 1983b). The same year Shin-Kobe announced similar blends - LDPE
with HDPE, PP and EP-block copolymer. The materials were reported to be used for
production of films with good modulus, tear strength and no-sagging behavior
(Shin-Kobe Electric Machinery Co., 1984).
In 1991, Hoechst disclosed blends having a bimodal molecular weight distribu-
tion. These materials comprised 5Q-80 wt % HDPE blended with either LLDPE, or
LDPE. The alloys were found suitable for molding or extrusion of tubes, pipes, and
other articles requiring high stress crack resistance (Boehm et al., 1992).
The same year Phillips Petroleum Company deposited applications describing
blends with improved processability. These comprised 30-70 wt % low-molecular-
weight high density polyethylene (HDPE; made using a chromium catalyst, having
density 2 955kg/m3 , MI = 25-400g/10min and Mw/Mn = 2-35), and 3D-70wt%
high MW ethylene copolymer (LLDPE; made using a titanium catalyst, having
density ::; 95Skg/m3 , MI = 0.1-SOg/lOmin and Mw/Mn = 2-10). The blends were
used to produce pipes, films and bottles with enhanced mechanical properties as
well as environmental stress crack resistance (ESCR) (Martin et al., 1994a). In
a following patent 5-40 wt % low MW HDPE (polymerized using a titanium
catalyst, with density 2 955kg/m3 , MI 2 25dg/min and Mw/Mn = 2--8), blended
with 60-95 wt % high MW HDPE (from chromium catalyst, with density
2 93kg/m3 , MI = 1.5-15dg/min and Mw/Mn = 6-100), yielded blends with
MI = 0.05dg/min and excellent ESCR (Martin et al., 1994b). In another application,
1Q-80wt% low MW LLDPE (density density 2 940kg/m3 , MI > 25dg/min and
Mw/Mn = 2-12) was blended with 2D-90wt% of a high MW LLDPE (density
::; 955kg/m3 , MI = 2-10dg/min and Mw/M n = 2-10). The blends were reported to
have MI > 0.05dg/min and improved optical properties (Coutant and Martin, 1995).
The following year, the company disclosed blends comprising 1-30wt% LDPE
(density = 91D-930kg/m3 , MI = 6dg/min) blended with 99-70wt% LLDPE (den-
sity = 91D-940kg/m3 , MI = 1dg/min and Mw/Mn = 6). The blends showed
improved tear strength and haze (Benham et a!., 1995). Similar effects were also
claimed for LLDPE blends with 10-40 wt % of an ethylene-vinylacetate copolymer
(EVAc; density = 92D-945kg/m3 , MI = 6-lOdg/min and 1D-20wt% VAc). The
materials had good processability, and the product showed high tear strength and
transparency (Benham and McDaniel, 1994).
14.4 PE/PP BLENDS

There have been many patented PE blends with polypropylene (PP). In most cases
the aim was to improve the low temperature impact strength of PP. The first one,
disclosed in 1960, described blends comprising 5D-95wt% PP (MW = 4Mg/mol)
with LOPE (MW = 1.6Mg/mol) as having high impact strength and low brittle
temperature (Sun Oil Co., 1964). The PP IPE blends are described later (Section 15.1).
14.5 PE/PS BLENDS

This section discusses the blends of PE with polystyrene (PS). The systems compris-
ing diverse copolymers of styrene or its derivatives are presented in section 14.6.
Two types of blends are of commercial interest: (1) PE/PS blends with little or no
compatibilizer used as plastic paper, and (2) well-eompatibilized blends with tail-
ored block copolymer, mainly used for blister packaging. As shown in Figure 14.1, it
is important that the two parts of the compatibilizing copolymer match the homo-
polymer structure.
Blends of PE with PS have been known since the early 196Os. For example, in 1959
Monsanto Chemical disclosed that PS having improved impact, elongation, and
tensile strength was obtained by blending it with polyethylene (1-10wt% PE)
and chlorosulfonated-polyethylene (Herbing and Salyer, 1963). In a contemporary
patent, PE was blended with either PS, PVC or PIB. The blend was compatibilized by
·addition of an appropriated graft copolymer (e.g., styrene or Vinyl acetate grafted on
PE) (Houillieres du Bassin-du-Nord et du Pas-de-ealais and Ethylene-Plastique,
1959). The following year, Union Carbide Corporation disclosed blends comprising
PS andlor PE with 4O-90wt% styrene-ethylene bulk copolymer (Gorham and Farn-
ham, 1964).
In 1983, Mobil Oil Corporation announced blends of linear low density polyethy-
lene (70 wt % LLOPE) with 30 wt % PS. The materials were found useful for manu-
facturing films for food wrapping with dead-fold and paper-tear characteristic
ABUSIVE INJECTION MOLDING at T = 300°C

BLEND COMPOSITION: PSILLDPEJCOPOL. = 50150110
:I: 800
~
z 01:] 01:]0 00 ElElEJ
~ 700
o 0 0 0 0
copol.= poly[styrene - b - 1,4 buladiene(hydrogenaledl]
~
~ 600
~
c...~
~~
o~
500
§
400
o
W
:I:
~ copol. = SEBS
~Z 300
' . . . ., •. -••--t•..-._...i--J.L............
200---+-----~-----~-----~
o 10
RESIDENCE TIME (min)
Figure 14.1 Effect of a compatibilizer on the impact strength of injection molded PE:PS=1:1
blends comprising 10 phr of compatibilizer (adapted from Brown et al., 1991).
PE/styrenics blends 241
(Canterino and Freudemann, 1985). In a later patent, blends comprising at least
90wt% of LLDPE with poly-p-methylstyrene were described. These resins were
developed for production of films with good mechanical properties in the machine
direction (Canterino et al., 1986).
In the early 1990s, the Dow Chemical Company introduced thermoformable,
chemically resistant blends, with a cocontinuous phase morphology, useful in the
preparation of refrigerator and freezer liners. The alloys comprised 45-70 wt % high
impact polystyrene (HIPS) 15-40wt% HDPE and 5-25wt% of a compatibilizing
triblock copolymer SBS or SIS. The selected HIPS comprised 1-25wt% of an elasto-
mer/ had three-modal distribution of rubber particles of diameters 0.1-{).8, 1.2-3
and 3-10 tlm, and the weight average molecular weight of the polystyrene chains
was 50-400 kg/mol. The selected block copolymer, SBS or SIS, comprised 35-45 wt %
of styrene and had M w = 2G-100kg/mol (Swartzmiller et al., 1993/ 1994).
In a contemporary deposition from BASF, blends of polystyrene (5G-80wt% PS or
HIPS) and polyalkene (2G-SOwt% PE or PP)/ were described. These were compat-
ibilized by addition of 0.05-50 phr non-symmetrical, linear tri-block copolymer
comprising 5G-85wt% styrene and butadiene (or isoprene). The block copolymers
had the structure Sl-D-S2 (where Sl and S2 are the polystyrene blocks, Sl ~ S2, and
D is a polydiene block). The moldable blends had good processability, high stress
cracking resistance, impermeability to water vapor, and improved impact resistance
(Hoenl et al., 1993).
14.6 PE/STYRENICS BLENDS

In an early patent application from Dow Chemical (dated in 1961)/ blends of either
HDPE, LDPE or LLDPE, with 2~ wt % styrene-acrylonitrile copolymer were
reported to show improved crack resistance. Synergistic effects were observed
when 0.1-1.0wt% 2/4/6-trialkyl phenol was added Uankens, 1963). In a 1967 patent
application from Asahi Chemical, to improve stress crack resistance PE was blended
with 1-95 wt % styrene-butadiene (SB or SBS) or a p-methylstyrene-isoprene block
copolymer (Minekawa et al., 1971b).
In 1976/ Shell Oil started patenting blends comprising the newly developed hydro-
genated poly(styrene-diene) block copolymer, such as styrene-ethylene/butylene-
styrene block copolymer (SEBS). In the disclosure granted in 1979 several blends
with different polymers, including PE, were described. Most of these blends, having
nearly equal weight fraction of the two main components, showed a cocontinuous
morphology, resulting in good toughening effects, dimensional stability, mechanical
behavior, resistance to shrinkage and distortion (Davison and Gergen, 1980). Also
in 1976 Mitsubishi Petrochemical announced that blends of HDPE with HDPE-
grafted with vinyl or vinylidene monomer had improved modulus. Thus blends
of HDPE with styrene-grafted HDPE resulted in significantly stiffer materials (Yui
et al., 1978).
A method of reclaiming mixed immiscible polymers by employing a compatibiliz-
ing agent was described in 1981. The studied system comprised HDPE, PS and SEBS.
These ternary blends showed considerable improvement of mechanical properties
over the binary HDPE/PS blends (Lindsey et al., 1981). Similarly, in a contemporary
Montefina patent application, HIPS was blended with 45 wt % HOPE and 10 wt %
SEBS to give materials with high impact strength (Castelein, 1982). In 1987 Shell
International Research Maatschappij announced that blending LLDPE, with SEBS
resulted in transparent, impact, and blush-resistant materials, suitable for packaging
(Holden and Hansen, 1989). In 1991 BASF disclosed similar molding blends,
comprising PS, LLOPE and SEBS. The materials were found to be resistant to impact
and to yellowing (Seelert et al., 1993).
In 1992, ICI Australia Operations Proprietary applied for a patent on blends that
comprised polyalkene (PP, HOPE, EPR or PMP), an impact modifier, 0.1-5wt%
colorant and/or 5-50wt% of opacifiers. The preferred impact modifier was a
styrene-dialkene block copolymer (SEBS, SEPS, radial SEB or SEP), grafted with
1-6 mol % of either acrylic acid, maleic anhydride or sulfonate functionality. To
improve scratch resistance the blend contained 1~3000ppm Zn stearate, and
Cl 6-22 fatty acid amide. The alloys were suitable for injection molding. The
moldings were found to be impact, scratch and abrasion resistant, useful for the
manufacture of the interior trim for vehicles and other applications where a scratch
and scuff resistant plastic material is required (O'Leary and Musgrave, 1993).
The same year, Neste Oy described blends comprising a PO (e.g., EVAc, PE, PP,
EPR), a vinyl polymer, 10-200 parts of vinyl monomer (e.g., styrene, styrene derivat-
ives, (meth)acrylates, vinyl chloride, glycidyl methacrylate, maleic anhydride, acry-
lonitrile, divinylbenzene), and 0.01-4.0 parts of a free radical initiator. The blends
were prepared in two stages. First, at 20-130 °C PO particles were impregnated with
the monomer and initiator. After 50-99wt% of the monomer was absorbed, the
particles were dispersed in water and the polymerization was initiated. Good adhe-
sion between components in the extruded or molded articles was achieved (Vestberg
and Lehtiniemi, 1994).
14.7 PE BLENDS WITH ACRYLICS

PE blends with acrylics are relatively rare. In most cases they comprise PE and an
elastomeric acrylic copolymer responsible for improving the impact properties.
For example, in 1985 Du Pont Canada disclosed PE blends with 10-40 wt % ethylene-
vinylcarboxylate or an acrylate copolymer. The materials exhibited notched !zod
impact strength more than three times larger than that of PE free of functional
groups (Broadhed, 1987).
In 1989, Exxon Chemical Patents disclosed compatibilized blends that comprised:
(1) 30-90wt% of a nitrile rubber, (2) EPR or EPOM, (3) ethylene-acrylate-acrylic acid
random terpolymer and (4) optionally carbon black, a vulcanization system, and
fillers, lubricants, plasticizers, tackifiers, coloring agents, blowing agents or
antioxidants (Arjunan, 1994). In 1992 the company announced compatibilized TPO
blends that comprised at least two elastomers and 5-20 phr of an ethylene-metha-
crylate-acrylic acid = 4-4O:5-35:2--8wt% terpolymer. The elastomers were selected
from the group: ethylene-propylene copolymers (EPR), ethylene-propylene-diene
terpolymers, polychloroprene, nitrile rubber, copolymers of butadiene with up to
35 wt % styrene and natural rubber. The blends were formed into power transmis-
sion belts, tire portions, belts, hoses or air springs (Arjunan and Kusznir, 1994). The
following year similar blends were announced. They comprised (1) an elastomeric
interpolymer, (2) at least one elastomer selected from SBR, EPR, EPOM, CR,
NBR, NR, IP, PB and hydrogenated nitrile rubber, and (3) 1-50 phr of a com-
patibilizer selected from polymers comprising ethylene-vinylacetate, ethylene-
alkyl(meth)acrylate or ethylene-(meth)acrylate-(meth)acrylic acid. The interpolymer
(1) was a terpolymer of isobutylene-p-methylstyrene-monobromo-p-methyl-
styrene, with 5-60 mol % of PMS units, giving a bromine content 0.1-5 mol %
(Arjunan, 1995).
In 1990, Advanced Elastomer Systems announced thermoplastic compositions
having improved adhesion. These comprised dynamically vulcanized polymer
PE blends with other commodity polymers 243
blends of (1) 15-{)Owt% of a thermoplastic non-elastomeric copolymer of ethylene
and vinyl acetate containing less than 30wt% vinyl acetate, (2) 14-40wt% of an
elastomeric EVAc having a vinyl acetate content at least 45-70 wt %, (3) 20-70 wt % of
an at least partially vulcanized elastomeric copolymer, and optionally a chlorinated
polyethylene. The elastomeric copolymer was either chlorobutyl rubber, an EPDM,
or a chlorinated isoprene-isobutylene (Puydak et al., 1995).
In a series of patent applications deposited by the Kanegafuchi Kagaku Kogyo in
1992, polyalkene blends with excellent processability, impact resistance, rigidity, and
surface properties were described. The blends comprised 100 parts of either PE or
PP, and 0.1-100 parts of a core-shell graft copolymer. The latter was prepared by
graft copolymerizing 5-60 wt % of a vinyl monomer whose polymer has a glass
transition temperature 2 25°C (e.g., styrene, methylmethacrylate) onto a crosslinked
rubbery polymer of Tg ~ 25°C (e.g., polybutadiene). The blends (reinforced or not)
were easy to process, and the products showed good impact resistance, rigidity,
surface property etc. The reduced melt viscosity and increased tensile strength made
it possible to use these alloys in extrusion, calendering, thermoforming, blow- or
injection-molding (Aoyama et al., 1993, 1994).
Also in 1992, Mobil Oil Corporation disclosed blends comprising 90-99wt%
LLDPE (a copolymer of butene, hexene or octene having a density of 910-
930kg/m3 ), an acrylic polymer, preferably polymethylmethacrylate (10-1 wt%
PMMA, Plexig/as™) and, optionally, a compatibilizing copolymer-impact modifier,
such as 5EB5, EPR or ethylene-styrene block copolymer. The blends manufactured
on conventional film blowing lines resulted in materials with improved tear in the
machine direction, high modulus, and impact strength (Dobreski and Donaldson,
1994).
In 1993, Eastman Chemical Company disclosed grafting of polyethylenes with
alkyl acrylate or alkyl methacrylate for use as hot-melt adhesives. The formula-
tions comprised 5-20wt% of a copolymer of ethylene and alkyl acrylate or alkyl
methacrylate (having an alkyl acrylate or alkyl methacrylate content of 4-15 mol %),
4G-70wt% of a PE grafted with an unsaturated polycarboxylic acid, anhydride or
ester, 15-35wt% of a tackifying resin selected from aliphatic hydrocarbon, polyter-
pene, and rosin ester resin, and 5-20 wt % of a high melting, low viscosity wax
selected from the group consisting of high density polyethylene waxes, Fischer-
Tropsch synthetic waxes, and microcrystalline waxes. The composition had a melt
viscosity of 0.3-4 Pa s at 177 °C (Godfrey, 1995).
14.8 PE BLENDS WI1H OTHER COMMODITY POLYMERS

Polyethylenes, homo-or copolymers, are frequently used as impact modifiers for a
variety of other thermoplastics. For example, in a 1957 patent application from
Dainippon Celluloid Company, it was claimed that addition of l-lOwt% of either
PE, CPE or CSR to PVC improved its moldability, stability, impact strength and
chemical resistance (Matsuda et a/., 1960; Matsuda, 1960). Similarly, in Monsanto
Chemical Company's disclosures of 1959, either PVC was blended with 5wt% of PE
(that was modified by incorporation of polar groups, e.g., by chlorination into CPE)
(Baer and Hankey, 1963), or polystyrene was blended with 1-10 wt % PE and/or CSR
to obtain alloys with improved resistance to impact, increased elongation and
strength (Herbing and Salyer, 1963).
Blends of PP or PE with 2wt% PVAI were disclosed in 1968 by Asahi Chemical.
The materials were primarily developed to improve the antistatic properties, but in
addition they showed good mechanical and hygroscopic behavior. These systems
have been used for the manufacturing of films, fibers, tubes and coatings (Minekawa
et a/., 1969).
To improve modulus of high density polyethylene, in 1976 Mitsubishi Petrochem-
ical blended the resin with HDPE grafted with vinyl or vinylidene monomer (e.g.,
styrene or vinyl chloride) (Yui et al., 1978). Blends of PE with polyvinylchloride were
also announced by other companies. For example, in 1983 blends comprising 100
parts of PVC, 10-300 parts HDPE and 0.1-5 parts chlorinated polyethylene (CPE, as a
compatibilizer), were disclosed. The alloys were found particularly suitable for the
manufacturing of weather-stripping gaskets for automobile windows (Nippon Zeon
Co., 1984).
In a Dow Chemical patent application of 1982, LDPE was blended with 1-40wt%
poly(2-ethyl-2-oxazoline) (PEOX). The blends showed good adhesion to substrates
such as PET (Hoenig et al., 1984).
In 1991, Mitsubishi Yuka Industrial Products Corporation asked for patent
protection for blends that comprised vinyl trimethoxysilane-grafted polyalkene
(e.g., PP, LDPE, EPR or EVAc) and ethylene-acryloyloxytetramethylpiperidine. The
water-erosslinkable blends were used to manufacture weather-resistant crosslinked
polyalkene pipes for outdoor applications (Ohnishi and Fukuda, 1993).
In 1992, Union Carbide Chemicals & Plastics Technology Corporation disclosed
polyethylene blends having toughness and elastic recovery comparable to those of
plasticized PVC. The blends comprised at least 50 wt % of a copolymer of ethylene
and either butene or hexene (LLDPE, density = 880-915 kg/m3 , MI ~ 1 dg/min,
long chain branching (LCB) = 0.5-1.5 long chains/1000c, M w > 200 kg/mol) and at
least 5 wt % of a copolymer of ethylene and either vinyl acetate or ethyl acrylate
(EVAc or EEA), and 5-30 wt % liqUid hydrocarbon oil. The blends showed essentially
no yield point, and behavior similar to that of crosslinked materials, although they
were not crosslinked (total strain recovery). These alloys were reported competitive
with plasticized PVC in terms of both physical properties and economics (Rifi, 1994).
The same year, Alcatel Alsthom Company announced blends that were specific-
ally developed for use as electrical insulation of high-voltage, direct current sub-
marine cables. The two-component blends were prepared by compounding PE, PP,
PS or their copolymers with 1-20 wt % of a copolymer prepared from either ethylene
or propylene and fluorinated vinyl ether. The extrudable, hydrophobic blends
showed good electrical insulation properties, mechanical behavior and stability.
They performed better than any previously available material for this application
(Barraud et al., 1993).
14.9 PE BLENDS WITH REDUCED PERMEABILITY

To reduce oxygen permeability through a PE film, either co-extrusion or blending
has been used. The latter method was first proposed in du Pont de Nemours' patent
application of 1979. Thus, 70wt% PE was blended with 20wt% of polyamide-66,
PA-66 and 3wt% of ethylene-fumaric acid graft copolymer. Films and containers
manufactured from the blends by the processing methods imposing biaxial stretch-
ing (film blowing or blow molding) showed overlapping lamellar structures. The
dispersed PA-66 lamellae caused high tortuosity for molecular diffusion, that
resulted in significant reduction of oxygen or solvent (e.g., gasoline) permeability.
In addition, the blends were found to have improved impact strength (Subramanian,
1980). In 1982 du Pont introduced Seiar™ blends. These pre-blended, slightly com-
patibilized dispersions of PAin PO matrix were specifically designed to reduce
permeability of a given PO resin when used as additives.
Electrically conductive PE blends 245
In a patent application deposited in 1990 by McGill University, blends of poly-
propylene with ethylene-vinylalcohol were described. The system was lightly com-
patibilized by addition of maleated polypropylene. The blends were extruded
through a specially designed sheet die that imposed biaxial stretching on the flowing
melt. The extruded sheets also showed overlapping lamellae of EVAI, and were
reported to significantly reduce permeability of gases or liquids (Kamal et al., 1992).
Obviously, the invention applies equally well to other blends.
Polyalkene blends with improved barrier properties were also disclosed in 1992 by
the Standard Oil Co. The system comprised 85-99.5wt% of a polyalkene (e.g., high
density polyethylene) and 0.5-15wt% of high nitrile polymer (e.g., an acrylonitrile-
butadiene copolymer). The alloys were found useful for molding plastic bottles,
automobile gasoline tanks, and other containers requiring limited or restricted
permeability to gases, vapors or organic liquids. These materials also showed
improved chemical resistance, strength and processability (Coffey et al., 1994).
14.10 ELECTRICALLY CONDUCTIVE PE BLENDS

Two types of electrically conductive polymer blends are recognized - those with low
conductivity used in applications requiring dissipation of the electrostatic charge
(ESD) and blends having high electrical conductivity (ECPB) comparable to that of
copper. Both types are discussed in more detail in Section 21.9.
Several electrostatic dissipating polyalkene blends have already been mentioned
in the text. For example, in the 1968 disclosure from Asahi Chemical PP or PE was
blended with polyvinylalcohol, 2 wt % PVAI. The resulting materials showed
improved mechanical, hygroscopic, and antistatic properties, useful for manu-
facturing films, fibers, tubes or coatings (Minekawa et al., 1969). In most cases, to
gain the antistatic performance PO must be blended with a polymer having -oH
groups, such as PVAl, EVAI, PVPh, Phenoxy, etc. The antistatic performance is
improved by the presence of moisture in the air. In some cases compatibilization
may be required.
Several polymers show high electrical conductivity (usually after doping), namely
polyacetylene (PAc), polyaniline (PANI), polypyrrole (PPy), polyparaphenylenes
(PPP) or polythiophenes, e.g., poly-3-octylthiophene (POT). Since they are expensive
and brittle, blending is highly advantageous. The percolation threshold for uniaxi-
ally stretched fibers is as low as 1.8 vol %. At these low loadings, provided that the
resin is well dispersed, compatibilization is rarely needed.
Electrically conducting polymer blends were described in a series of patent
applications deposited in the early 1990s by Neste Oy. The blends were prepared
in two steps. First, polyaniline (PANI) was blended with dodecylbenzene
sulfonic acid (DBSA) at a ratio of 1:10 to 3:1. The reaction product was heat treated
at 80-210°C for 10-12OOs. Next, the PANI salt was mixed with either PE, PP or PS,
and then melt-processed. The heat-treated reaction products as well as the blends
were soluble, Le., the systems were not crosslinked (Kama et al., 1994a).
A later patent disclosed modification of these blends. Thus, PANI was mixed with
protoning acid (sulfonic, phosphoric or carboxylic), and with metallic salt (oxides of
Zn, Cu, Mg, Ba, Ca, AI, Ti, Fe, Zr, Cd, Pb or Sn, with dodecylbenzene sulfonic acid).
The conductive material was mixed with either PE, PS, PP or ABS, and then molded
(Kama et al., 1994b). Electrically conducting plastic materials were also produced by
blending poly-3-octylthiophene (POT) with a matrix polymer (PP, PVC, PS, PE,
EVAc, PVC/ABS, etc.), introducing a doping agent (e.g., iodine), and then forming
the blend into the desired shape. The products were used for molding parts required
to screen out electromagnetic interference (EM!) or to dissipate the static charge
(Kokkonen et aI., 1994).
14.11 BIODEGRADABLE PE BLENDS

A large volume of polyalkene films is used in agricultural applications. For example,
in arid areas seedlings are being planted in fields covered with dark PO films, whose
role is to prevent excessive water evaporation. In advanced countries the film plays a
dual role, preventing excessive moisture loss as well as eliminating the necessity of
weeding, thus saving on the manual labor or costs of weed killers. However, there is
a problem with the collection and disposal of the large volume of the plastic film
after harvest. Thus, an ideal film should protect the field as long as it is needed, then
disintegrate under the influence of either UV irradiation or microorganisms. The
biodegradable blends are discussed in Section 21.11. Here only polyethylene blends
of this type will be summarized.
In 1990 three component biodegradable blends were disclosed. They comprised a
synthetic polymer (e.g., PS, PE, PP, EPR, NR, SBR, PI, PB or CA), a natural polymer
'(e.g., cellulose or starch) and an attacking agent. The latter agent was either bacteria,
fungi and/or enzymes used at a concentration of about one weight percent per
weight of the natural polymer (Guttag, 1992, 1994). The same year a patent applica-
tion from Fully Compounded Plastics disclosed, biodegradable blends prepared
from LOPE, starch and an acrylate copolymer (Willett, 1992). Starch-based blends
were also patented a year later by ETH-Ziirich. The compositions were prepared in
two stages. First, starch was esterified by reacting it with maleic anhydride, then the
ester was blended with polyalkenes, 1G-90wt% of either PE or PP, and 1-35wt%
acrylic copolymer, comprising ethylene, methylacrylate and maleic anhydride at
weight ratios 80-95: 5-15:0.2-1. In the following patent, uni- or multilayer films of
starch/HOPE blends (described in the first patent) were prepared by draWing them
uni- or bi-directionally, with draw down ratios :s 7. The films showed biodegrad-
ability and improved mechanical properties (Tomka, 1992; Tomka et ai., 1993).
In 1991, Ciba-Geigy Corporation patented a method of stabilization of commingled
polymers. Thus, blends of recycled thermoplastics recovered from domestic and
commercial waste, comprising 55-75wt% PE and/or PP, 5-25wt% PS,5-15wt%
PVC, G-10wt% of other thermoplastics and 3-20wt% compatibilizer, were stabil-
ized against light and thermo-oxidative degradation by addition of O.l-D.5wt% of
sterically hindered phenol(s) (e.g., pentaerythritol ester) and phosphite(s) (e.g., tris
(2,4-di-t-butyl) phosphite), at ratios 10:1 to 1:10 (Pauquet et ai., 1994).
In 1992, the University of Minnesota, invented biodegradable interpolymers, hav-
ing the domain sizes of 0.01-100 J.Lm. The blends were produced by reactive blending
1-95wt% of a synthetic polymer having suitable functional groups (e.g., PS, PE, PP,
TPU, PEST, PA, etc.), with 5-99;wt% of a biopolymer (e.g., carbohydrates (pre-
ferred), proteins or lipids). For example, either starches or proteins were blended
with either a maleated ethylene-propylene copolymer (EPR-MA) or styrene-maleic
anhydride (SMA). The blends were water-insoluble, with good mechanical proper-
ties, and limited water absorption. They could be extruded or molded into a variety
of shapes, films or foamed boards (Vaidya and Bhattacharya, 1994).
The same year, Ecostar International asked for patent protection for multicom-
ponent, biodegradable blends. These materials were obtained by mixing a polar
polymer (TPU, PS, PO, EVAc, EVA!, EAA, EMAc, EMAA, EMAc, PVAl, EVACO,
EBAc, PMMA and PEG), a biodegradable natural polymer (polysaccharide), less
than 15 wt % of a fatty acid peroxide or hydroxy peroxide, 0.01-D.2 wt % benzophe-
PE/PA blends 247
none, O.l-Q.5wt% ferric hydroxy stearate, 0.005-0.1 wt% copper stearate and hind-
ered phenol stabilizer (benzenepropanoic acid and 3,5-bis(l,l-dimethyl ethyl)-4-
hydroxy octadecyl ester). The resulting blends showed good mechanical properties
and were structurally stable until exposed to a suitable environment, where they
degraded by either chemical, photochemical and/or biodegradative mechanisms
into innocuous products (Chapman and Downie, 1994).
In 1993, The Industrial Technology Research Institute of Taiwan disclosed another
type of biodegradable polymer blend, containing 50-99 wt % of a synthetic polymer,
0.5-10 wt % of a peracid and starch. The synthetic polymer was selected from among
the following resins: PE, PP, PB, PMP, EPR, EVAc, EEA, EAA, PS, SBR, SBS, PVC,
PVDC, PVF, PVDF, POM, PEG, PPG, PVAl, PVAc, PMA, PEA, PA-6, PA-66, PET, CA
and their blends (the preferred resins were given as PE, PVC and PS). The peracid
contained at least one peroxycarboxylic group - COOOH) and another functional
group, such as carboxyl, aldehyde or cyanate, that increased the bio- and/or photo
degradability. The mechanical properties of the blends were reported superior to the
traditional ones that comprised a polymer, starch and unsaturated fatty acids or
esters (Hsu et al., 1994).
14.12 PE/PA BLENDS

The first information about blending polyalkenes with polyamides dates from 1958
when the Continental Can Company disclosed blends comprising 10-80 wt % PA-6
or PA-66 with either LOPE or PP. The materials, used to produce sheets, films, fibers
or bottles, had excellent processability, good printability and low liquid permeability
(Mesrobian and Ammondson, 1962). Interesting blends were disclosed in 1960 by the
Badische Anilin und Soda-Fabrik, BASF. Thus, it was reported that PE blended with
0.1-50% of a copolyamide (e.g., LOPE with 5wt% PE-PA-6 copolymer) showed
higher gloss, better transparency and elasticity, lower stress corrosion and reduced
permeability (Craubner et al., 1962).
By 1968, Gulf Research and Development established the reactive blending pro-
cedure. Thus, polymer alloys were prepared by blending PE or its copolymers with
lactams, then polymerizing these. Blends of PE with PA-6 were prepared for injec-
tion molding of articles with enhanced mechanical properties and reduced water
absorption (Hill et al., 1970). In a later patent from Bayer laboratories, PA-6 was
blended with LOPE or PIB using O.l-5wt% N-stearyl steramide as a dispersion
stabilizer. The injection molded articles showed high tenacity and excellent low
temperature impact properties (Gilch and Michael, 1970).
In 1971, Exxon Research and Engineering announced reactive grafting of PE or PP.
For example, an extruder was modified to make it possible to feed polymer, grafting
monomer and peroxide. As the deposited document described, PO could be grafted
with either maleic anhydride or acrylic acid (Steinkamp and Grail, 1976). These
acidified POs could be used directly as resins with improved paintability or adhe-
sion to metals and polar polymer. However, they also started a new series of POS
with polyamides or polyesters. First patent disclosure for this type of alloys dates
from 1972 when Imperial Chemical Industries announced blends comprising a
polyamide, 9Owt% PA, 9.5wt% PP and O.5wt% maleated PP as a compatibilizer.
The alloys showed higher maximum strain at break and notched impact strength,
than those of non-compatibilized blends (Davis, 1975).
In 1976, Shell Oil deposited a series of patent applications describing blends of
hydrogenated poly(styrene- b-butadiene) block copolymers (SEBS) with thermoplas-
tics. For example, 5 wt % SEBS was blended with polyamides (PA-6 or PA-66) for
improvement of the impact properties of the latter resins (Davison and Gergen,
1977). In later patents, PA-66, PE, PBT and PC resins were compounded with
SEBS. The compounds were claimed to have good impact properties (Gergen and
Davison, 1978). It has also been reported that at higher concentrations, where the
SEBS:thermoplastic weight ratio was close to 1:1, the blends showed cocontinuous
morphology, good dimensional stability and mechanical behavior, varying from
rubber-like to flexible. Good resistance to shrinkage and distortion was reported.
Blends of SEBS with PES, POM, TPU, PMP, fluoropolymers and acrylonitrile copoly-
mers were also disclosed (Davison and Gergen, 1980; Bull and Holden, 1977).
In 1981, Standard Oil disclosed that blends of 5-95wt% aromatic polyamide
(PARA) with 95-55 wt % PE show superior processability, elongation at break,
tensile and impact strength (Paschke et al., 1983). In a more recent Mitsui patent
application of 1989, PARA was blended with maleated-polyethylene (PE-MA)
or maleated polypropylene (PP-MA) and with hydrazine. The alloys were used for
the manufacture of sliding and/or electrical parts. Improved resistance to thermal
degradation when in contact with metals (e.g., Cu) was stressed (Yoshihara, 1990).
In several patents from 1982, that discussed the impact modification of PA-6,
better performance was observed for alloys comprising PA, an acidified elastomer
and PE. For example, first the EPDM was carboxylated, then PA-6 was reactively
blended with it and then PE was added (Unitika Ltd., 1983). Alternatively, 50-98
parts of PA-6 was blended with 1-40 parts of maleated EPR and 1-49 parts of PE or
EP copolymer. The alloys showed good flexibility and impact strength (Mitsui
Petrochemical Industries, 1984a). In 1983 Dainippon patented toughening of PA-66
by adding PE, maleated-PE and a compound containing two epoxy groups (Taguchi
and Mori, 1985).
In 1984, in a patent application from Mitsubishi Chemical Industries blends of 50-
90 wt % PA with PO were found to have good impact strength and water resistance.
In particular, 70 wt % PA-66 was blended with a PO mixture (comprising 82 parts PP,
6 parts HDPE and 12 parts EPR). The blends were easy to mold, and had good
mechanical properties even after 25 days of water immersion (Hasuo et al., 1985). In
1985 Mitsui Petrochemical Industries announced blends comprising 8Owt% PA-6
with 0.9wt% maleated EPR, 18wt% HDPE and maleated PP. The alloys showed
good rigidity and low temperature impact strength (Kondo and Tominari, 1987).
A new method for preparation of reactive POS was developed in 1992 in
Tonen Corporation laboratories. Thus, 100 parts PO (PE, PP or EPR) were grafted
with 0.01-20 parts of a monomer mixture comprising 5-50 mol % of glycidyl
(meth)acrylate and 95-50 mol % of either acrylamide, vinyl pyrrolidone, acrylic
acid ester and/or methacrylic acid ester. The grafted PO was then used as a modifier
for various engineering polymers, e.g., PA or PEST. The grafted PO also found
application as an adhesion improver for filled plastics (Teraya et al., 1994).
14.13 PE/PC BLENDS

To increase the rigidity of PE, the resins have been blended with several high-
modulus polymers, including bisphenol-A polycarbonate. For example, in a patent
application of 1960 (to Farbwerke Hoechst) it was disclosed that mechanical proper-
ties of polyalkenes were improved by blending them with O.5-SO wt % of PC. Blends
of LLDPE with 5 wt % PC showed improved impact strength of thicker sections,
modulus, stress crack resistance, hardness and HDT (Peters and Schuelde, 1963;
Dobkowski, 1980; Kunori and Geil, 1980; Dobrescu and Cobzaru, 1978; Gardlund,
1984). A year later, improvement of stiffness and flame resistance was disclosed by
PE/pC blends 249
the company when PE was blended with 5-50 wt % PVC (Rosenfelder and Rosen,
1962). In 1963 Esso Research and Engineering reported that PC also has a stabilizing
effect on PO against thermal de~dation (Schutze et al., 1972). Several impact
modified grades of PC (e.g., Lexan EM) are based on this technology (Freitag et
al., 1988, 1991).
At the opposite end of the concentration scale are the PC blends with a small
amount, usually 3-5wt% of a polyalkene. These compositions were also first
patented in the early 196Os, e.g., by Teijin Chemical (Yamada, 1963) or by General
Electric (Goldblum, 1963). The blends, formulated either for extrusion or injection
molding, were opaque, tough, stress-crack and solvent-crack resistant. To obtain
good dispersion of the antagonistically immiscible resins, the blending was carried
out at high temperature, above 290°C, using PE grades with a viscosity ratio at that
temperature of 7J(PE)/7J(PC) :s 0.6.
In several disclosures from General Electric Company, the beneficial effects of PE
addition to PC blends were described. Thus, in 1973 PC was blended with 0.01-
2wt% ABS and 4wt% PE (O'Connell, 1974). Four years later, PC was blended with
1-40wt% PE, and selectively hydrogenated chlorosulfonated butadiene-styrene
block copolymer (Bussink et al., 1978). In a 1980 patent application PC was blended
with 4.2 phr PE and 0.75 phr methyl-phenyl siloxane for good flowability and impact
properties after aging at high temperature (Rosenquist, 1982). In 1981 PC was
blended with 2 wt % LLDPE, and 4 wt % poly(butylacrylate-co-methylmethacrylate)
copolymer (O'Connell, 1983). The blends showed good processability, and an
absence of deposition during molding. The re-processed moldings showed
high impact strength and lack of embrittlement. In disclosures dating from 1982,
70-99 wt % PC, was blended with 0.5-20 % LLDPE and 9-45 wt % ABS (or ABS with
polysiloxane containing Si-H bonds, as in US Pat., 4,393,161). The alloys showed
good processability, thermal stability, weldline strength, and high notched impact
strength (Liu, 1983a, 1984b; Overton and Liu, 1984; De Van Abeelen and Munck,
1983).
During the following year, additional PC blends with PE were announced by the
company. Thus, PC was blended with either 6 wt % PP and 3 wt % LLDPE, or with
15wt% SBR and 5wt% EEA. Good processability and impact strength were
reported. The alloys showed improvements in the environmental stress cracking
and weldline strength. In 1983 GEC patent applications, PC Lexan™ was blended
either with 3 wt % LLDPE and 7 wt % ethylene-ethylacrylate copolymer (EEA) for
improved thick section impact and weldline strength, or with 10 wt % SEBS, 6 wt %
EEA and 2 wt % LLDPE for improved resistance to environmental stress crazing and
cracking (Overton and Liu, 1984).
A patent deposition of 1979 described reactive blending of PC with O.5-40phr
ethylene-I-butene copolymer (LLDPE) and 0.05-1.5 phr maleated LLDPE. The alloys
showed good, independent of thickness, impact strength (Mitsubishi Chemical
Industries Co., 1980).
In another series of disclosures dating from 1981, several blends of PC were
described. Thus, PC was blended with ethylene-glycidylmethacrylate copolymer
(EGMA) to improve the impact resistance, or with PE, acrylic and butyl elastomers
to enhance the impact and solvent resistance (Sumitomo Chemical Co., 1982, 1983).
The same year blends of 80-97 wt % PC with 1-10 wt % PE and 1-5 wt % SEBS were
prepared. The alloys showed improved processability, appearance, and good resist-
ance to solvents, heat and impact (Idemitsu Kosan Co., 1983). Two years later the
company disclosed blends comprising 20-94.6 wt % PC, 0.2-15 wt % PE, 5-50 wt %
PET and 0.2-15wt% acrylic impact modifier (MBA) as AcryIoid™KM. The alloys
were reported to have good resistance to solvents and high weldline strength (Endo
and Ishii, 1984). The following year, PC blends either with O.5-7wt% PE and acrylic
rubber, or maleated-PO were developed (Idemitsu Petrochemical Co., 1983a,
1984). In 1991 the company disclosed blends comprising branched polycarbonate
(l-99wt% bPC) with polymers selected from the group PET, PBT, styrenics (HIPS,
ABS, SMA), PA-6, PA-66, PE, PP and TPE (acrylic rubber, butyl rubber, EPDM or
SBS). These patents described the resulting alloys as materials having excellent
processability, solvent and impact resistance as well as good mechanical behavior
(Kozakura et al., 1992, 1994).
Also in 1981, to improve PC performance the following blends were described: (1)
to improve the impact strength, PC was to be blended with either PE, PP, or PMP
and acrylic rubber: (2) to introduce gasoline resistance and low temperature
impact strength PC was blended with either acrylic or hydrocarbon rubber (viz.
BR, EPR, EPDM, IR) and PO, and (3) to improve the low temperature impact
strength PC was blended with either a modified PP and HDPE, or with isobutene-
isoprene rubber (butyl rubber, IIR) and an acrylic elastomer (Teijin Chemicals, 1982a,
1983a). It has been observed that better toughening can be achieved using either EPR
or EPDM with either LDPE or HDPE. The mixture is easier to disperse into finer
particles into another resin, viz. polypropylene or an engineering polymer,
thus resulting in better processability, reproducibility and performance (D'Orazio
et al., 1982).
14.14 PE/PPE BLENDS

There are many patents describing blends of polyphenylene ethers (PPE) with
usually a small amount of PE. Owing to antagonistic immiscibility of these resins
the two-component PPE/PE blends do not have commercial importance. However,
since PPE is miscible with polystyrene the PPE/PE blends can readily be compat-
ibilized by addition of styrene-ethylene as either a block or graft copolymer. Poly-
alkenes are incorporated into the PPE blends mainly to improve chemical and
solvent resistance. Examples of these blends are listed below.
In a patent application of 1965, impact strength and crack resistance of PPE was
improved by blending it with polyalkenes, e.g., 3-5 wt % PE. Homogenous blends
were obtained by repeated extrusions (General Electric Co., 1966; Gowan, 1968). Five
years later, the company announced PPE blends with either SBR or HIPS, and PE.
The materials showed improved processability, mechanical properties and impact
strength. Heat stability of these resins was enhanced by addition of phosphite ester
and Sn mercaptide, or CdS, ZnS and ethanolamines (Summers et al., 1972).
At the opposite end of the concentration range, there are blends developed for
improved rigidity of PO. In these systems high modulus engineering resins are
dispersed in PO matrix, playing a role of organic, low density fillers. For example,
in 1973 Polish Institute of Chemical Industry announced multicomponent blends
comprising PE, up to 35wt% PP, up to 15wt% PDMS and 5-35wt% of either PPE,
PA-6, PC, PET or Phenoxy. The blends were injection molded to give products with
good processability, rigidity, impact strength, and long life under sterilization either
in boiling water or by irradiation (Plochocki et al., 1978, 1979).
Addition of a styrenic compatibilizer to PPE/PE blends has been a common
feature for a number of patents. For example in General Electric disclosures of
1973 and 1976, PPE was blended either with 4Owt% PS, hydrogenated styrene-
butadiene-styrene copolymer (20wt% SEBS; Kraton™GX1) and 1.5wt% PE (Haaf,
1979), or with 20wt% HIPS, 5wt% SEBS and 3wt% PE (Haaf and Lee 1978). The
PE/PEST blends 251
blends had excellent impact strength, good solvent resistance and aging character-
istics. These were the first uses of SEBS in PPE blends.
In a 1982 disclosure, PPE was blended with 10wt% hydrogenated SB block
copolymer, Shellvis™50, and 10wt% LDPE (General Electric Co., 1984). It is worth
noting that since miscibility of PE with SEBS is better than that with SBR or HIPS, the
improvement of performance of the latter PPE-blend was to be expected. Similarly,
1wt % of PE was incorporated into PPE blends disclosed in 1974 by Mitsubishi Gas-
Chemical (Yonemitsu et al., 1976), and 1wt% LLDPE was added to PPE blends with
HIPS and SEBS, as described in a BASF patent of 1984. The alloys showed high
impact strength, enhanced solvent resistance and HOT (Hambrecht et al., 1986).
General Electric disclosed in 1988 multicomponent blends: PPE/HIPS/SEBS/PE,
which had particularly high flexural modulus and HOT, as well as good weather-
ability (Ting, 1990). Three years later the company patented PPE blends with 0.75-
6.0wt% high-molecular-weight HOPE, to give non-dripping compositions for injec-
tion molding. The material was prepared in a two-step blending - first compounding
5-70wt% HOPE with a matrix resin (styrenics), then adding the pre-blend to PPE
(Bopp and Balfour, 1993).
14.15 PE/PEST BLENDS

The first aromatic polyester blends with PO were announced in 1965. Thus, blends
of polyethyleneterephthalate with O.5-SOwt% polyethylene or its copolymers,
were described. The blending was found to Significantly improve impact strength
(Glanzstoff A.-G., 1967). In du Pont's patent, also deposited in 1965, PET was blended
not with PE but rather with poly(ethylene-co-acrylic acid) copolymer, 5-1SOphr
polyethylene ionomer, as Surlin™. The blends showed high toughness and low
mold shrinkage (Cope, 1969).
In 1972, Teijin announced blends of poly(ethylene-2,6-naphthalenedicarboxylate)
with medium density polyethylene (l-SOwt% MOPE) and/or polypropylene. The
blends were mainly processed by injection molding, giving dimensionally stable
parts with good impact properties (Tokai and Sakai, 1973). Also in 1972, Allied
Chemical Corporation disclosed blends comprising PET, O.5-30wt% oxidized and
carboxylated polyethylene and optionally 2-70wt% glass fibers. The blends were
molded at 275°C. The products showed high impact strength (Segal, 1973).
In 1982, several patent applications from General Electric described polybutylene-
terephthalate (PBT) blends with either elastomers or polyalkenes. The materials were
developed to improve impact strength of PBT. In the first patent, PBT was blended
with polybutadiene (lOwt% PB), 5wt% LLDPE and 5wt% Pc. In the second
deposition, PB was replaced by acrylic rubber, as Acryloid™ KM 653 (Dieck and
Kostelnik, 1983; Agarwal, 1983). In the third, lo-90wt% PEST (e.g., 39wt% of either
PBT or PET) was blended with 5-65wt% PC and 0.1-20wt% LLDPE (Boutni and
Liu,1983).
Also in 1982, Goodyear Tire and Rubber Company applied for a patent describing
PET blends with O.5-lOwt% LLDPE. Addition of PE was reported to increase the
crystallization rate of PET, thus on the one hand making it possible to shorten the
molding cycle, and on the other hand enhancing the mechanical properties and
solvent resistance of the moldings (Smith and Wilson, 1984).
In 1991, du Pont de Nemours disclosed compatibilized PET blends with 5-20 wt %
polyalkenes (e.g., PE, PP, glycidylmethacrylate-modified PO, vinyl- or acrylic-grafted
PO). The blends were reinforced by incorporating 5-150 phr glass fiber. The materials
had high heat and moisture absorption resistance (Mukohyama, 1993). The same
year Enichem described blends comprising 70-30 wt % PET with a second
polymer selected from polyamides, polyalkenes (e.g., 30-70wt% LOPE, HOPE) or
their mixtures. The blends were compatibilized by an epoxidized-ethylene
copolymer, e.g., 5-30 % ethylene-ethylacrylate-glycidylmethacrylate (EEA-GMA)
as Lotader™ AX from Norsolor. The reactive compounding was conducted in a
twin-screw extruder. The materials showed excellent mechanical and impact
properties, especially the impact strength and tensile elongation (Natarajan et ai.,
1993, 1994).
In 1992, General Motors Corporation revealed blends comprising S0-90wt%
HOPE, 10-30wt% PET, a polyester elastomer (being a block copolymer of n-butyl-
terephthalate with ethyleneglycol and propyleneglycol5-3Owt% Hytrei™4074) and
I-Swt% of a mixture of two aromatic phosphites. The alloys showed improved
impact strength and flame resistance, as well as low permeation to gasoline (Abu-Isa
and Graham, 1993).
The same year, Teijin announced blends comprising S5-80wt% PBT, 10-30wt%
PC and modified polyolefin (10-20 wt % mPO). The latter resin was selected from
PE, PP or EPR, modified by grafting it with either 0.05-1S wt % glycidyl methacrylate
(GMA) and/or 0.1-2 wt % maleic anhydride. The alloys showed good processability,
in extrusion or injection molding. The moldings had excellent toughness, rigidity,
strength, dimensional stability and flexural modulus (Fujie, 1993).
14.16 PE/POM BLENDS

Owing to the simplicity of the polyoxymethylene (PaM) chain, the resin is difficult
to compatibilize. Thus, without compatibilization only small amounts of paM in PE,
or PE in paM, can be incorporated. However, compatibilization is possible if the
added modifier is able to form hydrogen bonding with paM macromolecules, or if
POM chain-ends are appropriately modified. As it will be evident from the following
text, ethylene-vinyl alcohol (EVAI) or thermoplastic polyurethanes having appro-
priate structure have been found suitable to compatibilize paM with po.
In a Canadian Industries Limited patent application of 1963, improved melt flow
properties, processability and extrudate appearance over that of neat LOPE were
reported for blends comprising LOPE with a small amount, l-lOwt% paM. The
blends also showed higher modulus and abrasion resistance (Rudin and Schreiber,
1964b).
Five years later, Sekisui Chemical announced that polyalkene blends, 100 parts of
either PE or PP, with amorphous ethylene copolymer (5-100 parts EVAc), and 1--80
parts of either paM, PMMA, PS or styrene-methylmethacrylate copolymer (SMM)
can be extruded into paper-like films (Yamamoto et ai., 1971).
In 1970, Hoechst announced paM blends with I-S wt % PE, EVAc, PEG or another
polymer giving dispersed particles with diameter 0.1-0.5 I-£m, and a small amount
(less than O.5wt%) of compatibilizing talc. The bends showed good processability,
impact resistance, hardness and stiffness (Burg et ai., 1972).
In Asahi Chemical Industry patent disclosure of 1972, paM was blended with
EVAc and HOPE. The resulting alloys were found to give abrasion resistant, glossy
moldings, having high elongation, excellent impact strength, dimensional stability
and high environmental stress cracking resistance (Ishida and Masarnoto, 1974).
In a patent application deposited by du Pont de Nemours in 1990, paM was first
blended with 20wt% TPU, then 20wt% of a third component (either PA, LLOPE,
PP, PBT or PET) was added. The blends had good toughness, impact strength,
elongation and recyclability (Flexman, 1992).
PE/Specialty Resin Blends 253
14.17 PE/SPECIALTY RESIN BLENDS
Since most specialty resins are high performance polymers that must be processed at
high temperatures, blending them with PE is limited. In most cases only a small
amount of PE is added to improve processability and surface appearance of the
specialty resin.
In 1966, General Electric disclosed that addition of 0.~5wt% polyalkenes (PE or
PP) and optionally other additives improved processability of polyarylene polyether
sulfone (PAES). Furthermore, the chemical and solvent resistance, as well as impact
strength was significantly enhanced (Gowan, 1969). The following year, Imperial
Chemical Industries announced blending of polyarylsulfone with polyalkenes
(either polyethylene, polypropylene, butyl rubber, EPR or EPDM). The resulting
materials showed improved melt flow, as well as solvent and impact resistance
(Hart, 1971).
Phillips Petroleum in the patent application of 1985 described polyphenylene
sulfide (PPS) blends with polydimethylsiloxane (0.1-25 parts PDMS), 0.01-5 parts
trialcoxysilane and 0.0~20 parts of either PE or PP. The blends had improved
processability and impact strength (Liang, 1987). Six years later, Bayer also dev-
eloped PPS blends with 0.~50wt% PE (and glass fiber and/or wax when needed),
compatibilized by addition of about 1 wt % of aromatic nitr<rcompound. The alloys
showed good impact performance (Kohler et ai., 1992).
Similarly, in 1980 polyarylamideimide. (PAl, as Torlon™ 4000 T) was blended with
a small amount of PE to give material with significant improvement of moldability,
and surface smoothness (Toray Industries, 1981b).
In 1988, Mitsui Petrochemical Industry deposited a patent describing blends of
polyalkenes with polyoxycyanoarylene (POCA). The alloys were compatibilized
using an ethylene-co-glycidylmethacrylate copolymer (EGMA). They showed excel-
lent moldability, impact strength and thermal properties (Hashimoto et ai., 1990).
More recently, British Petroleum Company patented PE (Rigidex™ or Innovex™)
blends with liquid crystal polyester (0.01-5.0wt% LCP) to give materials with good
melt processability, low viscosity and reduction of the specific energy during com-
pounding (Alder et ai., 1993).
15
Polypropylene
There are three types of polypropylenes on the market: amorphous (aPP), isotactic
(PP) and syndiotactic (sPP). Atactic aPP is a waxy substance and of little commercial
value. The commercially known PP is 90-95% isotactic - its production started in
1957. The metallocene polymerization of sPP was patented by Fina in 1986, and in
1992 Sumitomo Chemical began small scale production of this resin. Several other
companies such as Exxon Chemicals, Hoechst, Mitsui Petrochemicals and Petrofina,
also have pilot plant capability for production of sPP. The advantage of sPP over
isotactic PP is that the tensile modulus of sPP is fivefold higher than that of PP
(Kaminsky, 1992), and even when sPP specimens have modulus lowered by 50%
they show twice as large impact strength as that of PP. Furthermore, sPP has a lower
melting point than the isotactic variety [Tm (sPP) :=::: 133°C, Tm (PP) :=::: 165°C] which
facilitates processability.
Isotactic polypropylene is brittle, especially at temperatures below its glass transi-
tion temperature of O°c. This brittleness is related to the coarseness of the spherulitic
morphology. The fracture mechanics of the resin shows the predominant crazing-
cracking mechanism, in which the unstable crazing leads to crack propagation
(Kinloch and Young, 1983; Friedrich, 1983). In consequence, the discovery of PP in
1954 resulted in an immediate search for methods of improvement of its low
temperature impact behavior. These activities started in the late 1950s by blending
PP with polyethylenes or elastomers, then by co-polymerizing it with ethylene and
dienes into EPR and EPOM (Hogan and Banks, 1953, 1955). The first blends of PP
with polyisobutylene, PIB, were patented in 1958.
Blends of PP with PE, EVAc, PC and other polymers soon followed (Plochocki,
1978). In 1963 Standard Oil blended PP with 3-50wt% sPP. The blend was reported
to have excellent impact strength at low temperature, and freedom from surface
crazing upon repeated flexing (Emrick, 1966). Three years later, Chisso Corporation's
patent described PP blends with 3-30 wt % aPP. The alloy was also reported to have
good impact strength at low temperature (Tanahashi and Kojima, 1970).
The other reason for blending PP was to improve processability. As early as in the
1970s extemallubricants were used to enhance extrusion throughput. For example,
in a Bayer patent application of 1979 PP blends with 5wt% POMS were described.
The blending not only improved processability, but also the impact strength and the
elastic responses (Grigo et al., 1980).
Another early modification of PP involved grafting it with acidic monomers. This
approach opened several new vistas for the resin application. Presence of the acidic
groups improved adhesion to metals and polar polymers as well as enhancing
PP/PE blends 255
paintability. After neutralization, the presence of ionic groups engendered tempera-
ture-sensitive crosslinked structure, thus it improved impact strength and maximum
strain at break. However, most importantly from the perspective of this book, the
modifications made it possible to develop successful blends with polar polymers
such as polyamides, polycarbonates and polyesters.
In 1971, Exxon Research and Engineering disclosed a method of reactive grafting
of polyalkenes, either PE or PP, during extrusion. As the deposited document
described, PO could be grafted with either maleic anhydride or acrylic acid (Stein-
kamp and Grail, 1976). It is worth recalling that the advantages of maleation have
been known since the early 1960s - in 1963 Sinclair Petrochemicals commercialized
Cadon™, a copolymer of styrene with maleic anhydride. The first alloys of PP with
polyamides (e.g., 9Owt% PA, 9.swt% PP and O.swt% maleated PP as compatibil-
izer) were disclosed by ICI in 1972 (Davis, 1975).
In 1991, 3i Research Exploitation Limited disclosed a general method of polyal-
kene modification. Thus, a polymer was mixed with a monomer containing a
polymerizable group and at least one functional polymer-modifying group and a
free radical generator. For example, polypropylene or ethylene-propylene copoly-
mer, PP or EP respectively, was blended for 15 min in an internal mixer at 180°C in a
ratio of 90:10 with monomer selected from: HAEB, 2-hydroxy-4-(,B-acryloyloxy-
ethoxy)-benzophenone; AOTP, 4-acryloyloxy-2,2,6,6-tetramethyl piperidine;
TEPAA, tetraethylene pentamine monoacrylate; lMVS, vinyl trimethoxysilane;
AETS, ,B-acryloyloxyethyl trimethoxy silane; VBA, 4-vinylbenzoic acid; DBHBA,
2,6-di-t-butyl-4-hydroxybenzyl acrylate; or HVPB, 2-(2'-hydroxy-5'-vinyl phenyl)
benzotriazole. The simultaneously formed polyacrylate and an acrylic-grafted copo-
lymer of PP resulted in finely dispersed blends that showed good printability as well
as use in blends with engineering resins (Scott and AI-Malaika, 1995).
In 1994, General Electric Company announced a new method of grafting PP with
an ethylenically unsaturated t-alkylcarbamate. The graft copolymers were
reported to react with carboxy- or epoxy-functionalized polyphenylene ethers
(PPE) or other polymers at relatively low temperature and under mild conditions.
These copolymers could be used to compatibilize PPE/PP blends (Campbell and
Presley, 1995).
The PP blends are discussed by considering first their blends with commodity
resins, then with engineering and finally with specialty resins. As is evident from the
volume of the patent literature, the most important blends of PP are those with PE,
with elastomers, and then with polyamides. An extensive review of PP blends was
recently published (Utracki and Dumoulin, 1995).
15.1 PP/PE BLENDS

Blends of PP with polyethylenes (PE) have attracted much commercial interest. One
of the reasons for adding PE to PP is to improve the low temperature impact
behavior of the latter resin. Marked differences in properties between PP blends
containing different polyethylenes have been reported (Utracki, 1989a; Utracki and
Dumoulin, 1995). Most of the PP/PE blends contain the traditional low, linear low or
high density polyethylenes. (LDPE, LLDPE or HOPE, respectively). However, blend-
ing with ultra low density PE (ULDPE, density = 890kg/m3) and with ultra high
MW HOPE (UHMWPE, MW ~ 1000 kg/mol) are also known.
The great majority of these blends are immiscible. The miscibility of PP with PE
depends very much on the molecular weight and molecular structure of the compon-
ents. Compatibilization of PP/PE blends can be accomplished by addition of an
256 Polypropylene
ethylene-propylene copolymer, EPR or EPDM, by reactive blending, or by post-
blending treabnent, such as by using chemical crosslinking, electron beam or
,-radiation. The reactive compatibilization is usually accomplished by addition of a
peroxide, with tight controls of the process conditions. The reaction leads to con-
trolled degradation of PP and branching or crosslinking of PE. Both reactive compat-
ibilization and irradiation may lower blend crystallinity (Utracki and Dumoulin,
1995).
Owing to immiscibility, PE/PP blends show a two-phase structure that may be
detrimental to blend performance at large strains. However, blending enhances the
crystallinity and results in improvement of the mechanical performance. Since
moduli are measured at small deformations, the effect of immiscibility is small. On
the other hand, the properties measured at large strains clearly show the effect of the
two-phase structure - the maximum strain at break is usually the most sensitive
measure of immiscibility. The compounding plays a significant role on blend per-
formance - an increase in mixing time or its intensity not only improves the degree
of dispersion but also increases the thermal and/or mechanical degradation
(Dumoulin,1988).
It has been reported that PE/PP blends when uniaxially drawn show interesting
enhancements of properties. The crystallinity of both polymers changes differently
and non-linearly with composition. The concentration dependencies of Young's
modulus and tensile strength at break show strong maxima (occurring at different
concentrations of HDPE, e.g., respectively at about 15 and 20wt%), exceeding
performance of the homopolymers (Vlasov and Kuleznev, 1995).
In a 1960 patent application, 5Q-95wt% PP (MW = 4 Mg/mol) was blended with
PE (MW = 1.6 Mg/mol) for high impact strength and low brittle temperature (Sun
Oil Co., 1964). In a Hoechst patent document, also deposited in 1960, PP was blended
with 5-70wt% LLDPE. The alloy had good mechanical properties at low tempera-
ture (Holzer and Mehnert, 1963). Blends of PP with linear low density polyethylene
(LLDPE) were patented by Phillips Petroleum (Martinovitch and March, 1963) and
by Esso Research and Engineering (1963). In the latter document, PP was blended
(without compatibilization) with 2D-40wt% LLDPE, to give materials with high
impact resistance and low brittleness temperature. It is worth stressing that there
is a great variety of LLDPEs with different structures, chemical compositions and
molecular weight. Some of these polymers show enough thermodynamic interaction
with PP that compatibilization is not necessary. Several examples of such behavior
have been reported in the patent and open literature. In general, lowering the
molecular weight of PP (e.g., from melt index, MI = 1 to 4) was found to significantly
improve the fracture behavior of the uncompatibilized PP/LLDPE blends (Dumou-
lin et al., 1984).
However, in most cases to obtain good fracture properties, the blends of PP
with PE must be compatibilized. In 1961 the first patents on PP/PE compatibilized
by addition of EPR blends were disclosed by the Imperial Chemical Industries, ICI.
The resulting blends had improved low temperature brittle point and Izod impact
strength (Rayner et al., 1964; Crawford and Oakes, 1963, 1966). The following year,
Hercules Powder Company (Lehane, 1964) and Union Carbide Corporation Gayne,
1966) also disclosed blends comprising 5Q-96wt% PP, with 2-25wt% PE and
2-25wt% of either EPR or PIB. The use of EPR as a compatibilizer for PP/HDPE
blends was also described in 1966 by Asahi Chemical Industry (1969a). Here, to
improve the low temperature impact strength, PP was blended with a small amount
of high density polyethylene and EPR. In a patent application of 1966, high impact
strength PP blends were obtained by blending the resin with 15 wt % EPR and
PP/PE blends 257
15 wt % PE (Sumitomo Chern., 1968). In a sense, this method of PP IPE compatibili-
zation became a standard one, especially after commercialization of the ethylene-
propylene elastomers.
In 1963, Canadian Industries Limited discovered that the impact properties of
polyethylene (HOPE, LOPE or LLOPE) blends with PP can be improved by incor-
poration of an ethylene-propylene-diene terpolymer (EPOM) (Schreiber, 1966). A
year later, Esso patented blends of PP with varying amount of PIB and LOPE.
Blending was found to give marked improvement in the tear strength and impact
(Esso Research and Engineering Co., 1964). The patent application dating from 1965
by Asahi Chemical Industry described blends of PP with polybutadiene (5-15wt%
PB) and a linear polyethylene (2-15wt% of either LLOPE or HOPE). The blend
showed good balance of properties (Aijima et al., 1969).
Another interesting method of compatibilization of PP IPE blends, was described
in an early du Pont de Nemours patent document. The deposition of 1963 outlined
the general principles of compatibilization - the two blend ingredients were to be
grafted, one with a monomer having a basic group and the other with acidic ones,
then blended. For example, PE was modified by grafting it with methacrylic acid,
and PP with dimethyl amino ethylmethacrylate. The materials blended at a ratio 1:1
showed excellent mechanical properties (Langworth, 1967).
In a 1968 patent deposition from Hoechst, EP-block copolymers were used (Leu-
gering and Schaum, 1970). In an Exxon document deposited 8 years later, PP I LOPE
blend was compatibilized by addition of 2-22wt% EPR (Huff, 1978). The blending
was done in two stages, with the toughening elastomer being cured before a second
part of PP was added. The resulting material had good mechanical, low temperature
impact and optical properties. In 1969 Sumitomo Chemical claimed good improve-
ment of mechanical properties for blends comprising PP, EPR and 5-30wt% of
either hexene- or octene-type LLOPE (Shirayama et aI., 1972). In 1977 Sumitomo
Chemical announced blends comprising PP with 5-20wt% LOPE and 1-15wt%
EPR. The blend showed excellent transparency and good mechanical perfonnance
(Oita et al., 1978).
Another important step in the historical evolution of PP IPE blend technology was
the introduction in the late 1960s of the reactor-blending method. For example, in a
patent deposition of 1969 Showa Denko described a two-step process - first PP or its
copolymer, e.g., poly(pentene-co-propylene), was reactor-blended with ethylene-
butene, or ethylene-pentene copolymer then the product was melt blended with
the required amount of PP. The method provided materials with highly improved
perfonnance (Yamazaki and Fujimaki, 1970). In 1974 Hoechst disclosed reactor
blending of PP with PE and EPR, to give alloys with high impact strength, especially
at low temperature (Strametz et al., 1975). The modified Ziegler-Natta catalyst made
it possible to copolymerize diverse aIkenes, by living a-alkene polymerization
(Kontos et al. 1962; Kontos, 1964, 1968). The direct reactor blending of PE/PPIEPR
resulted in what became known as reactor-grade thennoplastic polyaIkene (R-TPO),
commercialized in 1979.
To bypass the need for compatibilization, in 1973 BASF disclosed simple, two-
component blends comprising 50 wt % PP with HOPE. The resins had matched melt
flow index, to ascertain the cocontinuity of phases that resulted in good flowability,
weld-line strength, surface quality, respectable mechanical properties and low tem-
perature impact strength (Moorwessel et al., 1974). The method is general and, as
several patents quoted in this book will show, it can be applied to any two-compon-
ents blends. However, as the value of the thennodynamic binary interaction para-
meter increases, the interfacial tension coefficient rises, and the rate of phase
258 Polypropylene
coarsening increases - the degree of dispersion in the blend may be so unstable as to
affect the blend performance. Thus, an addition of judiciously selected compatibil-
izer may lead to significant amelioration of blend behavior. This is particularly
important in the case of blends with antagonistically immiscible polymers, such as
PP/PA.
In 1979, Exxon announced a sequential blending of PP with EPR, then with PE that
.resulted in cocontinuous morphology. The compatibilized alloys showed excellent
impact and mechanical properties, superior to those observed for blends with a
particulate dispersion (Huff, 1980).
One of the first uses of PP/PE blends as a rigid engineering material was described
in a patent application from the Polish Academy of Sciences in 1973. Thus, PE was
blended with less than 35 wt % PP, not more than 15 wt % PDMS and 5-35 wt % of a
rigid engineering resin selected from PPE, PA-6, PC, PET, Phenoxy or their mixtures.
The blends were used for injection molding of products with good processability,
rigidity, impact strength, and long life under sterilization in boiling water or by
irradiation (Plochocki et al., 1978, 1979).
With time the PE/PP blends started to be increasingly complex. Four-component
blends, comprising PP, LDPE, HDPE and an EP-block copolymer, were developed in
1982 for films with good modulus, tear strength and sagging properties (Shin-Kobe
Electric Machinery Co., 1984). Two years later, Mobil Oil Corporation similarly
announced blends comprising LLDPE, lQ-45wt% LDPE, PP and/or 2-15wt%
EPR. The blends had high modulus and clarity (Bahl et al., 1985).
With new PO prepared by means of the single-site metallocene catalyst, new needs
and possibilities for blending emerged. Thus, in 1991 Exxon Chemical asked for
patent protection for blends comprising SOwt% PP, 1~50wt% LLDPE and a com-
patibilizer - low molecular weight plastomer (ethylene-butene copolymer). The
blends were reported useful for melt-spun or melt-blown fibers or fabrzics (Bartz
et al., 1993a). The following patent from Exxon disclosed blends that were heat-
sealable at 100°C. These materials comprised 30-70 wt % ethylene-a-alkene co-
polymer prepared using a metallocene catalyst, VLDPE or Plastomer™ (with density
88O-915kg/m3 ,MI = 1.5-7.5dg/min, Mw/Mn ~ 3.0 and Tm = 6O-100 oq, and 7~
3Owt% propylene-a-alkene random copolymer (with 88-100 mol % of propylene).
The blends showed good processability, resistance to tearing and tensile strength.
They were found particularly useful for manufacturing packaging films, tubes and
trays (Mehta and Chen, 1994).
15.2 PP /pm BLENDS

The first, patented by Montecatini in 1958, PP blends were with polyisobutylene
(5-20 wt % pm). The formulations were developed to enhance the low temperature
mechanical properties (especially flexibility and impact strength) of the new PP
resins (Ranalli, 1958; Schramm, 1960). The same year, blends of 25-40% pm with
low density polyethylene were also patented by Esso Research and Engineering
(Briggs et al., 1958). In a BASF patent application of 1961, O.5-40wt% pm (having
narrow molecular weight distribution) was used (Merkel and Cramer, 1963).
According to the early claims, pm was miscible with either PP or LLDPE. The
miscibility and the elastomeric character of PIB could impart low temperature
flexibility, improved transparency and strength. Blends of this type available on
the market include, from BASF, Lupolen™ a 250 or, from Paxon Polymer Company,
Pax-Plus™. The alloys usually contain about equal amounts of the ingredients (PO/
pm ~ 1:1). They are flexible and resistant to stress cracking. They also show good
PP blends with other polyalkenes 259
water-vapor properties, and are UV-resistant. They were formulated mainly for
extrusion, injection or blow molding. The weld-line strength, resistance to warpage,
and shrinkage depend on processing conditions. The PP/PIB blends are used for
general-purpose films, boil-in bags, medical over-pouches, industrial sacks and
liners. The blends compounded with carbon black serve as over-wraps for manu-
facture of tarpaulins, photographic films and papers as well as in a variety of out-
door applications (weatherability of the clear grades is poor).
15.3 PP BLENDS WITH OTHER POLYALKENES

Commercial, isotactic polypropylene, (PP) was reported miscible with atactic poly-
propylene (aPP) and polybutene-1, (PB; Romankevich and Frenkel, 1980; Lohse,
1986; Lohse and Wissler, 1991). In both cases, the miscibility is limited to the
amorphous phase of PP resulting in lower glass transition temperature. As shown
in Figure 15.1, addition of aPP to PP was found to systematically decrease the
melting point. The dependence can be described by the empirical relationship
T m (aPPIPP) = T m (PP) - 0.32365w + 0.0013393u1; for 0 ::; w ::; 80 wt %
Thus, an amorphous polyalkene (aPP or PB) may be considered a plasticizer for PP,
improving its low temperature impact strength. Alternatively, especially in blends of
PP with either LLDPE or HOPE, these resins can be used as compatibilizers. For
example, in a patent application of 1965 from Asahi Chemical Industry, blends of
PP with a linear polyethylene, 2-15wt% of either LLDPE or HOPE and 5-15wt%
BR, were described. The blend showed good balance of properties (Aijima et al.,
1969).
In 1985, Daicel Huels deposited a patent describing blends containing 100 parts
of polyalkene and 0.1-100 parts of polytransoctanamer (PTa). In particular, PP
blended with 9 wt % PTa was found to have five times higher Izoo impact strength
at -40 °C-23°C than neat PP (Kita and Hashimoto, 1987). In 1987 Sumitomo
Chemical applied for patent protection for blends of PP with polyoctadecene
Melting point of PP/aPP blends

475
465
455 L -_ _--'- ..I-_ _-----I. --'-_ _- - '
o 40 80
w (wt% aPP)
Figure 15.1 Melting point depression of isotactic polypropylene (PP) caused by incorporation
of atactic polypropylene (aPP).
260 Polypropylene
(POD). The alloys were found to show temperature-sensitive transparency (thermo-
chromic effects) (Tanaka et ai., 1988).
In 1991, Exxon Chemical developed blends of 55-90wt% PP with PB, and option-
ally withi;T to lOwt% of low-MW poly (Q-alkene-co-ethylene) an organometallic
Plastomer . The latter resin formed small pockets of amorphous material within the
crystalline matrix of PP, thus improving its spinnability. The alloys were found
useful for the manufacture of fibers and nonwovens, with good hand and tensile
strength (Bartz et ai., 1993b). Similarly, 2 years later, Shell Oil Company disclosed
polyalkene blends that contained at least 90wt% PP (MI < 20dg/min), less than
lOwt% of PB (MI > 45dg/min), less than lOwt% of a poly(l-butene-co-ethylene),
PBE (comprising 5.5 mol % ethylene, and MI = 1-400dg/min), poly-I-butene and
0.1-1 wt% of standard additives. The blends showed significantly improved (in
comparison with PP) processability, impact strength and optical properties (Hwo,
1994).
15.4 PP/ELASTOMER BLENDS

Blends of PP with elastomers constitute a large and commercially important class of
resins. To facilitate discussion of the evolution of technology the blends will be
reviewed in the following categories: PP with rubbers, PP with thermoplastic alkenic
elastomers (TPOs), PP with chlorinated polyalkenes, PP with styrenic elastomers
and PP with acrylic elastomers.
15.4.1 PP/rubber blends

The butadiene-styrene (SBR) or butadiene-acrylonitrile (NBR) elastomeric graft
copolymers were found to be particularly valuable for impact modification of PP.
The latter resin has been usually blended with 5-20 wt % of one of these copolymers.
The alloys were reported to have advantageous properties for blow molding of
bottles free from brittleness and stress cracking. In later patents, EPR, BP and pm
were used with a dicarboxylic acid (Shell International Research Maatschappij N. V.,
1962, 1963). In 1961 a patent document from Firestone disclosed PP blends with
linear polybutadiene (BR, Reid and Conrad, 1962). The same year, blends comprising
75-95wt% PP with at least two uncured rubbers (e.g., PB and SBR) were described
as having very high notched Izod impact strength at low temperature (Dow Chemi-
cal Co., 1963).
In Esso patent applications of 1958 and 1960, PP was blended (using a two-roll mill
at 138-157°C) with 5-SOwt% of chlorinated butyl rubber (CBR) in the presence of a
non-peroxide curative (e.g., oxides or sulfides of Zn, Cd, Mn, Fe or Ph). The dynamic
vulcanization resulted in materials useful for high tensile strength applications
(Gessler and Haslett, 1962). In a later patent, PP was blended with butyl rubber
(Esso Research & Engineering Co., 1962). In the applications dating from 1959 and
1960, PP was blended with 5-20wt% of rubbers to obtain materials suitable for blow
molding of impact-resistant bottles free from stress cracking.
In a series of patent applications dating from 1976, Monsanto disclosed
dynamic vulcanization of several systems, such as (1) 6Owt% PP with 4Owt% BR;
(2) 35-85 wt % EVAc with PE or PP; (3) chlorosulfonated polyethylene rubber,
~ 50wt% CSM, with either PE or PP; or (4) PP with EPDM. These co-vulcanized
blends showed excellent toughness, elongation, impact strength, a wide range of
Shore hardness, and dimensional stability (Coran and Patel, 1978; Coran et aI., 1978).
In later patents, a compatibilizing block copolymer was also used. The compatibil-
PPlelastomer blends 261
ization nearly doubled the blend tensile strength and increased its elongation at
break by a factor of four (Coran and Patel, 1978, 1979, 1981, 1982a).
15.4.2 PPIEPR or EPDM blends

As the molecular dynamics demonstrate, owing to the presence of few disruptions
of the tactic sequence, the crystallizing chains folds into lamellae with the non-
crystalline part of the chains forced in between these structures (Kavassalis and
Sundararajan, 1993). The crystallinity in polymers is only partial, dependent on the
chain structure, crystallization conditions and frequently on the temperature. By
analogy with the block copolymers, the idealized polyalkene elastomer would
have a structure consisting of soft and rigid blocks. In the case of the ethylene-
propylene copolymers (EPR) the first type of blocks should comprise random
sequences of ethylene and propylene monomers, while the required rigid domains
should be created by crystals of either PE or (preferably) PP segments, which play
the role of physical crosslinks.
It has been shown that it is not necessary for the amorphous and rigid domains to
be chemically bound to each other in the same polymer chain. In many instances it is
sufficient that these structures form a mixture, a blend of a thermoplastic resin and
an elastomer. Many EPR and EPDM thermoplastic elastomers show such a desirable
morphology. When dispersed in PP, these thermoplastic elastomers form an emul-
sion-like morphology that results in increase of viscosity over the log-additivity rule
(Figure 15.2).
Blends of PP with either EPR or EPDM provide the means for modifying the
crystallinity of the rigid component, thus for adjustment of properties, as well as the
PPIEPR blends
7
l
5
1'----------'- -'- .L.- ----' ---'
o 40 80
w (wt % EPR)
Figure 15.2 Viscosity--<:oncentration dependence for polypropylene blends with ethylene-

propylene copolymer. The initial sharp increase may indicate limited miscibility.
262 Polypropylene
economy. In most blends, the elastomer forms a dispersed phase. Additives, such as
carbon black or sterically hindered amines (HALS) are recommended for protection
against UV. The blends are characterized by high stiffness, high softening tempera-
ture, excellent low-temperature modulus and impact strength, dimensional stability,
low shrinkage, good mechanical properties in a wide range of temperatures, from
-40 to 150°C, ozone resistance, dynamic fatigue and abrasion resistance, as well as
high tear strength.
To facilitate compounding of EPR into PP a small amount of PE can be added
(D'Orazio et al., 1982). The PP/EPR or EPDM blends show good processability. The
morphology shows better stability under high stress forming conditions if the
elastomeric phase is slightly crosslinked (Dao, 1982, 1984). Even without crosslink-
ing, as evident from the data in Figure 15.2, the viscosity-concentration dependence
has a positive deviation from the log-additivity rule, indicating an emulsion-like
morphology, i.e., it is more difficult to extrude the blends than one could expect
from the neat resin properties. The blends can be processed by all the methods
used for PP, e.g., injection molding, extrusion, thermoforming (e.g., ~umTM from
Ferro Plastics), compression-, blow-, or transfer-molding (e.g., Vestolen from Hills
A.-G.), and calendering (e.g., Oleflex™ from Showa Denko). The formulations with
poor flow are extruded, blow molded, or compression molded at the melt tempera-
ture of ~ 250 0c. For injection molding, easy-flow molding compounds are used
at high screw speed, melt temperatures of 220-260 °C and mold temperatures of
~ 60 0c. The holding pressure is usually high, applied for a long time. The mold
shrinkage is less than that of PP by 0.2-0.3%. The orientation and warpage are also
smaller. The scrap is reusable.
Numerous commercial PP/EPR blends are known, such as Buna™ (Hulls),
Dutral™ TP (Himont), Epcar™ (RF. Goodrich), Epichlomer™ (Osaka Soda Co.),
Epsin™ and Santoprene™ (Monsanto), Esprene™ (Sumitomo Chemical), Ferrocline™
(Ferro Corporation), GafplyTM (GAF Corp.), Intolan™ (International Synthetic Rub-
ber), Kelburon™ (DSM), Larflex™ (Lati), Levaflex™ (Bayer), Milastomer™ (Mitsui
Polychemicals), Nordel™ (du Pont de Nemours), Royaltherm™ (Polycast), Trilene™
(Uniroyal) and Vistalon™ (Exxon Chemical). Most blends are post-reaction mechan-
ically compounded, but some are reactor-made, such as Kelburon™ from DSM.
Reinforced and filled grades (containing glass fibers, talc, CaC03 or other mineral
fillers) are also available.
Over 200 applications have been found for these materials. For example, they have
been used in the automotive industry, in appliances, hardware and plumbing,
medical tubings, shoe industry, sports equipment, toys, cases etc. The automobile
industry uses almost 90% of the PP/EPR blends for fenders, wheel-arches, trunk
linings, mud flaps, dashboards, consoles, profiles, steering wheel trims, door
pockets, radiator grills, front parts, spoilers, door sill covers and rubbing strips,
cloth hooks and seat covers.
E. I. du Pont de Nemours & Company started production of ethylene-propylene
(EPR) and ethylene-propylene-diene copolymers (EPDM) in 1962 (Gresham and
Hunt, 1960). The first patent application for low temperature impact modification
of PP by compounding it with 1Q-60wt% EPR was deposited by Hercules Powder
Company in 1960 (Schilling, 1966). Two years later Shell patented reactor powder
blending of PP with 0.1-10wt% EPR (containing 2-25% ethylene) (Short, 1967).
In 1968, Sumitomo Chemical deposited a patent describing polyalkene (PP or PE)
blends with EPR and ethylene-acetoxybicycloheptene copolymer, to give resins with
increased impact and tensile strength, as well as good brittle resistance (Shirayama et
al., 1971). In the following patent, PP and EPR were dissolved separately then
PP/elastomer blends 263
blended, precipitated and processed. The blends showed a fine, unifonn dispersion
of the elastomeric phase/ resulting in superior mechanical properties (Asada et al.,
1972). However, owing to the costs/ flammability and environmental problems,
solution blending has not been accepted by the plastics industry.
The following year, Showa Denko developed reactor-blends of either PP or LLOPE
with an ethylene-butene or ethylene-pentene copolymer. The product was melt
blended with additional amounts of PP to give an alloy with improved perfonnance
(Yamazaki and Fujimaki, 1970). In the subsequent patent, EPR was blended with PP
to give alloys with enhanced mechanical perfonnance (Yamazaki and Fujimaki,
1972).
In 1971/ Uniroyal announced development of blends comprising 40-20 wt % PE or
pp/ with 6O--80wt% of EPOM, and either an ethylene-propylene-dicyclopentadiene
(47.5:47.5:5) or an ethylene-propylene-ethylidene-norbomene (61:35:4) copolymer.
The ingredients were masticated and partially crosslinked with peroxides or
sulfur keeping the gel content at 4~96%. The resulting alloys could be shaped into
articles with good properties without further vulcanization (Fischer, 1972). Blends of
PP with ethylene-5-ethylidene-2-norbomene-propylene copolymer (EPOM) were
described in a 1975 patent application from B. F. Goodrich Company. Injection-
molded specimens showed unexpectedly high tensile strength (Stricharczuk, 1977).
In patent applications dating from 1976/ Monsanto disclosed dynamic vulcaniza-
tion of several systems including PP with either EPR or EPOM. These blends showed
excellent toughness, elongation, impact strength, a wide range of Shore hardness,
and dimensional stability (Coran and Patel, 1978; Coran et al., 1978). These activities
resulted in commercialization of the dynamically vulcanized PP/ elastomer blends
under the trade name Santoprene™ by Monsanto Chemical. The resins are character-
ized by high toughness and a wide spectrum of perfonnance characteristics, such as
composition-dependent (S 3Owt% EPR) hardness and heat resistance. A year later,
in an application from Japan EP Rubber Company, similar systems were described.
Thus/ l0-60wt% PP was dynamically blended with EPR, and a peroxide-eontaining
polyalkene copolymer to give a master-batch that subsequently was blended with
60% EPOM, to give elastomeric TPO alloys that produced moldings with excellent
mechanical perfonnance (Yamamoto, A. et al., 1979).
An interesting, sequential method of compounding was described in a 1979 patent
application from Exxon Research and Engineering Company. Thus/ PP was first
blended with EPR then with PE. The blend had cocontinuous morphology resulting
in excellent impact and mechanical properties, superior to those observed for blends
with particulate dispersions (Huff, 1980). Owing to a large difference of viscosity of
the ingredients, the sequence of blending was of great importance.
Another modification of the PP/EPR blend technology dates from 1981/ when
Montedison announced blends comprising 100 parts pp/ 8-25 parts of an amorphous
EPR, and 2-10 parts of a crystalline EPR. The alloys showed good balance of prop-
erties and improved impact strength (Galli and Spataro, 1983). The same year, PP
was blended with maleated LOPE, EVAc and inorganic filler, to give materials with
good melt strength and rigidity (Idemitsu Petrochemical Co./ 1983). Similar effects
were reported a year later, in a patent document describing blends comprising 50-
90wt% pp/ ethylene-propylene block copolymer and talc, having particles with
diameters of ~20 J1.m (Chisso Corp./ 1984).
In 1984/ Japan Synthetic Rubber Company, deposited a patent application for
blends comprising 100 parts PP and ~70 parts of bimodal ethylene-a-alkene co-
polymer (EPR). The materials were reported to show high impact strength and good
mechanical properties (Makino et al., 1986).
264 Polypropylene
Five years later, Exxon announced PP blends with either butyl or halogenated
butyl elastomer, 21 wt % of either BR or CBR, 25 wt % EPDM and fillers. The dynam-
ically vulcanized blends showed high tensile strength (Puydak et al., 1990, 1992). The
following year Sumitomo Chemical patented thermoplastic elastomer powders for
slush molding, comprising PP, EPDM and/or EPR, mineral oil and polydimethyl-
siloxane (PDMS), all partially crosslinked by the dynamic vulcanization method. The
blends were pulverized at -40 °C, then used to manufacture parts for automobiles,
home appliances, sport goods, industrial applications, furniture, briefcases, and
large plastic forms (Hikasa et al., 1994).
In a 1991 patent application from du Pont de Nemours, EPDM was blended with
PP and an ionomer ethylene-methacrylate-zinc, glycidyl methacrylate-acrylate, or an
epoxy, to improve the scuff resistance (Dawson, 1993). The same year Exxon
Research and Engineering disclosed a new, large class of blends comprising a
semicrystalline polymer with another polymer or copolymer, and methods of their
preparation. The blends were reported to show enhanced interspherulitic and inter-
lamellar strength. The first resin should have higher crystallinity and crystallization
temperature than the second. As an example, ~99,9wt% PP was blended with
ethylene-a-alkene copolymers, stereo-block polypropylene or ethylene-propylene
copolymer, EPR (Lustiger, 1993).
In a 1992 document from Hoechst, impact-resistant isotactic polyalkene molding
compositions were described, The blends comprised 20-99 wt % isotactic poly-
propylene (PP) and 80-1 wt% isotactic ethylene-propylene elastomer (EPR), having
Tg < - 20°C. The isotacticity index for both components was at least 85%. The blends
showed good hardness and low temperature impact strength (Winter et aI" 1993).
In 1992, Shell Oil disclosed blends of PP with 10-SOwt% EPR (comprising 38--60%
ethylene). Both PP and EPR were products of gas phase polymerization. The docu-
ment specified that the intrinsic viscosity ratio of EPR and PP should be 1.1-1.3, and
the EPR's crystallinity not higher than 8%. The blend showed high impact strength
and reduced stress whitening (McCullough and Ficker, 1993),
The same year, Himont announced PP blends with random crystalline terpoly-
mers (comprising 96-85wt% propylene, 1.5-5.0wt% ethylene and 2.5-10wt% C4-8
a-alkene). The blends were used to manufacture strands of multiple monofilaments
or staple fibers with high resiliency and shrinkage, for pile fabric, textiles, geotextiles
or carpets. The carpet yam had a twist retention of over 30%, shrinkage on heat
setting at 143°C of at least 15%, and uniform shrinkage (Clementini et al., 1993). In
the following patent application from the company, non-woven textiles formed from
PP/EPR blends were described. The blends comprised 5-95 wt % PP (or an EPR with
::; 10mol% ethylene) and 95-5wt% of a polyalkene, selected from EPDM, EPR,
LLDPE, etc. The materials have been used in disposable personal hygiene products,
or protective clothing, with improved strength, drapability, softness and bonding
performance (Ogale and Strasinic, 1994).
In 1992, Mitsui Petrochemical Industries developed blends that comprised
4-methyl-l-pentene (98-70wt% PMP), polyisobutylene (1-15wt% pm having a
kinematic viscosity of 2-5000 cSt at 100°C) and polybutene-l (1-15wt% PB, having
30-50% crystallinity). The alloys were used to prepare food overwrap films, with
excellent heat resistance up to 190 °C, flexibility, tackiness and transparency (Nagase
et al., 1994).
In 1993, Advanced Elastomer System disclosed new thermoplastic elastomer
blends having improved low temperature properties. The systems comprised
lo--90wt% crystalline polyalkene (PP, PMP, poly-I-butene, poly-l-pentene, poly(3-
methyl-I-butene) and their blends), 9G-I0wt% alkenic partially crosslinked rubber
PP/elastomer blends 265
(EPDM, EPM, BR, NR, IR, halogenated butyl rubber, copolymers of iso-monoalkene
and para-alkystyrene), and 1-250 phr of a low-molecular-weight ester plasticizer
(e.g., isooctyl tallate or n-butyl tallate), capable of lowering the glass transition tem-
perature of both ingredients and improving the low temperature impact strength,
while maintaining the desirable properties of low compression set, high tear strength
and dynamic properties. The blends have been designed for manufacturing auto-
motive elastoplastic components and TPO goods that need to be used at tempera-
tures above -40°C (Ellul, 1994).
Since the 1980s metallocene catalysis has created a revolution in polyalkene tech-
nology. The new resins with distinctly different properties opened a new category of
blends. In 1989, Hoechst disclosed new types of PP/EPR/LLDPE reactor blend.
These were obtained with high yield using a chiral metallocene catalyst and an
aluminoxane. The preferred blends comprised 60-95 wt % of a crystalline isotactic
PP homo- or copolymer, produced at the first stage, and a random copolymer of
ethylene-propylene (with possibly another I-alkene) produced at the second stage, as
well as a partly crystalline polymer of the second I-alkene. The moldable blends
showed good flow properties and a very good low temperature impact strength
(Schreck et a/., 1994).
The first EPR blends with syndiotactic polypropylene (sPP), were disclosed by
Mitsui Toatsu Chemicals in 1991. The blends were transparent and had good low
temperature impact resistance (Nakanishi and Inoue, 1992; Asanuma et al., 1992).
Also in 1991, Mitsubishi Petrochemical described blends of EPR, EPDM or their
mixtures haVing a melting point of 35-55 °C, with a metallocene ethylene copolymer
(very low density polyethylene VLDPE with density 885 kg/m3 and Tm = 65-90°C) a
PP (or PP-block copolymers) and D-7phr talc. The blends showed excellent mold-
ability, surface appearance and hardness, as well as good impact resistance (Nishio
et a/., 1992a). The following patent application from the company, disclosed blends
that comprised 1-70wt% of metallocene homopolymer or a PP copolymer with less
than 10 mol % ethylene or C z-zo (both polymers having a polydispersity index of
Mw/Mn ~ 3), and 3D-99wt% of another polydispersed EPR copolymer having
Mw/Mn = 3.5-10. The blends were used for production of films having excellent
low-temperature heat sealability and blocking resistance (Fujita, T. et a/., 1994). It is
noteworthy that the low temperature heat sealability originates from the low melting
point of the metallocene copolymers, e.g., LLDPE or VLDPE.
The following year the company asked for patent protection for blends comprising
5D-97wt% PP (or a PP-block copolymer with ethylene-block), and 5D-3wt% of an
ethylene/C4--18 a-alkene copolymer (a-alkene content = IG-60wt%, density
913 kg/m3 obtained by using a metallocene catalyst and aluminoxane). These alloys
were found useful for molding automobile exterior trims, or parts of electrical instru-
ments. The alloys showed high moldability, improved impact resistance at room and
low temperature, and good balance of rigidity and impact resistance (Schichijo, 1994).
15.4.3 PP/chlorinated elastomer blends

In 1972, Tokuyama Soda Company developed PP blends with 4.5wt% amorphous
chlorosulfonated polyethylene (CSR). The blends, usually filled with a large amount
of CaS04, showed good mechanical properties (Shikata et al., 1973).
VEB Chemiekombinat Bitterfeld in 1982 disclosed blends composed of 94wt% PP
and chlorinated polyethylene (6wt% CPE). The blends had good processability and
gave moldings with good mechanical properties (Newe et a/., 1984). In a contempor-
ary application similar blends, PP with 5-40 wt % styrene-grafted CPE, were
266 Polypropylene
disclosed. The materials were also reported to give high modulus and impact
resistance (Chisso Corp., 1983).
In 1990, the Dow Chemical Company asked for patent protection for blends
comprising CSR mixed with either PP or ultra-low density polyethylene. The blends
were first partially vulcanized (e.g., using a derivative of 2,5-dimercapto-1,3,4-
thiadiazole), then dispersed within a thermoplastic CSR. Finally, an inorganic filler
(o-l00phr of MgO, CaO, CaC03 and/or Ti0:2) was incorporated. The formulations
could also be plasticized using 0-150 phr of trioctyltrimellitate. The resulting systems
showed good processability, hot-weld strength, interplay adhesion and crack
resistance (Ainsworth, 1990, 1994).
15.4.4 PP/styrenic elastomer blends

To this group of blends belong mixtures of PP with either styrene-butadiene rubber
(SBR), styrene-diene block copolymers (SBS or SIS), hydrogenated styrene-butadiene
rubber (SEBS), or with acrylonitrile-butadiene-styrene terpolymers (ABS, ASA or
AXS).
In the early days of PP blending, for effective impact modification the elastomeric
graft copolymers (SBR) were usually incorporated at a level of 5-20wt%. Interest in
these materials remains strong. The blends were found suitable for blow molding of
bottles free from brittleness and stress cracking. For example, it was reported in 1961
that blends comprising 75-95wt% PP with at least two uncured elastomers (e.g., PB
and SBR) showed high notched Izoo impact strength at low temperature
(Dow Chemical Co., 1963). In 1977 Daicel announced PP blends with 15-85wt%
ABS, and 0.5 wt % of either chlorinated polyethylene (CPE) or low-molecular-weight
polystyrene (PS) as compatibilizers (Kamosaki et ai., 1978).
At the other end of the concentration scale, in 1963, to reduce the melt viscosity
of ABS (and thus improve its processability), the terpolymer was blended with
0.5-15wt% PP (Shinji Iwai Fudow Chemical Co., Chisso Corp., 1965).
In 1967, blends of PP with 20 wt % styrene-elastomer block copolymer, SBS or SIS,
were disclosed. These materials showed greatly improved impact strength, without
adversely affecting the other properties (Japan Synthetic Chemical Industry Co.,
1971). Seven years later, Sumitomo Chemical announced reversed composition
blends of SBS with 30 wt % PP or 20 wt % HDPE. The blending resulted in improved
mechanical behavior (Tabana and Maki, 1976).
In 1970, Shell International Research disclosed PP blends with hydrogenated
either butadiene-styrene or isoprene-styrene block copolymers with 6-8 wt % SEBS.
The alloys were used to manufacture materials with good transparency and
high impact strength (Porter, 1972). Seven years later the company developed
blends comprising a mixture of PS with 10D-45wt% HIPS, blended with 2-30 phr
PP and 5-20 phr SEBS. The claims specified that the alloys had good impact
and flexural strength, as well as good retention of tensile yield stress in cottonseed
oil-oleic acid test (Holden and Gouw, 1979). In a 1980 patent application from
Sweetheart Plastics, the blends of PP with 24 wt % PS were compatibilized by adding
4wt% styrene-butadiene block copolymer (SBS) or a multi-block copolymer (SB)n'
The alloys led to moldings with good mechanical properties (Grancio et ai., 1981,
1983).
In 1992, Kanegafuchi Kagaku Kogyo deposited a patent for a broad range of
materials prepared in two steps. First, an elastomer (having low glass transition
temperature of :S 25°C, e.g., polybutadiene) was grafted and crosslinked with
5-60 wt % of vinyl monomer (that, when polymerized, gave a polymer with
PPlelastomer blends 267
Tg ~ 25°C, e.g., styrene or methyl methacrylate) to produce a core-shell copolymer.
Next, 0.1-100 parts of this copolymer was blended with 100 parts of a polyalkene,
e.g., PP, LOPE and/or HOPE. The blends (reinforced or not) showed excellent
processability, impact resistance, rigidity, surface properties etc. The improved
melt viscosity and tensile strength made it possible to use the blends in
extrusion, calendering, thermoforming, blow or injection molding (Aoyama et aI.,
1993, 1994).
Also in 1992, Himont disclosed compatibilized PP/SBR blends. The materials
comprised 9D-I0wt% PP (having Mw/Mn = 8--60) 2-40wt% of either SBR, SBS or
an acrylic elastomer, and ID-90wt% of PP grafted with styrene (and/or acrylonitrile,
methacrylate, etc.). The alloys could also contain ID-l00 phr of filler (e.g., CaC03,
silicate and their mixtures, having a mean particle diameter of 0.5-4.0 JLm). The
compounds were found useful as stand-alone structural materials (DeNicola and
Conboy, 1994).
15.4.5 PP/acrylic elastomer blends

Blends of PP with acrylic copolymers, having good strength and heat resistance were
claimed in 1987 by du Pont de Nemours. These were prepared by reactive processing
of 35.7wt% PP, an ionomer (ethylene-butyl acrylate-acrylic acid Zn salt, in ratio
65:30:5) and EBA-GMA (ethylene-butyl acrylate-glycidyl methacrylate in ratio
68.6:26:1.4) (Salbnan, 1988, 1989, 1992). A few years later, the company deposited
a patent describing modifications of these blends. The new alloys comprised 2D-
3Owt% PP, 3D-50wt% ionomer, 2-3wt% EBA-GMA and 25-35wt% uncrosslinked
elastomeric ethylene-propylene-I, 4-hexadiene (EPDM, having 6D-80 wt % ethylene).
The blends were found useful in applications where a wide range of temperatures
and abrasive conditions were encountered (Dawson, 1993).
In 1990, Sumitomo Chemical Company disclosed similar three-component
PP blends comprising: (1) 1-99wt% of either acidified-PP, its mixture with PP or
a mixture of PP with carboxylic acid-modified EPR; (2) 99-1 wt% of a maleated
polymer (e.g., poly(methylmethacrylate-co-styrene-co-maleic anhydride; and (3)
an epoxy-group containing copolymer [e.g., 0.1-300 phr of either ethylene-
methylmethacrylate-glycidylmethacrylate (65:15:20), or ethylene-vinylacetate-
glycidylmethacrylate (85:5:10)). The blends were used to mold car bumpers and
fenders. The products showed good stiffness and low temperature impact resistance
(Abe et al., 1994).
In 1992, Neste Oy announced a new method of polyalkene modification. For
example, particles of PP having diameter 1-6mm were first impregnated (by mixing
them at 100 °C for 45 min) with equal amount of vinyl monomer (selected from
(meth)acrylates, styrenics, vinyl chloride, glycidyl methacrylate, maleic anhydride,
acrylonitrile and divinylbenzene), and with 0.01-4.0 parts of a free radical initiator
(a peroxy initiator). During this period most monomer was absorbed. Next,
water and emulsifiers were added to the reaction vessel, and the reaction was
carried out for 8 h at ID-14O 0c. The alloys were recovered as free flowing, white,
homogeneous particles. Good adhesion between components in the extruded or
molded articles was achieved. These materials could either be used as basic
resins or as compatibilizers in blends with engineering polymers (Vestberg and
Lehtiniemi, 1994).
Also in 1992, Rohm and Haas announced similar modification of polyalkenes
(polymers or copolymers of ethylene, propylene, butylene, 4-methylpentene, and
their copolymers with l-alkenes, vinyls, (meth)acrylates - but preferably PP). Thus
268 Polypropylene
PP was grafted at a ratio 1:9-4:1 with 1-20wt% of (meth)acrylic acid and at least
3Owt% of styrene and/or alkyl- and/or halo-substituted styrene, methacrylic ester
and D-6O % of other comonomers (e.g., vinyl aromatic, ester). At the last stage, a part
of the acid groups was neutralized with non-polymeric counterions, e.g., 90%
methylmethacrylic, 5% butylacrylic and 5% methacrylic acid with Ca++ or Mg++
ions. The resulting PP-ionomer could be blended with other resins either during or
after manufacturing. The blends could be extruded into a desired shape either
directly or after pelletization. In either case, the blends exhibited high sag resistance
without increase of the melt viscosity. The PP-ionomer was used for spinning fibers,
that in turn were used for strapping, netting, slit tape, rope, twine, bags, carpet
backing, foamed ribbons, upholstery, rugs, pond liners, awnings, swimming pool
covers, tarpaulins, bristles, sutures, non woven fabrics, bed sheets, bandages, diaper
liners and other products (Hamilton and McCarty, 1994a).
The same year, biologically acceptable filaments were developed by the United
States Surgical Corporation. The materials were produced from simple, two-
component blends composed of 8O-9Swt% PP (Mw = 2DO-350kg/mol,Mn = 50-
180 kg/mol, MI = 2--6 dg/min), and an ionically crosslinked ethylene-methacrylic
acid copolymer (EMA). Fiber spinning was carried out at 180-250 °C, then the fibers
were stretched at 60-160°C with a draw-down ratio of 3-8. The fibers were used as
sutures (Liu and Brewer, 1994).
15.5 PP/PS BLENDS

Blends of PP with 3-30wt% PS or HIPS were developed in 1971 by Sumitomo
Chemical Co. The resins were extruded into soda-straw tubes with pearly luster
(Ogawa et al., 1973). Similar blends were announced 9 years later by Sweetheart
Plastics, Inc. However, in the latter patent, blends comprising 24 wt % PS and 76 wt %
PP were compatibilized by addition of 4 phr of either a styrene-butadiene block
copolymer (SBS) or a multi-block copolymer (SB)n to give alloys with good mechan-
ical properties (Grancio et al., 1981, 1983).
In 1977, Shell announced blends composed of PS with l00-4Swt% HIPS, further
compounded with 2-30 phr PP and 5-20 phr SEBS. The document claimed good
impact and flexural strength, as well as good retention of the tensile yield stress
(Holden and Gouw, 1979).
In a patent deposition of 1990 from Rutgers State University uncompatibilized
polyalkene/styrene blends were reported to show good mechanical properties. The
authors used recycled HDPE and/or PP blended with PS. The advantageous proper-
ties were achieved by ensuring the presence of cocontinuous morphology, through
judicious selection of relative rheological properties and concentration of the
ingredients. Thus, in the blends the PS concentration was:::::: 3Swt%, and (at 200 °C
and frequency 10 Hz) the shear storage modulus was G' 2: 10 MPa. The components
could be contaminated with minor amount of other resins. The blends were
recyclable (Morrow et al., 1994).
Blends with good processability, stress cracking resistance, impermeability to
water vapor and improved impact resistance were prepared by BASF in 1991 from
50-80 wt % PS or HIPS, 20-50 wt % PE or PP and 0.05-50 phr compatibilizer. The
latter was a non-symmetrical, linear tri-block copolymer of styrene and butadiene (or
isoprene), having a structure SI-D-S2 (SI, S2 =polystyrene blocks and D = polydiene
block, containing 5D-8Swt% styrene) where SI 2: S2. The blends were mainly used
for molding applications (Hoenl et al., 1993).
PPjEVAc blends 269
Recently, single-site metallocene catalyst technology has been used to make pre-
viously unattainable compositions such as random and block copolymers of syndio-
tactic polypropylene (sPP) with syndiotactic polystyrene (sPS) (Razavi, 1994). These
new copolymers can be successfully used as compatibilizers for the syndiotactic
resins.
15.6 PP lEVAc BLENDS

In a 1960 patent application, Monsanto disclosed the first blends of PP with ethylene-
vinylacetate (EVAc). These materials were prepared to improve dyeability, flexibility
and toughness of PP. Thus, PP was compounded in a Banbury-type mixer with
7 wt % EVAc. Several other ethylene copolymers were also listed (Holladay
and Salyer, 1969). The following year, Miliprint announced that addition to PP of
18-32 wt % EVAc or ethylene-ethylacrylate copolymer (EEA) improved its impact
strength, elongation and low brittleness temperature (Miller and Reddeman, 1962).
Similarly, the Mitsubishi Petrochemical patent deposition of 1964 disclosed improve-
ments of PP impact strength by blending it with 0.5-25 wt % ethylene-aliphatic
esters, e.g., EVAc (Sakata et al., 1968).
There are numerous blends comprising PP lEVAc combined with other polymeric
or reinforcing ingredients. For example, in 1968 Sekisui Chemical developed multi-
component blends comprising polyalkenes, either PP or HOPE, with 5-100phr
EVAc and 1-80 phr of either POM, PMMA, PS or styrene-methylmethacrylate
copolymer (as well as inorganic fillers) to extrude into paper-like films (Yamamoto
et al., 1971). A year later, Chisso disclosed blends comprising at least 70wt% PP with
at least 5 wt % each of EVAc, ethylene-vinylacetate-vinylchloride copolymer
(PVCAc) and HOPE, to give alloys with excellent low temperature impact resistance
(Kojima and Tanahashi, 1972). In a patent application of 1981, blends comprising PP,
maleated-LOPE, EVAc and inorganic filler were described. These materials also had
good melt strength and rigidity (Idemitsu Petrochemical Co., 1983). In a patent
application of 1982 from Exxon, 35wt% PP blended with SOwt% PIB and 15wt%
EVAc gave blends that were described as useful for films, moldings and extrusions
(Shulman, 1984).
In 1985, General Electric deposited a patent for multicomponent polycarbonatel
polypropylene blends with EVAc as a compatibilizer. The alloys that comprised
lO-96wt% PC, 2-90wt% PP and 2-35wt% EVAc showed excellent solvent resist-
ance (Giles and Hirt, 1986). The following year, Exxon announced that chlorobutyl
rubber (CR) was dynamically vulcanized with ethylene-vinylacetate copolymer
(EVAc) to give a thermally shrinkable product with exceptional resilience (Hazelton
and Puydak, 1986).
In a more recent patent to Aluminum Company of America, three-component
blends of PP with EVAc, and poly-2-ethyl oxazoline (PEOX) were described. The
blends comprising lo-90wt% PP, 5-60wt% EVAc and 5-50wt% PEOX were
claimed to be miscible (for this system true thermodynamic miscibility is doubtful),
with good mechanical properties and reduced ~ permeability, making them suit-
able as materials for an intermediate layer in recyclable, multilayered gas barrier
sheets for food packaging (Sanchez et al., 1991). The contemporary patent application
from McGill University described extrusion of PP blends with ethylene-vinylalcohol
(EVAI) and maleated polypropylene (PP-MA) that resulted in sheets having over-
lapping layer morphology, providing for reduced permeability by gases or liquids
(Kamal et al., 1992).
270 Polypropylene
In 1991, Minnesota Mining and Manufacturing Company (3M) disclosed new
radiation-resistant, heat-sealable blends, that were softer and tougher than similar
blends with crystalline polypropylene, PP. The preferred compositions comprised
(1) mesomorphous PP or its copolymers, and (2) either EVAc or ethylene-acrylic
acid copolymer (EAA; both in the full range of concentration 1-99wt%), and
polybutene (PB). Films were prepared by blending the ingredients, extruding the
blend, and quenching the extrudate. The resins were found particularly useful for
manufacturing medical goods (ostomy bags, drug delivery patch, medical tape etc.),
tapes, or packaging materials (Wilfong and Rolando, 1993).
In 1991, Tonen Corporation deposited a patent describing modification of living
polypropylene or ethylene-propylene random copolymer chains (prepared in the
presence of a catalyst consisting of an organic aluminum and a vanadium com-
pound) by reacting terminal groups of these polyalkenes with a (meth)acrylic deriv-
ative, to give a substantially monodispersed copolymer, suitable for further
compounding and blending. Vinyl-, allyl-, trimethylsiloxyethyl-, 2-trimethylsiloxy-
propyl-, N,N-dimethylaminoethyl-, N,N-diethylaminoethyl-, glycidyl methacrylate
or acrylic acid chloride were used (Koyama et al., 1995).
15.7 PPfPVC BLENDS

The first PP blends with polyvinylchloride were disclosed in 1961 by Dublon, Inc.
Thus, PP was blended with 5-50 wt % PVC to give materials suitable for extrusion or
milling (Rosenfelder and Rosen, 1962).
In 1963, high impact strength PVC formulations for pipes or electrical insulation,
were obtained by blending PVC with 5wt% of either PE or PP, and 5wt% methyl-
methacrylate-butadiene-styrene copolymer (Baer and Hankey, 1967). In a Kanega-
fuchi patent, 5-30 wt % of acrylonitrile-butadiene-styrene-methylmethacrylate
copolymer (ABSM) was used as compatibilizer (Himei et al., 1967). A year later,
Ethyl Corporation applied for patent protection for blends containing either PP,
PE, PS or SBR with 5-100 phr of ethylene-vinylchloride copolymer (VCE). The
blends showed excellent HDT, flame resistance, impact and tensile strength
(Montgomery, 1966).
In 1968, Sanyo Kako Company developed PP blends with PVC and either PMMA
or PC, to give layered, wood-like materials with good machinability (Yahata et al.,
1971a). The following year, Chisso disclosed blends comprising at least 70wt%
PP, and at least 5 wt % of either ethylene-vinylacetate-vinylchloride (EVAc-VC),
ethylene-vinylacetate copolymer (EVAc) or HDPE. The blends showed good low
temperature impact resistance (Kojima and Tanahashi, 1972). Compatibilized PVC
blends with 1-40 wt % PP were developed in 1982. The alloys showed good
moldability and high HDT (Unitika Ltd., 1984a).
15.8 PP BLENDS WITH OTHER COMMODITY RESINS

In 1965, Tokuyama Soda Co. disclosed PP blends with polypropylene glycol
(3-30 wt % PPG) or its copolymer with allylglycidyl ether. The compositions showed
excellent tensile and impact strength (Awaya and Isobe, 1968).
In 1968, Asahi Chemical Ind. Co. developed PO blends with polyvinylalcohol (2%
PVAI) to be used for manufacture of films, fibers, tubes and coatings. The materials
showed good mechanical, hygroscopic and antistatic properties (Minekawa
et aI:, 1969).
PP/engineering resin blends 271
15.9 PP BIODEGRADABLE BLENDS
The problems associated with biodegradability and the methods used to make PP
biodegradable are similar to those associated with polyethylenes. The biodegrad-
ability of these latter resins is discussed in Section 14.11. The general discussion of
biodegradability of polymer blends can be found in Section 21.11.
15.10 PP/ELECIRICALLY CONDUCTIVE POLYMER BLENDS

Blends of polyethylenes with electrically conducting polymers were described
in Section 14.10. A more general discussion of electrical conductivity of
polymer blends can be found in Section 21.9. Since in most cases the reviewed
patents specified PP as an alternative to PE, the information already given is not
repeated here.
15.11 PP/ENGINEERING RESIN BLENDS
15.11.1 PPIPA blends

In the category of polyamide/polyalkene blends one may distinguish three types. To
the first belong blends with a small percentage of PO, either acidified or not,
specifically developed for improvement of PA impact resistance (Section 16.2.1).
To the second belong alloys with high component ratio, varying from 2/3 to 3/2.
These rigid materials with PA usually being a matrix and PP the dispersed phase,
have been developed primarily to reduce the water absorption of PA and improve its
impact properties - the blends need to be compatibilized. To the third type belong
elastomeric blends (e.g., PA with EPR or EPDM) with a small amount of dispersed
PA added mainly to increase rigidity. These materials (vulcanized or not) show good
processability, enhanced modulus and solvent resistance, as well as good mechan-
ical performance.
In 1992, Tonen Corporation disclosed a new class of grafted polyalkenes to be used
as modifiers or compatibilizers for engineering polymers, e.g., PEST or PA, and as an
adhesion improvers for filled plastics. Thus, 100 parts PO (PE, PP or EPR), was
grafted with 0.01-20 phr of a monomer mixture consisting of 5-50 mol % of glyci-
dyl(meth)acrylate and 95-50 mol % of acrylamide, vinylpyrrolidone, acrylic acid
esters and/or methacrylic acid esters (Teraya et al., 1994).
Toughened PA blends
The reason for toughening semicrystalline PAis obvious. The methods for doing this
are also straightforward - the addition of 2-5 wt % of either a polyalkene, an elasto-
mer, an ionomer, an acidified copolymer or a glycidyl copolymer.
In 1975, Imperial Chemical Industries announced blends comprising 90wt% PA
with 9.5wt% PP, compatibilized by addition of O.5wt% of maleated-PP (PP-MA).
The blend had improved maximum strain at break and notched impact strength,
over the non compatibilized version (Davis, 1975). This was the first use of PP-MA as
compatibilizer.
Also in 1980, PAs were blended with polyalkenes and ionomers, such as PP and
Surlyn™. For example, 50-95 wt % PA-12, was blended with 5-59 wt % ionomer then
compounded with 5-50 parts of a polyester-amide elastomer. The molded materials
showed excellent impact resistance, good tensile strength, toughness and elongation
272 Polypropylene
(Toyobo Co., 1981; Daicel Chern. Ind., 1982c). In Dainippon's 1983 patent applica-
tions, polyamides were toughened by addition of PO, maleated PO and a compound
containing two epoxy groups. In most cases PA was either PA-6 or PA-66, and PO
was polypropylene (PP). The usual concentration range was 4O-6Owt% PP, with this
resin forming the dispersed phase (Taguchi and Mori, 1985). Similar PA/PO blends
were also patented by Standard Oil (1983) and du Pont de Nemours (Subramanian,
1983, 1984).
PA/PP rigid blends

One of the main reasons for developing this second type of PA blend with PO has
been the need to improve dimensional stability and to reduce water absorbency.
However, blending does not significantly alter the chemical nature of the PA chain,
thus its hygroscopicity - at equilibrium, the intrinsic water absorption remains the
same. Blends immersed in water for sufficiently long will absorb the same amount of
water per gram of PA as neat P A. Alloying PA with PO reduces the rate of water
migration to and from the blends (Utracki and Sammut, 1991, 1992). With proper
morphology the kinetics of the water absorbency and desorbency can be slowed by
at least one order of magnitude. The other advantage of these blends is their high
stiffness combined with good impact strength. As Figures 15.3 and 15.4 indicate, the
notched Izod impact strength at room temperature shows a reciprocal relationship
with the tensile modulus. The blends have good potential for commercial success
(Girard, 1990; Moody, 1992).
In most cases, alloying has been a two-step reactive process: (1) preparation of a
compatibilizer, and (2) compounding PP and PA with the compatibilizer. The most
frequently used (but not necessarily the best) method for preparation of a com-
30 1.5
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Figure 15.3 Effect of addition of 5 vol % of a compatibilizer to a blend comprising 65 vol %

polypropylene and 30 vol % of polY'f-caprolactam. MA, AA and EMAA stand for maleic
anhydride, acrylic acid, and ethylene-methacrylic acid copolymer, respectively. The numbers
that follow the copolymer acronym express the acidic functionality in mmol/kg (adapted from
Millhaupt and ROsch (1994».
30 1.5
IE
----IB----
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-10
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Figure 15.4 (e) Notched Izod impact strength at room temperature; (NIRT); (EB) Young's
modulus versus reciprocal diameter of the dispersed phase (lid) for blends comprising
65 vol % PP, 30 vol % PA-6 and 5 vol % compatibilizer (see Figure 15.3; adapted from Miilhaupt
and ROsch (1994».
patibilizer is maleation of PP in the presence of peroxides. Other acids or anhydrides

(e.g., fumaric, acrylic or methacrylic) may also be used. Other compatibilizers (such
as maleated PP wax, maleated styrene-butadiene-styrene, maleated styrene-
ethylene/butylene-styrene tri-block copolymer, maleated EPR or EPDM, ethylene-
acrylic ester-maleic anhydride-glycidyl methacrylate, or an adduct formed by
reacting the acidic copolymer with an oligoamide) have also been used. The pre-
paration of a compatibilizer as well as compounding the PA/PP alloys is carried out
during reactive extrusion in a twin-screw extruder (Nishio et aI., 1990).
Compatibilization may cause reduction of the blend crystallinity. Since the glass
transition temperatures of both resins, PA and PP, are Iowa decrease of the blend's
crystallinity may be detrimental to performance. For this reason, the extent of
compatibilization must be optimized and carefully controlled. It has been observed
that in blends comprising PA-6, PP and maleated-PP as a compatibilizer, the con-
centration of the PA-g-PP copolymer changes with the dwell time during processing
as well as with reprocessing (it doubled!). Since compatibilization involves addition
of a relatively large quantity, 4-12wt% of a compatibilizer, the blends may show
significantly increased viscosity and yield stress, complicating the processability, as
well as reduction of the crystallinity that lowers the performance. For the same
reasons, recyclability of PP/PA blends compatibilized by addition of PP-MA may
be difficult.
The first patent on non-compatibilized polyamide/polyalkene blends was depos-
ited in 1958 by the Continental Can Company. The document specified that to
improve processability, 10-80wt% of either PA-6 or PA-66, was to be blended
with either LDPE or PP. Sheets, films, fibers or bottles produced from this
material showed good printability, and low liquid permeability (Mesrobian and
Ammondson, 1962).
274 Polypropylene
In a patent application of 1979, 6Owt% PP was blended with 20wt% of either PA-
6 or PA-66, and with 20 wt % glass fibers. The reinforced, toughened alloys showed
superior tensile and impact strength (Asahi Fiber Glass Co., 1981). In 1984 Mitsubishi
Petrochemical disclosed impact resistant blends comprising 1-99 wt % PP and
99-1 % PA-6, compatibilized by addition of 3 phr of a maleic anhydride-grafted
EPR (Katsura, 1986).
In a 1988 patent disclosure from Atochem, a reactive two-step compatibilization of
PA/PP blends was described. Thus PP was first maleated then reactively blended
with PA. The reaction usually resulted in formation of about 12 wt % of PP-PA
copolymer, to act as a compatibilizer for the non-reacted resins (Glotin et ai., 1989).
In the contemporary Nippondenso patent, PA was blended with acidified PP
and glass fibers. Excellent water resistance, moldability, improved thermal dete-
rioration resistance and low temperature impact strength were claimed (Iwanami
et ai., 1989).
The role of core-shell morphology in PP/PA-6 blends was recently studied.
Reactive compatibilization of 70 vol % PP with 30 vol % PA-6 was conducted in the
presence of maleic-anhydride-grafted either EPR or SEBS elastomers (EPR-MA or
SEB5-MA). The morphology of the resulting alloys comprised PP as a matrix, in
which core-shell domains were dispersed. The core-shell copolymer had a rigid PA-6
core and soft elastomeric shell. The reaction between PA-6 and maleated elastomer,
followed by formation of an elastomeric interphase at the PP/PA-6 interface were
responsible for, on the one hand, enhanced PA-6 dispersion (domains as small as
150nm were observed), and on the other, for the synergism of properties. Compar-
ing the effects of the soft EPM-MA with the more rigid'SEB5-MA, it was found that
the latter copolymer was better suited for the PP/PA-6 blends. It not only improved
the impact strength, yield stress and toughness, but also it caused only a smaller
reduction of the modulus (Rosch and Miilhaupt, 1994).
PP/PNeiastomer biends
In 1980, Monsanto disclosed five-component blends comprising 65 parts of a nitrile
rubber, (NBR, polybutadiene latex grafted with styrene, acrylonitrile and butylacry-
late), 50 parts EPDM, 50 parts PP, 35 parts PA-6-PA-66 copolymer and 10 parts of
maleated PP. The alloys were reported to have excellent impact strength, high stress
at break and high elongation, good ductility and high gloss. The alloys were found to
be water resistant (Tokas, 1981; Coran and Patel, 1982).
In 1984, Mitsubishi Chemical Industries disclosed blends comprising 50-90 wt %
PA with modified PO (e.g., comprising 82 parts PP, 6 parts HDPE and 12 parts EPR).
The materials were reported to have good impact strength and water resistance. In
particular, 70 wt % PA-66 blended with PP gave easy-to-mold alloys with good
mechanical properties even after 25 days immersion in water (Hasuo et ai., 1985).
The following year, Mitsui Petrochemical disclosed blending 80wt% PA-6 with
18wt%"HDPE, 0.9wt% maleated EPR and maleated PP. The alloys showed good
rigidity and low temperature impact strength (Kondo and Tominari, 1987).
In 1990, Ferro Corporation patented multicomponent blends comprising 6D-
9Owt% of either PP or ethylene-propylene (EPR), 5-25wt% polyamide (PA-6,
PA-66, PA-6T61 or PA-46) and 5-25 wt % of a compatibilizing copolymer mixture.
The latter contained a vinyl aromatic hydrocarbon and an unsaturated mono-or
dicarboxylic acid (e.g., a terpolymer: 6D-94wt% ethylene, 5-40wt% ac~lic ester
and l-lOwt% of either maleic anhydride or glycidylmethacrylate, Latader ), SMA,
maleated-SEBS, maleated-EPR, MBA, ASA, etc. The blends may also contain
glass fibers and/or mineral fillers. They can be extruded, thermo-formed, calen-
dered, laminated, stamped, pultruded, blow-, injection- or compression molded, etc.
These recyclable blends are useful for automotive, electrical, electronics, building,
furniture, small appliances and other applications (Chundury and Scheibelhoffer,
1994; Chundury and Bitsch, 1994).
Two years later, the company disclosed further improvements to these blends. The
patent described blends of 7G-90wt% PE or PP, with 5-25wt% PA and 5-25wt%
of a styrene-maleic anhydride (SMA). The resins were compatibilized by addition of
1-25wt% of at least two compatibilizers selected from SEBS (Kraton G 1652),
maleated-SEBS, glycidylmethacrylate or a copolymer of ethylene, propylene, acrylic
ester, maleic anhydride, (e.g., poly(ethylene-co-acrylic ester-eo-maleic anhydride,
Lotader™ 6600, comprising: 62.5 wt % ethylene, 27 wt % acrylic ester and 3 wt %
maleic anhydride). The alloys were prepared at 250°C in a counterrotating twin-
screw extruder with length-to-diameter ratio of 28. The high impact strength blends
could also be reinforced by addition of mineral fillers and/or glass fibers. These
materials were found suitable for extrusion, blow-, injection- or compression
molding, calendering, thermoforming, in lamination or co-forming processes, and
could be recycled (Chundury, 1994).
In the 1992 patent from Shell Oil, a maleated PP (1-70wt% PP-MA) was blended
with polybutylene to form adhesives for bonding to metals and polar polymers, such
as PA, PET or PC (Lee et al., 1994).
15.11.2 PPIPC blends

In these antagonistically immiscible blends the morphology determines the blend
performance. Addition of polycarbonate of bisphenol-A (PC) to PP leads to enhance-
ment of PP crystallinity and to a small increase of the crystallization temperature.
When the concentration of the minor phase exceeds 10 wt % compatibilization is
necessary. Note that compatibilization is limited to the amorphous phase - it binds
the amorphous part of PP to amorphous Pc. At the same time, compatibilization
that changes the chain mobility may also affect the crystallization rate as well as
total crystallinity. Indeed, Significant increases of both the kinetics and the total
level of crystallinity by addition of a compatibilizer were reported (Liang and
Williams, 1991).
Blends of PP with PC are in an early stage of development. Several industrial
laboratories in Europe, Japan and in the USA are looking for the compatibilization
method that will make it possible to explore performance of these blends within the
whole composition range. At present, in analogy to PE/PC blends, only the two ends
of the concentration range have been found useful. For example, an addition of about
5 wt % of PP to PC was found to reduce its melt viscosity, thus to improve process-
ability (e.g., for injection molding). Similarly, blends of PC with a small amount of
PP showed increased impact strength (especially in thick sections), and reduced
notch sensitivity and mold shrinkage (Dobkowski, 1980). At the other end of the
concentration range, addition of about 10 wt % of PC to PP improved processability
of the latter resin, enhanced the product appearance, as well as its hardness, modulus
and impact strength (Idemitsu Petrochemical Co., 1983a, 1984).
Several patents that describe PC/PP blends having mid-range composition demon-
strate the need for good compatibilization. Different types of (co)polymers have been
tried, namely (meth)acrylic (co)polymers, styrene-(ethylene/butylene)-styrene tri-
block copolymer (SEBS) ethylene-vinylalcohol (EVAI), SEBS grafted with either
maleic anhydride or fumaric acid, EPDM grafted with styrene and acrylonitrile,
276 Polypropylene
maleated pp/ polystyrene containing oxazoline moieties, polybutyleneterephthalate,
a PP-PC-PP triblock copolymer, poly(propylene-g-styrene), poly(propylene-g-
styrene-g-acrylonitrile), poly(propylene-g-styrene-g-n-butylmethacrylate), poly(pro-
pylene-b-n-butylmethacrylate), etc.
In 1962/ General Electric Company deposited a patent application for a broad
range of PC blends, comprising a small quantity of either PE, pp/ PIB, EPR, ethy-
lene-acrylic copolymer, cellulosics, PA, PVAc or TPu. For example, blends of PC
with 8wt% polyalkene showed good resistance to fracture and cracking (Goldblum,
1963/ 1964). The following year, Esso Research and Engineering also disclosed PC
blends with PO, but at the opposite end of the concentration range - it was dis-
covered that addition of at least 0.05 wt % PC into PP had a stabilizing effect against
thermal degradation - the blends remained stable at 100 °c for at least 142 days, and
at 120°C for 90 days (Schutze et al., 1972). In 1974/ to improve abrasion resistance of
PC/ Mitsui Petrochemicals Industries blended it with 2 wt % pp/ and 3.5 wt % poly-
tetrafluoroethylene (Kishimoto, 1976).
In 1981/ to improve its impact strength, PC was blended with either PE, PP or
PMP/ as well as with a compatibilizing and toughening acrylic rubber. Another
patent from the company disclosed that to improve the gasoline resistance and
low temperature impact strength, PC was compounded with acrylic or hydrocarbon
rubber (e.g., BR, EPR, EPDM, IR) and a polyalkene, preferably PP. In addition, to
improve the low temperature impact strength of PC the resin was blended with
maleated PP and either HDPE, butyl rubber, or isobutene-isoprene rubber and with
an acrylic elastomer (Teijin Chemicals, 1982a, 1983a).
The following year, General Electric deposited a series of patents for PC/PO
blends. Thus/ for improved environmental stress cracking and weldline strength,
PC was blended with either 6 wt % PP and 3 wt % LLDPE, or with 15 wt % SBR and
5 wt % EEA. In later patents PP/ SBR, acrylic rubber, EPR or EPDM replaced LLDPE,
and lQ-45wt% Acryloid KM was used as a compatibilizer. Good resistance to
solvents and weldline strength were reported (Liu, 1984b; Overton and Liu, 1984).
The following year the company announced blends covering the full range of
compositions, Le., comprising 2-90wt% PP, ID-96wt% PC and 2-35wt% EVAc.
Even though EVAc is not a good compatibilizer for PC/PP blends, the alloys were
described as having good mechanical properties and excellent solvent resistance
(Giles and Hirt, 1986).
In spite of years of research, PC/PP blends have not yet the been commercialized.
However, it is noteworthy that in Japan there have been attempts to introduce
these opaque blends as thin/ high strength photographic papers for special applica-
tions.
15.11.3 PPIPEST blends

PP blends with thermoplastic polyesters (PEST) are in an early stage of development.
Most PEST/PP blends used today have been formulated within the low concentra-
tion region of the dispersed phase: PP in PEST or vice versa. However, in spite of
these activities, there is no commercial PP/PEST blend on the market.
PP is antagonistically immiscible with PEST, and when the concentration of the
dispersed phase exceeds 5-10 wt % compatibilization becomes necessary. As in the
case of PC/PP blends, the problem rests in finding a good compatibilizer/impact
modifier - it was observed that addition of maleated PP to PEST/PP blends does not
improve the performance. Maleated elastomers, such as maleated SEBS, EPR or
EPDM provide better performance. However, grafts with (meth)acrylates (e.g., gly-
cidyl methacrylate) not only give better performing alloys, but also a better re-use
value.
As has been the case for most other systems, historically the first PP/PEST blends
were used as a uncompatibilized mixture of the two resins at low concentration,
mostly of PP in PEST. For example, in 1971 Unitika Company announced blends that
comprised aromatic, amorphous polyesters, polyarylates or polyarylphthalates,
produced by polycondensation of iso- and terephthalic acids with bisphenol-A,
blended with not more than 3Owt% of either PP, polyacrylate rubber, EVAc or PE
(Koshimo, 1973; Koshimo et al., 1973).
In 1974, BASF announced blends that comprised polybutyleneterephthalate and
polyalkene (1D-3Owt% PP). These materials were found to have significantly
improved moldability as well as high electrical tracking resistance (Seydl and
Strickle, 1976). Six years later, PBT was blended with a small amount of polyalkene,
e.g., O.05-lOwt% of PP. The blends were reported to have improved electrical
insulation properties (Dainishiseika Color and Chemicals Mfg. Co., 1982).
In 1990, Tonen Corporation disclosed compatibilized blends spanning the whole
range of compositions, comprising 10090wt% PP, 9D-lOwt% polyethylenetere-
phthalate (PET) or polybutyleneterephthalate (PBT), and 5-30 phr of a polyalkene-
polyester graft copolymer (containing 10--80 wt % PET and/or PBT and 90-20 wt % of
poly(propylene-co-diene) grafted with unsaturated carboxylic acid or maleic anhy-
dride) having 0.2-5mol% carboxyl groups and M w = 8-140 kg/mol. The blends
showed excellent impact strength, flexural modulus, HOT and peel resistance.
They were suitable for molding interior and exterior parts of automobiles, parts of
various electric appliances etc. (Fujita, Y. et al., 1994). The following year Bayer
disclosed that PEST bearing phenolic hydroxy groups can be used to prepare
polyester-earbonates (PEC) that in turn may be blended with 5-95wt% of PEST,
PO or polysulfone (Ebert et al., 1993).
In a contemporary disclosure from Globe-Union, blends comprising 80-85 wt % of
a mixture of PET with PP (at a PET:PP ratios of40:6O-{j():40) and 1~20wt% maleated
hydrogenated styrene-butadiene block copolymer (SEBS-MA), showed improved
impact strength while maintaining tensile strength, elongation and flexural modu-
lus. Furthermore, recycled PP and PET with a relatively small amount of SEBS-MA
provided blends useful for molding battery containers and other automotive com-
ponents (Tekkanat et al., 1994).
Similarly, in 1991, Johnson Service asked for patent protection for blends
of recycled PET with recycled PP. Again, these two resins were blended with
1~20wt% maleated SEBS elastomer at a ratio located between 1:4 and 4:1, to give
rigid materials with good mechanical properties, suitable for moldings of batteries
and fuel cells (Tekkanat et al., 1993). The same year, du Pont de Nemours announced
blends comprising PET, ~20 wt % PO (PE or PP), and either glycidylmethacrylate-
modified PO or Vinyl-grafted PO. The blends were reinforced by incorporating
5-150phr glass fiber. The material showed high heat and moisture absorption
resistance (Mukohyama, 1993).
Also in 1991, Polyplastics patented moldable, multicomponent blends that
comprised 2-98wt% of a compatibilizing Na sulfonate-containing polyester (PEST,
e.g., PET or PBT with sodium dimethyI5-sulfo-isophthalate), 2-98wt% of an alkene
copolymer, e.g., maleated PP, polyamide (PA-6 or PA-66) and, optionally, 0-96wt%
PEST. The blends had fine dispersion with diameter of 0.05-1 J-Lm and high tensile
and impact strength (Tajima et al., 1994).
The follOWing year, Teijin disclosed blends of 55-80wt% PBT, with 10-20wt%
modified polyalkene (PE, PP or EPR modified with O.O~15wt% glycidylmethacry-
278 Polypropylene
late and/or 0.1-2wt% MA) and ID-30wt% Pc. The alloys showed good process-
ability. The moldings had excellent toughness, rigidity, strength, dimensional stabi-
lity and flexural modulus (Fujie, 1993).
Also in 1992, Himont announced blends comprising 2D-60wt% of an engineering
resin (either PPE, PA or PEST), 3D-65wt% graft copolymer of propylene with
styrene and a glycidyl moiety (e.g., the total concentration of styrenic and glycidyl
moiety monomers was SD-2oophr, with 0.1-20.0wt% of the glycidyl moiety
monomer in it), and 2-1Swt% of an elastomer (e.g., EPDM, SBS, SEBS or EPR).
The blends showed excellent flexural and tensile strength, and increased resistance
to delamination, indicating good interactions between the components. These mate-
rials were reported useful for molding large articles, such as auto parts, appliances
and motor housings (Okamoto et al., 1993, 1994).
15.11.4 PPIPPE blends

In spite of the title there are no two-component blends of PP with polyphenylene-
ether (PPE). These two polymers are antagonistically immiscible, and PPE alone is
virtually non-processable (its glass transition temperature is 210 °C, while it is
thermally stable only ~ IS0 o q. To get any reasonable performance out of a PP/
PPE mixture, first PPE must be plasticized with a polymer or copolymer that can
lower its T g, thus making the processing possible, and then the blend must be
compatibilized. As the examples below illustrate, PP has been used only in many-
component PPE blends, entering as one of several ingredients to improve solvent
resistance and processability.
In a patent application of 1986 Mitsubishi Gas Chemical described reactive
blending of maleated polyphenylene ether (PPE-MA) with maleated polypropylene
(PP-MA), styrene-grafted elastomer, glycidylmethacrylate copolymer and/or phe-
nylenediamine binder. The reactive blending resulted in alloys showing excellent
solvent resistance, good moldability, impact and mechanical properties (Togo et a/.,
1988). Two years later General Electric developed blends comprising PPE with at
least 50% PP and less than 20% SEBS. The alloys were reported to have high
modulus, rigidity, tensile strength and heat deflection temperature (Lee, 1990).
The following year, Sumitomo Chemical deposited a series of patents for blends
having excellent processability, heat resistance and mechanical properties. The sys-
tems comprised a semicrystaUine matrix polymer, 35-98wt% of a resin selected
from PP, PE, PA-6, PA-66, PBT, PET, paM, PPS or PEEK, 1-65wt% PPE forming a
dispersed phase, 0.1-50wt% of a compatibilizer, and reinforcing talc and/or glass
fibers. The compatibilizer was selected from maleated-EPR, a copolymer of ethylene,
Vinyl acetate and glycidyl methacrylate, and a monomeric maleic anhydride or bis(4-
phenyl isocyanate). The reactive blending was conducted in a high-speed twin-screw
extruder, specially designed for reactive processing. The alloys had PPE dispersed
in the form of nearly spherical particles with diameter O.OI-IO/-Lm. They could
be extruded or molded into a variety of parts for the automobile, electrical and
electronic industries (Nishio et al., 1988, 1994; Abe et al., 1988).
In 1988, the company also disclosed blends of 1-90wt% PPE with ID-99wt% of
modified polypropylene (PP grafted with styrene and unsaturated carboxylic acid or
its derivative, e.g., PP-PS-MA). To this mixture 1-50 parts (per 100 parts of PPE + PP-
PS-MA) of an elastomeric copolymer was added. The latter resin was selected from
ethylene-vinylacetate-glycidylmethacrylate copolymer (EVA-GMA), or styrene-
grafted EPDM or EPR. The alloys showed good rigidity, as well as high heat,
chemical and impact resistance (Furuta and Maruyama, 1990). Two years later, the
company disclosed blends comprising PPE, PP and polythiophenylene (PPS), com-
patibilized and toughened by addition of hydrogenated styrene-isoprene block
copolymers. The alloys were reported to have good heat, impact and solvent resis-
tance (Maruyama and Mizuno, 199Oa).
In 1990, Mitsubishi Petrochemical described blends that comprised 10-90wt%
hydroxyalkylated polyphenyleneether (e.g., PPE modified by glycidol or epichlor-
ohydrin) and 10-90 wt % of a resin selected from a modified polyalkene (PP either
maleated or grafted with glycidyl methacrylate), and either a polyamide (PA) or a
polyester (PEST). The blends could also contain unmodified PPE, PO, styrenics,
additives, reinforcements etc. The alloys had excellent moldability, solvent and
heat resistance, as well as mechanical strength. They were found useful for manu-
facturing gears and cranks, automobile manifolds and electric parts (Nakano et al.,
1992). In another patent, 10-90wt% PPE was blended with unsaturated copolymer
resin (Arashiro et al., 1994). The following year the company disclosed blends of PPE
with PP, compatibilized by addition of a styrene-grafted propylene-methyloctadiene
(or hexadiene, containing about 3wt% of diene and 12wt% of styrene). The blends
showed good stiffness and impact strength (Tanaka et al., 1992).
Also in 1990, Himont introduced blends comprising (1) either PPE, PS or their
mixture, (2) a styrene-grafted polypropylene (PP-PS) (3) one or more block co-
polymers, e.g., SEBS, and (4) optionally, a polypropylene (PP). The alloys exhibited
excellent retention of heat resistance, high stiffness and tensile strength at elevated
temperatures, high chemical resistance, good gloss and surface appearance, melt
processability and high impact strength (DeNicola and Giroux, 1994).
In 1994, General Electric Company announced grafting of polyalkenes, such as PE
or preferably PP, with an ethylenically unsaturated t-alkylcarbamate. The grafted
t-alkyl-eontaining groups were found to easily decompose, providing amine or
carboxylic acid functionalization. Thus the PO copolymers were suitable for reacting
with carboxy- or epoxy-functionalized PPE, or other polymers. To minimizing
thermal degradation, the copolymers could be prepared under mild conditions at
relatively low temperature, then used as compatibilizers in PPEfPP blends (Camp-
bell and Presley, 1995).
11.15.5 PPIPOM blends

Polypropylene and polyoxymethylene (acetal or polyacetal) resins (PP fPOM) are
both semicrystalline and immiscible. As with other engineering resins, the first POM
blends were prepared by incorporating a small amount of one of these resins into the
other. However, the higher concentration blends have to be compatibilized. Since
POM can develop strong hydrogen bonding with acidic or epoxy groups, the PP f
POM blends are usually compatibilized by addition of acidified or epoxidified
polyalkenes. The PP fPOM blends are not available on the market.
In 1963, the Canadian Industries Limited (later known as CIL Inc., then AT
Plastics, Inc.) disclosed blends comprising either PP or LDPE and 1-lOwt% POM.
The materials showed improved melt flow, thus processability, good extrudate
appearance and improved mechanical performance (Rudin and Schreiber, 1964b).
In 1990, Hoechst Celanese applied for a patent for POM blends with PP, compati-
bilized by addition of muconic acid-grafted PP (Chen et al., 1991). The same year, du
Pont de Nemours disclosed high performance blends that contained 5O-80wt%
POM, 10-20wt% TPU, 10-30wt% crystalline polymer (e.g., PP, PA or PEST) and
ethylene-butylacrylate-glycidylmethacrylate copolymer (EBA-GMA.) as compatib-
ilizer (Subramanian, 1992).
280 Polypropylene
15.12 PP/SPECIALTY POLYMER BLENDS
Most specialty resins have relatively rigid macromolecules with strong intra and
intermolecular interactions, and as such they require high processing temperatures.
By contrast, PP has simple molecular structure, low glass transition temperature, and
is usually processed 30-50 °C above the melting point of 165 0c. At higher tem-
peratures PP is unstable - it easily degrades by thermal and shear degradation
mechanisms.
There are few patented blends of PP with specialty resins, and none have been
commercialized. This section discusses PP with aromatic polyamides (PARA) and
PP with liquid crystal polymers (LCP). These blends show high potential for com-
mercialization.
15.12.1 PPIPARA blends

Aromatic polyamides (aramids or PARA) are linear macromolecules comprising
aromatic rings connected with each other by amide groups. The first aramids were
liquid crystalline polymers with high melting point, such as poly(m-phen~ne
isophthalamide) Nomex™, or poly(p-phenyleneterephthalamide) Kevlar -49.
Having high melting points these polyamides have been used to manufacture high
strength fibers, spun from concentrated sulfuric acid. These aramids have not been
used as components of thermoplastic blends. However, their monomers have been
dissolved in thermoplastic resins, then polymerized, giving alloys with composite
structure on a molecular level, known as molecular composites.
In 1988, Mitsui Petrochemical introduced amorphous aromatic polyamide (a co-
polyamide from caprolactam, hexamethylenediamine and isophthalic and ter-
ephthalic acids, PA-6IT6). Three years later Amoco commercialized copolyphthala-
mides (PPA) as Amodel™. These amorphous polyamides are the main components
of thermoplastic polymer blends. Reinforced blends of PPA with polytetrafluoro-
ethylene (PTFE) are available on the market.
In 1983, Rehau Aktiengesellschaft disclosed, molecular composites, prepared by
dissolving 0.2-90wt% of monomer B [e.g., N-(p-amino benzoyl)caprolactam] in a
molten polymer A, selected from maleated-PP, PA-6 and PA-66. Polymerization of
monomer B engendered rigid, and in most cases linear, aramid microfibrils that
behaved as molecular reinforcements. To keep the negative influences, (e.g., weld-
ability) under control, the concentration of monomer B had to be below 10wt%.
Large increases of modulus (at small loss of the elongation at break) were reported
(Mulhaupt et al., 1994).
In 1989, several blends of PP with aromatic polyamide were introduced. Tonen
Sekiyu Kagaku's patent document described blends of PARA with maleated-
polypropylene (PP-MA) and phosphite ester as heat stabilizer (Iwanami et al.,
1990). In a Mitsui Petrochemical patent application, PARA was blended with
maleated-PE, or -PP and hydrazine. The alloy had improved resistance to thermal
degradation when in contact with metals (e.g., Cu), and it was used for sliding
electrical parts (Yoshihara, 1990).
In 1992, Amoco patented blends of copolyphthalamide (100 parts PPA, comprising
50-90 mol % of hexamethylene terephthalamide), with 5-200 parts PP and 2-20 parts
maleated PP. The alloys could also be reinforced by addition of 10-80wt% fibers
and/or mineral particulates (e.g., glass fibers and talc). Filled PPA/PP blends
showed improved processability and rigidity. They were useful for molding or
extruding goods requiring high levels of fiber reinforcement, operating in demand-
PP/specialty polymer blends 281
ing environment, e.g., at elevated temperatures and under corrosive conditions
(Paschke et al., 1993, 1994). In a contemporary patent deposition from the company,
100 parts PP were blended with up to 200 parts PPA. The blend was compatibilized
by addition of either maleated or acrylic acid grafted PP. The PPA contained 50-
80 mol % hexamethylene terephthalamide and hexamethylene isophthalamide. The
alloys could be reinforced by addition of up to 80 wt % glass fibers. The mechanical
properties and rigidity of the blends were better than those for neat PP, with no loss
in thermal processability (Brooks et al., 1993, 1994).
15.12.2 PPILCP blends

Owing to the cost differential, only PP blends with relatively small amount of LCP
have been developed. Usually these are non-compatibilized, aimed for improvement
of either processability or rigidity.
As far as processability is concerned, it has been reported that addition of LCP to a
variety of thermoplastic resins (e.g., PP, PPS, PC, PEST, PPE, fYfFE, etc.) reduces the
melt viscosity, thus facilitates extrusion and injection molding (Cogswell et a/., 1981,
1983, 1984; Bailey et al., 1982). Furthermore, in the ICI patents it was claimed that
moldings made of these blends had good surface finish, tensile strength and flexural
modulus. Within the range of low concentrations, the dependence can be
approximated by the fluidity additivity relationship 1/TJ = 'L(W;!f7i) originally
proposed by Heitmiller et a/. (1964).
The other reason for blending LCP with other polymers has been a need to
improve the mechanical performance of the latter resins. The reinforcement can
either be generated on the molecular level (molecular composites) or by blending.
In PP mainly the latter method of reinforcement has been developed.
The contribution of LCP depends on the blend's morphology - unoriented, spher-
ical suspension of LCP in PP is as effective as grains of sand. The reinforcing effect
depends very much on the orientation of the LCP crystals during the forming stages.
It is important that orientation extends to the molecular level. For this reason, mostly
uniaxially oriented films, fibers or moldings have been prepared. As in other blends,
the morphology of PP/LCP systems depends on concentration, viscosity and elasti-
city ratios, interfacial tension coefficient, flow type intensity, total strain, draw-down
ratio etc. The general recommendation for co-deformation of the dispersed phase -
thus, extensional flow field, the capillarity factor of > 2 and the viscosity ratio of 0.3-
1- seem to provide the optimum conditions (Heino et a/., 1994; Incarnato et al., 1994).
In 1987, Minnesota Mining and Manufacturing Company disclosed blends com-
prising a thermotropic liquid crystalline polymer (2 0.01 wt% LCP, Vectra™) and a
thermoplastic resin selected from PP, PET, PA, PC, PE, PVC, PVDC, PPS, PVDF,
PVF, PMMA, etc. The blends were used to produce oriented films with protrusions
that resulted in low friction. Other ingredients (::; Swt%) such as UV absorbers,
antioxidants, colorants, slip agents, could also be incorporated. The blends were
designed to form substrates for magnetic recordings, be binders for abrasive pow-
ders, reinforcing backings, adhesives, labels that provided writable and/or printable
surfaces, capacitor films, etc. (Wong, 1990, 1994).
Four years later, Foster-Miller disclosed similar systems. Thus, thermotropic
liquid crystalline polymer (about lOwt% Xydar™ or Vectra™) was blended with
thermoplastic polymers (e.g., PP, PS, PC or PI). To control LCP molecular orientation
the blends were multi-axially oriented during processing. For example, the orienta-
tion was imposed by extruding a pipe through a die having counter-rotating inner
282 Polypropylene
and outer surfaces. The alloys showed tailored coefficients of thennal expansion
(Haghighat et al., 1992).
In the early 1990s, Baird and his co-workers developed an ingenious method for
blending PP with LCP (Sukhadia et al., 1991, 1992). The method is based on the use of
two extruders operating at different temperatures, each appropriate for a given com-
ponent, and a relatively cold motionless mixer, where the streams of the two poly-
mers were combined. Within the motionless mixer the LCP phase became dispersed,
stretched and simultaneously crystallized, to fix the high aspect ratio of the reinfor-
cing LCP microfibrils. In the following patent (application of 1991 to Virginia Poly-
technic Institute and State University) blends of 1-99wt% PP with liquid crystal
polyester-co-amide (LCP, Vectra™ A or B) were compatibilized with 0.1-lOwt%
maleated PP (Baird and Datta, 1992). It was reported that compatibilization
improved the perfonnance well above that observed for two-component LCP/PP
blends.
15.12.3 PP blends with other specialty polymers

To improve processability of polyarylene polyether sulfone (PAES) in 1966 General
Electric Company blended it with low concentrations of polyalkene (0.5-5 wt % of
either PE or PP) and optionally other additives. Good solvent resistance and impact
strength were reported (Gowan, 1969). In 1982 the company announced blends of
polyetherimide (PEl) with either PP, PSF, PEC or PAr, ternary blends with PC and
PEST, etc. The blends showed good processability, as well as improved flexural and
impact strength (Giles and Schlicht, 1984).
For electrical insulation of high-voltage direct current submarine cables, in 1992
Alcatel Alsthom Company developed two-component blends, comprising either PE,
PP, PS or their copolymers, with 1-20wt% of an ethylene (or propylene)-fluorinated
vinyl ether copolymer, able to interact with the matrix polymer(s). The extrudable,
hydrophobic blends provided good electrical insulation, had excellent mechanical
properties and high stability. They were reported to perfonn better than any
previous insulating material (Barraud et al., 1993).
15.13 SUMMARY
Polypropylene blends constitute one of the most rapidly growing segments of the
plastics industry. Development of PP blends with polyalkenes is the most advanced.
However, owing to the rapid advance of single-site metallocene technology this
area is being revolutionzed. Many conflicting observations have been reported
regarding the effects of molecular parameters on the PE/PP blends' perfonnance.
The PP alloys with engineering resins (namely polyamides, polycarbonate or
polyesters) are at an early stage of development. The main source of difficulty for
development of these PP blends is their antagonistic immiscibility. The necessary
compatibilization leads to modification of the micro- and macromorphology. In
many cases, addition of a compatibilizer to a PP blend with an engineering resin
reduces the crystallinity, which in tum lowers the mechanical perfonnance. Optim-
ization of composition and blending methods is necessary. There are clear indica-
tions that the most popular method of compatibilization, using maleated PP, may
not be ideal - there is intensive activity to find better compatibilizers and/or
compatibilization methods.
Part Four
Engineering Resin Blends
16
Polyamide blends
Owing to the reactivity of polyamides, PAs, with Lewis acids, these resins are easy
candidates for blending. Polyamides have been blended with all principal thermo-
plastic resins belonging to the categories of commodity, engineering and specialty
polymers. In the following text the PA blends are presented in that sequence.
However, since PA blends with commodity resins are discussed as polyalkene
styrenics or vinyl blends, here only those aspects that are common to that class of
materials are presented.
There are many PA blends with elastomers, mostly with thermoplastic and to a
lesser degree with thermoset. Since blending with elastomers is carried out to
improve the impact strength, these blends (even when PA constitutes a minor
phase) are discussed with other methods used to toughen these polymers. The blends
with thermosetting resins are also presented there. Some of these blends were devel-
oped mainly to reduce viscosity of PA, thus enhance processability - the improve-
ment of modulus and/or the impact strength was rather secondary. For example, in a
1983 patent disclosure, PA-6 was blended with 3-30% Novolacs (PhOH + HCHO).
According to the document, blending decreased the molding temperature by at least
50°C, without affecting the moldings' physical properties (Aiwa Co., 1985).
16.1 EARLY BLENDS (UP TO 1970)
16.1.1 Early impact-modified blends

The first blend of PA was patented by du Pont de Nemours in 1948 - PA-66 was first
modified by reacting at least 5 % of the terminal -NH2 groups either with maleic
anhydride or by methoxy. The modified PA-66 was then blended with polyvinyl
acetate (4-96wt% PVAc). The alloys showed improved mechanical properties
(Hoover, 1948). Two years later, a patent from Standard Oil described a method
that rendered PA pliable by blending it with a random styrene-isobutylene copoly-
mer (PSffi). The alloys were used in electrical applications (Young and Sparks, 1950).
In 1953 a patent application from Polymer Processing described blends of PA with
polyethyleneglycol (PEG). The materials showed improved compression molding
characteristics (Doggett, 1962). In 1960 Japan Rayon disclosed that high performance
films can be prepared from blends of PA with lOwt% polyvinyl alcohol (PVAl). To
stabilize the morphology the films were irradiated with "'Y-rays (Okamura et aI., 1963).
In 1963 du Pont de Nemours applied for patent protection of new methods
developed for toughening polyamides. In this first of a series of disclosures, either
286 Polyamide blends
PA-6, PA-66 or PA-610 was blended with up to 99wt% copolymer of methyl-
methacrylate-methacrylic acid-ethylacrylate (MMA: MAc: EA = 90:6:4). The blends
showed good tensile and impact strength, as well as high elongation (Halliwell, 1965;
1966). Five years later, Oart Industry blended polyamides, such as, PA-6, PA-66 or
PA-61O, with an ionomer, alkene-a,J3-unsaturated acid copolymer, SurIyn™. The
blends showed improved toughness and impact strength (Boyer et al., 1970). Similar
improvements were described in an ICI patent application of 1969. In this case, PA
was blended with a copolymer of ethylene-2-hydroxyethylmethacrylate-methyl-
methacrylate or a similar one (Hepworth et al., 1970). Thus, during the late 1960s
the technology of PA toughening started to involve reactive blending (Boyer et al.,
1970; Kray and Bellet, 1968). This technology will dominate the field during the years
to come.
16.1.2 PAIPO early blends

The first patent on polyamide/polyalkene blends was deposited in 1958 by the
Continental Can Company. The uncompatibilized systems comprised 10-80 wt %
of either PA-6 or PA-66 with 9(}-20wt% of either LOPE or PP. The resins showed
excellent processability, good printability and low permeability. They have been
used to produce either sheets, films, fibers or bottles (Mesrobian and Ammondson,
1962). However, although the patent stresses that blending resulted in improvement
of the impact strength, the main interest for development of the systems was the
reduction of permeability. Advantages of compatibilization were discovered two
years later.
In several patent applications from Bayer dating from 196(}-68, a copolymer of low
density polyethylene (LOPE) with either PA-6 or PA-66 was blended with LOPE. In
the first document LOPE was blended with 5 wt % PE-PA-6 copolymer. The resulting
materials showed higher gloss, transparency, and elasticity, lower stress corrosion
and reduced permeability than determined for unmodified PE (Craubner et al., 1962).
In another document, PA-6 was blended with either LOPE or PIB, using 0.1-5wt%
N-stearyl steramide as a dispersion stabilizer. Injection molded parts showed high
tenacity and good impact properties down to -so °C (Gilch and Michael, 1970).
16.1.3 PAIPA early blends

The first polyamide/polyamide (PA/PA) blends were disclosed in 1958 by Polymer
Corporation. Thus, PA-66 was blended with either PA-6 or PA-610 for compression
molding of stress-free articles (Stott and Hervey, 1958). Eight years later, Uniroyal
announced PA-6 or PA-ll blends with lOwt% of partially crosslinked PA-66 - the
alloys showed excellent impact resistance (Uniroyal, Inc., 1968). In 1968 blends of
either PA-6, PA-66, PA-610, PA-ll or PA-12 with amorphous polycondensates of
terephthalic acid and isophthalic acid with hexamethylene-diamine (PARA) were
announced. The blends showed enhanced impact resistance and mechanical proper-
ties (DYnamit Nobel A.-G., 1969).
16.1.4 PAIABS early blends

In a patent deposition of 1961 from Borg-Warner Corporation, poly-€-eaprolactam
(PA-6) performance was significantly improved by blending it with 1(}-60 wt % ABS.
The uncompatibilized alloys showed good tensile strength, elongation, hardness and
stability during molding (Grabowski, 1964b, 1966).
PA/commodity resin blends 287
16.1.5 Early PA blends with engineering resins

Patents describing blends of polyamides with other engineering resins started to
appear by the end of the 19605. For example, in 1967 two companies, du Pont de
Nemours (Moncure, 1969), and Asahi Chemical, independently disclosed blends of
PA with polyoxymethylene (POM). The documents described POM alloys compris-
ing either a PA, amorphous aromatic polyamides (PARA) or a copolyamide ester. It
was reported that addition of a small amount of PA (l-4wt%) resulted in a sig-
nificant improvement of the color and thermal stability of POM (Asahi Chem. Ind.
Co., 1969b; Fukuma et al., 1976).
The following year, Toray Industries blended either PA-6 or PA-66 with POM and
polyethyleneterephthalate (PET). The alloys showed good mechanical properties
and low frictional resistance (Fujiwara, 1971). In a contemporary patent disclosure
from Allied Chemical, PA-6 blends with 30 wt % PET were reactively compatibilized
by addition of o,o'-dimethylol-propionic acid. The materials showed improved
impact and tear resistance (Reimschussel and Dege, 1969). In a 1969 patent,
20wt% PA-6-co-diisocyanate copolymer was blended with PET to generate alloys
with improved impact strength (TIling, 1970).
By the year 1970 the number of patents on PA blends started to increase rapidly.
The main effort was directed toward improvements of the ductility and process-
ability. Compatibilization, later reactive compatibilization, became an integral part of
the PA-blends technology. To facilitate observation of its evolution, the following
sections focus on PA blends either each with a single type of resin, or developed for a
specific application.
16.2 PA/COMMODITY RESIN BLENDS

These blends are divided into several categories, such as toughened PA blends,
elastomeric systems containing PA, rigid PA blends, blends with styrenics, vinyls,
blends formulated for reduction of permeability, biodegradable and/or recyclable
blends. 1bis division is an arbitrary one, and since frequently patent claims cover a
wide range of compositions (e.g., from 5 to 95wt% PA), it is not always valid. For
example, although at low PA loading the blend may belong to the elastomeric
category, at high loading it may be described within the toughened PA category.
Toughening can be accomplished either by chemical or physical means. The
chemical modification of PA usually involves addition of a low concentration of a
compatibilizing/toughening agent, such as a polyalkene or an elastomer, usually
with groups that are either reactive with the terminal amine groups of PA or capable
of forming associating complexes with amide groups. An alternative, physical alloy-
ing usually involves high energy shearing or solid state milling (that may lead to
bond breakage and reformation).
For example, PA-66 was recently blended with either ultrahigh-molecular-weight
polyethylene (UHMWPE) or acrylonitrile-butadiene-styrene copolymer (ABS). First,
the pellets of each of the resins were ball milled for S-24h in a specially designed
shaker ball mill at an acceleration 12.3 g, a frequency of 29 Hz and low temperature
of -150 0c. Next, the generated powders were combined in desired proportions and
milled together for another 24 h, obtaining the final powder with the particle dia-
meter of about 2 J.tm. 1bis powder was then placed under vacuum and consolidated
for 28h under pressure, at temperatures slightly above the melting point (e.g., 69
MPa and T - Tm ~ ~100 0c). The alloying resulted in homogenous materials, with-
out apparent phase separation. The moldings had higher hardness and tensile
strength, but lower maximum strain at break than what could be expected from the
additivity rule. Furthermore, these blends fractured by a different mechanism than
the melt-blended, compatibilized alloys. Mechanical alloying produced more brittle
materials (as judged by lower strain at break), but having higher impact energy of
fracture as determined in Charpy tests (Pan and Shaw, 1993, 1994; Shaw et al., 1993).
The authors claimed general applicability of the method to alloying powders of any
materials.
16.2.1 PA toughened blends

To this category belong polyamide blends formulated mainly for improvement of
toughness, i.e., blends with polyalkenes (e.g., polyethylene, polypropylene, or their
copolymers), elastomers (alkenic or not, vulcanizable or not, e.g., EPR or EPDM),
modified polyalkenes or elastomers, styrenic elastomers (e.g., ABS or SES), polygly-
cols, amorphous polyamides, etc.
Numerous PA/elastomer blends are available on the market. For example, PA
toughened by addition of either PO, EPR or EPDM (e.g., Grilon AlM from EMS-
Chemie or UltramicfIM from BASF), butyl acrylate-based elastomers (e.g., DurethanlM
from Bayer/Miles), ethylene-acrylic acid copolymer (e.g., Nycoa lM from Nylon Cor-
poration of America), ionomers (e.g., Zytel 300lM from du Pont de Nemours) or
cyclic polyalkenes (e.g., ElmitlM ZF from Mitsui Petrochemicals).
It was disclosed in a deposition from du Pont de Nemours dated in 1963 that to
improve PAs' impact strength and elongation at break the resins were blended with
a copolymer of methylmethacrylate-methacrylic acid-ethylacrylate (MMA: MAc: EA
=90:6:4) (Halliwell, 1965, 1966). In 1968, Dart Industry blended PAs, (e.g., PA-6, PA-
66 or PA-6lO) with an ionomer, SurlynlM (Boyer et al., 1970). One year later, for the
same purpose ICI used copolymers of ethylene-2-hydroxyethylmethacrylate-methyl-
methacrylate (Hepworth et al., 1970).
In 1970 Mitsubishi Chemical discovered that toughness of engineering resins can
be improved by incorporation of a bisphenol-A-epichlorohydrin polymer, Phenoxy
(Kimura, 1973). This was the beginning of a nearly general use of the resin as a
universal compatibilizer. As it will be evident from the examples given in the book,
in several patents it has been reported that too much Phenoxy can make the blend
miscible, what in turn may reduce its impact strength. In 1971 Union Carbide
Corporation patented Phenoxy blends with 5O-95wt% PA-6. The blends showed
superior environmental stress crack resistance (Schober, 1973). Four years later,
Celanese disclosed blends comprising PA-66, 0.5-3wt% Phenoxy and 1-29wt%
SEBS copolymer (Freed, 1975).
In 1979 du Pont de Nemours patented a wide range of elastomeric impact modi-
fiers for PA, such as maleated EPDM with 1 p,m particles (Epstein, 1979).
As is evident from the quoted examples, the amount of toughener may be as high
as SOwt% (as in Durethan Be 303lM from Bayer/Miles). In consequence, although in
toughened PA blends the elastomer domains are usually dispersed in PA matrix,
blends with cocontinuous structures are also available (as in TriaxlM 1000). The
toughening methods are similar for different types of polyamides, namely PA-6,
PA-66, copolymer PA-6,66, semi-aromatic polyamides, e.g., co-polyamide from
caprolactarn, hexamethylenediarnine and terephthalic acids, PA-6IT6, or aromatic
amorphous polyamides, PARA.
The toughened-PA blends have been developed for processing using all the basic
methods: extrusion, co-extrusion, injection, compression, transfer and blow molding.
They can also be thermoformed. The blends show good processability, low tempera-
ture impact strength, reduced water absorption, good dimensional stability, high
stiffness, heat resistance, and lower service temperature than homo-PA. Reinforced
grades with up to 40 wt % mineral filler or glass fibers are widely available. For
added lubricity they may contain PTFE.
The blends find use in a broad range of applications, including electrical (e.g., for
components subjected to low temperature impact), automotive (window and door
handles, door panels, sunroof frames, fan blades and shrouds, exterior mirrors,
splash shields, gears, and accelerator, brake and clutch pedals), tools (power tool
housings, lawn and garden tools), sport equipment (ski binding and accessories, ice
skate blade supports, roller skates, sailboat components), telecommunication, furni-
ture (office furniture parts, office chair seats, rollers, coasters, etc.), and industrial
(hydraulic cylinder components, gears, pulleys, propellers, pump parts, pipe fittings
and conveyer belt parts). Furthermore, articles molded from toughened PA (e.g.,
Star™ XD 1014 from Ferro, UltramitJfM from BASF or Zytel™ FE 8018 from du Pont
de Nemours) are used in antivibration applications, even when dry and at subzero
temperatures.
PA/PO blends
The basic reason for modifying PAs is to eliminate brittleness both of the freshly
molded parts, and of those exposed to low temperatures. The first problem can be
solved by annealing the moldings for a time, but at a risk of warpage and shrinkage.
However, annealing will not eliminate the second problem - the low temperature
brittleness. As early as in the 19605 it was discovered that blending PA with a small
amount of polyalkene can solve both these problems.
The first patent on non-{;ompatibilized PA/PO blends was deposited by Con-
tinental Can Company in 1958. Only 2 years later, in a disclosure from Bayer the
use of 5wt% of a compatibilizer, a PE-PA-6 copolymer, was described. In 1981
Standard Oil developed blends of amorphous, aromatic polyamide (prepared from
terephthalic acid, isophthalic acid and hexamethylenediamine) with 5-95wt% PE.
The materials showed superior processability, good elongation at break, as well as
high tensile and impact strength (Paschke et al., 1983).
Being non-polar, Pas are antagonistically immiscible with PA. However, if one
manages to finely disperse PO into subrnicron particles the discontinuities may
provide an adequate amount of stress concentration for toughening. The early
uncompatibilized PA/PO blends mark the beginning of an intensive search for
efficient methods that would lead to the toughening and reduction of moisture
sensitivity of the engineering resins, such as PA, PEST, Pc, etc.
In the early years of PA toughening, in principle, the two principal ingredients
were given, thus the work focused on the optimization of compatibilization by
ethylene copolymers with polar monomers, such as maleic anhydride (PE-MA),
vinyl acetate (EVAc), or (meth)acrylic acid (ionomers). The blends of PA with
these finely dispersed polymers showed significantly enhanced impact strength.
The maximum concentration of these modifiers varied from about 5 to 15 wt %.
During the following years numerous patents on toughening of PA were granted
to virtually every major PA producer or compounder. Other methods of impact
modification, by addition of ionomers, acrylic modifiers, multipolymers containing
glycidyl moiety, polyalkenes and elastomers followed (Utracki, 1989, 1991b).
The importance of these events extends beyond PAs. The observation that addi-
tion of a relatively small amount of finely dispersed PO or elastomer dramatically
changes the fracture behavior of PAled to impact modification of other resins, e.g.,
PET, POM, modified PPE, etc. Similarly, development of acidified polymers for
modification of PA resulted in blending them with polyesters and polycarbonates,
that led to a new type of polymer alloy. Whereas in the past blending was based on
mechanical incorporation of the ingredients, the newer technology introduced
another degree of sophistication - reactive blending. Several early patents on PA
toughening already required addition of a reactive ingredient (ionomers, adducts of
maleic or fumaric acids (or their anhydrides), succinic copolymers, etc). However,
during the last few years the importance of combined effects of chemistry, physics,
and engineering on performance of PABs was particularly noticeable. Reactive
blending of engineering polymers with maleated block styrene-butadiene copoly-
mers provided a more direct method of impact modification (Gelles, 1987; Modic
and Gelles, 1988; Lutz, 1989; Lutz et al., 1989; Gelles et al., 1993).
More recently, random and graft copolymers of ethylene with ethylenic unsat-
urated mono- or dicarboxylic acids, as well as with glycidyl methacrylate are gaining
popularity. PA blends with more than one impact modifier have also been intro-
duced. In 1983/ Dainippon Ink and Chemicals deposited a patent application for
toughening PA-66 by blending the resin with PE, maleated-PE and a compound
containing two epoxy groups. The alloys showed unexpectedly high impact strength
(Taguchi and Mori, 1985). In 1985 Mitsui Petrochemical Industries announced that
blends of 80 wt % PA-6, with 18 wt % HOPE, 0.9 wt % maleated EPR and maleated PP
had high rigidity and excellent low temperature impact strength (Kondo and Tomi-
nari, 1987).
Rigid PA/PO blends systems, especially those of the PA/PP type/ are of great
commercial interest. These are discussed in detail in a later section. Here, for
completeness, only a summary is given.
By definition, the rigid systems must contain at least 40 wt % PP/ and thus it must
be compatibilized. A precursor of these materials was disclosed in 1972 by ICI. The
alloy comprised 9Owt% PA, 9.5wt% PP and O.5wt% of maleated PP as compat-
ibilizer. It had improved maximum strain at break and notched impact strength,
over PA or its non-eompatibilized version (Davis, 1975).
The first reinforced rigid PA/PO blends were described in the 1979 patent applica-
tion. Blends comprising 6Owt% pp/ 20wt% PA-6 or PA-66 and 20wt% glass fibers
were reported as having superior tensile and impact strength (Asahi Fiber Glass Co./
1981). The first modem type PA/PP blends, compatibilized by adding maleated pp/ a
PP-MA, were disclosed in 1982 by llnitika and Mitsui Petrochemicals.
PNionomer blends
By definition, ionomer is a copolymer of ethylene with l-lOwt% (meth)acrylic acid
that has been partially converted into the (meth)acrylic salt of Li, Na, K, Mg or Zn.
lonomers were commercially introduced in 1963 by du Pont de Nemours as
SurlynTM. Blends with crosslinked copolymers of acrylic rubber and itaconic acid
were also disclosed (Epstein, 1979; Roura, 1981; Novak, 1983).
In 1981 the company announced blends of 20wt% PA-66 with an amorphous,
aromatic polyamide (80 wt % PARA, comprising isophthalic acid, terephthalic acid,
bis(p-arnino cyclohexyl)methane and hexamethylene diarnine, invented a year
earlier by Pagilagan). Molded blends showed high tensile strength, good elongation,
notched !zod impact strength and HOT. In the following paper, it was found
that addition of an ionomer (35 wt % of ethylene-methacrylic acid Zn-salt)
further improved the impact strength (Epstein and Pagilagan, 1983). The same
year the company also deposited a patent application that described blends of a
PNcommodity resin blends 291
semi-erystalline PA (either PA-6, PA-66 or PA-6lO) with up to 99wt% of a copoly-

mer of methylmethacrylate-methacrylic acid-ethylacrylate (90:6:4). The blends
showed good tensile and impact strength, as well as high elongation (Halliwell,
1965, 1966). Two years later the company disclosed blends of PA (having at least
69wt% amine end groups) with an ethylene-methacrylic acid copolymer. The result-
ing alloys showed large improvements of the impact and tear strength (Kohan et ai.,
1972). These systems are precursors of the PA/ionomer blends.
In 1968 Dart Industry disclosed similar blends, such as PA-6, PA-66 or PA-610,
with an ionic copolymer, alkene-a, ,a-unsaturated acid copolymer, SuriynlM from du
Pont. The blends had improved toughness and impact strength (Boyer et a/., 1970). In
an Imperial Chemical Industry patent document of 1969, PA was blended with a
copolymer of ethylene-2-hydroxyethylmethacrylate-methylmethacrylate or a similar
one (Hepworth et ai., 1970). Then, a year later, the company disclosed PA-66 blends
with ethylene-diethylaminoethylmethacrylate. These were reported to have
improved impact properties and flexibility over neat PA (Priddle et ai., 1972).
During the following three decades the PA blends with ionic ethylene-(meth)-
acrylic acid or ester copolymers have been of great commercial interest. These alloys
were found to be stable and had high toughness and impact strength.
In an Asahi Dow disclosure of 1975, either PA-6 or PA-66, was blended with 5-
50 wt % of a copolymer selected from ethylene-acrylic acid (EAA), ethylene-
carbonate (ECA), ethylene-ethylacrylate (EEA), ethylene-methylmethacrylate
(EMM) or ethylene-vinylacetate (EVAc). Significant improvement of impact strength
was claimed (Iwami et ai., 1976; Saito et ai., 1977). In a disclosure of a 1977 Asahi
Chemical Industries patent application, PA-6 or PA-66 were impact-modified by
addition of ionomer or acrylic acid-EVAc graft copolymer (Matsuki et ai., 1979). In
1979, PA-6 blends with ethylene-unsaturated carboxylic acid copolymer, e.g.,
20wt% SuriynlM 1702 ionomer, were described as having high impact strength
(Asahi-Dow Ltd., 1980).
In 1976, Bayer developed PA blends with graft copolymers of ethylene-ethyl-
acrylate-acrylic acid. The optimum ionomer concentration was reported to be
less than 20wt% (Meyer and Tacke, 1978). One year later the company disclosed
blends comprising PA-6, PA-66 or PARA, and a graft copolymer of acrylic acid,
ethylhexylacrylate, butylacrylate, maleic anhydride, acrylamide and/or similar
monomers onto PE or EVAc. The blends showed high impact and oxidation
resistance, homogeneity and good surface properties (Take et ai., 1979; Korbert et
ai.,1979).
In the late 1970s, carboxy-terminated nitrile rubber (CTBN) was used by
several manufacturers as an impact modifier for PAs. Thus, in 1976 Toray Industries
applied for patent protection for blends comprising PA-6 with 5-40 wt % CTBN,
and 30% GF. The compounded material was reported to have high impact
strength (Chiba et ai., 1978). Three years later, either PA-6 or PA-66 was impact
modified by blending it at a 1:1 ratio with CTBN ionomer, then with ZOO, MgO,
Na2C03, Ah03 or BaD. In the later patent, 0.1-20% epoxy resin was used instead.
These materials also showed excellent impact resistance (Ube Industries, 1980). In
1982 similar PA blends with CTBN and ZOO were disclosed. These were reported to
have excellent fracture resistance in a wide range of compositions (Bridgestone Tire
Co., 1983).
In a 1978 patent application Toyobo disclosed PA blends with excellent impact
resistance and mechanical properties. These were obtained by blending PAs with
polyalkenes and ionomers, (e.g., NyionlM T with polypropylene and SuriynlM,
Toyobo Co., 1981). In a contemporary Daicel patent, 5O-95wt% PA-12, was blended
with 5-59wt% ionomer, then compounded with 5-50 parts polyester-amide
elastomer. The alloys were reported to have good tensile strength, toughness and
elongation (Daicel Chem. Ind., 1982c).
In 1980, impact resistant PA-6 was prepared by blending with 5-100 phr Mg++-salt
ionomer - the blends showed no phase separation (Ube Industries, 1982). In a
contemporary du Pont de Nemours patent deposition, for good low temperature
impact properties, mixed polyamides PA-6 with PA-66 were blended with an iono-
mer and EPR (Roura, 1981). However, the following year, the company announced
that still higher impact properties were achieved by blending PA with a core-shell
acrylic elastomer (butyl acrylate-allyl acrylate-ethylene dimethacrylate) (Novak,
1983).
The toughening of PA by addition of an ionomer led to numerous patents issued
in 1981. Thus, AlliedSignal blended PA-6, with partially neutralized copolymers of
a-alkenes with unsaturated carboxylic acid, e.g., SurIynTM ionomer, and with their
esters. The resulting impact-resistant alloys were commercialized under the trade
name of Capron™ (Mason and Tuller, 1982, 1983). Similarly, 2D-95wt% PA-6 was
blended with 5-80wt% PA-6lO and with 1-40wt% ionomer. The alloys were used
for injection molding. The products had good toughness and high heat resistance
(Toray Industries, 1983b).
In contemporary Uniroyal patents, 5O-95wt% PA was blended with 1-45wt%
ionomer and O.5-40wt% ethylenic elastomer. An addition of 1D-30wt% of a par-
tially saponified PVAc was found to reduce oxygen permeability, reduce haze and
engender good mechanical properties (Ochiai and Sakurai, 1983). The company also
announced blends comprising 40-95 wt % PA, 5-60 wt % sulfonated-EPDM ionomer,
and 8-10wt% Zn stearate. First, a master batch with 6Owt% ionomer was com-
pounded, then the rest of the PA-11 was added. HOT, impact and tensile strength
were found to be improved (Weaver, 1983). In 1982, a patent application from the
company described blends comprising 69--88wt% of PA/PA mixtures (e.g., PA-6
with PA-11) and sulfonated-EPDM.ionomer. These alloys were found to have high
notched !zod impact strength at low temperatures (Weaver, 1985).
In 1982 further variations on the theme of PA/ionomer blends were described.
Thus, in a BASF application, 100 parts of PA-6 were blended with 11 parts of
ethylene-butylacrylate-acrylic acid copolymer. (E-BuA/AA) to give alloys with
high impact strength (Reimann et al., 1983). Similarly, 100 parts of PA-6
were blended with 2-100 parts of iononomer (e.g., ethylene-methylmethacrylate-
methacrylic acid partially neutralized with Mg++), and 1-70 parts EPDM to give
alloys with good impact resistance (Ube Industries, Ltd., 1983).
Addition of ionomers to PA usually results in increase of the shear viscosity, and
thus lower processability. Several methods for improvement of this aspect were
proposed, including additions of either a low-molecular-weight reactant or incor-
poration of an immiscible additive (e.g., liquid crystal polymers). For example, a
patent disclosure from 1983 described blends of PA-6 with 3-30wt% Novolacs
(PhOH + HCHO). Excellent processability was reported. Furthermore, the molding
temperature of the modified PA could be lowered by at least 50°C without any loss
of physical properties (Aiwa Co., Ltd., 1985).
In 1986 and 1987 further applications from du Pont de Nemours on PA/ionomer
blends were disclosed. Thus, PA was blended with either ethylene-butylacrylate-
methacrylic acid-Zn salt ionomer, and ethylene-glycidylmethacrylate copolymer, or
with PAr, EPDM and ethylene-ethylacrylate-glycidylmethacrylate copolymer
(EEAGMA). The resulting alloys showed high stiffness, impact and solvent resist-
ance, as well as superior mechanical properties and water resistance (Saltrnan, 1988;
Flexman and Sosnowski, 1988). Similar blends were also disclosed by Mitsubishi
Kasei Corporation (Urabe and Ikuhara, 1989).
PA/PO-MA blends
In 1971, a patent application from du Pont de Nemours described modification of
polyamide behavior by blending them with a polycaprolactam-polyethylene-maleic
anhydride graft copolymer (PE-MA/PA-6) (llling, 1973; Starkweather, 1976). Four
years later, the company introduced the super-tough polyamides, Zytel™ ST, pro-
duced by reactive blending of PA-66 with maleated-EPDM or a Zn++ salt of ethyl-
ene-isobutylacrylate-methacrylic acid, SurlynTM ionomer. Similarly, in 1976 General
Electric announced blends of either PA-6 or PA-66 with polyethylene-maleic anhyd-
ride graft copolymer (PE-MA). Significant improvements of impact strength were
claimed (Swiger and Mango, 1977).
In 1978 Asahi patented PA-6 blends with polybutadiene grafted with styrene and
maleic anhydride (50 wt % BR-SMA). The resulting alloys showed a set of properties
superior to those obtained for PA-6 blends with ABS (Asahi Chern. Ind. Co., 1983).
Two years later, simple blends of 5O-95wt% PA-6 with styrene-maleic anhydride
copolymer (SMA) or SMA-modified rubber (BR-SMA), were described. The blends
showed good processability, mechanical strength, impact resistance and HOT (Dai-
nippon Ink and Chern., 1982a, 1985).
The same year Monsanto deposited a patent describing that when PA-66 was
blended with butylacrylate-2-hydroxyethylmethacrylate copolymer and SMA, the
resulting alloys could be used for high impact strength applications (Woodbreyand
Moncur, 1982). During the early 1980s Monsanto Chemical Company deposited a
series of patents describing further impact modifications of PAs. For example, 55-
99wt% PA-66 was blended with a core-shell copolymer. The latter resin comprised
crosslinked butyl rubber core, grafted with styrene, acrylonitrile and ethyl maleate.
The alloys showed excellent processability, impact strength and mechanical proper-
ties (Baer, 1982, 1986, 1987).
Blends comprising 4O-99wt% PA-6 and an impact modifier were described in
1980. The latter component was either an ethylene-a-alkene copolymer grafted with
a, ,8-unsaturated carboxylic acid or its anhydride, hydrogenated SEBS grafted with
maleic anhydride, or LLDPE grafted with maleic anhydride (Mitsubishi Chern. Ind.
Co., 1982a). In a contemporary deposition from the company, blends that comprised
x parts of PA, Y parts of an ethylene-a-alkene copolymer, and z parts of an a,,8-
unsaturated carboxylic acid grafted ethylene-a-alkene copolymer, were disclosed.
The following proportions were claimed: [(y + z)jx] = 0.1-6, and (yjz) ~ 0.1. For
example, 80wt% PA-6 was blended with lOwt% ethylene-I-butene copolymer (E/
B) and 10 wt % maleated E/B to give high impact and tensile strength (Hayashi et al.,
1980). According to a contemporary Unitika's invention, PA blends with aromatic
polyester, containing 0.2-50wt% acid anhydride groups, showed nine times higher
impact strength than a similar blend containing 0.1 wt% anhydride groups (Kyo et
al., 1979).
Reactively-toughened PA blends
Reactive processing is an integration of fine polymer chemistry with precisely
executed polymer processing (mixing, compounding, extruding and forming). It
combines chemical kinetics with flow and thermal properties of the reaction
ingredients and products, integrating them into a mathematical model of reactive
extrusion or molding. It is worth noting that since the principal factor for the
polymer blend industry is the strong interrelation between processing, morphology
and performance, there is a major effort toward development of computational
methods, so as to be able to predict, and therefore control, the morphology evolution
during compounding or processing steps. However, there is another side of the coin.
To be able to understand and control the reactive processing one must know the
dynamics of the interface and the evolution of the morphology during the process.
Thus, the mathematical description, on the one hand is needed to optimize the
processing conditions for the sake of high throughput of blends with desired mor-
phology, but on the other hand the knowledge of the local evolution of morphology
during the reactive processing makes it possible to compute the extent of compat-
ibilization, that in tum affects the morphology.
A look through the patent literature indicates that, from the very beginning,
blending involved both chemical and physical aspects. The very first patent on
polymer blends (Parkes, 1846) described blending of NR and GP in the presence of
SCh that partially vulcanized the blend. Generation of NBR, HIPS and ABS all
involved well-eontrolled physical and chemical activities, so as to generate materials
possessing the desired performance characteristics. 1. G. Farbenindustrie patented
(1939) blends of polyvinyl alcohol with a multicomponent acrylic copolymer, con-
taining maleic anhydride. By the early 19405 corotating twin-screw extruders were
used by I. G. Farbenindustrie for reactive processing.
In a 1948 du Pont's patent, PA-66 was first maleated, then blended with PVAc.
Starting in mid-1960, reactive extrusion and compounding (leading to controlled
morphology, thus improved performance) began to be used for toughening and
modification of the engineering resins, namely PA, PET and PC, then PBT, POM
and PPE. For example, in the 1966 Bayer patent, PA-6/PVAI blends were obtained
by polymerizing €-eaprolactarn in the presence of PVAI. In 1973 Dow introduced
oxazoline-grafted polymers (e.g., PE and PS) to be used as compatibilizers in reactive
blending of, for example, either PC/PA or PS/PE. In 1975 du Pont introduced
the super-tough PA, Zytel-stJM, produced by reactive blending of PA-66 with
maleated-EPDM. Many commercial blends exist because of reactive processing. In
addition, the aforementioned super-tough polyamides, PO/PA and PPE/PA blends
(both introduced in 1979), or PC/PA (commercialized in 1988) also provide good
examples.
Many PA/PO blends discussed in the preceding parts were prepared by the
reactive processing methods without mentioning the fact. In this part only the blends
specifically described as resulting from reactive compatibilization/toughening will
be considered.
High impact strength PA blends, with good heat resistance blends were also
disclosed in 1977 by Toyobo Company. Thus, PA was compounded with impact
modifiers prepared by reactively grafting at 170°C of either EPDM or partially
saponified ethylene-vinyl acetate, EVAc. The graft was performed during reactive
extrusion at 170°C, using 3-10 phr of glycidyl methacrylate and dicumyl peroxide. It
was also reported that the blend properties could be further ameliorated by addition
of such inorganic fillers as talc or glass fiber (Yoshihara et a/., 1978, 1979; Shirai et a/.,
1979).
The following year Rohm and Haas announced that low-molecular-weight
polyamides (LMW-PA) can be impact-modified by preparing master batches of
high-molecular-weight polyamides, HMW-PA-66 with methylmethacrylate, butyl
acrylate, butylene glycol diacrylate, and diallylmaleate copolymer, then blending
them with 75wt% LMW-PA (Dunkelberger, 1979).
In a 1981 patent application, PA-6 was blended at a ratio of 1:1 with styrene-
methylmethacrylate-maleic anhydride copolymer (SMM-MA) (Asahi-Dow Ltd.,
1982). During the following year several PA blends, prepared in reactive processing,
were disclosed. For example, impact-resistant polyamides (PA-6) were invented in
Bayer laboratories by reactive blending it with styrene-methylmethacrylate-glycidyl
methacrylate (SMM-GMA) and a polyol (Muesing et al., 1984).
In a more general patent document, the strategy for reactive blending of PA with
PO or an elastomer was described. For example, in an extruder with at least two feed
zones, first the EPDM was maleated or carboxylated, then PA-6 was added and
reactively blended (Unitika Ltd., 1983a). Similarly, in another patent, 50-98 parts PA-
6 were blended with 1-40 parts maleated EPR, and 1-49 parts of either PE or EP-
copolymer, giving alloys with good flexibility and impact strength (Mitsui Petro-
chemical Industries, Ltd., 1984a, 1985).
16.2.2 PAlelastomer blends

The low temperature impact strength of PA has been enhanced by incorporation of
such elastomers as EPR, EPDM, ABR, BR, SBR, etc. The elastomer is usually selected
by considering the desired morphology and the method of compatibilization. The
type of morphology, size and size distribution of the dispersed phase, as well as the
degree of bonding between the disperse phase and the matrix, all are crucial factors.
The particle size and distribution are of prime importance since they control the
fracture mechanics, and thus are responsible for the toughness and strain at break.
The physical or chemical bonding can lead to significant changes of the impact
strength, even at high elastomer content. The elastomer-modified PA-6 or PA-66
exhibit high resistance to initiating and propagating stresses.
One of the best early examples of the impact modified polyamides is prOVided
by the 1976 patent deposition from Toray Industries. The impact properties of
polyamides, such as PA-6, were improved by blending with 5-40wt% carboxy-
terminated nitrile rubber and glass fibers (30wt% GF) (Chiba et al., 1978). Note
that here the carboxylic groups provided an excellent source of interactions with
PA, whereas the glass fibers directly bonded to PA segments (Goettler, 1983).
The high impact strength PAl elastomer blends can be injection molded without
pre-drying. The melt temperatures range from 260 to 290°C. The blends, e.g.,
BexloyTM from du Pont de Nemours, found many applications, namely for ski
bindings, ski and roller boots, surfboard mast holders, bicycle wheels, curtain rails,
office equipment housings, handles, electrical components, gears, safety helmets,
seals, sleeves, flexible couplings, cable sheathing, wheel trims and front spoilers for
cars, cattle troughs, bicycle saddles, swivel chair bases, etc.
PA blends with acidified EPR or EPDM

Maleation, although being the most popular method of acidification of elastomers to
be used in blends with PAs, is far from unique. Other acids (e.g., sulfuric or
carboxylic, as in partially saponified ethylene-vinyl acetate or polyvinylacetate),
their salts, derivatives and anhydrides have also been used.
In 1975 Du Pont de Nemours developed super tough nylon, Zytel-™ ST. Thus,
polyamide-66 (PA-66) was reactively blended with maleated-EPDM, EPDM-MA or
ethylene-isobutylacrylate-methacrylic acid 20++ salt, Surlyn™ ionomer. The com-
pany disclosed that impact properties of a variety of semicrystalline polyamides,
such as PA-6, PA-66, PA-610, PA-11 or PA-12, can similarly be improved by blending
them with a variety of elastomeric modifiers, for example, EPDM-MA having par-
ticles with about 1 tLm in diameter (Epstein, 1979; Roura, 1981; Epstein and Pagila-
gan, 1983; Novak, 1983).
Similar blends were also described in a series of patent applications from Toyobo
deposited in 1977. Thus, high impact strength, and good heat resistance PA-blends
were prepared by compounding them with modified elastomeric polymers, e.g.,
EPDM or a partially saponified ethylene-vinyl acetate. The modification involved
grafting these resins (during reactive extrusion at 170°C) with 3-10phr glycidyl
methacrylate and dicumyl peroxide. It was reported that blend properties can
further be ameliorated by addition of such inorganic fillers as talc or glass fiber
(Yoshihara et ai., 1978, 1979; Shirai et al., 1979).
In 1981 Uniroyal announced that PA blends with high heat deflection temperature
and impact and tensile strength were obtained by sequential compounding of 40-
95wt% PA with 5-60wt% sulfonated-EPDM, and 8-10wt% Zn-stearate. In the first
step, a master batch (comprising 4Owt% of PA and 6Owt% of sulfonated EPDM)
was prepared, then the rest of PA was incorporated. The examples described blends
of PA-ll (Weaver, 1983). The following year the company extended the method to
mixtures of polyarnides. For example, blends having high notched Izod impact
strength at low temperatures, were prepared by blending 69-88wt% of a PA-6
and PA-ll mixture with sulfonated EPDM (Weaver, 1985)
A method of bypassing the need for acidification of EPDM was described in a
patent application of 1982. Thus, 100 parts of PA-6 was blended with 2-100 parts of
an ionomer (e.g., ethylene-methylmethacrylate-methacrylic acid partially neutra-
lized with Mg++), and 1-70 parts EPDM. The latter polymer was compatibilized
by the judicious selection of an ionomer. Its presence enhanced the impact resistance
of the alloy (Ube Industries Ltd., 1983). Similarly, in 1983 PA-6 was toughened by
blending it with o-4Owt% EPR and 1--60% maleated ethylene-ethylacrylate copoly-
mer (Ube Industries Ltd., 1985).
Also in 1982 the controlled reactive extrusion for toughening of PA was described.
In an extruder with at least two feed zones first EPDM was carboxylated, then PA-6
was introduced and blended (Unitika Ltd., 1983a). Similarly, in a contemporary
patent 50-98 parts of PA-6 were reactively blended with 1-40 parts of maleated
EPR and 1-49 parts of either PE or EP copolymer. The blends had good flexibility
and impact strength (Mitsui Petrochem. Ind., Ltd., 1984a).
Several blends of PA with EPR-type elastomers were disclosed in 1983. Thus, PA
molding compositions with low temperature impact resistance and low moisture
absorption were obtained by blending 100 parts of PA with 1-100 parts of either
EPDM or EPR grafted with maleic anhydride, and with 1-100 parts of unmodified
EPR having a degree of crystallinity not greater than 40% (Mitsubishi Petrochemical
Industries Ltd., 1984b, 1985). One year later, the company disclosed impact resistant
blends comprising 99-1 wt% PA-6 and 1-99wt% PP, compatibilized by addition
of 3wt% of maleic anhydride-grafted EPR (Katsura, 1986). For similar applications,
in a contemporary patent application from Mitsubishi Chemical Industries,
blends containing 5O-90wt% PA and modified-PO were reported to have good
impact strength and water resistance. In particular, blending 70wt% PA-66 with
a modified PO mixture (comprising 82 parts PP, 6 parts HDPE and 12 parts EPR)
was found to yield alloys that were found easy to mold into parts having
good mechanical properties even after 25 days immersion in water (Hasuo et ai.,
1985).
In 1985 Mitsui Petrochemical Industries deposited a patent application for multi-
component blends comprising 80wt% PA-6, 0.9wt% maleated EPR, maleated PP
and 18 wt % HDPE. The alloys were reported to have good rigidity and low tem-
perature impact strength (Kondo and Torninari, 1987).
Multicomponent, multiphase blends were described in a series of patent applica-
tions from Ferro Corporation deposited in 1988. These blends comprised ~95wt%
PA, and 5-95wt% block or graft copolymer formed by coupling an elastomer (either
an ethylene-propylene-diene (EPDM), a multiblock SBR, polyisoprene (PI) or a
nitrile rubber (NBR) with unsaturated (di)carboxylic acid, an anhydride of a dicar-
boxylic acid, a monoester, a sulfonic acid and an epoxy or their salts. In these blends
PA formed a continuous phase, with the grafted elastomer forming the dispersed
one. The latter had particle diameters 3.5-Q.35/-Lm, with microparticles of PA
imbedded in it. The toughened blends had improved chemical resistance, high
notched impact strength at room and at low temperatures, and a heat deflection
temperature of 5O-75°C. The alloys were useful for manufacturing films, oriented
fibers, tubing, wire coatings and gaskets (Baghaii and Scheibelhoffer, 1990, 1992,
1993).
Others impact resistant polyamides were described in invention documents from
Surnitomo Chemical deposited in 1990. These alloys were to be prepared in sequen-
tial blending. First, PA was compounded with acidified elastomer (either SEBS, EPR
or EPDM), then the multipolymer was incorporated into PA. Note that in this case,
for reduction of the interfacial tension PAs having lower molecular weight could be
used. Good processability, mechanical properties and low temperature impact
strength were reported (Ohrnae et al., 1991, 1992). In a contemporary Arco patent,
PA was blended with two compatibilizers/impact modifiers, namely with a
maleated elastomer and styrene-methacrylic acid (SMAA). Good impact properties
were reported (Papazoglu, 1991).
In 1992 Goodyear Tire and Rubber Company deposited several patents describing
three-component EPDM alloys. These comprised functionalized ethylene-propylene-
diene (EPDM), an EPDM haVing grafted thermoplastic side chains, and a dispersed
engineering resin, such as PA, PEST or PPE. The preferred systems contained 4-
12phr PA-6, compounded with functionalized EPDM, nD-l25phr carbon black, 4-
6phr Zno, 4O-SOphr processing oils, 1-3phr stearic acid, 0.~2phr S and 4-8phr
accelerator. The material was used to manufacture radiator hoses exhibiting high
burst strength without the need for continuous yam reinforcement. This resulted in
reduced labor costs, process inventory and waste (Burlett et al., 1993).
It is appropriate to close this section with another invention from du Pont de
Nemours, disclosed in 1992. Thus, either PA-6 or PA-66 was blended with maleated
ethylene-propylene copolymer (10wt% EPR-MA), and with a semicrystalline ethyl-
ene-propylene copolymer (10 wt % EPR), to give materials with good flexural modu-
lus, tensile strength, elongation, and notched Izod impact strength at 23°C as well as
at -30°C (Dunphy et al., 1993).
PA blends with either SBS or SEBS

In 1976, Shell Oil introduced hydrogenated poly(styrene-diene) block copolymers
(SEBS). It was reported that polyarnides (e.g., either PA-6 or PA-66) were significantly
toughened by addition of only 5 wt % SEBS. When the copolymer concentration was
increased the blends had a tendency to develop a cocontinuous morphology. The
alloys showed good dimensional stability, and (depending on composition) the
mechanical behavior varied from rubber-like to flexible. Good resistance to shrink-
age and distortion was also reported (Davison and Gergen, 1977, 1980; Gergen and
Davison, 1978). In 1980, to improve the impact strength and reduced modulus,
Rhone-Poulenc Industries blended PA-6 or PA-66 with SBS block copolymer (Cerny
and Troncy, 1981).
Performance of this type of blend was further improved after introduction in 1979
of maleic anhydride adducts with a hydrogenated block copolymer, SEB5-MA by the
Firestone Tire & Rubber Co. For example, 90-50 wt % PA-6 blended with 10-50 wt %
SEB5-MA showed further improvement of impact strength (Hergenrother et al.,
1984). Similarly, in Mitsubishi patent documents deposited the following year, 40-
99 wt % PA-6 was blended with either an ethylene-a-alkene copolymer grafted with
a, ,a-unsaturated carboxylic acid or its anhydride, a maleated-LLOPE or a SEB5-MA
(Mitsubishi Chem. Industries Co., 1982a).
In 1985, Shell International Research Maatschappij disclosed blends comprising 50-
97 wt % PA, with SEB5-MA. It was claimed that these alloys exhibit very high notched
Izod impact strength (Gelles et al., 1987). Three years later, the company announced
that PA alloys with high impact strength can be produced by blending them with
hydrogenated and carboxylated styrene-isoprene diblock copolymers (Pottick and
Willis, 1991). In a contemporary Allied-Signal patent, blends suitable for manufactur-
ing packaging materials were prepared from a copolymer of lactam or aminoalkanoic
acid, aralkylene and aromatic diacid (Akkapeddi and Gervasi, 1989). In a later patent,
for improved performance, PA was blended with SEB5-MA (Bhoori, 1991).
PA/ABS blends
Details of these blends are discussed along with other systems containing ABS. The
two resins, PA and ABS, are antagonistically immiscible and, to avoid delamination
during processing, they must be compatibilized. For better heat and solvent resist-
ance it is preferable to keep PA as the continuous phase, but at the same time to
maximize the ABS contribution to toughness, this phase should also be continuous.
Hence, the key to success has been optimization of the amount and type of compat-
ibilizer to generate a cocontinuous morphology with appropriate fineness of disper-
sion (such as Triax™ 1000 from Monsanto).
The first PAl ABS blends were developed in the 196Os, in Borg-Warner laboratories
(Grabowski, 1964b, 1966). Twenty years later the company introduced the ABS/PA
blend ElemiJIM for use in automobile body panels. In 1981 the company also
announced new high performance blends of PA-6 with ABS containing 0.5-15wt%
unsaturated carbonamide (e.g., acrylarnide) with partially maleated SAN in the ABS
copolymer, or carboxylated EPOM. The alloys were reported to give high HOT and
impact strength (Grant and Meyers, 1983; Grant, 1985). In 1987, PA-6 or PA-66 were
toughened by blending with two types of impact modifiers: maleated (methac-
rylate)-acrylonitrile-butadiene-styrene copolymer (AB5-MA or MAB5-MA), and car-
boxylated ethylene-propylene copolymer (EPR or EPOM). For example, blends of
PA with AB5-MA and carboxylated EPOM were described as having high impact
resistance (Grant and Howe, 1988; Howe et al., 1989).
In 1980, PA-6 was blended at a 1:1 ratio with polybutadiene grafted with styrene
and maleic anhydride (SBMA, also BR-MA). The patent described the alloys as
showing a superior set of properties to those obtained by blending PA-6 with ABS
In the early 198Os, Monsanto patented blends comprising 55-99 wt % PA-66 and a
core-shell copolymer (AB5-MA). The alloys showed excellent impact strength (Baer,
1982, 1986, 1987). In 1985 the company deposited a series of patent applications for
blends comprising either PA-6, PA-6,66 or PA-66 and PA copolymers, each having
T g <: o°c. Thus, PA was reactively extrusion-alloyed (at ratios varying from 1:9 to
9:1) with emulsion-type ABS (AES or MBS) as well as with less than 4Owt% of an
acid-containing acrylic rubber, and a maleic anhydride-grafted SAN (SAN-MA). The
extruded or molded alloys showed good mechanical properties and impact strength
(Lavengood et al., 1986). In a later patent SOwt% of soft ABS (containing 4Owt% PB)
was blended with 6wt% SAN-MA and 44wt% PA to give alloys with excellent
impact strength (Lavengood 1987). Well performing blends with high impact resist-
ance were also obtained by blending PA with ABS or MBS, and with maleated
copolymer of styrene-acrylonitrile-methylmethacrylate (SAN-MA-MMA) (Laven-
good et a/., 1988). These discoveries led to commercialization in 1987 of TriIlx™-
1000, quite a successful PA/maleated ABS alloys with cocontinuous morphology.
In 1987 General Electric disclosed blends of amorphous copolyamide(s), either PA
or PARA, with ABS. The patent covered full concentration range from 1:9 to 9:1,
claiming improved impact properties. The copolyamide(s) were transparent, with no
detectable melting point and the heat of fusion below 0.2 J/ g. They were either
prepared from aromatic diamines and diacids, or were copolymers of polyamides
chosen from: PA-6, -66, -11, -12, -63, -46, -64, -610 or -612. Compared to the crystalline
blends, these had improved thermal stability and barrier properties, as well as lower
water absorption, hence better dimensional stability (Fox et al., 1989).
In AlliedSignal patent applications of 1987, maleated ABS and maleated EPR, were
described as suitable impact modifiers for amine-terminated polyamides (PA-6).
Here, PA-6 was reactively blended with a reaction product of EPR and C3- 12 lactams
(the reaction was carried out during reactive compounding), to give alloys with good
toughness and delamination resistance (Akkapeddi et a/., 1989). In the following
patents reactive extrusion was again used for preparation of PAl ABS blends. At the
first stage ABS was modified using either maleic anhydride or fumaric acid, then
PA-6 was added to the reaction product and compounded to generate the desired
morphology. Optionally, to enhance the blend ductility, a small amount of functio-
nalized EP-rubber was also to be incorporated (Akkapeddi et al., 1990, 1992a).
Furthermore, it was reported that addition of a few percent of maleated EPR to
maleated-ABS and pre-blending these elastomers before adding PA substantially
improved the notched Izod impact strength of the final ABS/PA blends (Akkapeddi
et al., 1993a).
In a 1990 patent application from the Industrial Technology Research Institute,
Taiwan, impact-resistant PA blends were described. These comprised 75-25 wt % of
either PA-6 or PA-66, a styrenic resin (e.g., 25-75wt% ABS) and lo-SOphr of an
impact modifier (e.g., carboxylated nitrile rubber NBR-MA, O.l-lOwt% MA). The
rubber reacted with PA and entangled with the elastomeric phase of ABS. Thus,
NBR-MA was found to be an efficient compatibilizer for the system, that engendered
good dispersion of phases and enhanced the impact resistance and dimensional
stability (Lin et al., 1993).
The main applications of ABS/PA alloys are the automotive, chemical, electrical,
electronics, consumer and sports industries. For example, these materials have been
used to mold large components for recreational vehicles, snowmobiles, tractors,
lawn and garden equipment, power tool housings, impellers, wheel covers, gears,
mirror housings and automobile interior components. The blends have been also
used in antivibration damping structures.
PA/acry/ics blends
Another method of impact modification of polyamides involves incorporation of an
acrylic copoly-elastomer. A great diversity of these materials has been developed.
The early ones were based on polyalkenes grafted with (meth)acrylics, the later ones
on the multicomponent core-shell latex technology developed in the early 1970s.
Since compatibilization interactions between the copolymer and PA are very
important, in most cases the acrylics have either acidic, acid anhydride or epoxy
groups. Thus, even the early impact modifiers had polymers with carboxylic groups
in the shell phase.
The core-shell polymer can be produced by continuous multistep seed emulsion
polymerization that covers the particles obtained during the preceding polymeriza-
tion step with another polymer. Thus, in the first step polymerization, a core phase
consisting of a rubbery polymer having a low glass transition temperature of
~ -30 0c, can be formed by polymerizing either a conjugated diene monomer (e.g.,
butene, isoprene or chlorobutene), an alkyl acrylate monomer containing 2-8 carbon
atoms in the alkyl moiety (e.g., butyl acrylate, ethyl acrylate, propyl acrylate, cyclo-
hexyl acrylate or 2-ethylhexyl acrylate), or a mixture of such monomers. The core
phase preferably accounts for 5O-9Owt%. If the core has a Tg higher than the
indicated limit, or when the amount of the core phase is below 50 or above
90 wt %, the impact strength may suffer. In the second step of polymerization the
shell phase is formed by copolymerizing an unsaturated dicarboxylic acid (e.g.,
maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, aconitic
acid or methylenemalonic acid) or its mono-alkyl ester (e.g., 1-20wt% of monoethyl
maleate) and monomers (e.g., ethyl or butyl acrylate, methyl or butyl methacrylate,
styrene, vinyltoluene, o-methylstyrene, acrylonitrile or methacrylonitrile). The shell
phase should preferably have Tg :?: 60 0c. The carboxyl groups contained in the shell
may be in the acid or salt form, i.e., - COOH or an alkali metal, alkaline earth metal or
ammonium salt. The preferred average particle size of the core-shell polymer is 120-
750 run. The polymer can be recovered from the latex by spray drying then extruding.
The early core-shell polymers developed for improving the impact strength of PA,
had in the shell polymers with carboxyl groups. Blends of these with PA-6 showed
good notched Izod impact strength values, but their efficiency for improving the
PA-66 performance was low and the melt viscosity was high, which resulted in poor
moldability. To ameliorate the situation, several blends were prepared in two steps,
first reactively blending the acidified core-shell copolymer with a low-molecular-
weight PA, then in the second step combining thus prepared compatibilized impact
modifier with the main, high-molecular-weight PA.
The first blends of the type PA/po-acrylic were deposited in 1965 by du Pont de
Nemours. The document described blends of PA (having at least 69 wt % amine end
groups) with an ethylene-methacrylic acid copolymer. The blending produced
super-toughened PA resins (Kohan et al., 1972). Eleven years later, to improve
toughness and impact strength of PA, Bayer blended the latter resins with ethyl-
ene-ethylacrylate-acrylic acid (EEA-AA). The optimum copolymer concentration
was reported to be less than 20wt% (Meyer and Tacke, 1978). In a sense these
patents are precursors of the PA/ionomer blends discussed previously.
In 1969 Imperial Chemical Industries disclosed blends of either PA-6, PA-66 or
PA-6lO, with a copolymer of ethylene-2-hydroxyethyl methacrylate-methylmeth-
acrylate or a similar one (Hepworth et ai., 1970). One year later the company
announced that for increased impact properties and flexibility PA-66 was blended
with ethylene-diethylaminoethylmethacrylate copolymer (Priddle et ai., 1972). In
these latter blends the effect of the impact modifier hinges not on acid-base reaction,
but on the hydrogen bonding. It is also worth recalling that good performance has
been also obtained from blends of PA with (co)polyvinyl alcohol - a partially
saponified ethylene-vinyl acetate (EVAc) or polyvinyl alcohol (PVAI). Thus the
acid-amine interactions are not the only ones that can be successfully used to achieve
compatibilization.
In 1975 Asahi Dow announced high impact strength blends of PA with 5-SOwt%
of either ethylene-acrylic acid (EAA) ethylene-carbonate (ECA), ethylene-ethylac-
rylate (EEA) ethylene-methylmethacrylate (EMM) or ethylene-vinylacetate (EVAc)
(Saito et al., 1977). Two years later Asahi Chemical Industry blended PA-6 with 5-
40 wt % of acrylic acid-grafted EVAc or ethylene-vinylacetate-acrylic acid graft copo-
lymer (EVAc-AA). The blends showed excellent impact resistance (Matsuki et al.,
1978,1979). In 1978 Bayer deposited invention reports for blends comprising either
PA-6, PA-66 or PARA, and a graft copolymer of acrylic acid, ethylhexyl acrylate,
butylacrylate, maleic anhydride, acrylamide and/or similar monomers onto PE or
EVAc. The blends showed good compatibility, high impact and oxidation resistance,
homogeneity and surface properties (Take et al., 1979; Korbert et al., 1979).
In 1970 Rohm & Haas Company developed a multistage copolymer that consisted
of a soft internal part, and a rigid external one, capable of reacting with amino
groups. The copolymer was prepared by two-step free-radical, emulsion polymer-
ization, first reacting 57wt% butyl acrylate and 13wt% of styrene, then 28wt%
methyl methacrylate and 2 wt % acrylic acid were added and copolymerized. After
drying, 10 wt % of the copolymer was compounded with polyamide-6 (PA-6) to give
facile-to-process blends with high impact strength (Owens and Clovis, 1972). Eight
years later the company announced the first blends of PA with an acrylic impact
modifier. Two-stage blending was used - first, PA-66 was pre-blended with poly
(methylmethacrylate-co-butylacrylate-co-butyleneglycoldiacrylate-co-diallyI-maleate),
then 75wt% of a low-molecular-weight PA-66 was added. The blends showed good
processability and high impact strength (Dunkelberger, 1979).
In 1978, Monsanto disclosed PA-66 blends with improved impact strength, com-
prising a mixture of two compatibilizers/impact modifiers, namely a butylacrylate-
2-hydroxyethylmethacrylate copolymer and a styrene-maleic anhydride copolymer
(Woodbrey and Moncur, 1982).
In 1981 Bayer developed PA-6 blends with 1-65wt% partially crosslinked butyl
acrylate-ethylene graft copolymer and butyl rubber. The wide range of claimed
compositions made it possible to generate not only the customary disperse morpho-
logy usually created to enhance the impact strength, but also the cocontinuous one,
responsible for achieving a hybrid performance combining the high modulus of PA
and elastomeric behavior of the acrylic copolymer. The patent reported high impact
performance of the alloys (Grigo et al., 1983).
In a contemporary patent application from du Pont de Nemours, to obtain high
Izod impact strength, PA-6 was blended with a core-shell acrylic elastomer, a butyl
acrylate-allylacrylate-ethylenedimethacrylate (Novak, 1983). The following year
BASF disclosed blends comprising 100 parts of PA-6 and 11 parts of ethylene-acrylic
acid-butylacrylate copolymer (EBA-AA). Blending produced high impact strength
materials (Reimann et al., 1983). Also in 1982 Rohm and Haas Company developed
high performance blends of polyamides with 1-99 wt % of imidized acrylic polymer,
containing at least 5% glutarimide units. The blends showed excellent processability
- high flow rate and high melt strength. Furthermore, molded specimens had good
impact strength, HDT, tensile strength and modulus. Performance of these materials
could be further enhanced by incorporation of impact modifiers (Staas, 1983).
In 1984 Du Pont-Mitsui Polychemicals Company announced similar impact-
modified blends - 60-95 wt % PA was blended with maleic anhydride-grafted
ethylene-ethylacrylate copolymer, 4O-5wt% EEA-MA (Narasaki and Yamamoto,
1985).
In 1986 Rohm & Haas developed an acrylic impact modifier for polyamides.
The material consisted of 50-90 wt % elastomeric core (from butyl acrylate,
tetramethylene methacrylate, methyl methacrylate, and acryloxyl propionic acid)
and 5O-10wt% shell (from butyl acrylate, methacrylic acid, and methyl methac-
rylate). Polyamide blends comprising either PA-6 or PA-66 with 15-3Owt% of the
copolymer had particularly good properties (Liu and Liwak, 1988).
More recently, in a disclosure from the Takeda Chemical Industries, 75-95 wt % of
either PA-6 or PA-66, was blended with core-shell polymer comprising an elasto-
meric core: poly(butylacrylate-co-l/4-butyleneglycoldiacrylate-co-allylmethacrylate)
having T g :S -30 °C/ and a glassy shell: poly(methylmethacrylate-co-ethylacrylate-
co-fumaric acid, itaconic acid or ethyl maleate) having Tg ~ 40°C. The alloys had
good impact strength at ~ -30 °C and were used for automotive parts/ office auto-
mation/ household, electric/electronic appliances, etc. (Oshima et al., 1994).
In 1993 Bayer Aktiengesellschaft announced three-component blends for injection
molding characterized by reduced water absorption, rigidity, and improved impact
strength at low temperatures. These comprised: (1) a PA; (2) a copolymer containing
up to 35 wt % of at least one (meth)acrylic acid ester of a tertiary alcohol, styrene or
(meth)acrylic esters (e.g., styrene/acrylonitrile/t-butyl (meth)acrylate); and (3) up to
35% of an elastomer having the glass transition temperature below -20°C. The
preferred elastomers are selected from between the graft polymers, e.g., buta-
diene/acrylic ester copolymers (based on butyl acrylate and/or ethylhexyl acrylate),
polyacrylic acid alkyl esters, copolymers of butadiene, acrylic acid alkyl esters and
vinyl alkyl ethers (viz. MABS), copolymers of ethylene, propylene and a diene
component, (viz. partially crosslinked EPDM-MA having particle diameter 150-
500 nm). For example, 10-95 wt % of PA-6, PA-66 or an aromatic semicrystalline
PA, was blended with copolymer comprising 30-75 wt % of either styrene or a-
methylstyrene, 20-40wt% of acrylonitrile, and 1.5-8wt% of butyl(meth)acrylate
haVing the particle diameter 150-500 nm, and optionally with up to 35 wt %
MABS. The blends may also contain stabilizers, pigments, dyes, etc. (Westeppe et
aI./1994).
Also in 1993/ in a patent assigned to The University of Akron, impact-modified
compositions of PA-66 with acrylic elastomer and fillers were described. Thus/
PA-66 formed a matrix in which polyethylacrylate (PEA or ACM) was uniformly
distributed in the form of discrete particles. As filler either precipitated silica (pre-
ferred) or carbon black was used. The filler provided an unexpected improvement in
retention of flexural modulus. The moldable blends were used for the production of
high-impact-resistant molded articles, namely housings for cameras, electronic
equipment and instruments and sports racquets, and automotive components such
as headlight housings. For example, 25 phr of precipitated silica was mixed for 9 min
with PEA at 50 rpm and a machine temperature of 100°C. An internal mixer with
Banbury type rotors was used. Next, the compound was dry blended with pre-dried
PA-66 and fed into a Japan Steel Work, JSW TEX-40, intermeshing and co-rotating
twin-screw extruder. The feed rate was 13Og/min, the screw speed was 200rpm,
and the residence time was approximately 5-6 min. The temperatures of the extruder
were set at 260-270 °C in the feeding zone, while in barrel zones 3 through 7 and for
the die 280 °C was set. The extrudate was quenched in water and pelletized. The
blend comprised approximately 80 wt % of PA-66, 16 wt % of PEA and 4 wt % of
silica (Nakajima, 1994).
The author offered a special comment regarding suitability of corotating, inter-
meshing twin-screw extruders (such as a JSW machine) for the blend preparation.
He noted that high shear, grinding action of the intermeshing screws ensured a short
residence time (to avoid thermal degradation), and enabled a high pressure build-up
over a short screw length. The co-rotating screws can provide high speed, strong
shearing forces and high outputs. With the screws rotating in one direction, the
materials are transferred from one screw to the other and undergo constant mixing.
This phenomenon is important for mixing and for heat transfer from or to the
surrounding inner wall.
Elastomeric PA blends
In this section the work carried out on elastomers modified by addition of poly-
amides will be summarized. These blends have been prepared to enhance the
solvent resistance of an elastomer, to increase its rigidity and/or to improve its
impact resistance.
In a 1980 patent application from Standard Oil, it was reported that addition of
6wt% of PA-ll improved impact resistance of either a high nitrile copolymer, or an
acrylonitrile-butadiene-methylacrylate copolymer (ABM) (Coffey, 1981).
In a series of inventions announced in 1980 by Monsanto, oil-resistant, elastomeric
alloys with high impact strength, high stress at break and high elongation, were
prepared by blending 2-40wt% of a PA-6-PA-66 copolymer (PA-6,66) with either
maleated (e.g., maleated PP, NBR or EPDM), or with carboxylated elastomers (e.g.,
acrylic elastomer, viz. ethylene-methyl methacrylate-acrylic acid copolymer 73-26-1,
VamaclM N123). For example, blends comprising 65 parts NBR, with 50 parts EPDM,
50 parts PP, 35 parts PA-6-PA-66 copolymer and 10 parts maleated PP were pre-
pared. The thermoplastic elastomers showed high impact strength, high stress at
break, high elongation and good oil resistance (Coran and Patel, 1982).
Two years later the company announced other elastomeric PA-blends, comprising
10-75wt% of either PA-6, PA-66 or PA-610, and 90-25wt% of cured, millable
polyurethane rubber (PU). The materials showed high strength, elongation, tough-
ness and impact strength. Vulcanization further increased the tensile properties and
toughness (Coran et al., 1983).
In 1990 Mitsui Petrochemical Industries disclosed polyalkene resin compositions
formed from 0-40 wt % of a cycloalkene resin, OS-55 wt % of a graft-modified
cycloalkene, 5-30 wt % of a graft modified a-alkene copolymer and 30-55 wt % of a
polyamide (e.g., PA-6, PA-66, PA-61O, PA-ll, PA-612, PA-MXD6 or PA-46). Mold-
ings obtained from these blends showed high impact strength, low surface delami-
nation, and excellent gloss. Furthermore, they had low water absorption and
excellent oil resistance (Moriya et al., 1994).
PA/CTBN elastomer blends

In 1976 Toray Industries applied for a patent protection for blends comprising PA-6
with 5-40 wt % carboxy-terminated nitrile rubber (CTBN) reinforced by addition of
glass fibers (30 wt % GF). The compounded material was reported to have high
stiffness and impact strength (Chiba et al., 1978). Three years later, PA-6 or PA-66
were impact modified by blending 1:1 with CTBN ionomer, then Zno, MgO,
Na2C03, Alz03 or BaO were added. In a following patent, 0.1-20wt% of an epoxy
resin was used instead. The material showed excellent impact resistance (Ube
Industries Ltd., 1980).
In 1982, PA blends with CTBN and Zno in the full range of compositions were
disclosed. The alloys were reported to have excellent fracture resistance in a wide
range of compositions (Bridgestone Tire Co., 1983).
P A/PDMS Rimplast elastomeric blends

In 1982 Petrarch Systems announced a new method of compatibilizing of siloxanes
with other thermoplastics. In particular, PA-66 or PA-6 were blended with vinyl-
terminated dimethylsiloxane, Si-H group-containing siloxane and Pt-catalyst. The
extrusion products (commercialized under the name of Rimplast™) showed high
tensile and flexural strength, and good notched Izod impact strength (Arkles, 1983).
PA/COPO elastomeric blends

In 1991 Shell Oil Company deposited a series of patents for blends comprising new
ethylene-propylene-earbon monoxide xyz-copolymers (Capo; where y:x = ()...(I.l,
MW = 2D-90kg/mol, and Tm ~ 220°C). For example, to obtain materials with
good balance of properties, COPO was blended with polyurethane (TPU) (George,
1992). In a later patent capo was blended with 2-20wt% PA-6 and a maleated-
hydrogenated styrene-butadiene-styrene block copolymer (O.5-20wt% SEB5-MA).
The blends showed excellent performance, such as a good balance of strength and
toughness (Machado, 1992).
In another patent of the series, blends of capo with a-methylstyrene-eo-acrylo-
nitrile (SAN, AN content = 55-80wt%) were found to be miscible. The blending
suppressed the capo melting point, thus it broadened the processing window
(Machado, 1993a).
16.2.3 PAIPO rigid blends

Polyalkenes such as polypropylene (PP) have been widely used in the form of
moldings, films, sheets, etc. These low density resins are relatively inexpensive,
have excellent processability, toughness, water resistance, gasoline resistance, chem-
ical resistance, etc. However, they are deficient in stiffuess, heat, impact and scratch
resistance, as well as in coating, adhesive or printing properties. To improve the
latter surface properties, grafting by an unsaturated carboxylic acid or an anhydride
(e.g., maleic anhydride) can be used. However, this does not improve physical
properties such as impact resistance, heat resistance and stiffness.
Thermoplastic polyarnides (e.g., PA-6 or PA-66) have been widely used in the
formation of mechanical and electrical parts for which excellent mechanical char-
acteristics, high heat resistance, stiffness, strength, oil and solvent resistance, and
good durability are required. PAs are widely used for automobile, electric and
electronic parts. Although polyarnides have good heat resistance and high mechan-
ical strength, they show poor impact resistance and notch sensitivity. Furthermore,
PAs have high density and they are Significantly more expensive than polyalkenes.
The impact resistance of the PA can be improved by blending with another polymer
or copolymer, usually a polyalkene or an elastomer. However, a major deficiency of
PAs is their tendency to absorb water, which may result in hydrolytic degradation
and loss of performance. Blending of PA with PO has been suggested as a method
for decreasing the total water absorption of the resin. Evidently, in the blends the
intrinsic water absorbency of PAis not reduced (since blending may reduce PA
crystallinity the intrinsic water absorption may be increased) but since a portion of
PAis replaced by hydrophobic PO the total water absorbency is expected to
decrease.
The physical blending of PA with these immiscible polymers provides only a
partial solution to the poor impact properties. The immiscibility makes it possible
to use only a low concentration of the elastomer, usually below the required level.
The interfaces between blend components introduce areas of weaknesses resulting in
mechanical failure. As the concentration of the toughening agent increases so does
the tendency to coalescence, as well as gross delamination during processing. As
a result, the products may show poor esthetics and loss of strength. The two-
component PA/PO blends at mid-eoncentration range, give products (extruded or
molded) showing great non-uniformity, ugly appearance and poor mechanical per-
formance. Consideration of PO and PA properties leads to the conclusion that only
compatibilization may produce materials in which the advantages of both these
resins can be fully explored. Furthermore, since both resins are relatively brittle, to
be useful the blends must also be toughened. The history of PA/PO blends is a
history of compatibilization and toughening - initially by means of addition of
diverse ingredients, more recently by reactive processing.
In a patent application of 1979 rigid blends of PP with PA were described. The
materials comprised 60 wt % PP, 20 wt % of either PA-6 or PA-66 and 20 wt % glass
fibers (GF). The materials were reported to have superior rigidity, tensile and impact
strength (Asahi Fiber Glass Co., 1981). These blends were not compatibilized - the
presence of GF was responsible for stabilization of the morphology.
Owing to inherent antagonistic immiscibility between PA and PO, the early
attempts to improve the impact strength of PA by blending it with PO were marginal
- it was difficult to obtain a good dispersion that would remain unaffected by
processing. It is known that the addition of a compatibilizer, for example a graft or
block copolymer of similar chemical structure to the blend components, may
improve quality of the dispersion. These additives were often added as a third
component to the blend. In this case it is important that the compatibilizer shows
good miscibility with both components of the blend.
For example, maleic anhydride grafted polypropylene (PP-MA) has been sug-
gested as a compatibilizer for PP/PA blends (Ide and Hasegawa, 1974). Here, the
PP-ehains provide good miscibility with the PP phase, whereas the maleic anhydride
groups react with the terminal-NH2 groups of the PA macromolecules. The PP-MA
has been also used as compatibilizer for polyethylene/PA blends (Chen et al., 1988;
Park et al., 1990). In this case, the blend performance depends on the miscibility of
the type of polyethylene used in the blend and the PP-chain of the compatibilizer.
Since PE and PP are usually immiscible, (excepting some low-molecular-weight
blends of PP with a LLDPE having suitable chain configurations) the compatibilizing
effect of PP-MA on the performance of PE/PA blends is expected to be marginal.
Several patents have described high impact strength PA blends comprising a
functionalized polyalkene or a polyalkene elastomer (e.g., TPO, EPR or EPDM).
The functionalized modifiers were obtained by reacting a PO or EPR with an
unsaturated mono- or polycarboxylic acid or its anhydrides, for example maleic
acid, maleic anhydride, fumaric acid, etc. Other monomers may also be incorporated
while introducing the functionality, e.g., acrylamide, acrylonitrile, styrene, vinyl
esters, vinyl ethers, etc. In particular it has been found that addition of styrene
increases the MA grafting rate and efficiency (Lambla et al., 1989).
Another more general method of impact improvement, that can be used for PA
blends with a variety of POS involves the addition of functionalized block copoly-
mers. In this case, the compatibilizer content is relatively high, 2(}-30wt%. The
method was initially introduced in a patent application of 1979 from Firestone Tire
& Rubber Company (Hergenrother et al., 1984). Today, the most frequently used
functionalized elastomers are the acidified, hydrogenated block copolymers, (SEBS).
Similarly to POs, these resins are also functionalized by grafting with mono- or
polycarboxylic acids (e.g., maleic acid, maleic anhydride, fumaric acid, etc.), and
may comprise other monomers (e.g., acrylamide, acrylonitrile, styrene, vinyl esters
or ethers, etc.).
In 1984 Asahi Chemical Industry deposited a general patent describing advant-
ageous blends comprising either PA (or another thermoplastic resin such as polye-
ster, polyurethane, Vinyl alcohol copolymer, etc). and at least one modified block
copolymer of substituted amino-vinyl, with an aromatic hydrocarbon polymer
block-A and at least one alkenic block-B. In the latter block at least one unit has
been grafted with at least one carboxylic acid group. The blends were reported to
have excellent impact resistance, adhesion, transparency, paintability, weatherability
and resistance to aging (Shiraki et al., 1986).
Development of PA blends with high concentration of PO (~4Owt%) was a
natural outgrowth of the work carried out to improve the impact strength of PA
by blending it with polyalkenes. Since most patents on PA toughening published
during the last 20 years involve reactive coupling, the basis for compatibilization was
also available (Ide and Hasegawa, 1974). In PO/PA alloys, usually about 4Owt% of
PO is dispersed in a PA matrix (Unitika, Ltd., 1982, 1983a; Paschke et al., 1983; Hobbs
et al., 1983; Deanin et al., 1990).
The most popular systems that belong to this category are PP blends with (in the
order of importance) PA-6, PA-66, PA-12, PA-rnXD6 (copolyamide from caprolac-
tam, m-xylylenediamine and adipic acid), or PARA (Utracki, 1989a). In these react-
ively compatibilized blends usually PAis the matrix, but those with PP as a matrix
are also available (e.g., ErefM from Solvay or OrgallayTM from Atochem). It is worth
noting that incorporation of PA into PP matrix causes a relatively small improve-
ment of properties, thus the type of PAis of little importance. On the other hand,
when PAis the matrix, the blend properties are intermediate between those of the
two polymers; low water absorption and permeability results from incorporation of
PP, whereas low oxygen permeability and high stiffness originate from the presence
of PA. The blends also show synergistic behavior regarding the flow (significant
reduction of shear viscosity facilitating blend processing, and making it possible to
injection mold thin-walled components). In blends, PA crystallization rate can also
increase, which shortens the injection cycle. In short, the performance of these blends
depends on the type of PA and its concentration, as well as on the type and extent of
compatibilization. Some grades are reinforced with up to 40 wt % mineral filler or
glass fibers. The blends are formulated mainly for injection molding and extrusion,
but compression, transfer, or blow molding grades are also available.
The often cited advantages of PA/PP blends are low moisture absorption, low
mold shrinkage, stiffness, impact and heat resistance (Davis, 1975; Subramanian,
1983, 1984; Glotin et al., 1989). Furthermore, the blends show good processability,
dimensional stability, low density (i.e., low cost per volume), low liquid and vapor
permeability, good resistance to alcohols, glycols and a mixture of gasoline with
ethanol (gasohol), improved heat aging, primer-less paintability, resistance to crack-
ing when exposed to metal halides (e.g., CaCh, commercialized in 1991 as System-
erTM S from Showa Denko). Principal blends applications include appliances,
automotive parts (e.g., under-the-hood moldings, cable ties, fasteners), power tool
housings, building materials, furniture and industrial (pump housing, impellers,
gears and bearing retainers).
In most cases, PA/PO alloying is a three-step reactive process: (1) modification of
PO by grafting on its chain acid or anhydride moieties (e.g., maleic, fumaric, acrylic,
methacrylic), (2) mixing the PO adduct with PA, (3) addition of remaining PO
(Nishio et al., 1990; Valenza et al., 1991; Liu et al., 1991; Hosoda et al., 1991). Two-
step blending of PA/PP by addition of the first-stage acidic copolymer (e.g., maleated
PP-wax, maleated styrene-butadiene-styrene or maleated styrene-ethylene/butyl-
ene-styrene tri-block copolymer) to a PA/PP mixture has been carried out as well.
In 1982 patents several PA/PO blends were described. In most cases either PA-6 or
PA-66 was blended with PP. The usual concentration range was 40-60 wt %, with PP
forming the dispersed phase (Standard Oil Co., 1983). In du Pont de Nemours' patent
PA-6 or PA-66 blends with PP were compatibilized by pre-compounding maleated
PP with PA, then adding the adduct to PA/PO blends. Again, the concentration
range was 40-60 wt %, with PP being the dispersed phase (Subramanian, 1983, 1984,
1985). In spite of compatibilization, in the compounded blends the PP drops were
spherical and well dispersed with an average drop diameter of 1 J.tm. During the
high-stress processing the drops deformed and coalesced into fiber-like structures,
especially evident on the skin part of an extrudate or an injection molded piece.
In 1984 Mitsubishi Petrochemical patented impact resistant blends comprising
1-99wt% PP, and 99-1 wt% PA-6, compatibilized by addition of 3phr maleic
anhydride-grafted EPR (Katsura, 1986). In a contemporary document from Mitsu-
bishi Chemical Industries, blends of 50-90 wt % PA with modified PO were found to
have good impact strength and water resistance. In particular, when 70 wt % of PA-
66 was blended with a mixture comprising 82 parts PP, 6 parts HDPE and 12 parts
EPR, the resulting alloys were found easy to mold. The moldings had good mechan-
ical properties even after 25 days immersion in water (Hasuo et al., 1985).
In a 1988 patent disclosure from Atochem, reactive, two-step compatibilization of
PA/PP blends was described. Thus, first PP was maleated, then reactively blended
with PA. The reaction usually resulted in formation of about 12 wt % of PP-PA
copolymer, to act as a compatibilizer for the non-reacted resins (Glotin et al., 1989).
In the contemporary Nippondenso patent, PA was blended with acidified PP and
glass fibers (GF). Excellent water resistance, moldability, improved thermal deter-
ioration resistance and low temperature impact resistance were reported (Iwanami et
al., 1989).
However, it should be recognized that reactive compatibilizations of PA with
maleated PO result in unstable systems - it has been reported that concentration of
the PA-PO copolymer can double during high temperature processing, from 12 to
25wt%. As a consequence, the crystallinity of the PA phase is reduced, the amount
of non-soluble gel is increased, which causes the blends to become more brittle and
more difficult to reprocess.
Also in 1988 Sumltomo Chemical Company disclosed blends comprising poly-
propylene (PP) with polyamide (PA-6 or PA-66). Thus, 100SOwt% of PA and 1-5%
by weight of an epoxy group-containing copolymer was compounded with a
maleated resin and fillers.
The maleated resin was obtained by grafting maleic anhydride onto a mixture of
1-99wt% PP with 99-1 wt% of an elastomer selected from the group consisting of
ethylenic copolymer rubbers, propylene-butene rubber, isoprene-butylene rubber,
polyisoprenes, polybutadienes, styrene block copolymers, linear low-density poly-
ethylenes and their blends. It was found advantageous to carry the reaction in a
single- or twin-screw extruder, while keeping the vents under vacuum to remove the
unreacted components (unsaturated carboxylic acid or derivative, unsaturated aro-
matic monomer, free-radical initiator, etc.), and such byproducts as oligomers and
various decomposition products of these reactive components. Although the react-
ion may be carried out in air, it is better to carry it out under a blanket of inert gas
(e.g., either nitrogen or carbon dioxide). When necessary, the unreacted components
and the byproducts may be also removed by solvent extraction at ~ 60°C.
The epoxy group-eontaining copolymers were obtained by copolymerization of
ethylene with 1~25 wt % of unsaturated epoxy compound, for example unsaturated
glycidyl esters. The epoxidized copolymer can be selected from a copolymer of
unsaturated glycidyl ethers and ethylene (EGMA), a terpolymer of an unsaturated
epoxy compound, ethylene and either vinyl acetate or methyl acrylate (e.g., EVAc-
GMA). These copolymers were produced in a high pressure radical polymerization
at 5O-4OOMPa and at 1DO-3OO°C.
The order of ingredient addition during the compounding is not critical. However,
it is simpler and more economical when maleation of either PP or an elastomer is
carried out in the first stage, then the remaining PP, PA resin and the epoxy group
containing copolymer (EGMA) are introduced. To 100 parts of the blend 0.01-300
parts of a filler may also be added. The filler can be selected from talc, mica, glass
fiber, carbon fiber, etc. Furthermore, flame retardants, lubricants, nucleating agents,
plasticizers, dyes, pigments, anti-static agents, antioxidants, weather resistance
improvers and others can also be added. The blends could easily be formed into
moldings, films or sheets, giving products that had a good balance in various physical
properties (especially high heat resistance, impact resistance and low temperature
impact resistance) and a uniform and smooth appearance (Mitsuno et al., 1994).
In 1990 Ferro Corporation disclosed blends that comprised 60-90 wt % of either PP
and/or EPR, 5-25wt% PA (either PA-6, PA-66, PA-6T61 or PA-46), and 5-25wt% of
a mixture of compatibilizing copolymers containing a vinyl aromatic hydrocarbon
and an unsaturated mono- or dicarboxylic acid (e.g., a terpolymer containing 60-
94wt% ethylene, 5-40wt% acrylic ester and 1-lOwt% maleic anhydride or glycidyl
methacrylate; EBA-GMA, Lotader™), styrene-maleic anhydride copolymer (SMA
Dylark™), maleated hydrogenated styrene-butadiene-styrene block copolymer
(SEBS Kraton TM G), maleated EPR, MBA, ASA, etc. The blends may also contain
glass fibers and/or mineral fillers. They can be extruded, thermo-formed, calen-
dered, laminated, stamped, pultruded, blow, injection or compression molded, etc.
These recyclable blends were reported useful for automotive, electrical, electronics,
building, furniture, small appliances and other applications (Chundury, 1994;
Chundury and Bitsch, 1994). In 1993 the company introduced reinforced PP/PA-6
blends with cocontinuous morphology under the trade name Gapex™.
It is worth mentioning that similar PA/PO blends were also developed using
amorphous, aromatic polyamides (PARA). For example, in 1989 Tonen Sekiyu
Kagaku and independently Mitsui Petrochemical disclosed such blends. The first
company patented blends of PARA with maleated polypropylene (PP-MA) and
phosphite ester heat stabilizer (Iwanami et al., 1990). In the other deposition, PARA
blends with maleated polyalkene, either PE-MA or PP-MA, were described. These
alloys were modified with hydrazine, and used for sliding and electrical parts.
Improved resistance to thermal degradation when in contact with metals (e.g., Cu)
was stressed (Yoshihara, 1990).
In 1991 Japanese patent depositions Mitsubishi Petrochemical Company disclosed
a new Class of rigid blends of polypropylene with engineering resins such as poly-
amides or polyesters. The alloys comprised 9~10wt% (preferably 7~30wt%) of a
semicrystalline (at least 20 % crystallinity by X-ray diffraction, XRD), modified co-
polypropylene with 1~90wt% (preferably ~70wt%) of either PA-6, PA-66, PET or
PBT. The co-polypropylene was a copolymer of propylene with 0.5-15 mol % of
either 7-methyl-1,6-octadiene or methyl-1,4-hexadiene copolymer. It was modified
by radical grafting with either 2-hydroxyethyl methacrylate, 2-hydroxyethyl
acrylate, 2-hyroxypropyl acrylate, glycidyl methacrylate or maleic anhydride.
Antioxidants, weather resistance improvers, and crystallization accelerators can be
added in amounts of D.1-5wt% each, and flame retardants, plasticizers and fluidity
improvers can be added in amounts of 5-30 wt % each. An organic or inorganic filler
(such as glass fibers, mica, talc, wollastonite, potassium titanate, calcium carbonate,
silica, etc.) can also be added in amounts of 5-60wt% for improving rigidity, heat
resistance and dimensional accuracy. To improve impact resistance up to 2Dwt% of
an elastomer can also be incorporated. Two-stage blending has been used. First,
dried components were uniformly mixed in an agitator such as a Henschel mixer,
then melted and kneaded in a single or twin-screw extruder. The resulting alloys
were found to possess good basic characteristics such as moldability, impact resis-
tance, rigidity, heat resistance, moisture resistance and chemical resistance, all of
which are required for molding materials for automobile parts, electrical parts, etc.
(Kihira and Nakano, 1995).
16.2.4 PAlstyrenics blends

Owing to immiscibility and relative brittleness of both polymers the blends of
polyamide with polystyrene, PA/PS blends are rare and of limited value. For
example, in 1989 Centrul de Cercetari pentru Fibre Chimice patented blends formed
during post-polycondensation of PA-6. Thus, granules of PA-6 and 5-1Dwt% PS of
finely dispersed particles were compounded together. The resulting blends showed
reduced water absorption and viscosity. The blends were used for extrusion of
profiles (Murariu et al., 1991).
By contrast, there is a large number of high performing PA blends comprising
styrene copolymers. In analogy to previously discussed PA/PO blends, the styrene
copolymer must show two attributes, (1) elastic properties and (2) enhanced mis-
cibility with P A.
There is a plethora of styrenic copolymers that show elastomeric character, such as
HIPS, SBR, SBS, SEBS, ABS, ASA, ACS, AES or SMA (Chapter 10). Also, incorpora-
tion of compatibilizing acidic or epoxy groups does not pose major problems. As a
result, there is a wide variety of PA blends with styrenics. Extrusion-blending of PAs
with copolymers haVing Tg < DOC was found to provide materials with excellent
mechanical properties. Thus, PA alloyed (at a ratio varying from 1:9 to 9:1) with
emulsion-type ABS (AES, AAS or MBS), as well as with not more than 4Owt% of
acid-containing acrylic rubber, and maleic anhydride-grafted SAN, was found suit-
able for extrusion or injection molding of articles with good mechanical performance
and impact strength.
Most PA/styrenics blends belong to the category of toughened PA alloys, pre-
pared by reactive compatibilization with acidified styrenic copolymers (e.g., N5 from
Thermofil, NovalloyTM-A from Daicel Chemical Industries, StapronTM_N from DSM,
Techniace™-TA from Sumitomo-Dow, Triax™-l000 from Monsanto, etc). However,
owing to the reactivity of styrene, one can easily modify styrenic components of the
blend, bringing in another functionality such as flame resistance. There are several of
this type of blend on the market, such as Akulon™ K228 from DSM, LatamitfI'M 66
from Lati, Starflam™ from Ferro Plastics, UltramitfI'M A3X from BASF or Zytel™ FR
from du Pont de Nemours. These fire-resistant, unreinforced blends, designed for
injection molding or extrusion, are primarily used in automotive and electrical
applications. They show excellent flame retardance, good mechanical properties
and dimensional stability.
In the following sections PA/styrenics blends are discussed under separate head-
ings, arranged in historical order of appearance - first PA blends with ABS
(announced in 1961), then with SBS block copolymers (1976), with SMA (1978),
with styrene-acrylics copolymers (SMBA, 1980), and finally with styrenics contain-
ing glycidyl methacrylate groups (PS-GMA, 1982).
P NABS blends
Polyamide blends with ABS were invented in 1961 (Grabowski, 1964a) and the same
year commercialized by Borg-Warner Corporation. Blending PA-6 with ID-60wt%
ABS produced materials having good tensile strength, elongation, hardness and
stability during molding. Twenty years later, the company disclosed blends of
PA-6 with modified-ABS (acrylonitrile-butadiene-styrene containing 0.5-15wt%
unsaturated carbonamide, e.g., acrylamide). The alloys showed high HDT and
good impact strength (Grant and Meyers, 1983; Grant, 1985). The same year ABS/
PA blends, ElemitfIM, were commercially introduced for use in automobile body
panels.
One of the most successful alloys of PA with maleated ABS has been Triax™-1000,
introduced by Monsanto in 1987. The PA-66/AB5-MA alloys have a cocontinuous
morphology and show excellent performance (Baer, 1982, 1986, 1987). Later it was
disclosed that incorporation of the maleic anhydride groups into the SAN chain
prOVides better control for the amount of acidic functionality of ABS (Lavengood et
al., 1986; Lavengood, 1987; Lavengood et al., 1988). The blends show stable, dispersed
morphology with high delamination resistance and excellent toughness. These alloys
were discussed earlier, along with other ABS blends.
In 1988, a patent application from General Electric described blends of an
amorphous polyhexamethylene isophthalamide (PARA) with rubber-modified poly-
styrenes. Optically clear, transparent materials, with near-zero birefringence, were
obtained (Angeli and Maresca, 1990).
PNSB-block copolymers blends

The styrene-butadiene (or isoprene) di-, tri- or multi-block copolymers were discov-
ered in 1956 (Porter, 1964; Holden and Milkovich, 1963, 1966). However, owing to
immiscibility of PA with SB the first blends of these two polymers were reported
only 20 years later.
Blends of PA with styrenic block copolymers date from 1976 when Davison and
Gergen from Shell Oil Company incorporated 5wt% of SEBS into PA-6 or PA-66,
and obtained good toughening effect (Davison and Gergen, 1977, 1980; Gergen and
Davison, 1978). Nine years later, maleated SEBS (SEB5-MA) was blended with 50-
97 % PA to give materials with very high notched !zod impact strength. The patent
described blends comprising 8Owt% PA-66 (with M n = 5 kg/mol and Tm > 200°C)
and 20wt% of a 1:1 blend of SEBS (with 29wt% of styrene) and a modified-SEBS
(with 1.6wt% of maleic anhydride). This was one of the first industrial uses of
maleic anhydride adducts with a hydrogenated block copolymer as an impact
improver for PA. The blends showed super-toughness, and could be readily formed
using any conventional method, such as extrusion, injection molding, blow molding,
pressure forming, rotational molding into sheets, films, foamed products as well as
injection-molded articles, blow-molded articles, pressure-formed articles and rota-
tional-molded articles having various kinds of shapes. The articles were used as, for
example, automobile, electrical, or mechanical parts, packaging or building mater-
ials, etc. (Gelles et al., 1987, 1988, 1994).
In 1985 Asahi Chemical Industry deposited a patent describing the use of
maleated styrene-butadiene block copolymers (SB5-MA). The resins were found to
be excellent impact modifiers for polar-group containing polymers, e.g., polyamides

(PA) or polyesters (PEST). For example, 8Owt% PA-6 was blended with SB5-MA to
give alloys with significantly improved impact strength, and elongation (Shiraki et
al., 1983).
In 1990 Sumitomo Chemical Company as well as Arco Chemical Technology
independently announced impact resistant polyamide blends comprising PA and
acidified elastomer. The first document described sequential blending method for
preparation of the alloy. First, an acidified elastomer (SEBS, EPR or EPDM) was
compounded with a polyamide, then the multipolymer was blended with PA. Good
processability, mechanical properties and low temperature impact strength were
reported (Ohmae et al., 1991). In the second document, PA was blended with
maleated elastomers and styrene-methacrylic acid copolymer for good impact prop-
erties (Papazoglu, 1991).
PA/SMA blends
The styrene-maleic anhydride copolymer was commercialized in 1963. Its blends
with polyamides were developed 15 years later. Thus, the patent deposition from
Monsanto of 1978 described PA-66 blends with SMA and/or with a butylacrylate-2-
hydroxyethylmethacrylate copolymer. High impact strength behavior was reported
(Woodbrey and Moncur, 1982).
Further developments of these blends were carried out mainly in Japan. In the
early 1980s several blends of PA with either SMA, styrene-methylmethacrylate-
maleic anhydride copolymer, SMM-MA, or SMA-modified rubber, SBMA were
disclosed. The blends had good processability, mechanical strength, impact resist-
ance and HDT.
Thus, in 1980, for good processability, mechanical strength, impact resistance and
HDT, ~95wt% PA-6 was blended with either SMA or with a styrene-butadiene-
maleic anhydride copolymer (Dainippon Ink and Chemicals, 1982a; Taguchi and
Mori, 1985). The same year, PA-6 was blended at a 1:1 ratio with polybutadiene
grafted with styrene and maleic anhydride (SBMA). The patent described the alloys
as having a superior set of properties to those obtained by blending PA-6 with ABS
Patent documents deposited in 1983 described PA blends with 5-SOwt% of
maleated PS as Diarex™ HF55 and/or with ID-SOwt% PBT. The alloys were found
to be water-resistant (Mitsubishi Petrochemical Industries, 1985).
PA/styrene-acrylic blends
In Monsanto patents of 1980, 55-99wt% PA-66 was blended with core-shell copoly-
mer (containing a cross-linked butyl rubber core, grafted with styrene, acrylonitrile
and ethyl maleate). The blends were reported to have excellent impact strength
(Baer, 1982, 1986, 1987). In 1981 Asahi deposited a series of patents describing high
impact strength blends of PA-6 with SO wt % of a styrene-methylmethacrylate-maleic
anhydride copolymer (Asahi-Dow, 1982; Shiraki et al., 1983; Kahata and Koyama,
1987).
In 1984, Phillips Petroleum announced that to improve impact properties PA-66
may be blended with a nitrogen compound-grafted styrene-butadiene copolymer
(Beever, 1986). One year later, Isover Saint Gobain's patent application described
blends comprising 25-SOwt% PA-6, ~75wt% PS and 2-10wt% of a rather
poor compatibilizer, a styrene-methylmethacrylate copolymer (SMM). The
dispersed phase diameter in the compression molded specimens were reported
large, 5-20 /l-m, indicating that the impact properties were most likely poor (Fayt et
al., 1986a).
PNGMA-containing copolymer blends

The first PA blends impact-modified by glycidyl methacrylate date from 1982/ when
Bayer disclosed PA-6 blends with polyol, and a styrene-methylmethacrylate-
glycidylmethacrylate copolymer (Muesing et al., 1984). Diverse GMA copolymers
have been used as compatibilizers and impact modifiers for multicomponent poly-
mer blends, such as PA/PPE, PA/PC or PA/PEST.
In 1985 Japan Synthetic Rubber Company aSR) announced blends comprising
polyphenylene ether (5-95wt% PPE), polyamide (1-90wt% PA), styrene-glycidyl
methacrylate (O.5-90wt% SGMA) and O-SOwt% of an impact modifier. The alloys
had good processability as well as fine solvent, oil and heat resistance (Motai et al.,
1987). Six years later GE Plastics Japan disclosed multicomponent blends of high
performance comprising 35-59wt% PPS Topren™, ~19wt% PPE, 11-29wt% of
either PA-6 or PA-12, 11-24wt% SEBS Kraton™ G/ and 1-14wt% of an acidified
polyalkene, e.g., ethylene/GMA or ethylene/vinyl acetate/GMA copolymer.
Furthermore, O.OI-lOphr of a low molecular weight compatibilizer (citric, malic or
agaricic acid), and 0.1-5phr of talc could be added to the blends. In these alloys PPS
was a matrix with the dispersed phase comprising PA containing PPE and filler. The
blends showed excellent dimensional stability and impact resistance, as well as good
heat resistance and surface appearance (Ishida and Kabaya, 1994).
In 1987 Stamicarbon patented PA blends with other engineering resins, namely
polycarbonate (PC) or polyarylate (PAr) compatibilized by incorporation of either
ethylene-glycidyl methacrylate grafted or a maleated acrylonitrile-butadiene-sty-
rene, AB5-MA or AB5-GMA, respectively (Yuichi and Suehiro, 1989). The same
year, Nippon Petrochemicals disclosed modification of ABS by incorporation of
either maleic anhydride or glycidyl methacrylate. These AB5-GMA copolymers
blended with polybutyleneterephthalate (PBT) gave alloys with outstanding heat,
chemical and impact resistance (Yasue et al., 1989; Orikasa et al., 1989). Owing to the
presence of carboxylic or epoxy groups the AB5-MA or AB5-GMA copolymers have
been particularly suitable for reactive blending in systems comprising PC, PA, PPE
or PEST, either as impact modifiers or compatibilizers.
In 1989 Oaicel Chemical Industries disclosed PA blends with polyesters, compa-
tibilized by addition of either SGMA or SMA. Thus/ a mixture of 5-95 wt % PA-6 and
95-5 wt % PBT and 0.5-30 wt % of SGMA was first prepared, then compounded with
PBT and with glass fibers (GF) when needed. The blends showed high modulus and
impact strength (Watanabe and Inozuka/ 1991). Two years later, Enichem announced
similar blends. Thus/ polyethyleneterephthalate (30-70 wt % PET) was blended with
70-30 wt % of either PA-6, LOPE, HOPE or LLOPE, and an epoxidized ethylene
copolymer, such as 1-10wt% EEA-GMA. The alloys had significantly improved
impact properties and tensile elongation (Natarajan et al., 1993/ 1994).
In 1992 Tonen Corporation patented blends that comprised 50-99wt% of either
PET or PA, polyalkene elastomer modified with glycidyl, 50-1 wt% PO-GMA and
polyalkene elastomer PO. The blends showed improved mechanical properties and
heat resistance of PET or PA, combined with the impact and weather resistance of
PO. They were used in automotive engineering, home electric appliances and indus-
trial machine parts, sports goods, and stationary and packaging materials
(Yokoyama et al., 1994).
16.2.5 PA/vinyls blends

Blends of PA with polyvinylchloride (PVC) polyvinylidene chloride (PVOC), poly-
vinylfluoride (PVF), polyvinylidene fluoride (PVDF or PVF2) or their copolymers are
rare, even when their compatibilization and toughening is relatively simple. The
reason for blending may be either a need for flame retardance, rigidity or a desire to
unite barrier properties of halide polymer with that of PA. The disadvantage of these
formulations is poor thermal stability of PVC at the temperatures required for
processing of PA. The PVC has a glass transition temperature Tg of 80°C and
normally is processed at a temperature of 1~2oo 0c. The PAs are usually melt
processable at a temperatures of 2 200 0C. The most popular PA-66 melts at 255°C,
polydodecamethylene dodecanoamide (PA-1212) has a melting point of 184 °C, PA-6
has a melting point of ;:::;: 215°C, and the amorphous aromatic polyamides (PARA),
prepared by condensation copolymerization of a mixture of adipic and isophthalic
acids with hexamethylene diarnine (e.g., a tetrapolymer of hexamethylene diamine
(HMD)/terephthalic acid (T), HMD/isophthalic acid (I), T/bis(p-aminocyclo-hexyl)
methane (PACM) and PACM/I, where the ratio of HMD to PACM was 94:6wt%
and the ratio of 1 to Twas 70:30wt%), had a glass transition temperature of 127°C.
In 1973 Showa Denko disclosed blends of PA-610 with polyvinylidene fluoride
(PVDF). The blending was done by the solution method. Thus, 75wt% PA-61O was
co-dissolved with 25wt% PVDF. The molded blends were immersed in water for
100 h at 30 °C - the water absorption was found to be significantly lower than that of
PA-610 alone (Saito, 1975). In 1986 the compatibilized PA/PVDF blends were de-
veloped by the Kureha Chemical Industries. The alloys were used for preparation of
impact resistant, gas impermeable films (Hizasurni et al., 1989).
In 1991 du Pont du Nemours disclosed blends comprising 40--60 wt % of either
PVC or PVOC and 40--60 wt % of a polyamide processable at a temperature below
220°C, such as PA-6, PA-1212 or PARA. The blends were compatibilized by addition
of 1-20wt% of an acrylic copolymer. The latter was composed of 5O-70wt% ethyl-
ene, 24-40wt% alkyl (meth)acrylate, vinyl acetate, or (meth)acrylic acid, 5-15wt%
of carbon monoxide and 0.1-5wt% acid anhydride. The preferred copolymer was
ethylene/n-butylacrylate/CO modified with succinic anhydride, for example, a
copolymer of 60 wt %-ethylene, 30 wt % n-butyl acrylate and 10 wt % carbon mon-
oxide, grafted with 0.9 wt % succinic anhydride groups.
Two-step blending was used - first PA and the compatibilizing copolymer was
homogenized, then PVC was introduced. To limit the thermal degradation of PVC
the blends had to be processed below 220°C, and 1 wt % of Irganox™ 1098 antiox-
idant was added. In the resulting alloys PVC was the continuous phase and PA was
the finely dispersed phase. The blends had been processed by extrusion or injection
molding into films, profiles, and moldings such as containers. The products showed
good notched Izod impact strength, elongation and tensile strength. The formulation
was found useful for recycling halide (co)polymers from commingled polymer scrap
into a variety of articles formed by extrusion or injection molding (Hofmann, 1994).
16.2.6 PA blends with TPU

In 1977, rigid blends comprising 15-26wt% PA-66 and 35-65wt% PA-6-co-PA-66
copolymer were toughened by addition of polyurethane (9-18wt% TPU). To
enhance stiffness, glass fibers have been added. The systems showed high strength
and heat resistance, making them suitable for molding automotive parts (McCarroll,
1979).
Two years later Bayer deposited a similar patent for PA-6 blends with 3wt% TPU
and 30 wt % GF. The resulting materials showed good processability and excellent
flexural, tensile and impact properties (Sanderson et al., 1981).
16.2.7 PA blends with reduced permeability

There are two types of PA-blends developed for reduction of permeability. On the
one hand an addition of PA to polyolefins, PO, reduces their permeability to gases
and liquids. On the other hand, PAs themselves can be rendered less permeable by
incorporation of another resin.
Early PA blends with reduced permeability

In 1966 Kurashiki Rayon Company deposited a patent for blends comprising PA-6 or
PA-66 with ethylene-vinylalcohol copolymer (EVAI) to obtain transparent materials
with high impact strength and low oxygen permeability (Watanabe et al., 1969).
Three years later, Bayer disclosed similar PA/EVAl blends. However, in the latter
case PA-6 was polymerized in the presence of EVAI. The blend showed high
modulus, as well as good tensile and impact strength (Bottenbruch et al., 1970).
Colorless PA blends with polyvinylpyrrolidone (0.OOI-10wt% PVP), showing
reduced permeability, excellent transparency and mechanical properties were
described in a 1967 patent application from Farbenfabriken Bayer (Hermann and
Schneider, 1971).
Blends with reduced permeability, containing PA

In 1979 du Pont de Nemours disclosed a highly successful method for reduction of
permeability by gases and liqUids of films and containers, formed from a polyalkene
(PO). For example, polyethylene (PE) was blended with 20 wt % PA-66 and a small
amount (e.g., 3wt%) of ethylene-fumaric acid graft copolymer as a reactive com-
patibilizer. The blending and compatibilization had to ensure that only relatively
large, uniformly dispersed PA drops were generated. During the subsequent film
or bottle blowing processes these large PA drops would easily deform into over-
lapping lamellae. The blends were found to reduce diffusion of gases or liquids,
and to improve impact strength (Subramanian, 1980). In 1982 the company intro-
duced Selar™ PA blends to be used as additive to PO for reduction of permeability
(Selar™ Barrier Resins, Bulletins E73971, E73973 and E73974 by du Pont de
Nemours).
In 1989 Rohm and Haas disclosed a new category of multicomponent blends.
These materials comprised (1) 2D-9Swt% of a polymer that constituted a matrix,
having less than 50 mol % of either (meth)acrylate or glutarimide moieties; (2) 2.5-
4Owt% of another polymer having less than SO mol % of vinyl alcohol moieties; and
(3) 2D-3Owt% of a polymer(s) that is miscible with the continuous phase (1). For
example, PMMA was blended with poly(p-hydroxy styrene), PVPh and EVAI; poly-
glutarimide (PGI) was blended with PVAl and PA-6; PGI with EVAI, PVC and MBA,
etc. The blends (formed into films, sheets, moldings or containers) showed good
barrier, physical, and optical properties (La Fleur et al., 1992, 1994a; Amici et al.,
1993).
In 1992 Bayer announced that transparent, gas-impermeable films were obtained
by blending polyalkene (e.g., LDPE and/or EVAc) with a semi-aromatic co-poly-
amide comprising 83-89wt% caprolactam and 17-11 wt% hexamethylenediamine
and isophthalic acid, PA-MXD6. The material was found to be useful for manufac-
turing food packaging films (Nielinger et al., 1993).
Blending for reduction of PA permeability

To reduce the permeability of PAs, one may add a less permeable resin (e.g.,
polyvinyl acetate, PVAc), a partially saponified polyvinyl acetate (PVAI), an acrylic
acid-grafted ethylene-vinylacetate copolymer (EVAc-AA), a partially saponified
ethylene-vinylacetate copolymer (EVAI), polyvinylidene chloride (PVDC), polyvinyl-
idene fluoride (PVDF), etc.
Addition of PVAc to PAs was also reported to improve their mechanical and
impact properties. For example, in a patent application from du Pont de Nemours
of 1948, polyamide-66 (PA-66) first had its ~ Swt% NH groups methoxy methylated
(or treated with maleic anhydride), then it was blended with 4-96wt% PVAc. The
barrier, as well as the mechanical and impact properties, were reported improved
(Hoover, 1948).
During the follOWing years improved methods of PA toughening were developed.
In many cases, instead of PVAc its saponified version, a polyvinyl alcohol (PVAI) has
been used to reduce oxygen permeability.
Others reported advantages of the PA/PVAI blends were a reduction of haze,
improved electrostatic discharge capability, and improvement of mechanical proper-
ties. For example, a patent application of 1960 from the Japan Rayon Company
described polyamide films with reduced permeability that were prepared by blend-
ing PA with lOwt% PVAI. The morphology, thus performance, was stabilized by
irradiation with ,-rays of the formed films (Okamura et al., 1963). Similarly, 6 years
later Kurashiki Rayon Company applied for patent protection for blends comprising
either PA-6 or PA-66 with EVAI. The resulting materials were reported to be
transparent and had high impact strength and low oxygen permeability (Watanabe
et al., 1969).
Blends of EVAl with PA have been used in packaging applications as barriers to
inhibit the passage of gases or liquids. However, miscible PA/EVAl mixtures show
poor forming characteristics, and even when successfully thermoformed and
stretched they show poor barrier properties. In blends designed for the reduction
of gas or liquid permeability EVAI should be immiscible, in the form of thin over-
lapping lamellae resulting in high turtuosity index. To make containers of oriented,
multilayer films, a solid phase thermoforming or a hot stretching is often used (e.g.,
70-9Swt% EVAI, haVing a degree of saponification 2Q-60mol %) was blended with
5-30wt% of an amorphous PA then hot-stretched. The compositions were useful as
a barrier layer in the thermoformed containers.
In 1977 Asahi Chemical Industry patented PA-6 blends with 5-40wt% of acrylic
acid-grafted EVAc. The blend showed excellent impact resistance and reduced
permeability (Matsuki et al., 1978). Four years later Uniroyal deposited a patent
application for blends comprising S0-9Swt% PA, 1-4Swt% of an ionomer, 0.5-
40 wt % ethylenic elastomer and 10-30 wt % of a partially saponified PVAc. It was
reported that the blends showed reduced oxygen permeability, improved film
clarity, as well as good set of mechanical properties (Ochiai and Sakurai, 1983).
In 1981 Allied Corporation developed a new set of principles for PA/EVAI blends
with improved oxygen barrier properties. Thus, it was specified that suitable PAs
should have a melting point above 175°C, so that PA-6, PA-ll, PA-12 or their
mixtures could be used. The resin was to be blended with 35-99wt% EVAI, dis-
persed as droplets with diameters not larger than 50 JLm (preferably 5-10 JLm). Films,
moldings or fibers having low penneability to gases (e.g., oxygen) were manufac-
tured from these blends at 235-260 °C (Mason and Tuller, 1983, Degrassi et al., 1984).
In 1982 Toyo Seikan Kaisha disclosed that blending 5-95wt% PA with an ethyl-
ene-vinylakohol copolymer (having lQ-9Owt% of ethylene), 95-5wt% EVAl, then
extruding into sheets produced materials having good drawability, barrier proper-
ties and high elongation at break (Maruhashi et al., 1983). Four years later compatib-
ilized PA/PVDF blends were developed by the Kureha Chemical Industries. The
blends were used for preparation of impact-resistant gas-impenneable films (Hiza-
surni et al., 1989).
It is known that EVAl in blends cannot be fonned at the relatively low temperat-
ures (that are required for processing many common materials) without rupturing
the EVAllayer. Fragmenting the EVAl layer results in a loss of the barrier properties.
For example, multilayer structures obtained by stretching the PA/EVAl blends at
temperatures below 110 °C exhibit poor barrier properties. The polyamides that have
been used in PA/EVAI blends have been semicrystalline resins, such as PA-6, PA-66
or PA-12. The blends may also comprise a mixture of two EVAl resins and a PA
resin. The ratio of the EVAls to the PA can be between 95:5 and 5:95.
More recently, amorphous, aromatic polyamides (PARA) became available. The
tenn 'amorphous aromatic polyamide' usually refers to those PAs that lack crystal-
linity, as shown by the absence of the crystalline melting peak. The amorphous
polyamides include resins in which one part of either the diamine or the diacid is
aromatic, and the other aliphatic. Examples are copolymers with mole ratios of 20:80
to 80:20 of hexamethylenediamine isophthalamide (PA-6I and PA-66, i.e., PA-6I/
PA-66), copolymers PA-61/PA-61O, copolymers PA-61/PA-612, etc. These resins
have low glass transition temperatures, making it possible to process them at
Significantly lower temperatures than those required for forming the more popular
semicrystalline PAs, such as PA-6 or PA-66.
In the period from 1987 to 1992, du Pont de Nemours developed several blends
comprising 30-85 wt % EVAl and 15-70 wt % of an amorphous polyamide (PARA;
e.g., copolymers of PA-6I with either PA-66, PA-61O or PA-612 (molar ratio 1:4 to4:1)
having a transition temperature of 3Q-100°C). In addition, up to about 1Owt% of
a liquid or solid plasticizer such as glycerol, sorbitol, mannitol or aromatic sul-
fonamide compounds, as well as small amounts of other materials such as other
polymers, processing aids, antioxidants, fillers or pigments, could be incorporated
into the blend. The polyamide fonned separate domains when blended with the
EVAI. The blends have been used either as films having low penneability to gases
and liquids, or as a barrier layer to inhibit the passage of atmospheric oxygen or
other gases in thennofonned multilayer containers or films (Chou, 1989, 1992).
The basic feature of these new materials was that they could be oriented and/or
thennofonned at temperatures below 110°C, while retaining the excellent barrier
properties of EVAI. Thus, the blends comprised 65-90 wt % EVAl (having an ethyl-
ene content 20-60 mol % and a degree of saponification at least 90 %) and 95-5 wt %
of an amorphous copolyamide haVing a glass transition temperature of 5o-90°C.
These blends have been prepared at 2OQ-230°C, typically using a twin-screw
extruder. The amorphous polyamides were found to fonn separate domains within
the EVAl matrix phase, which made it possible to stretch and fonn the blends at
temperatures below 110°C without destroying the continuity of the EVAI film. The
blends had been used for manufacture of films with multilayered structures, or to
generate such morphology by stretching or thennoforming. For example, multi-
layered containers, packaging films, and oriented multilayer shrink films with at
least one layer of such blends can be prepared from these alloys (Chou, 1994). The
PA/engineering resin blends 317
reversed compositions, 50-95 wt % of an amorphous PA blended with 5-50 wt %
EVAI (having at least Q-60mol %) ethylene units, and a degree of saponification
2: 90 mol %) showed oxygen barrier properties that were relatively independent of
humidity. The alloys were used to form packaging films, laminates and containers.
In 1988 AlliedSignal disclosed that amorphous copolyamide can be used as a
barrier layer exhibiting excellent oxygen barrier resistance when exposed to moist-
ure. The copolyamide was polymerized from (A) a lactam or aminoalkanoic acid,
such as caprolactam, (B) an aralkylene or cycloalkylene diamine, such as m-xylyl-
enediamine, and (C) one or more aromatic diacids, such as isophthalic acid and
terephthalic acid (Akkapeddi and Gervasi, 1989; Akkapeddi et al., 1989).
16.2.8 Biodegradable or recyclable PA blends

During the last few years, resulting from increasing concern for environment, a
growing number of patents for recycling of polymers have been issued. Among
these there are several that deal with biodegradability. For example, in 1991 Ems-
Inventa disclosed highly transparent, biodegradable blends comprising (1) 9(}-1 wt%
of a linear polymer, such as PA-6, PA-69, PA-66, PA-12, PEST, etc.; (2) 1(}-99wt% of
either a hydroxypropyl- or urea-starch; and (3) 4.9-50wt% of a plasticizer. The
blends were used for the manufacture of moldings or printable films (Buehler et
al., 1993). In the following patent, biodegradable transparent films were prepared
blending amylose with either a PA, PEST or POM, and gelatins. The materials were
found to be useful for transparent packaging films (Buehler et al., 1994).
Two years later, similar biodegradable polymer blends were disclosed by the
Industrial Technology Research Institute, Taiwan. These contained (1) 5O-99wt% of
a linear polymer selected from PE, PP, PB, PMP, EPR, EVAc, EEA, EAA, PS, SBR, SBS,
PVC, PVDC, PVF, PVDF, POM, PEG, PPG, PVAl, PVAc, PMA, PEA, PA-6, PA-66,
PET, CA and their blends (preferred are PE, PVC and PS); (2) 0.5-10 wt % of a peracid
that contained at least one peroxy carboxylic (-eOOOH) group and another func-
tional group, such as carboxyl, aldehyde or cyanate; and (3) starch. The function of the
peracid was to increase bio- and photodegradability of the blends. The mechanical
properties of these materials were reported superior to those of polymer and starch
that contained unsaturated fatty acids or esters as compatibilizers (Hsu et al., 1994).
In 1992 Bayer announced that impact-resistant, filled, molding blends were de-
veloped using polyamide (1(}-9Owt% PA-6 or PA-6, 66), polyethylene/polyamide
film scrap (1-50wt% PA/LDPE laminated film), 1-15wt% compatibilizing agent,
Q-6O wt % inorganic fillers and/or reinforcing materials, (}-30 wt % elastomers, and
(}-lOwt% other additives. As a compatibilizer either an ethylene-acrylic acid-t-alkyl
acrylate, ethylene-glycidyl acrylate, allyl glycidyl ether-t-alkyl acrylate, ethylene-
acrylic acid (or ester)-maleic anhydride or ethylene-maleic anhydride copolymer
was used. Blends containing recycled materials had good impact or notched impact
strength, combined with stiffness and toughness. They have been used for the same
applications as new materials, instead of haVing to be down-recycled (Timmermann
et al., 1994).
16.3 PA/ENGINEERING RESIN BLENDS
16.3.1 PAIPPE blends

Polyamide (PA) and a poly(phenylene ether) (PPE) are nearly ideal components for
alloying since, for this pair, polymer properties of one ingredient compensate for
deficiencies in the other. For example, in PA/PPE blends the latter resin provides
good heat deflection temperature and rigidity, whereas the former contributes
toward processability, impact strength, paintability and solvent resistance. However,
the two resins are antagonistically immiscible and must be compatibilized. The
commercial alloys usually contain 40-60 wt % PA, forming the continuous phase.
Some grades are also reinforced with up to 40 wt % glass fibes - these show moderate
processability. The blends have been mainly designed for extrusion, thermoforming,
blow molding, or injection molding. The manufactured products show high impact
strength, good tensile and flexural strength, high temperature creep, good solvent
and chemical resistance, and low moisture absorption. They are dimensionally
stable, paintable and platable. The principal use of PPE/PA blends is in the auto-
motive industry.
In 1983 General Electric introduced in Europe Noryl GTX, PPE/PA blends for
automotive applications. The blends having good heat and solvent resistance started
a new family of high performance blends from the company, as Noryl Plus™. Since
1985 several methods of PPE/PA compatibilization were patented by Allied-Signal,
Asahi, BASF, Borg-Warner, General Electric, Japan Synthetic Rubber, Mitsubishi
Petrochemicals, Sumitomo Chemical and others (Utracki, 1989, 1991, 1994).
Several commercial blends of PPE/PA are available, such as ArtleyTM from Sumi-
tomo Chemical, Dimension™ from AlliedSignal, LuranyITM from BASF, Lynex™ A
and Xyron™ A&G from Asahi Chemical Industries, NorylTM GTX from General
Electric, RemaloyTM from Mitsubishi Petrochemicals, UltranyITM from BASF, Ves-
toblencfIM from Hills, etc.
The first PPE blends with polyamide (PA) were disclosed in 1965 by General
Electric (Finholt, 1968). Incorporation of 0.1-25wt% PA was found to improve
processability of PPE - a five fold drop of die pressure was reported. Similarly, in
1971 Asahi disclosed improved processability and performance of PPE after blend-
ing it with up to 20wt% PA-12 (Komoto, 1972). However, the basic patent on
reactive compatibilization of the PPE/PA blends belongs to Sumitomo Chemical
Company. In the patent applications of 1979 the blends comprising 44wt% PPE,
44 wt % PA-66 and 12 wt % maleic anhydride-modified SBR were described. The
resulting alloys showed good solvent and impact resistance (Ueno and Maruyama,
1981, 1982; Maruyama and Ueno, 1982).
In a series of patent applications deposited in 1980-85 Asahi-Dow described
PPE blends with PA, compatibilized by addition of styrene-maleic anhydride
copolymer (SMA). Thus, a mixture of impact modified PPE with 5-70 wt % PA-6
and 2-50wt% SMA were reported to show high heat, solvent and oil resistance
(Kasahara et al., 1982). Sequential, reactive blending involved pre-blending PA
with SMA, then adding PPE. Blends comprising 4O-6Owt% PA, 25-35wt% PPE
and 5-25wt% SMA showed good processability, HOT and mechanical properties
(Asahi-Dow, 1982). In the following patent PPE blend with 20 wt % SMA and 50 wt %
PA-46 was used for electronic parts. The resulting materials were characterized by
good processability, HOT, high impact strength and solvent resistance (Harada,
1986).
In patents deposited in 1981 by Mitsubishi Petrochemical, PPE blends with poly-
styrene and either a polyester or polyamide were described. For example, PPE/HIPS
was blended with 1-15phr PA-66. The later resin was dispersed in form of drops
with diameters of 0.5-5 j.£m. Excellent moldability and mechanical properties were
reported (Mitsubishi Petrochemical Company, 1982, 1983b).
In 1983 General Electric disclosed blends of 70wt% PPE with PA-66, and poly-
carboxylic acid derivatives. The alloys were reported to have good processability,
PNengineering resin blends 319
chemical and impact resistance. Addition of phosphate esters made the systems
fireproof (Abolins et al., 1985). In the following patents, blends of PPE with PA-66,
were compatibilized by addition of 1wt % SMA. The resulting alloys had an HOT of
147°C and high impact strength (Van der Meer, 1985; Gallucci et al., 1985). The
following year it was reported that addition of oxalic dihydrazide induced resistance
to oxidation (Lohmeijer et al., 1986). Addition of benzoquinone was found beneficial
for morphology stabilization (Gallucci and Avakian, 1987).
Further improvements to the PPE/PA blends were revealed in additional patents
deposited in 1984-86 by the company. For example, addition of citric acid was found
to enhance the impact strength (Gallucci et al., 1985). The use of amino-terminated
PPE was reported beneficial when blending PA-adducts with maleic anhydride, PA-
MA (Fujii et al., 1987). Incorporation of SEBS improved the mechanical properties,
and resulted in low temperature ductility (Lee et al., 1987). Similar effects were
obtained by reactively incorporating core-shell impact improvers. In the later patent,
5-94wt% PPE was reactively compatibilized using l-SOwt% acrylic copolymer (its
core comprised butylacrylate-methylmethacrylate, while the shell contained styrene
and maleic anhydride) (Van der Meer et ai., 1987). Similarly, in 1987 Shell Interna-
tional Research announced that PA/PPE can be efficiently compatibilized and
impact modified by incorporating maleated hydrogenated styrene-butadiene block
copolymer (SEB5-MA) (Modic and Gelles, 1988).
In 1984 General Electric Company deposited a patent concerning compatibiliza-
tion of PPE with polyamide, selected from PA-6, PA-66, PA-ll, PA-12, PA-63, PA-64,
PA-610, PA-612 and their mixtures. The blends were prepared by melt-blending
PPE, PA and a reactive compatibilizer. The latter had acyl functionality and either a
carboxylic acid, acid anhydride, acid amide, imido, carboxylic acid ester, amino or
hydroxy group/ namely either trimellitic acid chloride, terephthalic acid chloride or
l-acetoxyacetyl-3/4-dibenzoic anhydride. Subsequently, the blends were neutralized
by metal oxides, namely 200/ CaO, MgO, Sb20J etc. Other additives, such as impact
modifiers, stabilizers, pigments and others, can also be added (Aycock and Ting,
1986/1987/1994). For example, PPE-oH end groups were capped in solution with
trimellitic anhydride acid chloride. The level of anhydride functionalization was
measured by appearance of carbonyl bands and diminution of hydroxy bands in
the IR spectrum. A mixture of 24.5 parts anhydride-functionalized PPE, 41 parts PA-
66 and 10 parts of SEBS was compounded in a twin-screw extruder at 290°C. Molded
test parts showed higher impact and tensile strength than test parts for blends
containing either non-functionalized PPE, or PPE grafted with MA. Solubility meas-
urements in formic acid and toluene showed that blends containing PPE end-
capped with the anhydride functionality had high levels of PPE-PA copolymer.
The same year BASF announced PPE blends with PA. The alloys were made self-
extinguishing by addition of either phosphorus acid derivatives, or oxides and fillers
(SeIer et al., 1986).
In 1984 Borg-Warner Chemicals announced reactive modification of PPE. Thus/
the resin was reactively extruded without peroxides with unsaturated either car-
boxylic acid or acid anhydride, for example maleic anhydride. Next, the maleated
resin (5-75wt% PPE-MA) was blended with polyamides, such as PA-66, and with a
hydrogenated styrene-butadiene-styrene copolymer (5wt% SEBS, Kraton lM G). The
resulting alloys were reported to show high solvent resistance, good impact strength,
elongation, and tensile strength (Grant and Jalbert, 1987; Grant et ai., 1987/ 1990). In a
later patent from the company PPE/PA-66 blends were reactively compatibilized.
First, PPE was reactively extruded with 1 wt% of tetracarboxyl cyclopentane. Next,
the adduct was combined at a 1:1 ratio with PA-66 and with 5phrSEBS (Kraton lM G).
The alloys were smooth, nondelaminating and ductile with good impact strength
(Grant and Jalbert, 1989).
The following year Chemische Werke Hills introduced interesting blends of PPE
with polytransoctanylene (PTO) and PA. These were prepared in two steps. For
example, first 60-98 wt % PPE was blended with 40-2 wt % PTO and maleic anhyd-
ride (0.1-5wt% MA), then this mixture was compounded with PA-12. It is worth
recalling that in previous patents the company claimed miscibility of the PPE/PTO
systems. Although there are some doubts if these polymers are indeed miscible
down to the molecular level, their blends do show interesting properties without
additional compatibilization. Furthermore, grafting with MA not only helped to
increase the miscibility of these two ingredients, but also made them interact with
PA-12. The resulting alloys had good processability, high impact strength, excellent
solvent resistance and an HOT of 156°C (Droescher et al., 1986).
Blends with excellent processability, heat resistance and mechanical properties
were disclosed in 1987 by Sumitomo Chemical Company. The alloys comprised 35-
98wt% of a semicrystalline matrix polymer (e.g., PA-6, PA-66,PBT, PET, PE, PP,
POM, PPS or PEEK), a dispersed phase 1-65wt% PPE, 0.1-50wt% of a compatibil-
izer, and reinforcing talc and/or glass fibers. As compatibilizer, either maleated-EPR
(a copolymer of ethylene, vinylacetate and glycidyl methacrylate, EVAc-GMA), a
monomeric maleic anhydride (MA), or bis(4-phenyl isocyanate) was used. The
reactive compatibilization was conducted in a high speed twin-screw extruder
developed in collaboration with Japan Steel Works specifically for the reactive
processing. The resulting blends had PPE dispersed into particles with diameters
of 0.01-10 J.Lm. The alloys could be extruded or molded into variety of parts, for the
automobile, electrical and electronics industries (Abe et al., 1988; Nishio et al., 1988,
1994).
The same year Asahi Kasei Kogyo Kabushiki Kaisha announced new, five-
component blends. These comprised: (1) 100 parts of a polyamide mixture, consisting
essentially of0-5Owt% aliphatic PA (e.g., PA-6 or PA-66) and 5o-1oowt% of a semi-
aromatic PARA having hexamethylene terephthalamide units (e.g., PA-6T/66,
PA-6T/61 or PA-6T/66/612); (2) 0.05-10 parts of polycaprolactone (PCL, having
Mn ~ 10kg/mol); (3) 0-35 parts of a mixture consisting of 6O-100wt% of an
ionomer, and o-4Owt% EPR; (4) 0-10 parts of a monomeric mixture consisting of
4o-80wt% of an oxide and/or carbonate (e.g., ethylene carbonate, ethylene oxide,
propylene oxide and butylene oxide) and 20-60wt% of a polyhydric alcohol (e.g.,
ethylene glycol, trimethylene glycol, butanediol, diethylene glycol, glycerin or pen-
taerythritol; and (5) 0-150 parts of PPE. The composition had improved moldability,
and excellent stiffness, not reduced by humidity. The composition could also contain
additional components to improve the impact properties. The blends have been used
for molding parts for the automotive, electrical or electronic industries (Hamada
et al., 1994).
Functionalized polyphenylene ether (e.g., maleated PPE-MA) was also used in
blends with PA that were disclosed by AlliedSignal in 1987-1990. Thus, PPE-MA
was reactively blended with 0.01-30 wt % substituted alkene (e.g., bis(2-hydroxyethyl
fumaramide), then mixed with 5-95wt% PA and 5-50wt% of a functionalized
ethylene-a-alkene elastomer. The final blends had high elongation and impact
strength. The functionalization, as well as subsequent blending, was carried out in
reactive extrusion. Unique combinations of toughness, HOT and dimensional
stability were claimed. The performance could be further improved by incorporation
of fillers, (e.g., glass fiber) to improve rigidity, or carbon black to improve weath-
erability (Akkapeddi et al., 1988, 1992). Dimension™ PPE/PA-6 blends for extrusion,
blow and injection molding were introduced in 1987. Grades with glass fiber are
mainly used in automotive applications (Utracki, 1994b).
A multistep method for blending PPE with (co)polyamides, e.g., PA-6, was dis-
closed in a Czechoslovak patent application of 1988. Thus, PPE was compounded
with 3-5 wt % PAin an extruder with heating zones stabilized at 250, 260 and 270°C.
Next, into this blend an appropriate amount of PA was incorporated. In the final
blend, PA formed the matrix in which composite particles of PPE-PA were dis-
persed. The blends showed better mechanical performance than comparable blends
prepared in a single step (Behner et al., 1991).
In 1989 General Electric announced new, flame-resistant blends. These comprised
functionalized polyphenylene ether (reacted with 3.5 wt % trimellitic anhydride acid
chloride and 3.5 wt % dimethyl-n-butyl amine, mPPE), a PA having low content of
terminal amine groups (e.g., PA-4, PA-6, PA-46, PA-66, PA-34, PA-ll, PA-12 or
PA-610), and poly(dimethyl-diphenyl siloxane (PDMDPhS) in a proportion of 0.1-
15 parts per 100 parts of a PPE/PA blend. The latter compound comprised at least
one of the following functional groups: amine, epoxy, carboxylic acid, anhydride or
ester. First, PPE and PA were mixed, then PDMDPhS was added. For enhanced
toughness the blends may also contain 1-20wt% of a styrenic impact modifier, such
as SEBS (Smith et ai., 1990, 1994). Two years later the company deposited patent
applications describing impact-resistant PPE/PA blends. The improvement was
achieved by addition of a compatibilizing agent and styrene-butadiene radial copo-
lymer. Thus, to the mixture of 3O-70wt% PPE with 7D-30wt% PA-66, 1-2phr of
either citric acid or chloroepoxytriazine and 9-15phr K-Resin™ from Phillips Petro-
leum, were reactively compounded. As a result, the Izod impact strength was
improved (in comparison to blends with HIPS) by a factor of three (Gianchandai et
ai., 1993). In the following patent an excellent impact strength was achieved by using
a tapered instead of a radial block copolymer. Thus, blends of PPE with PA at ratios
of 70:30 to 30:70 were impact modified by addition of 5-15 phr linear-5B copolymer,
citric acid and SEBS block copolymer (Yates, 1993). In another patent deposited in
1991, 25-75wt% PPE was blended with polyamide (25-75wt% PA). The later resin
was formed from a diamine, a second amine (selected from between triamines or
polyamines), and a dicarboxylic acid. To improve the impact strength, 1-3Owt% of
an impact modifier was also added. Compared with earlier formulations these
blends had higher melt strength and blow moldability (Chambers, 1993).
In 1992 GE Plastics Japan disclosed blends comprising 20-70 wt % of modified PPE
and 3Q-80wt% of a mixture of PAs (PA-6, PA-4, PA-66, PA-12 or PA-6lO). It was
reported that performance of these blends was enhanced when PA resin was com-
posed of a mixture comprising 3-20 wt % of PA having Mn ~ 11 kg/ mol having a
terminal amino group concentration of at least 7.0 x 10-5 mol/g, and 97-S0wt% PA
having Mn =9.5-32 kg/mol, and a terminal amino group content of not greater than
5.5 x 10-5 mol/g. The PPE resin was either grafted with styrenic units, and/or had a
proportion of the terminal groups replaced by epoxy, acidic or anhydride (e.g.,
trimellitic anhydride) groups. An impact modifier (e.g., SEBS Kraton™ KG) could
also be used. The alloys showed good combination of moldability and mechanical
properties (Kodaira et ai., 1994). In another contemporary patent from the company,
multicomponent blends of PPE with PA, and with other polymers were disclosed.
For example, the blends comprised: (1) 6-19wt% PPE, (2) 11-29wt% of either PA-6
or PA-12, (3) 11-24wt% SEBS Kraton™G, (4) 1-14wt% acidified polyalkene (e.g.,
maleated-EPR, ethylene/GMA, or ethylene/vinyl acetate/GMA), and (5) 35-59wt%
polyphenylene sulfide (PPS, Topren™). Furthermore, 0.01-10phr of a low-molecu-
lar-weight reactive compatibilizer (citric, malic or agaricic acid) and O.I-5phr of talc
were added. In the blends PPS formed a matrix, while the PA phase, containing PPE
and filler, formed the dispersed domains. The blends showed excellent dimensional
stability and impact resistance, as well as good heat resistance and surface appear-
ance (Ishida and Kabaya, 1994).
In 1991 Mitsubishi Petrochemical announced blends that contained 10090wt%
hydroxyalkylated polyphenylene ether (e.g., PPE modified by glycidol or epichloro-
hydrin), and 10-90 wt % of a resin selected from a polyalkene (PO) modified by
incorporation of either carboxyl-, epoxy-, or hydroxyl-groups (e.g., maleated-PP,
glycidyl methacrylate-modified PP, ionomers or EVAI), a polyamide (PA, e.g.,
PA-4, PA-6, PA-66, PA-46, PA-12 or PA-6lO), or a polyester (PEST, e.g., PET, PBT,
PCT, PEN or LCP). The blends could also contain unmodified PPE, PO, styrenics,
additives, reinforcements, etc. The new materials showed excellent moldability,
solvent and heat resistance and mechanical strength. They were used for production
of gears and cranks, automobile manifolds and electric parts (Arashiro et al., 1994).
The same year ECP Enichem Polimeri stated that blends obtained by compound-
ing 5-95 parts PPE, with 95-5 parts PA-6 or PA-66, 1-100 parts of an elastomeric
copolymer containing a vinyl aromatic polymer grafted on an alkenic elastomer (e.g.,
styrene-grafted EPDM), and with 1-10 parts of an organic diisocyanate (e.g., MDI),
had a particularly good balance of mechanical, thermal and process properties
(Pernice et al., 1992). In a contemporary patent from the company, blends of PPE,
PA and an aromatic nitro derivative were described. The moldings had excellent
balance of mechanical, physical and thermal properties, good chemical resistance
and processability. The shaped articles showed high impact strength, thermal stabi-
lity and low water sensitivity. The alloys were used for the manufacture of articles
that could be furnace-painted, such as automotive parts, parts entering into contact
with motors, household electrical apparatus, electronic articles and technical articles
in the form of cups, boxes, containers, panel sheets and rods (Bencini and Ghidoni,
1993).
In 1992 Mitsubishi Petrochemical.disclosed blends that comprised: (1) 15-75wt%
PPE; (2) 85-25wt% of a PA selected from PA-6, PA-66 or an amorphous PA; (3)
polyoxymethylene (0.01-5phr POM); and (4) 0.05-5phr (based on PA and PPE) of a
Lewis acid selected from trialkylborane, trialkylborate, boric acid or halogenated
boron. The alloys showed improved compatibility and had excellent heat and impact
resistance. They could be used to mold automobile parts (e.g., bumpers and door
panels). Moldings had excellent appearance and color hue after high temperature
molding (Takayanagi et al., 1994).
A contemporary deposition from Himont described multicomponent blends com-
prising (1) 2().-6()wt% of an engineering resin (either PPE, PA, polyester, PEST or
their mixtures; (2) 3O-65wt% propylene grafted with styrene and a glycidyl (the
total concentration of styrenic and glycidyl monomers was 50-200 phr, and the
glycidyl monomer was 0.1-20.0wt%; and (3) 2-15wt% of an elastomer (EPDM,
SBS, SEBS, EPR, etc.). The blends showed excellent flexural and tensile strength,
and increased resistance to delamination that can be considered an indicator of
improved miscibility. These materials were reported useful for molding articles
such as auto parts, appliances and motor housings (Okamoto, K.T. et al., 1993, 1994).
Also in 1992 General Electric announced further improvement to PPE/PA blends.
Thus, 5-95 wt % PPE functionalized by reaction with maleic anhydride was blended
with 95-5wt% of either PA-6 or PA-66, and with 5-25phr of a selectively hydro-
genated diblock copolymer of the A-B type. In the latter, resin A stands for styrene
(20-40 wt %) and B for an ethylene-propylene polymer, Kraton1M GX. It was reported
that when PA content exceeded 35 wt %, the resin formed matrix phase. The
saturated diblocks provided excellent heat aging characteristics, unexpected since
the previous work with saturated SEBS triblock had shown no improvement in this
regard (Lee, 1994). In the following patent from the company, first PPE was capped
with 2-7wt% of a salicylic acid ester, then blended with 6-200phr of a styrene-
butadiene-styrene copolymer. Next, the blend was dispersed in a selected matrix
resin, selected from PS, PA, PEST or polyetherimide (PEl). These moldable blends
showed high resistance to loss of impact strength after thermal recycling (Richards
and White, 1994).
The same year AlliedSignal described preparation of PPE/PA blends by first
dissolving ~wt% PPE in monomeric lactam(s) (e.g., caproyl-, lauryl- and/or
capro-lactam), then adding to the reaction mixture 1Q-20wt% of a compatibilizer,
such as maleated PPE, SAA or SMA, that is miscible with PPE. The polycondensation
of lactams was carried out at 230-270°C in an autoclave. The resulting blends had,
for example, a PA-6 matrix with PPE dispersed domains of diameter O.6-3fLm,
containing occluded PA-6 microdrops with diameters of O.2-o.4fLm. Grades with
glass fiber have been mainly used in automotive applications (Samuels, 1994).
Other interesting blends were described in a patent deposition of 1993 from East-
man Kodak Company. The document described a broad class of alloys comprising
(1) polyamide (e.g., PA-6, PA-66, PA-ll, PA-3Me6T or PA-MXD6), (2) a polymer
miscible with polystyrene (e.g., PPE, HIPS, PVME or 4MePC), and (3) 5wt% of a
copolymer of styrene and more than SOwt% vinyl phenol (Le., poly(vinylphenol-g-
styrene) PVPhS). The resulting materials showed good stress and strain at break,
tensile modulus, yield stress and the work to break. In most examples PA/PPE ratio
was 1:1. The alloys were used to produce moldings and films, used in engineering
and packaging applications (Landry et al., 1994).
16.3.2 PA(1)IPA(2) blends

The PA(1)/PA(2) blends are commercially available for injection molding or extru-
sion. For example, Zytel 3100™ from du Pont de Nemours is a blend of PA-6 with
PA-66, whereas Gri/onTM BT from EM5-Chemie is a blend of PA-66 with a semicrys-
talline polyamide. These materials show improved processability over that of the
component polymers, good solvent resistance, elongation, low t!!mperature impact
and tensile strength, as well as enhanced barrier properties against permeation by
gases and liquids. They find use in the manufacture of safety helmets, housings for
electrical and electronic parts or chassis, pulleys, fans, lock parts, levers, clamps, etc.
There is a large body of literature concerning polyamide(1)/polyamide(2) blends,
where the two polymers are chemically different. The first PA/PA blends were
patented in 1958 - Polymer Corporation patents described PA-66 blends with either
PA-6 or PA-610. The resulting materials were reported miscible in the amorphous
phase, and easy to compression mold into articles free of residual stresses (Stott
and Hervey, 1958). However, miscibility is not a rule in PA/PA blends. For
example, PA-66 was blended with a semi-aromatic polyamide, a poly(hexamethyl-
ene isophthalamide) (PA-6l) to produce fibers with improved modulus and
heat resistance, to be used for tire yarns. The polyamides were found to be
immiscible, showing strong intermolecular interactions, and a possibility of trans
reactions that resulted in improvement of the overall performance (Zimmerman
et al., 1973).
Using the heat of mixing approach and treating PA macromolecules as copoly-
mers (comprising an amide mer and either aliphatic or aromatic mers) Ellis was able
to describe the miscibility/ immiscibility observations for a great variety of PA
mixtures (Ellis, 1989/ 1990; Utracki, 1989a). There has been also other research
investigation into the miscibility and phase behavior of PA/PA blends (Takanayagi
et al., 1980; Hirakawa et al., 1985).
In 1982 Uniroyal patented toughened mixtures of polyamides that produced
alloys with high notched !zod impact strength at low temperatures. These were
prepared by blending 69-88wt% of the PA/PA mixtures (e.g., PA-6 with PA-ll)
with 12-31 wt% of a sulfonated-EPDM (Weaver, 1983/ 1985). The following year Du
Pont Canada described blends suitable for production of oriented films, comprising
75-98wt% PA-66, with another polyamide, selected from PA-6, PA-612, PA-ll or
PA-12. Blending these resins in a ratio of 94:6 to 10:90 was found to improve film
printability, clarity, barrier properties to oxygen permeability and dimensional
stability (Mollison, 1984).
The same year, to increase the impact resistance and flexural strength of PA-66, the
resin was blended with either 1-15wt% PA-6 and a mineral filler. The patent also
described PA-66 blends formulated for increase of the melt viscosity, making it more
suitable for vacuum forming. Thus/ PA-66 was blended with either O.5-40wt%
methylrnethacrylate-styrene-maleic anhydride, or with styrene-methacrylic acid
copolymer (SMM-MA). The alloys also showed high HDT and impact strength
(Asahi Chemical Industry Co./ 1985b).
In 1983/ blends of PA-66 with 1-15wt% PA-6, and mineral fillers were reported to
provide materials showing good impact resistance and flexural strength (Asahi
Chemical Industry Co./ 1987). Similarly, blends of PA-6 with PA-66, reinforced
with aminosilane-treated glass fibers, were found to give good impact strength
(Toray Industries, 1985).
16.3.3 PAIPARA blends

In 1968 semicrystalline polyamides (e.g., PA-6, PA-66, PA-610, PA-ll or PA-12) were
blended with amorphous polycondensates of terephthalic or isophthalic acid with
hexamethylene-diamine (PARA). The materials, compatibilized by transarnidation,
showed additive properties. The alloys had good balance of processability and
mechanical performance characteristics (Dynamit Nobel A.-G./ 1969). In a Unitika
patent application of 1981/ partially aromatic PA-616T was blended with another PA
at a 1:1 ratio. The materials were reported to be easily formable into tough and strong
fibers or films (Unitika Ltd., 1982b, 1983b).
In a patent deposited by du Pont de Nemours in 1982/ blends of PA-66 with PARA
(comprising isophthalic acid, terephthalic acid, bis(p-aminocycloexyl)methane and
hexamethylene diamine) were reported to be easy to mold, forming transparent and
solvent-resistant parts (Epstein and Pagilagan, 1983). Blending PARA with either
PA-6 or PA-66 was also reported in 1989 by Rhone-Poulenc Chimie. The latter
document described alloys of semicrystalline PA (e.g., PA-6 or PA-66) with amorph-
ous/ aromatic polyamides (PARA) as having good impact resistance (Prevost and
Roberjot, 1991).
In 1983 Mitsubishi Gas Chemical Company disclosed blends that comprised
PA-66 blended with an amorphous copolyamide (from caprolactam, m-xylylenedia-
mine and adipic acid (PA-mXD6», and PBT. The blends were reported to have had
good resistance to heat, chemicals, oil, impact strength and toughness. Seven years
later the company commercialized a similar blend of PA-6 with poly(m-xylenyle
adipamide) for the production of tough/ high temperature, food packaging films
with good barrier properties against permeation of oxygen (Mitsubishi Gas Chem-
ical Co./ 1985b).
In 1985 a patent document was deposited describing blends comprising 100 parts
PA-6 with 5-100 parts poly(trimethyl hexamethylene terephthalamide) TrogamiJIM
T. The blends were resistant to cracking when exposed to metal halides (Ube
Industries Ltd., 1984).
In 1987 Asahi Kasei Kogyo Kabushiki Kaisha announced new, five-component
blends. These comprised: (1) 100 parts of a polyamide mixture, consisting essentially
of ~50wt% aliphatic PA (PA-6, PA-66, etc.) and 5O-100wt% of a semi-aromatic
PARA having hexamethylene terephthalamide units (e.g., PA-6T/66, PA-6T/61 or
PA-6T/66/612); (2) 0.05-10 parts of polycaprolactone (PCL) having M n ~ 10 kg/mol;
(3) ~35 parts of a mixture consisting of 6O-100wt% of an ionomer and D-40wt%
EPR; (4) ~10 parts of a monomeric mixture consisting of ~wt% of an oxide
and/or carbonate (e.g., ethylene carbonate, ethylene oxide, propylene oxide and
butylene oxide) and 2~wt% of a polyhydric alcohol (e.g., ethylene glycol, tri-
methylene glycol, butanediol, diethylene glycol, glycerin or pentaerythritol; and (5)
~150 parts of PPE. The composition had improved moldability, and excellent stiff-
ness not lowered by humidity. The composition could also contain additional com-
ponents to improve impact properties. The blends have been used for molding parts
for the automotive, electrical and electronic industries (Hamada et al., 1994).
An Atochem patent application of 1991 disclosed transparent PA blends with high
resistance to chemicals. The materials comprised 1-99wt% PARA blended with 99-
1 wt % of a semicrystaUine PA, such as P A-12 (Maj and Blonde!, 1993). The same year
Viskase Corporation announced discovery of blends particularly suitable for pro-
duction of packaging film with at least 5% shrinkage at 90°C in at least one direction.
The blends comprised an amorphous copolyamide (1~50wt% PA-616T, without a
detectable melting point) and a copolyamide having Tm ~ 145°C, e.g., PA-612 or
PA-6,66. The blends could also contain l~30wt% of either PA-6, PA-ll or PA-12
(Vicik, 1994). Also in 1991, EM5-lnventa applied for patent protection for similar
blends that comprised 25-75wt% semicrystaUine PA-6 or PA-66, 75-25wt% of an
amorphous copolyamide (of aromatic dicarboxylic acid, dimerized fatty acid and
cydo aliphatic diamine), and ~30 parts of a compatibilizer (e.g., SMA, maleated
EPDM or MBA). The blends were developed for injection molding of solvent-resis-
tant parts that show good stress corrosion resistance as well as rigidity up to a
temperature of 100 °C (Schmid and Thullen, 1994).
The following year Bayer announced polyamide blends of 46-66wt% PA-66,
8-14wt% amorphous, aromatic copolyamide (85-95wt% PA-6 and 15-5wt% units
derived from isophthalic and/or terephthalic acid and 3-aminomethyl-3,5,5-tri-
methyl cyclohexyl amine or azelaic acid, m-xylylenediamine and hexamethylenedia-
mine), 6-10 wt % maleated elastomer with a glass transition temperature below O°C,
and with 3~20wt% mineral filler. The alloys were molded into parts that showed
improved low temperature impact strength and high HOT (Heger and Oeller, 1994).
16.3.4 PAIPOM blends

Polyoxymethylene (POM) is an engineering resin excellent in strength, fatigue resist-
ance and self-lubricating properties, while PA has excellent flexibility, as well as
impact, frictional and abrasion resistance. Both resins have been extensively used in
automotive, machine, electrical, electronic and other industrial applications. As time
progresses, increasingly stringent properties have become required from the mater-
ials, thus alloying is the most viable option. The POM/PA blends are immiscible.
For this reason, historically one sees the same evolution of the blend technology of
PA with POM as with other immiscible polymers, such as polyalkenes - in the
beginning only low concentration of one polymer in another was used until
adequate methods of compatibilization were discovered. The most critical is the
control of blend structure and morphology.
For example, POM/PA blends with component ratios of either 95:5 or 5:95 were
introduced. To improve modulus, up to 40 wt % of an inorganic powder was added.
It has been found that, for good mechanical perfonnance, the size of the dispersed
second polymer must be smaller than 10 J-Lm - to accomplish this without a compat-
ibilizer was not an easy task. The reinforcing effect caused by addition of solid
particles has been small - POM does not easily wet, thus bonding between the
resin and the filler particles is notoriously poor. Furthennore, addition of filler
reduced the natural lubricity of the POM and limited usefulness of the reinforced
blends. The first blends of polyoxymethylene (POM) with PA were disclosed in 1967,
in independent invention documents from du Pont de Nemours and Asahi Chemical
Industries. In du Pont's application POM was blended with 1 wt% of either PA-6,
PA-66 or PA-6,10. Blending was reported to improve color and thennal stability
(Moncure, 1969). In a 1980 patent document the company described multicomponent
POM blends. It was reported that stability of the resin can be improved by blending
it with 1.1 wt % polyethyleneglycol (PEG). The mechanical properties can be
improved by blending POM with PA-66, predispersed in ethylene-methylacrylate
copolymer (EMAC). In a later patent, thennal stability of POM was further improved
by blending it with 0.4-2 wt % PEG and 0.4-2 wt % PA (Kohan, 1982).
In Asahi patent disclosures deposited in 1967, POM was blended not with PA, but
with either a copolyamide-ester or an aromatic amorphous polyamide (PARA). The
blends comprising copolyamide-esters offered better stabilization, whereas those
with 4wt% PARA were reported to show improvements over the du Pont patent
claims (Asahi Chemical Ind. Co., 1969b; Fukuma et al., 1976).
In a Toray Industries patent application of 1968 blends of either PA-6 or PA-66
with POM and with polyethyleneterephthalate (PET) were described. The blends
showed good frictional resistance (Fujiwara, 1971). In 1988 Toshiba developed
POM/PA blends with excellent sliding properties (Torii, 1990).
In 1990 Asahi Kasei Kogyo described blends of POM with a PA and an encap-
sulated filler. The alloys were characterized as being excellent in high temperature
stiffness and lubricity, with good color tone. In particular, the invention provided a
method that made it possible to obtain a high reinforcing effect without loss of
lubricity. The polyamides had to have low melting point, 230 °C or less, for example
PA-ll, PA-12, PA-6 or PA-610. The matrix alloy comprised 90-60wt% of a POM, 10-
4Owt% of a PA and 0.1-10phr of, preferably, a melamine-derivative dispersant. The
dispersant was selected from hexaalkoxymethyl melamine, tetraalkoxy methyl urea,
methyl N-alkoxymethylamino fonnate and tetraalkoxyguanidine. The PA particle
size in the alloys was reported to be 0.03-10J-Lm and the aspect ratio less than 2.
Before incorporation in the alloys, the filler was coated with PA. For the optimum
effect, 5-40phr of a filler, preferably 7-35phr encapsulated in PA, was to be used.
The alloys showed excellent high temperature stiffness, strength and lubricity, and
good color (Tsukahara and Niino, 1992, 1994).
16.3.5 PAlPEST blends

Polyamide/polyester blends (PA/PEST) are immiscible, and usually require com-
patibilization. Furthennore, since in most cases both components are semicrystalline,
and blending may enhance the total crystallinity, the systems need toughening. The
obvious exceptions from this rule are those blends that contain amorphous PA or
PEST, toughened polyester systems, as well as blends used for manufacturing highly
oriented products, such as fibers or biaxially stretched forms or films. The PA/PEST
blends are being used in the plastics industry, but they are not available as com-
pounds on the open market.
The first patents on blends comprising PA with thermoplastic polyester (PEST)
date from the late 196Os. These were mainly prepared with polyethyleneterephtha-
late (PET). For this reason, the following sections cover blends of PA with PET, then
with polybutyleneterephthalate (PBT) and finally with polyarylates (PA). The con-
clusion is a short discussion of increasingly popular multicomponent blends, com-
prising PA, PEST and other resins.
PA/pET blends
In 1968 Allied Chemical deposited a patent document for PET blends with 70wt%
PA-6. To improve the impact and tear resistance, Q, Q-dimethylol-propionic acid was
used as a compatibilizer (Reimschussel and Dege, 1969). One year later, toughened
PET blends, comprising 20wt% PA-6-co-diisocyanate copolymer were described -
they were characterized by good impact strength (Dling, 1970).
Several patents focused on the ability of PA to enhance the crystallization rate and
the total crystallinity of PEST, as well as to reduce the spherulite size. The blending
resulted in improvement of the mechanical properties as well as the solvent and
chemical resistance. For example, in a patent deposition of 1980, Asahi Chemical
Industries described PEST blends with a small amount, O.O~10 wt %, of a nucleating
PA-66. The blends had high crystallization rates and good mechanical properties
(Nakamura and Neki, 1981). Similarly, in a patent deposited in 1985 by Toray
Industries, 6O-98wt% PA was blended with 15wt% PET. Blending was reported
to improve moldability, rigidity, strength and fire resistance (Chiba and Tanaka,
1986).
On the opposite end of the concentration scale similar effects were also observed.
For example, in 1987 Dow Chemical applied for the patent protection for PA/PET
blends, reporting that since addition of PET accelerates crystallization of PA the
blends can be injection molded more rapidly and the moldings have higher heat
distortion temperature than neat PA (Chen and Onder, 1989).
In the early 1980s reactive extrusion was introduced for compatibilization of PAl
PEST blends. Two approaches have been used - compatibilization was achieved
either by acid-eatalyzed amide-ester exchange reaction or by direct coupling. The
latter method is illustrated by a 1982 patent application. Accordingly, PET was first
modified by reacting it with acetobenzoic and acetoaminobenzoic acids, hence
transforming it into polyester-block-polyamide (PEA) that in turn was blended
with PA-6, to give isotropic moldings with an excellent set of properties (Mitsubishi
Petrochemical Ind., 1984b).
In 1982 the reactive compatibilization based on the acid-catalyzed amide-ester
exchange reaction between PA and PET was carried out in a twin-screw extruder,
using p-toluenosulfonic acid as a catalyst (Pillon and Utracki, 1984, 1986). Two
minutes residence time was adequate to generate sufficient copolymer concentration
to compatibilize the system. The reaction was primarily controlled by temperature,
much less so by other process variables including the amount of catalyst. Mild
treatment with diluted formic acid revealed that the copolymer was situated at the
interface between the PA and PET domains. Subsequent work demonstrated that, in
spite of good compatibilization, injection molded blend showed brittle behavior.
SurpriSingly, addition of an impact modifier was not needed for monofilament
spinning applications, but it was essential for use in other forming methods that did
not impose large orientation in the product.
A similar, general method of compatibilization was described in a 1990 patent
application from DSM. Thus/ PAs were reactively blended with PEST containing
toluenesulfonic acid groups. Good impact and heat resistance were observed 01an
Sluijs et al., 1992). In the following patent, PA was identified as Stany(fMKS3000
(polytetramethylene adipamide, PTA or PA-46), and PEST as PET (from recycled
bottles). The blends, reinforced by addition of 6O-100phr (relative to the blend
content) of glass fibers showed good impact resistance, high modulus and heat
resistance. The materials were used for production of automobile structural parts
(Bots and Statnik/ 1992).
Several patents described PA/PEST blends with excellent characteristics, engen-
dered by addition of compatibilizers and impact modifiers. For example, in 1986 an
application from Amoco Corporation described blends comprising 15-85wt% of
either PA-6, PA-66 or PA-61O, with either PET, PBT or their mixtures, compatibilized
by addition of 0.5-15 wt % polyhydroxyether of bisphenol-A, Phenoxy. The alloys
exhibited increased elongation, tensile strength, Izod impact strength and uniform-
ity. It was also reported that addition of an acrylic graft copolymer further enhanced
the heat and water resistance (Robeson, 1988). In the contemporary patent deposi-
tions from General Electric (Maresca and Shafer, 1988) and Ube (Tsumiyama et al.,
1988)/ polyamide-polyester block copolymer and ethylene-glycidylmethacrylate
grafted on butylacrylate-methylacrylate block copolymer, respectively, were used
as a compatibilizers.
In 1989 AlliedSignal described new PA-6 or PA-66 blends with 15-45wt% PET.
These were compatibilized by addition of O.05-lOwt% of phosphoryl azide reactive
coupler, then heating the blend for 2-20 min at 265-315°C, which lowered the
melting points of PA and PET. The compatibilization improved processability (Bhat-
tacharje et al., 1990).
Further examples of PA/PET blends can be found below, where the broad-elaim
patents are considered. These either describe a broad class of PA/PEST compatibil-
ized blends, where any combination of PA with PEST resins will lead to advanta-
geous alloys/ or increasingly popular multicomponent blends; such as PA/PEST/
PC/ PA/PEST/PO, etc.
PA/PBT blends
Polybutyleneterephthalate (PBT) was commercialized in 1969, independently by
Celanese and Hoechst. The resin had been blended with PESTs, POS and PCs before
trying to combine it with PAs. The first PA/PBT blends were announced only in
1981, independently by du Pont de Nemours and Toray Industries. The first com-
pany developed PBT blends with PA and ethylene copolymer containing ester or
acid functionality (Sheer, 1982). The second company announced PBT blends with
lQ-90wt% PA-6. Blending resulted in highly crystalline materials with finely dis-
persed minor phase (Toray Industries Inc./ 1983c). There is expected parallel evolu-
tion of PA/PBT blends to that observed for PA/PET systems.
The patent documents deposited in 1983 described PA blends with 5-SOwt% of
maleated PS, as DiIlrex™HF55, and/or with lQ-SOwt% PBT. The alloys were found
to be water resistant (Mitsubishi Petrochemical Industries, 1985). In a contemporary
disclosure, blends of PA-66 with poly(m-xylenyleadipamide), PA-mXD and PBT
were reported to have good resistance to heat, chemicals, oils, as well as high impact
strength and toughness (Mitsubishi Gas Chemical Co., 1985a).
Two years later, in a patent application from Toray Industries 6O-98wt% PA was
blended with either PET or PBT, to give good moldability, rigidity, strength and fire
resistance (Chiba and Tanaka, 1986). In 1988 Mitsubishi Kasei Corporation disclosed
PA/PBT blends compatibilized with an epoxy compound. The blends showed high
impact strength (Urabe and Ikuhara, 1989).
In 1989 Daicel Chemical Industries developed PA/PEST blends compatibilized
by addition of either a styrene-glycidyl methacrylate (SGMA) or a styrene-maleic
anhydride (SMA). Thus, a mixture of 5-95 wt % PA-6 with 95-5 wt % PBT and 0.5-
3Owt% of SGMA was first prepared, then compounded with PBT (and glass fibers
when needed). The blends showed high impact strength (Watanabe and Inozuka,
1991).
Impact-resistant blends for films or moldings with improved melt flow
were disclosed in 1991 by BASF. These materials were obtained by mixing
5D-99wt% of either PA-6 or PA-66 with low-molecular-weight aromatic poly-
ester, such as 1-50wt% PBT of molecular weight around 5000 (Goetz et a/.,
1993).
PAlPAr blends
Polyarylates (PAr) are aromatic, amorphous polyesters of bisphenol-A with a mix-
ture of isophthalic and terephthalic acids (Q--4>-{::(CH3 h-4>-CQ--4>-{::O)n' They have
been frequently blended with such thermoplastic polyesters, as PET, PBT, polyethyl-
ene-p-oxybenzoate (PEB) or others. The blends can be alloyed by means of well-
controlled transesterification. These alloys are used to manufacture transparent
moldings with good impact strength.
For example, in a series of patent applications deposited by Unitika in 1976,
polyarylates (100 parts PAr) were blended with engineering resin, PA, PET or PEB,
to give transparent, impact-resistant resins. Further property enhancement was
observed, when to PAr/PET blends a polyamide-6 (PA-6) was added at a 1:1 ratio
(Asahara et al., 1977; Kyo et al., 1978). Patents deposited in 1981, described that PAr
was blended with 150 parts PA, and either a Si compound, or 3-50 parts of a polymer
containing N-substituted amido groups, isophthaloyl-dichloride-piperazine-ter-
ephthaloyl-dichloride copolymer, or a paraffin wax. The blends had good processa-
bility and mechanical properties (Unitika Ltd., 1982b). It was described in a later
patent, that for improved moldability and mechanical properties, 8Q-99.9wt% PAr
was blended with aromatic oligoesters (Unitika Ltd., 1983b). In 1982 the company
announced further refinements of these disclosures, specifying that PAr was to be
blended with 50wt% PA-6 and 2.5wt% PET, to give moldings with particularly
good processability, high gloss, chemical, mechanical, electrical properties and HDT
(Unitika Ltd., 1983a, 1984b).
In 1988 Amoco Corporation asked for patent protection for PA blends with PAr
compatibilized with polyarylate-polyamide block copolymer (PA-co-PAr). The co-
polymer was found to enhance performance of other PA/PEST blends as well. Good
processability, mechanical properties, UV stability, heat, solvent, and stress-erack
resistance, were reported (Dean, 1990). Three years later the company announced
blends of aromatic polyesters containing 12-50 % t-butyl-substituted aromatic nuclei
(PAr) with aliphatic-aromatic polyamides having a ratio of aliphatic to aromatic
carbons of 1.4:2.5. Since the blends showed a single glass transition temperature,
they were declared miscible. The alloys showed excellent processability and
mechanical properties, as well as high solvent, weather, impact and stress-erack
resistance (Dean, 1992).
Multicomponent PA/PEST blends
Multicomponent blends are of growing interest to the industry. Not only do they
make it possible to incorporate a wide spectrum of performance characteristics in a
single material, but they have also been found to generate a more a stable morphol-
ogy, less affected by abusive processing. The reason for the latter behavior rests in
the fact that frequently a polymeric component can be found that has the thermo-
dynamic preference to locate at the interface between two principal blend compo-
nents, forming a protective layer against coalescence.
In 1987 General Electric announced blends of amorphous polyamide (10-90 wt % of
either PA or PARA) with 90-10 wt % of either PEST, polycarbonate, poly(ester carbon-
ate) or polyarylate, compatibilized with lo-S0phr of a polyamide-polyester block
copolymer (PA-b-PEST). The latter copolymer was obtained by heating in a first stage
a diaryl ester of a dicarboxylic acid with a diamine, followed by adding a dihydric
phenol and a diaryl ester of an aromatic diacid. The blends could also contain an
elastomeric impact modifier. The materials showed excellent physical properties after
molding, without any evidence of delamination (Maresca and Shafer, 1988).
The same year Nippon Petrochemical Company disclosed PA blends with other
polymers, such as PAr or polycarbonate (PC). These were compatibilized and impact
modified by incorporation of ethylene-glycidylmethacrylate graft copolymer, EGMA
(Yuichi and Suehiro, 1989). Similar blends comprising PAr with PA, compatibilized
with acrylonitrile-butadiene-styrene grafted with either maleic anhydride or glycidyl
methacrylate (AB5-MA or AB5-GMA, respectively), were described in a contempor-
ary patent application from Stamicarbon (Yasue et al., 1989).
In 1991 Enichem disclosed three-eomponent blends comprising 3O-70wt% PET,
70-30 wt % PA-6, and/or PO (LOPE, HOPE or LLOPE), and an epoxidized ethylene
copolymer, such as 1-10wt% of an ethylene-ethylacrylate-co-glycidylmethacrylate
copolymer (EEA-GMA). The alloys showed significantly improved impact proper-
ties and tensile elongation (Natarajan et al., 1994). The same year, Polyplastics
Company described multicomponent, moldable blends that comprised: (1)
2-98wt% of a compatibilizing Na sulfonate group-eontaining PEST (e.g., PET or
PBT with sodium dimethyIS-sulfoisophthalate); (2) 2-98wt% of an alkenic copoly-
mer with vinyl alcohol, and/or unsaturated carboxylic acid or its derivative (e.g., an
ionomeric copolymer of ethylene and Zn methacrylate, maleated-PP and EVA); (3)
PA (e.g., PA-6, PA-66, PA-612 or PA-ll); and (4) 0-96wt% PEST. The blends had
droplets with an averaged diameter of 0.05-1I-tm. The materials were characterized
by high tensile and impact strength (Tajima et al., 1994).
In 1992 M & G Ricerche disclosed similar compositions. Thus, (1) PET or PBT was
reactively blended with (2) 5-20wt% of either PA-4, PA-6, PA-66, PA-8, PA-ll or
PA-12, and (3) a functional compound containing reactive groups capable of reacting
in the solid state. The alloys were prepared by melt blending the three ingredients,
pelletizing and reacting in the solid state at ISO-220°C for sufficient time to increase
the intrinsic viscosity of the polymeric alloy by at least 0.1 dl/g, as compared to the
intrinsic viscosity of the starting polyester resin. The alloys were found useful for
the manufacture of films. The solid state reaction increased the molecular weight of
the alloy (compensating for any degradation that may have occurred during melt
blending), and improved its mechanical performance (AI Ghatta, 1994).
16.3.6 PAIPC blends

Blending PA with polycarbonates, i.e., polymers containing carbonic ester linkages,
poses similar problems encountered for PA blends with PEST. It was soon
recognized that PA/PC blends do not live up to expectations, as far as either the
combination of physical properties or their level can be attained. The blends are
immiscible; their melt viscosity is low; they are susceptible to thermal and hydrolytic
degradation. Moldings resulted in brittle parts, having poor impact properties. In
short, the PA/PC blends must be compatibilized and usually toughened.
The polycarbonates of bisphenol-A (PC) have been most frequently used in blends
with PAs to produce materials having various modified properties. Note that in
contrast to the most common PESTs, Le., PET and PBT, PC is amorphous. However,
there were reports that addition of PA to PC may lead to crystallization of the latter
resin, which results in further enhancement of the brittleness.
The PA/PC blends have been developed for use in electric insulation (1~20wt%
PAin PC), for easy to spin PA fibers (5-15 wt % PC in PA), for high moldability (PA:
PC = 1.5:1 to 1:100), for good melt-adhesive properties (5-40wt% of PC in PA), etc.
The first PA/PC blends date from 1973 when Mitsubishi Gas Chemical Company
developed PC blends with 1~20wt% PA-12. These materials, with pear-like gloss,
had good high voltage arc and anti-tracking properties, making them suitable as
electrical insulators (Okuzono and Kifune, 1975). In a later patent, PC/PA-12 mater-
ials were incorporated into a variety of engineering or specialty resins, namely PSF,
PPE or PET, to enhance moldability and mechanical performance (Okuzono and
Kifune, 1976).
In several patents deposited by Shell Oil, strong effects of hydrogenated styrene-
diene block copolymers were reported. As a rule, at low concentration SEBS stabil-
ized the morphology, reducing the phase separation during processing whereas at
higher concentration it was responsible for generation of phase cocontinuity. In 1977
it was reported that blends of PA with PC can significantly profit from incorporation
of 15 wt % SEBS. Good stability of morphology during processing, as well as
increased toughness, was observed (Gergen and Davison, 1978).
In 1979, a patent application described blends of an aromatic polyamide (PARA)
with 1~90 wt % Pc. The formed blends gave attractive, pearly-looking articles, with
good resistance to oils and boiling water, as well as with good mechanical properties
(Mitsubishi Chemical Industries Co., 1980). The same year Sumitomo-Naugatuck
Company disclosed molding compositions comprising 100 parts polyestercarbonate
(PEC), and 1-150 parts polyamide (Sakano et al., 1981c). In the following patent,
blends containing 60 wt % PC, 2 wt % PA-6, and a copolymer of butadiene-styrene-
acrylonitrile and acrylates, 40 phr MABS were described. These alloys were found to
have good solvent and stress cracking resistance (Sakano et aI., 1982).
In 1981, 5~90wt% PC was blended with 5--45wt% PA-6 and 5--45wt% SMA. The
compatibilization by addition of the styrene-maleic anhydride copolymers resulted
in two essential improvements: enhancement of melt viscosity and improvement of
the impact strength. Furthermore, it was reported that the new alloys were
moldable at relatively low temperature. The moldings also showed high oil and
hot water resistance, heat stability and flexibility (Dainippon Ink and Chemicals Inc.,
1983).
The following year, 100 parts of PC were blended with 1--80 parts PA, and 25 parts
of reinforcing glass fibers. Good processability, impact strength and chemical resist-
ance were indicated (Suwa Seikosha Co., 1983). Also in 1982, blends of PA with PC,
compatibilized by addition of polyethyloxazoline (PEOX) were developed. The
blends were found to give high modulus, thermal and solvent resistance, dimen-
sional stability, high elongation and impact strength. Polyalkyloxazolines were also
reported useful as compatibilizing agents in PC blends with other engineering resins
(Thill, 1989).
In 1986/ a patent application from Dexer Corporation described blends comprising
pc/ PA, polyesteramide, an elastomer and a maleated polyalkene, such as maleated
polypropylene or EP rubber (Perron, 1984/ 1988). Two years later the company
introduced Dexcarb™ PA/PC alloys.
In 1987 Nippon Petrochemical Company disclosed PA blends, with either PAr or
Pc. The blends were compatibilized and impact modified by incorporation of ethyl-
ene-glycidylmethacrylate graft copolymer (EGMA) (Yuichi and Suehiro, 1989). Sim-
ilar blends were described in a contemporary patent application from Stamicarbon.
They comprised either PC or PAr, blended with PA, and compatibilized by addition
of acrylonitrile-butadiene-styrene copolymer grafted with either maleic anhydride or
glycidyl methacrylate (AB5-MA or AB5-GMA) respectively (Yasue et al., 1989). The
same year General Electric disclosed blends comprising an aromatic, amorphous
polyamide (PARA, having a low concentration of -NH2 end groups) and Pc. The
resins were reported to show miscibility that resulted in preparation of alloys with
good impact strength and molecular weight retention (Gambale et al., 1988). It is
noteworthy that under shear PC/PARA blends have a tendency to form cocotinuous
phases responsible for enhanced combinations of properties.
Reactive extrusion was also used for preparation of PC/PA compatibilized blends.
For example, a hydroxy-terminated PC was end capped with anhydride groups
through reaction with trimellitic anhydride acid chloride. A mixture of 40 wt % of
the functionalized PC (4Owt% PA-6 and 20wt% of an acrylate styrene core/shell
impact modifier) was extruded on a counter-rotating twin-screw extruder at 277 0c.
Molded test parts showed excellent Izod impact strength and elongation. The pres-
ence of PC-PA copolymers was determined by selective extraction. Amorphous or
semicrystalline PAs could be used in these blends (Hathaway and Pyles, 1988/ 1989).
In 1989 General Electric applied for patent protection for PC/PA mixtures, compa-
tibilized by addition of polyamide-polycarbonate block copolymers, obtained using
glycidyl isocyanurate (Derudder, 1990).
Several patents on PA/PC blends were deposited in 1991. For example in a
disclosure from Dexer Corporation, blends of 2D-80wt% PC/ with 70-1Owt%
PA-6, were compatibilized using a complex system, comprising 20-2 wt % PEl
and/or TPU/ monoglycidyl epoxy compound (0.2-2 % butyl glycidyl ether), a ther-
moplastic elastomer and an epoxy ether. Furthermore, an impact modifier (e.g.,
maleated EPR or EPDM) could also be used. The new materials showed good
processability, paint adhesion, low temperature impact properties and HDT (Perron
et al., 1993). The same year, Idemitsu Petrochemical applied for patent protection for
a broad class of blends comprising branched polycarbonate (l-99wt% bPC) and at
least one polymer selected from: PET, PBT, styrenics (HIPS, ABS, SMA), PA-6, PA-
66/ PE, PP and TPE (acrylic rubber, butyl rubber, EPDM or SBS). The alloys were
reported to show excellent processability, solvent and impact resistance as well as
high mechanical properties (Kozakura et al., 1992/ 1994).
In a contemporary Bayer document, 4D-8O wt % of either a polycarbonate of bisphec
nol-A (PC)/ or a polyestercarbonate (PEC) was blended with 15-S0wt% PA-6,
5-10wt% of an acrylic copolymer, and with 5-20wt% acrylic elastomer. The alloys
had high impact strength (Heger et al., 1992). Later, 10-70 wt % PC was blended with
5-70wt% PA-6, 5-S0wt% ABS, 1-20wt% imidized polyacrylates, and D-40wt%
SAN. The alloys showed enhanced impact and solvent resistance (Leitz et al., 1992).
In a series of patent applications from General Electric filed between 1986 and
1990/ blends containing polyamides having controlled amine functionality and at
least one polymer having ester or carbonate linkages were described. For example,
PARAs having amine end-group concentration of less than 10gmeq/kg, e.g., poly-
PA/specialty polymer blends 333
hexamethylene isophthalamide (PA-6I) were blended with 1-99wt% PC in a
corotating twin-screw extruder at 250-270 0c. The resulting alloys showed improved
miscibility, as well as viscosity and molecular weight retention. The molded articles
had high impact resistance and tensile strength (Gambale et aI., 1988/ 1994).
16.4 PA/SPECIALTV POLYMER BLENDS
16.4.1 PAIPSF blends

Polysulfones (PSF, also abbreviated as PSU or PSO) are a class of high temperature
resins introduced by Union Carbide in 1965. PSF with the structure [-+-C(CH3 h+
CHP-~-</>-O-ln is known as Udei™. In 1971 Astrel™ polyarylsulfone with the
structure [+¢>-~+CHP-~ln was introduced by 3M Company. Several other
PSF resins, manufactured on several continents, are available on the market.
PSFs show high stiffness/ hardness, and thermal stability at temperatures from
-100 to +150 0c. They are transparent and have good resistance to radiation as well
as high flame resistance. On the other hand, they require high processing tempera-
ture/ and even at these temperatures they have high melt viscosity, thus are difficult
to process. PSFs also show susceptibility to stress cracking with certain solvents.
Blending aims at elimination of these detrimental characteristics.
In 1970 Imperial Chemical Industries announced the first blends of PSF with a
polyamide, PA-ll. The blends were found to be easy to process into films or fibers
and to have resistance towards folding. Furthermore, injection molded parts showed
good impact properties (Nield, 1971). The same year, Union Carbide disclosed
grafting PSF with lactams. The copolymers, poly(sulfone-g-Iactam) (PSF-L) could
be blended with 10-90 wt % of either PA or PSF to improve processability and
mechanical properties (McGrath and Matzner, 1972).
In 1977 Unitika announced blending of 2Q-80wt% PA-6 with 8O-20wt% PSF. The
alloys showed good processability as well as thermal and mechanical properties
(Kyo and Asai, 1978). Seven years later BASF applied for patent protection for blends
comprising an amorphous, aromatic polyamide (PARA) with polyethersulfone
(PES). The materials had a high heat deflection temperature of 172 °C/ and a good
set of mechanical properties (Hub et al., 1986).
In a 1990 patent application from Stamicarbon, 3Owt% of PA-46 was blended in a
twin-screw extruder with PES, then injection molded. The moldings showed good
balance of mechanical and thermal properties (Koning and Vroomans, 1992). In a
contemporary Amoco patent, PARA was used instead. High strength and HDT were
also found (Bapat et al., 1992).
In 1991 BASF announced thermoplastic molding compositions containing 15-
85 wt % of either a polyarylethersulfone (PAES) or a polyethersulfone (PES), com-
pounded with 15-85 wt % PARA and 5-35 wt % glass fibers. Here PAES was a
copolyarylethersulfone having at least two different repeating units: 3-97 mol % of
(+~+O)-and 3-97 mol % of -(¢>-C(CH3 h-</>-O-¢>-~+O)-, PES was a poly-
mer with the structure [-¢>-502-l/>-O-ln' and PARA was a copolyamide of terephtha-
lic acid, caprolactam and hexamethylenediamine (PA-6T6). The blends showed high
heat resistance and stiffness (Weber and Muehlbach, 1993).
16.4.2 PAlPPS blends

Polyphenylene sulfide (-(¢>-5-)n-'PPS) was commercialized in 1971 as Rayton™ R
by Phillips Petroleum. Several commercial PPS resins are on the market. The resin is
semicrystalline with a melting point of 288 °C, and a glass transition temperature of
194°C. PPS has high strength, hardness, stiffness, HDT and good dimensional
stability, as well as excellent chemical, solvent and flame resistance. The resin can
also be vulcanized by heat and/or sulfur.
In a 1980 patent application, Phillips Petroleum announced that polyarylamide
(PARA) blends with small amount of PPS Ryton™ showed improved moldability,
high HDT and high impact strength (Shue and Scoggins, 1981). Four years later, in a
patent disclosure from Stamicarbon, blends of PA-46 with 5-SOwt% PPS (and
optionally with reinforcing fibers) were described. The alloys were easy to mold,
and the moldings showed good impact and mechanical properties, high HDT, as
well as heat and chemical resistance (Chiba, 1986).
Interesting PA/PPS blends were disclosed in 1988. In a patent document from
Amoco, PPS was blended with crystalline polyphthalamide (PPA, AmodeITM) rein-
forced with bronze powder, glass and/or carbon fibers. High degradation temperat-
ure, chemical resistance, HDT, and good mechanical properties were reported
(Chen and Sinclair, 1990). Similarly, in an application from T&N Technology, PPS
was blended with polyterephthalamide (PARA) reinforced with glass fibers. The
molded alloys also showed good mechanical properties (Davies, 1990). Two years
later Mitsui Petrochemical Industries announced blends of PARA with 5-95 wt %
PPS. The material was found suitable for applications requiring high heat and
thermal aging resistance (Yamamoto and Toyota, 1992). In a contemporary disclos-
ure from Phillips Petroleum PPS was blended with PA, ethylene-propylene-diene
(EPDM) and maleic anhydride. Good impact and solvent resistance were found (Yu
and Beever, 1992). The same year Toray Industries announced blends comprising 5-
95wt% of a resin selected from PA-6, PA-66, PET or PBT, with 5-95wt% PPSS. The
alloys were reported to have good mechanical properties, HDT, dimensional
stability and chemical resistance (Ishio and Kobayashi, 1992).
In a 1991 patent application from Huels, blends comprising 95-5wt% PARA and
5-95 wt % PPS were found to be advantageous as far as melt flow and improved
processability are concerned (Poll et al., 1992). The following year, Solvay disclosed
blends comprising 100 parts PPS, 25-95 parts of polyamide, PA-66 or PA-MXD6, and
50-200 parts of Mg(OHh. These materials were reported to show excellent tensile
strength, as well as arc, tracking and heat resistance (Dubois et al., 1993).
16.4.3 PAlPhenoxy blends

Polyhydroxyether of bisphenol-A was commercialized in 1962 by Union Carbide
under the trade name PhenoxyTM. Since then the resin has been known mainly by its
shorter name. Phenoxy is an amorphous resin with a glass transition temperature of
100 0C. Replacing the bisphenol-A unit with another dihydroxy reactant can generate
other polyhydroxy ethers (some having liquid crystalline character) with
Tg = 8D-18O°C. Phenoxy has been frequently used as a universal compatibilizer in
engineering polymer blends. As the cited examples illustrate, compatibilization
seems to be the main role Phenoxy plays in blends with PA.
The first blends of PA with Phenoxy were disclosed by Union Carbide Corporation
in 1971. Thus, PA-6 was blended with 5-SOwt% Phenoxy to obtain materials with
superior environmental stress crack resistance (Schober, 1973). lhree years later,
Celanese announced blends of PA-66 with O.5-3.0wt% Phenoxy, and 1-29wt% of a
hydrogenated styrene-butadiene-styrene three-block copolymer (SEBS). Significant
improvements of the tensile and impact strength (well above the values of neat PA)
were obtained (Freed, 1975).
PA/specialty polymer blends 335
In 1986 Amoco Corporation announced blends showing good elongation, tensile
strength, !zod impact strength and uniformity of properties. The materials were
obtained by blending 15--8Swt% of either PA-6, PA-66 or PA-6lO, with either PET,
PBT, or with their mixture, and with 0.>-15wt% Phenoxy as compatibilizer. Incorp-
oration of an acrylic graft copolymer further enhanced their performance (Robeson,
1988).
In 1992 Rohm and Haas Company deposited a patent application for a broad class
of polymer blends. The document described blends that comprise: (1) 80-95 wt % of
at least one polar polymer selected from PVC, PC, PMMA, PA, PEST, PCI, and/or
SAN-eontaining resin, and (2) >-20 wt % of a copolymer containing 60-95 wt % of a
first polymer (having at least SO mol % of vinyl alcohol, and 5--40 wt % of a second
polymer containing at least 70% of alkyl(meth)acrylate(s) and up to 25% of either
vinyl(idene), amide or anhydride groups. For example, advantageous blends com-
prised lQ-95wt% of a difficult to process polar polymer, 5-90wt% of a polymeric
mixture (40-95 parts of a first polymer and 5--60 parts of a second polymer). Further
advantages could be obtained by incorporating 25-95 wt % of polyurethane, TPU
and/or Phenoxy, EVAl « 50 mol % VAl), COPO, modified cellulose, and/or poly-
alkylene oxide and >-75 wt % of the first blend. The blends were described as having
attractive physical, optical and barrier properties. They were melt-processable (with-
out PVAl degradation) into films, sheets or bottles with good barrier properties.
Blends containing PA were used for films, tubes, toys, gears, bearings, shafts, curtain
sliders, door rollers, etc. (La Fleur et al., 1994).
16.4.4 PAlPVDF blends

Polyamides have been blended with poly(vinylidine fluoride) (PVDF or PVF2 ) to
reduce permeability of PA, either in a sense of reduction of the moisture effects (on
PA) or permeability through PA-blend films or containers. For example, in 1973
Showa DenIm patented solution-blending of poly(vinylidene fluoride) with poly-
amide (75 wt % PA-6lO). After immersion for 100 h at 30 °c the material showed
significantly lower water absorption than PA-610 alone (Saito, 1975). Fifteen years
later, compatibilized blends of PA with PVDF, suitable for production of parts that
are impact resistant and impermeable to gases, were disclosed in 1988 by Kureha
Chemical Industry (Hizasumi et al., 1989).
16.4.5 PAlPEA blends

In a 1983 document, blends of polyamide (5-95wt% PA-12) with 95-5wt% of the
polyetheramide, (PEA GrilamiJIM ELY-60), were described. Molding of these alloys
gave tough, flexible heat and hot oil resistant parts (Sumitomo Chemical Co., 1984).
The same year, Atochem commercialized two blends based on their proprietary
polyether-block-amide (PEBA). The first, sold under the trade name of Orgater™,
was a blend of PEBA with PBT and EVAc, whereas Rilsan™ was that of PEBA with
PA (Arraou, 1986). The patent applications were deposited in 1985 ijacquemin and
Deleens, 1987; Couchoud et al., 1987). The latter blends comprised 3o-94.5wt% PA-6,
0.2--65 wt % PEBA and 5-SO wt % of an elastomer (ABS, MBS, NBR, SBR or EPDM).
The alloys showed good impact strength at low temperatures.
In 1989 Minnesota Mining and Manufacturing Company disclosed blends having
either a continuous or a disperse phase. The former was composed of Q-90wt% of a
thermoplastic resin and lDo-lOwt% of a block thermoplastic elastomer. The resin,
having a glass transition temperature of ? ISO °c was selected from PA, PEST, PI,
PAl, PSF, PEl, PC, PES, PEEK, PPS, PPE, etc. The block thermoplastic elastomer was
of the type polyether-b-polyamide or polyether-b-polyester (e.g., Pebax™ or
HytrefTM). Dynamically cured fluoro-elastomers formed the dispersed phase. The
blends were easy to mold, were flexible and elastic, with excellent chemical and
thermal resistance (Movak et al., 1994).
16.4.6 PAlPAI blends

Aromatic polyamide-imide was commercialized by Amoco in 1965 under the trade
name Torlon™. By 1977 PAl (Torlon™ 4OOOT), was blended with polyamide (0.1-
SOwt% of either PA-66 or PARA) and inorganic filler. The materials had good
processability and mechanical properties. In later patents from the company, PAl
was blended with O.I-SOwt% polysulfone (PSF, Udel™), or aromatic polyester,
(U-l00) and optionally with fillers. The alloys had good processability, and molded
parts showed high mechanical performance (Toray Industries Inc., 1979).
In 1992 du Pont de Nemours announced miscible blends that comprised at least
two polymers. The first was an aromatic polyimide, while the second was selected
.from between: PA, PAl, PI or their mixtures. The membranes cast from these blends
had superior selectivity to gas permeation. They were useful for separating H 2 , N 2 ,
Cf4, CO, C~, He and ~ (Ekiner and Simmons, 1993).
16.4.7 PAIPEI blends

Polyetherimide (PEl) was introduced in 1982 by General Electric Company under the
trade name Ultem™. The same year the company deposited a series of patents
describing PEl blends with a diversity of resins, namely block copolymer of poly
(carbonate-b-siloxane), with 5wt% of either EPDM, ABS, MBS, or such acrylate
copolymers as MBS or MMBA (Giles and White, 1983). For example, PEl with 5 wt %
EPDM showed higher impact strength than PEl alone. The following year, blends with
PA, PP, PSF, PEC, PAr, ternary blends with polycarbonate (PC) and polyesters (PEST),
etc., were patented (Giles and Schlicht, 1984). The blends showed good processability,
as well as improved flexural and impact strength. In the 1987 patent, blends of PEl
with 61 wt % PA-12 were described. The alloys showed reduced mold shrinkage and
water absorption in comparison to those of neat PA-12 (Giles, 1987).
Also in 1982, Union Carbide disclosed blends of PEl with PA-6, compatibilized by
incorporation of a PEI-PA block copolymer. Improvement of moldability and impact
strength was reported (Robeson and Matzner, 1984).
Patent applications deposited by General Electric in 1987 and 1989 described
compatibilized PEl blends with 5-95 wt % of either PA-6 or PA-66. Compatibilization
was achieved by incorporating 0.5-30 phr of one or more phenolic compounds, such
as a nonyl-phenolic additive. The blends were reported to have reduced water
absorption, low swell and good dimensional stability (Gallucci, 1988; Gallucci and
Rock, 1992).
In 1991 the company disclosed blends of copolyesteretherimide (PEEl, Lomo~)
with either semicrystalline or amorphous polyamides (PA or PARA). The alloying
resulted in materials characterized by their good thermal aging behavior (Angeli,
1992).
16.4.8 PAlLep blends

Polyamide blends with liquid crystal polymers are discussed together with other
LCP blends in Section 21.8.
17
Polyester blends
Thermoplastic polyesters, also known as saturated or linear polyesters, are semi-

aromatic polymers that contain the --COO- ester group. Historically, the amorphous
polyesters, initially manufactured by phosgenation of bisphenols, have been treated
as a separate class, known as polycarbonates, of which the polycarbonate of bisphe-
nol-A is the dominant representant. Blends of the latter materials are discussed in
Chapter 18.
The thermoplastic polyesters that are the principal objects of this part, are formed
by the polycondensation of at least one aromatic dicarboxylic acid (selected from
terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid and 2,5-
naphthalenedicarboxylic acid), with at least one diol (selected from a group consist-
ing of alkylene glycols, such as ethylene glycol, propylene glycol, butylene glycol
and hexylene glycol, or polyalkylene glycols such as polyethylene- or polytetra-
methylene-glycol). More popular polyesters include polyethyleneterephthalate
(PEn, polypropyleneterephthalate (PPT), polybutyleneterephthalate (PBT), poly-
hexyleneterephthalate (PHT), polycyclohexyleneterephthalate (a copolymer of
terephthalic acid and cyclohexanedimethanol-ethylene glycol; PCT), polyarylates
(amorphous copolymer of bisphenol-A, isophthalic acid and terephthalic acid;
PAr), poly(ethylene-2,6-naphthalene dicarboxylate) (PEN), polybutylenenaphthalate
(PBN), as well as amorphous copolyesters such as polyethyleneterephthalate-iso-
phthalate (PET/I) and polybutyleneterephthalate-isophthalate (PBT/1).
The first thermoplastic polyester (PET) was invented in 1941 by Whinfield and
Dickson. During the early years the resin was used for fiber spinning. (the fiber was
known as Terylene™ from ICI or Dacron™ from du Pont) In this application it
required little modification. The need for it appeared when injection molding was
attempted. To obtain good mechanical performance, high molecular weight PET and
nucleating agents had to be used. The resulting difficulties (high temperature and
long cycle), on the one hand focused attention on PBT and on the other hand on
blending. PBT was invented in 1940 by the same team that discovered PET;
commercialized in 1969 by Celanese as Celanex™, and by Hoechst as Hostadur™
as having a more flexible macromolecule.
The first PET blends with PBT were disclosed in 1960 by Siemens & Halske
(Heywang, 1966). The blends, used in electrical condensers, showed a stable level
of crystallinity. Two years later, to improve the dimensional stability of PET, it was
blended with polymethylpentene (PMP).
The first patent on PBT blends was deposited in 1964 by Goodyear Tire and
Rubber Company. Thus PBT was blended with an amorphous poly(hexylene-
338 Polyester blends
isophthalate-terephthalate), 4Owt% PAr. The blends were found useful for electrical
insulation, films, fibers or molded products (Wiener, 1969). The first semi-aromatic
PArs were patented in the late 194Os. However, today the abbreviation refers rather
to the wholly aromatic, amorphous polyesters, e.g., a product of condensation of
bisphenol-A with isophthalic and terephthalic acids (-</>-C(CH3h-</>-C~-</>-C~-)n'
The first commercial PAr was introduced in 1974 by Unitika as U-polymerTM, then
four years later by Amoco as Ardel™ D-1oo (Amoco Corp., 1985; Robeson, 1986).
In the late 196Os, PET was blended with several resins, namely 0.5-50wt% PE (for
improved impact strength) (Glanzstoff A.-G., 1967), with 5-150phr of an ethylene-
methyl methacrylate ionomer, Surlin TM (for high toughness and low mold shrink-
age) (Gander et al., 1977) with PC (for improved stress corrosion resistance) (Cziesla
and Bottenbruch, 1975), with EVAc (for improved processability, mechanical and
impact strength, hardness, abrasion and solvent resistance), with either poly(ethy-
lene-co-methylmethacrylate, 10% EMM), poly(ethylene-co-vinylacetate-co-metha-
crylic acid, 3 wt % EVAc-MA), or poly(ethylene-co-hydroxyethylmethacrylate), to
give crystalline materials for thick-walled moldings with good impact strength
(Dijkstra and Jones, 1969; Glans and Akkapeddi, 1991).
In a Toray patent, either PA-6 or PA-66 was blended with PET and POM. The
blends showed good mechanical properties and frictional resistance (Fujiwara, 1971).
The same year the company also issued a patent application on impact modification
of either PET or PBT by blending it with butyl rubber (Hiri and Kotama, 1971). Also
in 1968, Union Carbide blended PET with rubber-modified poly(meth)acrylates
(5-95wt% ABSM) and polydimethylsiloxane (1-20wt% PDMS). The alloys showed
good notched impact and embrittlement resistance (Sauers and Barth, 1970).
In 1969 PET was blended, under nitrogen at 240°C for 6h, with 25wt% Pc. The
alloys showed improved impact resistance and elongation, without lowering
the total crystallinity or the melting point (Horiuchi and Kamiya, 1974). Also in
1969 the first blends of a styrene-eontaining resin, e.g., ABS with either PBT or
poly(butylene-naphthalene-dicarboxylate) (PBNDC), were announced by Eastman
Kodak ijackson et al., 1971).
In 1971 PBT blends with PC (Matsukane and Azo, 1973; Kubota et al., 1973;
Hasegawa et al., 1974) or PPE (Nakamura and Toyomoto, 1974) were invented. The
same year, the first PET blends with aromatic amorphous PAr were disclosed
(Koshimo et al., 1973). In a General Electric patent application PET: PBT = 1:1 blends
were reported to show good crystalline properties without the need to control their
molecular weights, or for nucleating agents (Fox and Wambach, 1973). The first
blends of poly(ethylene-2,6-naphthalene dicarboxylate) (PEN) were also disclosed
by Teijin in 1971. The resin was blended with polyalkene, e.g., with medium density
polyethylene (of density 930-940 kg/m3), 1-SOwt% MDPE and/or PP. The blends
were found to be dimensionally stable, and had good impact properties (Tokai and
Sakai, 1973).
During the intervening years hundreds of patents on alloys including PEST have
been issued. The largest volume blends are those of PC with PEST (PBT, PET or PCT,
and frequently with 1D-20wt% of an impact modifier). The second large group of
PEST blends is from a different combination of these blended resins, e.g., PET/PBT
or more recently PET/PEN.
The PEST/PC blends are usually formulated for injection molding, extrusion and
blow molding, but they can also be transfer or compression molded, formed in the
solid state, or thermoformed. In most blends PC is the matrix phase. The impact
modifier can be PE, ABS or acrylic copolymer, such as MBS. The blends show good
processability, heat resistance, ductility, HDT, high modulus, impact, tensile and
Introduction 339
flexural strength over a wide temperature range, good adhesion, solvent, chemical
and UV resistance. They can be painted, hot stamped, metalized and plated. Some
blends (containing polybutadiene as an impact modifier) may have poor weather-
ability. The blends are mainly used by the automotive industry. The commercial
blends include AzloyTM from Azdel Inc., BCT 4201 from Toray, Defsan™ from
Russia, DialoyTM from Mitsubishi Rayon, Ektar™ MB and EastalloyTM from Eastman
Chemical Company, Idemitsu™ 5C 600 from Idemitsu Petrochemicals, MakroblenaTM
from Bayer, MB4300 from Mitsubishi Gas Company, Novadol™ from Mitsubishi
Chemical, PoeanTM from Bayer, R2-9000 from Thermofil, 5abre™ from Dow Chem-
ical, Stapron™ E from DSM Polymer International, UltrablenaTM KR from BASF,
Valox™ and XenoyTM 1000 from GE Plastics.
The reversed compositions, PC/PEST where either PET or PCTG constitutes the
major component, are also designed for common processing methods. They are
partially miscible, usually have a cocontinuous morphology, show good proces-
sability, solvent resistance, elongation, low temperature impact and tensile strength
(crystallinity may be reduced upon blending). They are primarily used in business
machines, appliances, consumer goods, garden tools, lightning, automotive, sports
equipment, fluid handling, etc. The commercial blends include Ektar™ from East-
man, Hyperlite™ from Kanegafuchi Chemical, Impact™ from AlliedSignal,
MakroblenaTM UT from Bayer/Miles, MB 3500 from Mitsubishi Gas, Petsar™ from
Polysar, Sabre™ 1600 from Dow Chemical and XenoyTM 2000 from GE Plastics. In
Ektar™ MB alloys, poly(cyclohexane-terephthalate-glycol) (PCTG) has been mixed
with PC and/or a styrene-maleic anhydride copolymer (SMA).
The PBT/PET blends have been designed primarily for improved processability
(in particular, moldability), good surface properties, HDT, impact strength and
dimensional stability, as well as economy. The commercial blends include Resin C
or CN from Teijin, Celanex™ from Hoechst Celanese, EMC™ from Toyobo and
Valox™ from GE Plastics.
Other popular commercial blends containing PEST are those with an elastomer,
elastomeric copolymer (e.g., SMA) or acrylic rubber. The alloys are formulated for
extrusion, injection, compression, blow and transfer molding. The blends with SMA
may contain up to 35wt% glass fibers. They show good processability, rigidity,
impact and tensile strength, as well as excellent weatherability. Examples of com-
mercial PET/Elastomer blends include ArloyTM 2000 from Arco Chemical (blends
with SMA), Celanex™ from Hoechst Celanese, Rynite™ from du Pont de Nemours
and 5C-150 from Idemitsu Petrochemicals.
There are many PBT blends on the market with an acrylic elastomer. Examples are
BU from Dai Nippon Ink, BX from Toray, Novadol™ from Mitsubishi Chemical and
Vandar™ from Hoechst. The other impact-modified PBT/ elastomer alloys, such as
BexloyTM I from du Pont de Nemours, Celanex™ from Hoechst Celanese, Gafite™
from GAF, MacroblenaTM from Bayer Miles, Pibiter™ HI from Montedipe, 5tarflam™
PBT from Ferro Plastics, Teehster™ T from Rhone Poulenc or Ultradur™ KR from
BASF, have been formulated for injection molding, but they can also be extruded and
thermoformed. They show good processability, good electrical properties, high
stiffness and strength, HDT, dimensional stability, impact strength, solvent and
chemical resistance.
A large group of impact-modified PEST formulations comprise ABS or AAS
copolymers. The blends may contain up to 30wt% of GF, or another mineral filler.
They have been designed for injection molding, but can be extruded, thermoformed
or solid state formed. These alloys show excellent processability, high gloss, stiffness
at high temperature, good electrical properties, thermal stability, and mechanical
strength, HDT, low shrinkage, good dimensional stability, impact strength, as well
as solvent (e.g., to gasoline and motor oils) and chemical resistance. Their main
consumption includes electronics, automotive, and electrical industry, as well as
office, sports and household equipment. Commercial alloys of this type include
Resin A and AN from Teijin, AlphaloyTM MPB from Kanegafuchi Chemical, BA
from Dai Nippon Ink, BaitaloyTM VL* from Hitachi Chemical, Cycolin™ from GE
Plastics, DiaaloyTM B from Mitsubishi Rayon, Lurmu™ from Lucky Company (now
LG Chemical Ltd), Malecca™ B from Denka K. K., MaxloyTM B from JSR, NovaloyTM B
from Daicel Chemical, Techniace™ TB from Sumitomo Dow, Triax™ 4000 from
Monsanto, UltrablenJIM 5 from BASF and VX from Toray.
The commercial PArjPEST blends are available from Amoco Corporation (PET j
PAr blends, Ardel™ D-240) or Unitika (U-BOOO). These blends have excellent proces-
sability, high HDT, toughness and high impact strength.
Owing to the presence of polar groups, ester exchange and the possibility of graft
modifications, PESTs are relatively easy to blend. Commercial blends of PBT with
polyoxymethylene (or acetal), include DuraloyTM from Celanese and Lynex™ T from
Asahi Chemical. These show good processability, high heat deflection temperature,
HDT, toughness, softness and high impact strength.
17.1 PEST BLENDS WITH COMMODITY RESINS
17.1.1 PETIPO blends

To improve dimensional stability of polyethyleneterephthalate (PET) moldings, in
1962 Vereinigte Glanzstoff-Fabriken incorporated into PET, 3-lOwt% of a well-
dispersed poly-4-methyl-l-pentene (PMP or TPX; Siggel et al., 1964). In 1965, PET
was blended with several alkenic resins (e.g., 05--50wt% PE, for improved impact
strength; Glanzstoff A.-G., 1967) or, in a du Pont de Nemours patent, PET was
compounded with .5-150 phr of ethylene-methylmethacrylate copolymer, a Surlyn TM
ionomer (for high toughness and low mold shrinkage; Cope, 1969).
In 1967 Imperial Chemical Industries (ICI) patented blends of PET with poly
(ethylene-co-methylmethacrylate) (10% EMM). The alloys were found useful for
molding and fiber spinning (Dijkstra and Jones, 1969). In another ICI document,
PET was blended with either poly(ethylene-co-vinylacetate) (EVAc), poly(ethylene-
co-methylmethacrylate) (EMM), or poly(ethylene-co-hydroxyethylmethacrylate)
(EHEM), to give crystalline materials for molding thick-walled articles with good
impact strength Oones et al., 1971).
In a contemporary patent from Hoechst, PET was blended with O.O.5-lOwt% of an
a-alkene-vinyl ester copolymer, such as EVAc. The blend showed good hardness,
abrasion and solvent resistance, and significantly improved impact strength. For
further improvement of the dimensional stability and impact strength, PET was
blended with poly(ethylene-co-acrylate) or poly(butylene-co-acrylate) copolymer
(e.g., O..5-lOwt% of either PEA or PBA; Brinkmann et al., 1968; Farbwerke Hoechst,
1969). In a patent application of 1972, Allied Chemical described blends of PET with
0..5-30 wt % of an oxidized and carboxylated PE -- the alloys showed high impact
strength (Segal, 1973).
Two years later, du Pont de Nemours disclosed impact-resistant PET blends,
replacing Surlyn TM with ethylene-eo-vinylacetate-co-methacrylic acid terpolymer
(3% EVAc-MAA) (Gander et al., 1977). However, in a continuous effort to improve
on the 1969 patent by Cope, in 1978 the company filed another patent application
describing PET blends with an ionomeric ethylene-methacrylic acid copolymer Na
PEST blends with commodity resins 341
salt, and triethyleneglycol caprate-caproate - the alloys had good processability,
impact properties and high crystallization rates (Deyrup, 1979, 1982). In 1980 further
blends of PET with ionomers were disclosed by du Pont. For example, alloys
comprising PET with 6 wt % ethylene-methacrylic acid Na salt, flame retardants
and glass fibers were developed for good flame retardancy without loss of thermal
stability or mechanical performance. For improved thermal stability and prevention
of discoloration, a silicone resin, Silicone DC2oo, could also be added (Berr and
Deyrup, 1981; Garrison and Jones, 1981). In the following patent, 82.8% PET was
blended with 8.6% ionomer and succinic acid-grafted EPDM, to give alloys with
good impact strength (Hoeschele, 1982). In later patents, 15-40% PET, was blended
with ethylene-methacrylic acid partially Zn++ -neutralized ionomer (SurlynTM) for
good heat and excellent impact strength at -40 °C (Ostapchenko, 1981; Coker, 1987).
In the second half of the 1970s a new method of impact modification of engineer-
ing resins, mainly polyamides or polyesters, started to be explored. For example, in
1975 Teijin announced polyester blends with 5-85wt% of a reactive mixture com-
prising glycidyl methacrylate, methacryloxypropyl trimethyl silane, and glass fibers.
Good processability, dimensional stability, tensile and impact strength were
reported (Inokuchi and Ono, 1976). In 1978 Toyobo announced blends comprising
69wt% PET with glycidyl-terminated polyethyleneglycol (mPEG) and mineral fil-
lers. The resulting reinforced alloys showed good moldability, as well as high
thermal and mechanical properties (Kobayashi et al., 1979). A year later, Toray
Industries announced reactive blends of PET with ethylene-glycidyl methacrylate
(lOphr EGMA). The alloys showed good moldability, toughness, resistance to moist-
ure and heat (Iida et al., 1980). The following year, blends of PET with EGMA, Ca-
stearate and GF were announced. These materials were formulated for injection
molding of parts requiring excellent gloss, high mechanical properties and low
warpage (Toray Industries, 1982a).
In 1978 du Pont de Nemours disclosed PET or PBT blends with a copolymer of
ethylene (meth)acrylic ester and glycidyl (meth)acrylate (having particle
diameters less than 3JLm). Thus, 81.5wt% PET was blended with 18wt% copolymer
of ethylene-butylacrylate-glycidylmethacrylate of composition 63.6:28:8.4. The
alloys showed good toughness at room and low temperatures (Deyrup, 1979, 1982,
1985).
In a 1982 patent from Allied Corporation, PET blends with polyethyleneglycol
(5wt% PEG) and 0.75wt% AI(OHh were said to show increased crystallization
temperature (Aharoni, 1983). Thus, block copolymers of PA-PEST were prepared by
reacting the selected PA with carboxylic acid-terminated PET or PBT. The acid-
catalyzed reaction was conducted during blend compounding in a twin-screw
extruder, in the presence of tertiary phosphite esters. For example, a mixture of
80 wt % PA-6, 20 wt % PET and 0.6 phr tributyl phosphite was compounded at a
temperature of over 200 °C, with a residence time of over 2 min. The extrudate
showed reduced viscosity, in comparison to a control blend made without phos-
phite. Copolymer formation with other polyamides was also reported. The process
was also claimed to be suitable for making graft copolymers of PA with EAA
copolymers (Aharoni and Largman, 1983; Aharoni et aI., 1984). Coincidentally, also
in 1982 the reactive compatibilization based on the acid-catalyzed amide-ester
exchange reaction between PA and PET was described. The reaction was carried
out in a twin-screw extruder, using p-toluenosulfonic acid as a catalyst (Pillon and
Utracki, 1984, 1986). Similarly as in the above patents, 2min residence time was
found adequate to generate sufficient copolymer concentration to compatibilize the
system.
Similar materials were also obtained by blending PET with carboxylic acid-mod-
ified PEG, carboxylic acid salt and a filler. Moldings from the resulting material were
uniformly crystalline, glossy and with good mechanical properties (Kanegafuchi
Chemical Industry Co., 1984). In a contemporary patent, PET blends with ionomers
were described as having a high crystallization rate. Further addition of PEG-
dimethyl ether improved the blend moldability (Kuraray Co., 1984). In Goodyear
patent applications of 1982, PET blends with either 0.5-10wt% LLDPE or with
polyethyleneisophthalate were disclosed. The aim of the first work was development
of partially crystalline moldings, whereas that of the second was to develop alloys
with good O2 barrier properties (Gartland, 1984, Smith and Wilson, 1984).
BIP Chemicals described PET blends containing less then 6 wt % PCL and less than
1wt% of sodium stearate (and optionally glass fibers). The resulting systems
showed good moldability and mechanical properties (Daniels and Williams, 1984).
Blends comprising 100 parts PET with 0.5-100 parts of poly(methylnorbornene
carboxylate) were reported to show improved moldability and impact strength
(Mitsubishi Petrochemical Ind., 1984a).
In a patent application of 1991 from Enichem, three-component blends comprising
'30-70wt% PET, and polyamide and/or polyalkene (7Q-30wt% PA-6, LDPE, HDPE
or LLDPE), were compatibilized by adding epoxidized ethylene copolymer, such as
l-lOwt% EEA-GMA. The blends had significantly improved impact properties and
tensile elongation (Natarajan et al., 1994).
The same year, Johnson Service Company disclosed blends of recycled PET with
recycled PP. The resins were compounded at ratios between 1:4 and 4:1. To compat-
ibilize and toughen the blends, 15-20 phr maleated SEBS elastomer was incor-
porated. The blending resulted in stiff materials with good mechanical properties,
suitable for batteries and fuel cells (Tekkanat et al., 1993). In a contemporary docu-
ment from du Pont de Nemours, blends of PET with 5-20 wt % PO were disclosed.
The compositions comprised PET with either PE, PP, glycidyl methacrylate-mod-
ified PO, vinyl or acrylic-grafted PO, etc. The blends could also be reinforced by
incorporation of 5-1S0phr glass fiber. The material showed high heat and moisture
absorption resistance (Mukohyama, 1993).
In 1992 Kao Corporation disclosed formulations and the method of compounding
of PEST blends for preparation of moldable compounds with good performance and
anisotropic luster. The document specified two-component systems, comprising
98-5Owt% of part A, either PET or PBT, and 2-50% part B (an immiscible resin,
e.g., PO, PMMA, PS, PC or PA). When the viscosity ratio T/A/"lB > 2, and the storage
Young modulus ratio E~ < EB, the dispersed phase was in form of prolate ellipsoids
with an axial ratio of 1-10 (Odajima et al., 1993).
In a contemporary patent application from General Motors, impact-modified
blends haVing reverse proportions of components were disclosed. Thus,
5D-90wt% HDPE was blended with 1Q-30wt% PET, 5-30wt% of elastomeric
block copolymer of n-butylterephthalate and ethyleneglycol/propyleneglycol
(Hytrel™ 4074), and l-Swt% of a mixture of two aromatic phosphites. The resulting
alloys showed improved impact strength and low permeation to gasoline fuels (Abu-
!sa and Graham, 1993).
17.1.2 PHT blends

Polybutyleneterephthalate (PBT) blends having compositions similar to those of
PET, have also been patented. Frequently, the same patent specified that either
PET or PBT can be advantageously modified by the discovered method. There are
several reasons why PET is more often mentioned - it is better known, less expensive
and, being stiffer, it can profit more from toughening.
Thus, for example, in a 1968 patent from Toray Industry, butyl rubber (0.5-50phr
IIR) was used to improve the impact strength of either PET or PBT (Hiri and Kotama,
1971). In a Dainippon patent application of 1976, for improved processability and
mechanical strength, PBT was blended with 1-30 wt % EVAc (Adachi, 1978). Several
patents from du Pont de Nemours deposited in 1978 described that either PET or
PBT can be toughened by addition of ethylenebutylacrylate-glycidylmethacrylate
copolymer, having particle diameters below 31Lm (Deyrup, 1979, 1982, 1985). Exam-
ples of the interchangeability of PET with other thermoplastic polyesters can be
found in numerous parts of this book.
In 1974 BASF announced polyester molding blends with high tracking resistance,
comprising PBT and polyalkene (1Q-30wt% PO) (Seydl and Strickle 1976). In a later
patent, PBT was blended with 10wt% ethylene-vinylacetate-acrylic acid graft co-
polymer (EVAc-AA). The alloys had improved low temperature impact strength
(Schlichting et al., 1976).
In 1979 Eastman Kodak disclosed blends comprising 7Q-90wt% PBT, 5-25wt%
EPR and 5-25wt% SurIynlM ionomer. The materials showed good melt flow, heat
resistance and impact strength (Seymour and Weemes, 1980). The following year,
Toray announced similarly performing PBT blends with ethylene-glycidylmethac-
rylate copolymer (EGMA) (Toray, 1981c). In a contemporary document, PBT blends
with 0.05-10wt% of either PE or PP were developed for improved electrical insula-
tion properties (Dainishiseika Color and Chemicals Mfg. Co., 1982). The following
year, PBT was blended with 1-150 phr maleated EPR and 2-150 phr glass fibers (GF)
to give moldings with high mechanical properties and high impact strength (Mitsu-
bishi Chemical Industries Co., 1983a). In a contemporary patent, PBT (containing
terminal COOH groups), was reactively blended with lOwt% carboxy-terminated
NBR, and O.OI-5wt% bisoxazoline. The alloys showed good notched impact
strength (Teijin Ltd., 1982b).
The year 1981 is notable for polymer blend technology - from that time on, blends
become increasingly complex, multicomponent (up to six polymeric functional
ingredients), with growing tendency for preparation by reactive compounding.
This change is particularly evident in the technology of engineering polymer blends,
including those with PEST. The PBT blends disclosed in 1981 provide good exam-
ples.
Thus, PBT was blended with ethylene-glycidylmethacrylate (EGMA), or with
15 phr EGMA and 15 phr EPDM, to give flowing, moldable materials with good
mechanical behavior (Toray Industries, 1982c, 198&). In a Dynamit Nobel patent,
PBT was reactively blended with acrylic impact modifier (15wt% MBS) and with
0.5 wt % of either triglycidyl isocyanurate (TGIC) or bisoxazoline. The blends had
good notched impact strength (Blaschke et al., 1982). Similarly, General Electric
reactively blended PBT with either ethylene-ethyl acrylate (EEA), ethylene-vinyl
acetate (EVAc) or with their mixtures. The alloys had good processability and high
impact resistance (Dieck et al., 1983). In a Shell patent, PBTwas blended with 57wt%
SEBS, 19wt% SMA and 5wt% extending oil (Durbin et al., 1983).
In a du Pont de Nemours patent application, also of 1981, high impact strength
alloys were prepared by blending PBT with either a polyalkaleneoxide (POM) or
polyamide (PA), and an ethylene copolymer containing ester or acid functionality
(Sheer, 1982). Three years later, the company disclosed blends comprising
6O-97wt% PET or PBT, and ethylene-butylacrylate-glycidylmethacrylate (EBA-
GMA). The alloys showed good toughness at low temperature (Deyrup, 1985).
Also in 1981, 97-3wt% PBTwas compounded with polycarbonate (PC), and with
20-300 phr of SAN-grafted EPDM. The alloys had good moldability, mechanical
properties and weldline strength (Sumitomo Naugatuck Co., 1983). In a contempor-
ary patent from Bayer, PBT was blended with PC, and with either an ABS resin
having a rubber particle diameter of ~ 0.4j.Lm (Binsack et al., 1982; Binsack and
Goldman, 1985), or with a graft copolymer of polybutadiene and (meth)acrylate
esters and possibly acrylonitrile-acrylate rubber (ACM) (Bier and Indner, 1982;
Neuray et al., 1982; Nouverte et al., 1982; Serini et al., 1982). The impact-modified
grades of PBT usually contain 20-30 wt % of a core-shell modifier with elastomeric
particles having an average diameter of ~ 0.3--{).4 j.Lm. The impact-modified PEST/
PC blends continued to be developed by the company over the next several years
(Weyer et al., 1984; Kleiner et aI., 1984).
The following year, to improve processability, mechanical properties and adhe-
sion to metal, PBT was blended either with EGMA copolymer and reinforcements, or
with polycaprolactone, PCL, and ethylene-diglycidyltetrahydrophthalate copolymer
(Toray Industries Inc., 1983a, 1984b). In a contemporary disclosure, large synergistic
enhancement of the impact strength, was disclosed by Uniroyal for compatibilized
and impact modified PBT IPC blends with SAN-grafted EPR or EPDM (~25 wt %
AES) (Wefer, 1984, 1985, 1988).
In 1982 General Electric improved processability and impact performance of PBT
by blending it with polyalkenes and elastomers, for example O.1-20wt% LLDPE,
5--65wt% PC and 1Owt% of either polybutadiene (PH), a copolymer from methyl-
methacrylate, butadiene and acrylonitrile, MBA or an acrylic rubber (Aerylaid KM
653; Dieck et al., 1983; Agarwal, 1983; Boutni and Liu, 1983; Liu, 1983c). In 1987 the
company patented glycidyl methacrylate-grafted ethylene-propylene-diene copoly-
mer (EPDM-GMA) as a general purpose impact modifier for thermoplastic poly-
esters (PET or PBI). The blends also showed good weld line strength (Pratt et aI.,
1988). In 1989 General Electric developed blends of PC, with PBT, EPDM, and (for
high gloss applications) polycaprolactone (PCL) (Natarajan and Mininni, 1991). Also
in 1982, BASF announced PBT blends with PC and ethylene-butylacrylate-acrylic
acid copolymer (EBA-AA) (Portugall et al., 1984).
In 1985 Teijin Chemicals invented blends comprising 50-84wt% PBT, 10-35wt%
PC, 5-15 wt % MBA and 0.5-5 wt % PO. The moldings showed excellent resistance to
chemicals and low temperature impact (Shinomiya and Kitamura, 1986).
In 1987 Sumitomo Naugatuck applied for patent protection for three-eomponent
blends comprising: (1) a polyester (PEST), e.g., PET or PBT; (2) a graft copolymer;
and (3) a rubber-reinforced resin. The weight ratio of (1) to (2) + (3) was 95:5-5:95;
the weight ratio of (2) to (3) was 100:0-5:95. The graft copolymer (2) was prepared by
copolymerizing 0.1-400 parts of glycidyl methacrylate and 0-1000 parts of other
copolymerizable monomer selected from a group consisting of aromatic vinyl,
cyanated vinyl, and alkyl unsaturated carboxylate monomers, in the presence of
EPR or EPDM elastomer (e.g., acrylonitrile-styrene-EPDM-glycidylmethacrylate
graft copolymer (AE5-GMA). For example, PBT/ AE5-GMA blends were prepared
in ratios of PBT to AE5-GMA varying from 95:5 to 5:95. These alloys were found
suitable for molding electrical, or automobile parts with improved balance of heat
resistance, chemical resistance, impact strength, weld strength, stiffness, reduced
mold shrinkage factor and appearance. In 1990 the company commercialized these
blends under the trade name Teehniaee™ TB (Hirai et al., 1988, 1989, 1992, 1994;
Nishikubo et al., 1994).
In 1990 Tonen Corporation announced blends comprising 10-90wt% PP,
90-10wt% PBT and 5-30phr of a polyalkene-polyester graft copolymer (containing
l0-80wt% PBT and 9D-20wt% of EPDM grafted with unsaturated carboxylic acid
or maleic anhydride) having 0.2-5 mol % carboxyl groups and M w = 8-140 kg/mol.
The blends showed excellent impact strength, flexural modulus, HDT and peel
resistance. They were suitable for molding interior and exterior parts of automobiles,
parts of electric appliances and for other applications (Fujita, Y. et al., 1994).
In 1991 Mitsubishi Petrochemical Company disclosed blends that comprised 90-
10wt% polyalkene modified by introducing a hydroxy, epoxy or carboxyl group,
and 1D-90wt% of either polyamide (PA-6 or PA-66) or polyester (PET or PBT). As
the polyalkene, copolymer of propylene with either 7-methyl-1,6-octadiene, or
methyl-1,4-hexadiene, a copolymer was used. Modification was obtained by radical
grafting the copolymer with either 2-hydroxyethyl methacrylate, 2-hydroxyethyl
acrylate, 2-hyroxypropyl acrylate, glycidyl methacrylate or maleic anhydride. The
blends were found suitable for use as a molding material for automotive, electrical
parts, etc. (Kihira and Nakano, 1995).
The same year, Nippon Petrochemicals announced high impact strength blends
(that did not deteriorate upon annealing) of 5D-99 wt % PBT with 1-50 wt % ethylene-
ethylacrylate-glycidylmethacrylate copolymer (EEA-GMA) and 0.1-15wt% (on PBT
with EEA-GMA) of a low-molecular-weight copolymer of ethylene-ethyl acrylate-
acrylic acid (EEA-AA) (Hayasaka et al., 1992). In a contemporary patent disclosure
Kanegafuchi Kagaku Kogyo described blends of PBT with 1D-90wt% of a polyary-
lester (PAr) and either EPR or EPDM grafted with glycidyl oxybenzyl acrylamide.
The blends showed good processability and high impact strength (Suzuki et al.,
1992). Similar blends (55-80wt% PBT, 1D-20wt% PO (Le., PE, PP or EPR) modified
with 0.05-15wt% glycidyl methacrylate and/or 0.1-2wt% MA, and 1D-30wt% PC)
were also disclosed in 1991 by Teijin. The alloys showed good processability. The
moldings had excellent toughness, rigidity, strength, dimensional stability and flex-
ural modulus (Fujie, 1993).
In 1992 Eastman Kodak disclosed blends of poly(l,4-cyclohexylenedimethylene
terephthalate) (PCT), or other copolyesters prepared from terephthalic acid,
1,4-cyclohexane dimethanol and ethylene glycol. For example, PCT was blended
with 15-40 wt % of an ethylene copolymer containing at least 5 mol % of a free radical
polymerizable comonomer selected from either vinyl acetate or an alkyl acrylate. The
blends displayed excellent melt flowability, heat resistance, improved impact
strength and stress crack resistance near O°C (Meyer et al., 1993).
By 1993 AlliedSignal had developed blends that comprised 4O-6Owt% PC, 2D-
6Owt% PEST (PET, PBT or PCT), 1D-20wt% aminated elastomer (EPR, EPDM or
NBR), a copolymer of PEST and the selected elastomer, and a graft-eoupling agent
such as poly(2,4,6-tri-isopropyl-1,3-phenylenecarbodiiInide). The alloys were
reported to show impact strength superior to that of blends without the amine
functionality. The reactive blending was carried out in a twin-screw extruder, first
mixing PEST with elastomer, then adding other ingredients downstream. The alloys
have been used for molding parts for garden use, sports, power tools, snowmobiles,
automobiles, and the electric and electronic industries (Akkapeddi and VanBuskirk,
1994).
17.1.3 PEST/elastomer blends

The impact-modified PBT blends are formulated for injection molding, but they can
also be extruded and thermoformed. They usually contain 2D-30 wt % of a core-shell
rubber modifier such as MBS, PMMA-g-poly(n-butylacrylate), SAN-g-poly(n-butyl
acrylate), SAN-g-PBD, etc., with elastomeric particle size of about 300nm (Neurey
and Ott, 1981). The elastomeric particles promote multiple crazing and localized shear
yielding in the matrix, thus high resistance to crack propagation (Hourston et al.,
1991). These resins show good processability (reportedly better when acrylic instead
of alkenic elastomer is used), excellent electrical properties, high stiffuess and
strength, high HDT, low water absorption, good dimensional stability, no tendency
for environmental stress cracking, good low and high temperature impact strength,
fine weatherability, water and chemical resistance, and resistance to heat aging.
The commercial blends containing acrylic elastomer include BU blends from Dai
Nippon Ink, BX alloy from Toray, Novadol™ from Mitsubishi Chemical Company,
Vandar™ from Hoechst and others. Numerous commercial PBT/alkenic elastomer
(e.g., EPDM) blends are available, including, BexloyTMJ from du Pont de Nemours,
Gafite™ from GAF, Macroblen~ from Bayer, Staiflam™ PBT from Ferro Plastics,
Techster™T from Rhone Poulenc or Ultradur™ KR from BASF.
The blends have been used for engineering parts, housings, sports gear, auto-
motive parts (such as door handles, windshield wiper arms, motor housings, printed
circuit boards, housings for electronic ignition system, fuel level sensors, bumpers,
sideswipe protector strips, air louvers, spoilers, head-lamp housings, distributor
caps, spark plug connectors), etc.
Commercial blends of PET with elastomer (e.g., Celanex™ from Celanese,
Rynite™ from du Pont de Nemours or SC-150 from Idemitsu Petrochemicals) are
formulated for injection molding, or extrusion, but can be compression, blow, or
transfer molded as well. Usually the blends contain up to 35 wt % glass fiber. They
show good processability, rigidity, impact and tensile strength, as well as excellent
weatherability. They are being used for molding furniture pieces, electrical or elec-
tronic housings in the automotive industry (windshield wiper arms, side roof rails,
sunroof frames, lamp sockets), hardware parts (e.g., for electric glue guns, garage
door openers, floor polish drives, lawn mower housings, outboard motor propel-
lers), bicycles, pumps, etc.
As previously indicated, polyalkenes have been used for impact modification of
PEST since the 1960s. Later, for the same purpose, alkenes were copolymerized with
monomers having acid or ester groups. The copolymers, namely ethylene-vinyl
acetate copolymer (EVAc), ethylene-ethylacrylate (PEA), ethylene-butylacrylate
(PBA), ethylene-methylmethacrylate (EMMA), ethylene-hydroxyethylmethacrylate
(EHEMA), or acrylic grafted ethylene-propylene copolymers (e.g., EPR-AA or
EPDM-GMA) have been successfully used, together with modified ABS resins. For
example, in a Union Carbide patent deposition of 1968, PET blends with rubber-
modified poly(meth)acrylates (5-95 wt % ABSM) and polydimethylsiloxane
(1-20wt% PDMS) were reported to show good notched impact and embrittlement
resistance (Sauers and Barth, 1970).
In the 1970s the PEST blends started to become more complex - on the one hand
PET has been blended with another polyester (e.g., PBT, PCT, PAr or PC), and on the
other hand the impact modifier became more sophisticated - offering elastomeric
copolymers with soft and rigid domains, multicomponent copolymers, core-shell
resins, etc. For example, in a patent application deposited in 1975 by Mobay Chem-
ical, PBT was blended with PBT-modified polyurethane (25% PBT-co-TPU) for high
impact resistance down to -70°C (Baron and Bailey, 1977). Three years later the
company disclosed 1:1 PBT blends with ester-type polyurethane (TPU) with good
ductility and hardness (Heiss, 1981).
In 1977, for good impact and weathering resistance, Mitsubishi Rayon Company
patented PET blends with 5-94 wt % PC and 1-40 wt % butyl-acrylate-styrene-triallyl
isocyanurate copolymer, grafted with methylmethacrylate-styrene (Kamata et al.,
1978). The same year, for good impact strength and solvent resistance, 25-95wt%
PET was blended with 1--8 wt % PC, and a core-shell butadiene-methylmethacrylate-
styrene-divinylbenzene copolymer (MBS) (Rohm & Haas Co., 1979), whereas for the
same purpose in Teijin patents, PET was blended with 4-94wt% PC and MBS
(Yamamoto and Shimizu, 1979).
In 1978 General Electric used hydrogenated styrene-butadiene copolymer (15 wt %
SEBS) to impact modify PET IPBTIPC blends (Wambach and Dieck, 1980). The
following year, the company described similar PET IPBTIPC blends, but impact
modified by addition of (SB)n and either a butadiene-caprolactone-styrene, or a
butadiene-caprolactone block copolymer (Dieck, 1980, 1981). In 1981 the company
disclosed blends comprising PC, 3-25wt% SBS and 2-20wt% acrylate polymer, as
AkryioiJIM KM. The alloys showed good moldability and resistance to thermal
embrittlement (Liu, 1982, 1984a; Boutni and Liu, 1984). In a contemporary Shell
patent, PBT was blended with 57wt% SEBS, 19wt% SMA and 5wt% extending
oil. The compositions showed good set of properties required in automotive applica-
tions (Durbin et ai., 1983).
In 1979, Rohm & Haas Company announced PET IPC blends compatibilized and
impact modified by addition of 15 wt % core-shell butylacrylate-butylenediacrylate-
diallylmaleate-methylmethacrylate copolymer (Fromuth and Shell, 1981). The same
year, Eastman Kodak disclosed blends comprising 70-90wt% PBT with 5-25wt%
EPR and 5-25wt% SurIyn'fM. The alloys had good processability, high heat resist-
ance and impact strength (Seymour and Weemes, 1980). In a GAF patent, high
impact strength alloys were prepared by blending PBT and/or PET with polyester-
polyether rubber, bisphenol-A-glycidyl ether and butylacrylate-glycidylmethacryl-
ate-methylmethacrylate copolymers (Charles and Coleman, 1981). In a Hooker
patent, impact strength and hydrolytic stability of PAr was improved by blending
with 10% MBS copolymer (Salee, 1981a).
In a patent application of 1980, blends comprising 70wt% PBT, 20wt%
maleated EPR and 10 wt % PC were described. The materials had high impact
strength and good appearance (Mitsubishi Chemical Industries Co., 1982c). In a
contemporary patent, PBT was toughened by blending it with ethylene-glycidyl
methacrylate copolymer (EGMA). The alloys showed excellent mechanical pro-
perties, high impact strength and recyclability (Toray Industries, 1981c). Also in
1980 a Celanese patent described PET blends with styrene-maleic anhydride
copolymer (10 wt % SMA) as having good low temperature moldability. Moldings
from these alloys showed good impact strength, as well as high mechanical and
adhesive properties (Froix et ai., 1981; Froix, 1981). About the same time Ethyl
Corporation also applied for patent protection for blends of PET with rubber-
modified styrene-maleic anhydride (SMA) at a 1:1 ratio (Hornbaker and Jones,
1981,1982). Two years later, for high heat deflection temperature, PET was blended
with either 10-90 wt % SMA, styrene-(meth)acrylic acid (SAA; optionally with an
ionomer or elastomer), or with rubber-modified maleimide-styrene (Hornbaker and
Jones, 1983).
In 1981 ABS-type impact modifiers returned to the scene. Thus, in a series of
patents from Bayer either PET IPBT, PET IPC, PBT IPC or mixtures of polycarbon-
ates were impact modified by blending with a graft copolymer of polybutadiene
and (meth)acrylate esters (and possibly acrylonitrile), an acrylate rubber, ACM and
ABS. Since the blends showed good toughness, hardness, stiffness and HDT, they
were reported to be commercially important (Bier and Indner, 1982; Neuray et al.,
1982; Nouverte et ai., 1982; Serini et ai., 1982). It is worth recalling that also in 1981
BASF deposited a series of basic patents on ABS/PC blends, with and without
styrene-maleic anhydride-acrylic acid (SMA-AA) copolymer (Brandstetter and Haaf,
1982; Brandstetter et al., 1982, 1983b).
In 1981 several patents were deposited for impact modification of PBT. For
example, 60-90 wt % PBT, was blended with multilayer acrylic elastomer, poly-
(methylmethacrylate-co-methylacrylate-co-butylacrylate-co-allylmethacrylate). The
blends showed good processability and high impact resistance (Mitsubishi Chemical
Industries Co., 1982d). In the following patent application from the company, 100
PBT was blended with 1-150 maleated EPR and 2-150 parts GF, to give moldings
with high mechanical properties and impact strength (Mitsubishi Chemical Indus-
tries Co., 1983a).
In a contemporary document, high notched impact strength PBT alloys were
prepared by reactive blending of PBT (having tenninal -COOH groups) with
lOwt% carboxy-tenninated NBR, and 0.01-5wt% bisoxazoline (Teijin Ltd., 1982b).
For good moldability, flowability, dimensional stability, impact strength and with
good mechanical behavior, PBT was blended with either ethylene-glycidylmethac-
rylate (EGMA) or with 15phr EGMA and 15phr EPDM (Toray Industries, 1982c,
1983c). In a Dynarnit Nobel patent disclosure, PBT was reactively blended with
15wt% MBS and O.5wt% of either triglycidyl isocyanurate (TGIC) or bisoxazoline.
The alloys had high notched impact strength (Blaschke et al., 1982).
Also in 1981, Stauffer Chemical announced that PET blended with 50wt% of an
interpolymer (comprising crosslinked methacrylate, crosslinked styrene-acrylOnitrile
and uncrosslinked styrene, ASA), showed good toughness and impact strength
(Silberberg, 1982a). For high notched impact strength, Dynarnit Nobel reactively
blended PBT with an acrylic impact modifier, 15 wt % MBS and with 0.5 wt % of
either triglycidyl isocyanurate (TGIC) or bisoxazoline (Blaschke et al., 1982).
A contemporary patent application from du Pont de Nemours described that high
impact strength PBT alloys were prepared by blending the resin with either POM or
PA, and with ethylene copolymer containing ester or acid functionality (Sheer, 1982).
In another disclosure, 100 parts PBT was blended with 97-3 parts of PC and 20-300
parts of SAN-grafted EPDM. The resulting materials had high impact strength, good
fluidity, moldability, mechanical properties and weldline strength (Surnitomo Nau-
gatuck Co., 1983).
In a General Electric patent of 1981, PBT blends with EEA, EVAc or their mixtures
were described. The alloys showed high impact resistance (Dieck et al., 1983). In a
Shell patent, blends of PBT with 57 wt % SEBS, 19 wt % SMA and 5 wt % extending oil
were reported to show a good set of properties required in automotive applications
(Durbin et al., 1983). One year later, the company deposited an application for blends
comprising 5-95 wt % of either PET or PBT, and either ABS, MBS or another co-
polymer. The molded alloys showed high gloss and good solvent resistance (Michel,
1985). In a contemporary patent disclosure, PET was impact modified by blending
with 0.2-5wt% isocyanate-tenninated butadiene rubber, HTP-9A (Unitika Ltd.,
1984b).
Diverse methods of PBT modification were announced in 1982. For example, PBT
was blended with either EGMA or with 20 wt % polyglutarirnide (generated from
reactive extrusion of PMMA with CH3 NH 2 ). The alloys showed excellent moldabil-
ity, good mechanical properties, and high HDT. Alternatively, PBT was blended
with polycaprolactone (PeL) and ethylene-diglycidyltetrahydrophthalate copoly-
mer. The materials with excellent mechanical properties were easy to metal-plate
(Toray, 1983a, 1984b). In another disclosure, PBT was impact modified by blending it
with thermoplastic polyester elastomer and ABS (Mitsubishi Rayon Co., 1984). PBT
blends with PCL (tenninated with either acetic anhydride or pentabromobenzoic
acid) and a filler showed good moldability, high modulus, impact strength, elonga-
tion, and in the latter case flame resistance (Teijin Ltd., 1983b, 1984). To obtain
impact-and flame-resistant materials PBT or PET was blended with either an acrylic
polymer, Kaneace™ FM, and halogenated epoxy resin (Dainippon Ink and Chem-
icals, 1984), or with poly(pentabromobenzylacrylate) (Mitsubishi Chemical Indus-
tries Co., 1984a).
As time progresses it is becoming increasingly difficult to assign a single reason
for developing a specific blend. For example, in 1984 Unitika announced PET blends
that, on the one hand were designed to crystallize rapidly, and on the other hand had
excellent impact strength. Thus, 100 parts PET was blended with 0.05-10phr nucle-
ating agent, 3-30 phr cis-eyclo-alkene carboxylic acid anhydride-grafted EPR, and
1-3Ophr ethylene-glycidylmethacrylate copolymer (Okamoto and Ohama, 1986).
Shock-resistant blends of PBT were disclosed by Ausimont in 1987. The materials
comprised 55-98wt% PBT, 1-35wt% butadiene and/or acrylic elastomer (e.g.,
butadiene/styrene/methyl methacrylate terpolymer, having a particle diameter
0.1-2j.tm, a glass transition temperature below O°C, and a crosslinking degree of
50-99%), and 1-10wt% of an elastomeric block-eopolyester with a melting point of
~ 190°C. The formulations may also contain 1-10phr of PC or TPU, and the
customary additives. The resulting blends showed good low temperature shock
resistance, very good resistance to gasoline and oils, as well as to light and
thermo-oxidation. The blends were used for impact resistant moldings for cars,
body protection and sports equipment (Chiolle and Andreoli, 1987).
In a 1987 disclosure from General Electric, blends comprising PET (or PBT) with
glycidyl methacrylate-grafted EPDM were described. The reactive blending resulted
in impact modification, giving materials with good weld line strength and improved
mechanical performance (Pratt et a/., 1988). At the same time the company also
announced blends of PC/PET or PC/PBT impact modified by addition of either a
polyacrylate elastomer, or HIPS (Boutni, 1989; Holub and Rock, 1989). In a contem-
porary document from AlliedSignal, either a maleated acrylonitrile-butadiene-styr-
ene (AB5-MA) or a maleated ethylene-propylene copolymer (EPR-MA) were
described as suitable impact modifiers for PEST, Le., PET and PBT (Akkapeddi et
ai., 1990).
In 1987 and 1989 Sumitomo deposited a series of patents for blends comprising 20-
4Owt% of a polyester (PEST, preferably PBT with M v = 18-88 kg/mol), 15-55wt%
ABS (PB content 5-30 wt % and a particle diameter of 0.05-5 j.tm), and an a-methyl-
styrene-acrylOnitrile copolymer (25-45wt% MeSAN) with 15-25wt% AN. The
alloys gave moldings with high impact, chemical and heat resistance, good flexural
modulus, and dimensional stability. This is one of the basic patents for Techniace™
TB, introduced in 1990 (Kodama et ai., 1990, 1992).
In a contemporary disclosure from Bayer, polyester molding compositions were
described. These contained 2D-80wt% PBT, 1-50wt% either PC and/or PEC, and
1-30 wt % of a grafted polymer with particle diameter 0.2--0.6 j.tm, obtained by graft-
ing 1D-40wt% of at least one (meth)acrylic acid ester and/or a mixture comprising
10-35 wt % acrylonitrile and 65-90 wt % styrene, onto 60-90 wt % of a butadiene. The
blends may additionally comprise lubricants and mold release agents, nucleating
agents, plasticizers, stabilizers, flame-resistant additives, fillers and reinforcing sub-
stances and/or dyestuffs (Freitag et ai., 1994). Blends of PBT with PC and styrene-
methylmethacrylate-butyl acrylate (MBS) were also discussed in patent depositions
from Rohm & Haas Company (Memon, 1992, 1994). Similar three-eomponent blends
were described by Rohm GmbH Chemische Fabrik. Thus, 99.9--0.1 wt% of a
blend comprising 0.1-99.9wt% of PBT and 99.9--0.1 wt% of a PC, was blended
with 99.~.1 wt% of a core-shell modifying copolymer (99-50wt% of butyl acrylate,
methyl (meth)acrylate and allyl methacrylate, and l-SOwt% of units with uv-
absorbing groups/ such as phenyl methacrylate or 2-ethylhexylthioglycolate). The
blends were used as molding compounds, such as injection molding of parts for
housings and bumpers (Fischer and Siol, 1993b, 1994).
In 1990 Mitsubishi Rayon disclosed PET (or PBn blends with a polyorganosilox-
ane-acrylic rubber graft copolymer. The new alloys had improved impact strength at
low temperature (Yamamoto, N. et al., 1992/ 1994a). In a contemporary patent from
General Electric, binary blends that comprised a polyester, e.g., poly(butylene cyclo-
hexanedicarboxylate), 75-99wt% PBCD and a poly(ether ester) elastomer (e.g.,
20wt% of either polyester-imide-ether elastomer, polyether ester elastomer
(LomocJTM RTM), ABS, polyetherimide ester or EVAc (Elvax™) were described as
having good tensile strength (Borman and Liu, 1994).
A year later, Hitachi Chemical announced impact resistant PEST blends. Thus/ 55-
1 wt % of either PET or PBT was compounded with 45-99 wt % modified ABS
copolymer. The copolymer comprised styrene and acrylonitrile grafted onto poly-
butadiene, already emulsion grafted with butylacrylate and triallylisocyanurate
(Bu-ABS). The resulting alloys were found to have high impact, heat and solvent
resistance (Mashita et al., 1993). Also in 1991/ Idemitsu Petrochemical patented blends
with improved processability, solvent and impact resistance, as well as high
mechanical properties. These systems contained a branched polycarbonate
(30-98wt% bPC; bisphenol-A polycarbonate branched by addition of 1,I,I-tris(4-
hydroxyphenyl)ethane, having M v = 15-40kg/mol), and a polymer(s) selected from
PEST, PA, styrenics (HIPS/ ABS or SMA), and TPE (acrylic rubber, butyl rubber,
EPDM or SBS). The preferred composition was bPC with 5-59 wt % PBT and I-SO wt %
of an elastomer, such as MABS Metablen™ W 529 (Kozakura et al., 1992/ 1994).
In 1991 Enichem announced blends comprising 70-30 wt % PET, 30-70 wt % PC
and 10-3Owt% (of the total amount of PC and PET) of either maleated or epoxidized
elastomer (e.g., ethylene-ethylacrylate-maleic anhydride copolymer). The alloys
were said to be chemically resistant with improved impact properties (Natarajan
and Arjunan, 1993). In the follOWing patent, 70-30 wt % PET was blended with either
a polyamide, a polyalkene or their mixture (e.g., 3O-70wt% LDPE), and an ethylenic
copolymer (5-30 wt % ethylene-ethylacrylate-glycidylmethacrylate (EEA-GMA),
Lotader AX from Norsolor). The reactive compounding was done in a twin-screw
extruder (Natarajan et al., 1993/ 1994).
In 1991 and 1992 Roehm patent depositions, a new class of impact-modified
polymer blends was described. Thus/ polymer mixtures were prepared by blending
at least two polymers that were chemically different but compatible. The polymers
should have tough and hard phases, where the glass transition temperature of the
tough phase(s) should be below 10 °C and that of the hard phase(s) above 30 0c. The
two phases should be, at least partly, covalently bonded. Thus/ a resin selected from
PBT, PET, PVC/ PS, PMS, PC or CR, was mixed with core-shell graft copolymer
prepared from EPDM, styrene-butadiene block copolymers, methacrylate graft co-
polymers or allyl cyanurate copolymers. The blends were injection molded, or
extruded into housings, car bumpers and bearings: they could also be reinforced
or laminated. The invention provided materials with high notched impact strength,
without adversely affecting the other desirable properties of the components, such as
the Vicat softening point (Siol et al., 1993b, 1995).
In 1992 General Electric announced blends comprising PC, PEST and/or poly-
ester-earbonate, and 10-20wt% of an impact-modifying mixture of ABS with an
acidified copolymer [ethylene, glycidyl methacrylate or maleic anhydride, and
(optionally) vinyl acetate, vinyl alcohol, styrene, acrylonitrile, (meth)acrylate(s»). The
alloys showed synergistically improved impact strength and a ductile-brittle trans-
mission temperature less sensitive to the molding conditions (Steendam et al., 1993).
The company also announced impact- and UV-resistant blends of poly(cyclohexa-
nedimethyleneterephthalate) (PCT). These were prepared by mixing PCT with poly-
estercarbonate and/or polyester (PEST) and an elastomer grafted with butyl
acrylate, 1,3-butylene diacrylate, diallyl maleate and methyl methacrylate impact
modifier (Liu, N., 1993).
In a contemporary patent from Dow, multi-eomponent blends were described.
These were prepared in two parts: (1) blending PC with PEST and not more than
5wt% of a copolymer (e.g., ABS-type with alkyl(meth)acrylates, glycidylmethacry-
lates, ethylene/propylene/diene copolymer, maleic anhydride, alkyl or aryl malei-
mides and oxazolinei and (2) blending polyphenylene ether (PPE) with at least one of
the following resins: PS, HIPS, SEBS, PA, PC, PEST and polyalkyl(meth)acrylate.
Parts (1) and (2) were compounded together and molded. The blends had low gloss
even when molded at high temperature. They were used to manufacture instrument
and appliance housings, car panels, radio components, etc. (Laughner, 1993). Later,
these PC/PET blends were impact modified by addition of glycidylmethacrylate
copolymer. The systems showed good flexural modulus, weld line strength and
solvent resistance (Laughner, 1994). The company also disclosed transparent blends
of PBT, PET and thermoplastic, rigid polyurethane (TPU). The blends were resistant
to deformation and decomposition when exposed to processing. Moldings showed
improved tensile strength, without reduction of transparency, toughness, thermal
resistance and hardness. They could also be converted into non-eellular shapes using
standard molding techniques, such as injection, RIM, casting, etc. These alloys found
use for production of safety glasses, industrial components, protective covers, fuel
handling systems, consumer products, etc. For example, a blend comprising 75 wt %
of PET and lsoplast™ 301 with Tg =224°C, was injection molded to give materials
with improved tensile strength and elongation, without loss of transparency (Moses
and Chen, 1993, 1994).
In a contemporary patent from Rohm and Haas Company, blends comprising
85-90wt% PET, 5-lOwt% of a core/shell polymer (butyl acrylate, diallyl maleate,
methyl methacrylate, trimethylol propane triacrylate), not more than 5wt% of a
nucleating talc, not more than 5wt% of a thermal and/or oxidative stabilizer,
1-8wt% PC, and 1-5wt% mold release agent (a copolymer of ethylene with vinyl
or vinylidene ester) were disclosed. The alloys, having high crystallization rate, were
extruded or molded into computer and business machine housings, automotive
parts, food containers, trays and containers. The ethylene copolymer drastically
reduced plate-out during molding, resulting in longer runs and fewer rejects (Lai
and Brady, 1994). The following patents generalized the method for manufacturing
tough, ductile and transparent polyester blends of either PET, PETG, PEN or PBT.
Thus the selected polyester was blended with an impact modifier that comprised
4O-65wt% of core polymer (40-60wt% vinyl aromatic, 4O-6Owt% 1,3-diene(s),
$ 10wt% of copolymerizable vinyl(idene) monomer(s) and $ 5wt% of graft-linking
or cross-linking monomer(s), such as emulsion polymerized styrene-butadiene-
divinylbenzene) and 35-60wt% of shell polymer (2-40wt% hydroxyalkyl (meth)
acrylate(s), 6O-98wt% vinyl aromatics and $25wt% of vinyl(idene) monomer(s),
such as hydroxyethyl methacrylate with methyl methacrylate, styrene, ethyl
methacrylate, etc.). For example, the core-shell impact modifier (with a refractive
index of 1.55-1.58) was blended in a twin-screw extruder with PET to give transpar-
ent alloys with high impact strength (Carson et a1., 1994).
Also in 1992, Polyplastics Company announced blends comprising 100 parts PEST,
0.5-10 parts of an acrylonitrile copolymer (51-97wt% acrylonitrile and 49-3wt%
epoxidized 0, IJ-unsaturated monomers), 0-10 parts of a styrene copolymer (e.g.,
40-97 wt % styrene, 60-3 wt % epoxidized 0, IJ-unsaturated monomers and 0-50 wt %
other vinyls, 0-100 parts of fillers, and/or 0-100 parts of a polyamide (PA). The
blends showed enhanced melt tension and improved blow moldability without
causing the parison draw down. Moldings had excellent mechanical properties
and thermal resistance, uniform thickness and an excellent appearance, even when
repeatedly recycled. The alloys were used for the production of hollow moldings, to
be used under severe conditions, such as an intake· manifold of an automobile,
suction and exhaust parts around the engine, vessels for high temperature liquids,
chemicals and solvents, pipes, floats and tubes (Shiwaku et al., 1994).
In 1993 AlliedSignal announced blends comprising 4O-6Owt% PC, 2Q-60wt%
PEST(PET, PBT or PCT), 10-20 wt % aminated elastomer (EPR, EPOM or NBR), a
copolymer of PEST and the selected elastomer, and a graft coupling agent such as
poly(2,4,6-triisopropyl-1,3-phenylenecarbodiimide). These alloys showed impact
strength superior to that of blends without amine functionality. The reactive blend-
ing was carried out in a twin-screw extruder, first mixing PEST and an elastomer,
then downstream adding other ingredients. The alloys have been useful for molding
parts (e.g., for garden and power tools, sport equipment and snowmobiles), and
have found application in the automotive, electric and electronic industries (Akka-
peddi and VanBuskirk, 1994).
17.1.4 PEST/styrenics blends

Aromatic polyesters (PEST) are immiscible with polystyrene (PS). Furthermore, since
both resins require toughening, so does their blend. For these reasons PESTs have
been blended not with PS, but with its elastomeric copolymers, styrenics. The blends
have been developed mainly to reduce costs and to improve the impact strength of
the engineering resin. Depending on the concentration of the PS domains in the
blend, the compatibilization should affect either only the PEST matrix, or both PEST
and PS phases. In the first case the styrenic copolymer must contain sufficient
concentration of reactive groups to bond to the PEST chain-end groups, thus it is
considered an impact modifier. In the second case the PS (or styrene-acrylonitrile,
SAN) domains must be toughened by incorporation of elastomeric particles within
the glassy PS or SAN phase. Thus, one may blend PEST with any of the styrenic
copolymers, namely HIPS, SBR, SEBS, ABS, ASA, etc., provided that the system is
compatibilized. In the follOWing text both strategies are illustrated. Several examples
of the use of styrenics with PEST are discussed in the previous section that deals with
PEST/ elastomer systems.
As an early example, in 1968 Union Carbide Corporation announced PET blends
with rubber-modified polyacrylates or methacrylates (5-95% ABSM) and optionally
a polydimethylsiloxane (1-20% POMS). The alloys had improved notched impact
and embrittlement resistance (Sauers and Barth, 1970). Three years later, to improve
processability and impact strength of polyarylates (produced by polycondensation
of isophthalic and terephthalic acids with bisphenol-A), Unitika Company blended it
with 30 wt % ABS. In the patents that followed, polyacrylate rubber (PP, EVAc or PE)
was also used for the same purpose (Koshimo, 1973; Koshimo et al., 1973). Similar
blends were announced in 1977 by Toray. In this case, to ensure good interaction
between PEST and ABS, the latter resin was modified by incorporation of carboxylic
groups. Thus, PBT was blended with 5-SOphr carboxy-modified ABS - either AB5-
MA or AB5-AA. Good resistance to shrinkage, warping and impact was found
(Tanaka et aI., 1979).
In 1976, an Asahi-Dow patent described polybutyleneterephthalate (PBT) blends
with 30 wt % SAN. Compatibilized blends showed good tensile, flexural and impact
strength behavior (Kasahara et ai., 1977). The same year, Shell Oil Company de-
pOSited a series of patents for blends of hydrogenated poly(styrene-b-butadiene)
copolymers (SEBS) with a variety of resins (including PEST, PC or PA). It was
reported that uncompatibilized 1:1 blends had cocontinuous morphology, good
dimensional stability, and fine mechanical behavior, varying from rubber-like to
flexible. SEBS was also found to stabilize morphology of the PBT I ABS blends
(Gergen and Davison, 1978). In 1978 General Electric announced four-component
PEST ISEBS blends, comprising 39.8 wt % PBT, 30 wt % PET, 15 wt % PC and 15 wt %
SEBS. The blends showed good impact, heat and tensile strength (Wambach and
Dieck, 1980). XenoyTM resins were introduced by General Electric in 1982 for molding
Ford Sierra car bumpers. In 1985 Shell Oil Company applied for several patents
describing blends of engineering resins with hydrogenated styrene-butadiene block
copolymer, that was grafted with maleic anhydride (SEB5-MA). The adduct was
particularly suitable as impact modifier, for PA or PEST (Gelles et ai., 1987, 1994).
In 1977 core-shell butadiene-methylmethacrylate-styrene-divinylbenzene co-
polymers (MBS) were introduced for amelioration of the impact strength and solvent
resistance of PEST. Thus, 25-95wt% PET, was blended with 1-8wt% PC and MBS
(Rohm & Haas Co., 1979); in a Teijin document, PET was blended with 4-94 wt % PC
and MBS (Yamamoto and Shimizu, 1979). The following year, Mitsubishi Rayon
Company announced blends with good processability and high impact strength,
giving materials with excellent and uniform iridescence. These materials were pro-
duced by blending 4-96 wt % PET with 2-94 wt % PMMA and 2-94 wt % PS (Kamata
et ai., 1980). The following year General Electric deposited a series of patents for
multicomponent PEST blends with styrenic impact modifiers; for example PBT was
blended with PET, PC or (SB)n' and either a butadiene-caprolactone-styrene, or a
butadiene-caprolactone block copolymer (Dieck, 1980).
In 1981, PBT/PC blends (comprising 97-3wt% PC), were compounded with
20-300 parts (per 100 parts of PBT IPC blend) of a SAN-grafted EPDM. The alloys
had good moldability, and the moldings showed high mechanical properties and
weldline strength (Sumitomo Naugatuck Co., 1983). In a Bayer patent, PET IPBT
blends were impact modified by addition of ABS (having rubber particles with
diameter::::: 0.4/-Lm (Binsack et ai., 1982). In the following patents from the company,
a further addition (either to these blends or to blends comprising PEST IPCI ABS) of
a graft copolymer of polybutadiene and (meth)acrylate esters, as well as an acrylo-
nitrile-acrylate rubber (ACM) resulted in the production of commercially important
alloys having good balance of properties, namely processability, toughness, hard-
ness, stiffness and HDT (Neuray et ai., 1982; Nouverte et aI., 1982; Serini et ai., 1982).
The same year, an aromatic, amorphous polyester of iso- and terephthalic esters
(PAr) was used in styrenic blends. BASF used 10wt% of PAr to improve process-
ability and mechanical properties of SAN - surprisingly, good weldline strength was
obtained (Brandstetter et ai., 1983b). At the opposite end of the concentration scale, to
improve the moldability of PAr, it was blended with 20wt% PS - the blend was
compatibilized by addition of lOwt% PAr-PS segmented copolymer (Unitika Ltd.,
1983a). In 1983, to improve processability of PAr, Union Carbide blended it with
4Owt% PET and optionally with either PC, ABS or PA (Robeson, 1985).
In 1983, the impact strength of PEST was increased by blending it with either
23wt% of ABS (Bayer) (Binsack et ai., 1985), with styrene-acrylonitrile-grafted
EPDM, at least 25wt% AES (Uniroyal) (Wefer, 1984), or with ABS and MBS (General
Electric) (Michel, 1985). The following year Mitsubishi Petrochemical Industries
announced PBT blends with SEBS, and maleic anhydride. The reactively compatibi-
lized alloys showed good moldability, low temperature impact strength, high HOT
and mechanical properties (Shiraishi and Goto, 1986). In a contemporary patent from
Dainippon Ink & Chemicals, 5D--95 wt % PEST (preferably PBT) was blended with
PB-Iatex grafted with styrene, acrylonitrile and methylacrylate (MABS). The alloys
had good resistance to heat, solvents and impact (Kawashima et al., 1985).
In 1985 several multicomponent blends comprising PEST and styrenics were
disclosed. For example, in Bayer documents the following blends (having improved
HOT) were described: 1-98wt% PET, D--3Owt% ABS, 1-98wt% PC (having
Mw = ID--200kg/mol), and 1-3Owt% PC-PPE block copolymer (Freitag et al.,
1987). Teijin Chemicals described blends containing 5-80wt% PET, IG-90wt% PC
and 0.5-10wt% MBS, to give moldings with good set of properties (Kitamura et al.,
1987). In a Toyobo disclosure, blends of PET, HIPS, styrene-glycidylmethacrylate
copolymer and PPE were described as having good miscibility and high flexural
strength (Hiramatsu et al., 1987). In General Electric documents, blends of copoly-
estercarbonates, PEC, PAr, PPE and styrenics were claimed to show better process-
ability, balance of heat resistance and mechanical properties than the individual
components (Allen, 1987).
As the commercial interest in blends of PPE/styrenics with PEST increased, the
number of patents on these systems grew. In many cases, these blends had other
polymeric additives, such as PC or PA. These systems are discussed in greater details
in the section describing PPE blends.
In 1987 Sumitomo depOSited a series of patents for blends comprising three parts:
(1) PEST, either PET or PBT; (2) a graft copolymer of unsaturated epoxide; and (3) a
rubber-reinforced resin of vinyl, nitrile or acrylic monomers, prepared in the pres-
ence of EPR or EPDM elastomer, such as acrylonitrile-styrene-EPDM-glycidyl
methacrylate graft copolymer (AE$-GMA). The weight ratio of (1) : (2 + 3) was
95:5-5:95, and the weight ratio of (2):(3) was l00:D--5:95. For example, blends were
prepared where the ratio of PBT to AE5-GMA was 95:5-5:95. The alloys were found
suitable for molding electrical or automobile parts, with improved impact strength,
weld strength, stiffness and reduced mold shrinkage factor (Hirai et al., 1988, 1989,
1992, 1994). Two years later, in another series of patents, the company disclosed
blends of 20-40 wt % PBT (with Mv = 18-88 kg/mol), 15-55 wt % ABS (PB content
5-30 wt % and particle diameter 0.05-5 ttm), and an a-methylstyrene-acrylonitrile
copolymer (25-45wt% MeSAN with 15-25wt% AN). The alloys gave moldings
with high impact, chemical and heat resistance, good flexural modulus, and dimen-
sional stability. These are the basic patents for Techniace™ TB, introduced in 1990
(Kodama et al., 1990, 1992).
In 1987, ABS grafted with either maleic anhydride or with glycidyl methacrylate
(AB5-MA or AB5-GMA) was used by AlliedSignal and by Nippon Petrochemicals
Company as reactive compatibilizers/impact modifiers for PEST and their mixtures
with PA (Akkapeddi et al., 1990, 1992; Orikasa et al., 1989). Two years later, Bayer
announced four-component blends of PBT with 1-50wt% PC and/or PEC, and
1-30wt% of an elastomer, prepared by grafting polybutadiene latex having particle
diameter of 0.2-0.6 ttm with at least one (meth)acrylic acid ester and a mixture
comprising ID--35wt% of acrylonitrile and 65-90wt% of styrene onto 6o--90wt%
of a butadiene (Freitag et al., 1994). Another patent from the company described PET
blends with ABS or MABS, barium sulfate and, optionally, glass fibers (Kirsch et al.,
1994). In a contemporary patent Rohm & Haas described new methylmethacrylate-
butylacrylate-styrene copolymer (MBS), having a high molecular weight of
> 1500 kg/mol, as suitable for use as an impact modifier and processing aid (for
blow molding, thermoforming, extrusion or foaming) for a variety of engineering
resins. As an example, blends of PBT with PC and MBS were cited as showing
significant enhancement of properties (Memon, 1992).
Interesting and potentially important linear, diblock copolymers were developed
in 1990 at the University of Akron. These materials comprised polystyrene (or
polyisoprene) and aromatic polyester blocks having number average molecular
weight of 21-30 kg/mol, such as PS-PBT or PS-PET. The first (anionically polymer-
ized) block was that of polystyrene (or polyisoprene), while the second block was an
aromatic polyester (either a polyethylene- or a polybutylene-isophthalate or ter-
ephthalate, or their mixture). These compatibilizing agents were used to make
uniformly dispersed blends of non-polar and polar polymers, characterized by
having stable morphology, low melt viscosity and high crystallinity (Quirk, 1993).
The same year, Shell Oil announced that super-tough compounds can be obtained by
blending an engineering polymer (e.g., PA, PEST, PPE, PPS, PSF, etc.) with B-35 wt %
hydrogenated styrene-butadiene radial polymer having 3-50 arms and modified by
grafting it with a monomer haVing either a carboxylic acid or a carboxylic acid
derivative group, such as 0.5-3wt% maleic anhydride (Gelles et al., 1993).
In 1991 Globe-Union described blends comprising 80--85 wt % of a PET/PP mix-
ture (at PET:PP ratios of 40:60 to 60:40) and 15-20 wt % maleated hydrogenated
styrene-butadiene block copolymer (SEBS-MA). The blends showed improved
impact strength while maintaining tensile strength, elongation and flexural
modulus. Furthermore, recycled PP and PET with a relatively small amount of
SEB5-MA provided blends useful for molding battery containers and other auto-
motive parts (Tekkanat et al., 1994). The same year Arco Chemical Technology
disclosed blends with cocontinuous morphology, consisting of ~wt% PBT and
~wt% of a styrenics, either SMAA (7o-92wt% styrene and B-30wt%
methacrylic acid) or SBR-MMA copolymer (styrene and methacrylic acid polymer-
ized in the presence of polybutadiene). Blends of PBT with either copolymer showed
excellent impact resistance and toughness (Yang and McCready, 1994).
In a contemporary patent from Eastman Kodak, a polyester from terephthalic acid,
ethylene glycol and 1,4-cyclohexanedimethanol (lo-90wt% PCT), was blended with
styrene-methylmethacrylate copolymer (SMM). At a temperature of 275°C and at a
shear rate of 15OOs-1, the blends had a viscosity of 200 Pas, suitable for injection
molding (Blakely and Seymour, 1993). In the following patent from the company, the
usefulness of a new compatibilizer, a styrene-b-vinylphenol block copolymer (PS-
VPh), was demonstrated. Thus, blends of any polymer miscible with the polystyrene
block (e.g., PS, PPE or TMPC), could be efficiently blended with any polymer
miscible with polyvinylphenol block (PVPh); for example, PEST = PBT, PET,
PETG, PCTG or PEN (Colby et al., 1993, 1994).
1992 was the year of new compatibilizers/impact modifiers, designed for reactive
blending of either PA, PC or PEST. Several examples are given below; others are
given in sections dealing with PA and PC blends.
General Electric announced that synergistic impact improvement was found in
blends of PC, PEST (and/or a polyester-earbonate) after incorporating 1O-20wt% of
an impact-modifying mixture of ABS with an acidified copolymer (ethylene, glycidyl
methacrylate or maleic anhydride, and (optionally) vinyl acetate, vinyl alcohol,
styrene, acrylOnitrile, (meth)acrylate(s». The alloys showed good impact strength
and had a ductile-brittle transition temperature less sensitive to the molding condi-
tions (Steendam et al., 1993).
Similarly, a contemporary patent from Rohm and Haas describes a core-shell
compatibilizer/impact modifier that comprised 4O-65wt% of core polymer
(40-60wt% vinyl aromatic, 4O-6Owt% 1,3-diene(s), not more than lOwt% of co-
polymerizable vinyl(idene) monomer(s), and not more than 5wt% of graft-linking
or cross-linking monomer(s), e.g., emulsion polymerized styrene-butadiene-divinyl-
benzene) and 35-60wt% of shell polymer (2-40wt% hydroxyalkyl (meth)acry-
late(s), 6O--98wt% vinyl aromatics, and not more than 25wt% of vinyl(idene)
monomer(s), hydroxyethylmethacrylate with methylmethacrylate, styrene, ethyl-
methacrylate, etc., MBs-DH. The copolymers were found particularly useful for
manufacturing tough, ductile and high strength polyester blends, namely, PET,
PETG, PEN or PBT. Furthermore, since by adjusting the composition of the impact
modifier its refractive index could be made to match that of PEST, the blending made
it possible to ensure alloys' transparency along with good impact properties and
other mechanical performance parameters (Carson et al., 1994).
Also in 1992, DSM introduced a copolymer of styrene, maleic anhydride and/or
imide, and 4wt% spirodilactone (SDL). Blends of PEST (and/or PA) with SDL and
optionally ABS were easy to mold into products with improved impact strength,
heat resistance and high HDT, for use as automotive parts under the hood (Fairley et
al., 1993, 1994; Reid et al., 1993, 1994).
The same year, Bayer announced novel AB5-type copolymers, developed for
blending with either PEST, PC and/or thermoplastic polyurethane (TPU). The new
ABS comprised 20-70 wt % of a copolymer from styrene, o-methylstyrene, methyl-
methacrylate and/or acrylonitrile (having Mw = 75-120kg/mol), 4-20wt% of a
copolymer of styrene (and/or o-methylstyrene) with acrylonitrile (having
M w = 30-55 kg/mol), 0.5-5 wt % of a copolymer made from same monomers, but
having M w = 2-{ikg/mol, and 1-40wt% grafted elastomer core particles of diameter
0.IG-O.45JLm and a glass transition temperature of ~ 10 0 e. Blending 2.5-15wt%
of the new ABS with either PC or PET gave materials useful for molding high-
surface-area parts, requiring long fl'lw paths, while retaining high toughness, HDT
and gloss (Eichenauer et al., 1993, 1994).
Also in 1992 Shell Oil disclosed new star-block copolymers with anionically poly-
merized arms made of polystyrene, polydimethylsiloxane and polydiene. These
were found useful for impact modification of engineering resins (e.g., PEST, PC
and ~PE) and for coatings (Hoxmeier, 1994). The same year the company announced
new compatibilizer/impact modifier, a modified, hydrogenated star-block copoly-
mer, (SI)nX where S is a polystyrene, I is an isoprene block, n ~ 10 and X a block of
divinyl benzene comprising 1.5-5 wt % glycidyl acrylate. As an example, blends of
6O--90wt% PBT (Mn = 25-50 kg/mol), with ID-40wt% (SI)nX (arms with
Mn = 35 kg/mol) were found to show significantly improved low temperature
impact strength, with ductile failure at -20°C (Modic, 1994).
In 1993 Kuraray Company patented blends comprising 35-98wt% PEST (prefer-
ably PBT, PET or PEN), with a partially hydrogenated diblock or triblock copolymer
of styrene with either isoprene or isobutylene, with an -DH group attached to the
styrenic block(s), having a number average molecular weight of Mn = 14-150 kg/ mol.
The alloys showed excellent processability, as well as heat, solvent and shock
resistance (Kinoshita et al., 1995).
17.1.5 PET/SMA Blends

Blends of PET with SMA are commercially available as ArloyTM 2000 from ARca
Chemical. These materials are transparent and are approved for food contact
applications. They are formulated for injection molding, but can also be extruded,
thermo- or vacuum formed. They find use in production of cookware, food proces-
sors, microwaveable containers, dishware, food containers, hair curlers, covers, etc.
In 1977 Sumitomo Chemical introduced reactive impact modification of PEST by
incorporation of polybutadiene grafted with styrene and maleic anhydride (PB-
SMA). For example, 15-85wt% PAr, was blended with 85-15wt% PB-SMA. The
blends had excellent heat deflection temperature and impact strength (Ueno and
Maruyama, 1979).
Three years later, Ethyl Corporation issued several patent applications for PET/
SMA blends. For example, PET compounded with rubber-modified SMA at a ratio of
1:1, resulted in alloys having high HDT and impact strength. Similarly, for high
HDT, PET was blended with either 1o-90wt% SMA, or with styrene-acrylic (or
methacrylic) acid (SAA) and optionally with an ionomer or elastomer. Good HDT
and mechanical properties were also reported for blends comprising PET with
rubber-modified maleimide-styrene. For example, blending increased the heat
deflection temperature by 27°C (Hornbaker and Jones, 1981, 1982, 1983).
In a contemporary Celanese disclosure, PET was blended with lOwt% SMA. The
alloy showed low temperature moldability, good mechanical and adhesive prop-
erties (Froix et al., 1981). Also in 1980, blends of PBT with 75wt% SMA were
developed for improved processability, high HDT and low shrinkage Oapan
Synthetic Rubber Co., 1982). The following year, in a Shell patent, PBT was blended
with 57wt% SEBS, 19wt% SMA and 5wt% extending oil for good set of properties
required in automotive applications (Durbin et al., 1983).
17.1.6 PEST/acrylics blends

As for PS/PEST blends, systems comprising PEST and the main acrylic resin, poly-
methylmethacrylate (PMMA), are of no commercial interest. The reasons are similar
- immiscibility and brittleness of both resins, augmented by the lack of interfacial
adhesion between the phases in the solid state. By contrast, as evidenced by the
examples cited in the preceding parts, acrylic copolymers constitute an important
class of compatibilizing and impact-modifying components in numerous PEST
blends. Only few additional examples will be given below.
The first incorporation of acrylic copolymer into polyethylene terephthalate (PET)
dates from 1965, when ICI disclosed that blends of this resin with lOwt% of an
ethylene-methylmethacrylate copolymer (EMM) resulted in materials particularly
useful for molding and fiber spinning (Dijkstra and Jones, 1969). Two years later, the
company deposited a patent describing PET blends with either EVAc, EMM or
ethylene-hydroxyethylmethacrylate. Blending resulted in crystalline materials, use-
ful for molding thick-walled articles having good impact strength Oones et al., 1971).
In 1967 PEST/acrylics blends were disclosed by several other companies, including
Hoechst and Dainippon. The following year Union Carbide announced the first
blends of PET with rubber-modified poly(meth)acrylates (5-95 wt % ABSM; Sauers
and Barth, 1970).
In a 1973 patent application from Mitsubishi Rayon, polybutyleneterephthalate
(PBT) was blended with not more than 50 wt % of a methylmethacrylate-methyl-
acrylate copolymer (MMMA). The alloys showed good moldability, bending
strength and pearl-like luster (Kamata et al., 1974). Five years later, 4-96wt% PET
was blended with 2-94 wt % PMMA and 2-94 wt % PS, to give materials with good
processability, excellent uniform iridescence and good impact behavior (Kamata
et al., 1980).
In 1976 Rohrn & Haas disclosed that to improve impact strength of PBT it was
blended with a core-shell modifier, having 25-95 wt % elastomeric blocks (core), and
5-75wt% hard blocks (shell). Thus, 9Owt% PBT was blended with butylacrylate-
butylenediacrylate-allylacrylate-methylmethacrylate copolymer, to give high impact
strength alloys (Farnham and Goldman, 1977, 1978).
In 1977 GAF patented PBT blends with PMMA, l,4-butanediolterephthalate-poly-
butyleneglycol copolymer (PBT-PBG) and fillers. Good resistance to shrinkage,
warping and impact was reported (Charles and Gasman, 1979). The same
year, Mitsubishi Rayon patented blends of PET with PBT, impact modified by
addition of butylacrylate-methylmethacrylate-styrene-triallylisocyanurate or acrylo-
nitrile-allylmethacrylate-butylacrylate-ethylacrylate-methylmethacrylate copolymer
(Kamata et ai., 1978a). In a contemporary Rohrn & Haas patent, PET and PC,
were compatibilized and toughened by incorporating a core-shell butadiene-
methylmethacrylate-styrene-divinylbenzene copolymer (MBS). In Teijin patents,
for good impact strength, PET was blended with 4-94wt% PC and MBS (yamamoto
and Shimizu, 1979).
In 1978 Mitsubishi Rayon blended 4-96 wt % PET with 2-94 wt % PMMA and 2-
94wt% PS, to obtain materials with good processability, excellent uniform irides-
cence, and high impact strength (Kamata et ai., 1980). The same year du Pont de
Nemours patented PET/PBT blends compatibilized by addition of acrylic copoly-
mers. For example, 81.5 wt % PET was blended with 18 wt % of a copolymer of
ethylene-butylacrylate-glycidylmethacrylate (with a component ratio of 63.6:28:8.4).
The alloys showed good toughness, both at room and low temperatures (Deyrup,
1979, 1982).
The following year several blends of PEST/acrylics were disclosed. For example,
Toray Industries reactively blended PET with ethylene-glycidylmethacrylate co-
polymer (10 phr EGMA) to give blends with good moldability, toughness, resistance
to moisture and heat (!ida et ai., 1980). (The company patented blends of PBT with
EGMA one year later; two years later PBT/EGMA/EPR blends were also disclosed).
Rohrn & Haas used 15 wt % of a core-shell butylacrylate-butylenediacrylate-
diallylmaleate-methylmethacrylate copolymer to compatibilize and toughen PET/
PC blends (Fromuth and Shell, 1981). General Electric blended PET and/or PBT with
a commercial acrylic impact modifier, AcryioiJIM KM330 (Dieck, 1980). Acryioid was
also used in Union Carbide's blends of PAr with PET (Robeson, 1980, 1981). GAF
disclosed blends of PET and/or PBT with a polyhydroxy ether of bisphenol-A,
Phenoxy, and a copolymer of butylacrylate-glycidylmethacrylate-methylmethacryl-
ate (Charles and Coleman, 1981).
In 1981 a new multilayer acrylic impact modifier, comprising methylmethacrylate-
methylacrylate-butylacrylate-allylmethacrylate (MMBA-AM) was developed for
PEST. For example, 6O-90wt% PBT was blended with MMBA-AM to obtain mater-
ials with good processability and high impact resistance (Mitsubishi Chemical
Industries Co., 1982d).
In a 1982 patent disclosure from General Electric, 51-96wt% PC was blended with
3-49wt% PET and 3--20wt% AcryioiJIM KM. The alloys had good processability,
high notched impact strength and weatherability (Allen et ai., 1984). Similar
compositions were described in applications from: (1) Idemitsu Petrochemicals
(2Q-94.6wt% PC, 5-50wt% PET, 0.2-15wt% PE and 0.2-15wt% Acryioid) (Endo
and Ishii, 1984); (2) Teijin Chemicals (1983c) (2Q-90wt% PC, 5-70wt% PET, 1-
15wt% BR, 1-20wt% of acrylic elastomer HIA-15 and D-15wt% PMP); or (3) from
Mitsubishi Chemical Industries (1983b) (5Q-95wt% PC, 1-40wt% PET and more
than 1wt% of a metallocene-made linear low density polyalkene with 1% acidic
groups, Tafmer™ A 20090). In a contemporary disclosure, either PBT or PET was
blended with acrylic impact modifier, for example with methylmethacrylate graft
copolymer Kaneace™ FM, and a halogenated epoxy resin. The resulting blends had
good processability, high impact strength and flame retardance (Dainippon Ink and
Chemicals Inc., 1984).
In a 1985 disclosure from General Electric, PC was blended with 14wt% PET,
6wt% of an acrylic elastomer AkryIoid™ KM660, lOwt% Phenoxy, and optionally an
acrylate-alkene elastomer. In these alloys Phenoxy provided enhanced compatibiliza-
tion between the three other ingredients. The materials showed excellent impact
strength, ductility and solvent resistance (Liu and Giles, 1986).
In 1988 Rohm & Haas Company developed high-molecular-weight acrylic co-
polymers able to improve melt flow and increase the sag time, thus facilitating
blow molding, thermoforming and extrusion of engineering resins (namely PC,
PBT, PET, PEC, PAr, PAI, PA, PPE+PS, PSF, PEl, POM, PI, SAN or SMA), and/or
their blends (e.g., PBT with PC and MBS). The copolymer with weight average
molecular weight above 500kg/mol (Mw > 1500kgjmol was cited in the follow-
ing disclosure), comprised methylmethacrylate-ethylacrylate-butylmethacrylate
(MMMA-BM) (Memon, 1992, 1994). The same year, Eastman Kodak developed
blends comprising 2D-50wt% poly(cyclohexanedimethylterephthalate) (PCT),
2D-45wt% PET, ID-50wt% PC, and 8-20wt% of MBA and/or EPR. The alloys had
high impact resistance (Romance, 1990).
In 1989 Mitsubishi Rayon developed blends with excellent moldability and ther-
mal resistance. These comprised 5-95 wt % of a polymethacrylimide (PM!; prepared
by condensation of PMMA with methylamine), 5-95wt% of either PEST (e.g., PET,
PBT or PEN) or PA (e.g., PA-6, PA-66 or PA-12), and 0.1-3phr of at least one
multifunctional compound selected from a multifunctional epoxy, oxazoline and
isocyanate (Yamamoto, N. et al., 1994b).
The following year Rohm Chemische Fabrik disclosed miscible blends comprising
0.1-99.9wt% of either PBT or PET, 99.9--0.1 wt% of a poly(p-methoxyphenylmetha-
crylate), and 0.1-10wt% of UV-protective agent. Compared to immiscible blends,
these compositions had better adhesion between layers and perfect recyclability
at any composition (Siol et al., 1993a, 1994b). The following patents described
blends that comprised: (1) 0.1-99.9wt% of a mixture made of 0.1-99.9wt% of
PBT and 99.9--0.1 wt% PC; and (2) 99.9--0.1 wt% of a core-shell copolymer made of
99-SO wt % of MMBA-AM and I-SO wt % of units with UV-absorbing groups, such as
phenyl methacrylate or 2-ethylhexylthioglycolate. The blends were used as molding
compounds for injection molding of parts for housings or bumpers (Fischer and Siol,
1993b, 1994).
In a 1991 patent from BASF, thermoplastic molding compositions based on PEST/
PMMA were disclosed. For example, 3D-94wt% PBT (or PET) was blended with
either PMMA or an acrylic core-shell copolymer. The resulting alloys could be
reinforced by the addition of 3-40 wt % glass fiber (GF). The formulations showed
good mechanical and surface properties (Bright et al., 1993). The same year, Nippon
Petrochemicals announced PBT blends with high impact strength, that did not
deteriorate after annealing. These comprised 50-99 wt % PBT, 1-50 wt % ethylene-
ethylacrylate-glycidylmethacrylate copolymer (EEA-GMA) and O.I-15wt% (on the
total mass of PBT with EEA-GMA) of a low-molecular-weight copolymer of ethy-
lene-ethylacrylate-acrylic acid (EEA-AA) (Hayasaka et al., 1992).
In 1992 Therma-Plate Corporation announced a process for the production of
impact-resistant polyester compositions, having reduced shrinkage and low gas
permeability. Thus, PEST (PET or PBT) and 1-30wt% impact modifier (having a
Tg of -150 to -20°C, e.g., ethylene butyl methacrylate) were heated to above
the melting point of PEST, keeping the blend at that temperature for 1-5 min until
the impact modifier was dissolved, then cooling the melt at 20-80 °C/min until the
impact modifier precipitated to form particles with a diameter of about 0.1-2JLm. To
the blend a nucleating agent, fillers and/or o-29wt% of a compatibilizing resin
(selected from PC, POM, PEEK, PAN, PAl, PAr, PEl, PA, PPE, PPS, PI, PSF, PAES,
TPU, EP or PEST) could also be added (Dalgewicz et al., 1993).
The same year General Electric Company disclosed impact- and UV-resistant
blends of poly(cyclohexanedimethyleneterephthalate) (PCT), prepared by mixing it
with polyestercarbonate (PEC) and/or another polyester (PEST), an elastomer
grafted with butyl acrylate, 1,3-butylene diacrylate, diallyl maleate and a methyl
methacrylate impact modifier (Liu, N., 1993).
Also in 1992 Rohm & Haas developed a new core-shell polymer that comprised
methyl methacrylate, butyl acrylate, diallyl maleate and trimethylol propane
triacrylate (MMBA-TPT). The copolymer was used to prepare impact-resistant, fast
crystallizing PEST blends. For example, 85-90 wt % PET was blended with 5-10 wt %
of a MMBA-TPT, not more than 5wt% of a nucleating agent (talc), not more than
5wt% of a thermal and/or oxidative stabilizer, 1-8wt% PC and 1-5wt% of a mold
release agent (copolymer of ethylene with vinyl or vinylidene ester). The blends
were used to manufacture computer and business machine housings, automotive
parts, food trays and containers, etc. (Lai and Brady, 1994).
17.1.7 PEST/vinyl blends

Blends of thermoplastic polyesters, PEST, with ethylene-vinylacetate (EVAc) and
other similar copolymers have been discussed. This section reviews PEST blends
with polyvinylchloride (PVC). These blends are infrequent because incorporation of
an engineering polyester into PVC may, in principle, enhance its stiffness without
increasing the density, but at high cost. (Incorporation of low-molecular-weight PET,
obtained by partial glycolysis of recycled soft drink bottles, into PVC was reported to
result in good plasticization and excellent performance, but commercialization was
difficult to justify on the economic basis.) However, incorporation of PVC into PEST
may result in improvement of the flame resistance, but at a danger of thermal
degradation of the former resin. Since the thermal degradation of PVC is rapid at
temperatures above 180 °C, it is important to keep the compounding temperature
low. In consequence, PVC has been blended mainly with aliphatic-aromatic polye-
sters.
Since necessity is the mother of invention, in the early days of the polymer technol-
ogy several attempts were made to blend PVC with PEST. For example, in 1969 Rohm
& Haas disclosed blends comprising PVC with 5-25 wt % of a polypropyleneter-
ephthalate (PPT). Addition of this relatively small amount of thermoplastic polyester
improved processability, thermal, irradiation and impact resistance over that of neat
PVC (Hurwitz and DeWitt, 1970). In 1971 du Pont de Nemours disclosed blends of
PET with PVc. The blends were prepared by first reacting PET with polybutylene-
glycol, PBG, and 1,4-butanediol, then incorporating PVc. The homogenous blends
had good low temperature impact strength (Crawford and Witsiepe, 1972).
Air Products and Chemicals' patent document of 1978, described PVC blends with
polyethylene carbonate (40wt% PECO). The alloys showed increased melt flow and
reduced oxygen permeability (Dixon and Ford, 1979). In 1985 B. F. Goodrich de-
veloped blends comprising PVC with 4Owt% of a semicrystalline polyester (pre-
pared from butanediol, dimethyl terephthalate and butylene adipate), and 3Owt%
PEST blends with engineering resins 361
glass fibers. The materials were suitable for injection or compression molding (yang,
1987).
In 1991, Labinal deposited a patent for blending plasticized PVC in a co-rotating
twin-screw extruder with an aliphatic polyester-aromatic polyester block copolymer,
Pelprene™. The blends with a physically crosslinked structure, and a service tem-
perature of 125 °C, were used to manufacture heat-resistant insulation for electric
cables Gean and Devauchelle, 1993).
More recently, miscible blends of PET with polyvinylphenol (PVPh) were
announced in 1991 by Eastman Kodak. Thus, PET (as Tenite™, Kodar™, Kodapak™,
Ektar PCTC™, or Ektar HPETC™), was blended in ratios ranging from 1:99 to 99:1
with PVPh. The miscible blends could be extruded into chemically resistant mater-
ials for clear packaging films (Massa et ai., 1993).
17.2 PEST BLENDS WITH ENGINEERING RESINS
17.2.1 PET blends with other PEST resins

Commercial PET fPBT blends are available, namely C and CN from Teijin, Ceianex™
from Hoechst Celanese, EMC™ from Toyobo and Vaiox™ from General Electric.
These alloys have good surface properties, high HOT, good impact strength and
dimensional stability, as well as good economy. The resins have different processing
temperatures (the melting points of PET and PBT are 255 and 223°C, respectively),
chain flexibility and resulting crystallizability. In spite of these differences these
blends are stable without compatibilization, relying on transesterification. Good
performance of PET fPBT blends has been attributed to crystallizability of the two
components, as well as to miscibility between the amorphous portions of these resins
(Escala and Stein, 1979; Mondragon et ai., 1989).
The first blends of PET with polybutyleneterephthalate (PBT) were disclosed in
1960 by Siemens and Halske (Heywang, 1966). The first impact-modified PET fPBT
blends were announced in 1968 by Toray Industries. As this document describes,
PET was blended with PBT and butyl rubber, 0.5-50 phr BR, to engender materials
with good mechanical and high impact strength (Hiri and Kotama, 1971).
In a 1971 application from Teijin, PBT was blended with either PET or polyhex-
eneterephthalate (PHT) for improved elongation and impact strength (Tsunawaki et
ai., 1973). The same year General Electric announced blends comprising PET fPBT,
blended at a 1:1 ratio. The materials were reported to show good crystalline pro-
perties without the need to control the molecular weights or to use nucleating agents
(Fox and Wambach, 1973). Three years later, Toray Industries developed blends of
PET with a copolyether-ester prepared from butanediol, dimethyl terephthalate and
polytetramethylene glycol. The alloy showed good impact and tensile properties
(Tanaka et ai., 1976).
Impact-modified PET/PBT blends were introduced in 1977 by Mitsubishi Rayon.
Thus, PET was compounded with PBT and butylacrylate-methylmethacrylate-sty-
rene-triallylisocyanurate or acrylonitrile-allylmethacrylate-butylacrylate-ethylacry-
late-methylmethacrylate. The blend was reinforced with glass fibers. The resulting
compositions showed good moldability and an excellent set of physical properties
(Kamata et ai., 1978a). One year later, Teijin patented PET blends with 5-100phr
polyhexamethylene terephthalate (PHT) and inorganic fillers. The materials were
also reported to have good moldability and high impact strength (Emi et al., 1979).
In a patent document deposited in 1978, blends of PET with poly(bis(4-methoxy
phenyl)terephthalate) and, for good processability, 2 phr liquid crystal polyester
(LCP) were described. The biaxially stretched alloys showed excellent mechanical
properties (Toray Industries Inc., 198Oa). In a contemporary deposition from Teijin,
for good impact strength, PET was blended with ~100 phr PHT and inorganic fillers
(Emi et al., 1979). The same year Sumitomo Chemical developed blends of PAr with
20 wt % of either PET or PBT. These alloys produced extrudates with improved
transparency, high HDT and impact strength (Fukushima et al., 1979a).
Also in 1978, a patent deposition from General Electric described blends compris-
ing 39.8wt% PBT with 3Owt% PET, 15wt% PC and 15wt% SEBS. The blends
showed good impact, heat and tensile strength (Wambach and Dieck, 1980). The
following year, blends of PET/PBT with the polyacrylate AcryIoid™ KM330 were
described (Motz, 1980). These alloys showed good moldability and high impact
strength. In another patent, PBT blends with butylene terephthalate copolyester,
aromatic/aliphatic ester (PC) and an impact modifier (conjugated diene grafted
with methacrylate) were described. The alloy had high impact strength and high
strain at break (Dieck, 1980). In a later disclosure, PBT was blended with PET, Ah03
and PC (Goedde et al., 1980).
In a contemporary document from GAF Corporation, PBT and/or PET was
blended with polyester-polyether rubber, bisphenol-A-glycidyl ether polymer Phe-
noxy, and a copolymer of butylacrylate-glycidylrnethacrylate-methylrnethacrylate.
The blends showed high impact strength (Charles and Coleman, 1981).
In 1980 blends of 20-75wt% PET, with liquid crystal polyester (~wt% LCP)
were described. The blends showed good processability and mechanical properties,
an HDT of 167°C and economy (Celanese Corp., 1981, 1984; Kiss, 1986). The follow-
ing year, PET was reactively blended with 2~50wt% (and later 8~95wt%), of an
aromatic copolyester from hydroxy benzoic acid with hydroxy naphthoic acid (LCP).
Good tensile and impact strength was claimed (Cincotta and Berardinelli, 1983,
1984).
Also in 1981, Standard Oil disclosed PAr blends with polymethylene benzoate
(50-90 wt % PMB). The alloys showed good miscibility, weatherability and process-
ability (Schwartz et al., 1984). The same year it was reported that electrical insulators
made from PET/PBT blends have better arc resistance then those from PBT alone
(Celanese Corp., 1983).
Several patent applications on toughening PET/PBT blends were issued by Bayer
in 1981. Thus, the polyalkyleneterephthalate mixtures were to be compounded with
grafted or homo-polymers for improved toughness, hardness, stiffness and HDT.
For example, PET/PBT was blended with either a graft copolymer of polybutadiene
and (meth)acrylate esters and possibly acrylonitrile, acrylate rubber based on ethyl-
acrylate with other acrylics (ACM) or ABS. The documents extended the protection
to other mixtures of thennoplastic polyesters, namely PBTfPC blends, blends of
different polycarbonates, as well as to single components. In particular, blends of
PET/PBT and PBTfPC with ACM and/or ABS, were found commercially interest-
ing. It was reported that for high impact strength and good balance of mechanical
properties the rubber particles should have an average diameter of :::::: 0.4 J-Lm (Bier
and Indner, 1982; Neuray et al., 1982; Nouverte et al., 1982; Serini et al., 1982; Binsack
et al., 1982).
In 1982 blends of PBT with the aliphatic polyester polycaprolactone (PCL) were
disclosed. Thus PBT was blended with PCL and an ethylene-diglycidyl-tetrahy-
drophthalate copolymer. The materials had excellent mechanical properties, and
were easy to metal-plate (Toray Industries Inc., 1984b). Another document described
PBT blends with PCL having chains terminated with either acetic anhydride or
pentabromobenzoic acid. The filled alloys had good moldability, impact strength,
elongation and flame resistance (Teijin Ltd., 1984). The same year, Goodyear Tire &
Rubber Company developed blends comprising either PET or PBT, and polyethylene
isophthalate. The alloys had good oxygen barrier properties (Smith and Wilson,
1984).
Also in 1982, Rohm & Haas disclosed blends comprising 70wt% PET, 14.1 wt%
PBT and methylmethacrylate-grafted polybutylacrylate. The alloys containing glass
fibers and talc had good mechanical properties, as well as improved crystallization
rate and surface appearance (Memon and Myers, 1983). Similar blends of PET with
PBT were developed for electrical insulators (Celanese Corp., 1983). Blending PET
with 0.5-100phr of poly(methylnorbornenecarboxylate) was reported to signifi-
cantly improve its moldability (Mitsubishi Petrochemical Co., 1984a).
In a Toray Industries patent application of 1985, 20wt% ethylene-glycidylmeth-
acrylate copolymer was added to 3:1 PET:PBT. After 7 days in gasoline, the blend
showed excellent elongation and impact strength (Yonetani et al., 1987).
In 1988 Eastman Kodak Company disclosed blends comprising 2D-45wt%
PET, 2D-50wt% poly(cyclohexanedimethylterephthalate) (PCT), 1D-50wt% PC,
and 8-20wt% of either EPR and/or acrylic core-shell copolymer, MBA. The alloys
had high impact resistance (Romance, 1990).
In 1991, GE Plastics Japan deposited an application for PBT compositions with
good moldability and improved resistance to repeated bending fatigue. The claimed
materials comprised 6O-99wt% PBT (having 40 < Mn < 60 (kg/mol» blended with
1-40wt% PBT (having Mn between 21 and 27kg/mol). These homologous blends
were found to be suitable for molding bodies with hinges (Yokoshima, 1993). A
contemporary patent from General Electric disclosed poly(1,4-butylene-1,4-
cyclohexanedicarboxylate) (75-99wt% PBCD) blends with polyetherester, poly-
etherimide ester or a block copolymer elastomer. The alloys had excellent tensile
properties (Borman and Liu, 1993).
In 1992 General Electric disclosed new blends comprising polyester (derived from
cyclohexanedimethanol and a dicarboxylic acid), 2D-90wt% PCT, 2D-70wt% of an
aromatic copolyester carbonate, and 1D-20wt% of an impact modifier. The blend
could also contain glass fibers. The materials showed improved impact strength and
UV resistance (Liu, N., 1993).
The same year, Toyo Seikan Kaisha developed blends for production of films,
containers and fibers. The alloys comprised PET/PBT in ratios varying from 99.9:0.1
to 91:9. The stretch-molded parts showed low initial residual stresses, excellent
shape, appearance, heat resistance, transparency, mechanical strength and dimen-
sional stability (Hamada and Maruhashi, 1994).
Also in 1992, ICI disclosed an interesting modification of PET molecular structure
that resulted in improved processability, especially the blow molding characteristics
of the resin. First, PET was modified by incorporation of (1) 0.5-5 mol % of isophtha-
lic acid (to disrupt the chain orientation), and (2) 0.OO7-D.045mol % of a chain
branching agent (e.g., trimethylol propane, dulcitol, adonitol, and/or meso- or
penta-erythrimethylol). Next, the modified PET was blended with standard PET to
give materials useful for manufacturing high-quality mineral water bottles. To
decrease the reheating time of the polymer, the alloys also contained Sn particles
that absorb radiation at 5OD-2000nm (Greaves et a!., 1993).
In 1994 Eastman Chemical Company announced blends containing 88-99wt% of
PET, and 1-12wt% of PCT (that contained more than 30 mol % 1,4-cyclohexanedi-
methanol). The blends could be used to thermoform such articles as frozen food
trays, that exhibited high impact strength at low temperature (Stewart and Bell,
1995).
17.2.2 PESTIPAr blends

Polyarylates or polyarylphthalates (PAr) with the structure -[....(Hp--C(CH3 h+
CO2+Co-l n are linear polyesters, usually produced by polycondensation of iso-
phthalic and terephthalic acids with bisphenol-A. Depending on the ratio of these
two acids, PArs are either amorphous or semicrystalline. The resins were first
commercialized in 1974 by Unitika as U-poiymer™, then in 1978 as Ardel™ 0-100
by Union Carbide, a year later as Ourei™ by Hooker Chemical Company, and in
1986 as Aryion™ NeW by du Pont de Nemours. Their glass transition temperature is
~ 188 °C and, depending on the molecular structure, their heat deflection tempera-
ture varies between 120 and 175°C.
The PAr/PET blends prepared in solution blending are immiscible, having two
glass transition temperatures, and slightly positive binary thermodynamic interac-
tion parameter (Chung and Akkapeddi, 1993). Commercial PET/PAr blends are
available from Amoco Corporation (Ardei™ 0-240) or from Unitika. These blends
are known for excellent processability, high HOT, toughness and high impact
strength. Owing to the presence of polar groups, ester exchange and possibility of
graft-modifications, PESTs are relatively easy to blend with PAr.
First PAr blends with either 5-90wt% PC, or with up to SOwt% PET were
disclosed in 1971 by Unitika. The materials showed good moldability and impact
strength (Koshimo et ai., 1973). In 1976, the company deposited several patents on
blends with PAr. For example, the resin was blended with 40 wt % of either PET, or
polyethylene-p-oxybenzoate, to give transparent, impact-resistant resins. Further
property enhancement was observed when the PAr/PET blends were combined
(at a 1:1 ratio) with PA-6 (Asahara et ai., 1977). In a contemporary application from
the company, blends of PET with PAr and PPS were also described. The alloys
showed further enhancement of properties (Kyo et ai., 1978).
In 1978 Sumitomo Chemical developed highly transparent blends comprising
PAr with 20wt% of either PET or PBT. The extruded alloys were reported to
have high heat deflection temperature and good impact strength (Fukushima et ai.,
1979).
In 1979 and 1980 Union Carbide Corporation deposited a series of patents for
PAr/PEST. For example, to improve processability, weatherability and impact resist-
ance, PAr was blended with 40 wt % of cyclohexanedimethylene terephthalate (PCT)
(Robeson, 1981). To improved modulus, while retaining strength and elongation,
blends of PET/PAr (mixed at a ratio of 2:3) were compounded with 80 wt % TPU
(Robeson et ai., 1981). In following patents, impact-resistant molding compositions,
with high HOT and impact strength, were disclosed. The alloys comprised PAr, PET
and 10wt% of the acrylic impact modifier Akryioi~ KM611. Blends of PAr, PET
and a polymer selected from TPU, PVC, polyarylether, polyesterether and Phenoxy,
were also described (Robeson, 1981). In a later patent PAr was blended with PET, a
copolymer of bisphenol-A and isophthaloyl chloride. The resulting alloy was found
to be particularly suitable for injection molding and the molded parts had a good
balance of mechanical properties and stress crack resistance (Robeson, 1982a).
In a 1980 patent, PAr blends with PET at a 4:1 ratio were compatibilized with
ethylene-ethylacrylate (1 wt % EEA). A good balance of hydrolytic stability and
mechanical properties was claimed (Robeson and Skoler, 1981). In a contemporary
patent, PAr was also blended with another PAr (but containing higher isophthaloic
acid content), and with 30 wt % PET. The alloys showed excellent balance of mechan-
ical properties and chemical resistance (Union Carbide Corp., 1983). In a 1983 patent
application from Union Carbide, PAr was blended with PEST, for example with
4Owt% PET and, optionally, PC, ABS or PA. The blending resulted in stable, highly
processable blends having a good set of properties (Robeson, 1985).
In 1982 Daicel Chemical announced that high impact strength polyester blends can
be obtained by blending 5-99wt% PBT with PAr (Toga and Okamoto, 1983). Simi-
larly, PET blends with high HDT and good transparency were obtained by reactively
blending the resin with 2-50% PAr. However, incorporation of 50wt% PA-6 and
2.5 wt % PET into PAr was reported to give moldings with excellent processability,
gloss, chemical, mechanical, electrical properties and HDT (Unitika Ltd., 1983b).
Three years later, the company developed high impact strength and high heat
deflection temperature PAr/PEST blends, having excellent performance character-
istics within a wide range of compositions. The reactive compatibilization and
toughening were conducted in two steps. First, PAr was blended with PEST in a
ratios of 1:99 to 99:1, then this blend was toughened by compounding with ethylene-
glycidylmethacrylate copolymer (1-5Owt% of EGMA) (Toyoda et al., 1986).
Blends comprising 10-90 parts of PAr, 90-10 parts of PEST (PET or PBT) and a
glycidyl oxybenzyl acrylamide-grafted elastomer (EPR or EPDM), were disclosed in
1991 by Kanegafuchi Kagaku Kogyo. The materials combined good processability
and impact strength (Suzuki et al., 1992).
17.2.3 PESTIPA blends

Blends of polyamides with thermoplastic polyesters (PA/PEST) are extensively
discussed in Section 16.3.5. In the following text a short summary of evolution of
these systems will be made.
Both PA and PEST are semicrystalline, brittle resins. Since their antagonistically
immiscible blends show large interfacial tension coefficient the dispersion is poor,
and the mechanical behavior shows brittle fracture, and atrocious impact strength
(Kamal et al., 1982). One could expect that, during the compounding and processing
steps, a degree of ester-amide exchange reaction could take place, improving the
interactions between the two phases. A review of the patent literature indicates that
the PA-PEST reaction is indeed feasible, but at 220-290°C in a continuously stirred
autoclave it required 5-30 h. However, since the reaction conducted during reactive
processing is more rapid than the one conducted in an autoclave, it was tempting to
co-react PA-6 with PET in a twin-screw extruder. Indeed, it was found that in the
presence of p-toluenosulfonic acid as catalyst, two minutes residence time in the
extruder was sufficient for the ester-amide exchange reaction to take place (Pillon
and Utracki, 1984). Furthermore, the extent of reaction could be controlled, provid-
ing alloys with good adhesion of the dispersed phase to the matrix. However, the
blends showed a brittle behavior (Pillon and Utracki, 1986). Thus, it is important that
any strategy of blending PA with PEST includes not only compatibilization, but also
toughening.
A Toray patent application of 1968, described PA-6 or PA-66 blends with PET and
POM as having good frictional resistance (Fujiwara, 1971). A year later, Allied
Chemical developed blends of PET with 70 wt % PA-6, compatibilized by addition
of a, a-dimethylol-propionic acid - the alloys showed good improvement of impact
and tear resistance (Reirnschussel and Dege, 1969). Dling's patent, deposited in 1969,
disclosed blends comprising 20 wt % PA-6-co-diisocyanate copolymer and PET. The
alloys had high impact strength (Dling, 1970).
In an Asahi Chemical application of 1980, it was reported that to enhance the
crystallization rate of polyesters they should be blended with 0.05-10wt% of either
polyamides (PA) or polyhydrazine. The rapid crystallization during molding
resulted in good mechanical properties of the products (Nakamura and Neki, 1981).
Similarly, in the patent deposited a year later, PBT blends with 10-90 wt % PA-6 were
reported to show high crystallinity and a fine dispersion of the minor phase, which
resulted in a good set of mechanical properties (Toray Industries Inc./ 1983).
In 1983 Upjohn disclosed that blends of polyesteramide (PEA) with 69.6 wt % PBT
show rapid crystallization of PBT and significant improvement of the impact resist-
ance (Chen and Onder, 1985). In 1987 the same two gentlemen revealed (in a patent
application assigned to Dow Chemical) that the rate of crystallization of polyamides
(PA) is higher in its blends with PET (Chen and Onder, 1989).
In a 1985 patent application from Toray Industries, 6O-98wt% PA was blended
with PEST (e.g., 15wt% PET). The alloys showed good moldability, rigidity, strength
and fire resistance (Chiba and Tanaka, 1986). A year later, a patent document
from Amoco described blends of 15-85 wt % PA with either PET, PBT or their
mixtures. The blends were compatibilized by addition of 0.5-15wt% of Phenoxy.
They exhibited increased elongation, tensile strength, !zod impact strength and
uniformity of material after injection. Incorporation of acrylic graft copolymer
further enhanced the heat and water resistance (Robeson, 1988). A Mitsubishi
Kasei patent document deposited in 1988 disclosed PA/PBT blends compatibilized
with an epoxy compound. The molded resin showed high impact strength (Urabe
and Ikuhara, 1989).
In an AlliedSignal patent application of 1987/ PA blends with 15-45 wt % PET were
described. The systems were compatibilized by addition of O.O5-lO wt % phosphoryl
azide reactive coupler. Subsequently heating the blend for 2-20 min at 265-315°C
lowered the melting points of PA and PET. The compatibilization was found to
improve processability of the blend as well as the performance of the products
(Bhattacharjee et al., 1990).
In a 1990 patent deposition from DSM, PA blends with PEST containing toluene-
sulfonic acid groups were described. Good impact and heat resistance were
observed (Van Sluijs et al., 1992). In the following patent, PA was identified as
PA-46, and polyester as PET. For the production of automobile structural parts, the
blends were reinforced with glass fibers (Bots and Statnik/ 1992). The same year
Eastman Kodak announced that PET blends with polyester-polyamide copolymer
result in alloys useful for manufacturing containers with good barrier properties
(Cox et al., 1992).
In a 1991 patent application from Enichem PET/PA blends were disclosed - 70-
3Owt% PET, was blended with either PA, PO or their mixture, and with 5-30wt%
EEA-GMA, as Lotader. The reactive compounding was carried out in a twin-screw
extruder (Natarajan et al., 1993). A contemporary document from BASF described
impact-resistant blends for films or moldings, comprising 50-99 wt % of either PA-6
or PA-66, and low-molecular-weight aromatic polyesters, such as 1-50wt% PBT
with a molecular weight of 5 kg/mol (Goetz et al., 1993).
The same year, Polyplastics Company described moldable blends containing 2-
98wt% of a compatibilizing, Na sulfonate group-containing polyester (PEST, either
PET or PBT with sodium dimethyl-5-sulfoisophthalate), 2-98wt% of an alkenic
copolymer with vinyl alcohol, and/or unsaturated carboxylic acid or its derivative
(e.g., ionomer, maleated-PPor EVAI), PA-6 and 0-96wt% PEST. The blends showed
fine dispersion with a particle diameter of 0.05-1 J-tm, resulting in high tensile and
impact strength (Tajima et al., 1994). The following year the company disclosed
blends comprising 100wt% PEST, O.5-lOwt% of an acrylonitrile copolymer,
0-100wt% PA, o-lOwt% styrene copolymer and o-l00wt% of fillers. The blends
showed enhanced melt tension and improved blow moldability without causing
parison draw down. Products had excellent mechanical properties and thermal
resistance, uniform thickness and an excellent appearance, even when repeatedly
recycled. These materials were used for the production of hollow moldings that were
to be used under severe conditions, such as an intake manifold of an automobile,
suction and exhaust parts around the engine, vessels for high temperature liquids,
chemicals and solvents, pipes, floats and tubes (Shiwaku et al., 1994).
Also in 1991, blends of PAr with aliphatic-aromatic polyamides having a ratio of
aliphatic to aromatic carbons 1.4 to 2.5 (PARA) were disclosed by Amoco. They were
reported miscible (single Tg), with excellent processability, mechanical properties,
solvent, weather, impact and stress-crack resistance (Dean, 1992).
In 1992 a general method of blending was disclosed by Kao Corporation. The
blends comprised 98-50wt% of part A and 2-SOwt% of part B. Part A was PEST
(e.g., PET) and part B was an immiscible resin, such as PA, PO, PS, PC or PMMA.
The resulting injection or blow-molded articles showed high anisotropic luster.
When the viscosity ratio TJA/11B was greater than 2, and the storage modulus ratio
E~ < EB, the dispersed phase was in the form of prolate ellipsoids with an axial ratio
of 1-10 (Odajima et al., 1993).
The same year, M. & G. Ricerche described compositions that comprised either
PET or PBT, and 5-20wt% of a reactive polymer. The latter resin was PA containing
end groups that could be made reactive, and a functional compound containing
reactive groups. The alloys were prepared by melt blending the three ingredients,
pelletizing and reacting in the solid state at 150-220°C. The alloys were used to
manufacture films. The solid state reaction increased the MW of the alloy, compen-
sating for any degradation that may have occurred during melt blending, and
improved the mechanical properties (AI Ghatta, 1994).
17.2.4 PESTIPC blends

Blends of thermoplastic polyesters (PEST) with the polycarbonate of bisphenol-A
(PC) constitute an important type of commercial blends. Solution-east blends of PET
or PBT prepared by mild melt blending are immiscible, with a PC glass transition
depressed by nearly 20°C (Wahrmund et al., 1978; Murff et al., 1984; Hanrahan et al.,
1985; Dekkers et al., 1990). This may be a result of a small transesterification (Hobbs et
al., 1987; Porter and Wang, 1992). However, since the latter process lowers PEST
crystallinity, and thus the alloys' modulus, this method of compatibilization is
usually avoided.
Since PC/PEST blends are immiscible and brittle, the commercial alloys usually
contain 15-20wt% of a compatibilizer/impact modifier. The latter resin can be
modified either PE, ABS or an acrylic copolymer, such as MBS. There are many
blends of this type available on the international market: DiaIayTM (PC/PET) from
Mitsubishi Rayon, Ektar™ from Eastman, Hyperiite™ from Kanegafuchi Chemical,
Impact™ from AlliedSignal, MakrobIenJfM (primarily PC/PBT impact modified by
addition of HOPE or ABS) from Bayer, MB 3500 from Mitsubishi Gas Company,
NovadoITM (PC/PET) from Mitsubishi Chemical Industries, Petsar™ from Polysar,
Sabre™ 1600 (PC with either PET or PBT) from Dow Chemical Company, SC from
Idemitsu Petrochemicals, Stapron TM E (PC with either PET or PBT and with PB) from
DSM, UltrabIfndTM KR (PC/PBT with ASA) from BASF, or XenayTM from General
Electric Plastics.
Most of these blends show high notched impact strength down to -40 0C. The
alloys, usually with cocontinuous morphology, have good processability, heat and
chemical resistance, elongation, low temperature impact and tensile strength.
However, it is critical to avoid reduction of PET crystallinity during blending or
processing. The blends have poor resistance to strong solvents and aromatic hydro-
carbons.
Blends of PC with either PET or PBT are of particular importance. Owing to
possible transesterification the system does not necessarily require additional com-
patibilization. However, controlling the extent of co-reaction is critical- too much of
it eliminates crystallinity of PEST, reducing the mechanical performance as well as
solvent and chemical resistance, whereas too little leads to poor interphase adhesion
and brittleness. As a result, most modem blends rely rather on reactive compatib-
ilization than on a transesterification. The compatibilization is usually combined
with incorporation of a multicomponent impact modifier, that improves the impact
strength of the resulting alloy.
The main advantages of the PC/PEST alloys is increased stiffness, low suscep-
tibility to stress cracking on contact with fuels, and an improved resistance to
chemicals and fuels. The blends are characterized by a set of properties to which
each of the three components contribute, namely excellent impact strength at room
and low temperature (contribution from PC and elastomer, respectively), low soft-
'ening temperature (contribution from PC and PEST), and good solvent resistance
(contribution of the semicrystalline PEST) - each compensating for the inherent
weakness of the other. The impact modifier, although it is necessary, may also be
responsible for poor UV resistance. Before processing, the blend should be dried for
5 h at 120°C in a high speed drier, to reduce moisture to below 0.02 %. The optimum
melt temperature is 265-280 0c.
The PC/PEST blends are mainly processed by injection molding. However, grades
for extrusion, blow molding as well as transfer or compression molding, solid state,
and thermoforming are also available. The blends show good processability, heat
resistance, ductility, HDT, high modulus, impact, tensile and flexural strength over a
wide temperature range, fatigue endurance, abrasion resistance, dimensional stabi-
lity (due to low shrinkage and minimal water absorbency), high gloss, good adhe-
sion, solvent, salt spray, biological and chemical resistance. They can be painted, hot
stamped, metalized and plated.
PC/PEST blends are mainly used in the automotive industry for automotive body
panels that require toughness at low temperatures, chemical resistance, heat resist-
ance and dimensional stability, such as dashboard, pillars, roof claddings, head lamp
housings and luggage racks. They are also used in outdoor power equipment (tractor
or lawn mower shrouds, consoles, grilles, trim and equipment parts), recrea-
tional applications, for the manufacture of consumer goods (vacuum cleaner hous-
ings and nozzles, utility locks, protective face guards, beverage containers, dishes,
food transport bins, dinnerware, mixing bowls, salad tongs and swimming pool
pump housings), telecommunications (radio housings, speakers and instrument
housings) and many others.
The first patent application for PC/PEST blends dates from 1966, when Bayer
alloyed PC with 1-5 wt % PET to improve the stress corrosion resistance - no hairline
cracks after 24h in boiling water (Cziesla and Bottenbruch, 1975). Three years later,
Teijin Chemicals developed PC/PET blends containing 75 wt % of the polyester. The
patent application specified that the materials must be blended under nitrogen at
240 °C for 6 h. The resulting alloys showed improved impact resistance and elonga-
tion, without a decrease of either the degree of crystallinity or the melting point
(Horiuchi and Kamiya, 1974). Similarly, prolonged blending of PC/PBI was pro-
posed in 1971 by the company. Thus PC was to be mixed with more than 50wt% of
PBI for 6h at 120°C (Matsukane and Azo, 1973; Kubota et al., 1973; Hasegawa et al.,
1974). Development of these two-component blends was of little commercial con-
sequence, since the long cooking at low temperatures was rather expensive. Further-
more, as the transesterification is sensitive to metallic salts (that were used to catalyze
the polycondensation of the blend components), the process was difficult to control.
Also in 1971, Unitika applied for patent protection for blends comprising
5-90wt% PC and less than SOwt% PET and PAr. The blends were reported to have
good moldability and impact strength (Koshimo et ai., 1973). In another application,
blending of PC with aromatic polyester, such as PAr at a ratio of 1:1, was reported to
give easily moldable materials with excellent mechanical properties (Unitika Ltd.,
1983). In a Sumitomo Chemical patent, PAr was blended with 99-1 parts of PC, to
give an excellent set of properties (Fukushima et ai., 1979).
In 1972 Teijin Chemicals discovered that three-component blends, e.g., ~3 wt %
PBT, 27-47.5wt% PC and 5-20wt% of a core-shell impact modifier (methylmetha-
crylate-butadiene-styrene graft copolymer, MBS), were easy to compound. The
blends showed good processability, and the product had good chemical resistance
and impact strength (Nakamura et ai., 1974). The use of MBS as a single, multi-
component compatibilizer and impact modifier constituted an important develop-
ment in the evolution of PC/PEST blends. In 1974 BASF announced blends of PBT
with 20wt% PC and a fireproofing compound (Horn and Seydl, 1975).
In 1975 Mitsubishi Plastics Industries Ltd applied for patent protection for blends
comprising 65-93 wt % PET with PC. The alloys were extruded then stretched into
films, with surface roughness 1.1 /Lm and good strength at temperatures Tg < T < Tm
(PET) (Ishiyama, 1976). Two years later, Mitsubishi Rayon Company disclosed PET
blends with 5-94wt% PC and 1-40wt% butyl-acrylate-styrene-triallyl isocyanurate,
grafted with methylmethacrylate and styrene. The alloys showed good impact and
weathering resistance (Kamata et al., 1978).
In 1978 and 1979 General Electric deposited several patent documents on PEST/
PC blends. For example, 8 ~rts PBT was blended with 15 parts PC and 5 parts of
acrylic copolymer, Acryioid KM 330, to give alloys with high notched impact
strength (Motz, 1980). In the following patent, blends comprising 4Owt% PBT,
with PC and 10 wt % aromatic polyester-earbonate (PEe) were reported to be trans-
parent (Dieck and Cohen, 1980), whereas those comprising PBT (and optionally PET)
with 15wt% PC, 7.5wt% SEBS Kraton, and mineral fillers, showed good impact
strength, low warpage and shrinkage (Dieck and Wambach, 1980). Other blends,
containing 39.8wt% PBT, with 30wt% PET, 15wt% 5EBS and 15wt% PC, showed
good impact, heat and tensile strength (Wambach and Dieck, 1980). In another
deposition, blends of PBT with PET, PC, (5B)n' and either a butadiene-caprolac-
tone-styrene or butadiene-eaprolactone block copolymer, were disclosed (Dieck,
1980). In a later patent, PBT was blended with PET, PC and Ah03 (Goedde et ai.,
1980). In a contemporary document the company described flame-retardant blends
comprising 47wt% PBT with 17wt% brominated PC, 10wt% PVAc and mineral
fillers. The reinforced blends had good mechanical properties, as well as high impact
and arc track resistance (Cohen et ai., 1980). In 1980 General Electric announced
molding compositions characterized by high impact strength and heat resistance,
prepared by blending 78.3wt% PBT, with lOwt% PC, and 10wt% polyacrylate
impact modifying rubber (Cohen, 1982). In 1982 the company commercialized the
highly successful XenoyTM alloys.
Similarly in 1979, R6hm & Haas Company deposited an application describing
PET moldable blends with 20 wt % PC and 15 wt % core-shell butylacrylate-butylene
diacrylate-diallylmaleate-methylmethacrylate (Fromuth and Shell, 1981). A contem-
porary Polish patent from Academia Techniczno-RoInicza Bydgoszcz described
blends comprising 5-50 wt % PET with PC, used for casting electrical insulators with
good processability, and high mechanical performance (Skraga et a/., 1983).
In 1981 several PEST/PC blends were announced. For example, Plastics Engineer-
ing disclosed three-<:omponent blends comprising 3O-9Swt% PET, 1-30wt% PC
and 2.5-10wt% PCT. These alloys were reported to show good toughness, strength,
humidity resistance and dimensional stability (Lee, C. J., 1982). Blends comprising
5-94.Swt% PET with 94.5-Swt% PC, O.5-30wt% acrylic rubber and octadecyl
stearate were found to give good moldability and mold release, as well as high
impact strength. Furthermore, it was reported that addition of O.I-lOwt% acrylic or
methacrylic-grafted polyalkene increased PET crystallization temperature to 202 0c,
improving blend moldability (Mitsubishi Chemical Industries Co., 1983b). Good sets
of mechanical properties were also obtained by blending 3-30 parts PET with 100
parts PC and 0.5-10 parts of butyl rubber, BR (Teijin Chemicals, 1983c). The same
year, Dow Chemical developed polyestercarbonate (PEC) blends with polycarbonate
(PC). The molding resins showed good impact properties without sacrificing
the tensile strength (Byrne and Feay, 1983).
Also in 1981, Bayer deposited a series of applications describing blends of PEST,
with either grafted or homopolymeric elastomers. These alloys were reported to
have good toughness, hardness, stiffness and HDT. Thus PET and/or PBT and/or
PC, when blended with graft copolymer of polybutadiene (PB) and (meth)acrylic
esters (and possibly acrylonitrile, acrylate rubber, ACM and/or ABS), produced
alloys that were found commercially interesting (Bier and Indner, 1982; Neuray et
al., 1982; Nouverte et al., 1982; Serini et al., 1982). A year later, another series of patent
applications was submitted for blends of 1-100 wt % PC with either PET or PBT, and
with 1-30~ EVAc (Weyer et al., 1984). This work led to commercialization of
Makroblend alloys.
The depositions of 1982 described further improvements of the blending techno-
logy for the manufacture of PEST/PC blends. In a General Electric document,
SI-96wt% PC, blended with 3-49wt% of either PET (or another PEST) and an
acrylic modifier, (3-20 wt % Acryloid KM), had good processability, high notched
impact strength and weatherability (Allen et a/., 1984). Another patent from the
company described high impact strength blends prepared from IG-90 wt % PEST,
5-65wt% Pc, 0.1-20wt% LLDPE, and an acrylic elastomer (MBA). Thus, blends
prepared by compounding 39 parts PBT (or PET), with 48 parts Pc, 4 parts LLDPE
and with 8 parts of MBA, were found to have good impact strength (Boutni and Liu,
1983; Liu, 1983a). PC was also blended with PET or PBT and acrylic impact modifier,
such as PET with IG-lSwt% PC and IG-lSwt% Acryloid™ KM 330, for improved
impact strength (Hepp, 1984).
Also in 1982, blends comprising 2G-90wt% PC with an aromatic polyester, such as
5-70wt% PET, with 1-ISwt% BR, an acrylic elastomer (1-20wt% HIA-15) and
G-lSwt% PMP were developed for improved solvent and low temperature impact
resistance (Teijin Chemicals Ltd., 1983). Reactive compatibilization was used to
obtain alloys characterized by high tensile strength, impact resistance and electrical
conductivity. Thus, SG-9Swt% PC was blended with 1-40wt% PET and with more
than 1 wt% of an elastomer containing acidic groups, Tafmer™ A 20090 (Mitsubishi
Chemical Industries Co., 1983).
Similarly, blends of PC with PAr were reported to be easily to mold, and the
moldings showed excellent mechanical behavior (Unitika Ltd, 1983). Daicel Chemi-
cal disclosed that reactive compounding of 20 wt % PC with PBT and with 2-methyl-
1,3-propanediol improved the heat deflection temperature, elongation and impact
strength (Yoga et al., 1983).
In a contemporary patent from BASF, high impact strength molding compositions

were described as being prepared by blending PBT with PC and ethylene-acrylic
acid-butylacrylate copolymer (Portugall et al., 1984). In a 1986 disclosure from the
company, high impact strength blends comprising either PET or PBT, 40-65 wt % PC
and 1-3Owt% acrylic rubber (a multilayered copolymer of ethylene-n-butylacrylate
with either acrylic acid, or glycidyl methacrylate, SAN-grafted n-butylacrylate, poly-
butadiene grafted with styrene and methylmethacrylate) were described (Lausberg
et al., 1987). These patents provide the basic formulations for the commercial PCI
PBT blend from BASF, the Ultrablend™.
A Montedison patent, also deposited in 1982 described similar effects from blends
of G--SO wt % PBT with PC and SO wt % of a styrene-o-methylstyrene-acrylonitrile-
butadiene copolymer (a modified ABS). The alloys showed good moldability,
mechanical properties and heat resistance (Biglione and Fasulo, 1983).
Also in 1982 several blends of PC with PEST were patented by Bayer. The
company disclosed that mixtures of l-l00wt% PC with PEST can be ameliorated
by incorporation of 1-30 phr EVAc. In a following patent, PC blends with IG--50 %
PBT were found useful for preparation of uniaxially drawn shrink films (Weyer et al.,
1984; Kleiner et al., 1984). The same year, Uniroyal Chemical reported highly syner-
gistic enhancement of impact strength of the PEST/PC blends, by incorporating a
proprietary impact modifier (either EPR or EPDM grafted with styrene and acrylo-
nitrile, an AES). For example, PC was compounded with IG-40wt% of either PET or
PBT, and with IG--30wt% of AES - large synergistic enhancement of the impact
strength was observed (Wefer, 1984, 1985, 1988). Similar blends, comprising PBT,
97-3 wt % PC and SAN-grafted EPDM, were reported to show good fluidity, mold-
ability, mechanical properties, and weldline strength (Sumitomo NaugatuckCo., 1983).
In 1983 depositions, the claims were directed primarily towards toughening of the
PESTfPC blends. For example, in a General Electric document, blending PET with
IG--15wt% PC and IG--15wt% acrylic impact modifier (Acryloid KM 330) was found
to result in alloys that were highly impact resistant (Hepp, 1984). In a following
patent from the company, 5-95 wt % PET (or PBT) was blended with ABS, MBS or
other suitable copolymer to give materials with high gloss and solvent resistance
(Michel, 1985). Similarly in Mobay Chemical patents, 43 wt % PET, was blended with
43wt% PC and 14wt% ABS, to give blends with high impact strength at low
temperature (Chung et al., 1985). In another contemporary document, blends of
either PET or PBT, with 5-50wt% PC, were further compounded with O.I-4wt%
talc. The alloys had good moldability, and the products showed improved warpage
resistance (Chung et al., 1985; Chung and Witman, 1985).
Two years later General Electric developed PC blends with 14wt% PET, 6wt%
acrylate elastomer (Akryloid KM 660), lO wt % Phenoxy and, optionally, acrylate-
alkene elastomer. The blends showed excellent impact strength, ductility and solvent
resistance (Liu and Giles, 1986). In a contemporary disclosure from Teijin Chemicals,
blends comprising IG--90wt% Pc, with 5-80wt% PET and O.5-lOwt% MBS graft
copolymer were reported to give moldings with good solvent and low-temperature
impact resistance (Kitamura et al., 1987).
In 1986 Mitsubishi Rayon announced blends comprising either PC or its mixtures
with either a saturated polyester, a polyester elastomer, or their mixtures, namely,
either PC, PC with PET, PC with PBT, or PC with a PET-PBT copolymer. The
materials were further blended with 0.5-60 wt % siloxane-based vinyl-grafted co-
polymer. The moldings showed excellent chemical, weather and low temperature
impact resistance (Hongo et al., 1987). A few years later the company commercialized
PC/PET blends as DialoyTM.
In 1987 patent applications from General Electric new blends of PC with either
PET or PBT were described. The overall properties of these alloys were improved by
incorporating polyacrylate rubbers (Boutni, 1989). Furthermore, the company
reported that the ester exchange reaction between PC and a polyester (either PET
or PBT) can be controlled by addition of sulfur phosphite stabilizer (Verhoeveven
and Roovers, 1988).
The following year, General Electric disclosed a new method of modification of the
PC/PEST. Thus, it was found that compounding them with a polyalkylene glycol
resulted in compatibilization and promotion of lacquer adhesion (De long et ai., 1991).
Two years later the company disclosed blends based on scrap PC and PEST. Thus,
50wt% of recycled PC was blended with 3Owt% PBT (or PET) and 20wt% virgin
PC/PEST blend compatibilized by addition of MBS and possibly ethylene-glycidyl-
methacrylate. These moldable alloys showed good impact properties (Scobbo et ai.,
1993). In a contemporary patent from the company, blends comprising PC with PBT
and ABS were reported to give materials with dispersed phase diameters of
8Q-220nm, having good impact and gasoline-staining resistance (Wang, 1993).
The same year, Takeda Chemical Industry patents described blends of PC/PEST,
modified by incorporating a core-shell acrylic-butadiene rubber copolymer (ethyl-
hexylacrylate-co-butylacrylate-co-butylenediacrylate) (Sakai et al., 1989). In a patent
document from Plastics Engineering the use of maleated polyethylene wax was
described to improve the impact strength properties of PC/PET blends (Liang, 1989).
In a 1989 disclosure from Enichem, similar effects were claimed for PC/PEST
blends compounded with EPDM and PCL (as those with a polyalkylene glycol).
Furthermore, the blends with PCL were said to be of particular value for high gloss
applications (Natarajan and Mininni, 1991). Two years later, the company disclosed
PETfPC blends modified by addition of maleated or epoxidized elastomers. For
example, alloys comprising 7Q-30wt% PET, 3Q-70wt% PC and lQ-30phr (on the
total mass of PC and PET) of, for example ethylene-ethylacrylate-maleic anhydride
copolymer (EEA-MA), resulted in chemically resistant materials with improved
impact properties (Natarajan and Arjunan, 1993).
In 1991, Idemitsu Petrochemical disclosed a wide range of blends comprising
branched polycarbonate (1-99wt% bPC) with a polymer selected from PET, PBT,
styrenics (HIPS, ABS or SMA), PA-6, PA-66, PE, PP and TPE (acrylic rubber, butyl
rubber, EPDM or SBS). The alloys were reported to show excellent processability and
solvent and impact resistance, as well as good mechanical properties (Kozakura et
ai., 1992). The same year Takeda Chemical Industries disclosed a method for pre-
paring multi-layered, multicomponent polymers, to be used as impact modifiers in
PC/PEST blends. The copolymers were prepared as core-shell graft copolymers,
with 12-42wt% of aromatic-vinyl polymer in the core, 48-78wt% elastomeric inter-
mediate layer, and 10-40 wt % glassy aromatic-vinyl polymer as a shell. It was
reported that blends comprising 5o-Swt% PBT, 5o-95wt% PC and 5phr of a
multi-layered copolymer (e.g., comprising 30 wt % styrene-methylmethacrylate-di-
vinylbenzene copolymer in the core, 55 wt % butadiene-ethylhexylacrylate-divinyl-
benzene copolymer as an intermediate layer, and 15 wt % styrene-acrylonitrile-
divinylbenzene copolymer forming the shell), showed a 10-fold increase of the
Izod impact strength (Fujii et ai., 1993).
In a 1992 patent from Eastman Kodak, modified PC/PEST blends were described.
Thus, to improve the processability and low-temperature impact strength, PC was
blended with a copolyester (Small and Gilliam, 1993). In another application, the
company described blends comprising 6o-30wt% PCT, 4o-70wt% PC (preferably
1:1 blends with either modified or branched PC) (Cox and Brooks, 1993). Blends of
PCT with PC are recognized for high toughness, HDT and chemical resistance.
Owing to miscibility (concluded from the presence of a single glass transition
temperature) (Mohn et ai., 1979; Smith et ai., 1981), they show a high degree of
transparency. These blends were found useful for molding parts requiring good
clarity, high tensile strength, and notched !zod impact strength. The perferred
compositions should contain a modified or branched PC. Since transesterification
probably takes place during compounding and forming, the observed miscibility
may be a function of the processing variables.
The same year Mitsubishi Petrochemical asked for patent protection for a broad
class of blends comprising: 5-95wt% of a non-erystalline thermoplastic resin (e.g.,
PC), 95-5wt% of a crystalline resin (e.g., PEST), o-SOwt% of a compatibilizer,
D-4O wt % of an impact modifier, and more than 1.0 phr of a solvent. The formulation
was compounded in a kneader equipped with vent ports, each having a vacuum line
attached to it, to reduce solvent content in the final composition to less than 1.0 wt %.
The blends had excellent dimensional stability, heat resistance, impact resistance,
solvent resistance and appearance, and were used to mold parts for automobiles,
electric and electronic equipment (ltou et ai., 1993).
Light-conducting, casing blends for sheath optical fibers were developed by Sie-
mens. The blends consisted of 74-45wt% PEST, 25-55wt% PC and 0.2-3wt% of a
carbodiimide of formula (X)m-(-N=C=N-Y-)p(-N=C=N-X)m (where X, Y = C6- 20
aromatic or aliphatic group, p=o-SO, m=0-1, and X can carry free isocyanate
groups). The blends with two-phase structure had improved thermal stability and
moisture resistance (Kamps et ai., 1994). The same year, blends comprising
53-71 wt % PC, 29-16 wt % PET and 13-18 wt % of carbon black (CB) were developed
by Bayer. The alloys were found suitable for preparation of films for packaging of
electronic parts. The films had thicknesses of 0.15-0.6 mm, surface resistivity of at
least 500 kn, and an elongation at break larger than 20% (Fausten et ai., 1993).
Also in 1992, Teijin invented moldable blends that comprised 55-80wt% PBT,
10-30 wt % PC, and 10-20 wt % modified PO (mPO). The latter resin was either aPE,
PP or EPR grafted with 0.05-15wt% of glycidyl methacrylate or with 0.1-2wt%
maleic anhydride. The alloys showed good processability, and the moldings had
excellent toughness, rigidity, strength and dimensional stability, not affected by
thermal shrinkage. The excellent properties of PBT resin, such as flexural modulus,
were unchanged by blending (Fujie, 1993).
In a contemporary document, synergistic impact improvement was reported by
General Electric for blends comprising PC, PEST and/or polyester-carbonate, with
10-20 wt % impact-modifying mixture of ABS with an acidified copolymer, for
example, ethylene, glycidyl methacrylate or maleic anhydride, and (optionally)
vinyl acetate, vinyl alcohol, styrene, acrylonitrile, (meth)acrylate(s). The alloys
showed good impact strength and had a ductile-brittle transition temperature less
sensitive to the molding conditions (Steendam et ai., 1993).
There are many multicomponent blends that comprise PC and PEST amongst the
polymeric components - the alloys of polyphenylene ether (PPE) are particularly
important. These are discussed later, along with other PPE blends. However, it
would be amiss not to give at least one example of these systems. Thus, a 1982
patent application from Dow Chemical described a new method of preparation of
multicomponent polymer blends by combining in the final stage two pre-blends,
part (1) and part (2). Part (1) comprised PC blended with PEST and not more than
5 wt % of an AB5-type copolymer with either alkyl (meth)acrylates, glycidyl meth-
acrylates, ethylene/propylene/diene copolymer, maleic anhydride, alkyl or aryl
maleimides and oxazoline. Part (2) comprised PPE, and/or a blend of PPE with
PS, HIPS, SEBS, PA, PC, PEST and a polyalkyl(meth)acrylate. Finally, the two parts
were compounded together and molded. The moldings had low gloss even when
processed at high temperature. They were used to manufacture instrument and
appliance housings, car panels, radio components, etc. (Laughner, 1993). In a later
patent, PC/PET blends were impact-modified by addition of a glycidylmethacrylate
copolymer. The systems showed good flexural modulus, weld line strength and
solvent resistance (Laughner, 1994).
In 1993 AlliedSignal applied for patent protection for blends comprising a poly-
ester, 2Q-60wt% of PEST (either PET, PBT or PCT), 4D-6Owt% PC, 1D-20wt% of an
amine-functionalized elastomer (either EPR, EPDM or NBR), and optionally an
effective amount of a graft coupling agent (for grafting the amine-terminated elast-
omer to PEST), e.g., polycarbodiimide. Blending was performed using a corotating
intermeshing twin-screw extruder. The extruder contained 10 heated barrel sections
with downstream feed capability at the 4th and 6th barrel sections. A typical
temperature profile had the first three sections at 250°C and the rest at 270 0c.
Mixing elements were located in sections 5 and 7. Materials were typically starve
fed at a screw speed of 200-250 rpm. The resulting materials showed several advant-
.ages: a relatively high impact strength, both at room and low temperatures (Le., 24
and -40 0C), and they retained a substantial portion of both room and low tempera-
ture impact strengths after annealing or heat treatment. They also had relatively low
melt viscosities, providing good processability. The alloys' properties were superior
to those shown by blends without amine functionality (Akkapeddi and VanBuskirk,
1994).
17.2.5 PESTIPPE blends

Polyphenylene ether (PPE) and thermoplastic polyesters (PEST) are immiscible and
brittle, hence they require compatibilization and toughening. In consequence, the
evolution of PPE/PEST blend technology is related to the evolution of compatibil-
ization methods.
There are several commercial blends of PPE/PBT available, such as DialoyTM X
from Mitsubishi Ra~n, BE from Dai Nippon Ink Company, Gemax™ from General
Electric or Iupi-ace from Mitsubishi Gas Company. The blends, in most cases
reinforced with glass fibers, are mainly injection molded, extruded or blow molded.
The PPE/PBT blends have excellent processability, high solvent and temperature
resistance and dimensional stability.
The evolution of PPE/PEST technology followed the common pattern. First, in the
early 1970s, two-component PPE blends with PET, PBT or PC were patented. The
three-component blends of PPE with either PEST or PC and an impact modifier
became known in the early 1980s (Chung and Witman, 1985). In 1985 Toray intro-
duced high performance, four-eomponent blends comprising PPE/PET/PC/EGMA
for automotive applicatiOns. Similar blends (PPE with either PBT or PET, SEBS and
PC), were described in the 1987 General Electric invention document. The alloy
showed good processability, improved impact and solvent resistance, as well as
high temperature and dimensional stability, making it suitable for automotive
body panels. It was shown that in the system SEBS is uniformly dispersed in the
PPE phase, that in tum formed dispersed domains in the PBT matrix, with PC
located at the PBT/PPE interface, stabilizing the blend morphology (Hobbs et aI.,
1992). The development of Gemax™ illustrates how the accumulation of knowledge
can lead to more complex, better performing and commercially successful blends
(Campbell et al., 1990).
The first use of PEST in PPE blends dates from 1970, when Asahi-Dow published a
series of patents on the sequential polymerization leading to PPE/PS blends, then
modification of either PPE or PPE/PS blends by incorporation of either poly(styrene-
co-methylmethacrylate) (SMMA) and 0.1-lOwt% low-molecular-weight polyalkene,
or 0.5-20 wt % of one resin from PEST, PMMA, PC, acrylates or Phenoxy (Nakanishi
et al., 1971, 1973; Izawa et al., 1973; Izawa, 1974; Izawa and Nakanishi, 1973). The
following year, Asahi Chemical Industry developed PPE blends with polybutylene-
terephthalate (80 wt % PBT). The blends showed good processability and mechanical
properties (Nakamura and Toyomoto, 1974).
In 1977 General Electric Company deposited a patent application for PPE blends
with PBT, Ph3 P04 plasticizer and styrene-butadiene-styrene block copolymer (SBS).
The blends had low viscosity, with good impact and tensile strength (Lee, 1978).
In a series of patents dating from 1981 several types of PPE blends were described.
For example, PPE was blended with PS, and either PEST or PA dispersed as 0.5-5 p,m
diameter particles. The alloys had good moldability and impact strength (Mitsubishi
Petrochemical Co., 1982a).
In 1985 an important development in PPE-blends technology was disclosed by
General Electric. Thus, 1Q-45wt% PPE was blended with 1Q-45wt% PBT, 8-25wt%
SEBS and 3-40 wt % Pc. Separation of the toughening (provided by SEBS) from the
stabilization of morphology (provided by PC) resulted in excellent processability,
high impact strength and solvent resistance (Brown et al., 1987). As will be evident
from the examples cited below, during the follOWing ten years this fonnula was often
modified, but the basic composition - PPE/SEBS/PEST IPC - remained the some.
The same year, blends of copolyestercarbonates (PEC) polyarylates (PAr), and PPE/
PS were reported to show improved processability, balance of heat resistance and
mechanical properties, compared to its components (Allen, 1987). In another patent,
the company described PPE blends obtained by reactively compounding it with SBS
and maleic anhydride. The functionallzed mPPE was in turn mixed with either PEST
or PA. The materials showed high impact strength and chemical resistance (Van der
Meer and Yates, 1987). The following year the company offered the first modification
of Brown's patent. New blends comprised 1~wt% PPE, 1o-75wt% HIPS,
2-lOwt% PEST, 1-25wt% styrene polymer having reactive 2-oxazoline groups
and, optionally, polycarbonate (PC). The blends could also include SBS as an impact
strength modifier. They showed improved impact strength over those of prior art,
with a favorable combination of properties, such as mechanical strength, resistance
to chemicals and solvents, and flow properties in the melt (Avakian et al., 1988).
Also in 1985, in a disclosure from Bayer, PC was blended with PET, ABS and a PC-
PPE block copolymer. The blend was reported to have high HDT (Freitag et al., 1987).
The same year Toray Industries announced binary blends comprising PPE and
5-95 wt % PBT. It was reported that the alloys had good mechanical properties,
molding appearance and dimensional stability (Yonetani et al., 1987).
In 1986 Mitsubishi Petrochemical Company deposited a patent describing PPE
blends with PET, and glycidyl methacrylate-grafted SEBS (SEB5-GMA). The reactive
blending resulted in alloys possessing excellent solvent resistance, moldability,
impact and mechanical properties (Mayumi and Omori, 1988). The use of SEB5-
GMA in PPE/PEST blends was another crucial event in the development of the
technology.
The same year, Sumitomo Chemical Company disclosed a new, general method of
reactive blending. Blends with excellent processability, heat resistance and mechan-
ical properties, comprised 35-98wt% of a semicrystalline matrix polymer (e.g., PBT,
PET, PA-6 PA-66, PE, PP, POM, PPS or PEEK), 1--65wt% PPE to fonn a disperse
phase, O.1-50wt% of a compatibilizer, and reinforcing talc and/or glass fibers. As
compatibilizer either a maleated EPR, a copolymer of ethylene, vinylacetate and
glycidyl methacrylate, a monomeric maleic anhydride or a monomeric bis(4-phenyl
isocyanate) was used. The reactive compatibilization, conducted in a high speed
twin-screw extruder, resulted in PPE particle size having diameters of O.01-lOJLm.
The alloys could be either extruded or molded into a variety of parts for the auto-
mobile, electrical and electronic industries (Nishio et al., 1988, 1994; Abe et al., 1988).
In a later patent, high impact strength blends were obtained by adding SEBS and
urea-butylated resin to a mixture of PPE with PBT (Mizuno and Maruyama, 1990).
In the years 1987-1989, several patents on PPE/PEST blends were deposited by
General Electric. Blends comprising 20-40 wt % PPE, 25-75 wt % of either PBT or
PET, 8-25wt% SEBS and 5-40wt% PC were developed. When high modulus mate-
rials were required, mica was added (Brown et al., 1987; Yates, 1987, 1989, 1993). A
method of PPE modification by grafting it with unsaturated dicarboxylate (e.g.,
fumaric acid) was also made public (lshihara, 1989). The grafted PPE was then
reactively blended with PBT, PC and SEBS, resulting in materials having good
mechanical properties and low gloss. Furthermore, the solvent and impact resistance
could be enhanced by grafting PPE with dimethylsiloxanes and then blending it with
SEBS (Brown, 1989; Brown et al., 1992a). In another patent deposited in 1988, blends
with a wide variety of properties were prepared from a PPE having a low content of
non-neutralized amino nitrogen, an elastomeric polyester (PET or PBT) and at least
one polymer containing a substantial proportion of aromatic polycarbonate units
(e.g., PC) as a compatibilizer. The blends did not require an extraneous impact
modifier (Brown, 1989). High impact strength PPE blends were prepared by blend-
ing the resin with PEST, PS, PC, SEBS and/or an acrylate impact modifier (Yates and
Lee, 1990). In 1989 the company disclosed another modification of Brown's PPE/
SEBS/PESTfPC blends. The new alloys comprised PPE, with either PBT or PET,
5-20wt% PC-PBT copolymer (having 3-20wt% PC) and 21 wt% of SEBS as Kra-
ton™ G-1651. Excellent rigidity and impact strength were reported (Chambers et al.,
1995). These patents provide the basis for the commercial blend Gemax™. The resin
is known for its good impact and solvent resistance, excellent surface finish and low
coefficient of thermal expansion.
In 1990 Mitsubishi Petrochemical disclosed a new family of blends that comprised
1D-90wt% hydroxy alkylated PPE (e.g., PPE modified by glycidol or epichlorohy-
drin), and 1D-90wt% of a resin selected from between a carboxyl-, an epoxy-or a
hydroxy-eontaining polyalkene (e.g., maleated-PP, glycidyl methacrylate modified
PP, ionomers or EVAI), a polyamide, (e.g., PA-4, PA-6, PA-66, PA-46, PA-12 or
PA-6lO), and a polyester (e.g., PET, PBT, PCT, PEN or LCP). The blends could also
contain unmodified PPE, PO, styrenics, additives, reinforcements, etc. The alloys had
excellent moldability, solvent and heat resistance, and mechanical strength. They
were used for manufacturing gears and cranks, automobile manifolds, and electric
parts, etc. (Arashiro et al., 1994). Two years later, the company announced a new
method of PPE blending. Thus, blends were prepared by melting and kneading in
the presence of solvent (1) 5-95wt% of either PPE or hydroxy alkylated-PPE: (2) 95-
5wt% of a crystalline resin (e.g., PP, EPR, PA-6, PBT, etc.): (3) D-SOwt% of a
compatibilizer (e.g., maleic anhydride, tetrabutyl phosphonium bromide, glycidyl
methacrylate or titanium tetra(2-ethylhexyloxide): (4) o-4Owt% of an impact modi-
fier (e.g., SEBS): and (5) at least l.Ophr of an organic solvent (xylene). The com-
pounding took place in a kneader equipped with vent ports attached to a vacuum
line, maintaining reduced pressure to reduce the organic solvent content in the final
composition to less than l.Owt% (Takagi et al., 1994).
Also in 1990, General Electric announced further variations on the PPE/SEBS/
PEST/PC theme. Thus, 15-SOwt% PPE was blended with 2Q-60wt% PBT and 15-
30wt% of a block copolymer of the A-B-A type (where A is PC and B is a PS block,
preferably with PC:PS = 1:1). The compositions could also contain o-lOwt% PC and
o-25wt% of either SEBS Kraton™ or a core-shell type (Brown and Fewkes, 1992,
1994). In another document PPE capped with an epo~azine was blended with
PBT, a linear tapered block copolymer (SBS Finaclear ), and a block copolymer,
Kraton™ RTM. The blends showed good processability, tensile elongation and
strength, as well as chemical and impact resistance (Yates, 1995). The following
year the company disclosed PPE blends with PEST, modified by addition of fatty
acid amides that improved processability, and enhanced low temperature ductility.
For example, 30 wt % epoxy-or phosphate-functionalized PPE, was blended with
46wt% of either PBT or PET, palmitamide, 1-3Owt% SEBS, and 1-3Owt% poly-
carbonate (Yates, 1993). In a contemporary patent, blends were prepared by com-
pounding 5-95 wt % epoxy-functionalized PPE, 95-5 wt % PEST and 0.05-5.0 phr of
liquid hydrogenated poly-a-alkene. The alloys showed improved processability and
impact resistance. Owing to the inclusion of poly-a-alkene as a processing aid, they
were found moldable at lower temperatures (Hasson and Yates, 1993). In 1992 the
company disclosed blends prepared in two steps: (1) PPE capped with 2-7wt%
salicylic acid ester was blended with 6-200 phr of SEBS: (2) the blend was dispersed
in a matrix of either PA, PEST, PEl or PS. The moldable blends showed improved
resistance to loss of impact strength after thermal recycling (Richards and White,
1994).
In a 1991 Dow Chemical patent application, four-eomponent blends were
described. Thus, 55-75 parts PC was blended with 1-8 parts PPE, 10-57 parts PET
(or PBT), and 1-15 parts of either an elastomeric impact modifier (e.g., Kraton™ G), a
core-shell grafted copolymer, or an alkenic elastomer. The resulting alloys were
reported to give a good balance between the impact properties, HDT S 295°C, and
chemical resistance (Laughner and Farah, 1992). The following year the company
deposited a patent application for preparation of multi-eomponent blends. This was
to be accomplished in three steps: (1) compounding PC with PEST and 0-5wt%
of an AB5-type copolymer with alkyl (meth)acrylates, glycidyl methacrylates,
ethylene/propylene/diene copolymer, maleic anhydride, alkyl or aryl maleimides
and oxazoline: (2) compounding either PPE or its blend with at least one of the
polymers PS, HIPS, SEBS, PA, PC, PEST or polyalkyl(meth)acrylate; (3) the two
blends (1) and (2) were compounded together and used for injection molding of
instrument and appliance housings, car panels, radio components, etc. The blends
had low gloss even when molded at high temperatures (Laughner 1993).
Also in 1991 Eastman Kodak discovered that PEST (e.g., Tenite™, Kodar Koda-
pak™, Ektar PCTG™ or Ektar HPETG™, thus either PETG, PCTG, PET, PBT or
PEN), when blended with polyvinylphenol (PVPh) at ratios from 1:99 to 99:1 pro-
duce miscible blends, that can be extruded into chemically resistant materials for
clear packaging films. However, even more important was that vinyl phenol can be
readily copolymerized with styrene, to produce either block, graft or random co-
polymers (Ps-VPh). In consequence, PEST blends could be compatibilized by addi-
tion of Ps-VPh with any polymer miscible with PS, namely PPE, HIPS or TMPc.
These blends showed significantly improved mechanical properties, high yield
stress, strength and elongation at break, as well as excellent toughness (Colby et al.,
1993, 1994).
In 1992, Eastman Kodak described blends of 5-95wt% PCT (Ektar™ or Koda-
pak™) melt-blended with 95-5 wt % PPE. The new alloys were clear, transparent,
suitable for injection molding or extrusion. It was stressed that the ratio of the two
bihydroxy units in PCT, EG:CHDM, should be within the limits from 69:31 to 97:3. A
compatibilizer/impact modifier may also be used (Stewart and Massa, 1993).
The same year, Himont announced blends that comprised 2()....6()wt% of either
PPE, PA, and/or PEST, 3O--6S wt % PP grafted with styrene and a glycidyl moiety
(the total concentration of styrenic and glycidyl moiety monomers was 50-200 phr,
and the glycidyl moiety monomer was 0.1-20.0wt% of it), and 2-15wt% of an
elastomer, namely EPDM, SBS, SEBS, EPR, etc. The blends showed excellent flexural
and tensile strength, and increased resistance to delamination, indicating strong
interchain interactions. The materials were used to mold articles such as auto
parts, appliances and motor housings (Okamoto, K.T. et al., 1993a, 1994).
In a contemporary report from Mitsui Toatsu Chemicals, blends of PPE with
Q-40wt% PS, and 1-40wt% of a dicarboxylic acid ester copolymer (obtained from
a vinyl monomer and an unsaturated dicarboxylic acid ester, e.g., styrene-dibutyl-
maleate having M w < 60 kg/mol) were described. H necessary, the blends could also
contain 1-40wt% of a conductive carbon, or an A-B-A' type or A-B'-B" type elasto-
meric block copolymer, such as Kraton™ G-1650 or Dynaron™ 191OP. Owing to
excellent moldability, as well as good fine performance of the finished articles, these
alloys were found useful for molding parts for automobile industry, home, electronic
or electric devices, as well as to produce industrial parts and components (Yoshi-
mura et al., 1995).
Also in 1992, Mitsubishi Petrochemical Company developed blends comprising
lo-90wt% PPE, 9O-1Owt% PEST, 0.1-10phr of an organic phosphorous acid
compound (having a boiling point of 35-300°C), and o-lOphr of an acid receptor.
The blends had the mechanical strength of PPE with the good processing and
impact resistance characteristics of PEST. The materials have been used to
mold components for engineering and electrical applications (Tsukahara, T. et al.,
1994a).
17.2.6 PESTIPOM blends

Polyoxymethylene (POM) is a semicrystalline polymer with a set of performance
parameters far superior to what could be expected from its rather limited market
volume. Owing to the simple molecular structure, it is immiscible with all known
polymers which, to date, has limited its use. Blends of POM with PEST have been
patented. Several commercial alloys of this type are available, such as DuraloyTM
from Celanese and Lynex™ T from Asahi Chemical Company. The blends show high
heat stability, high HDT, toughness, softness and high impact strength.
In 1976 du Pont de Nemours announced that for improved processability of
acetate-capped POM it was blended with 5 wt % 1,4-butanediol-dimethylisophtha-
late-dimethylterephthalate-polytetramethyleneglycol copolymer (PAr) (Gale, 1978).
Five years later, the company disclosed a unusual method of impact modification of
polybutyleneterephthalate (PBT) by blending it with either POM or PA, and an
ethylene copolymer containing ester or acid functionality acting as a compatibilizer
(Sheer, 1982).
In 1989, Toray Industries disclosed four-eomponent blends comprising POM,
POM-eopolymer, an aliphatic polyester, and an aliphatic polyether. The copolymer
was prepared from trioxane, a cyclic ether (e.g., ethylene oxide), and at least one of
the monomeric species phenyl glycidyl ether, styrene oxide or naphthyl glycidyl
ether. The blends showed excellent processability, high crystallization rate, low
shrinkage, as well as good heat aging characteristics and mechanical performance.
PEST blends with specialty resins 379
The alloys were used to mold automotive, electric and electronic parts (Makabe et al.,
1991).
The following year, similar blends were disclosed by Asahi Chemical Company.
Thus, 5O-97wt% POM was compounded in a twin-screw extruder with an aliphatic
polyester resin. The blend showed good processability, paintability and surface
appearance (Niino, 1991). In another document from the company, preparation of
a polyester from aliphatic dicarboxylic acid, aliphatic diol and a semi-aromatic
dihydroxy compound was described. The resin could then be blended with any of
the engineering resins PA, PC, PPS, PPE or POM. The blends had high heat resist-
ance and good processability, as well as high impact strength and mechanical
performance (Doyama et al., 1991).
Also in 1990, du Pont de Nemours deposited a patent that described blends
comprising 5()...8{)wt% POM, IO-20wt% TPU, and IO-3Owt% of a semicrystalline
polymer (selected from between PA-612, PA-6, PP or PET), and an ethylene-butyla-
crylate-glycidylmethacrylate copolymer (EBA-GMA) (Subramanian, 1992).
The follOWing year Polyplastics Company described blends capable of providing
molded articles haVing exceptionally reduced surface gloss characteristics and able
to maintain the inherent mechanical properties and moldability. These alloys con-
tained 100 parts POM, with 1-50 parts of a polyalkylene terephthalate copolymer
(either modified PBT or PET, having processing temperature::; 210°C), and 0.1-10
parts of an isocyanate or isothiocyanate coupling agent. For example, PET and PBT
were modified incorporating not more than 30 mol % of either naphthalene dicar-
boxylic acid, isophthalic acid, and/or cyclohexane-dimethanol. The copolymer was
blended with POM, and either isophorone diisocyanate (trimer), or 4,4-methylenebis
(phenyl isocyanate). The alloys had good processability, making it possible to man-
ufacture parts with good mechanical properties and low gloss (Katsumata and
Matsunaga, 1993, 1995).
17.3 PEST BLENDS WITH SPECIALTY RESINS
17.3.1 PEST/polysulfide blends

Thermoplastic polyesters (PEST) are immiscible with polyarylsulfides (PAS or PPS)
and the blends should be compatibilized. The early, uncompatibilized blends pro-
vided advantageous performance within three (well known from other polymer
pairs) ranges of concentration: at 5-10wt% of the dispersed (either PPS or PEST)
phase, and at the phase cocontinuity concentration (determined by the relative
viscosity of ingredients, that existed at the compounding or forming conditions).
The first patent on PEST/PPS blends was deposited in 1976 by Sumitomo Chem-
ical Company. Thus, polyarylate (PAr) was blended with 1-99wt% PPS. The blends
were reported to have good processability, impact strength, fire and abrasion resis-
tance (Matsunaga et al., 1978). The following year, later similar blends, comprising
75 wt % PAr and 25 wt % RytonTM PPS, were disclosed by Hooker Chemicals and
Plastics Corporation. To the blends dodecachloro-dodecahydro-dimethano-di-
benzocyclo octene was also added. The alloys showed good hydrolytic stability,
moldability and flame retardance (Salee, 1980, 1981b).
Blends of polyphenylenesulphidesulfone (5-95 wt % PPSS) with either PEST or PA
were disclosed in a Toray Industries patent application in 1990. The blends of PPSS
with 95-5wt% of either PET, PBT, PA-6 or PA-66 were reported to have good
mechanical properties, high HOT, dimensional stability and excellent chemical
resistance (Ishio and Kobayashi, 1992).
The same year, in a series of patent applications from Ube Industries, compati-
bilized PPS/PEST blends were announced. Thus, 55-98wt% PPS, was blended with
45-2wt% PEST and with 1D--60phr of a copolymer containing 0.17-Q.20mg/mol of
epoxy groups, and with D--6O phr of acid anhydride groups containing copolymer.
The blends, with high strength and high impact strength, were used to mold auto-
motive, electronic, electrical or machine parts (Nishiyama et al., 1990, 1991). In a later
patent from the company, 1G-98wt% of PPS was blended with 2-90wt% of PEST
and a thermoplastic elastomer (3-60 phr TPE). The blends with good processability
were used to manufacture car, electronic and electrical parts, that had high impact
strength, and good flexibility and mechanical properties (Nishiyama and Nakakita,
1991).
Also in 1990, Tosoh Corporation announced that G-95 wt% PPS, was blended with
an aromatic thermoplastic polyester (G-95wt% PEST), and with 1-99wt% of a PPS-
PEST copolymer. The blends showed good processability, and mechanical properties
(Suenaga and Ishikuwa, 1991). Two years later, blends comprising poly(l,4-cyclo-
hexanedimethanolterephthalate) (PCT) and PPS, were described. Optionally, to
these alloys a mineral reinforcing agent (glass fiber, talc, mica, wollastonite or clay)
could be added. These materials showed excellent processability, and their moldings
had high unnotched impact strength (Gary, 1993).
17.3.2 PEST/polysulfone blends

Polyarylsulfone is a polymer of the general formula -(Ar-~)n-' where Ar stands
for an arylic group, that in most cases includes a phenyl-ether moiety +0-. The
first commercialized polyarylethersulfone (PAES) was Victrex™, introduced by ICI
in 1972. Other PAESs, for example Udel™ [+~-</>-O--4>-C(CH3)+O-ln and
Rndel™ [-¢r-O-¢>-~+4>-~-ln (both developed by Union Carbide - now avail-
able from Amoco), Astrel™ [+o-¢>-~+¢>-~-ln from Carborundum, Ultrason
E™ from BASF, Talpa™ 1000 from Mitsui Toatsu and Sumilite™ FS-13oo from
Surnitomo Chemicals soon followed.
In 1984 Union Carbide Corporation disclosed a large family of blends comprising
polyarylethersulfone (25 wt % PAES) of structure -[0-4>-O-¢>-~+lo.25n-(-0-</>-
~+lo.75n -, with either PAr, PEST, PC or their mixtures. The alloys were found
to have well-balanced mechanical properties and good environmental stress
cracking resistance (Robeson and Harris, 1985, 1986). In a follOWing patent, 6Owt%
PAES was blended with polyetheretherketone (40wt% PEEK). The blends had low
warpage and mold shrinkage, high tensile and flexural moduli, good stress cracking
and impact resistance, as well as a high heat deflection temperature of 157°C.
Mixtures of two different PAESs were reported miscible, transparent, suitable for
printed-circuit boards, and had good heat and solvent resistance (Harris and
Robeson, 1986, 1987).
Blends of PAES Udel™ with 4Owt% PET were disclosed by Amoco in 1991. The
alloys showed high HDT, good mechanical properties and flame retardancy (EI-
Hibiri et al., 1992). In an accompanying ~tent, a method for improving the flame
retardancy was disclosed. Thus, PSU Udel P17OO, was blended with ~ wt % PC
Lexan™ and 1G-35wt% PET Cleartur 7202. Synergistic flame retardancy was
achieved by incorporating a mixture of zinc borate (3-5 wt % ZnB03) with 5-
lOwt% polytetrafluoroethylene crack et al., 1993).
The same year, a patent application from USSR described blends suitable for
injection molding of articles where high performance, as well as good solvent and
chemical resistance were required, namely the aerospace, electronic or automotive
industries. The blends comprised 85-90wt% of a polysulfone (PSF), 5-lOwt% PC
and 5-lOwt% of either PET or PBT. For increased modulus and HDT, the alloys
could be reinforced with glass fibers (Militskova et ai., 1993).
17.3.3 PEST/polyimides blends

Polyetherimide (PEl) was commercialized by General Electric in 1982. In 1979 the
company applied for patent protection for blends comprising 2S % PEl with poly-
arylester (PAr). The blends showed good moldability and excellent mechanical
properties (Holub and Mellinger, 1981).
The same year, PEl blends with other polymers were announced. For example, in a
patent deposition from Union Carbide, PEl was blended at a 1:1 ratio with poly-
amideimide (PAl) to produce materials with good mechanical properties and excel-
lent environmental stress crack resistance (Maresca et ai., 1981). In a later document
from the company, polyarylethers were blended with polyetherimides (PEl) to give
good environmental stress cracking resistance (Robeson et ai., 1981). In 1982 Union
Carbide announced blends comprising PEl, PA-6 and PEI-PA block copolymer. The
resulting alloys showed improved moldability and impact strength (Robeson and
Matzner, 1984).
In a 1981 patent application from General Electric, polyestercarbonate (PEC)
was blended at a 1:1 ratio with either PEl, PA, PI, PAl or their mixtures, to give
alloys characterized by high HOT and tensile strength (Quinn, 1984). The following
year three-eomponent blends comprising PEl, PAr and 0-30 wt % PC were
announced by the company. The blends showed improved moldability, flexural
strength and modulus. The PC-containing blends had high heat, flame and impact
resistance (Holub, 1990; Holub and Schlicht, 1990). In 1984 the company developed
blends that contained 2Swt% PEl, SOwt% PET and 2Swt% PEe. The material had
good processability and impact strength similar to PEl (Quinn and Holub, 1986).
In a 1987 disclosure from General Electric, it was reported that addition of HIPS to
PC/PEl blends resulted in alloys showing excellent high temperature properties,
flexural modulus and impact resistance (Holub and Rock, 1989). In a patent applica-
tion dating from 1989, it was disclosed that addition of ABS to PEl/PEST blends may
further enhance impact resistance (Gaafar, 199Ob). High-molecular-weight poly-
esters derived from 1,4-cyclohexane-dimethanol have been available since the early
1960s. In a 1992 patent application from the company, blends of PEl as Ultem™, with
10-30wt% poly(cyclohexanedimethylenearylate), (e.g., PCT) were disclosed. The
alloys were prepared in a single-screw extruder at 290-340 0e. It was found that
the impact strength of these alloys was superior to that of either PEl or its blends
with PBT (Minnick, 1994).
In 1989 Sumitomo Electric Industries announced that when 100 parts of PEl were
blended with 5-S0 parts of PBT and lo-S0 parts of a crosslinking agent (comprising
triallyl cyanurate and triallyl isocyanurate), the resulting alloys showed high thermal
deformation resistance and HOT (Hosoi, 1991).
Besides PEST blends with polyetherimides (PEl) several patents described PEST
blends with others thermoplastic polyimides. For example, in 1982 PBT was blended
with 20 wt % polyglutarimide (PGI) obtained in reactive extrusion of PMMA with
CH3 NH2 (Toray Industries, 1983a).
A 1989 patent from Mitsubishi Rayon Company described blends comprising
1-99 wt % PEST, a methacrylimide-eontaining polymer (having at least lO wt % of
methacrylimide units), 1-99wt% PMI and O.05-lOphr of a compatibilizer, selected
from epoxy, oxazoline or isocyanate polyfunctional compounds. The blends
showed good processability and HDT (Yamamoto et al., 1990, 1991). In a contem-
porary deposition from Sumitomo Naugatuck Company, 5-SOwt% PEST, was
blended with a copolymaleimide (5-SOwt% CPMI), 1D-40wt% SAN and 1~
50 wt % ABS. CPMI was obtained by copolymerizing maleimide with acrylonitrile,
styrene and/or a-methyl styrene. SAN was a copolymer of acrylonitrile and a-
methyl styrene, while ABS was a rubber grafted with acrylonitrile and styrene. The
blends were used for molding automotive, electrical and office equipment parts, that
had high impact strength and HDT, and good chemical resistance (Abe and
Kodama, 1991).
17.3.4 PESTIPEA blends

Thermotropic polyesteramides (PEA) were developed in the late 1970s. The macro-
molecules were synthesized from 6-hydroxy-2-naphtoic acid, p-acetooxyacetanilide
and hydroquinone diacetate, combined in various proportions (Clundan, 1986). In
1981 it was discovered that blending 5-95wt% PEA with PET (or PA-6) resulted in
materials with excellent softness, fleXibility, dimensional stability and water resis-
tance (Toray Industries, Inc., 1982). In 1990, Eastman Kodak disclosed blends of PET
with PEA that were developed as material suitable for molding containers with
improved barrier properties (Cox et al., 1992).
17.3.5 PESTILCP blends

Blends of liquid crystal polymers (LCP) with other thermoplastic resins are dis-
cussed in Section 21.8; here only a summary of LCP/PEST blend evolution is
given. Orientation and stretching is crucial to the performance of LCP blends. The
orientation not only affects the form of the dispersed LCP phase, but also provides
molecular orientation within the LCP domains.
The first blends of PET with LCP were disclosed in 1980. The blends were reported
to have good processability and mechanical properties, a high HDT of 167°C and
economy (Celanese Corp., 1981, 1984; Kiss, 1986). Three-component LCP/PESTfPC
blends were announced in 1991 by Enichem America. The blends were prepared in
two steps, first blending PC with LCP, then adding PET (Cottis et al., 1993). In a
contemporary patent document from AKZO, 1-35wt% LCP (a block copolymer of
the type -[rodlx-[coilly-) blended with PET resulted in alloys suitable for spinning
highly drawn fibers with higher mechanical properties and lower shrinkage than
those of PET (Dashevsky et al., 1993, 1994). Addition of PhenOxyTM was also found to
prOVide good compatibilization of PEST with polyester-type LCPs.
17.3.6 PEST/inorganic glass blends

In 1989 Coming Incorporated announced a new class of inorganic low temperature
glasses (LTG). These materials are based on mixed alkali (Na, K, Li) zinc phosphate
with a structure resembling short-chain polymers, viz. -[-Zn-0-P(02Na)-0-
P(~Li)-0-P(~Na)-0-1-(Bahn et al., 1991; Bahn and Quinn, 1991). The new mate-
rials are durable, water resistant and, most importantly, have low glass transition
temperatures of 300-400 °C, which makes it possible to blend them with organic
polymers. These glasses can be extruded or molded in their own right. Furthermore,
it was discovered that the structure of the glass can be sufficiently modified to
control wetting and adhesion, thus ensuring that the dispersed LTG phase will
interact with the selected organic matrix (Frayer, 1993, 1994).
The LTGs have been blended with a diverse range of engineering polymers, such
as PET, PBT, PEK, PEEK, PPS, PEl, LCP or PC, as well as with fluorinated resins. The
blends containing up to 65 vol % of LTG were reported to have good mechanical
properties (Bahn and Quinn, 1991; Frayer, 1993, 1994). These systems have been
compounded and formed by regular polymer processing methods. Controlled injec-
tion molding can result in a variety of morphologies, such as spheres, fibers or
ribbons, with dimensions down to the nanometer range (without agglomeration),
smaller than that of any commercial glass fibers. The fine fibers and ribbons were
shown to be bent, twisted and entangled, providing for excellent reinforcement. The
systems also show low viscosity, hence they give the high speed moldability and
precision molding advantages. The technology makes it possible to generate fine
dispersion of the reinforcing LTG phase, to achieve good bonding between the LTG
and organic matrix and to control the shape of the dispersed phase.
In 1994 Corning introduced Cortem™ Alloys. The strategy for blending involves
tailor-making of the LTG, characterized by (1) specific interactions with the selected
polymer, and (2) matching its glass transition temperature. The first offerings were
of LTG blends with either a liquid crystal polyester (LCP or with PEEK). The alloys
comprised up to 80 wt % of LTG, forming a disperse phase. The blends were
reported to have high creep resistance, good flexural strength (up to 150MPa), and
low stress relaxation, as well as an exceptional elastic modulus (E = 14 GPa). In
addition, the moldings showed non-flammability, low smoke, low heat release,
excellent dimensional stability and high temperature performance - their heat
deflection temperatures were quoted as 280-300 0c.
18
Polycarbonate blends
Polycarbonate of bisphenol-A (PC) was rediscovered in the early 1950s (Schnell,

1956). Bayer's production plant started in Europe in 1959, whereas General Electric's
plant in the USA started in 1960 (Rubin, 1990). Nearly 30000 patents have been
issued for Pc. The annual world production is about one million tonnes. The most
popular polycarbonate is based on 2,2-bis (4-hydroxyphenyl) propane, better known
as bisphenol-A. It has Tg = 149°C and a processing temperature of 220-230 OC.
To improve the processability, impact properties and solvent resistance of PC, it
must be modified. Owing to its chemical nature, this task can be readily accom-
plished. The first PC blends with PO and those with ABS were developed in 1960.
The latter blends were commercially introduced in 1967 (Grabowski, 1964a). Other
PC alloys followed rapidly - PC was blended with polysiloxanes in 1961, PAES in
1965, PET in 1966, POM in 1968, PSF and ABS in 1969, PES in 1970, PBT in 1971, PA
or PPE in 1973, PPS in 1974, PS in 1976, styrene-maleimide (SMI) in 1977, polyaramid
(PARA) in 1979, etc. Dimensionally stable molding compositions containing PVC,
PC and an elastomer were patented in 1975 (Hardt et al., 1975).
18.1 PC BLENDS WITH COMMODITY RESINS
18.1.1 POpolyalkene blends

Blends of PC with polyalkenes (PO) are discussed in Sections 14.13 and 15.11.2. Here
only a brief summary will be given.
To increase the rigidity of PE, the polymer has been blended with several high-
modulus resins, including Pc. Since these early blends were not compatibilized,
5-lOwt% PC was usually used (Peters and Schuelde, 1963). PC is also known to
have a stabilizing effect on PO (PE or PP) against thermal degradation (Schutze et al.,
1972). At the opposite end of the concentration scale, there are the PC blends with a
small amount, usually 3-5 wt %, of PO (Yamada, 1963; Goldblum, 1963).
In the early 1970s, General Electric Company deposited several patents on com-
patibilization of PO/PC blends. Examples are: PC with 0.01-2wt% ABS and 4wt%
PE (O'Connell, 1974); with 1-40wt% PE, and selectively chlorosulfonated SEBS
(Bussink et al., 1978); with 2wt% LLDPE and 4wt% poly(butylacrylate-co-methyl-
methacrylate) copolymer (O'Connell, 1983); and either with 6wt% PP and 3wt%
LLDPE, or with 15wt% SBR and 5wt% EEA (Overton and Liu, 1984).
In the late 1970s, reactive blending of PC with either O.5-40phr LLDPE and 0.05-
1.5phr maleated LLDPE (Mitsubishi Chemical Industries Co., 1980b), or with
PC blends with commodity resins 385
EGMA, PE, acrylic and butyl elastomers (Sumitomo Chemical Co./ 1982/ 1983)/ were
described. These were followed in the early 1980s by multicomponent blends,
comprising pc/ polyester, PEST, PO and an impact modifier. Examples are: 2~
94.6wt% pc/ 0.2-15wt% PE, 5-SOwt% PET and 0.2-15wt% MBA as Acryloid™
KM (Endo and Ishii, 1984)/ and blends comprising branched polycarbonate with
polymers selected from PET, PBT, styrenics (HIPS/ ABS, SMA), PA-6, PA-66, PE, PP
and TPE (Kozakura et al., 1992).
Blends of PP with PC are at an early stage of development. It was reported that the
addition of about 5 wt % PP to PC reduces the melt viscosity (an interlayer slip), and
leads to enhancement of PP crystallinity. Only when the concentration of the minor
phase exceeded 10wt% was compatibilization necessary (Liang and Williams, 1991).
Also, blends of PC with a small amount of PP showed increased impact strength
(especially in thick sections)/ and reduced notch sensitivity and mold shrinkage
(Dobkowski, 1980).
For mid-range compositions, compatibilization is required. Different types of
(co)polymers have been explored, such as (meth)acrylic (co)polymers, SEBS,
maleated SEBS, EVAc, EVAI, EPDM grafted with styrene and acrylonitrile (AES),
maleated pp/ PS with oxazollne moieties, PP-PC-PP copolymer and PP grafted with
either styrene and acrylonitrile or with styrene and n-butylmethacrylate. For exam-
ple/ PC was blended with pp/ SBR, acrylic rubber and either EPR or EPDM, and
ID-45wt% Acryloid KM (Liu, 1984b; Overton and Liu, 1984b). PC was also blended
with 2-90wt% PP and 2-35wt% EVAc (Giles and Hirt, 1986).
18.1.2 PC/styrenics blends

Blends of PC with styrenics are discussed in Sections 10.5/10.6 and 10.9. Here only a
brief summary will be given.
Blends of polystyrene (PS) with PC are immiscible but, since many copolymers
show good affinity with both of these resins, modified blends of PS/PC were
developed relatively early. The first compatibilized and toughened blends of PC
with PS were developed in Mitsubishi Rayon laboratories in 1976-77. Thus PC was
blended with: (1) 20wt% SAN and lOwt% styrene-allylmethacrylate-butylacrylate-
methylmethacrylate; (2) SAN and 20 wt % multilayered copolymer from styrene,
allylmethacrylate, benzylacrylate and divinylbenzene (Kishida et al., 1978); or (3)
with ~94wt% ps/ 5-45wt% SAN and 1-30wt% styrene-grafted acrylic rubber
(Kamata et al., 1979). In 1976 PC was dispersed in water, then styrene was added and
subsequently polymerized, to give intimate PC/PS blends (Kanai et al., 1978). In 1978
PS/PC blends were compatibilized by addition of ~25wt% MBS (Lee, 1980b).
The first use of SEBS with PC was described in 1976 - addition of 30wt% SEBS
engendered cocontinuous morphology, with high modulus up to 140 DC (Figure 10.3
Gergen and Davison, 1977). In 1977/ blends of PC with polyethylene (l-40wt% PE)
and selectively chlorosulfonated SEBS were developed (Bussink et al., 1978). In a
1981 patent application, 8~97% PC was blended with 1-10% PE and 1-5% SEBS
(Idemitsu Kosan Co./ 1983). The same year, PC blends with 1-20 parts of either SBS,
EGMA or MBS were also reported (Sumitomo Chemical Co./ 1982/ 1983). The
following year, lQ-60wt% PC was blended with a mixture of SMA and SBS (Daicel
Chemical Industries, 1984). Also in 1981/ PC bends with either SB-teleblock and SEBS
(Lee 1983b) or with 3-25wt% SBS, and 2-20wt% acrylate polymer, AkryloicflM were
described (Liu, 1982/ 1984a). Two years later, PC was blended with 10wt% SEBS,
6 wt % EEA and 2 wt % LLDPE, for improved resistance to environmental stress
crazing and cracking (Liu, 1984b).
386 Polycarbonate blends
The PC/ABS blends are amorphous and show good dimensional stability, low
distortion and shrinkage, low moisture absorption, high softening point (Vicat B =
112-134 ec, increasing with PC content), stiffness and hardness comparable to that of
PC, good notched impact strength down to -so ec, and good electrical properties in
the low voltage/low power range. Since the mid-19805, these blends have become
increasingly important, as their properties fall between those of ABS and PC, and
their cost-to-performance ratio is low. By varying the composition and morphology
it is possible to tailor performance to requirements. ABS/PC alloys offer the proces-
sability of ABS together with the superior mechanical properties, impact and heat
resistance of PC. For example, by varying the component ratio the heat resistance can
be adjusted to fall within the range 80-113 ec. For processing, the ABS/PC blends
show excellent flow characteristics, especially at the high shear rates typical of
injection molding, making them suitable for thin-wall, complex parts.
The first, easy moldable ABS/PC blends were developed in 1960 (Dow Chemical
Co., 196Oa; Grabowski, 1964a). Commercial ABS/PC blends, with widely varying
compositions, were introduced in 1967. The blends are compatibilized by dipole-
dipole interactions between PC and SAN, particularly evident in alloys with SAN
having at least 25% AN (Keitz et al., 1984; Morbitzer et al., 1985; Kress et al., 1986; Kim
and Burns, 1988). When the PC-SAN interactions are insufficient, modification of
ABS by incorporation of either acrylic, acidic or epoxy groups can provide an easy
solution.
By the mid 196Os, multicomponent PC/ABS blends started to be developed: PC,
ABS and a grafted butadiene-acrylate elastomer (Grabowski, 1964a); PC, ABS and
styrene-o-methylstyrene-acrylonitrile, MSAN (Grabowski, 1970, 1971, 1972); PC,
PAES and either ABS or MBS (Yamauchi et al., 1974); PC, ABS and 1Q-45wt%
polyethersulfone (PES) (Weaver, 1972); PC, ABS and EVAc (Hasegawa et al., 1974);
PC, ABS and PMMA (lkura et al., 1974); PC, PVC and ABS (Hardt et al., 1975;
Mietzsch et al., 1975).
Easy-to-mold, impact-resistant PC alloys were prepared in 1976 by blending PC
with a variety of skin-core copolymers (Sakano et al., 1978). In the beginning of the
19805 the reactive blending of PC/ABS started to dominate the technology. Two
methods have been used in parallel: (1) the introduction of acid or acid anhydride
units into ABS (maleic anhydride, acrylic acid, glycidylmethacrylate, etc.), and (2)
preparation of multicomponent blends comprising PC, ABS and acid-group-contain-
ing copolymer, such as PC with either ABS or ASA, and with either SMA or a
styrene-maleic anhydride-acrylic acid (SMA-AA) copolymer. The following systems
may serve as examples: (1) PC was blended with styrene-methylmethacrylate-gly-
cidylmethacrylate copolymer (SMM-GM), then styrene and acrylonitrile were
polymerized in situ; (2) PC was blended with SMM, a three-stage copolymer
(styrene-diallylmaleate-butadiene-methylmethacrylate); (3) PC was blended with a
copolymer prepared by dissolving SBR in styrene, maleic anhydride and acrylo-
nitrile, the solution was polymerized; (4) PC was compounded with SEBS and SMA
(Daicel Chemical Industries, 19813, 1983, 1984).
In the 198Os, several patents described three-component alloys of great commer-
cial interest comprising ABS or ACM, PC and a thermoplastic polyester, PEST (Bier
and Indner, 1982; Neuray et al., 1982; Nouverte et al., 1982; Serini et al., 1982; Wefer,
1984, 1988; Chung et al., 1985).
In 1983 a patent for blends containing PC, ABS and SMMA-MA Oones and
Mendelson, 1985) provided the base for the development of highly successful
Triax™ 2000. Ten years later, in April 1993 the company commercialized Triax™
XP40 comprising ABS/PC blended with PET. PC was also reactively blended with
PC blends with commodity resins 387
ABS, SAN-GMA and NBR (Lindner et al., 1985), or with graft acrylonitrile-buta-
diene-o:-methylstyrene-methylrnethacrylate (MeABS) and acrylonitrile-o:-methylsty-
rene-methylrnetha,grlate copolymer (MeSAN) (Kress et al., 1986), providing the
basis for Bayblend resins. In 1991 blends containing PPS, PC, PPE, ABS and a
multiphase copolymer, either styrene-glycidylrnethacrylate (SGMA) or ethylene-
glycidylrnethacrylate (EGMA), were described (Orikasa and Sakazume, 1992).
In 1992 General Electric Company disclosed PC blends having reduced gloss.
The alloys comprised PC with either styrene-acrylonitrile (SAN) or acrylonitrile-
butadiene-styrene (ABS) copolymer. The latter, moldable resins were blended
with 1-90wt% of a gloss-reducing acrylonitrile polymer containing gels. Consistent
quality products were obtained with reduced yellowness and gloss (Wildi et al.,
1994).
The PC/ABS blends are available from numerous sU.f8liers: Baybiend™ from
Bayer, Puise™ from Dow Chemical Corporation, Cycoloy from General Electric,
RyuIex™ from Dainippon Chemical, Lastiiac™ from Lati, Terblend™ B from BASF.
18.1.3 PC/acrylics blends

These systems are described in Section 13.2.6 - here only a synopsis is given here.
Initially, the PC/PMMA blends were not considered miscible, thus transparency
was not an issue. Since both resins require toughening, their blends were usually
impact modified, for example with ABS (Ikura et al., 1974; Sakai et al., 1975),
poly(acrylate-co-styrene-co-acrylonitrile) terpolymer, ASA (Giles and Sasserath,
1986), etc.
Polycarbonate has been also toughened by incorporation of an acrylic elastomer.
For example, in 1971 Texaco developed impact-modified PC by blending the resin
with 3-35wt% of a high molecular weight polybutylacrylate (PBA; MW = 100-
2000 kg/mol) (Holder et al., 1973, 1976).
The most important type of alloy that belongs to the PC/acrylics category is that
comprising PC with acrylic impact modifiers, such as either acrylic-modified ABS, or
the core-shell elastomers (PMMA-g-polybutadiene, PMMA-g-SBR or PMMA-g-n-
butylacrylate). The modifiers usually contain small well-dispersed elastomeric par-
ticles with an average diameter of ~ 100nm. They are known to improve both the
thick-section, and low temperature notched !zod impact strength of PC (Witman,
1981; Neuray and Ott, 1981). The affinity between PC and acrylics has long been
known, thus use of acrylic elastomer has been relatively straightforward. The ques-
tion was only as to which of the many possible copolymers will produce the best set
of properties. In a series of patents from 1979, PC was blended with rubber-modified
SMA and ABS, or with styrene-acrylic acid copolymer, styrene-acrylic acid co-
polymer, and ethylacrylate-methylrnethacrylate (EAMM) (Henton, 1980, 1982,
1983, 1984).
Although PC's affinity to acrylates has been widely recognized (Kyu et al., 1991),
only in 1986 was PC miscibility with polymethylrnethacrylate (PMMA) commer-
cially explored. A General Electric patent described blends of PC/PMMA having the
lower critical solubility temperature (LCST) above 140 0c. Furthermore, modifying
the PC chain ends increased the LCST to 300 °C, making it possible to compound and
process these blends as a single phase resin. The blends have been used for glazing
materials and optical disks (Kambour, 1988). In 1991 another patent application was
filed for miscible PC blends with an aliphatic polyester of neopentyl glycol. These
blends were also reported to possess good optical properties and impact strength
(Lundy et al., 1991).
18.1.4 PClPVC blends

Blends of polyvinylchloride (PVC) with PC are discussed together with other PVC
blends in Section 11.9.6. These materials are characterized by good heat and flame
resistance, as well as dimensional stability. Since both resins require toughening,
ABS has been usually added (Hardt et ai., 1975; Mietzsch et ai., 1975). Recently,
blends comprising PVC, and PC containing at least 15 wt % of bishydroxyphenyl-
hexafluoropropane (6F-PC) were reported miscible (Drzewinski, 1993a, 1994a).
18.1.5 PCffPU blends

Thermoplastic polyurethanes (TPU) were invented by Otto Bayer in 1937. In the USA
they were commercialized in 1946 (Schollenberger et al., 1958). Although the resins
are popular components of blends containing PVC, POM, PEST or PA, with PC they
are less common. However, PC/TPU alloys have been explored by several com-
panies including Bayer, Dow Chemical and Corvita Corporation. They were found
to show good mechanical strength, solvent, environmental stress cracking and
impact resistance. With the introduction of the polyester-urethane TPUs, blending
with PC became easier.
Texin™ 3000 and Texin™ 4000 (with polyester-urethane being the matrix in the
first and dispersed phase in the second blend), are commercial blends of PC/TPU
from Bayer. The blends are designed mainly for extrusion or injection molding, but
they may be thermoformed, compression, transfer or blow molded as well. Applica-
tion of these alloys depends on composition, thus Texin™ 3000 is used for produc-
tion of gears, sleeves, tubing, housings, top-lifts and extruded profiles, whereas
Texin TM 4000 is used for the manufacture of articles used in automotive cladding,
fascias, bumpers and a variety of extruded and injection molded consumer goods.
In a series of 1987 patents from General Electric, PC was modified by blending
with: siloxane and elastomers (to improve the impact resistance); either SEBS and
acrylate elastomers or with polyurethanes (to enhance the solvent resistance); ethyl-
ene and acrylate copolymers (to improve impact and solvent resistance); and block
polyester-polyoxyalkylene (to improve fluidity and processability) (De Boer and
Heuschen, 1988; Liu and Ishihara, 1988; Boutni, 1988).
In. 1990 Corvita Corporation developed PC/TPU blends for crack-resistant med-
ical and industrial uses (Pinchuck, 1991).
In 1989, the Dow Chemical Company disclosed that PC was blended with TPU
to enhance mechanical behavior, as well as the solvent, environmental stress
cracking and impact resistance (Skochdopole and Wright, 1990). The following
year the company announced multicomponent blends that comprise 6Owt% PC,
20 wt % PET, glycidylmethacrylate copolymer (5 wt % EVA-GMA), thermoplastic
polyurethane elastomer (5wt% TPU) and, optionally, a graft copolymer of the
core-shell type and/or lOwt% ABS. Talc, clay and mica could also be added.
These moldable blends had good flexural modulus, strength, weldline strength,
solvent resistance and impact behavior (Laughner, 1994). In 1991, blends of
35-65 wt % PC, with a thermoplastic polycaprolactone-polyurethane resin
(35-65wt% TPU, Pellethane™) and 1-20wt% impact modifier (e.g., methacrylate-
butadiene-styrene (MBS) or methylmethacrylate butylacrylate rubbers (MBA,
Paraioid™) containing 45-90 wt % elastomer) were described. The alloys had excel-
lent processability, heat resistance, flexibility, solvent resistance and low tempera-
ture toughness. They were suitable for molding articles such as bumper fascias
(Henton et ai., 1993).
PC blends with engineering resins 389
18.2 PC BLENDS wrm ENGINEERING RESINS
18.2.1 PCIPA blends

Blends of polycarbonates with polyamides (PC/PA) are discussed in Section 16.3.6;
here only a summary is given.
Blending PA with polymers containing carbonic ester linkages poses similar
problems to those for blends with PEST, i.e., the blends are immiscible, their melt
viscosity is low and they are susceptible to thermal and hydrolytic degradation, as
well as to reaction between the ester and amide groups. 1bis lowers PA crystallinity,
which in turn results in brittle material with poor impact properties. There were
reports that addition of PA to PC may lead to crystallization of the latter resin, which
tends to further increase the brittleness. In short, PA/PC blends must be alloyed, i.e.,
compatibilized and toughened.
The first PA/PC blends date from 1973 when Mitsubishi Gas Chemical Company
developed PC blends with either lo-20wt% PA-12, or another resin selected from
other engineering and specialty polymers, such as PSF, PPE or PET (Okuzono and
Kifune, 1975, 1976). In several patents, strong effects on blend performance by
hydrogenated styrene-diene block copolymers (SEBS) were reported. In 1977 Shell
Oil announced that properties of PA/PC blends can be significantly improved by
incorporation of 15wt% SEBS (Gergen and Davison, 1978).
The first reactive compatibilization of PC/PA blends dates from 1981, when about
equal amounts of PC, PA-6 and SMA were compounded together (Dainippon Ink
and Chemicals, 1983). In a 1986 patent application from Dexer Corporation, blends
comprising PC, PA, polyesteramide, an elastomer and a maleated polyalkene were
described (Perron, 1988). Two years later the company introduced Dexcarb™.
In 1987 PA/PC blends were compatibilized by addition of a glycidyl methacrylate
graft copolymer, either an EGMA (Yuichi and Suehiro, 1989) or AB5-GMA (Yasue et
ai., 1989). The same year General Electric disclosed PC/PA blends, comprising PC
end-capped with anhydride groups and 20wt% of an acrylate styrene core/shell
impact modifier (Hathaway and Pyles, 1988, 1989).
In the 1990s blend complexity increased. For example, Dexer Corporation
blended PC with PA-6, PEl and/or TPU, butyl glycidyl ether, a thermoplastic
elastomer, an epoxy ether and maleated EPR (Perron et ai., 1993). Idemitsu Petro-
chemical mixed branched polycarbonate (bPC) and at least one polymer selected
from PET, PBT, styrenics (HIPS, ABS, SMA), PA-6, PA-66, PE, PP and TPE (acrylic
rubber, butyl rubber, EPDM or SBS) (Kozakura et ai., 1992). Bayer compounded
either PC or PEC with PA-6, an acrylic copolymer and an acrylic elastomer (Heger
et ai., 1992).
18.2.2 PClPEST blends

The PEST/PC blends are discussed in detail in Section 17.2; here only a summary is
given.
Blends of PC with thermoplastic polyesters (e.g., PET or PBT) constitute an
important category of commercial blends. Owing to possible transesterification, the
system does not necessarily require additional compatibilization. However, control-
ling the extent of co-reaction is critical- too much of it eliminates crystallinity of PET
or PBT, reducing the mechanical performance as well as solvent and chemical
resistance, whereas too little leads to instability of morphology and to brittleness.
As a result, modem blending relies on reactive compatibilization rather than trans-
esterification. Furthermore, the blends require toughening, thus compatibilization is
usually combined with impact modification, which improves the overall perfor-
mance of the alloy.
Although PC/ABS blends show high heat distortion temperatures and good
impact strength at low temperatures, alloying PC with thermoplastic polyester
(PEST) results in increased rigidity and improved resistance to chemicals and
fuels. The three-component blends are characterized by a set of properties to
which each component contributes, namely excellent impact strength at room and
low temperature (contribution from PC and elastomer, respectively), low softening
temperature (contribution from PC and PEST), and good solvent resistance (con-
tribution from semicrystalline PEST). The main advantage of these blends is the
lower susceptibility to stress cracking on contact with fuels than that of PC.
The commercial PC/PEST blends usually contain either PBT or PET, and
lO-20wt% of an impact modifier. In most blends PC is the matrix. The impact
modifier can be based on either PE, ABS or an acrylic copolymer. For example,
MakrobleruJTM from Bayer is a PC/PET blend modified by addition of either HDPE
or ABS, Sabre™ from Dow Chemical is an impact-modified blend of PC with either
PET or PBT, Stapron™ E is a blend of PC with either PET or PBT and polybutadiene,
PB, while Ultrablentf"M KR from BASF is a PC/PBT/ ASA system. The blends have
been developed mainly for injection molding, but grades for extrusion and blow
molding as well as transfer or compression molding, solid state or thermoforming
are also available. The blends show good processability, high heat resistance, duct-
ility, HOT, high modulus, impact, tensile and flexural strength over a wide tempera-
ture range, fatigue endurance, abrasion resistance, dimensional stability (due to low
shrinkage and minimal water absorbency), high gloss, good adhesion, solvent, salt
spray, biological and chemical resistance. They can be painted, hot stamped, meta-
lized and plated.
The PC/PEST blends are mainly used in automotive industry for body panels,
dashboards, pillars, roof claddings, headlamp housings, luggage racks, etc. They are
also used in outdoor power equipment (tractor or lawn mower shrouds, consoles,
grilles or trim equipment parts), recreational applications, for the manufacture of
consumer goods (vacuum cleaner housings and nozzles, utility locks, protective face
guards, beverage containers, dishes, food transport bins, dinnerware, mixing bowls,
salad tongs, swimming pool pump housings), telecommunications (radio housings,
speakers, instrument housings) and many other applications.
The first patent application for PC/PEST blends dates from 1966, when Bayer
disclosed PC blends with 1-5wt% PET for improved stress corrosion resistance
(Cziesla and Bottenbruch, 1975). Three years later Teijin Chemicals developed PC/
PET blends haVing a component ratio of 1:3. The application specified that the
materials must be blended under nitrogen at 240 °C for 6 h. As a result of transesteri-
fication, the material showed improved impact resistance and elongation, without a
loss of crystallinity or a decrease of the melting point (Horiuchi and Karniya, 1974).
Similarly, a method of compatibilization involving 6 h mixing at 120°C of PC with at
least SO wt % PBT was proposed by the company in 1971 (Matsukane and Azo, 1973).
The same year, Unitika applied for patent protection for blends of 5-90 wt % PC and
less than SOwt% of either PET or PAr. The blends were reported to have good
moldability and impact strength (Koshimo et al., 1973). In another patent, blending
PC with PAr at a ratio 1:1 gave easily moldable alloys with excellent mechanical
properties (Unitika Ltd, 1983b). In a Sumitomo Chemical patent PAr was blended
with 99-1 parts of PC, to give materials having an excellent set of properties
(Fukushima et al., 1979a).
These early two-component PC/PEST blends had little commercial consequence,

as the required long cooking time at low temperature made them expensive. Further-
more, the transesterification is sensitive to the presence of metallic salts, which
makes the process difficult to control.
In 1972 Teijin Chemicals discovered that three-component blends, such as
4O-63wt% PBT, 27-47.5wt% PC and 5-20wt% core-shell impact modifier, methyl-
methacrylate-butadiene-styrene graft copolymer (MBS), are easy to compound, and
show good processability, chemical resistance and impact strength (Nakamura et al.,
1974; Yamamoto and Shimizu, 1979). A similar approach was adopted by MitSubishi
Rayon, who in 1977 announced PET/PC blends with a butylacrylate-styrene-triallyl
isocyanurate-g-methylmethacrylate-styrene (Kamata et al., 1978a). PBT/PC blends
with AES were developed by Sumitomo Naugatuck Co. (1983), and Uniroyal (Wefer,
1984, 1988).
BASF developed PBTfPC blends with either ethylene-acrylic acid-butylacrylate
(Portugall et al., 1984) ethylene-n-butylacrylate-acrylic acid, ethylene-n-butylacry-
late-glycidylmethacrylate, SAN-grafted n-butylacrylate, or polybutadiene grafted
with styrene and methylmethacrylate (Lausberg et al., 1987). Ultrablend™ is the
PC/PBT blend commercially available from the company.
In 1978 General Electric announced blends of PBT with PET, PC, and either SEBS
(Wambach and Dieck, 1980), or (SB)n and butadiene-caprolactone-styrene (Dieck,
1980). Later, PBT was blended with PC, LLDPE and either MBA (Boutni and Liu,
1983), or Aeryloid KM 330 (Hepp, 1984). These discoveries led to the highly successful
XenoyTM series of polymer alloys.
Blends of PET with PC, and core-shell butylacrylate-butylenediacrylate-diallyl-
maleate-methylmethacrylate were formulated for injection molding in R6hm & Haas
laboratories (Fromuth and Shell, 1981). In a Montedison patent, PBT was blended
with PC and poly(styrene-eo-o-methylstyrene-eo-acrylonitrile-eo-butadiene) copoly-
mer for good moldability, mechanical properties and heat resistance (Biglione and
Fasulo, 1983). Bayer blended PET and/or PBT with PC, and either a graft copolymer
(polybutadiene grafted with (meth)acrylate esters, and acrylonitrile - an acrylate
rubber, ACM or ABS) (Bier and Indner, 1982; Neuray et al., 1982; Nouverte et al.,
1982; Serini et al., 1982), or EVAc (Weyer et al., 1984). This work led to the commer-
cialization of Makroblend™ alloys.
Another important step in the evolution of PC blend technology was the introduc-
tion of reactive blending. For the PC/PEST blends this meant incorporation of a
reactive impact modifier. In 1982 General Electric used the acrylic impact modifier
Aeryloid KM (Allen et al., 1984), while others used an elastomer containing acidic
groups (TaJmer™ A 20090) (Mitsubishi Chemical Industries Co., 1983b), ethylene-
ethylacrylate-maleic anhydride copolymer (EEA-MA) (Natarajan and Arjunan, 1993).
18.2.3 PClPPE blends

Blends of polyphenylene ether (PPE) with polycarbonate (PC) were first patented by
General Electric (Fox, 1965). The patent described variations of the heat deflection
temperature over the whole range of PC/PPE compositions. The two resins are
immiscible and brittle, thus they must be compatibilized and impact modified.
Owing to the similarity of the chemical structure of PC and PEST, the methods
developed for PPE/PEST blends should be useful for blends of PPE with PC.
However, PC has been mainly used as a minor component in multicomponent
PPE/PEST blends, whose role is to provide a barrier against shear coalescence, Le.,
stabilization of morphology.
In 1971 Asahi-Dow developed PPE blends with 0.5-20wt% of either polystyrene
(PS) or poly(methylrnethacrylate-co-styrene) (SMMA) then adding either PC, PEST,
acrylates or Phenoxy (Izawa and Nakanishi, 1973; Izawa, 1974). Two years later,
Mitsubishi Gas Chemical Company disclosed blends comprising PC (10-80 wt %
PA-12), and either PSF, PPE or PET. The blends had good moldability and mechan-
ical properties. They showed pear-like gloss, good high voltage arc and antitracking
properties (Okuzono and Kifune, 1975, 1976). In a contemporary patent disclosure
from the company, PPE was blended with styrene- and chlorostyrene-grafted poly-
butadiene (SBR) and PC. Blends had good moldability, impact strength, fatigue and
tensile strength, as well as high HDT (Yonemitsu et al., 1974).
In 1984 Borg-Warner Chemicals disclosed blends of a polyphenylene ether copoly-
mer (lOwt% PPE) with 90wt% PC. The alloys showed better processability,
toughness and heat deflection temperature than those containing PPE homopolymer
(Falk and Khait, 1984).
In 1985 General Electric announced development of blends containing ID-45wt%
PPE, ID-45wt% PBT, 8-25wt% SEBS and 3-40wt% Pc. Note that here SEBS is the
impact modifier only for the PPE dispersed phase, whereas PC forms an intermedi-
ate layer around it, acting as a compatibilizer (because of transesterification with
PBT) and stabilizing the morphology. The alloys showed good processability, high
impact strength and solvent resistance (Brown et al., 1987). This patent is but the first
in a series of disclosures of blends comprising PPE, with SEBS, PEST and PC. During
the next lO years, many variations on this theme have been patented.
The following year, the company disclosed blends of ID-65wt% PPE, with
lQ-75wt% HIPS, 2-10wt% PEST, PC, SBS, and a styrene polymer having reactive
2-oxazoline groups (1-25 wt % PSOX). The alloys showed improved impact strength
over those of prior art, with a favorable combination of properties, such as mecha-
nical strength, resistance to chemical solvents and flow properties in the melt
(Avakian et al., 1988). In 1987 the company deposited patent disclosures for
blends comprising 20-40wt% PPE, 25-75wt% of either PBT or PET, 8-25wt%
SEBS, 5-40wt% PC and, if high modulus was required, mica (Yates, 1987, 1989).
The blend, Gemax™, had improved impact and solvent resistance, excellent surface
finish and a low coefficient of thermal expansion.
In 1987 General Electric disclosed grafting PPE with unsaturated dicarboxylate
that subsequently was used in blends. For example, fumaric acid-grafted PPE was
reactively blended with PC and SEBS. Good mechanical properties with low gloss
were obtained (Ishihara, 1989). In later patents, PPE (having a low concentration of
non-neutralized amino nitrogen) was reactively blended with PC and PBT. A wide
variety of desirable tensile properties were obtained by varying the compositions.
The solvent and impact resistance were enhanced by grafting PPE with dimethylsi-
loxanes and SEBS (Brown, 1989; Brown et al., 1992). The following year, high impact
strength blends of PPE with PEST were obtained by compounding these resins with
PS, PC, SEBS and/or an acrylic impact improver (MBA) (Yates and Lee, 1990).
In 1989 General Electric disclosed another modification of PPE blends with PEST,
incorporating 5-25 phr of a copolymer of bisphenol-A polycarbonate (3-20 wt %) and
polybutyleneterephthalate (PC-PBT). The blends could also contain up to 21 wt% of
an elastomeric impact modifier, such as SEBS Kraton™ G-1651. Excellent rigidity and
impact strength were reported (Chambers et al., 1995). Next year, 15-50wt% PPE
was blended with 20-60 wt % PBT and 15-30 wt % of a block copolymer of the A-B-A
type (where A is PC and B is PS block, preferably with PC:PS = 1:1). The composi-
tions may also contain up to 25wt% impact modifier, such as Kraton™ G, D, RTM or
a core-shell type, and not more than 10wt% PC (Brown and Fewkes, 1992, 1994).
PPE blends with PEST, were also modified by addition of fatty acid amides that
improved blend processability, and enhanced its low temperature ductility. Thus,
30 wt % epoxy- or phosphate-functionalized PPE, was blended with 46 wt % of either
PBT or PET, palrnitamide, 1-3Owt% SEBS and 1-3Owt% PC (Yates, 1993).
Also in 1990, Teijin Chemicals announced the blending of 10-1oowt% PC, with
9O-Qwt% of another polymer selected from PS, POM, PA, PEST, PPE, PSF or PO.
The blends were compatibilized by addition of 5-1oophr of a block copolymer,
composed of PC-b-PO, for example. The alloys showed good processability and
chemical resistance (Hashimoto et al., 1991). The same year, Dow Chemical Com-
pany disclosed blends comprising 55-75wt% PC, with 1--8wt% PPE, 10-57wt%
PET or PBT, and 1-15wt% of elastomeric impact modifier (such as Kraton™ G, a
core-shell grafted copolymer, or EPR) to give balanced impact properties,
HDT :S 295°C and good chemical resistance (Laughner and Farah, 1992).
In 1992, BASF announced that blends prepared from 5D-90 wt % PC, 3-25 wt %
PPE, 3-25wt% elastomeric graft copolymer (e.g., polybutylacrylate grafted with
styrene and acrylonitrile), 3-40wt% SAN, 1-20wt% PS, 0-20wt% phosphate esters,
0-2 wt % PTFE and 0-25 wt % SEBS were fire resistant, with a good set of mechanical
properties and HDT. The ingredients were compounded at 260 °C in a twin-screw
extruder, then injection molded (Niessner et al., 1993).
Also in 1992 Dow Chemical developed multicomponent blends, prepared in two
parts: (1) PC/PEST with not more than 5wt% of a copolymer (e.g., ABS-type with
alkyl(meth)acrylates, glycidylmethacrylates, ethylene/propylene/diene copolymer,
maleic anhydride, alkyl or aryl maleirnides and oxazoline); (2) PPE, and/or a blend
of PPE with either PS, HIPS, SEBS, PA, PC, PEST or polyalkyl(meth)acrylate. Parts 1
and 2 were compounded together and molded. The blends had low gloss even when
molded at high temperature. They were used to manufacture instrument and appli-
ance housings, car panels, radio components (Laughner, 1993). In a later patent, PC/
PET blends were impact modified by addition of glycidyl methacrylate. The systems
showed good flexural modulus, weldline strength and solvent resistance (Laughner,
1994).
18.2.4 Pc/pOM blends

Blends of polycarbonate with polyoxymethylene are immiscible and, since both
resins require toughening, the blends should be not only compatibilized but also
toughened. Addition to amorphous PC of a semicrystalline paM improves the
solvent and chemical resistance. The paM/PC blends are not yet on the market,
and only a few significant patents on these systems have been deposited.
For example, in a Baychem patent deposited in 1968, PC was blended with paM to
improve its solvent resistance (Miller, 1972). In 1989, Dow Chemicals disclosed that
PC blends with paM and thermoplastic polyurethane (TPU) are easy to mold into
articles having high impact strength (Silvis et aI., 1990). The following year, Teijin
Chemicals announced a new category of blends, comprising 10-1oowt% PC and
9D-Owt% of another polymer selected from PS, paM, PA, PEST, PPE, PSF or PO.
The blends were compatibilized by adding 05--100 phr of a polycarbonate-polyal-
kene block copolymer (PC-b-PO). The alloys had good processability and chemical
resistance (Hashimoto et al., 1991).
In 1991, Bayer disclosed an aliphatic-aromatic polyether-b-polycarbonate, (POM-b-
PC) that could be used either as a modifier of performance of such polymers as PES,
PEEK, PA, PAN or as a compatibilizer (Dhein et al., 1993). Next year, blends
for molding laser recording disks were developed by BASF. The alloys contained
4O-99wt% POM homo- or co-polymer, 1-30wt% PC, D-SOwt% impact-modifying
polymer, and D-SOwt% filler. The moldings could be marked with radiation using a
Nd/YAG laser. They showed good surface structure and good contrast between
markings and background (McKee et ai., 1994).
18.3 PC BLENDS WITII SPECIALTY RESINS
18.3.1 PGsiloxane resin blends

The first blends of polycarbonate (PC) with polydimethylsiloxane (PDMS) were
patented in 1961 by Osaka Kinzoku Kogyo. Thus, PC was solution blended with
PDMS, then cast into homogenous films that had good physical, chemical and
electrical properties (Caird, 1961).
In 1986 Mitsubishi Rayon Company disclosed blends of either PC, or its mixtures
with PEST (e.g., with either PET, PBT or a PET-PBT copolymer), with 0.5-60wt%
siloxane-based vinyl-grafted copolymer. The blends had good chemical, weather,
and low temperature impact resistance (Hongo et ai., 1987).
In the early 1990s, the General Electric Company deposited a series of patents for
blends of PC with polysiloxanes. Thus, in 1991 blends of PC with polyaryloxysilox-
anes, e.g., poly(dimethylsiloxybiphenyleneoxide) (PArSi), were announced. The
blends were transparent and flame resistant, with excellent mechanical properties
and impact strength Gordan and Webb, 1992). In another document, blends of PArSi
with either PPE, PEST, PC or PEl, and with SBS were described. Incorporation of
PArSi was found to provide good flame retardance. In many cases, the flame-
retardant blends were found to exhibit improved chemical resistance, impact resis-
tance and improved HDT, in comparison to the neat polymers. For example, PBT
was rendered flame resistant by blending it with an equal amount of PArSi Gordan
and Webb, 1994). In 1991 the company also announced blends comprising polycar-
bonate-poly(dimethyl)siloxane block copolymer and either 5D-95wt% PC, or poly-
estercarbonate (PEC). The alloys showed low flammability and good impact strength
over a wide temperature range (Hoover, 1993). The same year, blends comprising
75-99 wt % PC and a multi-stage, elastomeric polyorganosiloxane/ polyvinyl-based
graft copolymer (containing, for example (meth)acrylates, styrene and acrylonitrile)
were announced. This method was also found to generate thermally stable, low-
temperature ductile, impact- and heat-resistant alloys (Derudder and Wang, 1993).
18.3.2 PClPSF blends

There is a great diversity of commercial polysulfones, haVing different molecular
structures and properties. Since there is frequently confusion with the abbreviations,
the blend properties must be considered wherever possible in relation to the mole-
cular structure of the components.
The first polysulfone of bisphenol-A (PSF, also abbreviated as PSU or PSO),
was commercialized in 1965 by Union Carbide, initially as Bakelite Poiysulfone,
then as Udei™, with T g = 190°C. The resin was a condensation product of the
disodium salt of bisphenol-A and 4,4'-dichlorodiphenylsulfone, having the struc-
ture: [-rP-C(CH3h-tj>--CHp-S02-<P--O-1n' In 1971 Astrei™ polyarylethersulfone
(PAES) with T g = 288°C and structure [+4>-~-¢r-O--4r-SOdn was introduced
by 3M Company. The follOWing year Imperial Chemical Industries commercialized
polyethersulfone (PES) with T g = 228-232 DC, under the trade name Victrex™. The
resin is a condensation product of the dipotassium salt of 4, 4'-dihydroxydiphenyl-
PC blends with specialty resins 395
sulfone and 4,4'-dichlorodiphenylsulfone, with structure (+SCh-</r-O-)n. In 1976
Union Carbide introduced polyphenylethersulfone (PPSF) with Tg = 220°C and
structure [~SCh-</r-O-ln' Radei™ R. Another PAES was introduced
by Amoco as Radei™ A, with structure [--<::HP-SCh+ln-[-"(~<hfr-lm and
Tg = 217°C. In 1986 Celanese commercialized polyimidesulfone (POO) and the
following year Oainippon Ink & Chemicals came up with polythioethersulfone
(PTES) as Amoroon™.
The first blends of PAES with 1-99wt% PC were announced in 1965. Blending
induced improvements of the impact and tensile strength, as well as elongation at
break (Union Carbide Corp., 1966). Similar blends were disclosed 4 years later by the
Sumitomo Chemical Company. Thus, PC was blended with 1-99wt% PAES, then
toughened by adding either a butadiene-methylmethacrylate-styrene, 1-90 parts
MBS, or an ABS. The blends had good heat and impact resistance (Yamauchi et ai.,
1974). In a contemporary patent application by Borg-Warner, PC was blended with
polysulfone (PSF) at a ratio of 1:1, and then with 10-90wt% ABS. Good impact and
tensile strength, and high HOT were reported (Grabowski, 1971). In the following
patent, an addition of 5-40 wt % halogenated norbornene methano-naphthalene
compounds to these blends was reported to further increase their heat deflection
temperature (Grabowski, 1972).
In the early 1970s, Uniroyal deposited a series of patents for blends of polyaryl-
ethersulfones (PAES). Thus, in 1970 blends comprising 1Q-45wt% PAES with
10-50% PC, and ABS were described as showing good processability, HOT and
impact strength (Weaver, 1972). Two years later, the company developed PAES
blends with 2-25 wt % epihalohydrin rubber (CHR) for good impact and fire resist-
ance (Lauchlan and Snodgrass, 1973).
In 1977 Bayer announced blends of PSF with 20 wt % PC. Both linear and branched
polymers were used. The blends showed similar mechanical properties to those of
PSF, but better solvent resistance than either one of the components (Binsack et al.,
1979). In 1980 General Electric developed blends of copolyester-earbonate (PEe)
with 50 wt % PSF. The alloys were reported to show high impact strength and
flame retardance (Quinn and Rosenquist, 1982).
In 1983 Union Carbide developed blends of polyarylethersulfone (25wt% PAES)
having the structure [c>-</>-o-¢r-~+lo.25-[(H)-~+lo.75'with either PC, PAr,
PEST or with their mixtures. The alloys had well-balanced mechanical properties
and environmental stress cracking resistance, superior in performance to neat PC
(Robeson and Harris, 1985, 1986). The same year, General Electric developed high
impact strength blends comprising 90wt% PC Lexan™, and polycarbonate-sulfone
grafted with ethylhexyl acrylate (Tyrell et ai., 1984).
In 1990 Teijin Chemicals disclosed that blends of 10-100 wt % PC with 90-0 wt % of
a polymer, selected from PS, POM, PA, PEST, PPE, PSF and PO, can be compatib-
ilized by addition of 5-100 parts (per hundred parts of PC + the selected polymer) of
a block copolymer composed of polycarbonate and modified polyalkene blocks, PC-
b-PO. The alloys showed good processability and chemical resistance (Hashimoto et
al., 1991). The same year blends comprising 85-90wt% PSF, 5-10wt% PC, 5-10wt%
of either PET or PBT, and glass fibers were reported suitable for injection molding of
articles where high performance and solvent and chemical resistance are required,
namely the aerospace, electronic and automotive industries (Militskova et ai., 1993).
Also in 1990, BASF deposited a patent describing blends of aromatic polyaryl-
ethersulfone, 40-87.5 wt % PAES, having the formula [-¢r-SCh-</r-O-l n and/or
[-¢r-CMez-¢>-O-¢r-SCh-</r-O-ln, 10-40 wt % PC, and 2.5-20 wt % of a core-shell
copolymer, MBA (core of butadiene grafted with methacrylate, styrene and/or
acrylonitrile; shell of methacrylates, styrene and/or acrylonitrile). The blends
showed a combination of good thermal dimensional stability and toughness. The
alloys have been used for the production of fibers, films and moldings, suitable for
electrical and electronic equipment and internal fittings for cars (Weber and Muehl-
bach, 1993). The following year, in other disclosures from the company, ~90wt%
PAES with two or more different repeat units, (e.g., 3-97 mol % of [-</>-SOr<f>-O-D
and 3-97 mol % of [-¢....C(CH3h-</>-O-4>-~-</>-O-1 was blended with 10-35 wt %
Pc. The blends showed good processability. They have been used to mold parts with
high impact resistance (Muehlbach et al., 1993).
18.3.3 POfluoropolymer blends

The first fluoropolymer, polychlorotrifluoroethylene (PCTFE, Hostaflon TM) was
introduced in 1934 by Hoechst. In 1942 du Pont de Nemours commercialized poly-
tetrafluoroethylene (PTFE, Teflon™ TFE). In 1961 the company introduced fluorin-
ated ethylene-~pylene(FEP) as Teflon™ FEP, in 1972 perfluoro alkoxy polymer
(PFA) as Teflon PFA, and poly(ethylene-co-tetrafluoroethylene) (ETFE) as TeJzeITM.
Polyvinylidenefluoride (PVDF) was commercialized in 1961 by Pennwalt Chemical
Company as Kynar™, then in 1973 by Dynamit Nobel as Dyflon™. Fluoropolymers
have been used in blends of engineering and specialty polymers either to improve
processability or to induce lubricity and abrasion resistance.
In 1973 Teijin Chemicals announced blends of polycarbonate (PC) with O.5-SO wt %
of ethylene-tetrafluoroethylene copolymer (ETFE). The blends showed good
processability and mechanical properties (Kawai and Miyauchi, 1974). Sixteen
years later the company disclosed blends of PC with 0.5-5 wt % PTFE. The blending
was carried out in a single-screw extruder using microfibrous PTFE. The materials
showed good moldability (Akega, 1991). The following year, Mitsui Petrochemicals
announced that abrasion resistance of PC can be reduced by blending it with poly-
propylene (2wt% PP) and with 3.5wt% PTFE (Kishimoto, 1976).
Polycarbonate (PC) blended in 1985 by Roehm with PVDF, was compatibilized by
addition of an acrylic copolymer. With sufficient quantity of the latter resin, the
blends could be made miscible, to form yellowish films with a single glass transition
temperature of 120°C (Leibler and Ringenberg, 1986). In a Bayer patent, PC was
blended with ABS, PTFE, and cresol novolak phosphate oligomers. The material
showed non-dripping processability and fireproof behavior (Fuhr et al., 1992).
18.3.4 POpolyimide blends

There is a great diversity of thermoset and thermoplastic polyimides (PI) with
Tg = 180-420 0c. The early ones were produced in a reaction between aromatic
dianhydride and aromatic diamine. In 1962 du Pont de Nemours introduced Kap-
ton™. In spite of its linear chain structure the resin did not behave as a thermcr
plastic. To improve the processability of PI several modifications have been tried to
increase the main-ehain flexibility, by introducing either aliphatic-aromatic
segments, or chemical groups with higher degree of mobility, such as ether,
amide, sulfone, etc. Polyamide-imide (PAl) with Tg = 275°C, was commercialized
in 1965 by Amoco Chemical Corporation as Torlon™. Polyetherimide (PEl) with
Tg = 217°C, was commercialized by General Electric Company in 1982 as Ultem™.
Polyimidesulfone (PlSO) with Tg = 273°C, was introduced by Celanese in 1986.
Polycarbonate (PC) has been blended with several thermoplastic PIs, mainly to
improve mechanical performance - especially the modulus and strength. In this
PC blends with specialty resins 397
section blends of PC with PI other than PEl are discussed; PC/PEl blends are
summarized in the following section.
In 1977 Arco developed blends of PC with styrene-maleimide copolymer (SOwt%
SMI). The alloys showed high HDT, stiffness and tensile strength (Fava, 1979).
In 1989 Asahi Chemical Company disclosed blends comprising 60-95 wt % PC and
40-5 wt % PAl. The latter resin was prepared from caprolactam, aromatic tri- or
tetracarboxylic acid (capable of forming at least one imide ring), polyoxyethylene
glycol and C2- 10 diamines. The blending was carried out in a twin-screw extruder.
The alloys were suitable for molding high impact strength materials with good
mechanical and antistatic properties, as well as fine appearance (Shimamura and
Suzuki, 1991).
Light-conducting casing blends for sheath optical fibers were developed in 1992
by Siemens. These consisted of 74-4Swt% PEST, 25-5Swt% PC and 0.2-3wt%
carbodiimide of structure (X)m-(-N=C=N-Y-)p-(-N=C=N-X)m (where X and
Y = C6-20 aromatic or aliphatic group, p=o-SO, m=o-l, and X can carry a free
isocyanate group). The blends with two-phase structure had improved thermal
stability and moisture resistance (Kamps et al., 1994).
18.3.5 PClPEI blends

Poly[2,2'-bis(3,4-dicarboxyphenoxy)phenylpropane]-2-phenylene-bisimide, also
known as polyetherimide (PEl) has the structure [-N(COh-4>-O-</>-C(CH3h-cf>-
O-<P(COhCN-4>ln' The polymer has exceptionally high mechanical properties, a
glass transition temperature of 215-220°C, a heat deflection temperature of 217°C,
no weight loss below 400 °C, and good processability. The resin was commercialized
in 1982 by General Electric as Ultem™.
The first blends of PEl were disclosed by General Electric Company in 1982. For
example, PEl was blended with poly(carbonate-b-siloxane) block copolymer, 5wt%
EPDM, ABS, MBS and acrylate copolymers (e.g., MBS or MMBA). The blends
showed higher impact strength than PEl alone (Giles and White, 1983; Giles,
1983a). In other patents, the company announced PEl blends with a wide variety
of polymers, such as PP, PSF, PEC, PAr, mixtures of PC and PEST, polyacrylate
elastomers, PA, etc. (Giles and Schlicht, 1984; Giles, 1983b, 1984). These alloys
showed good processability, as well as improved flexural and impact strength.
Also the same year, the company disclosed PEl blends with polyarylate (PAr) and
0-30wt% Pc. The blends showed improved moldability, flexural strength and
modulus. The PC-containing blends had high heat, flame and impact resistance
(Holub, 1990; Holub and Schlicht, 1990). In an application from 1987, addition of a
phenyl phosphate stabilizer to PEl/PC was reported to greatly improve melt stabi-
lity (Peters and Rock, 1989). In a contemporary patent from the company, PEl was
blended with PC, and a high impact polystyrene (HIPS). Moldings prepared from
these alloys had excellent high temperature properties, flexural modulus and impact
resistance (Holub and Rock, 1989).
Blends of PEl with bisphenol-A polycarbonate (PC) were commercialized by
General Electric in 1992 under the trade name Ultem™ LTX. The blends have been
designed for injection molding, but extrusion grades are also available. The alloys
show higher impact resistance than PEl and higher heat resistance than Pc. They
also retain the stain and chemical resistance, as well as the long term hydrolytic
stability, of PEL Before processing, the alloys should be dried for 12-24 h at 150°C.
The processing temperature ranges from 300-340 °C for the extrusion grades to
340-380°C for the injection molding grades. The blends have been used to
manufacture microwaveable cookware, electrical parts, automotive headlamps,
firefighter helmets, air handling and other parts used at high temperature (Utracki,
1994b).
More recently, in 1991, Dexer Corporation disclosed multicomponent blends
comprising 20-80wt% PC, 7D-I0wt% PA-6, 2D-2wt% PEl and/or TPU, O.2-2wt%
of a butyl glycidyl ether, a thermoplastic elastomer, an epoxy ether and a
maleated EPR or EPDM. Good processability, paint adhesion, low temperature
impact properties and HOT were found (Perron et al., 1993). The following year,
Enichem - Istituto Guido Donegani deposited patent applications for blends of PEl
with aromatic alkyl methacrylates (e.g., polybenzylmethacrylate). The blends were
reported to be miscible and transparent, with good processability and toughness in
comparison to the PEl, as well as to have improved HOT, modulus and tensile
strength in comparison to the acrylate. Furthermore, it was found that PEl/PC
blends can be compatibilized into single-phase blends by addition of an appropriate
polyaromaticalkylmethacrylate. For example, 1-79wt% PEl was blended with 1-79
wt % PC and 2D-98 wt % of an aromatic alkyl methacrylate, to give transparent
materials with good processability and high mechanical properties (Drzewinski,
1993c). In a follOWing patent, blends of block aryl(alkyl)methacrylate copolymers
with PC were reported to be transparent (Drzewinski 1994d).
18.3.6 PClLCP blends

Blends of polycarbonate with liquid crystal polymers (PC/LCP) will be discussed in
Section 21.8.4; here only a summary is given.
The first blend of PC with LCP was disclosed by Celanese in 1980. According to
the patent, 5-75wt% PC blended with a wholly aromatic polyester, 95-25wt% LCP,
gave materials with good mechanical, tensile and flexural properties (Froix, 1982).
Blends of PC with PAr and LCP were discovered by Kawasaki Steel Corporation.
These alloys showed low anisotropy and high heat and impact resistance (Izumi et
al., 1992). In a Foster-Miller patent, 10wt% of LCP (Xydar™ or Vectra™) was
blended with thermoplastic polymers (e.g., PP, PS, PC or PI) then multiaxially
oriented during processing to control the molecular orientation of the LCP as well
as the coefficient of thermal expansion (Haghighat et aI., 1992).
19
Polyoxymethylene (acetal resins)
Polyoxymethylene (POM, also known as either acetal or polyacetal) was commer-

cialized in 1959 by du Pont de Nemours as Delrin™, and by Celanese, poly(oxy-
methylene/ethylene) as Celcon™. These two types of POM are still available: (1) the
homopolymers originally developed by du Pont de Nemours are end-capped with
formaldehyde, and (2) the copolymers are obtained in a cationic reaction of trioxane
with ethylene oxide. Several POM resins are available, such as homopolymeric
Delrin™ from du Pont de Nemours, Tenac™ from Asahi Chemical, copolymeric
Celcon™ from Hoechst Celanese, Duracon™ from Daicel Polyplastic, Hostaform™
and KemataITM from Hoechst, Ultraform™ from BASF, etc.
POM resins are crystalline; thus on the one hand they are rigid, brittle and
chemically unreactive, and on the other hand they are immiscible with other poly-
mers. Thus, the most common type of POM blend is POM/POM, i.e., homologous
blends of POMs having different molecular structure (linear, branched or cross-
linked), different molecular weight or with different end groups. Introduction of
reactive end groups provides means of compatibilization of POM with other resins.
The most common commercial blends of POM are those with TPU, preferably
with a thermoplastic polyester-urethane elastomer, such as that obtained from
butaneadipatediol and methylene-bis-biphenyl diisocyanate (MOl) (Flexman, 1989;
Flexman et al., 1990). POMs are also being blended with core-shell acrylic rubbers
(Kusumgar, 1987), poly(methylmethacrylate-g-styrene-co-butadiene) (Schuette et al.,
1986), or poly(methylmethacrylate-g-polybutadiene) type (Burg et al., 1985). Com-
mercial blends of POM with PEST (e.g., PBT) are also available.
Polyoxymethylene has found a wide use as an engineering polymer, excelling in
mechanical, electrical and chemical properties. However, its use is limited by an
inferior impact resistance compared to that of other engineering plastics. Owing to
this, as well as to the difficulties in compatibilization, POM blending mainly focuses
on toughening of POM. Since the early 1960s, several types of impact modifiers have
been used to improve impact strength, namely polyalkenes (PE, EPR or PP), PVAc,
PVAI, polyoxyethylene, POE, styrenic copolymers (SAN, MBS, ABS, SBS or SEBS),
polyurethanes, etc.
Most POM blends with commodity resins are discussed in Sections 10.8, 11.9.4,
13.2.10,4.16 and 15.11.5. Several POM blends with engineering polymers are sum-
marized in Sections 16.3.4, 17.4.6 and 18.2.4. According to the adopted strategy, in
the present section only the remaining POM blends are summarized, namely those
with acrylics, TPU, POM, PPE and with specialty resins, (e.g., polyetheretherketone,
(PEEK), polyetherirnide (PEl) etc).
400 Polyoxymethylene (acetal resins)
19.1 POM BLENDS WfIH COMMODITY RESINS
19.1.1 PaM/acrylics blends

Many polyoxymethylene (PaM) blends have been made with acrylic copolymers.
The main reason for incorporating these copolymers is the need for POM toughen-
ing. In some cases, the blending can improve other properties, such as processability
or surface gloss.
In 1984 Hoechst mixed POM with 3Owt% of either methacrylate-grafted
polybutadiene (MBA) or methyl methacrylate-grafted styrene-butadiene rubber
(MBS). High-impact-strength alloys were obtained (Burg et al., 1985). The following
document from the company enlarged the concentration scale (paM was blended
with 5-70 wt % of MBS), and specified that the elastomeric particles should have
diameters of 0.0~2JLm (Schuette et al., 1986).
In 1986, Celanese Corporation announced paM blends with a multiphase
acrylic impact modifier, 1-50wt% AcryloiQfM KM 300. The reactive compatibiliza-
tion was facilitated by addition of reactive titanates. The blends showed improved
toughness (Kusumgar, 1987). Two years later, Toshiba Corporation disclosed
that blending paM with ethylene-methylmethacrylate graft copolymer resulted
in tough materials characterized by low values of the friction coefficient (Endo
et al., 1990).
In 1989 Takeda Chemical Industries developed a core-shell polymer, useful
for blending with 90 wt % POM. The copolymer comprised ~90 wt % of an
elastomeric core (poly(butylacrylate-co-l,4-butyleneglycoldiacrylate-co-allylmetha-
crylate) with Tg :s: -300C) and 100SOwt% of a glassy shell (poly(methylmethacryl-
ate-co-ethylacrylate or styrene) with Tg 2: 40°C). The POM/acrylic alloys showed a
good set of mechanical properties, such as high impact strength above -30°C,
high elongation, good weldline strength, etc. The blends were used to mold gears,
reels and other parts (Sasaki et al., 1991, 1994a). The following year, the company
deposited a patent application describing another core-shell polymer, suitable for
blending with paM. The emulsion copolymer had a rubbery core of conjugated
diene and/or alkyl acrylate (Tg:S: -30°C), while the shell was mainly PMMA
(Tg 2: 60°C). paM blends, containing ID-80phr of this copolymer, showed
improved impact strength, elongation, weatherability and thermal stability (Sasaki
et al., 1994b).
In 1990, Asahi Chemical Company disclosed blends of linear polyoxymethylene
(PaM) with 0.1-90wt% of a branched paM (polymerized from formaldehyde or
trioxane, or copolymerized from these monomers with cyclic ether in the presence of
polyhydroxy alcohol, containing more than three -oH groups). The blends showed
good flowability and processability (Nagasaki et al., 1991; Hanezawa and 000,1991).
In the following patent, three-eomponent blends were described. These comprised
100 parts paM, 1-700 parts of a block copolymer of oxymethylene with vinyl
monomers, and 0-1200 parts of a polyvinyl resin. The blends were used for lamina-
tion. High peel strength was reported (Hata and Matsuzaki, 1991; Nagasaki et al.,
1991).
In 1991 Polyplastics Company announced blends of paM, with acrylic core-shell
copolymer (MM-GMA, 1-50wt% methyl methacrylate copolymerized with
either hydroxyethyl methacrylate or glycidyl methacrylate) and 0.01-5 parts of a
weathering agent (e.g., benzotriazole). The alloys were used to mold parts with
reduced glossiness and good weatherability and light stability (Katsumata and
Matsunaga, 1992).
POM blends with commodity resins 401
The same year, Hoechst blended POM with 0.5-10wt% acrylic (co)polymer hav-
ing particle diameters of 2D-600 p.m, and with 0.5-1 wt % Si~ powder (d = 3 -5 p.m).
The blends showed good processability, mechanical properties and matte surface
(Schleith and Sabel, 1992). In a contemporary patent from BASF, POM blends with
imide group-eontaining polymers were disclosed. These multicomponent alloys
comprised 60-98 wt % POM, 5-8 wt % poly-N-eyclohexylmethacrylimide, 0-50 wt %
elastomeric core-rigid shell impact modifier, and 0-50 wt % glass fibers. The mater-
ials showed good heat and light resistance, as well as good color retention (McKee
et al., 1993).
Also in 1991 du Pont de Nemours announced POM blends with 0.01-15wt%
EGMA (ethylene-glycidyl(meth)acrylate copolymer with styrene, ethylene-acrylate,
etc.). The matte blends were used to mold parts for electrical/electronic applications,
with excellent tensile properties, even after long term aging in grease (Takahashi and
Kobayashi, 1992). In a following patent, the weathering resistance of POM was
improved by incorporation of 0.01-5 wt % UV absorber and/or light stabilizers
together with 0.1-30wt% graft copolymer containing epoxy or oxazolyl units,
such as EGMA, EGMA/ AS, EGMA/PMMA or their mixtures (Kobayashi and
Shinohara,1993).
In 1992 Asahi Chemical Industry Company disclosed that 100 parts POM, was
blended with 1-100 parts of a multiphase acrylic interpolymer, comprising rigid and
elastomeric phases. The interpolymer particles had either a two-phase structure
(elastomeric core) or a three-phase structure (elastomeric intermediate phase). The
particles had average diameter of ~ 1 p.m. The elastomeric phase had T g ~ 25°C
while the rigid phase had Tg 225°C. The alloys were used to mold interior auto-
mobile trim with a matte surface and a good flexural modulus (Nagasaki and
Nakai, 1993).
19.1.2 POM/fPU blends

The oldest method of toughening POM is by blending it with thermoplastic poly-
urethane (TPU). The first POM blends were commercialized in 1960 (Delrin™ from
du Pont de Nemours). Today, there are several other brands, namely Celcon™ from
Celanese, DuraloyTM from Hoechst-eelanese, FormaldafilTM from Wilson-Fiberfil,
Fulton™ KL from LNP, Hostaform™ from Hoechst, RTP 800 from RTP Corporation,
TC from Polyplastics, or Ultraform™ from BASF.
The POM/TPU blends are distinguished by Significantly higher than POM capa-
city to absorb impact energy, higher strain and good elastic recovery. These proper-
ties depend on the mixing ratio of both polymers and the morphology, as well as on
the compounding and processing conditions.
The impact strength of any multiphase system depends on whether the two-phase
structure is able to efficiently dissipate energy during plastic deformation either by
cavitation, crazing-and-cracking or shear deformation. These processes have differ-
ent activation energies and activation volumes, thus the particle size and size
distribution of the modifier play important roles. It has been demonstrated that
blending high viscosity POM, with up to 30wt% low viscosity TPU, resulted in
the morphology characterized by finely dispersed TPU phase regions with optimum
particle size and size distribution for most efficient dissipation of energy (Niedem-
berg, 1983).
In most POM/TPU blends, to achieve good impact-modification, 10-30wt% TPU
has been used. With increasing TPU content the impact strength increases at the
cost of rigidity. Depending on the composition and compounding method, the
morphology may be either dispersed (paM being the matrix), or cocontinuous. The
cocontinuity engenders an especially good set of performance parameters. When
high rigidity is required, the POM/TPU blends can be reinforced with glass fiber
(these alloys are also available on the market). For high lubricity in bearings, bush-
ings, cams and other antifriction applications, some grades contain up to 20 wt %
PTFE, as either fine powders or microfibers.
The POM/TPU blends are formulated for injection molding, extrusion, compres-
sion, blow and transfer molding. They are known for their good processability but,
contaminated with thermally degrading polyvinylchloride (PVC), they may sud-
denly decompose uncontrollably. The POM/TPU alloys show good rigidity, high
impact strength, excellent resilience and toughness, high fatigue strength, good
flexural and tensile strength, low water absorption and high resistance to chemicals.
However, they are sensitive to UV radiation, thus specifically they require light
stabilization.
The POM/TPU blends find many uses in the automotive industry, mechanical
engineering, household appliances, precision engineering, telecommunication, sani-
tary engineering, the building industry, plumbing, sport and recreation (e.g., for
chain wheels and surfboard mast feet), switch buttons, clips for toys, car body parts
and fuel lines, blow moldings, etc.
In 1969 Celanese Corporation disclosed that paM elasticity was improved by
blending it with OH-, NCO-or NC5-terminated polyurethanes, for example with
SO wt % of a TPU (McAndrew, 1971). In the early 1980s American Cyanamid blended
paM with polyurethane elastomer (PU). The blends with high impact resistance,
even at low temperatures, were found useful for automobile exterior body parts
(Megna and Obal, 1981).
In 1983 Hoechst announced impact resistant paM blends, comprising polyur-
ethanes (PU) and inorganic fillers (Reske and Wolters, 1984). The same year, du
Pont de Nemours developed blends of an acetate end-capped polyoxymethylene
(PaM) with thermoplastic polyurethane, 15-40 wt % TPU (preferred composition
30 wt % TPU). The blends were further stabilized by the addition of 0.3 wt % poly-
carbodiimide. Moldability of these alloys could be further improved by addition of
0.1-1 wt% ethylene-bis-stearamide (Richardson, 1984; Flexman, 1984; Waggoner,
1984).
In 1984, Celanese Corporation disclosed blends comprising S0-9Swt% paM and
So-S wt % TPU (from methylenebisphenylisocyanate, diols and polyoxytetramethy-
lene glycol). The blends had good processability and high impact strength, even at
low temperatures, making them suitable for the use as automobile body parts (Drzal
et al., 1986). Next year, in several patent applications, the company described paM
blends with 4--30 wt % TPU as suitable for molding automobile bumpers. Also, paM
was blended with 1Q-40wt% of an amino-prepolymer (condensate of HCHO with
guanidine, urea, guanamine or melamine), to give materials with improved mechan-
ical properties (Celanese Corporation, 1987).
In 1988, Polyplastics Company announced paM blends with polythioisocyanate
(TPU). The blends were reported to have good impact strength and flexural resist-
ance (Sugiyama and Mochizuki, 1990). In the patents that followed, an addition of
ethylene-methacrylate copolymer was found to further improve abrasion resistance,
whereas addition of polymethylmethacrylate (PMMA) and benzotriazole improved
weatherability (Endo et al., 1990; Okuda, 1990). The following year, in a Dow patent,
polycarbonate (PC) was blended with paM and TPU. The alloys were used to mold
parts with high impact resistance (Silvis et al., 1990). The same year, Osaka
Gas Company disclosed POM blends with 3-60 wt % of carbon fibers coated with
POM blends with engineering resins 403
O.I-lOwt% thermosetting polyurethane (PU). The reinforced blends showed good
mechanical properties, high impact and bending strength, as well as high moduli
(Ueno et al., 1991).
In 1990 du Pont de Nemours developed blends that contained 4O-98wt%
paM, 1-40wt% TPU and 1-59wt% of at least one amorphous polymer selected
from SAN, ABS, AES, PC, PA, PAr, PPE, HIPS, acrylics, imidized acrylics and
SMA. The blends also had the customary additives, namely stabilizers, tougheners,
nucleating agents and fillers. The multicomponent alloys had lower mold shrinkage
than POM/TPU blends, and a good balance of properties such as stiffness, elonga-
tion and toughness (Flexman, 1992). Later patents described blends comprising
5O-80wt% paM, 10-20wt% TPU and 10-30wt% of a crystalline polymer, selected
from PA-612, PA-6, PP and PET. The blends were reactively compatibilized by
addition of ethylene-butylacrylate-glycidylmethacrylate (EBA-GMA) (Flexman,
1992,1994; Subramanian, 1992). In a contemporary patent, Dow Chemical Company
disclosed that 4o-BOwt% POM blended with either TPU or thermoplastic
elastomeric copolyesters and ABS, showed good processability. Its moldings had
good thermal and dimensional stability, as well as chemical and creep resistance
(Guest et al., 1991).
In a series of disclosures dating from 1992, Mitsubishi Gas Chemical Company
described a new method of impact modification of paM, that involved high shear
compounding with TPU and a polyhydric alcohol (having at least three hydroxy
groups per molecule). The latter compound was selected from glycerin, trimethylol
ethane, trimethylol propane, hexantriol, triethanol amine, diglycerine, pentaerythri-
tol, tetraethanol-ethylenediamine, methylglucosite, aromatic diamine-tetra ethanol
adduct, sorbitol, dipentaerythritol, cyclodextrin, Phenoxy and PVAI. The blending
was conducted at high shear stresses and at temperatures of 180-250°C. The alloys
were found suitable for either injection molding or extrusion. The injection-molded
parts showed well-balanced properties, namely tensile strength and elongation at
break at the weld-line, impact resistance, etc. The blends were used to manufacture
such parts as clips, springs, gears, bearings, cams, levers and the like, for electrical
and electronic machines, office equipment, automobiles, industrial machines, toys
and/or sports goods, etc. (Nagai et al., 1993, 1994).
Also in 1992, BASF announced development of blends comprising paM homo- or
co-polymer, 10-97wt% paM, 3-50wt% TPU, a polyether-ester or polyether-amide
derived from polyether-polycarbonate-diols, 0-50 wt % filler and 0-30 wt % of other
additives and processing aids. The blends had excellent multiaxial impact strength,
dimensional stability and resistance to motor fuels. The materials were used for the
production of moldings (especially gasoline tanks), fibers and films (Kielhom-Bayer
and Groll, 1994).
19.2 paM BLENDS WITH ENGINEERING RESINS
19.2.1 POMIPOM blends

Polyoxymethylene (PaM) was commercialized in 1959. The first paM/paM blends
were patented soon thereafter. For example, in 1965 Asahi Chemical Industry
deposited a report of an invention in which high molecular weight paM was
blended with its low molecular weight homologue. Blending resulted in significant
improvement of processability, with good retention of performance (Ishida and Sato,
1970). However, it is worth remembering that such a method of plastification, by
addition of a low-molecular-weight fraction has been successfully used, and
surprisingly often patented, for nearly all polymers. This method has been found
particularly useful in the semicrystalline polymers.
In 1980, a Celanese patent disclosure described paM blends with improved
properties, obtained by blending one POM with 1.5-40 wt % of another POM
(Froix and Kusumgar, 1983).
In the late 1980s, Asahi Chemical Company gave evidence of intense activity in
research on paM blends. For example, in 1989 the company deposited a series of
invention reports in two fields that are of interest in this part, namely in blending of
different types of POMs, and in modification of the POM resin by blending it with
another paM resin, having macromolecules differently end capped. Thus, linear
POM was blended with 0.1-1Swt% of a crosslinked POM and 0.01-lOwt% of a
branched POM. The blends could be either molded or extruded into a variety of
parts having high impact strength (Matsuzaki, 1991). In other patents, paM copoly-
mer was blended with 5-70 parts of a linear paM, end-capped with alkyl or aryl
(substituted or otherwise) groups. The alloys showed good dimensional stability,
lubricating properties, tensile characteristics and good heat stability (aka and
Kamiya, 1991; Hata and Komatsu, 1991; Watanabe and Fukuda, 1991; Masamoto,
1991).
In another series of patent disclosures from the company, linear paM was blended
with 0.1-90wt% of a branched paM, obtained by polymerization of either formal-
dehyde or trioxane, or copolymerization of these monomers with cyclic ether, in the
presence of polyhydroxy alcohol, containing more than three -DH groups. The
blends showed good flowability and processability (Nagasaki et al., 1991). A later
patent described three-component blends, comprising 100 parts paM, 1-700 parts of
a block copolymer of oxymethylene with vinyl monomers, and 0-1200 parts of a
polyvinyl resin. The blends could be later laminated. High peel strength was
reported (Hata and Matsuzaki, 1991; Nagasuki et al., 1991).
In still another series of disclosures from Asahi Chemical Company (dating from
1990) linear paM (having MW = 10-Sookg/mol) was copolymerized into di- or
triblock copolymers with a prepolymer: [(CF2XCX')n-Dp-(CH2-(CRIR2»m-
(CF20)q]' where the X, X' and Rj groups are H, CI, F, alkyls, alkoxyls, fluoro alkyls
or fluoro alkoxyls, -¢, -NH2, -eoo-ester- etc. To obtain the copolymer, formalde-
hyde or trioxane was polymerized in the presence of such a prepolymer having an -
OH group on either one or both chain ends (Nagasaki et al., 1991). In another
disclosure, the block copolymer was blended with similarly formed graft copolymer.
The alloys showed high wear resistance and excellent antifriction properties (Hane-
zawa and 000, 1991). Clearly, this method of paM modification opens the door for
incorporation of the resin into virtually any polymer or polymer mixture. The
traditional difficulties for compatibilization of paM blends have been overcome.
19.2.2 POMIPPE blends

The use of polyoxymethylene (PaM) in blends with polyphenylene ether (PPE) has
been infrequent. For example, in 1972 Asahi Chemical Industry Company,
to improve the processability and mechanical properties of paM, blended it with
4-40 wt % of PPE, and optionally PS (Ishida and Masamoto, 1974). In a contemporary
patent deposited by Nippon Steel Chemical Company, it was reported that blends of
paM with 5-S0 wt % of either PPE or polysulfone (PSF) showed the heat deflection
temperature to be increased by 20°C (Ikeguchi and Nagata, 1974).
More recently, in a patent disclosure of 1992 by Mitsubishi Petrochemical Com-
pany, paM was incorporated into PPE/PA blends that comprised 15-7Swt% PPE
POM blends with specialty resins 405
and 85-25wt% of either PA-6, PA-66 or an amorphous PA. It was reported that
addition of 0.01-5phr POM, and 0.05-5phr of a Lewis acid (e.g., trialkylborane,
trialkylborate, boric acid and halogenated boron) improved compatibilization and
induced excellent heat and impact resistance. The new alloys have been used to
mold automobile parts (e.g., bumpers and door panels). The moldings showed
excellent appearance and color hue after high temperature molding (Takayanagi et
aI.,1994).
19.3 POM BLENDS WITH SPECIALTY RESINS

Owing to its good resistance to abrasion, paM has been used in blends with
specialty plastics lacking this performance characteristic. For example, in 1985
Toray Industries discovered that blends comprising 100 parts paM, 10 parts poly-
etheretherketone (PEEK) and / or polyetherimide (PEl) showed excellent wear resist-
ance without loss of slipperiness, making them suitable for the use as nibs of pens
(Suzuki and Nagahama, 1987).
In a 1989 patent application from Polyplastics Company, blends of paM with
1-40wt% of PMMA and 1-20wt% of a fluoropolymer (selected from PTFE, PVF,
PVOF and copolymers of tetrafluoroethylene with either hexafluoropropylene or
ethylene) were disclosed. The blends could be further weather-stabilized by
addition of benzophenone, benzoate, cyanoacrylate oxalic anilide or hindered
amines. Note that PMMA forms a miscible blend with PVOF that shows good
weatherability. As a result, the new paM blends showed excellent weatherability,
making them useful for manufacturing of exterior automobile parts, electrical
appliances and cameras, as well as industrial and building components for exterior
use (Katsumata, 1991).
The following year, the company announced POM blends with 0.5-25 wt % of a
low-molecular-weight polydimethylsiloxane (POMS) having a shear viscosity of
~ 200 Pa s. Before blending with paM the POMS oil was absorbed by fine silicone
powder, with particle diameters of 5-300 p.m. The blends were used to manufacture
sliding parts, characterized by good sliding properties and high wear resistance
(Takayama et al., 1991). The same year, for similar applications, the NOK Corpora-
tion developed paM blends with 2-30wt% PTFE and 2-30wt% of expanded gra-
phite impregnated with a lubricating oil. The blends showed excellent abrasion
resistance (Ishioka, 1991).
Also in 1990 Shell Oil discovered that paM was miscible with polyvinylphenol
(PVPh) (Machado and French, 1992). Furthermore, blends of linear alternating copo-
lymers of carbon monoxide and at least one unsaturated hydrocarbon (CaPO) with
2D-45wt% paM, could be compatibilized by addition of O.5-10wt% PVPh. The
resulting alloys were used for molding parts for the automotive and construction
industries. The blends also found application as coatings for either glass or metal
(Machado, 1993).
In 1991, Mitsubishi Gas Chemical Company disclosed blends comprising 80-
99.9wt% paM, PVOF and optionally a lubricant (e.g., silicone oil or polyalkene
wax). The molded blends showed excellent resistance to frictional wear and high
heat stability (Shibata et al., 1992). A contemporary patent application from du Pont
de Nemours described similar compositions. Thus, 80-99 wt % POM, was blended
with O.5-lOwt% of lubricant (e.g., wax, PTFE, silicone oil or PEG), and O.5-lOwt%
of ethylene-X-Y copolymer (where X = methyl-, ethyl- or butyl-acrylate, and Y =
glycidylmethacrylate, glycidylacrylate or glycidylvinyl ether). For example, POM
was first compounded with EBA-GMA, then PEG, wax and ethylene distearate were
incorporated. The blends showed good processability, wear and heat resistance. The
materials were used for manufacturing conveyor chains, belts, pipes, films, gears,
cams and other parts requiring good mechanical properties and resistance to fric-
tional wear (Takahashi and Kobayashi, 1993).
20
Polyphenyleneether
In August 1956 Allan Stuart Hay, attempted to produce bisphenol by oxidative

coupling in the para position of 2,6-dimethyl phenol. The reaction was conducted
in pyridine at room temperature, by bubbling air in the presence of CuCI catalyst.
The reaction resulted in a rapid increase of the solution viscosity - the coupling not
only produced the bisphenol, but also the first poly(2,6-dimethyl-1,4-phenylene
ether) (PPE) (Hay et aI., 1959; Hay, 1959, 1962, 1964, 1967, 1968, 1976, 1995). Sub-
sequent studies made it possible to identify a more efficient catalyst, achieving much
better selectivity and efficiency of the reaction. The first scale-up of the polymeriza-
tion was made in 1958, and the first miniplant was constructed in 1961. The PPE
macromolecules are slightly branched. Two years later the company formed Poly-
mer Products Operation (PPO) with the task of commercializing the resin - PPE was
commercially introduced in New York City in 1964.
In 1965 polymerization of a-cresol was announced (Hay and Enders, 1965). The
following year polymerization of p-bromophenol into polyoxyphenylene was
patented (Stamatoff, 1966).
PPE is an amorphous resin with a glass transition temperature of 210 0c. PPE can
be crystallized upon annealing or by slow crystallization from solution - its melting
point is 257°C. However, the resin is thermally stable only up to about 150 0c, thus
for processing it should be stabilized and plasticized by blending. Furthermore, since
oxidation of the methyl groups begins at 125°C, the continuous use temperature is
usually limited to this level. The polymer has good rigidity, creep resistance, dimen-
sional stability, high melting point, as well as electrical, chemical, water and flame
resistance. The main disadvantages of neat PPE are poor processability (i.e., high
melt viscosity), susceptibility to oxidative degradation at 125°C and above, low
impact strength, as well as sensitivity to UV and visible light, with the consequence
of a notorious instability under weathering conditions. The NarylTM resins (intro-
duced by PPO in 1966, simultaneously in New York, Amhem and in Tokyo) were
developed to fill the gap between the commodity and engineering resins that existed
in the mid-1960s.
In 1965 Westlake Plastics Company started production of Alphalux™ 400, extruded
rods, sheets and tubing of PPE. Today, PPE is being manufactured by numerous
companies world-wide. Its current annual production and growth rate are, respect-
ively, 300 kt and 9%. In the USA alone, 109 kt of PPE was produced in 1994.
In 1960 General Electric applied for patent protection for blends comprising PPE,
polystyrene (PS) and polydiphenylsiloxane (PDPS). The alloy was reported to be a
clear, transparent, colorless solid at 65°C that turned into liquid at 85 0C. It was a
408 Polyphenyleneether
good insulator and was used for the manufacture of recording media with high
resistivity and flexibility (Boldebuck, 1962). This is the first record of PPE/PS mis-
cibility that, for several years, went largely unnoticed. To improve resistance to
embrittlement, PPE resin was mixed with up to lOwt% sulfur (Fox, 1967).
In 1965, blends of PPE with PS were disclosed in patent applications from General
Electric (Gowan, 1968; Cizek, 1968). The latter patent claimed blends comprising
1-99wt% PPE with 99-1 wt% of a styrene resin (PS, SAN or ABS). The same year
Rexal Drug and Chemical Company applied to patent the incorporation of 2-10 wt %
PPE into styrene before polymerizing it in suspension. The modification was found
to improve the toughness of PPE by a factor of three (Erchak et al., 1968). The
following year in a patent application deposited by Dart Industries, the same authors
described rubber-modified PPE/PS blends comprising poly(styrene-co-butadiene)
(HIPS) (Erchak et al., 1969). The blends contained 84wt% PS, 10wt% PPE and
4-8wt% elastomer. They showed about three times higher impact strength than PS
without any loss of the heat deflection temperature.
In 1969 several patent applications were deposited for toughening PPE. For ex-
ample, General Electric demonstrated large effects engendered by addition of about
20wt% of styrene-butadiene-styrene block copolymer (Kambour, 1970). Sumitomo
Chemical Company disclosed the use of styrene-grafted EPDM (ASA) to toughen
PPE (Nakashio et al., 1971, 1972, 1973). Thus, addition of up to 20wt% ASA was
found to improve Charpy impact strength by a factor of 3.5. A few years later the
rubber toughening of Noryl was announced by General Electric (Abolins and
Cooper, 1977; Cooper and Katchman, 1978). The first patent described alloys com-
prising 50wt% PPE, 35wt% PS and 15wt% of an elastomer (such as EPDM or a
graft copolymer of acrylic and styrene on polybutadiene). The later document
described addition of EPDM (particle size 1 /-Lm) grafted with styrene (whose intrin-
sic viscosity was larger than O.5dl/g).
Addition of PS to PPE was found to decrease the glass transition temperature, and
thus the melt viscosity, improving the processability while leaving some PPE proper-
ties unchanged; however, heat, flame and chemical resistance were reduced. Addi-
tion of brittle PS to brittle PPE does not improve the impact strength of the latter
resin. In 1964, the Richardson Company began manufacturing miscible blends of
PPE with crystalline PS. Since the materials were brittle, the venture was not a
commercial success. Clearly, the PPE/PS systems required toughening.
As an interim solution, in the mid-1960s General Electric introduced NoryzTM - a
family of PPE blends with high impact polystyrene (HIPS) initially prepared at a
ratio of 1:1 (Boldebuck, 1962; Cizek, 1968). Later, various styrene-containing elas-
tomers were used. To improve rigidity, HDT and flame resistance, glass fiber
reinforced and flame-retardant grades were soon introduced by the General Electric
Company. It is said that the company no longer manufactures neat PPE, but rather
its modified varieties, such as a poly(2,6-dimethyl-1,4-phenyleneether-g-styrene) - a
graft copolymer manufactured by first polymerizing PPE by the oxidative coupling
of 2,6-dimethyl phenol, then grafting the polymer with styrene.
After expiration of the original General Electric patent, several manufacturers
(e.g., BASF, Hills, Borg-Warner, Asahi, Engineering Plastics Ltd and Mitsubishi)
began sales of their own blends based on PPE or its copolymers. In 1979 Asahi-
Dow introduced the styrene-grafted PPE blend Xyron™ (lzawa et al., 1973, 1977;
Izawa, 1974, 1992). In 1984 Borg-Warner started production of Prevex™, a copolymer
obtained by oxidative coupling of 2,4-dimethyl phenol with 5-lOwt% of 2,4,6-
trimethyl phenol (Grant et al., 1990; Bartges, 1990). Both the PPE homo- and co-
polymer are only available as blends. The original Noryl underwent several
PPE blends with commodity resins 409
modifications. PPE has been blended with high impact polystyrene (HIPS), styrene-
butadiene di- and triblock copolymers, as well as other styrenics. Modified PPE
grades are available (e.g., reinforced by incorporation of glass fibers, self-extinguish-
ing, structural foams, etc). Their major application is in the transportation industries,
as well as for office/hospital furniture, electrical and electronic parts, and many
others (Deanin, 1982; Bartges, 1990; Feth, 1990).
As the sophistication of PPE blending technology grew it became possible to
incorporate crystalline thermoplastic resins. The new alloys are usually superior in
heat resistance, stiffness, strength and oil resistance. The disadvantage they share
with PPE is low impact resistance that makes it necessary to incorporate elastomeric
copolymers, which in turn leads to reduction of heat resistance and surface hardness.
Another disadvantage of the crystalline thermoplastic resins is low melt viscosity
that causes difficulties in processing (poor melt strength), especially during molding
within a relatively narrow range of processing conditions. Since crystallization leads
to increase of density, and processing imposes anisometric residual stresses, the
semicrystalline polymers show large mold shrinkage that is difficult to predict and
control. Moreover, most of these resins are sensitive to water, which not only
changes their properties and dimensions, but also the appearance.
In a standard blending strategy, the advantages and disadvantages of PPE must be
balanced by complimentary properties from a crystalline thermoplastic resin. The
common disadvantage, the brittleness, can be eliminated by incorporation of a
common impact modifier. Furthermore, owing to large differences of melt viscosity,
blending of PPE with a semicrystalline polymer may be difficult. An easy solution is
to select an impact modifier that will effectively increase the viscosity of the semi-
crystalline polymer and/or decrease the viscosity of PPE. The key to successful PPE/
semicrystalline polymer blends is reactive compatibilization-eum-impact
modification. Thus, blends comprising at least three components are expected to
show the best properties of both main components and to have improved process-
ability and impact strength.
In summary, PPE must be blended. The three major types of PPE blends are with
styrenics (PS), with polyamides (PA) and with thermoplaStiC polyesters (PEST).
Owing to miscibility with PS, its incorporation is relatively easy. Furthermore,
since there are many elastomers containing styrene, impact modification by the
incorporation of a styrenic elastomer does not pose a problem. Blending of PPE
with either PA or with PEST is more difficult because these systems require both
compatibilization and toughening. Several blending strategies have been developed,
as discussed in the following sections.
20.1 PPE BLENDS WITH COMMODITY RESINS
20.1.1 PPEIPS blends

Polyphenyleneether (PPE) blends with styrene polymers or copolymers constitute
the most important category of commercial PPE blends. Since the mid-1960s it has
been known that PPE/PS blends are miscible. The miscibility was concluded from
the presence of a single glass transition temperature (Schulz and Gendron, 1972;
Fried et al., 1978), and electron microscopy (Kambour et al., 1980). The calorimetry
showed a negative heat of mixing over the entire composition range (Weeks et al.,
1977). However, more recent nuclear magnetic resonance studies indicate that
miscibility does not extend to the molecular level - the resins have been found
miscible down to the 10 nm scale, but immiscible at 2 nm - at least 70% of the
blend components exist in the same environment as in the homopolymeric
phase, with less than 30% showing some evidence of PPE-PS interactions (Takahashi,
1991).
The blend density is higher than that given by the additivity rule. As a result,
several mechanical properties (e.g., modulus or yield stress) show synergistic effects
(McCarthy and Rogers, 1987). The densification of the PPE/PS blends may be taken
as indication of the specific interactions. The flow of PPE/HIPS depends on com-
position and flow characteristics of the component resins. Owing to the reduction of
the free volume, the blends have higher viscosity than could be predicted from the
log-additivity rule (Prest and Porter, 1972; Schmidt, 1979).
Over the years, PPE blends with most styrenics have been patented, namely with
SB, SBS, SEBS, SBR, MBS, SMA, ABS, SMI, SAN, PMS, AES, etc. PPE was also
blended with PO in 1964, with ionomer in 1965, EPR in 1972, poly(ethylene-co-
glycidyl methacrylate) (EGMA) in 1982, as well as with styrene-modified EPDM
(an AES), terpolymer of styrene-maleimide-butadiene, a multipolymer of styrene-
acrylic acid-methacrylate, rubber modified by grafting styrene and t-4-butylstyrene,
sulfonated PS, etc. (Utracki, 1989).
The characteristic properties of PPE/PS blends are good processability, low den-
sity, high strength, stiffness and dimensional stability over a wide range of tempera-
ture, low water absorption, good electrical properties, better resistance to oxidation
than PPE, good resistance to hydrolysis, low mold shrinkage, self-extinguishing,
non-dripping, etc. The blends must be toughened, which invariably causes a loss of
some thermal properties. The toughened, unreinforced grades fracture by the advan-
tageous yielding mechanism. Fillers and reinforcements can compensate for the loss
of rigidity and the thermal properties. Elongation at break is relatively high (tll =
50--55%). The strength of the unreinforced material at 85°C is about 85% of that at
room temperature. In unreinforced grades the notched impact strength is high, even
at -50°C, exceeding 120J/m, whereas in glass fiber reinforced grades it is above
70J/m. The commercial PPE/HIPS blends on the market today contain 25-60wt%
of PPE, and in consequence have a heat distortion temperature of 90--150°C.
The glass transition temperature of the PPE/PS blends varies from 80 to 100 0C. To
improve the resistance to oxidation, phosphites or phosphonites and octadecyl-3-
(3,5-di-t-butyl-4-hydroxyphenyl)-propionate are often used. Owing to the presence
of hydroperoxides, UV radiation is absorbed even at wavelengths of 380 nm. Metal
complexes of sulfur-containing compounds have proved to be effective hydroper-
oxide decomposers. Stabilizing reactions also result from interactions between
hydroperoxides and sterically hindered amines. As flame retardants, the alkyl sub-
stituted aryl phosphates are widely used. Depending on the additives, the blends are
resistant to dilute acids, strong alkaline solutions, alcohol, detergents, fats and oil,
but not to concentrated acids, ketones, chlorinated hydrocarbons or aromatics. They
also swell in many aliphatic solvents. Owing to the presence of PS they are suscept-
ible to stress cracking. The long-term heat resistance in air and water in the presence
of oxygen is inferior to that of paM.
Several commercial PPE/styrenics systems (mainly with high-impact polystyrene
(HIPS» are on the market: Biapen™ from Chemolimpex, Gecet™, Gemax™ (contain-
ing PBT), NorylTM and Prevex™ from General Electric, Iupiace™ from Mitsubishi Gas
Chemical, LuranylTM from BASF, Necofene™ from Ashland Chemical, Nerafen™
from Spolane, Tamoform™ from Nitrogene Works Tarnow, Verton™ and Vestoran™
from Huls, Xyron TM 200 from Asahi, etc.
PS/PPE blends with 25-60wt% PPE have been developed mainly for injection or
blow molding, extrusion, calendering, vacuum- or thermoforming, and structural
foam molding. At low-PPE contents, the blends can be considered as upgraded PS
resins, with moderately higher prices. Some grades are reinforced with up to 30 wt %
glass fiber. They show good processability and recyclability, low mold shrinkage,
good dimensional stability, heat resistance, HDT = 9O-1S0°C, good impact strength
and toughness, resistance to hot water, low moisture absorption, flame retardance,
low density and cost/performance ratio. Note that these blends have poor resistance
to aromatic and polar solvents.
Before processing, these materials should be dried at 110°C for 1-2h. Depending
on the grade, the processing temperature varies from 260 to 300 °C, the mold
temperature from 110 to 120°C and the injection pressure should be at least
100 MPa. The observed initial shrinkage is 0.5-0.7%, but subsequently the moldings
do not shrink. Owing to thermo-oxidative degradation, the cycling time should be
short. Screen printing and hot embossing are common. Vacuum metalizing, as well
as alkyd-, acrylic- and epoxide-based lacquers are used for coating. Surface tempera-
tures of 260 to 290°C are selected for heated tool welding. Friction welding takes
place at speeds of 1200rpm and contact pressures of 20N/mm 2 . Ultrasonic and
resistance wire welding are also used. The PPE/PS blends can be bonded using
solvents such as dichloroethylene, toluene or chloroform. High tensile and shear
strengths are achieved with rubber, epoxide resin, silicone, cyanoacrylate and TPU
adhesives.
The PPE/PS blends are used for automotive interior trim, door columns, rear
window shelves, seat belt fasteners, instrument panels, steering wheel covers, venti-
lation and heating systems, wheel caps, housings for computers, teleprinters, tele-
copiers, printers and telecommunication equipment, electrical engineering, cable
ducts, lightning trunking and busbars, distributor boxes, terminal strips, mountings,
housings for appliances (coffee machines, controllers, timers, chargers), panels for
TV sets, chassis for video-recorders, engineering (pump rotors, parts for water flow
meters, hOUSings for instruments, heat exchangers), for manufacture of accessories
for radios and televisions, switch cases, coil cores, electric kettles, moldings for
dishwashers, washing machines, hair dryers, fittings, water meter housings, parts
for office equipment, cameras, projectors, metalized moldings for the automotive
industry, ventilation systems, grills, wheel covers, dashboards, instrument and light
housings, locks, etc.
The historical evolution of PS/PPE blends is discussed in Section 10.11; here only a
brief summary is given.
The first blends comprising PPE, PS and polysiloxanes were described in a
patent deposition of 1960 from General Electric Company (Boldebuck, 1962;
Cizek, 1968). The first toughened blends were disclosed in 1967. Thus, to PPE/PS
blends a polybutadiene (6.5wt% PB) was added (Chemische Werke Huels, 1968). In
a Uniroyal patent PPE/PS blends were impact modified by blending in not more
than SOwt% of either PB, SBR or NBR (Lauchlan and Shaw, 1970). In 1970 and 1971,
Asahi-Dow issued a series of patents describing a two-step polymerization. First, a
solution of dimethyl phenol in styrene was oxidatively polymerized, then
the solution was dispersed in water and styrene was polymerized by free
radical reaction, to give solid particles with diameters 2 5J.Lm (Nakanishi et aI.,
1971, 1973).
In 1973, Kanegafuchi Chemical Industries announced blends of PPE with 4Swt%
PS and 6wt% of a vinyl-terminated ethylene-propylene-styrene terpolymer (SEP).
The reactive processing resulted in materials with excellent impact strength (Shioji et
al., 1974). The same year, General Electric applied for a patent for blends of PPE with
40 wt % PS, hydrogenated styrene-butadiene-styrene copolymer (20 wt % SEBS,
Kraton™ GXn, and 1.5wt% PE (Haaf, 1979). This was the first application of SEBS
in PPE blends.
In the early 198Os, a series of applications was deposited for PPE/PS blends with
either 1-15phr PA-66 (Mitsubishi Petrochemical Co., 1982a), with 0.1-50wt% PPE-
polyalkene graft copolymer, with epoxy-terminated liquid polybutadiene rubber,
with maleated PP, SEBS and CaC03 (Mitsubishi Petrochemical Co., 1983b), with PS,
SBR and SBS (Mitsubishi Gas Chemical Company Inc., 1985a), or with 4Owt%
ABS Gapan Synthetic Rubber Co., 1985a). In 1985, Mitsubishi Gas Chemical
Company blended PPE/PS with 5 wt % SBS, and 10 wt % radial-SB copolymer
(Sugio et al., 1987).
As time progresses it is increasingly difficult to find patents for PPE blends
that comprise only PS with a styrenic impact modifier. In the late 1970s reactive
processing became the increasingly popular production method, making it more
economic to produce complex blends. Furthermore, reactive modification of PPE
macromolecules made the use of styrenics less important. Thus, on the one hand the
attention was progressively shifted to PPE blends with polyamides (PA), thermo-
plastic polyesters (PEST), polycarbonates (PC) and specialty blends, and on the
other hand, the PPE/PS blends became a part of more complex, multicomponent
systems. It is also important to recognize that in many patents describing PPE
blends, PS is treated as an integral part of PPE, that makes it possible to adjust the
Tg to match the required processing conditions. With growing frequency, PS is
incorporated into the package of standard additives that include stabilizers, lubri-
cants, metal scavengers, plasticizers, etc. The following examples well illustrate the
point. Owing to the multicomponent nature of these blends, further examples can be
found in sections discussing alloys with other resins, such as with PA, PEST, PC, etc.
In 1986 General Electric Company disclosed blends comprising 1Q--65wt%
PPE, lo-75wt% HIPS, 2-lOwt% polyester(s), PS haVing reactive 2-oxazohne groups
(1-25wt% PSOX) and optionally PC and SBS. The blends showed improved impact
strength in comparison to earlier blends, having a favorable combination of proper-
ties, such as mechanical strength, resistance to chemical solvents, and flow proper-
ties in the melt (Avakian et al., 1988). The following year, antistatic PPE/PS blends
were invented in Borg-Warner laboratories. The systems comprised 55-90wt% of
either PS/PPE, HIPS, ABS, MBS, SAN or SMA, 2-50wt% of an epihalohydrin
copolymer and 2-SOwt% of an acrylate polymer (e.g., PMMA). The blends had
good antistatic properties with the ability to rapidly dissipate static electricity
charges, reduced delamination and improved ductility (Gaggar et al., 1988,
1989, 1993).
In 1988 General Electric and Sumitomo Chemical independently disclosed high
impact strength PPE/PS blends with polybutyleneterephthalate (PBT) and SEBS,
obtained by compounding these resins with either polycarbonate (PC) and an
acrylate copolymer impact improver (yates and Lee, 1990) or with urea-butylated
resin (Mizuno and Maruyama, 1990).
Two years later, Himont announced that blends of PPE/PS with SEBS, a styrene-
grafted polypropylene (PP-PS) and a polypropylene (PP) showed excellent melt
processability and heat resistance. The products had high stiffness, tensile strength
at elevated temperatures, high chemical resistance, good gloss and high impact
strength (DeNicola and Giroux, 1994).
In 1991 Eastman Kodak reported that polyesters (namely PETG, PCTG, PET, PBT
or PEN), are miscible with polyvinylphenol (PVPh) at ratios from 1:99 to 99:1.
Furthermore, blends of these polyesters with polymers that are miscible with PS
(e.g., PPE, HIPS or TMPC) can be compatibilized by addition of styrene-Vinyl phenol
either block, graft or random copolymer P(5-b-VPh). The resulting alloys showed
significantly improved mechanical properties, higher yield stress, strength, and
elongation at break as well as excellent toughness (Colby et al., 1993, 1994). The
same year, BASF announced that two major drawbacks of the PPE/PS blends,
namely thermo-oxidation and impact resistance, can be improved by incorporation
of an aromatic vinyl compound, a hydroxy di-t-butyl phenyl phosphonate anti-
oxidant and a heat stabilizer (Zeltner et al., 1993).
In a contemporary patent application from Nippon Petrochemicals, polyarylene-
sulfide (60-80wt% PPS) was blended with 2G-40wt% PPE, O.l-lOOphr of a graft
copolymer comprising 5-95wt% of an epoxidized multiphase copolymer (e.g.,
ethylene-glycidyl(meth)acrylate, (meth)acrylic acid alkyl ester) and 95-5wt% of
either PS or SAN. The alkenic dispersion had a particle diameter of 0.001-10 JLm.
The blends showed high impact resistance, while retaining stiffness, heat resistance,
moldability and appearance. They have been used for the manufacture of automo-
bile parts, electrical and electronic components, industrial parts, etc. (Orikasa and
Sakazume,1994).
Multicomponent blends were disclosed in 1992 by BASF. These comprised
50-90wt% PC, 3-25wt% PPE, 1-20wt% PS, 3-40wt% SAN, 3-25wt% elastomeric
graft copolymer (e.g., polybutylacrylate grafted with styrene and acrylonitrile),
0-25 wt % SEBS, 0-2 wt % PTFE and 0-20 wt % phosphate esters. The blends were
compounded at 260 °C in a twin-screw extruder, then injection molded. The
specimens were fire resistant, with a good set of mechanical properties and
HDT (Niessner et al., 1993). In another document from the company, blends contain-
ing 5-90wt% PPE (Mw = 12-25 kg/mol), 5-90wt% high-impact polystyrene (HIPS,
containing either 2G-40wt% soft phase with encapsulated particle morphology
and diameter of 0.1-0.7JLm, or 5-15 wt % polybutadiene of diameter ~ 3.5 JLm), and
Q-6O wt % usual additives and processing aids were described. The resulting
molding materials had good dimensional stability, stress cracking resistance, and
multiaxial impact strength that was relatively unaffected by reprocessing (Seelert et
al., 1993a).
The same year, General Electric deposited a document describing blends of modi-
fied PPE. Thus, poly(2,6-dimethyl-1,4-phenyleneether) was capped with 2-7wt%
salicylic acid ester, then blended with 6-2oophr SEBS. Next, this blend was dis-
persed in a matrix, e.g., polyamide (PA), polyester (PEST), polyetherimide (PEl) or
polystyrene (PS), engendering moldable blends with improved resistance to loss of
impact strength after thermal cycling (Richards and White, 1994).
Also in 1992, DSM announced blends of 25-75wt% PPE and two graft copoly-
mers. The first comprised a vinyl aromatic, a vinyl nitrile and a third monomer
grafted on a rubber (ABS), whereas the second comprised styrene grafted on a
copolymer of a vinyl aromatic monomer and an 0, ,B-unsaturated dicarboxylic
anhydride. The molecular weight of the PS chains in the second copolymer was
15-150 kg/mol, there were 1-300 functional groups per 3000 monomer units termin-
ally bound to the backbone. The blend could also contain an elastomer that was at
least partly miscible with the ingredients. Having increased notched Izod impact
resistance, the materials were used for moldings (Koning and Borggreve, 1994). In a
contemporary disclosure from Mitsui Toatsu Chemicals, PPE blends were described.
These also comprised G-40wt% PS and 1-40wt% of a dicarboxylic acid ester
copolymer (obtained from a vinyl monomer and an unsaturated dicarboxylic acid
ester, e.g., styrene-dibutylmaleate) having M w :S 60 kg/mol. If necessary, the alloys
may further contain 1-40wt% of a conductive carbon, A-B-A' type or A-B'-B" type
elastomeric block copolymer (such as Kraton™ G-1650 or Dynaron™ 191OP), as well
as other standard ingredients. Owing to its excellent moldability, mechanical proper-
ties and heat resistance, the blends were used to mold parts for the automobile
industry, home electronic or electric appliances and industrial components (Yoshi-
mura et ai., 1995).
Blends comprising a liquid crystal polyester (LCP) are discussed separately; here
only one example is given. In 1992 the University of Akron applied for patent
protection for PS/PPE blends, reinforced by incorporation of a LCP. The alloys
were composite in form and showed excellent mechanical properties. The seU-
reinforcing effects were reported for PPE blends with a thermoplastic flexible poly-
mer and LCP whose melting temperature was above that of the matrix, thus the
melt-processable system was capable of forming submicroscopic fibers. The forming
steps comprised blending under conditions inducing orientation of the LCP, stretch-
ing and cooling to orient the LCP at the molecular level, and shaping the blend below
the melting temperature of the LCP. The moldings had good mechanical properties,
namely modulus, tensile and impact strength (Isayev, 1993, 1994).
20.1.2 PPElPMMA blends

Acrylic polymers such as polymethylmethacrylate (PMMA) are infrequently used in
blends with PPE. The binary blends are immiscible and brittle. Furthermore, at
temperatures above 150°C PMMA thermal degradation by the unzipping mechan-
ism may be catastrophic. Blends of PPE with PMMA are readily compatibilized by
addition of copolymers containing styrenic and acrylic components, such as MABS.
In a 1971 General Electric patent application, PPE was first modified by blending it
with a methylmethacrylate-cis-polyisoprene AB5-type copolymer, then by blending
with PMMA. The low viscosity alloys were easy to process, and the products
showed high impact resistance (Abolins and Reinhardt, 1976). Later GEC patents
described PPE blends having significantly enhanced impact resistance that
comprised SBR and another elastomeric compound, such as methylmethacrylate-
cis-polyisoprene copolymer, acrylonitrile-butadiene-styrene, ABS mixed with
polymethylmethacrylate (PMMA), styrene-grafted EPDM, etc. (Cooper and
Abolins, 1976).
20.1.3 PPEIPE blends

These blends are discussed in Section 14.14, thus only a summary is provided.
Owing to antagonistic immiscibility, two-component blends of PPE with poly-
ethylene (PPE/PE) do not exist. However, since PPE is miscible with PS the PPE/PE
blends can readily be compatibilized by addition of styrene-ethylene either a block
or graft copolymer.
It was found that addition of usually a small amount (e.g., 1.5-5wt%) of PE
improves the flowability of PPE blends and makes the product more solvent resist-
ant (General Electric Co., 1966; Summers et ai., 1972). Addition of a styrenic compat-
ibilizer to PPE/PE blends has been a common feature for a number of patents. For
example, in disclosures of 1973 and 1976, PPE/PS was blended either with SEBS and
PE (Haaf and Lee 1978; Haaf, 1979).
At the opposite end of the concentration range, in 1973 patent applications from
the Polish Institute of Chemical Industry described PE/PP blends with 5-35 wt % of
either PPE, PA-6, PC, PET or Phenoxy. Here, the engineering resins were used as low
density fillers, giving alloys with good processability, rigidity, impact strength and
long life under sterilization (Plochocki et ai., 1978, 1979).
PPE blends with engineering resins 415
20.1.4 PPEIPP blends

These blends are also discussed in the Section 15.1, dedicated to PP blends with
engineering resins; hence only a short summary is given here.
Similar to PPE/PE blends, PPE/PP blends are antagonistically immiscible. Since
PPE alone is non-processable, the PPE must be plasticized with a polymer or
copolymer that lowers its T g , then the blend must be compatibilized. In consequence,
PP has been used only in multicomponent PPE blends, entering as one of several
ingredients to improve processability and solvent resistance. Blends comprising only
a small quantity of PP in PPE/styrenic blends, as well as those where the dispersed
PPE/styrenic phase plays a role of a low density filler, are known.
For example, a 1986 patent application from Mitsubishi Gas Chemical described
reactive blending of maleated PPE (PPE-MA) with maleated PP (PP-MA), styrene-
grafted elastomer, glycidylmethacrylate copolymer and/or phenylenediamine binder
(Togo et al., 1988). In 1994 General Electric Company announced grafting of poly-
alkenes (PO) with an ethylenically unsaturated t-alkylcarbamate. The grafted groups
easily decomposed, providing amine or carboxylic acid functionalization. Thus the
PO copolymers were suitable for reaction with carboxy- or epoxy-functionalized
polyphenyleneethers (PPE) or other polymers (Campbell and Presley, 1995). Simi-
larly, Himont introduced blends comprising PPE/PS, a styrenic grafted polypropy-
lene (PP-PS), a block copolymer (e.g., SEBS) and PP. These materials exhibited
excellent melt processability and heat resistance. The products had high stiffness,
tensile strength at elevated temperatures and high impact strength, as well as high
chemical resistance, good gloss and surface appearance (DeNicola and Giroux, 1994).
The second type of blend with low PPE-content is more common. For example, in
1988 General Electric developed blends comprising more than 50wt% PP, less than
20wt% SEBS and PPE. These alloys had high modulus, rigidity, tensile strength and
heat deflection temperature (Lee, 1990). Sumitomo Chemical disclosed blends having
a semicrystalline matrix, such as polymer selected from PO, PA, PEST, POM, PPS or
PEEK, 1-65 wt % PPE forming a dispersed phase and 0.1-50 wt % of a compatibilizer
(e.g., EPR-MA or EVAc-GMA, alternatively a monomeric additive such as maleic
anhydride or bis(4-phenyl isocyanate). The reactive blending produced alloys having
PPE dispersed as approximately spherical particles with diameters of 0.01-10 J-Lm
(Nishio et al., 1988, 1994; Abe et al., 1988). In 1990 Mitsubishi Petrochemical described
blends that comprised 1G-90wt% hydroxy alkylated PPE (e.g., PPE modified by
glycidol or epichlorohydrin) and 1G-90wt% of maleated or glycidyl methacrylate-
grafted PO, with either a PA or a PEST (Nakano et al., 1992; Arashiro et al., 1994).
20.1.5 PPElvinyl resin blends

A unique patent on PPE blends with polyvinylchloride (35-80 wt % PVC), was
issued to Bayer Aktiengesellschaft (Braese et al., 1977). The molding blends were
characterized by high heat distortion temperatures, and respectable room tempera-
ture impact performance as well as other mechanical properties.
As stated in the introduction to this section on PPE blends, one drawback of these
systems is poor weatherability. However, the miscible polymethylmethacrylate
(PMMA) blends with polyvinylidene fluoride (PVDF) are known for their excellent
outdoor performance. In 1987 General Electric deposited a patent application for
PPE blends comprising SEBS, PVDF and a poly(styrene-co-methylmethacrylate).
Excellent impact strength, elongation, weatherability, chemical and solvent resist-
ance were obtained (Van der Meer et al., 1989).
20.2 PPE BLENDS WITH ENGINEERING RESINS
20.2.1 PPFlPA blends

Blends of polyamides (PA) with polyphenyleneethers (PPE) are discussed in Section
16.3.1 together with other PA blends with engineering resins. The principal reasons
for incorporation of PPE (dispersed phase) into PA-66 are reduced water absorption,
reduced moisture effects on the mechanical properties and improved stiffness up to
190 0c. Here only the most important features will be summarized.
Several commercial blends of PPE/PA are available, including ArtleyTM from
Sumitomo Chemical, Dimension™ from AlliedSignal, LuranylTM from BASF, Lynex™
A from Asahi Chemicals, NoryI"fM GTX from General Electric, Rema/oyTM from
Mitsubishi Petrochemicals, or Ultrany/TM from BASF and VestoblerufI'M from Hills.
Most commercial alloys contain 40-60 wt % PA to form the matrix, with PPE playing
the role of low density filler. The PPE/PA blends show moderate processability,
good dimensional stability, high impact strength, good tensile and flexural strength,
high temperature creep, solvent and chemical resistance, and low moisture absorp-
tion. These blends have been primarily designed for injection molding, extrusion,
blow molding or thermoforming. They are readily paintable and platable. The main
use of these alloys is in the automotive industry.
The first PPE blends with polyamide (PA) were disclosed in 1965 by General
Electric (Finholt, 1968). Incorporation of O.l-25wt% PA was found to improve
processability of PPE - a five-fold drop of die pressure was reported. Similarly, in
1971 Asahi disclosed improved processability and performance of PPE after blend-
ing it with up to 20wt% PA-12 (Komoto, 1972).
The basic patents on the reactive compatibilization of PPE/PA blends belong to
Sumitomo Chemical- in 1979 the company disclosed alloys comprising PPE, PA-66
and maleated SBR (Ueno and Maruyama, 1981, 1982; Maruyama and Ueno, 1982).
Since that date many methods of reactive compatibilization of PPE with PA have
been developed. In broad terms, one must form a copolymer with parts that are
miscible with the major polymeric components, one with PPE and the other with PA.
However, since for good performance of PPE/PA blends the crystallinity may be
important, it is preferred that the compatibilization involves the terminal amine
groups. Obvious exceptions from this rule are blends of PPE with aromatic, amor-
phous polyamides (PARA). Furthermore, since the two resins are brittle, the blends
must be toughened. Successful reactive processing strategy should incorporate all
these three elements.
In 1981, an impact-modified PPE was blended with 5-70wt% PA, and compat-
ibilized by addition of styrene-maleic anhydride copolymer (Asahi-Dow, 1983).
General Electric compatibilized PPE/PA-66 blends with polycarboxylic acid deriva-
tives (Abolins et al., 1985). In following patents the company disclosed blending
amino-terminated PPE with PA adducts of maleic anhydride (PA-MA) (Fujii et al.,
1987). In other patents from the company, PPE/PA blends were reactively compat-
ibilized using an acrylic copolymer (comprising styrene and maleic anhydride) (Van
der Meer et a/., 1987), by maleated hydrogenated styrene-butadiene block copolymer,
SEB5-MA (Modic and Gelles, 1988) or by addition of a reactive compatibilizer such
as trimellitic acid chloride, terephthalic acid chloride or 1-acetoxyacetyl-3,4-diben-
zoic anhydride (Aycock and Ting, 1986, 1987, 1994).
In 1984 Borg-Warner Chemicals blended maleated PPE with PA-66 and SEBS
(Grant and Jalbert, 1987; Grant et al., 1987, 1990). Later the company developed a
method of PPE modification by reactively extruding it with tetracarboxyl cyclopen-
tane. The modified resin was subsequently compounded at a 1:1 ratio with PA-66
and SEBS (Grant and Jalbert, 1989). Functionalized (e.g., maleated) PPE was also
reactively blended with PA, as disclosed by AlliedSignal in 1987-1990. Thus, PPE-
MA was blended with bis-2-hydroxyethyl fumaramide, then mixed with PA and a
functionalized ethylene-a-alkene elastomer (Akkapeddi et at., 1988, 1992b). The
company also disclosed PPE/PA blends compatibilized by addition of either
maleated PPE, SAA or SMA (Samuels, 1994). In 1985 Huls blended PPE with poly-
transoctanylene (PTa), PA and maleic anhydride (Droescher et at., 1986).
In 1987 Sumitomo Chemical Company reactively blended PPE with a semicrystal-
line matrix polymer (e.g., PA-6, PA-66, PBT, PET, PE, PP, paM, PPS or PEEK), and a
compatibilizer such as maleated EPR, a copolymer of ethylene, vinylacetate and
glycidyl methacrylate (EVAc-GMA), a monomeric maleic anhydride (MA) or a
bis(4-phenyl isocyanate) (Abe et at., 1988; Nishio et at., 1988, 1994).
In 1989, General Electric reactively blended functionalized PPE (reacted with
trimellitic anhydride acid chloride and 3.5wt% dimethyl-n-butyl amine) with PA
having low content of terminal amine groups (Smith et ai., 1990, 1994). Two years
later, the company deposited patent applications describing PPE/PA blends, com-
patibilized by addition of either citric acid or chloroepoxytriazine (Gianchandai et ai.,
1993; Yates, 1993).
In a 1991 disclosure from ECP Enichem Polimeri, PPE/PA blends were reactively
compatibilized by addition of an organic diisocyanate (e.g., MOl; Pernice et at., 1992).
In a contemporary patent from the company, blends of PPE/PA with an aromatic
nitro derivative were also described (Bencini and Ghidoni, 1993).
In 1992, GE Plastics Japan deposited a patent describing blends comprising modi-
fied PPE with a mixture of PAs. The PPE resin was either grafted with styrenic units
and/or had a portion of the terminal groups replaced by an epoxy, acidic or anhy-
dride (e.g., trimellitic anhydride) group (Kodaira et at., 1994). In another contempor-
ary patent from the company, PPE/PA blends were reactively compatibilized by
addition of acidified polyalkene (e.g., maleated EPR, ethylene-glycidylmethacrylate
copolymer or ethylene-vinylacetate-glycidylmethacrylate copolymer), and a low-
molecular-weight reactive compatibilizer (citric, malic or agaricic acid) (Ishida and
Kabaya, 1994). The same year, Mitsubishi Petrochemical disclosed PPE/PA blends
with paM, compatibilized by addition of a Lewis acid selected from trialkylborane,
trialkylborate boric acid and halogenated boron (Takayanagi et at., 1994). A contem-
porary deposition from General Electric announced PPE/PA blends formed by
reactive blending of maleated PPE with PA (Lee, 1994). In another patent from the
company, PPE was first capped with a salicylic acid ester, then toughened by com-
pounding with SEBS and dispersed in either PA, PEST or polyetherimide (PEl)
(Richards and White, 1994).
In 1993 Eastman Kodak Company discovered miscibility of thermoplastic poly-
esters (PEST) with polyvinylphenol (PVPh). Graft copolymer, poly(vinylphenol-g-
styrene) (PVPhS), was found to be a good compatibilizer for blends comprising
either PEST or PA, with a polymer miscible with PS, such as PPE, HIPS, PVME or
4MePC (Landry et at., 1994).
20.2.2 PPEIPEST blends

Blends of PPE with thermoplastic polyesters (PEST) are reviewed in Section 17.4.5;
here only a summary is given.
PPE blends with PEST are immiscible, hence they require compatibilization. Since
both resins are brittle, their compatibilized blends must be toughened. Thus, the
evolution of PPE/PEST blends is the evolution of compatibilization and impact
modification. Owing to miscibility of PPE with styrenics, toughening of the PPE
phase is relatively easy. The principal difficulty is to find a method for compatibil-
ization of PEST and impact modification of its phase. There is a similarity in behavior
of PA and PEST in these blends. Thus, the methods discussed for PPE/PA blends
can be largely adapted for PPE/PEST systems. As for the former blends, the most
advantageous methods are based on reactive compounding, preferably involVing
terminal groups. The reactions involving the ester linkages must be strictly con-
trolled, otherwise the crystallinity of PEST will be reduced. Obviously, the latter
comment is immaterial for PPE blends with amorphous, aromatic polyesters such as
PAr.
There are several commercial PPE/PBT blends, including DialoyTM X from Mitsu-
bishi Rayon, BE from Dai Nippon Ink, Gemax™ from General Electric and Iupi-ace™
from Mitsubishi Gas Company. The blends have been designed mainly for injection
molding, extrusion or blow molding. They are compatibilized, and in most cases
reinforced with glass fiber. The PPE/PBT blends are known for their excellent
processability, high solvent and temperature resistance, and dimensional stability.
The first blends of PPE/HIPS with either PET, PBT or PC were patented in the
early 1970s, when Asahi-Dow sequentially polymerized PPE/PS blends, then modi-
fied them by incorporating SMMA and one of PEST, PMMA, PC, acrylates or Phenoxy
(Nakanishi et a/., 1971, 1973; Izawa et a/., 1973; Izawa, 1974; Izawa and Nakanishi,
1973). However, the blends were relatively brittle. This problem was soon solved by
incorporation of an additional impact modifier, such as a styrene-butadiene block
copolymer (Lee, 1978; Chung and Witman, 1985). In 1985 Toray introduced more
complex, four-eomponent blends, such as PPE/PET/PC/EGMA. The high perform-
ance alloys were used for automotive applications. Similar blends comprising PPE,
either PBT or PET, SEBS and PC were also disclosed by General Electric (Brown et a/.,
1987; Campbell et al., 1990; Hobbs et al., 1992). During the following 10 years this
formula has often been modified. For example, either an acrylic impact modifier
(Yates and Lee, 1990), or a PC-PBT copolymer (Chambers et a/., 1995), has been used.
These patents provided the basis for the manufacture of Gemax™. Also in 1985,
Bayer disclosed blends of PPE, PC, PET, ABS and a PC-PPE block copolymer (Freitag
et a/., 1987).
II) 1985 General Electric described functionalization of PPE, obtained, for example,
by reactively compounding it with SBS and maleic anhydride. The modified PPE
was in tum mixed with either PEST or PA (Van der Meer and Yates, 1987). Later, to
facilitate compatibilization of blends with either PA or PEST, PPE was grafted with
unsaturated dicarboxylate, such as fumaric acid (Ishihara, 1989), or end-eapped
with either an epoxytriazine (Yates 1995; Hasson and Yates, 1993), or a salicylic
acid ester (Richards and White, 1994).
Another route was used by Mitsubishi Petrochemical Company, who blended
PPE/PEST with glycidyl methacrylate-grafted SEBS (SEB5-GMA) (Mayumi and
Omori, 1988). The use of SEB5-GMA in PPE/PEST blends was another crucial
event in the development of the technology. The same year, Sumitomo Chemical
Company revealed a general method of reactive blending of PPE with a semicrystal-
line matrix polymer (e.g., PEST, PA, PO, POM, PPS or PEEK). The systems were
compatibilized by addition of either a maleated EPR, a copolymer of ethylene
vinylacetate and glycidylrnethacrylate, a monomeric maleic anhydride or a mono-
meric bis(4-phenyl isocyanate) (Nishio et a/., 1988; 1994; Abe et a/., 1988).
In 1991 Eastman Kodak discovered that PEST form miscible blends with poly-
vinylphenol (PVPh). As a result, PEST blends with polymers miscible with PS
(such as PPE, HIPS or TMPC), could be compatibilized by addition of styrene-
vinylphenol either block, graft or random copolymer, P(5-b-VPh) (Colby et al.,
1993, 1994).
It is important to note that, in many PPE/PEST blends, polycarbonate of bisphe-
nol-A (PC) is also present. The reason has little to do with compatibilization. It was
discovered that owing to its spreading coefficient, the PC forms a layer surrounding
the PPE/SEBS drops in the PEST matrix, thus providing excellent stabilization
against stress coalescence. The blend morphology was found to be unaffected by
abusive processing or forming steps.
20.2.3 PPEIPC blends

Blends of polyphenyleneether (PPE) with polycarbonate of bisphenol-A (PC) are
discussed in Section 18.2.3; only a summary will be given here.
PPE and PC are immiscible and brittle, thus they must be compatibilized and
impact modified. Owing to the similarity of the chemical structure of PC and PEST,
the methods developed for PPE/PEST blends can be used for blends of PPE with Pc.
However, there are few reasons to blend two amorphous polymers having similar
properties. PC has been mainly used as a minor component in multicomponent
PPE/PEST blends, whose role is to provide a barrier against shear coalescence, i.e.,
stabilization of morphology.
The first PPE/PC blends were patented by General Electric (Fox, 1965). The heat
deflection temperature of the blends was found to be a continuous function of PC/
PPE compositions. In 1971 by Asahi-Dow, who developed PPE alloys with either PS
or SMMA, then added either PC (PEST), acrylates or Phenoxy (Izawa and Nakanishi,
1973; Izawa, 1974). Blends with reversed proportions were disclosed 2 years later by
Mitsubishi Gas Chemical Company. Here PC was blended with 1D-80wt% PA-12,
and either PSF, PPE or PET (Okuzono and Kifune, 1975a, 1975b, 1976). In 1984 Borg-
Warner Chemicals disclosed blends comprising 90wt% PC and 10wt% PPE (Falk
and Khait, 1984).
In 1985, General Electric announced blends containing PPE, PBT, SEBS and PC
(Brown et al., 1987). This patent was the first in a series of disclosures of blends
comprising PPE with SEBS, PEST and Pc. During the next 10 years, many variations
on this theme have been invented.
In a 1990 Teijin Chemicals disclosure, PC blends with 90-0wt% of either PS, paM,
PA, PEST, PPE, PSF or PO were described. These were compatibilized by addition of
5-100phr of a block copolymer such as PC-b-PO (Hashimoto et al., 1991). In 1992
BASF announced multicomponent blends of 50-90 wt % PC, 3-25 wt % PPE,
3-25 wt % of a polybutylacrylate grafted with styrene and acrylonitrile, 3-40 wt %
SAN, 1-20wt% PS, 0-20wt% phosphate esters, 0-2wt% PTFE and 0-25wt% SEBS
(Niessner et al., 1993). Also in 1992 Dow Chemical developed multicomponent
blends comprising PC, PEST, PPE, polyalkyl(meth)acrylate and an AB5-type copoly-
mer containing alkyl (meth)acrylates, glycidyl methacrylates, ethylene/propylene/
diene copolymer, maleic anhydride, alkyl or aryl maleimides and oxazoline
(Laughner, 1993, 1994).
20.2.4 PPEIPOM blends

Polyoxymethylene (PaM) forms immiscible blends with PPE that are difficult to
compatibilize. The early blends of paM had low concentrations of dispersed uncom-
patibilized PPE, behaving as an organic filler. For example, in 1972 Asahi blended
POM with 4-4Owt% of PPE and optionally with PS (Ishida and Masamoto, 1974),
whereas Nippon Steel Chemical used 5-50 wt % of either PPE or polysulfone (PSF)
(Ikeguchi and Nagata, 1974).
In 1992 Mitsubishi Petrochemical developed blends having PA as a matrix, in
which PPE and 0.01-5 phr POM were dispersed. The blends were compatibilized by
addition of either trialkylborane, trialkylborate, boric acid or halogenated boron
(Takayanagi et al., 1994).
20.3 PPE BLENDS WITH SPECIALTY RESINS
20.3.1 PPEIPPS blends

Polyarylsulfide, or polyphenylenesulfide, [t/>-5-1 n (PPS) was commercialized in 1971
as Rayton™ R by Phillips Petroleum. The resin is semicrystalline with a melting
point of 288 °C and a glass transition temperature of 194°C. As a linear polymer it
can be formed from the melt or solution. It also can be vulcanized by heat and/or
sulfur. The PPS blends with PPE are relatively recent - the first patent was depOSited
by Phillips Petroleum in 1975 (Bailey, 1977).
The commercial PPS/PPE blends are reactively compatibilized, usually with PPE
as the dispersed phase. The blends are preferably reinforced with up to 40 wt % glass
fiber. Performance of the blend depends critically on the level of crystallinity in the
PPS phase. The first commercial PPS/PPE blends, DIe PPS from Dainippon Ink &
Chemicals, were commercialized in 1982. Today several other blends are available,
including NoryITM APS from General Electric Company.
The PPS/PPE blends have been designed mainly for injection molding, but extru-
sion, compression molding or thermoforming grades can also be found. The compat-
ibilized alloys show good processability, reduced flash in injection molding,
toughness, and high heat and chemical resistance. They find application in the
electrical and electronic industries {for parts and multiconnectors), as well as in
mechanical engineering (e.g., pump impellers). A brief summary of the evolution
of technology follows.
In 1981 PPS was compounded at 280 °C with a styrene-grafted PPE (PS:PPE ratio
of 1:1), and with 5 phr of polyetherester rubber (Pelprene™ P70B). The resulting
alloys showed good toughness, impact and tensile strength (Dainippon Ink and
Chemicals, 1982).
In 1987 Sumitomo Chemical Company disclosed a general method for reactive
blending. The process, conducted in a high speed twin-screw extruder resulted in
dispersion of PPE particles into nearly spherical drops with diameters of 0.01-10 JLm.
Blends with excellent processability, heat resistance and mechanical properties com-
prised 35-98wt% of a semicrystalline matrix (e.g., PA, PEST, PO, POM, PPS or
PEEK), a dispersed phase of 1-65wt% PPE and 0.1-50wt% of a compatibilizer,
and reinforcing talc and/or glass fiber. As a compatibilizer, either maleated EPR, a
copolymer of ethylene, vinylacetate and glycidyl methacrylate, or a monomeric
maleic anhydride or bis(4-phenyl isocyanate) was used. The alloys can be extruded
or molded into a variety of parts, such as for the automobile, electrical and electronic
industries (Nishio et al., 1988, 1994; Abe et al., 1988). In a contemporary patent from
the company, blends comprising 70-90wt% PPS, and PPE were compatibilized by
adding 1-30wt% EBA-MA (a copolymer of ethylene (50-90 parts), acrylate (5-49
parts) and maleic anhydride (0.5-10 parts». The alloys showed high impact
strength, good flexural modulus and HDT. They were used for electric, electronic
and automotive parts (Inoue et aI., 1989). In 1989 the company disclosed PPS/PPE
PPE blends with specialty resins 421
blends with SEBS and PP. The materials were reported to show high heat, impact
and solvent resistance (Maruyama and Mizuno, 199Oa).
In 1988, Ube Industries applied for a patent on reactive compatibilization of PPS/
PPE blends with styrene-glycidylmethacrylate copolymer (SGMA). The fine disper-
sion of PPE in PPS matrix resulted in excellent mechanical, impact and thermal
properties (Nishiyama et al., 1990). The same year, Mitsubishi Rayon Company
disclosed that PPS/PPE blends compounded at a ratio of 1:9 with butylacrylate-
allylmethacrylate, polymerized in the presence of silicone rubber latex (particle
diameters 80-600 run), then grafted with styrene. The alloys showed high impact
resistance without yellowing (Sasaki et al., 1989). In a contemporary patent from
General Electric, blends of PPE with PPS were mixed with 0.05-5 phr of a polycar-
boxylic acid compatibilizer to improve homogeneity of the blend. For example, PPE
with acid groups obtained using 3.5 phr of trimellitic anhydride acid chloride and
3.5 phr of dimethyl-n-butylamine was used. The blends also contained an impact
modifier, either a core-shell MBS or SEBS (Dekkers, 1994).
In 1989 Toa Gosei Chemical Industry Company announced that PPS was blended
with either ABS, PPE, PC, PA or PEST. The compounding was conducted in the
presence of a graft copolymer of these resins prepared by a macromer method. The
graft copolymer had a vinyl monomer backbone with an epoxy group, and a branch
miscible with the selected polymer (Tsuda and Azuma, 1991). The same year,
Dainippon Ink & Chemicals disclosed block copolymers of PPS with polyphenylene
sulfide-sulfone (PPSS) solution-blended with either PPE, PC, PA or POM. The
resulting alloys could be used for extrusion or molding of parts for the electrical,
electronic, automotive and aerospace industries. The products were reported to
show good impact strength and mechanical properties (Ono et al., 1991).
In, 1991 Nippon Petrochemicals Company disclosed blends comprising 1-99wt%
PPS Fortran, with either PC or PPE. They were compatibilized with 0.1-1oophr of a
styrenic copolymer. In the case of the PPE-containing blends, either styrene-gly-
cidylmethacrylate (SGMA) or ethylene-glycidylmethacrylate (EGMA) was used,
whereas for the PC-containing blends ABS was the preferred component. Optionally
the blends were reinforced by addition of fillers (e.g., glass fiber). The alloys that
showed good processability, impact strength, heat resistance and appearance were
used to manufacture automotive, electrical or electronic parts (Orikasa and
Sakazume, 1992). In the following patent from the company, blends comprising
6O-8Owt% PPS, 2D-40wt% PPE and 0.1-1OOphr of a graft copolymer (comprising
5-95wt% of epoxidized multiphase copolymer (e.g., ethylene-glycidyl(meth)acry-
late or (meth)acrylic acid alkyl ester) and 95-5wt% of either PS or SAN). The alkenic
dispersion had particle diameter of 0.001-10 /lm. The blends showed improved
impact resistance while retaining their stiffness, heat resistance, moldability and
appearance. They have been used for the manufacture of parts for the automotive,
electrical and electronic industries, as well as for industrial parts, etc. (Orikasa and
Sakazume,1994).
In a 1992 Sumitomo Chemical disclosure, blends of PPE with PPS, compatibilized
with polymethylene polyphenylene polyisocyanate were described. These materials
could also contain glass fibers. They had excellent mechanical and welding proper-
ties, as well as good solvent resistance, making them useful in injection or extrusion
molding of cases, frames, connectors, switches in electric, electronic and OA fields,
magnet fly wheels, door mirror stays, lamp reflectors, cylinder head covers, gears in
the automobile field and various housings, pulleys, handles, etc. (Gotoh and
Nagaoka, 1993a). In a contemporary patent from the company, PPE blends with
PPS having terminal - SNa groups were described. The alloys could contain poly-
(methylene phenylene isocyanate) as well as glass fibers. These inexpensive blends
showed excellent impact properties, suitable for manufacturing frames, connectors,
switches for electric and electronic applications, parts for automobiles, housings,
pulleys and handles (Gotoh and Nagaoka, 1993b).
Also in 1992 Eastman Kodak developed co-poly(arylene sulfides) (PPS). These
resins, with the structure [(-</>-5--h_A-tj>-5--5--),,ln with x = 0.5--0.001 and n = at least
25, were blended with 1-99 wt % PPE. The blends had good processability, and in the
solid state the interfacial adhesion between components of the blend was high,
resulting in good mechanical properties. The blends were injection molded,
extruded or melt spun (Bagrodia et a/., 1994a).
20.3.2 OTHER PPE BLENDS WITH SPECIALTY POLYMERS

Poly(2,6-dimethyl-p-phenyleneether) (PPE) was blended with most polymers,
including those known as the specialty resins. The latter polymers usually enter
the formulation as a minor component - with the exception of the PPE/PPS systems
discussed in Section 20.3, there are no commercial blends of PPE with speciality
resins.
20.3.2.1 PPE blends with fluorinated polymers

The first patent for PPE blends with a fluorinated polymer was deposited in 1970 by
Uniroyal. Thus, poly(2,6-dimethyl-p-phenyleneether) (PPE) was blended with 5 wt %
poly(hexafluoropropylene-co-vinylidenefluoride), FKM or Viton™B, to obtain ther-
moformable materials with high HOT and flame resistance (Snodgrass and Lau-
cWan, 1972).
In 1987 General Electric disclosed PPE blends with polyvinylidenefluoride
(PVDF), poly(styrene-co-methylmethacrylate) (SMMA), and a hydrogenated sty-
rene-butadiene block copolymer (SEBS). Improved impact strength and elongation
were claimed (Van der Meer et a/., 1989).
In a 1992 deposition from International Business Machines Corporation,
curable blends that comprised fluorine-containing polycyanurates and a thermo-
plastic polymer, such as PSF, PPE or PEEK were described. The polycyanurate
was cured at 180-325°C into a network that contained dispersed, submicron parti-
cles. The blends had a glass transition temperature of 180-320°C, and heat
stability up to 430-500 0c. They were reported to have flame retardancy, as well as
a controlled coefficient of thermal expansion and/or a low dielectric constant. The
filled materials were found useful as insulation, heat- or electrically conducting
materials, prepregs for electronic packaging, adhesives for aerospace structures,
in the fabrication of printed-circuit boards, semiconductor chip carriers, metal-
core boards, chip modules, and multi-layer thin film circuits (Ardakani et al.,
1994).
20.3.2.2 PPEIPSF blends

Few blends of PPE with polysulfone (PSF) have been reported. The first PPE/PSF
blends were discovered in 1966 (Behr and Schneider, 1967). The patent described
alloys of 40-95 wt % PPE with 60-5 wt % of a polysulfone (polyether comprising
diphenylsulfone and bisphenol-A units). Within the range of 10-30wt% PSF, a
large enhancement of the impact strength with an insignificant decrease of the
Vicat temperature was reported.
Other PPE blends with specialty polymers 423
In 1972 Nippon Steel Chemical Company deposited a patent for blends of

polyoxymethylene (POM) with 5-50wt% of PPE and/or polysulfone (PSF). The
blends had the heat deflection temperature increased by 20°C (Ikeguchi and Nagata,
1974).
In 1974 Mitsubishi Gas Chemical Company disclosed polycarbonate (PC) blends
with polyamide (1Q-80wt% PA-12) and with PSF, PPE, and/or PET. Addition of a
small amount of these (uncompatibilized) high temperature polymers was reported
to enhance moldability and mechanical performance (Okuzono and Kifune, 1975,
1976). The following year, Phillips Petroleum Company announced blends compris-
ing polyphenylene sulfide (PPS), 25 wt % PSF, PPE and/or Pc. The blends showed
improved physical behavior (Bailey, 1977).
20.3.2.3 PPEIPI blends

The term polyimide identifies the polymers having an imide group in the chain:
-R-N=(COh=R'- . For a polyimide (PI) to be incorporated into a blend, it must be
melt processable. Owing to variety of the Rand R' groups, there are many PI types.
When R and R' groups are aliphatic, the PI has softening point below 150°C.
However, fully aromatic PIs have such high softening points that, in spite of the
linear macromolecular structures, they must be considered thermosets. To make
them more amenable to processing they are often modified by incorporation of
flexible linkages, such as ethers, amides, etc. Consequently, in this part, PPE blends
with variety of PI are summarized.
In 1980 Asahi-Dow developed PPE blends having high HDT, impact and solvent
resistance. These materials comprised 5-95 wt % of a styrene-phenyl-maleimide
copolymer and (}-90 wt % styrene-butadiene block copolymer (SB, SBS or SEBS)
(Fukuda and Kasahara, 1982). The same year, Arco Polymers disclosed PPE blends
with an SBR grafted with styrene and maleimide (SBMI) at a 1:1 ratio. Good impact
and flexural properties were claimed (Fava and Doak, 1980; Fava, 1981).
In 1985 Raychem Corporation developed PIs having in the backbone phenylin-
dane amines and/or dianhydride moieties. These resins were blended with other
polymers and cured, to provide rigid and stable matrices for manufacturing fiber
reinforced composites. Thus, PI was blended with polyetherimides (PEl Ultem™),
polyethersulfones (PES, Victrex™), polycarbonate (PC, Lexan™) polyarylate (PAr,
Ardei™), polyetheretherketone (PEEK, Victrex™), polyphenyleneether, (PPE,
Noryi™), etc. For example, a plaque prepared from PI:PEEKPEI = 1:1:1 had
Tg = 175°C, and was used to prepare crack-resistant coatings with good adhesion
to metal (Camargo et ai., 1985, 1986). Similar blends were disclosed two years later by
Mitsui Toatsu Chemicals. Thus, an aromatic polyimide, 5(}-99.9wt% PI, was
blended with engineering or specialty thermoplastic resins, namely polysulfides
(PPS), polyarylethers (PPE), polyetherimide (PEl) or polysulfones (PSF). Blending
markedly improved moldability, temperature stability, chemical resistance, and
mechanical strength of the thermoplastic resins (Ohta et al., 1988).
Also in 1987, General Electric deposited a patent for polyetherimide (PEl,
Ultem™) blends with maleated polyphenyleneether (PPE-MA). Good compatibility
and mechanical performance were reported (White and van der Meer, 1989). Three
years later, the company disclosed blends comprising at least two PPE resins with
1-50 wt % polyetherimide-silane copolymer. The blends showed good processability,
flame retardant properties and impact strength (Haaf, 1992).
In 1992 General Electric developed a method of end-capping poly(2,6-dimethyl-
1,4-phenyleneether) (PPE) with 2-7wt% salicylic acid ester. The modified PPE was
blended with 6--200phr of a styrene-butadiene-styrene copolymer, then dispersed in
a matrix resin selected from polyetherimide (PEl), polyamides (PA), polyesters
(PEST) or polystyrene (PS). The moldable blends showed improved resistance to
loss of impact strength after thermal recycling (Richards and White, 1994).
Also in 1992 Mitsubishi Gas Chemical Company disclosed polyamideimide (35-
BOwt% PAl) blends with polyphenylene sulfide (PPS). PAl was obtained from
solution polymerization of trimellitic anhydride with either m-phenylene diisocyan-
ate, tolylene diisocyanate or 4,4'-diphenylmethane diisocyanate, under the condi-
tions where first, at 6O-100°C, an amide group was formed and then, at 105-1BOoC,
an imide group was obtained. The two resins were compounded in a twin-screw
extruder at 360 0c. The blends could also contain such additives as filler (GF),
pigment (Zn~), compatibilizer (aromatic polyisocyanates), lubricant (zinc monta-
nate), ultraviolet absorbent, plasticizer and flame retardant (tricresyl phosphate).
Furthermore, a variety of other resins or elastomers can be added, namely poly-
amides (PA-6, PA-lO, PA-12, PA-66, PA-MXD6, PA-46, PA-6T and PA-6I), aliphatic
or aromatic polyesters (acrylic, PET, PBT, LCP, etc.), PC, PPE, PSF, PES, PEl, PSK,
PEK or PEEK, as well as elastomers based on PPS, PEST, PA, PEA or siloxanes. The
blends had excellent flowability. The molded parts showed high heat resistance and
mechanical strength (Kawaki et al., 1995).
20.3.2.4 PPFJLCP blends

Liquid crystals were recognized by Reinitzer in 1888; polymeric liquid crystals
(LCP) have been studied since the 19408. Du Pont de Nemours introduced the
lyotropic polyamides Keviar™ in 1965. The first wholly aromatic, melt processable
LCP was a polyester, Ekkcel™, introduced in 1972 by Carborundum. In 1974, East-
man Kodak developed thermotropic aromatic/'*Phatic copolymers. Several LCP
resins have been commercialized, such as Xydar by Dartco in 1984, Vectra™ by
Celanese in 1985, E-konoI™ in 1985 by Sumitomo, X-7G by Mitsubishi Chemical in
1985, etc.
In 1987, Amoco Corporation disclosed the first blends of either PPE or a poly-
aryletherketone (PAEK) with liquid crystal polymers (LCP), polyimide (PI), poly-
arylethersulfone (PAES) or thermoplastic polyester. Good mechanical properties,
processability (warp-free moldings) and high HDT were reported (Harris and
Michno, 1988; Harris et aI., 1988; McKenna, 1988; Matzner and Papuga, 1988;
Duska and Field, 1988).
In a patent deposited in 1992 by the University of Akron, PS/PPE blends were self-
reinforced by incorporation of 2-98wt% of the LCP Vectra™ A950. The PPE/PS and
the LCP must have a temperature range in which both are melt processable. Further-
more, within this range of the processing conditions, the LCP viscosity must be
lower than that of the matrix resin. Under these circumstances the melt processable
system is capable of forming long, continuous, submicroscopic fibers. The forming
steps comprised blending under conditions inducing orientation of the LCP, as for
example, in an extruder-static mixer setup, or a twin-screw extruder, then stretching
to orient the LCP at the molecular scale, and cooling. The resulting system contained
predominantly unidirectionally oriented fibers having diameters within the range
1-10 /-Lm, well distributed in the PPE/PS matrix. The blends showed high tensile
strength, high modulus, satisfactory elongation, good impact strength and good high
temperature properties, especially when the LCP content was above 40 wt %. The
blends were subsequently formed in standard processing machines, provided that
during this stage the temperature did not exceed the melting point of LCP (Le.,
Miscible PPE blends 42S
Tprocessing < Tm(LCP». The moldings had good mechanical properties, such as
modulus, tensile and impact strength (Isayev, 1994).
Also in 1992, Mazda Motor Corporation revealed three-component polymer
blends, com~sing a matrix resin, a liquid crystal polyester or polyesteramide
(LCP, Vectra , E-conoI™ or 2aida™) and a compatibilizer. The LCP should have
a crystal transition temperature higher than the molding temperature. LCP was melt
extruded into fibers. The compatibilizer was added to prevent formation of short
fibers with an aspect ratio of ~ 3. The fiber-forming concentration range of LCP
depended on the matrix: in PPE/PS it was 3-60wt%, in PA it was 40-80 wt %, in
ABS it was 3O-75wt%, in PC/ABS it was 3-70 wt %, in PC/PBT it was 20-60wt%,
in PPE/PA-6 it was 3--65wt%, in PP it was 2-70wt%, in PC it was 3-70wt% and in
PBT it was lo-70wt%. The blends have been used as replacements for fiber rein-
forced plastics. They could be easily recycled. The tensile strength was not lowered
on molding, and the reinforcing property was improved, due to increased orienta-
tion of LCP fibers (Tomita et al., 1993, 1994).
20.3.2.5 PPFJPEBA blends

In 1990 General Electric deposited a patent describing blends of a thermoplastic
elastomer, polyether-block-amide (PEBA) with PPE. Thus, at least 5 wt % of PPE was
blended with less than 95wt% PEBA PEBAX™, and o-3wt% of triglycidyl isocya-
nurate. The blends showed non-delaminating behavior and good mechanical prop-
erties (Brown et al., 1992b).
20.3.2.6 PPE/polysiloxane blends

In 1991, General Electric disclosed blends with good flame retardance, comprising
a poly(aryloxysiloxane) (PArSi, e.g., poly(tetraalkylsilyloxybiphenyleneoxide) or
poly(dimethylsiloxybiphenyleneoxide), and any of the following polymers: PPE,
PEST, PC, PEl or SBS. In many instances, the flame retardant blends also exhibited
improved HOT, as well as chemical and impact resistance (as compared to the neat
resin). For example, PBT was rendered flame resistant by blending it with an equal
amount of poly(dimethylsiloxybiphenyleneoxide) Gordan and Webb, 1994).
In 1992 Hoechst-deposited a series of patents for blends prepared from bisphenol-
A dimethylsiloxanes and 7o-97wt% of an amorphous high performance polymer
having a heat deflection temperature above ISO °C (e.g., PPE, PAr, PI, PEST, PC, etc).
Addition of siloxanes reduced the melt viscosity to less than 100 Pa s, without
reducing the HDT. The molded blends showed high impact strength, heat resistance
and HOT. The alloys have been used for the manufacture of microwave ovens,
toasters, irons, safety lamps, sterilizable, fireproof electrical, electronic and space
travel equipment, terminals, IC components, chip carriers, automotive and aircraft
parts (Herrmann-Schoenherr and Land, 1993, 1994).
20.4 MISCIBLE PPE BLENDS

Miscibility of PPE with polystyrene (PS) has been known for 30 years and explored
in the majority of commercial PPE alloys. For example, PPE blends are usually
toughened by addition of an elastomeric copolymer of PS, either grafted or more
frequently block type. Similarly, in many cases the compatibilizer is developed with
a PS chain miscible with PPE and another part able to interact with another blend
component(s).
Recently, two other PPE blends were announced miscible.
The most intriguing blends of PPE are those with polytransoctenylene (PTa,
available from Chemische Werke Hiils as Vestoran™). In the 1984 disclosures, PPE
was initially blended with high impact polystyrene (HIPS) and with PTa. The blends
showed excellent processability and high thermal stability. In the later patents, HIPS
was found to be detrimental because it lowered the heat deflection temperature. The
PPE blends with PTa were reported to have a processing temperature of 260°C,
whereas the finished parts were reported to have high impact strength and HOT
exceeding 194 0c. Since the blends can be processed at relatively low temperatures,
without reducing the heat deflection temperature of neat PPE (values of 205-208°C
were reported), the patents suggest that PTa is miscible with PPE. It is worth
recalling that reduction of HOT has been the principal disadvantage of PPE/PS
blends, where HOT linearly decreased with increasing concentration of PS Oadamus
et al., 1986, 1987). The follOWing year, the company disclosed blends of PPE/PTa
with the polyamide PA-12. These were prepared in two steps: first, 6Q-98wt% PPE
was blended with 4Q-2wt% PTa and 0.1-5wt% maleic anhydride, then PA-12 was
added. The resulting alloys had good processability, high impact strength, excellent
solvent resistance and HOT of 156°C (Droescher et al., 1986; Droescher and Jadamus,
1988).
In 1990 Roehm Chemische Fabrik disclosed development of new miscible blends
of PPE, that are significantly more resistant to UV and visible light, without simul-
taneously reducing the quality of other physical properties of the polymer blend. The
miscible blends comprise 5Q-90wt% of a PPE and 5Q-lOwt% of a polyaryl(meth)
acrylate copolymer. The latter resin comprises the part that ascertains miscibility
with PPE, and another part (0.1~5wt%) that is responsible for absorbing the UV
radiation. For example, 50:50 blends of PPE with such polymers as polyphenyl-
methacrylate, poly(p-methoxyphenylmethacrylate), poly(benzylmethacrylate) or
poly(3-phenylpropylmethacrylate), showed lower critical miscibility temperatures
of 105-150°C. UV protection was offered by copolymers, comprising the miscible
and UV-resistant parts, for example, 55 wt % styrene, 35 wt % benzylacrylate and
10 wt % 3-(2-benzotriazolyl)-2-hydroxy-5+octylbenzyl-methacrylamide. Further-
more, the (co)polymers were used as impact modifiers and cover layers that pro-
tected the PPE substrate from UV irradiation. The miscibility of the cover layers
provided, on the one hand, for good adhesion and, on the other hand, coated
substrates were recyclable without loss of properties (Fischer and Siol, 1993a, 1995).
Polyesters based on terephthalic acid, ethylene glycol and 1,4-cyclohexanedi-
methanol (PCT) are useful for producing clear articles by injection molding or
extrusion with sufficient thermal dimensional stability. However, for applications
such as medical devices requiring steam sterilization, there is a need for improve-
ments by blending with either PS, ABS or SMA. Unfortunately, the blends are
typically opaque. There is a pressing need for polymeric systems having good
thermal dimensional stability, clarity, ease in processing and economic feasibility.
In 1992 Eastman Kodak disclosed clear thermoplastic molding compositions
obtained by blending 5-95 wt % of PCT with 5-95 wt % PPE (haVing an intrinsic
viscosity of 0.15-0.60dl/g). The PCT polyester, either Ektar™ or Kodapak™, was
derived from terephthalic acid, ethylene glycol and 1,4-cyclohexanedimethanol,
wherein the mole ratio of ethylene glycol to 1,4-cyclohexanedimethanol was 66:34-
98:2. The resin had an inherent viscosity of 0.3-1.2 dL/g. The blends may be pre-
pared either by compounding in a single-screw or twin-screw extruder, or by dis-
solution in a common solvent and then precipitation. When necessary,
compatibilizers can be added, as long as they do not substantially reduce the clarity.
Miscible PPE blends 427
The blends showed good thermal dimensional stability, good processability, good
economical feasibility, and good clarity (Stewart and Massa, 1993). As these patents
stipulate, the peT /PPE blends are clear, but they are immiscible and may require
compatibilization. Apparently, clarity was achieved by closely matching the refrac-
tive indices at the usage temperature.
21
Specialty Resin Blends
Blends of specialty resins with commodity and engineering resins have already been
discussed under the headings of the latter resins. Here only the specialty/ specialty
resins will be considered. Out of the long list of what are now considered specialty
resins, the following ones will be discussed: polyphenylenesulfide, PPS, polysul-
fones, PSF, polyetherketone, PEK, PEEK, PEKK, polyetherimide, PEl, polyarnidei-
mide, PAl, molecular composites, and LCP blends.
21.1 POLYARYLENE SULFIDE BLENDS

The first patent for the preparation of polyarylenesulfides (PPS) of structure (4)-5- )n'
was deposited by Phillips Petroleum Company in 1963. The resin was molded at
290°C to give rigid, and heat resistant parts (Edmonds and Hill, 1967). Eight years
later, the company commercialized PPS as Rayton™R. The resin is semicrystalline
with a melting point of 288°C, and a glass transition temperature of 194 0c. PPS has
relatively poor impact resistance. Furthermore, during molding it tends to adhere to
the mold surface, and to flow into mold crevices, a feature known as flash. Blends
have been developed to alleviate these problems.
To toughen PPS the resin has been blended with either EPR, EPDM, ethylene/
acrylate or butyl acrylate elastomers. Owing to the immiscibility of PPS with the
elastomers, it was difficult to improve its impact strength without affecting the heat
resistance and mechanical properties. Under pressure in wet and hot environments,
the impact strengths of these blends rapidly deteriorate. Furthermore, the molded
parts show poor surface appearance. The problem partially rests in the molding
temperature of PPS - at least 290 0c. At these temperatures these elastomers degrade.
Clearly, blending PPS with commodity resins did not solve the basic problems. In
consequence, a strong tendency emerged to blend PPS with higher performance
resins. The first PPS blends with 25wt% of either polysulfone (PSF), polyphenylene
ether (PPE) or polycarbonate (PC) were deposited by Phillips in 1975 (Bailey, 1977).
Several commercial PPS blends are available, such as those with PPE, aramid,
PARA or polytetrafluoroethylene (PTFE). The first commercial PPS/PPE blend, DIe
PPS from Dainippon Ink & Chemicals, was commercialized in 1982. A similar blend,
NorylTM APS-440, is available from General Electric Company. These materials have
been designed for injection molding, but extrusion, compression molding, or ther-
moforming grades can also be used. The blends show good processability and
reduced flash. The products are tough, and have high heat and chemical resistance.
They find application in the electrical and electronic industries (e.g., parts and multi-
Polyarylene sulfide blends 429
connectors), as well as in mechanical engineering (e.g., for pump impellers). Blends

of PPS with aramid fiber, PARA and/or PTFE, are available from RTP Company as
RTP 1300. Blends of PPS with 13-20 wt % PTFE are also manufactured by LNP
Engineering Plastics (a business unit of ICI America) as LubricompTM PPS. The
materials are reported to show excellent wear, as well as solvent, chemical and
oxidation resistance.
As discussed in the following sections, PPS has been blended with the following
specialty resins: polysulfones (PSF), polyarylates (PAr), aromatic polyamides
(PARA), polyimides (PI), polyamideimides (PAl), polyetherketones (PEK), polysi-
loxanes, fluoropolymers, liquid crystal polymers (LCP) and with molten inorganic
glasses.
21.1.1 PPSIPSF blends

Polyarylsulfone (PSF, also abbreviated as PSU or PSO), has the general structure
(-Ar-~-)n' where Ar stands for an arylic group that in most cases includes a
phenyl-ether moiety, -</>-0-. The first PSF was introduced by Union Carbide in 1965.
The resin, having the structure [-<P--C(CH3h--4>-O-4>-SOz-</>-O-ln' was initially sold
as Bakelite Polysulfone, then as Udel™ with Tg = 196°C and a continuous use tem-
perature (CUT) of 160 0c.
In 1971 Astrel™ polyarylethersulfone (PAES), with the structure [+4>-~-</>-O
I/>-~-]n and Tg = 288°C, was introduced by 3M Company. The following year,
Imperial Chemical Industries commercialized polyethersulfone (PES) under the
trade name Victrex™, with Tg = 228-232°C and the structure [+~-</>-O-ln'
Then, in 1976, Union Carbide introduced polyphenylethersulfone (PPSF, Radel™ R)
with the structure [-</>----CHP-I/>-~-</>-O-ln' and Tg = 220°C. Another PAES
was introduced as Radel™ A, of structure [~~+ln-[~]m with
Tg = 217°C (both developed by Union Carbide - now available from Amoco Per-
formance Products). Other PAESs are, for exa~le, Astrel™ of structure [--4>-0-4>-
~+4>-~-ln from Carborundum, Ultrason E from BASF, Talpa™ 1000 from
Mitsui Toatsu and Sumilite™ FS-1300 from Sumitomo Chemicals. In 1986 Celanese
commercialized polyimidesulfone (PISO) and the following year Dainippon Ink &
Chemicals came up with polythioethersulfone (PTES) Amoron™.
The first PPS blends with polysulfone (PSF) were disclosed in 1980. Thus, to
improve the impact strength, 100 parts PPS were blended with 50 parts PSF and 45
parts of a styrene-butadiene rubber (SBR) (Asahi Chemical Industry Co., 1981).
Blends of PPS with a PSF, and polytetrafluoroethylene (5-40 wt % PTFE) were dis-
closed in 1982 by Electricite de France. The materials were reported to have good
processability. The molded parts had a fibrillated PTFE phase, that provided
enhanced resistance to corrosives (Bailleux et al., 1984).
Starting in 1985 Dainippon Ink and Chemicals deposited a series of patents for PPS
blends. The PSF/PPS blends were compatibilized by addition of a PSF-PPS block
copolymer. The alloys showed improved impact strength, uniformity and cohesion
(Hashimoto, 1986). Four years later, a block copolymer of PPS with polyphenylene
sulfide-sulfone (PPSS) was solution blended with either PPE, PC, PA or POM. The
resulting alloys, with good impact strength and mechanical properties, could be
used for extrusion or molding of parts for the electrical, electronics, automotive and
aerospace industries (Ono et al., 1991).
In 1991 Eastman Kodak disclosed blends of a new type of PPS, a co-polyarylene-
sulfide having the structure [(+5-)l_x(I/>-5-5-)xln' where x = 0.001-0.5 and n > 25.
The resin, 15-85 wt % PPS, was blended with polycarbonate (PC) to give
430 Specialty resin blends
materials with enhanced toughness and chemical resistance. To improve the inter-
facial adhesion, a copolymer of polysulfide and polycarbonate (PPS-PC) was added.
In the following patent, 1-99wt% PPS was blended in a twin-screw extruder with
polyarylsulfone (PSF) or polyphenylene-sulfide-sulfone (PPSS). The blends showed
excellent interphase adhesion (Bagrodia et aI., 1993b). Next year, the company
described similar blends comprising 85-15wt% of the co-poly(arylene sulfide)
with 15-85wt% PSF. The alloys have shown excellent interphasial adherence and
improved the mold shrinkage characteristics. The blends were found useful for
electric and electronic applications, pipes, tanks, pumps and other equipment
(Bagrodia et al., 1994b).
In 1992 Ford Motor Company asked for patent protection for blends containing
amorphous polysulfone (45-60wt% PSF), a semicrystalline polyphenylenesulfide
(25-45 wt % PPS) and methylrnethacrylate-butadiene-styrene copolymer (0-10wt%
MBS, Paraloid™ EXL). The alloys were prepared by first compounding PPS with
MBS to form a toughened matrix preblend, then dispersing PSF in it. Molded articles
showed good resistance to impact at high temperatures and other adverse environ-
mental conditions. Applications included car body panels (Golovoy and Cheung,
1994).
21.1.2 PPSIPAr blends

Polyarylates (PAr) with the structure [~1>-C(CH3h-1>-C~-1>-Co-]n are fully
aromatic, linear polyesters that, depending on the ratio of iso- and terephthalic
acids, are either amorphous or semicrystalline. However, the crystalline polyesters
showing thermotropic liquid crystal behaviors do not belong to the PAr category -
they form their own group of liquid crystal polyesters (LCP). In most cases, PAr is
obtained by condensation of aromatic diacid(s) with bisphenol-A.
The first PAr was introduced in 1974 by Unitika as u-~lymerTM, then in 1978
as Ardel D-WO™ by Union Carbide, a year later as Durel by Hooker Chemical
and in 1986 as Arylon™ NCW by du Pont de Nemours. The glass transition
temperature of these resins is ~ 188°C, and the heat deflection temperature is
120-175°C. They have been frequent components of blends, especially with other
PESTs.
In 1976 Unitika blended PAr with polyethyleneterephthalate (40wt% PET) and
with PPS for enhancement of properties (Kyo et al., 1978b). The same year Surnitomo
Chemical announced PAr blends with 1-99wt% PPS. The blends had good proces-
sability, impact strength, fire and abrasion resistance (Matsunaga et al., 1978). The
following year similar blends were disclosed by Hooker Chemicals and Plastics
Corporation. Thus, 75wt% PAr, was blended with 25wt% PPS as Ryton™, and
dodecachloro-dodecahydro-dimethano-di-benzocyclooctene. The alloys showed
good hydrolytic stability, moldability and flame retardance (Salee, 1980, 1981b). In
a later patent, the hydrolytic stability of aromatic polyesters was further improved
by incorporating 10 wt % of either an ABS resin, or a crosslinked copolymer of
butylacrylate, 1,3-butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate
and methyl methacrylate (Salee, 1982).
21.1.3 PPSIPARA blends

Amorphous aromatic polyamides (PARA) have been known since 1969. To this
category also belong polyphthalamides (PPhA, e.g., Amodel™, commercialized in
1991 by Amoco, having T m = 310 °C, HDT = 285°C, Tg = 127°C and a continuous
use temperature of 180 0C). However, the fully aromatic crystalline polyaramides
belong to the liquid crystal polyamides (LCP) category.
In 1980 Phillips Petroleum announced blendin,taromatic, amorphous polyaryla-
mide (PARA) with a small amount of PPS Ryton . The presence of the latter resin
was found to improve moldability, HDT and impact strength (Shue and Scoggins,
1981). At the opposite end of the concentration scale there are blends disclosed in
1988 by T&N Technology. Here, PPS was blended with polyterephthalamide (PPhA)
and reinforced with glass fibers. The material had excellent mechanical properties
(Davies, 1990). Since there is good interaction between the amide groups and
glass fiber, as well as between PPS and the aromatic part of PPhA, the latter resin
was an excellent choice as a sizing agent that did not deteriorate at the high
temperatures required for processing the system. Similar blends were also described
in a contemporary patent disclosure from Amoco - PPS was blended with
PPhA and polyoxycyanoarylene (POCA). The blends were reinforced with a
bronze powder, glass and/or carbon fibers. High degradation temperature, chemical
resistance, HDT and good mechanical properties were reported (Chen and Sinclair,
1990).
In 1990 Mitsui Petrochemical deposited a patent for binary blends comprising
95-5 wt % PARA with 5-95 wt % PPS. The blends were reported to show high
resistance to heat and thermal aging (yamamoto and Toyota, 1992). Next year,
Hills described similar compositions (95-5 wt % PARA with 5-95 wt % PPS) as
having improved melt flow (Poll et al., 1992).
In 1992 Solvay blended 100 parts PPS with 25-95 parts of PA (either PA-66 or
PA-MXD6) and 50-200 parts of Mg(OHh. The blends showed excellent tensile
strength, as well as arc, tracking and heat resistance [Dubois et al., 1993].
21.1.4 PPSIPI blends
The term polyimide identifies polymers that have an imide group in the main chain,
-R-N=(COh= R'-. Owing to the variety of R and R' groups, there is a great diversity
of thermoset and thermoplastic polyimides (PI) with T g = 150-420°C. The early
aromatic polyimides were produced in a reaction between aromatic dianhydride
and aromatic diamine. In 1962 du Pont de Nemours introduced Kapton™, that did
not behave as a thermoplastic in spite of its linear chain structure. Other PIs are
either XU-218 (having Tg = 320°C) from Ciba-Geigy or PI-2080 (having Tg = 310°C)
from Dow Chemical.
To improve the processability of PI, several modifications have been aimed at
increasing the mainchain flexibility, either by introducing aliphatic-aromatic seg-
ments, or chemical segments with higher mobility. These activities resulted in gen-
eration of a family of hyphenated polyimides, namely polyamide-imide (PAl),
polyether-imide (PEl) and polyimide-sulfone (PISO).
The first polyphenylenesulfide blends with polyimide (PPS/PI) were introduced
in 1976. Thus PPS was blended with 6Owt% PI to produce resin that can be easily
injection molded at 310°C. The molded specimens showed HDT = 276°C, low
friction coefficient and good mechanical properties (Alvarez, 1977). In 1987 Mitsui
Toatsu Chemicals announced blends of an aromatic polyimide, SO-99.9wt% PI with
at least one of the following polymers: polysulfide (PPS), polyphenylethers (PPE),
polyetherimide (PEl) and polysulfones (PSF). Blending markedly improved the
moldability of PI. The alloys showed high temperature stability, chemical resistance
and mechanical strength (Ohta et al., 1988).
21.1.5 PPSIPAI blends

Aromatic polyamide-imide (PAl) with Tg = 275°C, was commercialized by Amoco
in 1965 under the trade name Torlon™. By 1977 PAl had been blended with poly-
amides, polysulfone (PSF) or aromatic polyester (Toray Industries, Inc., 1979). The
first blends of PAl with PPS, and polyaryletherketone (PEEK) were announced by
Upjohn in 1984. The blends showed high solvent resistance and hydrolytic stability
(Harris and Gavula, 1986).
Heat-resistant blends that comprised 20-65wt% PAl, 80-35wt% PPS and 0.5-
5 phr of a 4,4'-diphenyl methane diisocyanate were announced in 1990 by Mitsubishi
Gas Chemical Company. PAl was obtained by solution polymerization of trimellitic
anhydride with either m-phenylene diisocyanate, tolylene diisocyanate or 4,4'-
diphenylmethane diisocyanate. First, at 6O-100°C, amide groups were formed and
then, at 105-180 °C imide groups were formed. The blends had good processability,
heat, chemical and solvent resistance, mechanical strength and electrical character-
istics (Kawaki et al., 1994). The following year the company deposited a patent
describing preparation of a heat-resistant blends comprising 35--65 wt % PAl pre-
-cursor, 65--36 wt % PPS and 0.01-20 phr of an isocyanate compound (with at least two
isocyanate groups per molecule). The system showed excellent processability. The
moldings had high tensile strength, HDT and rigidity (Kawaki et al., 1992).
In the disclosure of 1992 from the company, 5-95wt% (preferably 35--80wt%)
PAl was blended with PPS. The two resins were compounded in a twin-screw
extruder at 360 0c. When required, the blends may also contain such additives as
fillers (GF), pigments (Zn~), compatibilizers (aromatic polyisocyanates), lubricants
(zinc montanate), ultraviolet absorbents, plasticizers and flame retardants (tricresyl
phosphate). Furthermore, a variety of other engineering resins or elastomers can be
added to the basic PAI/PPS system, namely PA (e.g., PA-6, PA-10, PA-12, PA-66,
PA-MXD6, PA-46, PA-6T and PA-6I), aliphatic and aromatic PEST (PET, PBT, LCP or
PAr), PC, PPE, PSF, PES, PEl, PSK, PEK or PEEK, as well as elastomers based on PPS,
PEST, PA, PEA or siloxanes. The blends showed excellent flowability. The molded
articles had high heat resistance and mechanical strength (Kawaki et al., 1995).
21.1.6 PPSIPEK blends

Polyaryletherketone (PEK) having the structure [-4>-Co-¢-o-~ln' was synthe-
sized by Imperial Chemical Industries in 1977, test marketed in 1978, and commer-
cialized in 1980 as Victrex™. It is a tough, semicrystalline thermoplastic with a glass
transition temperature of 143°C and a melting point of 334 0c. The resin is usually
processed at 370-380°C, and conditioned at 185°C to encourage crystallization. In
the presence of oxygen, at temperatures above 400°C the resin crosslinks and
degrades. The polymer represents a family of aromatic resins having ether and
ketone linkages in the main chain, such as PEK, PEEKK, etc. (Domininghaus, 1993).
In 1981 Union Carbide Corporation announced the blending of 10-90wt% PPS
Ryton™, with PEEK. The materials were reported to show good processability, as
well as synergistically enhanced tensile, flexural strength and impact resistance
(Robeson, 1982b). Ten years later, Phillips Petroleum Company disclosed blends
comprising 30-70wt% PPS, polymethylpentene (0.1-3wt% PMP), PEEK (claimed
to be used as a nucleating agent), 29.9-SOwt% reinforcing long glass fibers, 0.01-
2 wt % of an organosilane (lubricant) and carbon black (pigment). The injection
molded alloys showed improved mold release and reduced molding flash. The
blends could also be air-eured (Hindi et al., 1994).
21.1.7 PPS blends with polysiloxanes

Silicones, with the general formula [-RnSi-D(4-n)/2-] (where R is either H or not
necessarily identical aliphatic or aromatic moieties and n = 1-3), belong to a large
family of organosilicon compounds, out of which the linear polysiloxanes,
([-DSi(RR')-]; invented in 1937 by Kipping) constitute the largest group. Poly-
dimethylsiloxane (PDMS) has Tg = -127°C, whereas polymethyphenylsiloxane
has Tg = -86°C. PDMS was first introduced by Dow Coming Corporation as Dow-
Corning PDMS - experimentally in 1938, and on a full scale in 1943. Three years later
General Electric also started production of these resins.
In 1985 Phillips Petroleum Company announced blends of polysulfide (100 parts
PPS) with polydimethylsiloxane (0.1-25 parts PDMS), 0.01-5 parts triakoxysilane
and 0.05-20 parts of either polyethylene (PE) or polypropylene (PP). The materials
showed improved processability and impact strength (Liang, 1987).
To improve the heat and impact resistance of PPS, in 1990 Mitsubishi Rayon
Company proposed blending PPS with 5-40 phr of silicone and acrylate elastomers
latex. The latter compound was a copolymer obtained by graft-polymerizing one or
more kinds of vinyl monomers (at least one haVing an epoxy group) onto an
elastomer in which a polyorganosiloxane and a polyalkyl(meth)acrylate elastomer
have been inseparably united with each other. For example, a copolymer of styrene,
acrylonitrile, glycidyl methacrylate, allyl methacrylate and methacryloyl oxypropyl-
dimethoxymethylsilane and a polyorganosiloxane have been used. The alloys may
also contain a filler. The moldings retain their dispersed morphology, and show
excellent impact resistance. The blend is not affected when exposed to wet and hot
conditions under pressure. For example, PPS was blended with 5-30 wt % of an
elastomer. The latter resin was obtained by graft-polymerizing vinyl monomers
onto a polyorganosiloxane rubber and a polyacrylate rubber (united with each
other). The acrylic rubber was prepared from styrene, glycidyl methacrylate, acry-
lonitrile, allyl methacrylate and methacryloyloxypropyldimethoxymethylsilane.
The graft copolymer had an average particle diameter of 0.08--0.6 j.£m. The blend
could be reinforced by incorporation of 10-300 parts of a filler per 100 parts of the
blend (Koshirai et ai., 1994).
The following patent disclosed blends comprising 6D-99wt% PPS, and 1-40wt%
of a polyorganosiloxane copolymer (obtained by graft-polymerizing vinyl mono-
mers onto an elastomer having an average particle size diameter of ~ 80--600 nrn,
consisting of 1-99wt% of a polyorganosiloxane and 1-99wt% of a polyacrylate
elastomer, both inseparably entangled with each other). Furthermore, O.OI-lOphr
of an epoxidized organic silane and 10-300phr of glass and/or carbon fibers was
added. The blends showed a markedly improved impact resistance as compared
with the common compositions obtained by blending PPS with either a diene or a
polyalkene elastomer. They also showed good surface appearance (Yamamoto et ai.,
1994c). A contemporary patent application from the company also described tough-
ening of PPS by addition of an acrylate-grafted polydimethylsiloxane elastomeric
latex, having particle diameters of ~ 0.2j.£m (Koshirai et ai., 1992).
The same year, Polyplastics Company disclosed PPS blends with improved che-
mical resistance, toughness and impact strength. The alloys were prepared by
blending PPS with polyester (40wt% PBn and an aminopropylethylsilane. The
alloys were reactively reinforced with glass fibers (Serizawa et al., 1992).
In 1992 General Electric Company announced blends of amine-functionalized
polyarylene sulfide (PPS) with 0.1-25 phr (preferably 1-10 phr) epoxy-functionalized
polysiloxanes. The latter was a polydimethylsiloxane with epoxy groups
obtained from 2-ehlor0-4-(2/4/6-trimethyl phenoxy)-6-glycidoxy-l,3,5-triazine
(PDM5-G). The moldable blends showed improved tensile elongation and strength
compared to similarly prepared blends without functionalization of PDMS (Han,
1994)
21.1.8 PPS/fluoropolymer blends

Polychlorotrifluoroethylene, as Hostaflon, was first commercialized by Hoechst in
1934. Polytetrafluoroethylene (PTFE) was rediscovered in 1938 and experimentally
introduced in 1942 by du Pont de Nemours as Teflon-TFE - full scale production
started in 1950. In 1951 the company announced FEP-fluorinated EPR; tetrafluor-
oethylene/hexafluoro propylene rubber (Sauer, 1951). Polyvinylidenefluoride
(PVDF) was commercialized by Pennwalt Chemical Company in 1961. The fluor-
ine-containing polymers are characterized by stability at high temperatures (the
degradation temperature is 425-440°C)/ toughness and flexibility at low tempera-
tures/ non-adhesive and low friction properties, insolubility and inertness to
chemicals, as well as low dielectric losses and high dielectric strength. For
example, commercial PTFE is a crystalline polymer with 92-98% crystallinity/
melting point 342 °C and melt viscosity ~ 10 GPa s - in practical terms the material
does not flow. To improve the processability the tetrafluoroethylene was copolymer-
ized into FEP/ ETFE or PFE/ which lowers the melting point (respectively to 260/
260 or 304 0C), and the processing temperature (respectively to 315-400/ 300-350 or
315-425°C).
There is also a large family of copolymeric fluoroelastomers with low glass
transition temperatures, i.e., < -20 °C/ namely those of vinylidenefluoride and either
chlorotrifluoroethylene (Kel-F™ commercialized in 1955)/ hexafluoropropylene
(Fluorel™ and Viton™ commercialized in the late 1950s) or propylene (AflasTM).
These resins are insoluble, have high resistance to chemical attack, and are difficult
to compatibilize. They are mainly used in small quantities to reduce the frictional
properties.
For example, Supec™ W331 is a blend of crystalline PPS with PTFE and 30wt % of
glass fibers, available from General Electric. The material is characterized by extra
wear resistance, lubricity, high heat and chemical resistance. The blends have been
used for manufacture of pumps/ gears, valves, etc.
In 1990 Sumitomo Chemical Company disclosed blends comprising 0.3-50 wt %
of a low molecular weight PTFE (having melting point :::; 350°C) with engineering
resins. The reason for blending was to improve antifriction properties in the
latter polymers (Asai et al., 1991). In a contemporary patent from Daikin Industry,
polyphenylenesulfide (PPS) was similarly blended with PTFE (Yamamoto, Y. et al.,
1991).
In 1992 Imperial Chemical Industries disclosed blends that comprised a fluoro-
polymer, a polyphenylenesulfide (PPS) and poly(aryleneetheretherketone) (PEEK).
The fluoro(co)polymers contained 5D-l00wt% of 2-3C perhaloalkene and an alkenic
monomer (not a fluoroalkene). The blends were reinforced by addition of either
carbon fiber, glass fiber, glass powder, metal powder, ceramic fibers and powders,
metal chalcogenide, calcium fluoride or a siliceous filler. The materials were found to
be wear resistant with a short break-in period for forming a self-lubricating film that
engendered low friction behavior. The materials were used to manufacture wear
parts that, in contact with metal, did not require lubricants, such as shaft bearings
and piston rings in either domestic appliances, cars or hydraulic equipment (Davies
and Hatton, 1994).
21.1.9 PPSILCP blends
Since the late 1970s it has been recognized that liquid crystal polymers (LCP) when
used as a minor component may improve processability of engineering and speci-
alty polymers - the disclosures from Celanese Corporation and from Imperial
Chemical Industries make this quite evident (Froix, 1981; Froix et al., 1981; Cogswell
et al., 1981, 1983, 1984). Furthermore, a small amount of LCP was also reported to
affect crystallization of either engineering or specialty polymers. For example,
addition of a polyesteramide, Vectra™ B950 from Hoechst-Celanese (a copolymer
comprising 20 mol % of terephthalic acid, 20 mol % 4-aminophenol and 60 mol % of
2-hydroxy-6-naphthoic acid) to PPS, caused an accelerated crystallization rate of the
latter resin (Minkova et al., 1992; Hong et al., 1992).
In 1980 Celanese Corporation described blends comprising 5-95 wt % PPS and
5-95 wt % of wholly aromatic liquid crystalline polyesters and liquid crystalline poly-
(esteramides). The blends were reported as having a lower melt viscosity than that of
either polymeric component, thus to be easier to process. Molded articles made
from these materials had improved physical properties compared with average
performance of the component polymers (Froix, 1981). The blends have been
found useful for the electronics industry.
In 1992 Minnesota Mining and Manufacturing Company deposited a patent
application for blends co~rising at least 0.01 wt % of a thermotropic liquid crystal-
line polymer (e.g., Vectra ) and at least one polymer selected from PET, PA, PC, PE,
PP, PVC, PVOC, PPS, PVDF, PVF, PMMA, etc. The blends were used to manufacture
oriented films with small protrusions that resulted in low friction. Other standard
ingredients, in amounts not exceeding 5 wt % (such as UV absorbers, antioxidants,
colorants, slip agents, etc.) could also be incorporated. The blends served as a
substrate for magnetic recordings, a binder for abrasive powders, reinforcing back-
ings, adhesives, to provide writable and/or printable surfaces, capacitor films, etc.
(Wong, 1987, 1994).
In 1993 Hoechst Celanese Corporation announced blends comprising 20-80 wt %
PPS and 2D-80wt% of LCP (condensation product of 6-hydroxy-2-naphthoic acid
and 4-hydroxybenzoic acid), and a liquid crystalline polyesteramide (LCP Ai con-
densation product of 6-hydroxy-2-naphthoic acid, terephthalic acid and 4-arnino-
phenol). In the blends, LCPA constituted 0.5-50 wt % of the total LCP and LCPA
content. The blends were prepared in a twin-screw extruder. The three-component
alloys had melt viscosity lower by at least 5% than corresponding binary blends of
PPS with LCP (as measured at 310°C at a shear rate of 1200 S-I). In other words, the
melt viscosity was reduced when LCPA replaced a portion of the LCP.
This effect was surprising since LCPA has a higher melt viscosity than LCP. It
was reported that replacement of 0.33 wt % of LCP by LCPA resulted in a 20%
reduction of the melt viscosity (in an alloy comprising 33 wt % of LCP + LCPA
and 67% PPS). Furthermore, viscosity reductions of about 5-15% were observed even
when other additives were included in the blend, such as solid fillers or reinforcing
glass fibers. The viscosity was reduced over a wide range of compositions. The
materials were used to mold parts for the electronic industry. The low melt viscosity
was advantageous when molding intricate parts with small cavities (Yung and
Linstid, 1995).
21.1.10 PPS/inorganic glass blends

In 1989 Corning disclosed the development of a new class of inorganic low tempera-
ture glasses (LTG). These materials are based on zinc phosphate, and have molecular
structures that resemble short-chain polymers (Bahn et al., 1991). The new materials
were found durable, water resistant and, most of all, had a glass transition tempera-
ture ~ 300 0C. The water resistance and the relatively low softening temperature
made it possible to blend these glasses with organic polymers. Furthermore, it was
discovered that the structure of the glass can be sufficiently modified to make the
dispersed glass phase interact well with the organic matrix (Frayer, 1993, 1994).
Good mechanical properties were reported.
The LTG was blended with diverse engineering polymers, such as PPS, PET, PBT,
PEK, PEEK, PEl, LCP, PC and fluorinated polymers. The blends containing up to
65 vol % of LTG showed good mechanical properties (Bahn and Quinn, 1991; Frayer,
1993, 1994; Quinn and Beall, 1991). In 1994 Corning introduced Cortem™ Alloys
comprising LTG and a polymer having a similar Tg value. The first blends had either
liquid crystal polyester (LCP) or polyetheretherketone (PEEK) as the matrix, in
which up to 80 wt % of LTG particles was dispersed. The blends were reported to
have very high elastic modulus of 14GPa.
21.2 POLYSULFONE BLENDS
21.2.1 General
Polyarylsulfone (PSF) or, more exactly, polyarylethersulfone (PAES) is a polymer of
the general formula (-Ar-S02-)n' where Ar stands for an arylic ~up that in most
cases includes a phenyl-ether moiety, -</>-0-. The first PSF, Udel , introduced by
Union Carbide in 1965, has the structure l-</>-C(CH3h-<P-O+~-cf>-O-ln' and
Tg = 196°C. In 1971 Astrel™ polyarylethersulfone (PAES) with T g = 288°C and
structure [--<f>--4r-~-<P-O+~-]n'was introduced by 3M Company. The follow-
ing year ICI commercialized polyethersulfone (PES) as Victrex™, with the structure
[+~-</>-O-ln and having Tg = 228-232°C. In 1976 Union Carbide introduced
polyphenylethersulfone (PPSF) as Rildel™ R, with the structure l+cf>-O-</>-O-<Ir-
~-cf>-O-]n' and Tg = 220°C. The newer PSF Rildel™ A has the structure [--G--</>-
~+]n-[--O-4r4r]m and Tg = 217°C. Several other PSFs are on the market.
The first patent for blends of PSF was deposited in 1965 - PSF was blended with
polycarbonate, 1-99wt% PC (Union Carbide Corp., 1966). The following year, Gen-
eral Electric patented PSF blends with 0.5-5 wt % of a polyalkene, either PE or PP
(Gowan, 1969), and 2 years later Uniroyal (Ingulli and Alter, 1969) and Union
Carbide (Barth, 1970), described PSF blends with either ABS or AES. In 1968, the
latter company announced PSF blends with siloxane-polyarylene polyether copoly-
mers, designed to improve impact strength and resistance to failure under stress
(Noshay et ai., 1969). The following year, Uniroyal blended PSF with 1-25wt% EVAc
or 1-50wt% MBS (Lauchlan, 1971).
In 1969 Sumitomo Chemical Company and Borg-Warner Corporation announced
toughened PSF/PC blends. The first company blended PSF with 1-99wt% PC and
with 1-90 parts per 100 parts of PSFfPC blend of either MBS or ABS (Yamauchi et ai.,
1974). The other company blended PC with PSF at a ratio of 1:1, and then with
IO-90wt% ABS (Grabowski, 1971a, 1972a).
21.2.2 Summary of PSF blends

Blends of PSF with commodity and engineering resins have been discussed together
with other blends of these polymers. As far as the commodity resins are concerned,
PSF has been blended with acrylonitrile-butadiene-styrene copolymers (ABS)
Polysulfone blends 437
and less frequently with polyalkenes, such as PE, PP or EPR. PSF has been added
to ABS types to improve toughness (particularly the notched Izod impact
strength), plateability, hydrolytic stability and shape retention at high
temperatures. The PSF effect was similar to, but more effective than, that of PC.
However, the addition of either ABS or PO to PSF was to improve processability and
economy.
In line with the global trend in polymer blends technology, PSF/ ABS blends have
recently been incorporated into more complex formulations as, for example,
with such compatibilizers as Phenoxy, ethylene-vinyl acetate-glycidyl methacrylate
(EVA-GMA) (Gaafar, 199Oa; Orikasa and Sakazume, 1990), SMA copolymers or
methacrylate-butadiene-styrene (MBS) (Golovoy and Cheung, 1994). These more
complex blends also comprised other high performance resins, such as PPE, PPS,
PTFE, etc.
Mindel™ A, and Arylon™ from Amoco are examples of several commercial ABS/
PSF blends available on the market. The former blend is composed of PSF, high heat
ABS - based on a-methylstyrene, Phenoxy as compatibilizer - and MBS core-shell
rubber as impact modifier. These blends show good processability, toughness,
plateability, heat and water resistance.
There are numerous patents for blends of PSF with polyamides (PA), polyesters
(PEST), polycarbonate (PC) and modified polyphenyleneethers (PPE). Blends of PSF
with polyoxymethylene (POM) are also known. For example, as described in a
Nippon Steel Chemical Company patent application of 1972, blending POM with
5-50 wt % of either PPE or polysulfone (PSF) increased its heat deflection tempera-
ture by 20°C (Ikeguchi and Nagata, 1974).
Polysulfones have been blended with aliphatic polyamides, such as PA-6, PA-66,
PA-46, PA-H, etc. The alloys showed good processability and impact strength. To
enhance performance, compatibilization and reinforcement by addition of glass
fibers often had to be used. However, of greater interest seem to be PSF blends
with amorphous, aromatic polyamides (PARA). The materials showed high heat
deflection temperature heat resistance, strength and stiffness.
Blends of PSF with PEST (either PET, PBT, PAr or their mixtures) have
been prepared with the aim to balance their properties - HDT, mechanical
performance and flame retardancy. In most cases these blends also comprise com-
patibilizers and/polycarbonate (PC). The PSF/PEST/PC alloys were described as
having well-balanced mechanical properties and environmental stress cracking
resistance.
Blends of PSF with polycarbonate (PC) have been known since 1965. The blending
induced improvements in the impact and tensile strength, as well as elongation at
break. When PC was blended with 1-99% PAES, toughening by either MBS, ABS or
a core-shell copolymer was required. The blends had good processability, and their
moldings showed a combination of good thermal dimensional stability and tough-
ness.
In Section 21.1.1, polyphenylenesulfide (PPS) blends with PSF are described.
The blends were developed to improve processability and impact strength. The
materials were compatibilized (e.g., by addition of a PSF-PPS block copolymer)
and toughened (e.g., by addition of a styrene-butadiene rubber (SBR) or a
methylmethacrylate-butadiene-styrene copolymer (MBS». The alloys are character-
ized by good heat resistance, high HDT, good mechanical performance, as well as
resistance to impact at high temperatures and other adverse environmental
conditions.
In the following text, the PSF alloys with specialty resins are reviewed.
21.2.3 PSF blends with PAl, PI or PEl

In 1978 and 1979 Toray Industries deposited several patent applications for blends of
an aromatic polyamideimide (PAl, Torlon™ 4000D with O.l-SOwt% of either PA-66,
PARA, PSF Udel™ or an aromatic polyester U-l00, and optionally with fillers. The
blends had improved melt flow, and good mechanical properties (Toray Industries,
Inc., 1979, 1980b, 1981a).
In 1981 Exxon Research and Engineerin&Company blended PES with polypara-
banic acid (PPBA) as Tradlon TM or Tradlac . The latter resin, with T g = 200-300 °C,
is used to form high temperature lacquers or films. Blends of PES with PPBA formed
homogenous, clear sheets (Patton and LaMarre 1983).
In 1982 General Electric disclosed a series of blends comprising a then new resin,
polyetherimide (PEl). Binary blends of PEl with either PSF, PP, PEC or PAr, and
ternary blends with PC and either PEST, PAr or PA were described. The alloys
showed good processability, as well as improved flexural and impact strength (Giles
and Schlicht, 1984; Giles, 1983a, 1984b).
The same year, polyimide (PI), films with good blocking resistance were manu-
.factured by solution casting from N-methylpyrrolidone then drying at ~ 350°C. The
films comprised 100 parts of PI and 0.01-10 parts of polysulfone (PSF) (Mitsubishi
Chemical Industries Co., 1984).
In 1985 Raychem Corporation developed polyimides (PI) having in the
backbone phenylindane amines and/or dianhydride moieties. These resins were
blended with other polymers and cured, to provide a rigid and stable matrix
for fiber reinforced composites. Thus, PI was blended with at least one of the
polymers PEl Ultem™, PES Victrex™, PAr Arde/™, PC Lexan™, PEEK Victrex™,
PPE Nory/TM, etc. For example, a plaque prepared from PI:PEEK:PEI = 1:1:1 had
Tg = 175°C, and was used as crack-resistant coatings with good adhesion to metal
(Camargo et al., 1986).
Two years later, Mitsui Toatsu Chemicals announced similar blends, comprising
an aromatic polyimide, 5O-99.9wt% PI, with at least one of the resins PSF, PPS, PPE
or PEL Blending markedly improved moldability, temperature stability, chemical
resistance and mechanical strength (Ohta et a/., 1988). In 1992 the company patented
a broad category of high performance mixtures comprising 99.9-SOwt% of one or
more high performance resin (such as PES, aromatic polyimide, PI, PEl, PAl, PEK or
PEEK) and O.l-SOwt% of one or more liquid crystal-type polyimide (PI). The
blends were characterized by remarkably good processability and excellent thermal
stability. The best properties of each component resin were well preserved in these
alloys (Okawa et al., 1994).
In the early 1990s, Amoco Corporation disclosed several compositions co~rising
PSF. Thus, in 1990 the company blended the polyethersulfone (PES) Victrex , with
PEl, to get materials with improved HDT (Melquist, 1993). The following year,
miscible blends of PES with an imide-containing copolymer of sulfonyl bis(phthalic
anhydride), 1,4-bis(p-amino cumyl) benzene and diamine(s) were announced. The
systems showed good processability, solubility and a unique combination of
mechanical and thermal properties (El-Hibri and Melquist, 1993).
In a contemporary patent application from the University of Massachusetts, high-
performance blends were described. These comprised 99-1 wt% PES Victrex™ and
1-99wt% aromatic polyimide (PI) such as XU-218 from Ciba-Geigy or PI-2080 from
Dow Chemical. Judging by the presence of a single Tg , the blends were miscible,
shOWing the upper critical solubility temperature. The systems offered significant
advantages, as they could be processed either as a single phase or as phase-separated
Polysulfone blends 439
blends. The moldings had high moduli, tensile strengths and impact strengths
(Karasz and Macknight, 1994).
21.2.4 PSF blends with fluoropolymers

F1uoropolymers, linear thermoplastic or fluoro elastomers, have low brittle point,
high thermal degradation temperature and have high resistance to chemical attack.
They have been used with high performance resins in relatively small quantities, to
reduce the frictional properties, Le., to produce self-lubricating materials.
In 1982 Electricite de France patented blends of PSF with PPS and 5-40wt%
polytetrafluoroethylene WIFE) in the form of fibrils. The blends had good proces-
sability, lubricity, and resistance to corrosives (Bailleux et al., 1984). Similarly, in a
Sumitomo Chemical patent, PES was blended with O.3-SOwt% low molecular
weight PTFE, melting at temperatures below 3SOoC (Asai et al., 1991).
In 1991 Amoco Corporation developed flame-retardant blends of PSF as UdeI™,
with 4O-60wt% PC and/or PET,3-5wt% ZnB03 and 5-10wt% PTFE. The presence
of ZnB03 and PTFE was reported to have synergistic effects (Jack et al., 1993).
The following year, International Business Machines disclosed blends, curable at
180-325°C, that comprised fluorine-containing polycyanurates and a thermoplastic
polymer (e.g., PSF, PPE or PEEK). The cured polycyanurate network contained
dispersed, submicron particles of the latter polymer. The blends were flame retar-
dant, with controlled coefficient of thermal expansion, low dielectric constant,
Tg = 180-320°C and heat stability up to 430-SOO°C. These filled formulations were
used for insulation, as heat- or electrically conducting materials, in prepregs for
electronic packaging, as adhesives for aerospace structures, in the fabrication of
printed-circuit boards, semiconductor chip carriers, metal-core boards, chip modules
and multilayer thin film circuits (Ardakani et al., 1994).
21.2.5 PSF blends with PEK

In 1984 Union Carbide blended PAES, with the structure [--O-¢>--O-4rSCh+]O.2S-
[--O-4rS02+]O.75- with 40 wt % PEEK. The blends had low warpage and mold
shrinkage, high tensile and flexural moduli, HOT = 157°C, with good stress cracking
and impact resistance (Harris and Robeson, 1986). It was also reported that mixtures
of two different PAESs were miscible, transparent, suitable for use in printed-circuit
board technology, and had good heat and solvent resistance (Harris and Robeson,
1987).
In 1981, Imperial Chemical Industries disclosed miscible blends of polyethersul-
fone (PES) with poly(p-phenyleneether-co-p-phenylenesulfonyl). Solvent-cast films
were transparent, and had good water and chemical resistance (Newton, 1981). Four
years later, the company developed multicomponent blends, comprising at least
5 wt % of PES and PEEK, as well as at least 10 wt % of a polyimide, e.g., PEl. For
example, blends of 20wt% PES, 6Owt% PEEK and 20wt% PEl, were found to have
good compatibility and high heat resistance (Rostami, 1987).
In a contemporary deposition from Sumitomo Chemical, 5-75 wt % PES was
blended at 360 °C with 95-75 wt % PEEK. The blends showed good chemical and
hot-water resistance (Tsumato et al., 1987).
In a series of patent disclosures dating from 1985-87, Amoco Corporation
described multicomponent blends of either a polyaryletherketone (PAEK), polyaryl-
ether (PAE) or polyphenyleneether (PPE) with either a liqUid crystal polymer (LCP),
polyimide (PI), polyarylethersulfone (PAES) or thermoplastic polyester. Good
mechanical properties, processability (warp-free moldings), and high HOT were
reported (Harris and Michno, 1988; Harris et al., 1988; McKenna, 1988; Matzner
and Papuga, 1988; Duska and Field, 1988).
21.2.6 Diverse PSF blends

In a 1981 patent application, blends of PSF with 70wt% of an aromatic polyether-
amide (PEA) were described. The alloys showed good moldability, and the moldings
had high mechanical properties and HDT (Hitachi Chemical Co., 1983).
The same year Mobay Chemical Corporation announced blends comprising PSF
with an acrylic elastomer and polyphosphates. The alloys showed good thermal
stability, flame retardance and impact strength (Schmidt, 1983).
Blends of PES with PhenOxyTM were developed in 1990 by Gelman Sciences as
materials useful for preparation of filtration membranes with good chemical resis-
tance and tensile strength (Kraus et al., 1991). The following year, Toray Industries
blended PSF with hydrophilic polymers [e.g., polyvinylpyrrolidone (PVP) or poly-
ethyleneglycol (PEG)]. These blends were subsequently radiation crosslinked, to
produce selectively transmissive either membranes or hollow fibers (Kobayashi
and Tanaka, 1992).
The thermal properties of such biodegradable polymers as polylactic acid (PLA) or
polyglycolides were improved by blending them with a polymer having Tg = 75-
200 °C and the solubility parameter differing by not more than 3 MPa1/ 2 from that of
the biopolymer. For example, in a Novacor Chemicals patent application of 1991,
PLA was blended with either PSF, PC, PI, PPE, siloxanes and silicones, or imidized
polymethylmethacrylate (Nemphos and Kharas, 1993).
In 1992 Mazda Motor Corporation developed solvent-free molecular composites,
characterized by high modulus and strength. The rod-shaped reinforced polymer
was dispersed at a molecular level in a flexible polymer matrix - the diameter of the
rods was found to be less than 70 om. The composite was prepared by mixing a
monomer (to form the rigid-rod polymer, e.g., p-acetoaminobenzoic acid), with
selected flexible polymer, then polymerizing it at a moderate shear rate 2.0-13s- 1 .
For example, PES blends with polyoxybenzoyl acid were prepared for the manufac-
ture of fibers and rod-shaped extrudates (Tochioka, 1993).
21.3 POLYETHERETHERKETONE BLENDS

Polyaryletherketone (PEEK) having the structure [-¢r-CCMP-O--¢r-O-l n , was
commercialized in 1980 by ICI as Victrex™. It is a tough, semicrystalline thermo-
plastic with Tg = 143°C and Tm = 334 0c. The resin is usually processed at 370-
380 °C, then annealed at 185°C to increase the crystallinity. In the presence of
oxygen, at temperatures of 2: 400°C the resin crosslinks and degrades. (Oomining-
haus, 1993).
Several commercial blends of PEEK are available, such as SumiployTM SK and
SumiployTM EK from Sumitomo Chemical. The first blend contains PES as a dis-
persed phase, whereas the second contains oriented fibers of liquid crystalline
polymer (LCP) Sumikasuper™ LCP E6ooo. The PEEK blends have been designed
mainly for injection molding, but extrusion, compression molding or thermoforming
grades are also available. The SK 1660 grade contains glass fibers. The blend's
performance depends on composition, the level of PEEK crystallinity and morphol-
ogy. These materials show good processability, high strength and stiffness, creep
resistance, excellent high temperature performance and HOT (EK grades show low
Polyetheretherketone blends 441
melt viscosity and a soldering resistance temperature of 300 0q, chemical and hot-
water resistance. The blends found application as gear shift pads, bearing retainers,
heat insulating parts for hair irons, parts for soldering equipment and for hot water
applications.
In 1981, i.e., 1 year after the commercialization of PEEK, Union Carbide disclosed
blends comprising PEEK and 10-90wt% PPS Ryton™. The alloys showed improved
processability, synergistically enhanced tensile, flexural strength and impact resis-
tance (Robeson, 1982b). Two years later, the company developed blends comprising
60 wt % polyarylethersulfone (PAES) and 40 wt % PEEK. The alloys had low war-
page and mold shrinkage, high tensile and flexural moduli, HDT = 157°C, good
stress cracking and impact resistance (Harris and Robeson, 1986). The same year, in
an Upjohn patent, blends of PEEK with polyamide-imide (PAl) and optionally with
PPS were described. The alloys were found to have high solvent resistance and good
hydrolytic stability (Harris and Gavula, 1986).
In 1985, ICI disclosed that blends comprising at least 5wt% PES, at least 5wt%
PEEK, and more than 10wt% PEl (for example 20wt% PES, 6Owt% PEEK and
20 wt % PEl), showed good sets of properties, including high heat resistance
(Rostami, 1987). A contemporary patent application from Sumitomo Chemical,
reported that 95-75 wt % PEEK blended with 5-75 wt % PES at 360°C resulted
in alloys having high chemical and hot-water resistance (Tsumato et al., 1987).
Also in 1985, Toray Industries disclosed blends with excellent wear resistance (with-
out loss of slipperiness), useful for nibs of pens. The blends contained polyoxy-
methylene (100 parts POM) and 10 parts of PEEK and/or PEl (Suzuki and
Nagahama, 1987).
In 1988 Amoco Corporation developed injection-moldable blends of polyetherke-
tones (PEK) with polyamideimides (PAl) stabilized with zinc sulfate hydrate. The
blends showed inhibited ketimine reaction, good moldability and high impact
strength (Smyser and Brooks, 1990).
The following year, Minnesota Mining and Manufacturing Company disclosed
blends that comprised a continuous and a disperse phase. The former was composed
of 0-90 wt % of a high performance polymer (having T g ~ 150 o q, selected from PA,
PEST, PI, PAl, PSF, PEl, Pc, PES, PEEK, PPS, PPE, etc., and a block thermoplastic
elastomer (TPE) of the type polyether-b-polyamide or polyether-b-polyester (e.g.,
Pebax™ or HytreI™). Dynamically cured fluoroelastomers formed the dispersed
phase. The blends were easy to mold, flexible and elastic, with excellent chemical
and thermal resistance (Movak et al., 1994).
Also in 1989, Idemitsu Kosan Company announced blends of a liquid
crystal copolymer (LCP) composed of the units [+(CN)~J and [-r/>-CD-
r/>-CD-4>-O-4>-4>-O-J (having 10-80 mol % of the first unit), and 10-90 wt % of at least
one polymer selected from PC, PES, PEl, PEEK, PEST, PAr or PPS. The blends could
also contain a filler. The materials were found to have good processability, high
mechanical strength, and heat and flame resistance. They were used to mold parts
for the electronic, electrical and engineering industries (Murakami et al., 1991).
The following year, blends of thermotropic liquid crystalline polymers were dis-
closed by Toray Industries. Thus, O.I-99wt% LCP having HOT < 190°C, was
blended with at least one polymer selected from PA, PSF, POM, PC, PEST, PPS,
PES, PAr or PEK. The blends showed good processability and mechanical properties
(Yamanaka et al., 1991). In a contemporary patent from the company, blends com-
prising 1-100 wt % LCP (with HDT = 150-280 0q with at least one of the polymers
listed in the first application, as well as with Br- and Sn-eontaining compounds, an
epoxy compatibilizer and a filler, were described. The materials showed high heat
resistance, HDT, flame retardancy, with good appearance and electrical character-
istics (Okamoto et al., 1991).
Also in 1989/ du Pont de Nemours announced blends comprising 6O--80wt% of a
lyotropic polyaramid (poly(p-phenyleneterephthalamide) (PPD-T; Kevlar™), and
2Q-40wt% of at least one polymer selected from polyetherketoneketone (PEKK),
polyacrylonitrile (PAN), polyhexamethylene adipamide (PA-66), poly-f-eaproamide
(PA-6) and an amorphous polyamide (PARA). Oriented, shaped articles were pro-
duced by first forming a biphasic solution of the polymers (the concentration had to
be sufficiently high, 12-20wt%, that the solution was biphasic). The solution was
spun/ coagulated and stretched sixfold, to produce continuous LCP fibrils extending
along the length of the article (when viewed in a TEM at a magnification of 9000). The
blends, as spun/ could be formed by the application of heat and pressure directly into
fibers, films and consolidated parts, shaped and oriented (Coburn and Yang, 1994).
The same year, Mitsui Toatsu Chemicals announced blends comprising: (1)
99.9-50wt% of a polyimide (PI) and (2) O.I-SOwt% of PEK and/or LCP capable of
forming an anisotropic molten phase at :S 420°C. For example, amorphous PI was
prepared from bis[4-(3-aminophenoxy)phenyl]sulfide and pyromellitic dianhydride
having T g = 235°C, whereas a semicrystalline one, from 4,4'-bis(3-aminophenoxy)
biphenyl and pyromellitic dianhydride, had Tm = 387°C. The PEK used was com-
mercial Victrex™ PEK 220P from ICI, while the LCPs were either U-polymer™ U-l00
from Unitika/ Xydar™ SRT-SOO from Dartco, Econol™ E-6ooo from Sumitomo Che-
mical/ etc. For specific applications these blends could also contain other additives
such as phenolic resin (PF), fluoropolymers (e.g., PTFE)/ graphite, carbon fibers,
aromatic polyamide fibers, potassium titanate fibers, crystallization accelerator, etc.
The blends were reported to be easy to process. The products showed HOT ~ 230°C,
with excellent mechanical strength, thermal and chemical resistance (Tsutsumi et al.,
1994). In 1990 the company commercialized Aurum™ PIILCP blends.
Also in 1989 Coming deposited a patent for blends of engineering polymers with
low-temperature inorganic glasses or ceramic glasses. The resins were PEK, PEEK,
PPS/ PEI, LCP, PC/ PET, PBT and fluorinated polymers. The glasses had Tg < 300 °C
and the ability to selectively interact each with a specific polymer. Good mechanical
properties were reported. In May 1994 the company commercialized Cortem AlloysTM
- blends with either LCP or with PEEK (Bahn et al., 1991; Bahn and Quinn/ 1991).
In 1991 Hoechst blended 6O-96wt% of a crystalline polyetherketone (PEK) with
35-2wt% of an amorphous PEK and 35-2wt% of a polyarylester (PAr). The alloys
had good flowability and processability (Falk and Herrmann-Schoenherr, 1992). In a
contemporary patent disclosure from Bayer, blends useful for manufacturing filtra-
tion membranes were described. These comprised aliphatic-aromatic polyether-b-
polycarbonate (e.g., POM-b-PC) with 5-95 wt % of such a film-forming thermoplastic
polymer as PES, PEEK, PA or PAN (Dhein et al., 1993). The same year, Phillips
Petroleum Company disclosed PPS blends with PEEK as a nucleating agent. Reinfor-
cing long glass fibers, 0.01-2wt% of an organosilane (lubricant) and carbon black
were also added. The injection molded alloys showed improved mold release and
reduced flash. The blends could also be air-eured (Hindi et al., 1994).
In 1992/ a patent deposited by the University of Calgary described a new method
of alloy preparation. First, pellets of each of the component resins were milled in a
specially designed shaker ball-mill at acceleration of 12.3 g/ a frequency of 29 Hz, and
at liquid nitrogen temperature, Le., -150°C. Next, the resulting powders were
combined in the required proportions and milled together, yielding the final powder
with a particle diameter of about 2 p.m. This powder was then placed under vacuum
and consolidated for 28 h under pressure of at least 5 MPa, and at a temperature of
Polyetherimide 443
below Tm - 3 to 100 °C, where Tm is the melting point. The polymer(s) were selected
from PC, PMMA, PAl, ABS, PEEK, PF, PEST, Acrylics, PES, PAN, PVC, PVAI, PA,
PS, EP, PCTFE, polycyanate, PMP, PVC, PVOC, PVDF, PE, PVF, etc. Alloying of
these antagonistically immiscible resins resulted in homogenous materials, without
apparent phase separation. The alloys exhibited superior hardness and tensile
strength, but lower maximum strain at break than that expected from the additivity
rule. Furthermore, these blends fractured by a different mechanism than for the
melt-blended, compatibilized alloys. The properties were superior to similar blends
made by conventional methods (Shaw et al., 1993).
Also in 1992, BASF patented a broad class of blends for the manufacture of impact-
resistant moldings with a matte surface. The toughened blends, that comprised any
of the resins ABS, ASA, HIPS, toughened PMMA, PVC, PC, PEST, polyester carbo-
nate, PPE, PEEK, PES, PSF, PPE and/or PPS, were compounded with a matting
copolymer. The latter resin was made of 3o-BOwt% elastomer grafted with alkyla-
crylate, polyfunctional crosslinking monomer, acid group containing monomer,
ethylenically unsaturated monomer, e.g., SEBS, and core-shell graft copolymers.
Moldings prepared from these blends had a matte surface and high toughness.
They were used to produce automobile interior parts, window profiles, garden
furniture, boats, signs, toys, etc. (Niessner et al., 1994)
21.4 POLYETHERIMIDE
Poly[2, 2'-bis(3,4-dicarboxyphenoxy)phenylpropane1-2-phenylene-bisimide1, also
known as polyetherimide (PEl), has the structure [-N(COh-<P-O-¢--C(CH3h-<P-O-
iP(COhCN+l n • The resin has exceptionally high mechanical properties, Tg = 215-
220°C, HDT = 217°C, and no weight loss at $ 400 0c. It was commercialized in 1982
by General Electric as U1tem™. This amorphous resin has high tensile and a flexural
modulus of 3,309 MPa, approaching that of many glass-reinforced resins, even at
elevated temperatures. In 1990 General Electric introduced PEl blends with bisphe-
nol-A polycarbonate (PC) as U1tem™ LTX. Several grades, such as looB, 200A and
2ooB, are unreinforced, non-transparent, food contact compliant, and heat and
chemical resistant. Grade 233B comprises 33 wt % of glass fibers. The blends were
formulated to balance heat and impact properties. They exhibit higher impact
resistance than PEl and higher heat resistance than Pc. They also have stain and
chemical resistance, as well as the long-term hydrolytic stability of PEl. Before
processing, the alloys should be dried for 12-24 h at 150 0c. The processing tempera-
ture ranges from 300-340 °C for the extrusion grades, to 340-380 °C for the injection
molding grades. The blends have been used to manufacture microwaveable cook-
ware, electrical parts, automotive headlamps, firefighter helmets, air handling and
plenum space. Grades with flame-retardant capabilities are also available (Utracki,
1994b).
Although PEl was commercialized in 1982, the first patents describing PEl blends
with engineering and specialty polymers were applied for in 1979. For example,
General Electric blended PEl with polyarylate (PAr) to give materials with good
molding and mechanical properties (Holub and Mellinger, 1981; Holub 1990; Holub
and Schlicht, 1990; Mellinger et al., 1985).
Also in 1979 a deposition from Union Carbide described PEl blends at a 1:1 ratio
with polyamideimide, (PAl). The materials had good mechanical properties and
excellent environmental stress crack resistance (Maresca et al., 1981). In a later
document from the company, polyarylethers were blended with polyetherimides
(PEl), to give good environmental stress cracking resistance (Robeson et al., 1981). In
1982 Union Carbide announced blends comprising PEl, PA-6 and PEI-PA block
copolymer. The resulting alloys showed improved moldability and impact strength
(Robeson and Matzner, 1984).
To obtain materials with high heat deflection temperature and tensile strength, in
1981 General Electric Company blended PEl with polyestercarbonate (Quinn, 1984).
Three years later, these blends were modified by incorporation of polyethyleneter-
ephthalate (PET). Thus, 25 wt % PEl was blended with 25 wt % PEC and 50 wt % PET
to obtain alloys with good processability and impact strength, comparable to that of
PEl (Quinn and Holub, 1986).
In 1982 General Electric deposited a series of patents describing PEl blends with a
diversity of resins, such as block copolymer of poly(carbonate-b-siloxane), with 5 wt %
of either EPDM, ABS, MBS or acrylate copolymers such as MBS or MMBA (Giles and
White, 1983). The following year, binary blends with PA, PP, PSF, PEC or PAr, and
ternary blends (e.g., with PC and PEST) were patented (Giles and Schlicht, 1984). In
the patent granted in 1987, blends of PEl with PA-12 were described (Giles, 1987).
In 1985, to improve mold release properties, PEl was blended with 0.5-20 wt % of a
fluoropolymer. The blends also showed high heat resistance and low shrinkage
(Sumitomo Chemical Co., 1985). Also in 1985, Imperial Chemical Industries de-
veloped blends comprising at least 5 wt % of polyethersulfone (PES) at least 5 wt %
of a polyetheretherketone (PEEK) and at least 10 wt % of a polyetherimide (PEl). For
example, 60 wt % PEEK was blended with 20 wt % PES and 20 wt % PEl, to produce
alloys showing good compatibility and high heat resistance (Rostami, 1987).
Two years later, Mitsui Toatsu Chemicals, disclosed blends of an aromatic polyimide
(50-99.9wt% PI) with polysulfides (PPS), polyethers (PPE), polyetherimide (PEl) or
polysulfones (PSF). Blending markedly improved moldability, temperature stability,
chemical resistance and mechanical strength (Ohta et al., 1988).
Patent applications deposited by General Electric in 1987 and 1989 described
compatibilized PEl blends with 5-95 wt % of either PA-6 or PA-66. Compatibilization
was achieved by incorporating 0.5-30 phr of one or more phenolic compounds, such
as a nonyl-phenolic additive. The blends were reported to have reduced water
absorption, low swell, and good dimensional stability (Gallucci, 1988; Gallucci and
Rock, 1992). Similarly, PEl was blended with maleated polyphenyleneether PPE-
MA) - good compatibility and mechanical performance were found (White and van
der Meer, 1989). Also in 1987 the company blended PEl with polycarbonate (PC) and
with phenyl phosphate stabilizer to obtain better melt stability (Peters and Rock,
1989). In a later patent ABS was added to PEl/PEST blends to further enhance the
impact resistance (Gaafar, 1990b).
In 1988 Rohrn & Haas Company asked for patent protection for a broad category of
blends comprising an engineering resin selected from PC, PBT, PET, PEC, PAr, PEl,
PA, PPE with HIPS, PSF, PEl, POM, PI, SAN, SMA and/or their blends (e.g., PBT
with PC and MBS), and an acrylic copolymer (e.g., methYlmethacrylate-ethYlacry-
late-butylmethacrylate with molecular weight> 500 kg/mol). The high-molecular-
weight acrylic improved melt flow and increased the sag time, facilitating blow
molding, thermoforming, extrusion or foaming of the engineering resin to be used
for manufacturing automotive bumpers, body panels, containers, architectural wall
panels, and other parts (Memon, 1992, 1994).
Four years later, the company deposited a patent application for blends compris-
ing 100 parts of a polar resin (e.g., PVC homo- or copolymers, ABS, PSF, PEl or LCP),
1-15 parts of a segmented polymer comprising non-polar, non-rubbery polyalkene
haVing M w = 50-1000 kg/mol (e.g., PP, PE or their copolymers), and a polymer
derived from at least BOwt% of an alkyl, aryl, alkaryl or methyl methacrylate ester
Polyetherimide 445
and not more than 20 wt % of an acrylic or styrenic monomer, having M w = 20-
200kg/mol. The blends were mixed while heating until fluxed. The blending
improved processability, for example by decreasing the time to flux of PVC and
the temperature and pressure requirements for injection molding, and improving the
melt strength of ABS. The blends were used for extrusion or injection molding of
pipes and pipe fittings, garden tools, electrical, automotive and business machines or
appliance parts, toys, sporting goods, footwear, battery cases, conduits, construction
profiles, wire coatings, garden hose, packaging film, and profiles for medical
applications, automotive or furniture seating, wall coverings and bottles (Williams
and llenda, 1993).
In 1989 Idemitsu Kosan Company developed blends that comprised: (1) 10-90 wt %
of a polyetherketone copolymer, (2) 10-90wt% of least one polymer selected from
PC, PES, PEl, PEEK, PEST, PAr or PPS, and (3) a filler. The polyetherketone
copolymer was composed of two types of units: A = [-¢(CN)--o-<t>--<t>--Ol and
B = [-<f>-C0-</>-C0--q)-0-~1. The type A unit content varied from 10 to
SOmol%. The alloys were reported to show good processability. Their moldings
had high mechanical strength, as well as heat and flame resistance. They were used
for the manufacture of electronic, electrical and machine parts (Murakami et al., 1991).
The same year, Minnesota Mining and Manufacturing Company described blends
of dynamically cured fluoro-elastomers dispersed in a polymer mixture composed of
o-90wt% of an engineering resin having Tg 2:: 150°C (for example, PA, PEST, PI,
PAl, PSF, PEl, PC, PES, PEEK, PPS or PPE), and 100-10wt% of a block thermoplastic
elastomer (TPE) of the type polyether-b-polyamide or polyether-b-polyester (e.g.,
Pebax™ or Hytrel™). The blends were easy to mold into moldings that were flexible,
elastic and self-lubricating, having excellent chemical and thermal resistance (Movak
et al., 1994).
Also in 1989 Surnitomo Electric Industries developed blends containing 100 phr
PEl, 5-50 phr PBT and 10-50 phr of a crosslinking agent comprising triallyl cyanu-
rate and triallyl isocyanurate. The blends showed high thermal deformation resist-
ance and HDT (Hosoi, 1991). The same year, Corning disclosed blends of special low
temperature inorganic glasses or ceramic glasses with engineering or specialty
resins such as PEK, PEEK, PPS, PEl, LCP, PC, PET, PBT and fluorinated polymers.
The glasses had a sufficiently low glass transition temperature, below 300 DC, and the
ability to selectively interact with the polymer. Good mechanical properties were
reported. In May 1994 the company commercialized Cortem AlloysTM.
The following year General Electric blended amino-terminated PEl with liquid
crystal polyester (LCP), generating high strength alloys (Bookbinder and Sybert,
1992). In 1991 the company patented a broad category of blends of poly(aryloxysi-
loxane) (PArSi) with such polymers as PPE, PEST, PC, PEl, ABS or SBS. Incorpora-
tion of PArSi provided good flame retardance. In many instances, the blends also
showed improved chemical resistance, impact resistance and HDT, as compared to
the neat polymer Gordan and Webb, 1994). Another application described impact-
resistant materials obtained by blending block polyether-polyimide-siloxane copoly-
mer, with l-lOwt% of a low-molecular-weight PEl. The blends had high melt flow,
thus excellent processability (for injection molding, extrusion and wire coating). The
moldings showed good elongation, impact resistance and HDT (Durfee and Rock,
1993). In a contemporary patent application the company announced surprising
blends of PEl with 5-95 wt % of a copolymer comprising an a-alkene and a vinyl
ester (e.g., EVAc). The blends showed good processability, compressibility, elasticity,
low temperature impact strength, UV-resistance, chemical resistance, dynamic fati-
gue properties and paintability (Stahl and Geyer, 1993).
Also in 1991 General Electric disclosed blends of copolyesteretherimide (PEEl;
LomoJIM) with either a semicrystalline or an amorphous polyamide, PA or PARA.
The alloying resulted in materials characterized by good thermal aging
behavior (Angeli, 1992). In 1992 the company announced that poly(2,6-dimethyl-
1,4-phenyleneether) (PPE) was capped with 2-7wt% salicylic acid ester, then
blended with 6-200 phr of a styrene-butadiene-styrene copolymer. Next, the blend
was dispersed in a matrix, such as polyamide (PA), polyester (PEST), polyetherimide
(PEl) or polystyrene (PS). The moldable blends showed improved resistance to loss in
impact strength after thermal recycling (Richards and White, 1994). General Electric
also developed Supec™ CTX530, a PPS/PEI blend reinforced with 30 wt % glass fibers.
The material is characterized by high flow and no flash. The blends have been used
for manufacture of infrared-solderable surface mount electronic applications.
In 1991 Hoechst deposited several patents for PEl blends with liquid crystal
polymers (LCP). Thus, 2-SOwt% PEl, was blended with 5D-98wt% LCP to obtain
materials having high impact and heat resistance, with good elongation at break
(Roemer and Schleicher 1993a). In another application, 5-95wt% PEl was blended
with 5-95wt% LCP, and 0.5-10 phr of a compatibilizer (p-amino benzoic acid or
pyromellitic anhydride). The moldable resins were used as matrices for composites.
It was reported that addition of the compatibilizer improved elongation at break and
ultimate tensile strength (Roemer and Schleicher, 1993b).
The same year, blends of one or more liquid crystal-type polyimides (0.1-50wt%
LCP-PI) with 99.9-SOwt% of one or more engineering or specialty resin (namely
aromatic polyimide (PI), polyetherimide (PEl), polyamideimide (PAl), polyethersul-
fone (PES) or polyetherketone (PEK or PEEK», were developed by Mitsui Toatsu
Chemical. The invention prOVided blends that preserved the excellent properties of
each resin, and in addition were characterized by remarkably good processability
and excellent thermal stability (Okawa et ai., 1994).
In 1992 Hoechst Celanese announced that thermo-oxidative stability of articles
(manufactured from blends comprising a polybenzimidazole, 5-100wt% PBI and
D-95wt% of PEl, as Ultem™) was achieved by treating the PBI-eontaining article
with a solution of 2-10wt% of phosphoric acid for sufficient time to produce an
acid-treated surface, then by removing the excess acid, and drying. Next, the article
was heat treated in an inert atmosphere, at ~ 400-500 °C, to form a phosphate barrier
layer on the surface. It was reported that articles retained more than SO % of their
weight after isothermal aging at 315°C for at least 300 h. The preferred PBI used in
the blends was poly-2, 2'-(m-phenylene)-5,s'-bibenzimidazole (Haider and Chene-
vey, 1994).
Also in 1992 Istituto Guido Donegani blended PEl with aromatic alkyl methacry-
lates (e.g., polybenzylmethacrylate) to give transparent, miscible materials. The
blends showed good processability and toughness in comparison to PEl, as well as
improved HDT, modulus and tensile strength in comparison to the methacrylates.
Mixtures of PEl with polycarbonates (PC) were also compatibilized into single phase
blends by addition of a polyaromatic alkyl methacrylate. Thus, 1-79wt% PEl was
blended with 1-79wt% PC and 2D-98wt% aromatic alkyl methacrylate, to give
transparent materials with good processability and mechanical properties (Drze-
winski,1993d).
21.5 AROMATIC POLYAMIDES

In 1929 Carothers and Arvin described the preparation of linear polyesters from di-
acids and di-alcohols. After studying a large number of polyesters, neither Carothers
Aromatic polyamides 447
nor apparently du Pont expected them to be of value as fiber-spinning polymers - the
melting point of these polyesters was too low. Furthermore, in 1930 Carothers and
Berchett reported a conversion of an w-aminocaproic acid that resulted in gray, waxy
polyamides, with molecular weights below 3000 g/mol (Carothers and Hill, 1932).
Effort was then concentrated on the preparation of fiber-forming superpolyamides,
and the work on aliphatic polyesters was discontinued. Ten years later, Whinfield
and Dickson of Calico Printers' Association discovered fiber-forming aromatic
polyesters, for example polyethyleneterephthalate (PET), soon commercialized by
ICI as Terylene™.
Thus, crystalline fiber-forming resins with excellent mechanical properties were
obtained using either aliphatic polyamides or aromatic polyesters, whereas the
aliphatic polyesters showed poor performance. It seems that, in aromatic polyesters,
1l'-1r bonding between the aromatic rings plays a similar role to the amide-arnide
interactions in polyamides. If so, then polymers combining 1l'-1r bonding together
with amide-amide interactions are expected to show extraordinary performance
characteristics.
It was historically just that the discovery of super-performing aromatic polya-
mides took place in the laboratories where Carothers carried out his pioneering
research - the aromatic polyamides were developed by du Pont de Nemours. The
first patent was issued in 1958, and three years later the company started production
of poly(m-phenyleneisophthalamide) Nomex™. The lyotropic poly(p-phenylene
terephthalamide) Kevlar™-49 was invented in 1965 and introduced commercially
in 1970 (Cassidy, 1982). These polyamides have such strong intermolecular interac-
tions that they are difficult to form. This created the need to develop aromatic
polyamides with higher chain mobility - the amorphous type.
There is a great diversity of amorphous, either aromatic or semi-aromatic poly-
amides. The first amorphous aromatic polyamides (PARA) were introduced in 1969
by Dynamic Nobel as TrogamiJIM. In 1980 by du Pont de Nemours disclosed
transparent, amorphous, aromatic polyamides, prepared by reacting 60-90 % iso-
phthalic and 40-10% terephthalic acid with 92~% hexamethylenediamine and
8-92 % bis(p-aminocycloexyl)methane (Pagilagan, 1982a, 1983). In 1988 Mitsui Petro-
chemical introduced a co-polyamide from hexamethylenediamine, caprolactam, and
isophthalic and terephthalic acids (PA-6IT6). Polyphthalamide was commercialized
in 1991 by Amoco as Amodel™.
Since 1965 a variety of PARAs has been blended. For example, in 1967 PARA was
blended with POM. A significant improvement of toughness and impact strength
was obtained (Asahi Chemical Industry Co., 1969b). In 1969, Dynamit Nobel, and
later du Pont de Nemours, developed blends of PARA with semicrystalline poly-
amides (PA-6, PA-66, PA-6lO, PA-ll or PA-12), mainly to improve the oxygen
barrier properties (Dynamit Nobel, 1969; Epstein, 1976, 1979). Aromatic polyamide-
imide (PAl) as Torlon™ 4000T was blended with polyamide (PA-66 or PARA) for
improved processability and mechanical properties, and in later patents with poly-
ether-sulfone (PE5-UdeZ'rM) or aromatic polyester (PAr; U-100) for improved melt
flow and mechanical properties (Toray Industries, 1979, 1981).
Blends of PARA with other engineering or specialty resins were also patented:
with PC for pearly looking blends, having good resistance to oils and boiling water,
and good mechanical properties (Mitsubishi Chem. Ind. Co., 198Oa); with the PPS
Ryton™, for improved moldability, HDT and impact strength (Shue and Scoggins,
1981); with partially aromatic polyamide, PA-6I6T, for the manufacture of strong
fibers or films (Unitika Co., 1982a); with PES for increased HDT and mechanical
performance (Hub et al., 1986); with maleated either PP (Iwanami et al., 1990) or PE,
to obtain materials suitable for production of sliding and electrical parts, having
good resistance to thermal degradation when in contact with metals (e.g., Cu)
(Yoshihara, 1990); with rubber-modified PS for optically clear, transparent materials,
having near-zero birefringence (Angeli and Maresca, 1990); and with PAr to obtain
miscible blends, characterized by excellent processability, mechanical properties,
HDT, solvent, weather, impact and stress-erack resistance (Bapat et al., 1992; Dean,
1992).
In 1988 T&N Technology blended PPS with polyterephthalamide (PPhA) then
reinforced the alloys with glass fibers (Davies, 1990). In 1990 Mitsui Petrochemical
deposited a patent for binary blends comprising 95-'swt% PARA with 5-95wt%
PPS (Yamamoto and Toyota, 1992). One year later, Hills claimed similar composi-
tions (Poll et al., 1992).
Blends of PARA are also discussed together with other blends of polyamides,
under the appropriate headings (Chapter 16).
21.6 POLYARYLATES
Polyarylates (PAr) with the structure [--<:Mt>-C(CH3h-<t>-C~-</>-Co-ln' are
linear polyesters, usually of bisphenol-A, with isophthalic and terephthalic acids.
Depending on the ratio of the iso- to terephthalic acid, PArs are either amorphous or
semicrystalline. The resins were first introduced in 1974 by Unitika as U-polymer™,
then in 1978 as Ardel 0-100™ by Union Carbide, a year later as Ourel™ by Hooker
Chemical, and in 1986 as Arylon™ NeW by du Pont de Nemours. Their glass
transition temperature is ::::: 188 °C, and HDT = 120-175°C. They have been frequent
components of blends. The high cost of PAr has to be balanced with their
transparency, good weatherability and high HOT. Three types of PAr blends are of
particular importance - those with polyesters (PEST), polyamides (PA) and with
polyphenylenesulfide (PPS).
In 1971 Unitika issued a series of patent applications for blends of PAr, for
example with either 30 wt % ABS, polyacrylate rubber, PP, EVAc, PE, or with
5-90wt% PC and up to 50wt% PET (Koshimo, 1973; Koshimo et al., 1973). PAr
blends with PET are transparent and impact resistant (e.g., U 8000 from Unitika or
ArdeITM 0-240 from Amoco). Further enhancement of properties was obtained by
blending PAr: PET = 1:1 system with either PA-6 or PPS (Asahara et al., 1977; Kyo et
al., 1978). In a later patent, hydrolytic stability of aromatic polyesters was further
improved by incorporation of 10 wt % of either ABS or a crosslinked copolymer of
butylacrylate, 1,3-butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate and
methyl methacrylate (MBS) (Salee, 1982).
Another important type of PAr blend is that with polyamides (e.g., with PA-6 sold
by Unitika as U-polymer™ X-9) showing good processability and mechanical proper-
ties (Unitika Ltd., 1982b; 1983b). In 1991 Amoco announced that aromatic polyesters
containing 12-SOwt% tertiary butyl substituted aromatic nuclei (PAr) were blended
with aliphatic-aromatic polyamides (PARA) having a ratio of aliphatic to aromatic
carbons from 1.4 to 2.5. Judging by the single Tg, the blends were considered
miscible. They showed excellent processability, mechanical properties, solvent,
weather, impact and stress-erack resistance (Dean, 1992).
Sumitomo Chemical developed PAr blends with 1-99wt% polyphenylenesulfide
(PPS), characterized by good processability, impact strength, fire and abrasion resist-
ance (Matsunaga et al., 1978). Similar resins were disclosed by Hooker Chemicals and
Plastics Corporation. Thus, 75wt% PAr, was blended with 25wt% PPS Ryton™,
and with dodecachloro-dodecahydro-dimethano-di-benzocyclooctene. The alloys
Molecular composites 449
showed good hydrolytic stability, moldability and flame retardance (Salee, 198Ob,
1981b).
In 1987 Hoechst Celanese discovered that blends of polybenzimidazole (PBI) with
PAr are miscible (Chen et al., 1990). Since the 1970s PAr has been blended with nearly
all commercial resins, including ABS, EPDM, ionomers, LCP, PA, PB, PBI, PBT, PC,
PEl, PEK, PET, Phenoxy, PMB, PS, PPE, PPS, etc. These systems are discussed in the
appropriate sections of this book.
21.7 MOLECULAR COMPOSITES

The tensile strength a of fiber reinforced composites depends on their length to
diameter ratio, LID. The a versus LID dependence reaches a plateau value for
LID 2:: 500 (Piggott, 1986). Since the absolute size of the reinforcing fibers is not
important, it has been postulated that the fracture and impact toughness as well as
the mechanical properties of a conventional, flexible-chain resin can be significantly
improved by incorporation of molecular-scale fibers, Le., the rigid-rod macromole-
cules. In this concept the reinforcement is provided by individual macromolecules,
not their phase-separated domains, Le., the rigid-rod polymer must be dissolved
down to individual molecules within the thermoplastic resin. In short, the systems
known as molecular composites (MC) must be miscible. The immiscible systems
with rigid-rod polymers in which phase separation occur, should be treated as
blends with anisometric dispersions. These blends belong to the category of liquid
crystal polymer (LCP) blends with thermoplastic polymers (Section 21.8).
The first attempts to generate MC date back to the late 1970s. Thus, rigid
microfibrils of aromatic polyamides, such as poly(l,4-benzamide) (PBA), poly(l,4-
phenyleneterephthalamide) (PPTA) or their block copolymers, were dispersed in
either PA-6 or PA-66. It was reported that addition of a small quantity of these resins
resulted in enhancement of the modulus and thermal properties. Morphological
studies revealed dispersion of high-modulus discrete fibrils dispersed in a PA
matrix. However, these systems were not miscible (Takayanagi et al., 1980).
Shortly after, at the Air Force Materials Laboratory, the phase diagrams of a blend
comprising rigid-rod poly(p-phenylenebenzobisthiazole) (PBZf) and a flexible-chain
polymer (either poly(2,5,(6')-benzimidazole) (PBI) or poly(2,5,(6')-benzothiazole)
(PBZ) were studied. The results demonstrated that molecular level composites
(MC) of highly oriented PBZf macromolecules were obtained in these flexible
matrices. Films and fibers prepared from solutions in strong acids had high modulus
and strength, which could be further improved by heat treatment (Hwang et al.,
1983; Ulrich, 1987). It was demonstrated that molecular dispersion can exist only
below a thermodynamically defined critical concentration - above it the system
phases separate. In 1987 Hoechst Celanese Corporation reported that PBI is miscible
with polyarylates (Chen et al., 1990). More recently, it was reported that several
wholly aromatic, para-linked rodlike polymers, (namely polyamides, polyesters, or
polyesteramides) form molecular composites in some flexible polymers (Stein et al.,
1992). These MCs were prepared either by dissolving a rod-like polymer in a mono-
mer containing photoinitiator, then photopolymerizing it, or by solution casting of
a homogeneous solution of the two polymers. For example, the aromatic polyamide
[-eD--</>(CF3)-¢(CF3)-eONH-¢(CF3)-¢(CF3)-NH-] was dissolved in either 4-vinyl
pyridine, vinyl pyrrolidone or methyl vinyl ketone, then the monomer was photo-
polymerized to give stable systems devoid of any sign of phase separation - true MC
As is evident from these early studies it is difficult to find a miscible pair compris-
ing a rigid-rod and a flexible chain polymer. The basic problem stems from the
strong interactions that exist in solid, highly crystalline rigid-rod polymers. In some
polymers, these interactions can be broken by dissolution in low-molecular-weight
solvents, but dissolution in a thermoplastic polymer matrix is difficult and time
consuming. Furthermore, even when a molecular level dispersion is achieved (e.g.,
by dissolution) there is a danger that the rigid-rod molecules will coalesce and phase
separate during thermal treatment or in shear flow during processing. This
was demonstrated by preparing blends of poly(p-phenyleneterephthalamide)
(PPTA) with PA-6 or PA-66 by rapid coagulation of methanesulfonic acid solutions
in water. At concentrations above 70wt% of PPTA, PA-6 or PA-66 crystallization
disappeared, implying miscibility. However, thermal treatments resulted in phase-
separated blends (Chuah et al., 1989; Kyu et al., 1989).
Another method of generating MC is based on dissolution of either the rigid-rod
polymer in a solvent that can be subsequently polymerized, thus engendering the
thermoplastic matrix polymer, or by dissolving a monomer of the rigid-rod polymer
in a thermoplastic resin. There are three critical steps: (1) selection of a soluble
monomer/polymer pair, (2) control of the polymerization rate, and (3) control of
the phase separation rate. The decrease of the configurational entropy during poly-
merization increases the free energy of mixing that for most systems results in phase
separation. However, using the interpenetrating polymer network approach one
may be able to lock the dispersed structure into a metastable system with sufficient
stability for processing (Utracki, 1994a).
In 1991 Rehau Aktiengesellschaft deposited a patent describing formation of
molecular composites (Me) by the method of dissolution of N-activated lactams in
a thermoplastic polymer haVing a melting point above 100 °C (e.g., in polyamides
(PA) or modified polyalkenes (PO», then polymerizing it into a rigid-rod (e.g.,
poly(p-arninoethylbenzoate) (PAEB». Thus, molecular composites were prepared
by reacting O.2-90wt% of monomer B (e.g., N-(p-arnino benzoyl) caprolactam) in a
melt of thermoplastic polymer A (maleated PP, PA-6, PA-66 or PARA) to form the
rigid linear, branched or cross-linked aramid microfibrils as reinforcements.
For example, when N-(p-arninobenzoyl)-eaprolactam was polymerized in PA-6,
aromatic/aliphatic copolyamides were formed. These were then dispersed as micro-
fibers in the PA-6 matrix. The addition of only 5wt% of N-(p-arninobenzoyl)-
caprolactam doubled the elastic modulus of PA-6. Due to the small dimensions of
the fjbers, the surface of molded pieces made from such a polymer mixture was
smooth. At the customary concentrations, 2-lOwt% of the rigid-rod polymer, the
negative influences such as weldability or weldline formation were negligible
(Millhaupt et al., 1994).
Also in 1991, Hoechst Celanese Corporation disclosed blends comprising poly-
benzimidazoles, 5-95 wt % of PBI, and an aromatic polyamide (PARA: selected from
aromatic polyamide-hydrazides or aromatic polyamides containing heterocyclic
linkages) - these kinds of polyamides are characterized as generally having high
Tg and HOT). Although PBIs generally have high thermal stability and good solvent
resistance, they are expensive with high moisture regain. Certain structures of the
polyamides were found capable of developing high tensile properties in the
drawn state, and were less expensive than PBI, but they did not have good non-
flammability characteristics. Blending should result in materials showing compen-
sation of properties. The PBI/PARA blends should be less expensive than PBI,
should have higher thermal stability and be less flammable than PARA, and have
low price-to-performance ratio. The PBI/PARA ingredients were solution blended in
dimethylformamide (DMF). In most cases the resulting mixtures were found mis-
cible, as indicated by film transparency and a single T g that followed the rule of
Molecular composites 451
mixtures. Fourier Transform Infrared analysis (FI1R) indicated intermolecular
hydrogen bonding, and X-ray diffraction analysis confirmed that the component
polymers interacted on the molecular scale. In spite of miscibility, the blends
showed true MC character, with reinforcing elements on the molecular scale,
evidenced by the physical properties of the blends as well as by scanning electron
microscopy.
For example, in a Hoechst Celanese Corporation patent disclosure of 1992, either
Hoechst HMA (an aromatic polyamide made from terephthaloyl chloride and a
mixture of three diamines), or aromatic polyamide-hydrazides (e.g., polyterephtha-
lamide of p-aminobenzhydrazide), were blended with poly-2,2'-(m-phenylene)-5,5'-
bibenzimidazole (5-95 wt % of PBI). The blends were found miscible, with good
processability, high HOT, environmental and fire resistance. They were used for
coatings, films, fibers, etc. The blends could also be molded at :::::: 450°C (Calundann
et al., 1992, 1994).
In 1992, several blends of polybenzimidazole (PBI) were disclosed. Thus, Hoechst
Celanese Corporation applied for patent protection of PBI (poly-2,2'-(m-pheny-
lene)-5,5'-bibenzimidazole, CeiazoIe™ U-60) blends with 0-65 wt % of poly(arylether-
ketone) (PEEK, Victrex™ from ICI). The blends were prepared by solution blending
in one of the following solvents: N,N' -dimethylacetamide (OMAc), N,N'-dimethyl-
formamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, formic acid, acetic acid,
sulfuric acid, polyphosphoric acid and methanesulfonic acid. The preferred system
was 1 wt% solution of the selected polymers in OMAc.
Blends of PBI with PEEK are known for their excellent mechanical, thermal and
chemical resistance properties, and are used to manufacture gaskets, seals, valve
seats and O-ring backups. However, these articles are not durable or wear-resistant
when subjected to friction environments. They tend to overheat and degrade under
friction after short periods of time. New compositions were developed in the
Hoechst Celanese laboratories in 1992, that had sufficient amounts of internallubri-
cants to make the PBI/PEEK blends suitable for low friction applications. The
compositions contain 65-85wt% of a PBI/PEEK blend and 15-35wt% of internal
lubricants - a mixture of graphite and boron nitride in a ratio from 1:10 to 10:1. The
compositions were found useful for preparation of shaped articles, such as bearings,
bearing sleeves and rings with good mechanical and physical properties as well as
wear resistance in frictional environments (Andres et al., 1995).
In a 1992 patent deposition from Rohm and Haas Company, melt-processable
rigid-rod blends were disclosed. They comprised a thermoplastic polyglutarimide
copolymer, 7D-99wt% PCI, and either a polybenzimidazole (PBI) or a liquid crystal-
line copolyester (LCP) Vectra™ (58 mol % 6-hydroxy-2-naphthoic acid, 21 mol %
terephthalic acid and 21 mol % p-hydroxyacetanilide, or 70 mol % p-hydroxybenzoic
acid and 30 mol % 6-hydroxy-2-naphthoic acid). The blends of PCI with LCP could
also contain other polymers, such as PET or Pc. Blending was carried out in a twin-
screw extruder at 300 0c. The blends showed a good balance of toughness, tensile
modulus and HOT. They have been used for molding bottles, fuel tanks, automotive
bumpers, automotive body panels, electrical connectors, PCBs or housings for elec-
trical components (Hallden-Abberton et al., 1994).
Also in 1992, Mazda Motor Corporation described solvent-free molecular compos-
ites having increased modulus and strength. The systems comprised rod-shaped
reinforced polymer dispersed at molecular level in a flexible polymer matrix. It was
found that the rod diameter was less than 70 nm. The composite was prepared by
mixing a monomer (for forming a rigid polymer, e.g., p-acetoaminobenzoic acid),
with a flexible polymer, then polymerizing the system at a moderate shear rate of
2.0-13s- 1 . Thus, polyethersulfone (PES) was blended with polyoxybenzoyl acid for
manufacturing fibers and rod-shaped extrudates (Tochioka, 1993).
21.8 LIQUID CRYSTAL POLYMER BLENDS
21.8.1 Introduction to LCP blends

The liquid crystalline state was recognized by Reinitzer in 1888. Low-molecular-
weight substances, such as chloresterylbenzoate, can show this behavior. In princi-
ple, the molecules of these substances, or mesogens, are highly anisometric, either
rigid or able to adopt rigid configurations, ordered over large distances, to impart
some solid-like properties. They show anisotropic mechanical, optical and electrical
behavior. One of the characteristic properties of these substances is a drastic change
of viscosity within certain ranges of temperature and pressure, which makes them
particularly useful as high performance lubricants.
The natural liqUid crystal polymers (LCP), namely tobacco mosaic virus, collagen,
cellulose derivatives (such as hydroxypropyl cellulose), polypeptides (such as poly-
-y-benzyl-L-glutamate), and many others, have been studied since the 194Os. The
LCPs may have the mesogenic groups either as side chains or as parts of the main
chain, with either rigid or flexible linkages between them. In the latter case the LCP
behavior originates from formation of rigid helices. Thus, LCPs show a high degree
of order in the three-dimensional ordering and positioning of mesogens in the
crystalline region, and high disorder in the liquid region.
In 1958 du Pont de Nemours applied for patent protection for aromatic poly-
amides (having at least 90wt% aromatic repeating units) having a melting point
above 300 0c. The resins were prepared by condensation of isophthaloyl chloride
with Et3N·HCl in CH2Ch. The liquid crystal poly(m-phenyleneisophthalamide),
used for spinning fibers, was characterized by high tenacity and self-extinguishing
character (Kwolek et al., 1962). It was soon discovered that solutions of these resins
showed liquid crystalline behavior. In later patents other aromatic liquid crystal
polyamides were described; poly(m-phenyleneisophthalamide) (PPA), commercial-
ized as Nomex™; poly(p-phenylene-2,6-naphthalamide) (PPN), and poly(p-pheny-
leneterephthalamide) (PPT), commercialized in 1965 as Keviar™ (Kwolek, 1970).
The$e LCP resins could be fiber spun from sulfuric acid, but they were not process-
able in the molten state.
In the early 1970s wholly aromatic polyesters were also synthesized. The inter-
molecular interactions in polyesters are not as strong as in polyamides, nevertheless
several LCP polyesters, such as poly-p-oxybenzoate or poly-p-phenylenetere-
phthalate, had such a high melting point that they also could not be melt processed.
The first melt-processable LCP was a copolyester obtained by condensation of
p-hydroxybenzoic acid, terephthalic acid and 4,4'-bisphenol, introduced in 1972 by
Carborundum as EkkceITM 1-2000. At processing temperatures of ~ 400 °C, the resin
was not entirely stable, causing serious difficulties for either fiber spinning or
injection molding. Clearly, lower-melting-point materials were needed.
Development effort went into (1) softening the LCP polyester molecular chain by
the introduction of either flexible links or aliphatic chain segments and (2) blending.
In 1974 Eastman Kodak developed a thermotropic copolymer that comprised poly-
ethyleneterephthalate and polyhydroxybenzoate segments (PETHB). In 1978 poly-
[bis(4-methoxyphenyl)terephthalate) was blended with polyethyleneterephthalate
(PET) to give alloys with good processability. The blends were biaxially stretched.
They showed excellent mechanical properties (Toray Industries Inc., 1980a) A good
Liquid crystal polymer blends 453
review of the processing and properties of LCPs and their blends has been published
(Acierno and La Mantia, 1993).
Several LCP resins have been commercialized, such as Xydar™ by Dartco in 1984,
Vectra™ by Celanese in 1985, E-konoffM by Sumitomo in 1985, X-7G by Mitsubishi
Chemical in 1985, as well as Ultrax™ by BASF, KU 1-90 by Bayer, Granlar™ by
Montedison, Novoaeeurate™ by Mitsubishi Chemicals, Rodron™ by Dnitika and
Vietrex™ by ICI.
Since the late 1970s it has been recognized that LCP can be used as a minor
component to improve processability of engineering and specialty polymers. Inde-
pendent disclosures from Celanese Corporation and from Imperial Chemical Indus-
tries support these findings (Froix, 1981; Froix et al., 1981; Cogswell et al., 1981, 1983,
1984). Furthermore, addition of a small amount of LCP was also reported to enhance
crystallization of some high performance, semicrystaUine polymers, thus making it
possible to reduce the injection molding cycle. For example, addition of the poly-
esteramide Veetra™ B950 from Hoechst-eelanese (a copolymer comprising 20 mol %
of terephthalic acid, 20 mol % 4-amino phenol and 60 mol % of 2-hydroxy-
6-naphthoic acid) to polyphenylenesulfide (PPS) caused accelerated crystallization
of the latter resin (Minkova et al., 1992; Hong et al., 1992; Jang and Kim, 1995). It has
been demonstrated that replacement of composites by the LCP blends is particularly
advantageous in applications where fatigue strength is important. For example,
addition of about lOwt% of PETHB (40% PET and 60% PHB) to polybutylenetere-
phthalate (PBT) not only improved the mechanical properties but also the fatigue
behavior (Yamauchi et al., 1991).
In 1994 several LCP blends were commercialized. For example, in May 1994
Coming announced alloys of low-melting-point inorganic glasses with either LCP
or PEEK. The blends with very high glass content were sold under the trade name
Cortem AlloysTM. In September, blends of LCP with PET were commercialized by
Polymer Incorporated, under the name Superex™. These materials were reported to
be useful for manufacturing films with high barrier properties. Finalli'Min October,
Polyplastics Company introduced blends of polycarbonate with Veetra (PC/LCP).
These resins were designed to mold electronic equipment housings.
21.8.2 LCP blends with commodity resins

Since the processing temperatures of commodity resins and LCPs are widely differ-
ent, blends comprising LCP and a commodity resin are relatively rare. However, as
the cited examples illustrate, since the early 1990s there is a growing interest in these
systems.
In 1991, Virginia Polytechnic Institute deposited a patent application for blends
comprising 1-99wt% of a polyalkene (PO, mainly polypropylene) with liquid
crystal polyester-eo-amide (LCP) Vectra™. The blending method required two sin-
gle-screw extruders, each operating at the appropriate processing temperature for
the corresponding blend component. The melt streams were combined in a static
mixer, kept between the melting point of PP and the crystallization temperature of
LCP. As a result, highly elongated, infinitely long fibers of LCP were formed in the
PO matrix. For example, PP was blended with Veetra™ A or B to give alloys
with high rigidity. It was also reported that superior properties can be obtained
using O.l-lOwt% of a maleated PP as compatibilizer (Baird and Datta, 1992).
The same year British Petroleum blended polyethylene (PE) Rigidex™ or
Innovex™, with a small quantity of a liquid crystal polyester (0.01-5wt% LCP).
The resulting materials showed good melt processability, low viscosity and
reduction of the specific energy required for compounding (Alder et al., 1993). Also in
1991, Hoechst disclosed that polymers or copolymers of cycloalkenes (COP), obtained
by metallocene polymerization, were blended with 1-60wt% LCP, to give alloys
with good moldability, flow properties and mechanical behavior (Epple et al., 1992).
Also in 1991, Foster-Miller incorporated about lOwt% of LCP, either Xydar™ or
Vectra™, into commodity or engineering resins such as PP, PS, PC, PI, etc. To control
the molecular orientation of the LCP, the blends were multi-axially oriented during
processing. For example, they could be extruded through a pipe die having counter-
rotating lands. The alloys showed tailored coefficient of thermal expansion
In 1992, Raychem Corporation disclosed radiation-crosslinked blends of a thermo-
plastic resin with LCP, developed for manufacturing heat recoverable articles. As an
example, a blend of polyvinylidenefluoride (PVDF) with LCP was described (Toyet
al., 1994).
The same year, Neste Oy asked for patent protection for a class of blends compris-
ing 95-5wt% of a matrix polymer, 5-SOwt% LCP and 0.1-30wt% of a compatibi-
lizer (having O.I-30wt% of functional groups). The selected LCP was Vectra™ A950,
having p = 1400kg/m3 , Tg = 9O-100°C and Tm = 280°C. Blending involved com-
pounding the matrix polymer (for example PP) with 10-30 wt % of LCP and 5 wt % of
a reactive compatibilizer, followed by forming by injection or blow molding. Under
high stresses the LCP phase formed long, reinforcing microfibrils. Upon additional
drawing the materials showed greatly improved, anisometric properties. The tensile
and flexural strengths of the blends were higher than those of the matrix polymer. It
was reported that addition of LCP lowered the Tg of PP, whereas addition of a
reactive compatibilizer increased it. Presence of the compatibilizer also reduced
anisotropy of blend behavior. The blends have been used either to mold parts of
electrical and optical networks, or to extrude tubes, pipes, sheets or fibers (Heino et
al., 1993).
21.8.3 LCPIPA blends

In the late 1970s, rigid microfibrils of aromatic polyamides, such as poly(I,4-benza-
mide) (PBA) poly(I,4-phenyleneterephthalamide) (PPTA) or their block copolymers,
were dispersed in either PA-6 or PA-66. It was found that the addition of a small
percentage of the rigid polymers resulted in enhancement of modulus and improve-
ment of the thermal behavior. Morphological studies revealed that the dispersion
had ensured discrete fibrils of rigid macromolecules in the PA matrix. Since this was
not in a miscible system, the reinforcement could be considered as equivalent to
addition of high performance LCP fibers to a thermoplastic matrix (Takayanagi et al.,
1980).
In 1989 du Pont de Nemours described an interesting method for preparation of
blends with highly stretched and oriented liquid crystal polyamides. The blends
comprised 6Q-80wt% of a lyotropiC polyaramid (such as poly(p-phenylene tere-
phthalamide) (PPD-T), Keviar™), and 2Q-40wt% of a second phase polymer com-
prising at least one thermoplastic polyamide (e.g., PA-66, PA-6 or PARA) and
another polymer selected from PEKK or PAN. Oriented, shaped articles were pro-
duced by first dissolving the polymers in a suitable solvent (e.g., in 100.5% H2SO4 at
80 0q. The total concentration had to be sufficiently high (e.g., 12-20wt%) to make
the solution biphasic. Next, the solution was spun into water, coagulated and
stretched sixfold, to produce continuous PPD-T fibrils extending along the length
of the article (when viewed in a TEM at a magnification of 9000). The blends, as spun,
could be formed directly into fibers or films, or used to compression mold shaped
and oriented parts (Coburn and Yang, 1994). In essence, the patent described an
ingenious method for reinforcing blends of PA with a thermoplastic resin by incor-
poration of continuous KevIar™ microfibers.
In 1992, Mazda Motor Corporation described three-component blends comprising
a matrix resin, a liquid crystal polyester or polyesteramide (LCP) and a compatib-
ilizer. As the matrix, the following polymers and their blends have been identified:
PA, ABS, PC/ABS, PC/PBT, PPE/PA-6, PPE/HIPS, PP, PC, PBT, etc. The LCP
should have a crystal transition temperature higher than the molding temperature,
thus either Vectra™, EconoITM or Zaida™ were reported suitable. During the com-
pounding, LCP was deformed into fibers. The role of a compatibilizer was to prevent
formation of short fibers, with an aspect ratio below 3. It was found that the fiber-
forming concentration range of LCP depended on the system; for example, in
PA it had to be 4O-80wt%, in ABS 3O-75wt%, in PC/ABS 3-70wt%, in PC/PBT
2Q-60wt%, in PPE/PA-6 3-65 wt %, in modified PPE ~wt%, in PP 2-70wt%, in
PC 3-70wt% and in PBT lQ-70wt%. The blends produced have been used as a high
performance, low density replacement for glass fiber reinforced materials. The alloys
could be easily recycled without a loss of tensile strength. The reinforced behavior
originated in fibrillation of the LCP phase (Tomita et al., 1993, 1994).
21.8.4 LCPIPC blends

Addition of LCP (usually lQ-20wt%) to PC has been carried out for two reasons: (1)
to improve processability of PC by improving its flow characteristics during injection
molding, and (2) to generate dispersed LCP fibers, to act as a reinforcement. To profit
from these effects one must optimize the relative rheology of the components, and
their processing conditions. Since the blends are antagonistically immiscible, the
morphology is not stable. It is more important to control the processing parameters
than it is to prepare the blends. Elongational flow created by non-parallel flow lines
during processing can be efficiently used to stretch the dispersed LCP phase into
reinforcing microfibrils (Michaeli et al., 1993).
The first blends of PC with LCP were disclosed by Celanese in 1980. According
to the patent, 5-75wt% PC, when blended with a wholly aromatic polyester
(95-25 wt % LCP) gave materials with good mechanical, tensile and flexural prop-
erties (Froix, 1982).
In 1990, blends of PC with PAr and LCP were disclosed by Kawasaki Steel. The
alloys showed low anisotropy, high HOT, as well as good heat and impact resistance
(Izumi et al., 1992). In a Foster-Miller patent, lOwt% of LCP (either Xydar™ or
Vectra™) was blended with thermoplastic polymers (e.g., PP, PS, PC or PI) then
multiaxially oriented during processing to obtain molecular orientation of LCP
In 1991 Enichem America disclosed blends comprising lQ-15wt% LCP with
9D-55wt% PC and a polyester, being lQ-45wt% of either PET or PBT. The
alloys showed improved ductility and toughness, tensile and flexural strength, and
HOT, as well as flexural modulus, over the corresponding binary blend
without LCP. Two-step blending produced a unique morphology. Thus, PC was
first blended with LCP, then the pre-blend was compounded with PEST and
extruded under the conditions favoring formation of LCP's nematic phase. The
surface morphology of the extruded or injection molded objects contained essentially
no LCP fibrils, while the core contained LCP ellipsoids of low aspect ratio (Cottis
et al., 1993).
The following year General Electric Company also developed LCP fPC blends.
The patent reports that the systems showed good compatibility and mechanical
properties. The molded articles were free of delamination (Ishiwa, 1994).
21.8.5 LCPIPEST blends

Owing to the chemical similarity between liquid crystal polyesters (LCP) and ther-
moplastic polyesters (PEST), blends of these two resins have been published since
the early 1970s. The early efforts were disappointing. Compounding at the high
temperatures required for LCP processing, on the one hand, caused degradation and
transesterification, that reduced the performance of the LCP component; on the other
hand, crystallization into physically separated phases caused void formation around
the LCP domains. Thus, in spite of transesterification, these systems showed poor
mechanical performance.
It is worth pointing out that, as a rule, compatibilization can only be achieved
within the amorphous phase of a blend. There are so very few co-crystallizing
systems that one must assume that crystallization of either a semicrystalline polymer
or an LCP must lead to phase segregation (Utracki, 1989a). To a certain extent the
performance of such blends can be controlled by careful modification of the crystal-
line phase via nucleation and orientation, but the systems will remain brittle. One
way out of this dilemma is to build tie-molecules that partially reside in the crystal-
line and partially in the amorphous phases. For the LCP blends these tie-molecules
can be LCP-PEST copolymers, either engendered by coupling or by a modification of
the PEST chain by reaction with, for example, polyoxybenzoate (Kimura and Porter,
1984).
As the examples cited in this part will demonstrate, the technology has greatly
improved since the 1970s, but the problems discovered by the pioneering researchers
are still lurking for unwary experimentalists.
In one of the first patents on LCPfPEST blends deposited in 1978, PET blends with
poly[bis(4-methoxyphenyl)terephthalatel,2 phr of a LCP were described. The alloys
showed improved processability and, after being biaxially stretched, excellent
mechanical properties (Toray Industries Inc., 1980a). Two years later it was reported
that blends of 20-75wt% isotropic aromatic polyester (e.g., 3Owt% PET) with
anisotropic aromatic polyester, (80-25 wt % liquid crystal polymer (LCP) showed
good processability, mechanical properties, a high HDT of 167°C and economy
(Celanese Corp., 1981, 1984; Kiss, 1986). Next year Celanese disclosed reactive PET
blends with 25-50wt% (and later 85-95wt%) of an aromatic copolyester from
hydroxybenzoic acid with hydroxynaphthoic acid, LCP Vectra™ A. The blends
showed good tensile and impact strength (Cincotta and Berardinelli, 1983, 1984).
In 1990 Unitika disclosed LCP blends with polyalkyleneterepthalates (PEST).
As the LCP, p-hydroxybenzoic acid-ethyleneterephthalate having Tm S 300 °C
(5-50 wt % LCP) was used. The preferred PEST was a polybutyleneterephthalate
(50-95 wt % PBT). To these blends 0.2-5 phr of a thickener, a phenylene-bisoxazoline
was also added. The latter compound, by reacting with the LCP, increased its high
shear viscosity at 1000 s-1 to the same or higher level than that of PBT. The resulting
alloys were molded at S 300 dc. Improved orientability of the LCP crystals led to
enhancement of the mechanical performance (Suenaga, 1994). The same -ritear,
General Electric reactively blended LCP Vectra™, with 50-95wt% PBT Valox , in
the presence of 0.05-25wt% triglycidyl isocyanurate (TGIC) Araldite™. The blends
were found to have increased stiffness and improved drip characteristics (Dekkers
et al.~ 1992).
Three-component LCP I PEST IPC blends were announced in 1991 by Enichem
America. For example, lo-15wt% LCP was blended with 90-55% PC and 10-45%
of either PET or PBT. The blends were prepared in two steps by melt compounding,
that produced a unique morphology. First, PC was blended with LCP, then PET was
added. The mixture was extruded under conditions that favored the LCP to enter the
nematic phase. The surface morphology of the extruded or injection molded objects
contained essentially no LCP fibrils, while the core contained LCP drops of low
aspect ratio. The method was reported to give materials with improved ductility and
toughness, tensile and flexural strength, HDT and flexural modulus over the corres-
ponding binary blends without presence of LCP (Cottis et al., 1993).
In a contemporary patent document from Akzo, blends comprising a segmented
LCP block copolymer of the type -[rod]..-[coil]y- were disclosed. Preferably, the
copolymer rod block was -[0--</>--COO-(CH2kDCCH/>-OCG-c/>-CG-]..- with x =
2-50, while the flexible block was PBT chain. Blending 1-35wt% of this copolymer
with PET resulted in alloys suitable for spinning highly drawn fibers with higher
mechanical properties and lower shrinkage than those of PET. In another disclosure,
preparation of blends comprising a flexible-eoil polymer matrix and a segmented
block copolymer LCP was described. The flexible block should be substantially
similar to the matrix polymer. These resins were tumble mixed for about 3 h under
nitrogen at temperatures above Tg, but below Tm of the flexible component, to yield a
stable preblend. The document stresses that the flexible coil blocks should be sub-
stantially similar to the matrix polymer, selected from PBT, PET, PA-6 or PA-66. For
example, 0.5-49.9wt% LCP was blended at temperatures above Tg but below Tm of
the flexible matrix polymer, e.g., PET. The method provided blends with good
interfacial adhesion and uniformity (Dashevsky et al., 1993).
The following document from the company described blends of a fiber-grade PET
with 1-35wt% of the previously discussed LCP-type rod-and-coil block copolymer,
having for the rigid block -[0--</>--COO-(CH2kOC0-¢>-ocG-c/>-C0-]..-, with
x = 2-50 and a PBT-type chain for the flexible block. The LCP additive acted mainly
as a nucleating agent, affecting the crystallization behavior of PET - the blend had a
higher crystallization temperature and a narrow temperature range where crystal-
lization occurred. The blend also showed a high melt flow rate (the melt index with
2.160 kg weight at 270°C for the blend containing lOwt% LCP was about five times
higher than that obtained for PET alone even at 285°C) which made it possible to
process it at temperatures 20-40 °C lower than required for PET. Fibers prepared
from the blends had significantly improved tensile properties as well as shrinkage
resistance as compared to PET fibers. The drawing temperature of the as-spun fibers
should be adjusted according to Tg. As spun, blend fibers demonstrated improved
drawing properties as compared to fibers made from PET alone. SEM analysis of the
blend fibers showed a fine morphology without phase separation (Dashevsky et al.,
1994).
Also in 1991, the University of Massachusetts deposited an application for blends
of PBT with liquid-crystalline segmented block copolymer, LCP-b-PBT. The materi-
als were reported to have uniformly dispersed domains with diameter ~ 0.1 p.m. The
blends were drawn into fibers that showed improved modulus and strength (Farris
and Jo, 1993).
Hoechst Celanese announced in 1992 melt-processable blends of an isotropic and a
thermotropic polymer. The blends were obtained by in situ polymerization of a
liquid crystal polymer (LCP) in a thermoplastic polymer matrix, selected from
PEST, PC, PAs, PI, etc. The bicomponent systems showed good physical properties
(Gupta et al., 1994). In a contemporary patent from the company, alloys comprising a
liquid crystalline aromatic copolyester or copolyesteramide, 85-97wt% LCP, and an
amorphous polyarylester, 3-15wt% PAr, were described. These alloys were used as
matrices for composites that could be conventionally processed by injection molding
or extrusion to give sheets, fibers, films or parts with a complex shape (Roemer and
Schleicher, 1993c, 1994).
The same year, blends of an aromatic thennotropic polyesterimide copolymer
(5-30wt% PEI-LCP) with thennoplastic polymers, chosen from PC, PBT or
PA, were described in a document from Eniricerche S.p.A. The PEl block comprised
4-carboxy-N-(p-carboxyphenyl phthaIimide, a diacyloxy derivative of t-butyl-hydro-
quinone, and an acetoxy derivative of hydroquinone, The polyesterimides have self-
reinforcing characteristics and improved rigidity. They also require lower processing
temperatures. Thus, the blends showed a Significant reduction of viscosity, and
enhanced mechanical behavior of the products (Bonfanti et aI" 1993).
Also in 1992, Mazda Motor Corporation described three-component blends com-
prising a matrix thennoplastic resin (e.g., PEST, PC, PA or modified PPE), a liquid
crystal polyester or polyesteramide (LCP, Vectra'IM, Econol'IM or Zaida'IM) and a
compatibilizer. The LCP should have a crystal transition temperature higher than
the molding temperature. The recyclable blends have been used as replacements for
fiber reinforced plastics (Tomita et aI" 1993, 1994).
In 1994 Superex Polymer Inc. (a subsidiary of Foster-Miller) introduced Superex'IM
blends of PET with 10-15wt% LCP as Vectra'IM A-950. The blends are compatibi-
Iized, non-transparent and non-white. The material is easy to process, it shows good
mechanical properties (improvement by a factor of 2.5-5), and half lower oxygen
and moisture penneability than PET. The proprietary compatibilization process was
labelled as "dual-material compatibilization." It involves the addition of two com-
patibilizers, that on the one hand each interact either with LCP or PET, and on the
other bond to each other, The blends can be recycled (Bonis and Adur, 1995).
21.8.6 LCPIPPE blends

The theory of fiber-reinforced composites states that when the length to diameter
ratio L/D of a fiber reaches values 2 500 the reinforcing effect reaches a maximum
plateau level, identical to that engendered by a continuous fiber (Piggott, 1986). The
theory indicates that the absolute scale of the reinforcement is not important. How-
ever, there are clear advantages, from the processing and surface esthetics points of
view, to have these reinforcements of the smallest possible size. When the reinforce-
ment is made of individual dissolved rigid-rod molecules, such miscible systems are
known as molecular composites (Section 21.7). In the LCP blends with a thermo-
plastic polymer the macromolecules phase separate. The basic aim of processing
such a system is to ascertain that the LCP microcrystals are stretched to provide
molecular alignment of the chains, that the aspect ratio of the microcrystals is high,
and that their absolute size is relatively small.
In 1987 Amoco Corporation disclosed the first blends of either a polyphenylene
ether (PPE) or a polyaryletherketone (PAEK) with liquid crystal polymers (LCP)
polyimide (PI), polyarylethersulfone (PAES) or thennoplastic polyester, Good
mechanical properties, processability (warp-free moldings) and high HDT were
reported (Harris and Michno, 1988; Harris et al., 1988; McKenna, 1988; Matzner
and Papuga, 1988; Duska and Field, 1988).
In 1990 Mitsubishi Petrochemical announced blends containing 10-90 wt% of a
hydroxyalkylated polyphenyleneether (e.g., PPE modified by either glycidol or
epiehlorohydrin), and 10-90 wt% of a resin selected from a carboxyl-, an epoxy-, a
hydroxy containing polyalkene (e.g., maleated-PP, glycidyl methacrylate modified
PP, ionomers or EVAl), a polyamide (PA; e.g., PA-4, PA-6, PA-66, PA-46, PA-12,
PA-610) and an isotropic or mesomorphic polyester, PEST or LCP. The blends may
also comprise other polymeric components (e.g., unmodifed PPE, PO or styrenics),
additives, reinforcements, etc. The resulting alloys had excellent moldability, solvent
and heat resistance, and mechanical strength, useful for gears and cranks, automo-
bile manifolds and electrical parts (Arashiro et ai., 1994).
In a series of patents from the University of Akron a general method for produc-
tion of self-reinforcing sheets was developed. It was found necessary that: (1) the
thermoplastic resin and the LCP have a common processing temperature, (2) at the
processing temperature the shear viscosity of the LCP phase is lower than that of
the matrix polymer(s), and (3) the melting point of LCP is significantly higher than
that of the matrix polymer. For example, the following resins have been used: PP,
PPE, PPE/PS, PC, PEl, etc. A two-stage process was developed. First, the prepreg
sheets of a LCP dispersed in a thermoplastic matrix were produced using a single-
screw extruder, a static mixer, a coat hanger die and stretching rolls. In the second
step, up to 16 prepreg sheets were stacked at various orientations (e.g., 0°, 45°, 90°
and 135°), then consolidated (e.g., by compression molding) at temperatures lower
than the melting point of the LCP microcrystals. For example, the flexible matrix was
composed of PPE/PS Nory(fM, whereas 2.5-90 wt% of the wholly aromatic polyester
was either Vectra lM A 950 or UltraxlM KR-4002. Mechanical properties of the com-
posites were reported superior to those of the base polymers, especially at higher
LCP loading (Isayev, 1991, 1993a; Isayev et ai., 1994).
In following disclosures, PS/PPE blends, self-reinforced by incorporation of 2-98
wt% of the LCP Vectra lM A950, were described. The selected pair of PPE/PS and
LCP had a common processing temperature range, within which the LCP viscosity
was lower than that of the PPE/PS blends. Under these conditions the system was
capable of forming long, continuous, submicroscopic fibers. The forming steps
comprised blending under conditions inducing orientation of the LCP (as for ex-
ample, in an extruder-static mixer setup, or a twin-screw extruder), then stretching
to molecularly orient the LCP, and quenching. The resulting system contained
predominantly unidirectionally oriented fibers having diameters within the range
1-10 /-Lm, well distributed in the PPE/PS matrix. The blends showed high tensile
strength, high modulus, satisfactory elongation, good impact strength and good high
temperature properties, especially when the LCP content was above 40 wt%. The
blends were subsequently formed in standard processing machines, provided that
during this stage the temperature did not exceed the melting point of LCP. The
moldings had good mechanical properties, namely modulus, tensile and impact
strength (Isayev, 1993b, 1994).
Also in 1992 Mazda Motor Corporation revealed three-component polymer
blends, comprising a matrix resin, a liqUid crystal polyester or polyesteramide,
LCP (VectralM , E-cono(fM or Zaida lM ) and a compatibilizer. The LCP should have
a crystal transition temperature higher than the molding temperature. The
compatibilizer was added to prevent formation of short fibers with an aspect
ratio below 3. The fiber-forming concentration range of LCP depended on the
matrix: in PPE/PS it was 3-60 wt%, in PA it was 40-80 wt%, in ABS it was 30-75
wt%, in PC/ ABS it was 3-70 wt% in PC/PBT it was 20-60 wt% PPE/PA-6 it was
3-65 wt%, in PP it was 2-70 wt%, in PC it was 3-70 wt% and in PBT it was 10-70
wt%. The blends have been used as a recyclable replacement for fiber reinforced
composites. The tensile strength was not lowered by processing (Tomita et ai.,
1993, 1994).
21.8.7 LCPIPEI blends
In 1987, novel self-reinforced polymer compositions of polyetherimide (PEl) with a
melt processable aromatic polyester (35-95 wt% LCP), were disclosed in an applica-
tion from the University of Akron. Blending was carried out at a temperature above
215°C (the glass transition temperature of PEl), at which both resins were melt
processable. The aromatic polyester was in the form of predominantly unidirection-
ally oriented continuous fibers having diameters of 1-10 J-tm, distributed in a matrix
of PEL The blends were reported to have high tensile strength, high modulus,
satisfactory elongation, good impact strength and good high temperature properties
(Isayev and Swaminathan, 1987, 1989).
In 1990 General Electric developed blends of amino-terminated polyetherirnide
(PEl), with liquid crystal polyester (LCP). The blends showed high tensile
strength (Bookbinder and Sybert, 1992). The following year, Hoechst disclosed blends
comprising 2-50 wt% PEl and 50-98 wt% LCP. The blends showed high impact and
heat resistance, with good elongation at break (Roemer and Schleicher 1993a). In the
follOWing patent, 5-95 wt% PEl, 5-95 wt% LCP and O.5-lOphr compatibilizer
(p-amino benzoic acid or pyromellitic anhydride) were blended to give moldable
resins, useful as matrix for composites. Addition of compatibilizer improved elonga-
tion at break and the ultimate tensile strength (Roemer and Schleicher, 1993b).
Also in 1991, blends of one or more liquid crystal-type polyimides, 0.1-50 wt%
LCP-PI with 99.9-50 wt% of one or more engineering or specialty resins (namely
aromatic polyimide (PI), polyetherirnide (PEl), polyamideirnide (PAl), polyethersul-
fone (PES) or polyether ketone (PEK or PEEK», were developed by Mitsui Toatsu
Chemical. The invention provided materials that preserved the excellent properties
of each resin, and in addition were characterized by remarkably good processability
and excellent thermal stability (Okawa et a/., 1994).
Interesting miscible blends were found in Foster-Miller laboratories. Thus, blends
of Aurum™ 450C PI (Tg = 252°C) with Ultem™ 6000 PEl (Tg = 228°C) were found
miscible at concentrations up to 50% PEl. The blends showed vastly improved
adhesion to Cu while maintaining excellent electric properties. Suppression of crys-
tallization of PI has also been reported (Blizard and Druy, 1995).
21.8.8 PPSILCP blends

In 1980, Celanese Corporation described blends comprising 5-95 wt% PPS and 5-95
wt% of wholly aromatic liquid crystalline polyesters and liquid crystalline poly-
(esteramides). The blends were reported to have lower melt viscosity than that of
either polymer component, thus showing improved processability. Molded articles
made from these materials had improved physical properties compared with the
average of properties of the individual polymers (Froix, 1981). The blends have been
found useful for the electronics industry.
In 1992 Minnesota Mining and Manufacturing Company deposited patent appli-
cation for blends comprising at least 0.01 wt% of a thermotropic liquid crystalline
polymer (LCP) Vectra™ and at least one polymer selected from PET, PA, PC, PE, PP,
PVC, PVDC, PPS, PVDF, PVF, PMMA, etc. The blends were used to manufacture
oriented films with small protrusions that resulted in low friction. Other standard
ingredients, in amounts not to exceed 5 wt % (such as UV absorbers, antioxidants,
colorants, slip agents, etc.) could also be incorporated. The blends served as a
substrate for magnetic recordings, a binder for abrasive powders, reinforcing back-
ings, adhesives, to proVide writable and/or printable surfaces, capacitor films, etc.
(Wong, 1987, 1994).
In 1993 Hoechst Celanese Corporation announced blends comprising 20-80wt%
PPS and 20-80 wt % of a mixture of a liquid crystalline polyester (LCP; condensation
product of 6-hydroxy-2-naphthoic acid and 4-hydroxybenzoic acid), and a liquid
crystalline polyesteramide (LCPA; condensation product of 6-hydroxy-2-naphthoic
acid, terephthalic acid and 4-amino phenol). In the blends, LCPA constituted 0.5-50
wt% of the total LCP with LCPA content. The blends were prepared in a twin-screw
extruder. The three-component alloys had melt viscosities at least 5% lower than the
corresponding binary blends of PPS with LCP (as measured at 310°C at a shear rate
of 1200 S-I). In other words, the melt viscosity of the alloys was reduced when LCPA
replaced a portion of the LCP, so that the melt viscosity of the three-eomponent
blend was lower by at least 5% than that of a binary PPS/LCP blend, having the same
PPS content. The viscosity reduction was surprising since the LCPA has a higher
melt viscosity than the LCP. Replacing even such a small amount as 0.33 wt% of LCP
by LCPA resulted in a 20% reduction of melt viscosity (in an alloy comprising 33
wt% of LCP + LCPA and 67% PPS). Furthermore, viscosity reductions of about 5-
15% were observed even when other additives were included in the blend, such as
fillers or reinforcing glass fibers. The viscosity was reduced over a wide range of
compositions. The blends were used to mold parts for the electronic industry,
particularly connectors. The reduction in melt viscosity was advantageous when
molding intricate parts with small indentations (Yung and Linstid, 1995).
21.8.9 PSF blends with LCP

In 1972 Imperial Chemical Industries commercialized polyethersulfone (PES) as
Victrex1M . As discussed in preceding sections, during this period numerous blends
containing PSF were developed in ICI laboratories, but systems with speciality resins
were less frequent. For example, in 1979 an addition of liquid crystal polymers (LCP)
to engineering or specialty resins, such as PSF, was found to improve flowability and
processing (Cogswell et al., 1981).
In 1992 Mitsui Toatsu Chemical patented a broad category of high performance
mixtures. These blends comprised 99.9-50 wt% of one or more high performance
resin (e.g., PES, PI, PEl, PAl, PEK or PEEK) and O.l-SO wt% of one or more liquid
crystal type polyimide (PI). The blends were characterized by remarkably good
processability, excellent thermal stability and preservation of the excellent perform-
ance characteristics of each resin (Okawa et al., 1994).
Also in 1992, Mazda Motor Corporation described three-component blends com-
prising a matrix resin, a liquid crystal polyester or polyesteramide (LCP; Vectra1M ,
EconoJ1M, or Zaida1M ) and a compatibilizer. The LCP should have a crystal transition
temperature higher than the molding temperature. During processing, the LCP was
melt-formed into fibers, while the compatibilizer prevented formation of short fibers,
with an aspect ratio smaller than three. The fiber-forming concentration range of
LCP depended on the matrix: in PA it was 40-80 wt%, in ABS 30--75 wt%, in PC/ABS
3-70 wt%, in PC/PBT 2D-60 wt%, in PPE/PA-6 3-65 wt%, in modified PPE 3-60
wt%, in PP 2-70 wt%, in PC 3-70 wt% and in PBT it was 10--70 wt%. The blends have
been used as recyclable replacements for fiber reinforced plastics. The tensile
strength was not lowered by moldings (Tomita et al., 1993, 1994).
21.8.10 LCP blends with other specialty resins

In 1985-7 Amoco Corporation deposited several patents for a broad category of blends
comprising a liquid crystal polymer (LCP), polyimide (PI), polyarylethersulfone
462 SpeciJllty resin blends
(PAES) or thermoplastic polyester (PEST), with polyaryletherketone (PAEK),
polyarylether (PAE) or polyphenyleneether (PPE). Good mechanical properties,
processability (warp-free moldings) and high HDT were reported (Harris et al.,
1988; McKenna, 1988; Matzner and Papuga, 1988; Duska and Field, 1988).
In 1987, Minnesota Mining and Manufacturing Company disclosed blending at
least 0.01 wt% of LCP Vectra lM , with at least one polymer selected from PET, PA, PC,
PE, PP, PVC, PVDC, PPS, PVDF, PVF, PMMA, etc. Other ingredients in amounts
below 5 wt% (e.g., UV absorbers, antioxidants, colorants or slip agents) could also be
incorporated. Processing resulted in formation of oriented films with protrusions
that were found responsible for low friction coefficient. The blends served either as a
substrate for magnetic recordings, a binder for abrasive powders, a reinforcing
backing, adhesives or capacitor films (Wong, c.P., 1987, 1990, 1994).
Stamicarbon announced in 1988 that processability, thermal stability, and mechan-
ical properties (particularly in machine direction) of ester-based liquid crystal poly-
mers (LCP) were improved by blending them with either a Phenoxy, or an
esteramide-based LCP (Koning et a/., 1990; Vriesma, 1990).
In 1989 Corning revealed development of low temperature, water resistant inor-
ganic glasses or ceramic-glasses (LTG) haVing a low glass transition temperature of
< 300°C and ability to selectively interact with the polymer. The LTG could be
blended with engineering or speciality resins, using the standard methods of poly-
mer processing. For example, the tested matrix resins included: PEK, PEEK, PPS,
PEl, LCP, PC, PET, PBT and fluorinated polymers. The blends could have very high
loading of LTG, forming the dispersed phase. The resulting materials had good
mechanical properties, with particularly high modulus (Bahn et a/., 1991; Bahn and
Quinn, 1991). In 1~4 the company introduced CortemlM Alloys, comprising either
LCP or PEEK as a matrix resin in which up to 80 wt % of LTG was dispersed. The
blends were rigid, with a Young's modulus of 14 GPa.
The same year, Mitsui Toatsu Chemicals announced blends that comprised: (1)
99.9-SOwt% of a polyimide (PI) and (2) 0.1-50wt% of polyetherketone (PEK) and/
or liquid crystal polyester (LCP) capable of forming an anisotropic molten phase
at temperatures of ~ 420°C. For example, amorphous PI was prepared from bis-
[4-(3-aminophenoxy)phenyl]sulfide and pyromellitic dianhydride (its glass transi-
tion temperature was 235°C), whereas the semicrystalline one was prepared from
4,4'-bis(3-aminophenoxy) biphenyl and pyromellitic dianhydride (its melting point
was 387°C). Commercial PEK resin (VictrexlM PEK 220P from ICI) was used. Simi-
larly, commercial resins (either U-po/ymerlM U-l00 from Unitika, Xydar lM SRT-SOO
from Dartco or Econo/lM E-6ooo from Sumitomo Chemical) were used as LCPs. For
specific applications the blends could be modified by incorporation of other addit-
ives such as phenolic resin (PF), fluoro-polymers (e.g., PTFE), graphite, carbon fibers,
aromatic polyamide fibers, potassium titanate fibers, crystallization accelerator, etc.
The blends were reported as easy to process. The products showed HDT ~ 230°C,
excellent mechanical strength, as well as high thermal and chemical resistance
(Tsutsumi et a/., 1994).
The following year the company commercialized AurumlM PI/LCP blends. The
alloys were described as having good processability, low viscosity, HOT and
water absorption. In 1994 AurumlM TP grades, reinforced by 30wt% of carbon
fibers, were introduced for use in gears, valve seats, piston rings, bearings, thrust
washers, etc. Annealing was reported to increase crystallinity and mechanical
performance.
In 1992 Mitsui Toatsu Chemical developed blends comprising 99.5-50wt% of a
thermoplastic, aromatic polyimide (PI) and O.I-SOwt% of a liquid crystal type
aromatic polyimide (LCP-PI). The blends showed low melting points of ~ 300 0c.
The fluidization effect of LCP-PI was large even when used in a small amount. For
example, at 400 °C, the systems PI:LCP-PI = 90:10 and 70:30 had melt viscosities of
406 and 207 Pa s, respectively. The moldings had excellent chemical resistance, flame
retardance and mechanical strength, as compared to other heat-resistant resins
(Asanuma et aI., 1993).
In 1990, Hoechst Celanese Corporation deposited a patent claiming improved
blends of liquid crystal polymers (LCP). These were produced by melt mixing 2-50
wt% of a thermotropic LCP (selected from amongst aromatic polyesters, aliphatic-
aromatic polyesters, poly(ester-arnides), poly(ester-earbonates) and their mixtures)
with rectants needed to form a second LCP (e.g., a poly[co(4-0xybenzoate/1,4-
phenyleneisophthalate). The method was reported particularly useful when
the second LCP was either biphasic, or difficult to synthesize or melt-process.
The blends showed good processability, enhanced physical properties, high heat
deflection temperature (~ 200°C) and high impact strength (Charbonneau et ai.,
1995).
In 1991 Hoechst Celanese blended LCP with polyetherketones, (2-98wt% PEK).
Moldings from these alloys showed high toughness, excellent elasticity and high
impact strength (Falk and Hermann-Schoenherr, 1992). The following year the
company commercialized blends of PPS with LCP Vectra™ V-140 for the manufac-
ture of electrical connectors. The moldable blends were also prepared by compound-
ing 5O--99wt% LCP, with 1-50wt% of a silicone elastomer and additives. The LCP
was either an aromatic polyester with MW = 0.2-200 kg/mol or a copolyesteramide.
The blends, characterized by improved elongation at break, could be used either
for moldings or as matrices for composites (Roemer and Schleicher, 1993a). In a
contemporary patent application from the company, a thermotropic copolymer
from p-hydroxybenzoic and 2,6-hydroxynaphthoic acids was blended with a non-
thermotropic polymer and a silane (e.g., 3-glycidoxypropyltrimethoxysilane, 2-
mercapto-ethyltriethoxysilane or vinyl-triethoxy-silane). The blends could be
formed into small, finely detailed electronic components for cameras, video and/
or audio parts, etc. The blends were inexpensive and easy to process by spin-
ning, extrusion, calendering or molding. Their properties included good phase
morphology, interfacial adhesion and thermal and mechanical behavior (Haider
et ai., 1993).
In a 1992 patent deposition from Rohm and Haas Company, melt-processable
blends were disclosed. They comprised a thermoplastic polyglutarimide copolymer
(7Q-99wt% PCI) and either a polybenzirnidazole (PBI) or a liquid crystalline copoly-
ester (LCP) Vectra™ (comprising either 58 mol % 6-hydroxy-2-naphthoic acid,
21 mol % terephthalic acid and 21 mol % p-hydroxyacetanilide, or 70 mol %
p-hydroxybenzoic acid and 30 mol % 6-hydroxy-2-naphthoic acid). The blends of
PCI with LCP may also contain other polymers, such as PET or Pc. The blending
was carried out in a twin-screw extruder at 300 0c. The alloys showed a good balance
of toughness, tensile modulus and HOT. They have been used for molding bottles,
fuel tanks, automotive bumpers, automotive body panels, electrical connectors, or
housings for electrical components (Hallden-Abberton et ai., 1994).
In 1993, University of Massachusetts Lowell applied for patent protection of
blends of a polyamideirnide (PAl) with 3-30wt% LCP. The PAl was Torion™
4203L from Amoco, while LCP was either HX4000™ from du Pont de Nemours or
Vectra™ A950 from Hoechst Celanese. The presence of LCP significantly decreased
the melt viscosity of PAl without affecting its mechanical performance (Lai
et ai., 1994).
21.9 ELECTRICALLY CONDUCTIVE POLYMER BLENDS
21.9.1 Introduction
Polymers do not readily conduct electrical current, are inexpensive in comparison to
other known insulating materials and are sufficiently durable and heat resistant.
Since the beginning of the rubber and plastics industries these materials have been
used as wire and cable insulators. Owing to their sensitivity to oxidation and
solvents, they were frequently blended to generate better electrical insulating alloys.
However, in several applications the high electrical resistivity of polymers may be
detrimental. For example, the accumulated surface charge may rapidly discharge,
causing fires, explosions, damage to electronic components, nasty electric shocks to
people, etc. Thus, in parallel with a need for better insulators, there is also a need for
electrostatic dissipating polymeric compositions (ESD).
More recently, polymers have been synthesized that can conduct electricity as well
as metals. It was reported that in 1990 stretched, low density (300 kg/m3 ), Irdoped
polyacetylene (PAc) achieved the same conductivity as that of copper (Ito, 1995).
.Since, in principle, polymers are more flexible, easier to process, are corrosion
resistant, and have much lower density than metals, there has been a great interest
in the development of these materials. Unfortunately, most conductive polymers
are stiff, difficult to process and brittle. To ensure that the electrically conductive
material meets all the desired performance criteria, it is necessary to disperse the
electrically conductive polymers in inexpensive matrix polymers that are flexible and
resistant to environmental factors. These systems are known as electrically conduct-
ive polymer blends (ECPB).
This section briefly describes the evolution of these two types of electrically
conductive materials, the ESD and ECPB.
21.9.2 Static dissipation

The electrostatic dissipating (ESD) compositions must have sufficient resistivity to
cause slow dissipation of a static charge, but not so low as to allow the charge to
move too quickly through the material, thereby causing an arc or spark. A surface
resistivity of lOS-10l 2 n em is considered desirable. Several methods have been used
to achieve this performance. The initial one was to coat the polymeric parts with
electrostatic dissipative materials, but this solution was found to be a temporary one
since these materials could easily be wiped off.
Another method involved addition of either graphite, metal fibers or particles
(Kozlowski, 1995). For example, in 1982 Allied Corporation announced that thermo-
plastic interpenetrating polymer network (IPN) technology had been used to pro-
duce electrically dissipative blends based on ethylene-vinylacetate copolymer
(EVAc) and carbon black (Sorensen, 1984). Ten years later Sumitomo Chemical
Company disclosed blends comprising either poly(2,6-dimethyl-1,4-phenylene
ether) (PPE) or its polyalkene-grafted copolymer, with lOwt% of either Kraton™
G, or a styrene-grafted EPR (and optionally (HIPS», 5-20wt% of either talc, mica or
wollastonite, 5-40 wt % of carbon black and 5-25 wt % of a mineral oil. Owing to the
presence of the carbon black, the blends had good electroconductivity, namely with
surface resistivities of 1010 n (Fujii and Ishikawa, 1994).
Unfortunately, this approach is expensive, the incorporation of solids makes
processing more difficult it is not always esthetically acceptable (these parts cannot
be painted), and it often lowers the mechanical performance.
Electrically conductive polymer blends 465
A popular and easy method for achieving antistatic properties has been the
incorporation of low-molecular-weight ingredients, known as antistatic agents. For
example, in 1982 BASF disclosed blends comprising styrene-acrylonitrile copolymer
(SAN), with either an a-methylstyrene-acrylonitrile copolymer (ABS) or styrene-
maleic anhydride-acrylic acid copolymer, and ethoxylated octyl phenol. The alloys
had good processability, high HOT, good appearance and antistatic properties
(Brandstetter et al., 1983a). Unfortunately, incorporation of low-molecular-weight
organic semiconducting materials (antistatic agents) requires that these substances
migrate to the surface where, as for coatings, they can be wiped off.
The problem can be minimized if the antistatic agent is polymeric in nature and
constitutes a part of the general formulation of polymer blend. Some polymers are
known to posses inherent antistatic properties. For example, in 1942 Thiokol Cor-
poration patented blends of aliphatic polysulfides (TM), with polybutadienes (PB).
The blends were used to mold static charge-free rolls and guides for the textile
industry (Patrick, 1942). ObViously, it was TM that provided the ESD behavior. In
1968 Asahi Chemical Industries disclosed polyalkene (either PE or PP blends with
polyvinylalcohol (2 wt% PVAI). The materials showed good mechanical, hygro-
scopic and antistatic properties, and were suitable for the manufacture of films,
fibers, tubes and coatings (Minekawa et al., 1969). Here it was the PVAI that played
the role of an ESD agent. Similarly, in 1982 it was announced that blends of
polycarbonate of bisphenol-A (5~95 wt % PC) with polyethyleneterephthalate
(1-40 wt % PET) can be toughened and rendered electrically dissipative by
incorporation of more than 1 wt% of an elastomer containing acidic groups
(Tafmer™ A 20090). The alloys showed high tensile strength, good impact resistance,
and electrical conductivity (Mitsubishi Chemical Industries Co. 1983b). In this case,
Tafmer™ A 20090 was the ESD additive.
As the cited examples indicate, the antistatic properties are observed for materials
having either -SH or -DH groups (either phenolic, alcoholic or acidic). Since the
mid-1980s the most frequently used ESD has been a copolymer of ethylene oxide and
epichlorohydrin (EO-CHR) usually having less than 40% of the latter component. To
provide good ESD behavior, these components usually require the presence of
moisture in the air.
In 1984 Borg-Warner Chemicals disclosed antistatic thermoplastic compositions
containing at least SOwt% of ABS (with ~ 6Owt% elastomer), and not more than
20 wt % of an epihalohydrinoxirane copolymer (EO-CHR) preferably containing less
than 50wt% of epihalohydrin (Federl and Kipouras, 1986; Kipouras and Federl,
1988). Three years later, the company applied for world-wide protection for three-
component blends comprising ~96 (preferably 55-90) wt % of a styrenic copoly-
mer, 2-SOwt% of EO-CHR and 2-50wt% of a compatibilizing acrylate (co)polymer.
The styrenic copolymer that had to provide the blends with sufficient impact
strength and hardness was selected from ABS, HIPS (comprising 5-50wt% of such
elastomer as PB, SB, MBS, EPDM, etc.), MBS, SAN, SMA and PS/PPE and similar
blends. For example, 55-90wt% ABS was blended with 5-25wt% EO-CHR and
5-25wt% of polymethylmethacrylate (PMMA). The blends showed good antistatic
properties with rapid dissipation of static electrical charges, reduced delamination
and improved ductility (Gaggar et al., 1988, 1989, 1993).
In 1985 B. F. Goodrich Company announced that either thermoplastic or thermoset
resins can be rendered antistatic when compounded with either homopolymers or
copolymers of an epihalohydrin. Thus, the antistatic properties of such resins as
polyvinylchloride (PVC), chlorinated polyvinylchloride (CPVC), polycarbonate
(PC), polyester (PEST), epoxy (EP), phenolic (PF) or their mixtures were improved
by addition of EG-CHR (Barnhouse and Yu, 1988). Similar patents were deposited
by the company two years later. Here, either a chIorin~ontaining polymer (e.g.,
PVC, CPVC, etc.) or a styrenic (e.g., SAN, ABS, PS, etc.) was blended with 3-35 wt %
of a semicrystalline copolymer of ethylene oxide and epihalohydrin (having ~
4Owt% EG-CHR. The antistatic properties were improved, without affecting the
mechanical properties, and thermal stability of the matrix (Yu, 1988). In 1991 the
company disclosed the next generation of antistatic blends. First, the oxirane co-
polymer was prepared by copolymerizing ethylene oxide with either a heterocyclic
or vinyl monomer. Next, the copolymer was blended with a matrix polymer, and if
necessary with a third polymeric or reinforcing ingredient. For example, 45-90wt%
of a matrix polymer (e.g., PA, PO, CPVC, PVAc, PVC, ABS, SAN, SMA, HIPS or
SMMA) was blended with ID-40wt% of a copolymer comprising 5-95wt% of
either ethylene oxide or propylene oxide and epichlorohydrin (EG-CHR). To the
alloys 5-30 wt % of glass fiber was added to improve the mechanical as well as
the electrostatic dissipating characteristics (Lee, B. L., 1993).
In 1989 Asahi Chemical Company deposited a patent for polycarbonate (6(}-95
wt% PC) blends with a polyamide-imide elastomer (40-5wt% PAl). The latter
resin was prepared from caprolactam, aromatic tri- or tetracarboxylic acid capable
of forming at least one imide ring, polyoxyethyleneglycol and a C2- 10 diamine. The
blends were compounded in a twin-screw extruder. They were found suitable for
molding high impact strength materials having good mechanical and antistatic
properties, as well as good appearance (Shimamura and Suzuki, 1991).
In 1992 General Electric disclosed blends of a styrenic (co)polymer (40-96 wt % PS)
with an epihalohydrin-oxirane copolymer (2-50wt% EG-CHR) and 2-50wt% of a
polyalkylenelactone, selected from alkylenelactone copolymers comprising more
than 50wt% acrylate. For example, blends containing 55-92wt% PS, 5-25wt%
EG-CHR and polycaprolactone (3-25 wt % PCL), were used for molding parts hav-
ing excellent static dissipative properties and good tensile elongation (Giles and
Vilasagar, 1994).
Independently of these ESD formulations, there is growing interest in developing
blends with a controlled degree of electrical conductivity. Here the aim is electrical
conduction, thus reduction of the resistance to values comparable to those of Cu or
Ag. Some of these formulations can also be used in ESD applications.
21.9.3 Electrical conductivity

The term electrically conductive polymer (ECP) is used to indicate a polymer capable
of electrical conductivity, regardless of whether or not it has been rendered electric-
ally conductive by doping. Electrically conductive polymers (ECP) can be used to
replace metallic conductors and semiconductors in such applications as batteries,
photo-electric components, printed-circuit boards, antistatic packaging and electro-
magnetic interference suppression materials. Their potential advantages are light
weight, 'mechanical properties, stability in corrosive environments, and lower costs
in preparation and processing. Unfortunately these materials are expensive, difficult
to process and fragile. For these reasons there is a vivid interest in blending them
with thermoplastics, Le., in development of electrically conductive polymer blends
(ECPBs).
The ECPBs have been studied since the 1970s. Blends of ECPs with thermoplastics
have been known since the early 1980s. For example, polyacetylene (PAc) was
polymerized into a polyethylene (PE) film impregnated with a catalyst (Galvin and
Wnek, 1982). Similarly, using electrochemical methods, polypyrrole (PPy) can be
Electrically conductive polymer blends 467
polymerized in a resin matrix, to provide an electrically conducting material with
improved mechanical properties over those of pure PPy (Lindsey and Street, 1985).
There are several excellent reviews on the topic (Cao et al., 1992; Yang et ai., 1993).
Since the mid-1980s there has been intensive activity to transform the ECPBs from
academic curiosities into commercial products.
In 1982 Raychem Limited disclosed blends comprising: (1) an electrically conduct-
ive polymer (ECP), and (2) a polymeric dopant that has electrically charged groups
and can form associations with the ECP. The polymer (1) was selected from polyani-
line (PANI) and polypyrrole (PPy). These ECPs are positively charged, thus the
dopant polymer (2) should have strong anionic groups such as sulfonic, carboxylic
or phosphonate (e.g., sulfonated PE, sulfonated SEBS, sulfonated-PS or sulfonated
polyacrylamidomethylpropane) (Cross and Lines, 1995).
Starting in 1990, Neste Oy deposited a series of patents for electrically conducting
plastic materials. The ECPBs were produced by blending a conducting polymer (e.g.,
poly-3-octyl thiophene (POT) with a matrix polymer (PP, PVC, PS, PE, EVAc, PVC/
ABS, etc.), introducing a doping agent (e.g., iodine, lz) and forming the resulting
blends into desired shapes. The blends were used either as EMI or ESD materials
(Kokkonen et ai., 1994).
In a following patent, ECPBs were produced by blending PANI with dodecylben-
zene sulfonic acid (DBSA) at a ratio that could vary from 1:10 to 3:1. The reaction
products were heat treated at 80-210 °C for ID-1200 s, mixed with either PS, PE or PP,
and then melt processed. The heat-treated reaction products, as well as their blends
with thermoplastics, were soluble (Kama et ai., 1994b). A later patent disclosed
modification of these blends. Thus, PANI was mixed with protoning acid (sulfonic,
phosphoric or carboxylic) and with metallic salts (oxides of Zn, Cu, Mg, Ba, Ca, AI,
Ti, Fe, Zr, Cd, Ph or Sn with dodecylbenzene sulfonic acid). The conductive material
was mixed with a polymer having a softening temperature below 350°C (e.g., PE, PS,
PP or ABS) and then melt formed (Kama et ai., 1994a).
In 1992 the company announced ECPB that comprised a matrix polymer and an
electrically conducting thermotropic liquid-erystal polymer (LCP) having a rigid
main chain selected from poly(3-undecylthiophene), poly(3-dodecylthiophene),
PANI, PAc, PPy and polyparaphenylene. The ECP contained either ferric chloride
or iodine as a dopant. The matrix polymer was selected from PE, PP, PB, pm, PMP,
EPR, CPE, CSR, PS, polyalkanes containing styrene, acryl, vinyl, or fluoroethyl
groups and their blends. The ingredients were melt blended either in the liquid-
crystal or isotropic state, but at room temperature the conducting component was in
the liquid crystal phase. A filler and a pigment could also be added. The conductivity
of the system was reported as 1O- 1O-1()2 S/cm. The blends were manufactured into
fibers or films (Ho and Levon, 1995).
Polyaniline (PANI) was also used in blends developed by DSM in 1991. Thus, the
resin was first grafted onto a thermoplastic polymer by mixing the amine-terminated
PANI with a thermoplastic polymer comprising a functional group capable of react-
ing with -NH2, such as maleic anhydride. (For example, PANI was melt blended
with SMA having I-SO mol % MA). These processable materials were suitable for use
as electric conductors. However, most often they were further compounded with
polymers, fillers (such as talcum, glass, steel or graphite fibers) and/or electrically
conductive solids Gongeling, 1993).
The same year, Americhem Incorporated announced blends of polyvinylchloride,
5D-99wt% PVC (or another non-conductive polymer) with doped PANI and at least
one other additive (e.g., impact modifier, plasticizer, acidic surfactant), to give
electrically conductive blends. Following patents described ECPB blends comprising
1-30wt% PANI,99~wt%of a thermoplastic polymer (selected from PA-6, PA-66,
PA-ll, PA-12, PET, PC, TPU, CPE, etc.), and 0-10wt% carbon black. The materials
were used to produce intrinsically electrically conductive films or fibers (Kulkarni
and Wessling, 1992, 1994).
In 1992 AlliedSignal disclosed electrically conductive materials that comprised
particles of polyaniline tosylate (prepared by adding ammonium persulfate to ani-
line and p-toluene sulfonic acid), PANI, blended with poly(ethyleneterephthalate
glycol), 40 wt % PETG). These pre-blends were subsequently diluted by incorpora-
tion of PETG. Thin sheets molded from the blends had conductivities of 2.2 and
0.785/cm, respectively, at 40 and 18.5 vol %. The blends were useful for the manu-
facture of films, printing inks, fibers and coatings, and in shielding, antistatic and
adhesive applications (Shacklette et al., 1993).
Also in 1992, International Business Machines deposited a patent application for
blends curable at 180-325 °C, that comprised fluorine-eontaining polycyanurates and
a thermoplastic polymer (e.g., PSF, PPE or PEEK). The cured polycyanurate network
contained dispersed, sub-micron particles of the selected polymer. The blends had
good flame retardancy, combined with either a controlled coefficient of thermal
expansion and/or low dielectric constant, Tg = 180-320°C and heat stability up to
430-500 dc. The filled materials were useful as insulation, heat- or electrically con-
ducting materials, prepregs for electronic packaging, adhesives for aerospace struc-
tures, in the fabrication of printed-eircuit boards, semiconductor chip carriers, metal-
core boards, chip modules, and multi-layer thin film circuits (Ardakani et al., 1994).
22
Recycling and biodegradable blends
22.1 RECYCLING
22.1.1 Introduction
The world production of synthetic polymers exceeds 100 million tons per year - the
quantity sufficient to annually wrap the Earth in a foil about one micron thick. In the
foreseeable future this quantity will increase by a factor of ten. Thus, it is becoming
increasingly important to recycle plastics. The methods of recycling must differ,
depending on the polymer types and locations. Recycling within the resin manufac-
turers' plants is the easiest, more difficult is that in processing plants where com-
mingled polymeric scrap is generated, but the most difficult is recycling of post-
consumer polymers.
There are three basic methods of recycling: (1) direct, (2) of commingled plastics,
and (3) feedstock type. In the first case, the polymeric materials are sorted, cleaned and
either incorporated into a virgin resin, or used in less demanding applications (namely
cascade recycling). The second type can also be divided into two main sub-groups, the
first of these being the direct reprocessing of unsorted plastics into either plastic wood
or plastic concrete, while the second involves a partial sorting, cleaning and subse-
quent blending to generate upgraded plastics materials. Finally, feedstock recycling
may involve depolymerization (hydrolysis of polyesters or polyamides, free radical
unzipping of polystyrene, polymethylmethacrylate, etc.) or pyrolysis.
In this section only those aspects of recycling that are related to polymer blending
are discussed. Three areas are pertinent: (1) compatibilization and upgrading of
resins in direct recycling; (2) compatibilization and upgrading of commingled plas-
tics for reprocessing; and (3) recycling of polymer blends. In case I, the most
important is compatibilization of (partially!) sorted polyalkenes (e.g., polyethylenes,
usually contaminated with a small amount of polypropylene). In case 2, extensive
efforts have been directed toward amelioration of the performance of commingled
resins, such as binary mixtures of polyalkenes with either polyamides or polyesters,
or multicomponent mixtures comprising polyalkenes, styrenics, vinyls, etc. The
amelioration may be achieved either by more efficient compatibilization, reinforcing
with anisometric particles, or by solid-state processing. In case 3, the main efforts are
directed toward generation of sturdy enough blends that can tolerate reprocessing
(in the same sense as the single-phase resin can be reprocessed).
Recyclability should be incorporated into the list of desired performance para-
meters when designing new blends. The decision as to whether to use a given type of
470 Recycling and biodegradable blends
material is based on calculations that include the cost of materials, forming, assem-
bling, decorating, customer satisfaction, esthetics, service life-spans, ease of disposal
and recycling. Thus recyclability, as well as the recommended strategy for re-
cycling, should be an initial consideration, for example, when selecting materials
for fenders or bumpers that, after 10 years, can be taken off scrapped automobiles
and recycled.
As the automobile industry moves closer to the all-plastics car it is inconceivable
that the volume of polymer used in millions of new vehicles every year can be either
buried or burned. In 1984 only 1% of the total 133 million tons of plastics waste was
recycled (Franklin Associates Ltd., 1988). At present, recycling is limited to but a few
polymers: polyethylenes (PE), polyethyleneterephthalate (PET) and in some cases
industrial or municipal plastics waste. The bright sign on the horizon is a serious
effort of General Electric's marketing division towards the integrated flow of engin-
eering materials. It is proposed that a resin will be reused sequentially in progress-
ively less critical applications. The company also demonstrated that such
engineering materials as PPE, PC or PBI from automobiles can successfully be
recycled after 10 years of weathering.
22.1.2 Compatibilization
Compatibilization is discussed in Section 6.1. Here, only those aspects pertinent to
recycling are presented.
Compatibilization is a general term describing several operations that are to
produce alloys with optimized, stable and reproducible properties. Since the mater-
ial performance depends not only on the ingredients and their concentration, but
also on morphology, the requirement means that the morphology must either remain
stable under the processing conditions, or the changes must be predictable and
reproducible. Compatibilization involves either an addition of compatibilizer, a
chemical reaction between the blends' components, or a high stress deformation
process (either in the solid state or in the melt), to engender high orientation and
large interfacial areas. The lattice theory of the interface predicts that (1) the surface
free energy is proportional to the square root of the binary thermodynamic interac-
tion parameter X1 / 2; (2) the chain ends of both polymers concentrate at the interface;
(3) low-molecular-weight components are forced by thermodynamic forces toward
the interface; and (4) the interfacial tension coefficient increases with molecular
weight to an asymptotic value: V12 = Voo - QoM- 2 / 3 (Helfand and Sapse, 1975; Hel-
fand and Fredrickson, 1989).
Compatibilization must accomplish three tasks: (1) decrease the interfacial tension
coefficient v between the two immiscible polymers, thus making it possible to
generate the desired morphology; (2) stabilize the morphology during the formation
stage in high stress fields; and (3) improve adhesion between the phases in the solid
state.
Initially, the polymer blends comprised two main polymeric ingredients and some
additives. Today, they may comprise up to six polymeric ingredients (and the more-
or-less standard package of additives). The increase of the number of polymeric
components n is not trivial, since the number of interfaces between them grows as
N = n(n - 1)/2. Thus, compatibilization of multicomponent polymer blends is much
more difficult. There is also another, often neglected, aspect of multicomponent
blends - that of adverse reaction between various additives present in commercial
resins. It has been demonstrated that, owing to such a reaction, the interfacial tension
coefficient can double (Luciani et al., 1996). However, the compatibilization of mod-
Recycling 471
em, multicomponent blends also provides valuable insight into the compatibiliza-
tion required for recycling of a commingled, multicomponent scrap.
One of the strategies developed for compatibilization of a multicomponent blend
involves addition of at least one ingredient with highly reactive groups that can
interact with several polymeric components, such as either a multicomponent
copolymer that plays a dual role, that of a compatibilizer and impact modifier, or a
low-molecular-weight additive that at different stages of the reactive blending binds
to different components (e.g., ethylene-glycidyl methacrylate, triglycidylisocyanu-
rate). In consequence, the preferred method of compatibilization is reactive blending
(Brown, 1992).
The first task of compatibilization, to decrease the interfacial tension coefficient,
can be accomplished when locally, within the interphasial regions, the miscibility
between the polymeric ingredients is improved. This can be achieved by either an
addition of a small quantity of well-tailored ingredient (a copolymer or co-solvent),
incorporation of a multipolymer (e.g., ethylene-acrylate-maleic anhydride, glycidyl
methacrylate-ethylene-vinylacetate,ethylene-glycidylmethacrylate-methylmethacry-
late) or by reactive blending. Controlled reactive processing is most suitable for
compatibilization of blends comprising condensation-type polymers (e.g., polye-
sters, polycarbonates, polyamides, polyoxymethylenes, polysulfides, amino or
epoxy resins, furan polymers).
Compatibilization may also affect the crystallization kinetics and the total crystal-
linity of the blend. This is particularly important for reactive blending of scrap
comprising semicrystalline polymers, such as PE, PP, PA, PEST, POM, etc. Reactive
compatibilization introduces covalent bonding that interrupts the regularity of the
macromolecular chains, which may result in reduction of crystallinity and thus
performance. For economic as well as for reasons of blend performance, it is
important not to overcompatibilize the systems.
Addition of copolymers reduces interfacial tension and alters the molecular struc-
ture at the interface. A significant penetration of properly designed copolymer into
the homopolymer phases has been reported (Brown, 1989, 1992c; Cho et al., 1990).
One disadvantage of the use of copolymers is their tendency to form micelles. This
not only lowers their efficiency as compatibilizers, but also the micelles that form a
separate phase usually increase the viscosity, and may reduce the fracture energy.
For these reasons, the copolymer must be designed in such a way as to (1) maximize
miscibility of the appropriate parts of its macromolecule with each of the principal
copolymeric components of the blends, (2) minimize its molecular weight to just
above the entanglement molecular weight for each interacting segment, and (3)
minimize its concentration in the blend - addition of 0.5-2wt% of well-designed
block copolymer has been found sufficient.
The second task, stabilization of morphology, can be accomplished either by:
(1) increasing the thickness of the interphase, (2) partially crosslinking any of the
three principal phases, or (3) introducing an additional polymeric ingredient C
that has the ability to form a protective layer around the dispersed phase.
The thermodynamic conditions for this to take place require that the three bina~
thermodynamic interaction parameters follow the dependence x~i > x~l- X~B
(Yeung et al., 1994).
The third task, the improvement of adhesion between the phases in the solid
state, can be achieved by providing good bonding between the phases. In the
case of copolymer addition that results in placing one segment in one phase
and another in another, a covalent bond is formed between the phases. In semi-
crystalline polymer blends, there is significant change of specific volume upon
crystallization, thus a tendency to open up the gap between the two phases. The
presence of an adequate density of covalent linkages must be ensured to reduce this
effect.
Another method of improving bonding between the phases in the solid state
involves the principle of adhesion - in the solid state the phases are "glued"
together. This method is particularly useful in multicomponent systems comprising
scrap. For example, in 1979 Aktiebolag Akerlund och Rausing deposited a patent
application for the use of polyetherimine (PEIm) as a universal coupling agent for
unsorted, post-eonsumer polymeric waste (preferably polyalkenes), containing up to
6Owt% of solids (e.g., paper, cardboard and metal foil) (Bjoerkengren and Joensson,
1980).
Intensive mechanical dispersion of immiscible blend components, then interlock-
ing them into a stable, desired morphology can also produce satisfactory blends. The
stabilization can be achieved either by chemical (e.g., crosslinking by electron beam
irradiation) or physical means (e.g., by controlled crystallization). During the 1970s
Patfoort developed an extruder with residence time of > 7 s (Patfoort, 1976). The
machine generated such a high shear stress that extruded, immiscible polymers (e.g.,
recycled PS and PE) showed good mechanical properties. Apparently, during the
extrusion there was enough chain scission and recombination to generate a sufficient
amount of copolymer in situ, capable of stabilizing the systems.
Reactive blending requires that there is: (1) sufficient mixing for adequate renewal
of interfaces, (2) presence of a reactive functionality, and (3) high enough reaction
rates. During reactive processing block or graft copolymers are usually formed. The
chemical reaction leads to covalent or, less frequently, ionic bonds. Many commer-
cial blends exist today only because of reactive processing. The method has also been
used for recycling. It has been reported that reactive compatibilization engenders
formation of thick interfaces that not only compatibilize the ingredients, but also
prOVide stable morphology.
The most difficult to recycle is the post-eonsumer commingled plastics scrap that
comprises many different types of plastics. This makes it unsuitable for recycling by
the conventional techniques used for single resins. Technologies have been devel-
oped for reclaiming the most valuable and most readily identifiable constituents of
such a mixed waste stream, such as soft drink and milk containers made principally
of polyethyleneterephthalate (PET) or high density polyethylene (HDPE). These
containers constitute an appreciable fraction of post-eonsumer scrap and can be
identified by their size and shape so that it is feasible to segregate them either
manually or by means of automatic sorters equipped with an infra-red detector.
After segregation of the PET and HDPE containers, there are tailings, which consists
of many different types of plastics, formed into films, laminates or composites.
Polyalkenes, in particular polyethylenes, constitute 50-75 wt % of these materials,
and styrenics about 25 wt %. These tailings can be cleaned, comminuted, melted and
melt-formed into variety of articles having relatively poor physical properties, such
as low compressive modulus and yield stress. It was reported that mixing tailings
with high melt strength polystyrene resulted in materials having good modulus and
impact strength.
An important aspect of recycling is re-stabilization of recycled material against
thermal and light-induced degradation. There is a substantial amount of information
on this topic in the patent and open literature (La Mantia, 1992). For example, in
1991 Ciba-Geigy Corporation patented a method of stabilization of commingled
polymers. Thus, blends of recycled thermoplastic polymers recovered from domestic
and commercial waste (comprising 55-75wt% PE and/or PP, 5-25wt% PS,
Recycling 473
~15wt% PVC, D-lOwt% of other thennoplastics and 3-20wt% compatibilizer),
were stabilized against light and thenno-oxidative degradation by adding 0.1-
O.5wt% of a sterically hindered phenol (e.g., pentaerythritol ester) and a phosphite
(e.g., tris(2,4-di-t-butyl phenyl) phosphite), at a ratio varying from 10:1 to 1:10
(Pauquet et ai., 1994). Over the years the company has developed extensive in-
house knowledge pertinent to upgrading the perfonnance of most recycled plastics,
e.g., PVC, PP, PP/EPR blends, PEs, styrenics, etc. The general recommendation has
been to mix recycled polymers with a combination of phenolic antioxidants and
phosphite stabilizers. For outdoor application light stabilizers, hindered amine light
stabilizers, (HALS) with UV-absorbers of the benzotriazole type, are strongly recom-
mended (Herbst et ai., 1995).
In the following section, examples of the technologies developed for recycling
polymers and their blends are discussed in chronological order, first discussing the
commodity then the engineering resin blends.
22.1.3 PSIPE recycling

Since polystyrene (PS) is immiscible with any of the polyalkenes (PO) compatibil-
izers must be used. The addition of 5-B copolymers may homogenize these mixtures
so well that they can be employed in high-quality applications. However, the
recycled plastics need to be freshly stabilized. Although stabilizers for inhibiting
thennal-oxidative and photo-oxidative degradation were originally incorporated in
the neat plastics, some have been lost through migration, extraction or degradation
during the usage of the plastics and storage of the waste. Moreover, recycled plastics
need a higher concentration of stabilizers than neat polymer, as sites of attack for
oxidative degradation will have already fonned (Sadnnohaghegh et ai., 1985). Since
each type of polymer makes specific demands on the stabilizers, stabilization of post-
consumer scrap would require addition of a combination of different stabilizers. This
is a difficult, complicated and costly proposition.
In 1959 Monsanto announced that PS with improved impact, elongation and
strength can be obtained by blending it with polyethylene (1-10wt% PE) and
chlorosulfonated-polyethylene (CSR) (Herbing and Salyer, 1963). The chlorinated
or chlorosulfonated polyethylenes have been the most frequently used compatibil-
izers for commingled polymeric scrap. The patent is one of several, in which
addition of a small amount of one polymer to another improved toughness and
elongation. This blending strategy was successfully used to enhance perfonnance of
nearly all polymers, including polyalkenes, engineering and specialty resins. Many
examples of the application of this strategy have been given when discussing PO, as
well as engineering polymer blends. The philosophy of toughening virgin polymer is
not very different to that used for recycled materials.
Toughening a brittle polymer requires optimization of size and concentration of
the heterogeneity introduced. For most thennoplastics, the optimum diameter of
the dispersed drops is < 3 J.Lm and its volume fraction should be within the range
0.0~.1O. The accepted mechanism of toughening considers the heterogeneity as a
stress concentrator, generating excessive crazing and/or shear banding of the matrix,
thus requiring higher amount of energy to cause fracture. The stress concentration
factor has been expressed as 'Y r:x 11(1 - at/l/3 ) where a depends on the matrix
(Bucknall et ai., 1973, 1984; Bucknall, 1977; Vollenberg et ai., 1988; Partridge, 1992).
Generation of fine dispersion without degrading the polymers has always been a
serious problem. In the early 1970s Patfoort at the University of Liege designed a
new extruder for PVc. The machine had a short screw with LID = 5, residence time
of about 10 s, and an adjustable gap between the screw and the die plate that worked
on the principle of the Weissenberg normal stress effect, Le., similar to the Maxwell
normal stress extruder. Owing to the short residence time, as well as to the controlled
stress field, the machine was soon found to be particularly useful for blending and
recycling. The patent application was deposited in 1975, and the license given to
Fabrique Nationale Herstal. Patent applications described the generation of homo-
genous blends from uncompatibilized, immiscible polymers, prepared within low
residence times and at high stresses engendered in the Patfoort extruder. Thus
LLDPE was blended with PS to give blends with good mechanical properties
(Patfoort, 1976; Fabrique Nationale Herstal, S. A., 1977). For years, these machines
constituted the basis of post-eonsumer plastics recycling lines installed by the city of
liege.
In 1978 Shell International Research developed blends comprising lD0-45wt% of
either PS or HIPS with polyalkene (2-30 wt % PP) and hydrogenated butadiene-
styrene block copolymer (5-20 wt % SEBS). The blends had good impact and flexural
strength, as well as tensile yield retention in the cottonseed oil-oleic acid test
(Holden and Gouw, 1979). Two years later, Sweetheart Plastics disclosed thermo-
formable blends comprising polystyrene (PS), alkene polymer (PP) and styrene-
butadiene rubber (SBR) or block copolymer (SB)n (Grancio et al., 1983). Similar
compositions were also disclosed by BASF. Thus, polystyrene (1Q-90wt% PS) was
blended with a polyalkene (1Q-90wt% PO, e.g., LLDPE) and 5-40wt% SEBS (com-
prising at least SOwt% styrene). The system showed good resistance to impact and
yellowing (Seelert et al., 1993a). Addition of the hydrogenated styrene-butadiene
block copolymers was found to be expensive but useful in many recycling processes.
In 1990 Rutgers State University deposited a patent for recycling PO/PS, without
compatibilization. The claimed compositions comprised 30-40 wt % PS having stor-
age modulus, E' 2: 1 MPa, and a PO (either HDPE, LDPE, PP or their mixtures). The
high melt strength PS, haVing relatively high melt viscosity at 200-220°C (required
for compounding the PO tailings), was capable of forming, relatively stable cocon-
tinuous structures that changed little during the solidification processes. Thus, PS
and PO formed interspersed phases, one consisting predominantly of PS and the
other of PO. The fibrous phase of PS provided reinforcement to the PO phase and
high modulus to the blend. Within the specified composition range, the process
yielded particularly good physical properties such as high compression modulus,
high yield stress, and compression strength.
The extraordinary properties achieved in this range resulted from the co-
continuous morphology, as well as from the decreased total crystallinity of PO.
The performance was found unaffected by contaminants present in the PO phase,
such as pigments, additives and other plastics. Uniaxially stretching the PS fibrils
(having a mean length to diameter ratio of 2: 8, and a mean diameter of 15 JLm)
further enhanced the performance. At 200 °C and a frequency of 10 Hz, the storage
shear modulus of PS should be G' 2: 10 MPa, and its concentration about 35 wt %.
The blends can be recycled (Morrow et al., 1994).
In 1990 a patent application described the process of forming laminated trays of
foamed PS that contained a barrier polymer such as ethylene vinyl alcohol (EVAI).
The trays could be regranulated and re-extruded with virgin PS at least 20 times. The
method used to recycle these thermoformable barrier sheets comprised: (1) extrud-
ing and foaming the PS pellets, with CO:! (2) laminating onto it O.OOOI-30wt% of a
flexible barrier film (selected from EVAI, SAN, PA, PAR or mixtures thereof) with a
bonding layer, and (3) thermoforming the resultant laminate. Steps (2) and (3)
generated scrap that, after grinding and pelletizing, could be re-used at concentra-
Recycling 475
tions of O.OOI-I00wt% to make the foamed part of the laminated sheets (Gusavage et
al., 1992, 1994).
In 1991, Ciba-Geigy Corporation disclosed that recycled thermoplastic polymers
recovered from domestic and commercial waste (comprising 55-75wt% PO,
5-25wt% PS, 5-15wt% PVC and 0-10wt% of other thermoplastics) can be stabilized
against thermo-oxidative degradation by adding a combination of two stabilizers. To
facilitate blending, and to improve performance, to the scrap materials 3-20 wt %
styrene-b-butadiene block copolymer was also added. The blends were further
stabilized against light and thermo-oxidative degradation by the addition of
O.I-Q.swt% of a sterically hindered phenol (e.g., pentaerythritol ester) and
phosphite(s) (e.g., tris(2,4-di-t-butyl phenyl) phosphite) at ratios ranging from 5:1
to 1:5. When necessary, other stabilizers, such as thiopropionic acid, benzophenones,
oxalides, benzotriazoles or sterically hindered amines could also be added. The
stabilized recycled scrap showed good long-term performance (e.g., lifetime to
embrittlement exceeding 270 days at 110°C) and retention of over 62% of the original
impact strength after exposure for 6000h to the artificial weathering protocol (63 °C,
60% RH) (Pauquet et al., 1994).
In 1992 Idemitsu Kosan Company announced blends of 0-99 wt % of a syndiotactic
polystyrene (sPS) mixed with 100-1 wt% of a modified sPS (by copolymerizing
styrene with either p-methyl styrene, divinyl benzene, maleic anhydride or glycidyl
methacrylate), l-l00phr of an elastomer reactive with the functional group of sPS
(e.g., SEBS, SBS, SBR or EPDM) and 1-350phr glass fibers. The compositions showed
improved impact resistance, elongation and retention of physical properties after
recycling without detriment to heat resistance and modulus (Okada, 1994).
Also in 1992 Novacor Chemicals deposited an application for polyethylene blends
to be used for the manufacture of thin films having enhanced stiffness. The alloys
comprised: (1) low density polyalkene, 99-85 (preferably 97.4-94)wt% LLDPE
(96-93wt% ethylene and 7-4wt% of a copolymerizable C4-8 alkene, haVing a
density of 940kg/m3); (2) O.5-lOwt% of one or more polymers selected from homo-
polymers comprising one or more CS-12 vinyl aromatic monomers, either unsubsti-
tuted or substituted by a C l -4 alkyl radical (such as styrenic copolymers, HIPS, PS or
polymethylstyrene), graft copolymers containing 5-15wt% of an elastomer (either
butadiene or isoprene); and (3) 0.3-5wt% of either polybutylene-l or a copolymer of
butylene-l and ethylene. The resins may be either virgin, recycled or mixed (virgin
and recycled). In the latter case a weight ratio of virgin to recycled material should be
within the range from 25:75 to 75:25. The alloys were found useful for the manufac-
ture of tough and stiff thin-gauge films for consumer bags (Sato, 1995).
The same year, Mobil Oil Corporation deposited a patent for ternary
blends containing 87-96wt% LLDPE (with either butene-I, hexene-l or octene-l),
l-lO wt % isotactic polybutene and l-lO wt % PS. The blends may also contain
0.01-10wt% of additives, such as pigments, processing and antiblocking agents.
The blends were used to blow films that showed improved process efficiency in
terms of extruder power consumption, while retaining the inherent strength of the
LLDPE. The compositions were used for blown films and for the manufacture of
waste bags (Evans and Shirodkar, 1993).
22.1.4 Polyalkene blends

In 1992 Mobil Oil Corporation developed a method for recycling laminated polyalk-
enes (PO), such as biaxially oriented PP/PE/EPR, films laminated with polyvinyl-
idenechloride (PVOC) and having an adhesive layer in between. The method
required that first the scrap be soaked at 25-140°C in a caustic solution comprising
0.1-50wt% NaOH and 0.05-1 wt% of a wetting agent. Next, the PO layer was
separated from the PVOC layer, and washed. Finally, the recovered polymers were
reprocessed by blending them with virgin polymers, and subsequently re-used (Su
and Lilly, 1994).
Approximately 3 million tons of high density polyethylene (HOPE) is consumed
for blow molding applications. This material is relatively easy to collect, sort and
recycle, but when recycled it often had a bad smell. The odor originated mainly from
volatile components of the packaged liquids, chemicals or other products, that were
absorbed into the HOPE. Unfortunately, this penetration is not easily reversed. Since
the absorbent rarely affects the critical polymer properties, the problem is not to
remove it from the polymer but, rather, to eliminate its odor. In many recycled
plastics odor may cause problems, ranging from a need to evacuate recycling facil-
ities, to the loss of sales due to smelly moldings made of the recycled plastics. Odor
problems have been addressed (with different degrees of success) by improved
management of bottle collection and storage, as well as by changes in the recycling
procedures. However, a need exists to resolve these problems in a simpler, more
reliable and more cost efficient manner.
In 1993 du Pont de Nemours developed a method of recycling PE (and to use in
end-use products) that eliminates the unwanted odors. Noxious odors of recycled
plastics (e.g., HOPE, LOPE, LLOPE, ULOPE, PP, PET and vinyl or acrylic copolymers)
were reduced by incorporating polyethyleneimine (0.001-30phr PEtI of structure
H-[-(CH2)n-NH-lm-H) that has aldehyde-scavenging attributes. In some cases an
acidic compatibilizer, such as maleated PO, may need to be used to secure good
dispersion of PEtI within the recycled polyalkene scrap. The blending has been carried
out in a corotating twin-screw extruder (Visioli and Brodie, 1994).
The same year, Dow Chemical Company disclosed blends that comprised two or
more polyalkenes (PO) haVing a solid state processing temperature T p , such that
T ml < T p < T m2, where the Tmi terms are the melting points of the blend components,
with Tml - Tm2 > 20°C. The components were PE, PP, PS and polydienes - either
virgin, recycled or both. Preferred POS were PE and PP, and preferred blends were
those containing at least one PE, particularly a substantially linear ethylene polymer
(Lai and Edmondson, 1995).
Also in 1993, Sealed Air Corporation described compositions of low density
polyethylenes (either LOPE or LLOPE) with recycled high density polyethylenes
(2-60 wt % HOPE) and, as a compatibilizer, an effective combination comprising
0.1-1.5 (preferably 0.4--0.8)wt% Zno and 0.1-2 (preferably 0.6-1)wt% glycerol
monostearate. It was reported that the compatibilizer produced blends that could
be formed into commercially appealing products, either as foamed cushioning
material or as films for use in forming bubble wrap and the like. The system showed
compatibilizing benefits on blending structurally different polyethylenes. To control
the density a conventional physical blowing agent (for example gases such as
hydrocarbons, halogenated hydrocarbons or C~) may also be added in an amount
of 5-30 (preferably 10-20) phr. It was found that when waste HOPE was used to
make cushioning foams, up to 30 (preferably 4-15) wt % may be blended to produce
compositions that are devoid of fish scales and bumps and form aesthetically
appealing products. When films were produced, significant property improvement
was reported for compositions with up to 60 wt % of LLOPE. The blends could be
extruded, molded, or cast to form films having up to 100% increase in elongation and
50-90% increase in transverse film strength over LOPE alone. The products were
used by the packaging industry (Lee, 1995).
Recycling 477
22.1.5 Biodegradable or recyclable PA blends
In recent years, owing to increasing concern for the environment, a growing number
of patents for the recycling of polymers have been issued. Among these there are
several that deal with biodegradability. For example, it was disclosed in 1991 that
environmentally friendly, disposable, degradable and/or recyclable plastic articles
can be produced from water-soluble, miscible, high-molecular-weight polymeric
blends that comprised 65-95 wt % of a high-molecular-weight water-soluble thermo-
plastic resin having an inverse solubility characteristic, and 35-5 wt % of at least one
polymer miscible with the inversely soluble resin. The articles were insoluble when
used for their intended purposes, but become soluble when exposed to tepid or cool
water, and degradable when buried in a landfill or compost. The inversely soluble
resins comprise high-molecular-weight polyethyleneglycols (PEG). The miscible
polymer was selected from: polyamides (PA-ll, PA-12 or PA-6); polyethylene-co-
acrylic acid (EEA); polyethylene-co-methacrylic acid (EMAc); polyethylene-eo-vinyl-
acetate (EVAc); and polyethylene-co-vinylalcohol (EVAI). The articles were hydro-
degradable, Le., flushable, biodegradable and compostable, and could be recycled if
desired, thereby eliminating the trash and garbage problems inherent in the use of
nondegradable plastics (Petcavich, 1994).
In 1991 Ems-Inventa developed highly transparent, biodegradable blends com-
prising (1) 90-1 wt% of a linear polymer, e.g., PA-6, PA-69, PA-66, PA-12, PEST, (2)
1o-99wt% of either a hydroxypropyl-starch or urea-starch, and (3) 4.9-SOwt%
plasticizer. The blends were found useful for the manufacture of either moldings
or printable films (Buehler et al., 1993). In the following patent, biodegradable
transparent films were prepared by blending amylose with either PA, PEST or
POM with gelatins. The materials were found to be useful for transparent packaging
films (Buehler et al., 1994).
Two years later, similar biodegradable blends were announced by the Industrial
Technology Research Institute, Taiwan. These materials contained: (1) 5O-99wt% of
a linear polymer selected from PE, PP, PB, PMP, EPR, EVAc, EEA, EAA, PS, SBR,
SBS, PVC, PVOC, PVF, PVDF, POM, PEG, PPG, PVAl, PVAc, PMA, PEA, PA-6,
PA-66, PET, CA and their blends (preferred are PE, PVC and PS); (2) O.5-lOwt%
peracid that contained at least one peroxy carboxylic group (--eOOOH) and another
functional group, such as carboxyl, aldehyde or cyanate; and (3) starch. The role of
the peracid was to increase the biodegradability and photodegradability of the
blends. The mechanical properties were reported superior to those of polymer and
starch blends that contained unsaturated fatty acids or esters as compatibilizers (Hsu
et al., 1994).
In 1992 Bayer announced the development of impact-resistant, filled, molding
blends comprising polyamides: 1o-90wt% of either PA-6 or PA-6,66, 1-50wt% of
a polyethylene/polyamide laminated film scrap (PA/LDPE), 1-15wt% of a compa-
tibilizing agent, o-6Owt% of an inorganic filler and/or reinforcing materials,
o-30wt% of elastomers, and o-lOwt% of other additives. As a compatibilizer either
an ethylene-acrylic acid-t-alkyl acrylate, ethylene-glycidyl acrylate, allyl glycidyl
ether-t-alkyl acrylate, ethylene-acrylic acid (or ester)-maleic anhydride or ethylene-
maleic anhydride copolymer, was used. Blends containing recycled materials had
good impact and notched impact strength, combined with stiffness and toughness.
They have been used for the same applications as new materials, instead of having to
be "down-recycled" (Timmermann et al., 1994).
Also in 1992, General Electric announced further improvements to the PPE/PA
blends. Thus, 5-95 wt % PPE functionalized by reaction with maleic anhydride was
blended with 95-5wt% of either PA-6 or PA-66, and with 5-25phr of a selectively
hydrogenated diblock copolymer of the A-B type. In the latter resin A stands for
styrene (20-40 wt %) and B for an ethylene-propylene polymer, such as SEB Kraton™
ex. It was reported that when the PA content exceeded 35 wt %, the resin formed the
matrix phase. The saturated diblocks provided excellent heat aging characteristics,
unexpected since previous work with saturated SEBS triblocks had shown no
improvement (Lee, 1994). In a following patent from the company, PPE was first
capped with 2-7wt% of a salicylic acid ester, then blended with 6-200phr of a
styrene-butadiene-styrene copolymer. Next, the blend was dispersed in a matrix
resin, selected from PS, PA, PEST or polyetherimide (PEl). These moldable blends
showed high resistance to loss of impact strength after thermal recycling (Richards
and White, 1994).
22.1.6 Other blends

In 1990, General Electric disclosed blends of poly(2,6-dimethyl-l,4-phenyleneether)
(PPE) that resisted loss of impact strength upon being subjected to recycling at
temperatures of 250-350°C, or to thermal aging at 50-200 0c. The alloys comprised
100 parts PPE, 5-400 parts diene-based rubber (SBS, Kraton™) and an effective
amount of an antioxidant/metal deactivator. In a latter patent, it was reported that
PPE and 5-400 phr SBS, can be stabilized against changes in the impact strength
upon thermal cycling between 50 and 200 °C by addition of 1-6 phr dioctylamine.
The blends could be recycled (Richards and Kelly, 1992, 1994; Richards and Pickett,
1995).
The following year, the company announced blends of copolyesteretherimide
(PEEl, LomoQfM) with either a semicrystaUine or amorphous polyamide (PA or
PARA). The alloying resulted in materials characterized by good thermal aging
behavior (Angeli, 1992).
In 1992 the company announced further variations on the PPE/SEBS/PESTfPC
theme. Thus, PPE blends were prepared in two steps: (1) PPE was capped with
2-7wt% salicylic acid ester, then blended with 6-200 phr SEBS; (2) the modified PPE
was blended with 6-200 phr of a styrene-butadiene-styrene copolymer, then dis-
persed in a matrix resin selected from PEl, PA, PEST or PS. The moldable blends
showed improved resistance to loss in impact strength after thermal recycling
(Richards and White, 1994).
In 1991 du Pont de Nemours disclosed blends comprising 40-60 wt % of either
PVC or PVOC, and 40-60 wt % PA processable at temperatures not exceeding 220°C
(e.g., PA-6, PA-1212 or aromatic, amorphous PARA). The blends were compatibi-
lized by addition of 1-20wt% of an acrylic copolymer (comprising 50-70wt%
ethylene, 24-40wt% alkyl (meth)acrylate, vinyl acetate or (meth)acrylic acid, 5-
15wt% CO and 0.1-5wt% anhydride). To prevent degradation of PVC or PVOC
the blends were processed below 220°C. The formulations were found useful for
recycling halide (co)polymers from commingled polymer scrap into a variety of
articles formed by extrusion or injection molding (Hofmann, 1994).
The same year, Dow Chemical disclosed thermoformable blends comprising
45-70wt% HIPS (having a three-modal distribution of rubber particles: 0.1-0.8,
1.2-3 and 3-lOJ.Lm), 15-40wt% HOPE and 5-25wt% of a compatibilizing styrene-
butadiene-styrene, or styrene-isoprene-styrene (SBS or SIS) block copolymer. The
alloys with good interfacial properties were developed for the manufacture of liners
for refrigerators or freezers. The blends were found to be easy to process into parts
with good impact strength and high resistance to solvents (Swartzmiller et ai., 1993).
Recycling 479
The same year, BASF disclosed blends of lo-90wt% PS with lo-90wt% PO (e.g.,
LLDPE) and 5-40wt% styrene-hydrogenated butadiene star-block copolymer (at
least SOwt% of styrene). The system showed good resistance to impact and yellow-
ing (Seelert et al., 1993a).
In 1993 a general method for the re-use of rubber scrap was announced. The
process involved the follOWing procedure: cryogenically comminuting cured rubber,
drying it, preparing a liquid plasticizer/binding agent, then heating and blending it
with the dried rubber particles to swell and plasticize them. The plasticizer/binding
agent contained the following ingredients: l-SOwt% rosin acids, l-SOwt% fatty
acids, 1-90wt% dimerized fatty acids, 1--60wt% trimerized fatty acids, 1-50wt%
esters, 1-20wt% neutrals and 1-20wt% unsaponifiables. The blends comprised 5-
6Owt% of the plasticizer/binding agent and 4O-95wt% of the rubber particles. The
method involved further compounding the homogenous rubber composition with
materials selected from PE, PET, TPU, PU, PVC, polyisocyanurates, polyacrylics and
epoxies, to form composites useful for combining with other materials to impart
elastomeric properties (Segrest, 1995).
Also in 1993 a closed loop recycling process was developed. It included testing the
recyclable materials, comparing the properties with targeted near virgin properties,
admixing additives in a twin-screw extruder, steam devolatilization during extruding
and filtering out unwanted solids and paint flakes. The twin screws of the extruder
were provided with a number of screw sections, each having a thread with predeter-
mined degrees of chamfer and pitch length. Kneading blocks were mounted on certain
screw sections before a vacuum vent port disposed along the feed path of the melt
stream in the extruder. The extruded materials were tested to determine if any
property differences existed. H no unacceptable differences are found, the extruded
material was prepared for reuse in place of or in conjunction with virgin material
having the same properties and characteristics. In particular, the invention was found
suitable for recycling automotive scrap plastics parts (bumpers or fenders) comprising
PC, PEST, ABS, PA, etc. As a property-enhancing compatibilizer, copolymers of
butadiene, (meth)acrylates and styrene (5-15 wt % MBS) were used (Lieberman, 1995).
In 1994 du Pont de Nemours developed polyester foam production that comprised
three steps: (1) blending a branched polyethyleneterephthalate C~ 25wt% bPET)
with recycled, cleaned PET and either a chain extender or a crosslinking agent; (2)
injecting a blowing agent into the melt stream; and (3) extruding the mixture to an
area of low pressure, thereby facilitating the development of a stable closed cell foam
structure. The bPET with [11] = 0.65-1.4dI/g, was derived from a diacid, and com-
prised about 1.5-6.0 equivalents of a branching agent (having a functionality above 2
and MW = 50-5000 g/mol) per 100 moles. Other type of PEST resins could also be
incorporated (Muschiatti and Smillie, 1995).
Discussion of plastics' recycling would be incomplete without mentioning
solid-state processing. It has been already mentioned that physical alloying can be
accomplished by means of high energy shearing or solid-state milling. The success of
these processes may originate either in the development of large interfacial areas of
interaction, orientation effects, bond breakage and re-formation leading to genera-
tion of compatibilizing copolymers, or some combination of these mechanisms.
There are several aspects to this technology:
1. Immiscible polymers were first alloyed by ball-milling the pellets of each of the
resins for 8-24 h in a specially designed shaker ball-mill at acceleration of 12.3 g, a
frequency of 29 Hz and at a temperature of -ISO 0c. Next, the resulting powders
were combined in the required proportions and milled together for another 24 h,
to yield the final powder with particle diameters of about 2/-Lm. This powder was
placed under vacuum and consolidated for 28 h under a pressure of 69 MPa and at
the temperatures, T - Tm ~ 3 to 100 0c. Alloying resulted in homogenous mater-
ials, with high hardness and tensile strength (Pan and Shaw, 1993, 1994; Shaw
et al., 1993). The authors claim general applicability of the method to alloying
powders of any materials.
2. Commingled resin performance was upgraded, without going through the melt-
ing and compatibilization stage, by a solid-state sheet rolling process.
3. A novel solid-state shear extrusion (SSSE) pulverization process was developed
for commingled plastics waste. The process involves passing the waste plastics
through a corotating, intermeshing twin-screw extruder, and cooling the knead-
ing disk comminution zone. The uncompatibilized powders, with the particle size
ranging from 30 to 2000 /-Lm, were subsequently injection molded to form speci-
mens that showed smooth appearance and good mechanical behavior (Khait,
1994, 1995).
22.2 BIODEGRADABLE BLENDS
22.2.1 Introduction
Biodegradability may be an important requirement in specific applications, as in
agriculture. The ideal film, on the one hand, should prevent excessive moisture loss
and weed growth and, on the other hand, when no longer needed it should disin-
tegrate under the influence of either UV irradiation or such microorganisms as
bacteria or fungi.
Most synthetic polymers having molecular weights higher than about 1000 g/mol
are resistant to microorganism attack. Exceptions are polymers having ester groups
in the main chain, such as polycaprolactones, polyvalerolactones, polybuthylene
succinate (PBS), polybuthylene adipate (PBA), polyhydroxybutyrate, polyglycolic
acid (PGA), poly-L-Iactic acid (PLLA), polyester-based urethanes (especially suscep-
tible to fungi), etc. Both PGA and PLLA have been used as biodegradable suture
fibers, VicryzTM. PBS is marketed by Showa as Bionolle™ for fiber, film or blow
molding. Synthetic polymers, such as PET, can be rendered more susceptible to
biodegradation by copolymerizing with some of these polylactones. Some of these
polymers can also be synthesized by microorganisms, such as microbial poly..,-
glutamic acid, poly-f-Iysine or poly(,B-hydroxybutyric acid) (PHBA), produced by
bacterium Alcaligenes eutrophus. Many natural polymers (e.g., polysaccharides, pro-
teins or lipids) are biodegradable.
Another group of polymers, pertinent to the preparation of biodegradable mater-
ials, is resins with controlled, reversed miscibility, namely polyglycoles.
The strategy adopted for preparation of biodegradable polymer blends usually
involves blending a thermoplastic resin with a biodegradable one. The blending
must produce fine enough dispersion that, after disintegration of the biodegradable
part, the remaining thermoplastic part will not contaminate the environment.
When the particle size of the thermoplastic resin is fine enough, some of these
polymers (e.g., polyesters, polyamides or polyoxymethylens), will slowly decom-
pose. Polymers with pure carbon backbones (e.g., PE or PP) are resistant to biode-
gradation. However, they may be rendered susceptible to it after being subjected to
UV degradation, thus several methods of sensitization of hydrocarbon chains to UV
degradation have been developed. The simplest one is based on the incorporation of
metallic oxides or salts, such as Fe:zOJ. In the late 1960s Guillet developed a sophist-
Biodegradable blends 481
icated process of incorporation of a ketone side group -e(R)(COR')- into the poly-
mer chain. Depending on the concentration of these groups, as well as on the nature
of the R and R' moieties, the UV susceptibility could be adjusted at will. The
polymers were sold as Ecolyte™ 5 (for polystyrene), E (for polyethylene) or P (for
polypropylene) (Guillet, 1973; Lenz/ 1993).
Blends comprising a thermoplastic and a biodegradable polymer must also be
compounded for a specific morphology, which requires proper compatibilization. In
the case of natural polymers this may require chemical modification or grafting as
described below.
22.2.2 Blends with polysaccharides

Polysaccharides constitute a large family of chemical compounds comprising starch,
cellulose, dextran, glucose, galactan, mannan, etc. Owing to their abundance, they
have been the prime candidates for incorporating into biodegradable blends. In
particular, starch (neat or modified) has been frequently used.
One of the first patents for biodegradable blends comprising starch was deposited
in 1976 by Kuraray Company. The document described blends of polyvinyl alcohol
(PVAI) with saponified vinylacetate grafted starch. Not only were the blends biode-
gradable/ but they also showed improved properties over those of the neat PVAl
(Yoshitake et al., 1978).
In 1990/ three-component biodegradable blends were disclosed. These comprised
a synthetic polymer (selected from ps/ PE, pp/ EPR, NR, SBR, PI, PB or CA), a natural
polymer (either cellulose or starch) and an attacking biological agent. The role of the
latter agent was played either by bacteria, fungi or enzymes, used at a level of one
weight percent per mass of the natural polymer (Guttag/ 1992/ 1994). The same year,
Fully Compounded Plastics disclosed biodegradability of blends comprising low
density polyethylene (LDPE), starch and an acrylate copolymer (Willett, 1992).
Starch-based blends were also patented a year later by ETH-Ziirich. These mater-
ials were prepared by mixing starch ester of maleic anhydride with polyalkene
(0-90% PO, either PE or PP) and 1-35wt% of an acrylic copolymer (ethylene-
methylacrylate-maleic anhydride copolymer, containing 80-95/5-15 and 0.2-1 wt%
of the respective monomers). In a following patent, uni- or multilayered starch films
of starch/HDPE blends (described in the first patent) with improved mechanical
properties were obtained by drawing them uni- or bi-directionally, with a draw
down ratio of ~ 7 (Tomka, 1992; Tomka et al., 1993).
In 1991 Ems-Inventa developed highly transparent, biodegradable blends com-
prising 10-99wt% hydroxypropyl-starch or urea-starch (containing 4.9-50wt% of a
plasticizer), and 90-1 wt % of a linear polymer, such as PA-6, PA-69, PA-66, PA-12 or
PEST. The materials were found useful for the manufacture of printable moldings or
films (Buehler et al., 1993/ 1994). In a contemporary patent, biodegradable transpar-
ent films were prepared by blending amylose with PA, PEST, POM and gelatins. The
materials were found to be useful for manufacturing transparent packaging films
(Meier, 1993).
Also in 1991 Nordmann Rassmann GmbH disclosed biodegradable, moldable
blends, that comprised 60-95 wt % starch, 40-5 wt % latex of either natural rubber
or a synthetic polymer, and 0-20 phr fillers. The mixture was prepared in the form of
powder, granulate, flakes, pellets, or a dough. It could be molded or extruded to
form parts particularly useful for food packaging (Munk, 1993). The same year
Henkel used thermomechanically converted starch in blends with a polyester or
a polyamide (prepared from unsaturated fatty acids, with diarnines or dimer
diolbased glycols). These thermoplastic blends were used to manufacture packaging
films or moldings (Ritter et ai., 1993).
In a 1992 disclosure from the University of Minnesota, biodegradable interpoly-
mers, with domain size O.OI-I00mm, were disclosed. The blends were produced
by reactive blending of 1-9Swt% of a synthetic polymer (PS/ PE, pp/ TPU/ PEST, PA,
etc.) that was modified by incorporation of suitable functional groups)/ with 5-
99wt% of a biopolymer (e.g., carbohydrates (preferred), proteins or lipids). For
example, either starches or proteins were blended with either a maleated ethylene-
propylene copolymer (EPR-MA) or a styrene-maleic anhydride copolymer (SMA).
The blends were water insoluble, with good mechanical properties, and limited
water absorption. They could be extruded or molded into a variety of shapes, films
or foamed boards (Vaidya and Bhattacharya, 1994).
The same year, Ecostar International asked for patent protection for multicompon-
ent, biodegradable blends. These materials were obtained by mixing together a
polar polymer (TPU, PS, PO, EVAc, EVAl, EAA, EMAc, EMAA, EMAc, PVAI,
EVACO, EBAc, PMMA or PEG), a biodegradable natural polymer (polysaccharide),
less than ISwt% of a fatty acid peroxide or hydroxy peroXide, 0.0I-02wt% benzo-
phenone, O.I-o.swt% ferric hydroxy stearate, 0.005-0.1 wt% copper stearate, and
a hindered phenol stabilizer (benzenepropanoic acid and 3,5-bis(I,I-dimethyl ethyl)
4-hydroxy octadecyl ester). These blends showed good mechanical properties and
were structurally stable until exposed to a suitable environment, where they
degraded by either chemical, photochemical and/or biodegradation mechanisms
into innocuous products (Chapman and Downie, 1994).
Also in 1992Solvay blended a linear low-density polyethylene (LLDPE) with starch,
and at least one ionic compound (in such an amount that the concentration of anions
and cations varied between 0.002 and 5 mol/kg) to produce high frequency sealable
articles. It was reported that starch could contain up to SOwt% of a plasticizer. The
alloys could be processed by calendering, extrusion, etc., to produce multilayer films
and sheets that could be welded or iealed by high frequency induction heating. The
blends were found useful for packaging, paper making, etc. The presence of the starch
improved the long-term biodeterioration of the materials (Dehennau et al., 1994).
In a contemporary patent deposition from Beltec International, biodegradable
tableware was produced by grinding non-consumable agricultural products to par-
ticles having an average diameter of 1-1000 /Lm, coating the powder with an adhes-
ive, and impact molding. The preferred adhesive was a blend known as Fuller's hot
melt adhesive (Liebermann, 1994).
In 1993 The Industrial Technology Research Institute of Taiwan disclosed other
types of biodegradable polymer blends. These contained SQ-99wt% of a synthetic
polymer, O.5-lOwt% of a peracid and starch. The synthetic polymer was selected
from the following resins: PE, pp/ PB, PMP/ EPR, EVAc, EEA, EAA, PS, SBR, SBS,
PVC, PVDC, PVF, PVDF, POM, PEG, PPG, PVAI, PVAc, PMA, PEA, PA-6, PA-66,
PET, CA and their blends (preferred are PE, PVC and PS). The peracid contained at
least one peroxy carboxylic group (-COOOH) and another functional group, such as
carboxyl, aldehyde or cyanate, that increased bio- or photodegradability. The
mechanical properties of these blends were superior to the traditional ones that
comprised a polymer, starch and unsaturated fatty acids or esters (Hsu et ai., 1994).
22.2.3 Blends with biodegradable synthetic polymers

In the late 1970s ICI developed a process for bacterial synthesis of poly(B-hydro-
xybutyric acid), PHBA. In 1980 the company deposited a patent application for
Biodegradable blends 483
blends of PHBA with chlorinated polyethylene (lQ-40wt% CPE). The blends were
reported to show good impact properties and HDT (Holmes et al., 1982). Similar
biodegradable blends were announced by ICI Americas in 1990. They contained
ethylene-vinylakohol copolymer (EVAI), and 3-hydroxybutyrate-valerate copoly-
mer (Webb et al., 1992).
Similar compositions were also announced the follOWing year by Camelot Tech-
nologies of Novacor Chemicals. Thus, biodegradable polymer alloys with good
flexibility were produced by blending 6(}-98 wt % polylactic acid (PLA) with
another polymer (nine types were listed, including PEO, EVAc, EVAI, EPDM and
SBR) (Kharas and Nemphos, 1992). In other patent applications from the company it
was announced that to improve the thermal properties (e.g., the heat
distortion temperature) of biodegradable polymers, such as PLA, polyglycolides,
polybutyric acid or copolymers or butyric and valerie acid, these should be blended
with 25-50wt% of a thermoplastic resin having glass transition tem~erature of
75-200 °C, and a solubility parameter differing by not more than 3 MPa 1 2 from that
of the selected biopolymer. For example, PLA was blended with polycarbonates
(PC), polysulfones (PSF), polyimides (PI), modified polyphenyleneethers
(PPE), siloxanes, silicones, polymethylmethacrylate (PMMA), imidized-PMMA, etc.
(Nemphos and Kharas, 1993, 1994).
In 1992 Zeneca Limited developed compatibilizing block A-B copolymers, with an
A:B ratio of 5:1-1:5. The main polymer chain was poly(meth)acrylic acid and the side
chains were attached by ester linkages. In block A at least SO wt % of side chains were
C5-20 alkylene, whereas in block B at least SOwt% of the side chains were hydro-
xybutyric acid residues with the rest being the hydrovaleric acid residues. The block
copolymers were found useful as compatibilizers for the preparation of biodegrad-
able blends of polyalkene (PO) with polyhydroxybutyrate (PHB). The blends were
used to manufacture disposable napkins, ostomy bags and ordinary wrapping with
reduced disposal problems after use. The oriented films showed improved proper-
ties (Ballard and Buckmann, 1993).
22.2.4 Blends with other polymers

It was disclosed in 1991 that environmentally friendly, disposable, degradable and/
or recyclable plastic articles can be produced from water soluble, miscible, high
molecular weight, polymeric blends that comprised 65-95 wt % of a high-molecu-
lar-weight water-soluble thermoplastic resin having an inverse solubility character-
istic, and 35-5 wt % of at least one polymer miscible with the inversely soluble resin.
The articles were insoluble when used for their intended purposes, but become
soluble when exposed to tepid or cool water, and degradable when buried in landfill
or compost. The inversely soluble resin comprised a high-molecular-weight poly-
ethyleneglycol (PEG). The miscible polymer was selected from polyamides (PA-ll,
PA-12 or PA-6), polyethylene-co-acrylic acid, polyethylene-eo-methacrylic acid, poly-
ethylene-eo-vinylacetate and polyethylene-eo-vinylakohol. The articles were hydro-
degradable (i.e., flushable, biodegradable or compostable) and could be recycled if
desired, thereby eliminating the trash and garbage problems inherent in the use of
nondegradable plaStics (Petcavich, 1994).
In 1992 Rohm and Haas Company deposited patent applications for a large group
of blends of the type 80-95 wt % polar polymer(s) (e.g., PVC, PC, PMMA, PA, PEST,
PGI and/or SAN-containing polymer) and 5-20wt% of a copolymer (6(}-95wt%
first polymer with 2: SO mol % vinyl alcohol, 5-40 wt % of a second polymer contain-
ing 2: 70wt% alkyl (meth)acrylate(s) and up to 25wt% of vinyl(idene), containing
either amide or anhydride). Advantageous blends comprised 1D-95wt% unproces-
sable polar polymer with 5-90wt% of a polymeric mixture (40-95 parts of a
first polymer and 5-60 parts of a second polymer). For example, blends comprised
25-95 wt % TPU and/or Phenoxy, EVAl with less than 50 mol % of vinyl alcohol units,
COPO, modified cellulose and/or polyalkylene oxide, and 5-75wt% of the first
blend. The blends had attractive physical, optical and barrier properties, and were
melt-processable without PVAl degradation. They could be transfonned into films,
sheets or bottles with good barrier properties. Blends containing PA were used for
films, tubes, toys, gears, bearings, shafts, curtain sliders, door rollers, etc. The blends
with elastomers were reported suitable for improved wiper blades. Blends with
biodegradable polymers, those with water-soluble or -dispersible polyesters were
also prepared. Blends with water-extractable polymers and/or electrolytes were
found useful to fonn porous structures (La Fleur et al., 1994).
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Appendix I
See Page xvii for details of abbreviations used in the Appendices.
INTERNATIONAL ABBREVIATIONS FOR POLYMERS AND POLYMER

PROCESSING
'Abbreviation
Description
A
aPP Amorphous polypropylene
AAS,ASA Copolymer of acrylonitrile, acrylate (ester) and styrene
ACM Acrylate rubber, based on ethyl acrylate with other acrylics
ACS, ACPES Acrylonitrile-chlorinated polyethylene-styrene copolymer
ABA Acrylonitrile-butadiene-acrylate copolymer
ABR Elastomeric copolymer from an acrylate (ester) and butadiene
ABS Thermoplastic terpolymer, an acrylonitrile-butadiene-styrene
copolymer
AB5-MA Maleated acrylonitrile-butadiene-styrene copolymer
ABM Copolymer of acrylonitrile-butadiene-methyl acrylate
ABMA Copolymer of acrylonitrile-butadiene-methacrylic acid
ABSM Graft copolymer of acrylonitrile-butadiene-styrene-
methylmethacrylate
ABSMA Graft copolymer of acrylonitrile-butadiene-styrene-maleic
anhydride
ABVC Thermoplastic terpolymer, an acrylonitrile-butadiene-
vinylchioride copolymer
ACM Acrylic elastomer, e.g., alkyl acrylate-2-chloroethyl vinyl ether
copolymer
ACPES Acrylonitrile-chIorinated polyethylene-styrene copolymer
ACRYL Poly-or copolymethylmethacrylate (acrylic)
ACS Thermoplastic blend of acrylonitrile-styrene-chlorinated PE
terpolymer
AEM Elastomeric ethyl (or other) acrylate-ethylene copolymer
AES,AEPDM Terpolymer from acrylOnitrile, ethylene-propylene elastomer
and styrene
AF Aniline-formaldehyde molding resins
AFMU Terpolymer of tetrafluoroethylene, trifluoronitrosomethane and
nitrosoperfluorobutyric acid
Appendix I 561
Abbreviation Description
AK Alkyd resin
AMAB Copolymer from acrylonitrile, methyl acrylate and butadiene
rubber
AMC Alkyd molding compound
AMMA Thermoplastic copolymer from acrylonitrile and methyl
methacrylate
AMS Q-Methyl styrene
AN Acrylonitrile
ANM Acrylate rubber, based on ethyl acrylate with acrylonitrile
AP,APR Elastomeric ethylene-propylene-diene copolymer; now EPDM
APET, aPET Amorphous polyethyleneterephthalate
APP, aPP Atactic PP
AR Elastomeric copolymer from acrylates and alkenes
ARP Thermoplastic polyester; polyarylterephthalate liquid crystal
copolymers; also PAr, PAT
AS Acrylonitrile-styrene copolymer (also PSAN, SAN)
ASA,AAS Thermoplastic copolymer from acrylonitrile, styrene, and
acrylates
ASR Alkylene sulfide rubber
AU Elastomeric polyester or polyurethane with polyester segments
B
BA Polybutylacrylate, (sometimes, incorrectly, also used as an
abbreviation for acrylic elastomer, ACM)
BAAN Butyl acrylate-acrylonitrile copolymer
BAMM Butyl acrylate-methylmethacrylate copolymer
BFE Bromotrifluoroethylene polymers
BIIR Brominated elastomer from isobutene and isoprene; bromobutyl
rubber
BMC Bulk molding compound (UP resins)
BMI Bismaleimide
BMMM Butyl methacrylate-methyl methacrylate copolymer
BOPP Biaxially oriented polypropylene film
BPor BR Polybutadiene or an isobutene/isoprene copolymer; butyl or
butadiene rubber
bPC Branched polycarbonate of bisphenol-A
BPA Bisphenol-A
BR Butadiene rubber
Bu-ABS Graft copolymer of butylacrylate and triallyl isocyanurate on
polybutadiene, in turn emulsion grafted with styrene and
acrylonitrile
C
CA Cellulose acetate
CAB Cellulose acetate-butyrate
CAN Cellulose acetate-nitrate
CAP Cellulose acetate-propionate
CB Cellulose butyrate
CBR Chlorinated butadiene rubber
562 Appendix I
CDB Conjugated diene butyl elastomer
CE Cellulose plastics, in general
CEM Polychlorotrifluoroethylene (also CFM/ CTFEP/ PCTFE)
CF Cresol-formaldehyde resins
CFM Polychlorotrifluoroethylene (also CEM, CTFEP/ PCTFE)
CHR Elastomeric copolymer from epichlorohydrin and ethylene oxide
CUR Post-ehlorinated elastomeric copolymer from isobutene and
isoprene
CM (1) Chloro-polyethylene: (2) Compression molding
CMC Carboxy methyl cellulose, (or critical micelle concentration)
CMHEC Carboxy methyl hydroxy ethyl cellulose
CMPS Poly(chloromethyl styrene)
CN Cellulose nitrate (Celluloid; also NC)
CNR Elastomeric terpolymer from tetrafluoroethylene,
trifluoronitroso methane, and a small amount of an
unsaturated monomer, e.g., nitroso perfluoro-butyric acid;
nitroso or carboxy nitroso rubber
co Polychloromethyl oxirane elastomer, epichlorohydrin rubber
COP Cycloalkene polymers or copolymers
CO-PAl Copolyamideimide
COPE Copolyester elastomer
CO-PI Copolyimide
COPO Poly(carbon monoxide-co-polyalkene), such as linear,
alternating terpolymer: ethylene-co-propylene-co-carbon
monoxide
COX Carboxylic rubber
CP (1) Cellulose propionate; (2) chlorinated polyethylene (also CPE)
CP2 Alternating copolymer from vinyl ether and maleic acid
CP4 Copolymer from acrylic acid and maleic acid
CPE Chlorinated polyethylene
CPET Crystallizable (or chlorinated) polyethyleneterephthalate
CPI cis-Polyisoprene (also IR)
CPVC Chlorinated poly(vinyl chloride)
CR Chloroprene, or Neoprene, rubber
CRM Chlorosulfonated polyethylene
CRP Carbon fiber reinforced plastics
CS Casein
CSM/CSPEor Chlorosulfonated polyethylene
CSR
CTorCTA Cellulose triacetate
CTBN Carboxy terminated nitrile rubber
CTFE Polychlorotrifluoroethylene (also CEM, CFM/ PCTFE)
CTFEP Polychlorotrifluoroethylene (also CFM/ CEM, PCTFE)
CV Viscose; see also VI
D
DAC Diallylchlorendate
DAF Diallylfumarate
Appendix I 563
DAIP Diallylisophthalate
DAP Diallylphthalate
DMC Dough molding compound
DOP Di-ethylhexylphthalate
E
E-PVC Emulsion polyvinyl chloride; PVC polymerized in emulsion
E-SBR Polymerized in emulsion styrene/butadiene copolymer
E/B Copolymers of ethylene and I-butene
E/P Copolymers of ethylene and propylene
EA,EAA Ethylene acrylic acid copolymer
EAM Elastomeric copolymer of ethylene and vinyl acetate
EBA Ethylene butyl acrylate copolymer
EBA-GMA Ethylene-butyl acrylate-glycidyl methacrylate copolymer
EBA-AA Ethylene-butyl acrylate-acrylic acid copolymer
EBM Extrusion blow molding
EC Ethyl cellulose
ECA Ethylene-carbonate copolymer
ECB Blends from ethylene copolymers with bitumen
ECO Elastomeric copolymer from ethylene oxide and
epichlorohydrin (see also ED-ECH, CO)
ECPE Extended chain polyethylene
ECfF,ECTFE Poly(ethylene-co-ehlorotrifluoroethylene)
EEA Elastomeric copolymer from ethylene and ethyl acrylate
EEAAA Polyethylene grafted with ethyl acrylate and acrylic acid
EEA-GMA Ethylene-ethyl acrylate-glycidyl methacrylate copolymer
EGMA Ethylene-glycidyl methacrylate copolymer
EHEC Hydroxy ethyl cellulose
ELAST Elastomer
EMA Copolymer from ethylene and maleic anhydride or ethylene-
methyl acrylate
EMAc Copolymer from ethylene and methacrylic acid
EMAC Ethylene methacrylate copolymer
EM! Electromagnetic interference
EMM Copolymer from ethylene and methylmethacrylate
EMP Ethylene-propylene copolymers (ethylene modified
polypropylene)
ED-ECH Copolymer of ethylene oxide and epichlorohydrin (also
ECO,CO)
EP Epoxy resins
E/P Ethylene-propylene copolymer
EP-G-G Prepreg from epoxy resin and glass fabric (German literature)
EP-K-L Prepreg from epoxy resin and carbon fiber fabric (German
literature)
EPD Ethylene-propylene-diene copolymer
EPD,EPDM Elastomeric terpolymer from ethylene, propylene, and a non-
conjugated diene
EPDM-MA Maleic anhydride-modified ethylene-propylene-diene
terpolymer
564 Appendix I
EPE Ester of an epoxy resin
EPM Ethylene-propylene copolymer
EPR, EPM Elastomeric copolymer of ethylene and propylene
EPR-MA Maleated ethylene-propylene rubber (EPR)
EPS Polystyrene foam; expanded PS
EPT,EPTR Ethylene, propylene, and a non-conjugated diene terpolymer
(also EPDM)
ES Ethylene-styrene block copolymer
ESD Electrostatic dissipation
ETE Engineering thermoplastic elastomer
ETFE Copolymer from ethylene and tetrafluoroethylene
ED Polyether urethane
EVA Ethylene-vinyl acetal copolymer
EVAc Copolymer from ethylene and vinyl acetate
EVAc-AA Ethylene-vinyl acetate-acrylic acid graft copolymer
EVAc-CO Ethylene-vinyl acetate-carbon monoxide copolymer
EVAc-MA Copolymer from ethylene, vinyl acetate, and methacrylic acid
EVA-GMA Ethylene-vinyl acetate-glycidyl methacrylate copolymer
EVAl,EVAL Copolymer of ethylene and vinyl alcohol
EVAVC Ethylene-vinyl acetate-vinyl chloride copolymer
EVC Copolymer from ethylene and vinylene carbonate
EVE Ethylene-vinyl ether copolymer
EVM Ethylene-vinyl acetate copolymer, a thermoplastic elastomer
EVOH Ethylene vinyl alcohol copolymer
EVP Ethylene vinyl pyrrolidinone copolymer
F
FE Auorine containing elastomer
FEP Auorinated EPR; tetrafluoroethylene/hexafluoropropylene
rubber
FF Resin from furan and formaldehyde
FFKM Perfluoro rubbers of the polymethylene type, having all
substituent fluoro, perfluoroalkyl or perfluoroalkoxy groups
on the polymer chain
FK Fiber reinforced plastic (also FRP, GRP)
FKM Hexa-fluoro propylene-vinylidenefluoride copolymer
FMQ Methyl fluoro silicone rubber (also MFQ)
FP Auoroplastic
FPM Vinylidenefluoride/hexa-fluoro propylene elastomer; rubbers
with fluoro and fluoroalkyl or fluoroalkoxy groups
FPVC Aexible PVC film
FQ Elastomeric silicone with fluorine containing substituents
FRE Fiber reinforced epoxy
FRP Glass fiber reinforced polyester (also FK, GRP)
FVMQ Silicone rubber with fluorine, vinyl, and methyl substituents
G
GECO Epichlorohydrin-ethylene glycol-glycidyl ether elastomeric
copolymer
Appendix I S65
GEP Glass fiber reinforced epoxy resin

GF Glass fiber, or glass fiber reinforced plastic
GF-PF Glass fiber reinforced phenolic resin
GF-UP Glass fiber reinforced unsaturated polyester resin
GMA Glycidyl methacrylate
GMT Glass mat reinforced plastics
GP Gutta-percha
GPO Elastomeric copolymer from propylene oxide and allyl glycidyl
ether
GPPS General purpose polystyrene (also PS)
GPSMA General purpose styrene-maleic anhydride copolymer (also
SMA)
GR 'Government Rubber' from state-owned factories in the USA
duringWWll
GR-I Butyl rubber
GR-N Nitrile rubber; now NBR
GRP Glass reinforced polyester (thermoset; also FK, FRP)
GR-S Styrene-butadiene rubber
GUR Ultrahigh-molecular-weight polyethylene (UHMWPE)
H
HALS Hindered arnines (antioxidants)
HAO Higher a-alkens
HBV Poly(3-hydroxy butyrate-eo-valerate)
HDPE High density polyethylene (~ 960 kgjm3 )
HEC Hydroxy ethyl cellulose
HIPS High impact polystyrene
HISMA High impact styrene-maleic anhydride copolymer
HM Hot melt adhesive
HMC Sheet molding compound with high glass fiber content
HMW High molecular weight
HMW-PE Polyethylene with high molecular weight
H-NBR, HNBR Hydrogenated acrylonitrile-butadiene elastomer
HPC Hydroxy propyl cellulose
HPMC Hydroxy propyl-methyl cellulose
HR High resiliency foams
HTE Hydroxy-terminated polyether
1
ICP Intrinsically conductive (or connecting) polymer
lEN Interpenetrating elastomeric network
IHPN Interpenetrating homopolymer network
IIR Isobutene-isoprene rubber (butyl rubber)
1M Polyisobutene (also pm)
10 lonomer
IPN Interpenetrating polymer network
IPS Impact resistant polystyrene
IR Synthetic cis-l,4-polyisoprene, synthetic isoprene rubber
566 Appendix I
L
L-SBR Solution polymerized SBR
LCP Liquid crystal polymer
LOPE Low density polyethylene (::::::: 918 kgjm3 )
LIM Liquid impingement molding; now RIM
LIPN Latex interpenetrating polymer network
LLOPE Linear low density polyethylene (also MOPE)
LMOPE Linear medium density polyethylene
LPE Linear polyethylene
LRM Liquid reaction molding; now RIM
LRMR Reinforced liquid reaction molding
LSR Liquid silicone rubber
LTG Low temperature zinc phosphate glasses
M
M-PVC Polymerized in bulk polyvinylchloride
MA Maleic anhydride
MAS Copolymer from methyl methacrylate, acrylonitrile and styrene
MABS Copolymer from methyl methacrylate, acrylonitrile, butadiene
and styrene
MAN Copolymer from methyl methacrylate and acrylonitrile
MBA Copolymer from methylmethacrylate, butadiene, and
acrylonitrile
MBS Copolymer from methylmethacrylate, butadiene and styrene
MC Methyl cellulose
MOl Methyl di-isocyanate
MOPE Medium density polyethylene (::::::: 930 - 940 kgjm3 )
MeSAN Copolymer from a-methyl styrene and acrylonitrile
MF Melamine-formaldehyde resins
MFK Metal fiber reinforced plastic
MFQ Silicone rubbers with methyl and fluorine substituent groups
(also FMQ)
MFR Melt flow rate
MI Melt index
MIPS Medium impact strength polystyrene
MMA Methylmethacrylate
MMA-MAc-EA Copolymer of methyl methacrylate, methacrylic acid and ethyl
acrylate
MMBA Copolymer from methyl methacrylate and butyl acrylate
MMBA-TPT Copolymer from methyl methacrylate, butyl acrylate, diallyl
maleate and trimethylol propane triacrylate
MMEA Methyl methacrylate-ethyl acrylate copolymer
MMPMI Methylmethacrylate-co-N-phenylmaleimide copolymer
MMS Copolymer from methyl methacrylate, and a-methylstyrene
MMVAc Methyl methacrylate-vinyl acetate copolymer
MMVAc-AA Copolymer of methylmethacrylate, vinyl acetate and acrylic acid
MMW Medium molecular weight
MPF Melamine-phenol-formaldehyde resin
Appendix I 567
MPQ Silicone rubbers having both methyl and phenyl substituent

groups (also PMQ)
MPR Melt-processable rubber
MPS Poly(a-methyl styrene)
MPVQ Silicone rubbers with methyl, phenyl and vinyl groups (also
PVMQ)
MQ Elastomeric silicones with methyl substituents
MSABS Methylstyrene-styrene-acrylonitrile-grafted polybutadiene
MSAN Thermoplastic copolymer from a-methylstyrene and
acrylonitrile
MSMA Copolymer of methylmethacrylate, p-methyl-styrene and maleic
anhydride
MVQ Silicone rubbers having both methyl and vinyl substituent
groups (also VMQ)
MWR Molding with rotation
N
NBR Elastomeric copolymer from butadiene and acrylonitrile; i.e.,
nitrile rubber
NC Cellulose nitrate (also CN)
NCR Elastomeric copolymer from acrylonitrile and chIoroprene
NOPE Low density polyethylene (also LDPE)
NIR Elastomeric copolymer from acrylonitrile and isoprene
NK Natural rubber (also NR)
NP Network polymer
NR Natural rubber (also NK)
o
OEP Oil-extended polymer
OPET Oriented polyethyleneterephthalate
OPP Oriented polypropylene, film or bottles (also PP)
OPR Elastomeric polymer from propylene oxide
OPS Oriented polystyrene films
OPVC Oriented polyvinylchloride
OSA Olefin-modified styrene-acrylonitrile copolymer
P
P-S/ PSA Pressure-sensitive adhesive
P3FE Poly(trifluoroethylene)
PA Polyamide, the abbreviation PAis normally followed by a
number, a combination of numbers, a letter or a combination
of letters and numbers. A single number refers to the
polyamide from an a, w-amino acid or its lactam. A
combination of two numbers is often separated by a comma.
The first number following the symbol PA indicates the
number of methylene groups of aliphatic di-amines, the
second number the number of carbon atoms of aliphatic
568 Appendix I
di-carboxylic acids. An I stands for isophthalic acid, a T for
terephthalic acid. For example, co-polyamide from
caprolactam, hexamethylenediamine condensed with
isophthalic and terephthalic acids is PA-6IT6, and that from
caprolactam, m-xylylenediamine and adipic acid is PA-rnXD6.
PA-6 Poly-c-eaprolactam
PA-46 Poly(tetramethylene adipamide) (also PTA)
PA-66 Poly(hexamethylene diamine-adipic acid), polyhexamethylene-
adipamide
PA-6IT6 Poly(caprolactam-eo-hexamethylene diamine-isophthalic and
terephthalic acids)
PA-rnXD Poly(m-xylylene adipamide)
PA-rnXD6 Poly(m-xylylenediamine and adipic acid-co-eaprolactam)
PAA Polyacrylic acid
PAAE Polyarylamide-polyether
PAAM Polyacrylamide
PABM Polyaminobismaleimide
PAC Polyacrylonitrile fiber (also PAN); polyacrylate
PADC Poly(allyl diglycol carbonate)
PAEB Poly(p-aminoethyl benzoate)
PAE Polyarylether
PAEI Polyacrylic ester imide
PAEK Polyaryletherketone
PAES Polyarylethersulfone
PAl Polyamide-imide
PAK Polyester alkyd
PALL Polyallomer, a block copolymer of propylene, ethylene (1.5-3%),
butene (8%) and hexene (5%)
PAMS Poly-a-methylstyrene
PAN Polyacrylonitrile
PANI Polyaniline
PAPA Polyazelaic polyanhydride
PAPI Polymethylenepolyphenylene isocyanate (also PMPPI)
PAr,PAR Polyarylate [-</>-C(CH3 h-</>-C02-</>-CCh-]n' amorphous
polyester of bisphenol-A isophthalate and terephthalic acids
PArSi Poly(aryloxysiloxane), e.g.,
poly(dimethylsiloxybiphenyleneoxide)
PARA Polyaryl amide (aromatic, usually amorphous polyamide)
PARS Polyaryloxysiloxane
PAS Polyarylsulfide copolymers (especially in German and Japanese
literature)
PAS, PASU Polyarylsulfone [--SCh-<l>-O-]0.875 [-<1>-0-]0.125
PAT (1) Polyaminotriazole; (2) also polyarylterephthalate, an
aromatic LCP polyester
PAUR Polyester urethane
PB Poly-I-butene, i.e., polybutylene on elastic polydiene fiber
PBA (1) Polybutylacrylate; (2) also poly(I,4-benzamide)
Appendix I 569
PBAN Poly(butadiene-co-acrylonitrile)
POCD Poly(butylene cyclohexane dicarboxylate)
PBE Poly(l-butene-co-ethylene)
PBG Polybutylene glycol, also known as polytetrahydrofuran (PTHF)
PBI Polybenzimidazoles
PBMA Poly-n-butyl methacrylate
PBMI Polybismaleimide
PBNOC Poly(butylene-2,5-naphthalene-dicarboxylate)
PBN Poly(butylene-2,6-naphthalene dicarboxylate)
PBO Polybutyleneoxide
PBR Copolymer from butadiene and vinyl pyridine
PBS Copolymer from butadiene and styrene (also GR-S, SBR)
PH-SMA Styrene-maleic anhydride-grafted polybutadiene
PBT,PBTP Polybutyleneterephthalate
PBT-PBG Copolymer of 1,4-butanediol-polybutylene glycol-terephthalic
acid
PBZ Polybenzobisoxazole
PBZT Poly(p-phenylenebenzobisthiazole)
PC Bisphenol-A polycarbonate
PCA Polycarbonate-acrylic
PCD Polycarbondiimide
PCDP Polydicyclopentadiene
PCDT Poly(l,4-cyc1ohexylene dimethylene terephthalate)
PCE Polycycloenes
PCF . Polychlorotrifluoroethylene fiber
PCHMA Polycyclohexyl methacrylate
PCI Poly(l,4-cyclohexylenedimethylene isophthalate)
PCME Poly(2,2-dichloromethyltrimethylene ether)
PCN Poly(2-cyano-5-norbornene)
pca Polycycloalkene
PC-Ph Co-polycarbonate from phosgene with bisphenol-A and
phenolphthalein
PCT Polycyclohexyleneterphthalate, cyclohexanedimethanol-
ethylene glycol terephthalic acid copolymer
PCTFE Polychlorotrifluoroethylene (also CEM, CFM, CTFE)
PCTG Poly(cyclohexane terephthalate-glycol); with ~ 34 mol %
ethylene glycol and 2: 66 mol % cyclohexylene dimethanol
PCU Polyvinyl chloride (old German literature)
PDAP Polydiallylphthalate
PDCP Polydicyclopentadiene
PDMDPhS Poly(dimethyl-diphenyl siloxane)
PDMS Polydimethylsiloxane
PE Polyethylene
PEA Polyetherarnide
PEsA Polyesterarnide
PEAc Polyethylacrylate
PEB polyethylene-p-oxybenzoate, A-Tell ™
PEBA Thermoplastic elastomer, polyether-block-arnide
570 Appendix I
PEC (1) Polyestercarbonate; (2) chlorinated polyethylene (usually
CPE)
PeCe Chlorinated PVC (also CPVC, PC, pvcq
PECO Polyethylene carbonate,
PEE Polyester ether fibers (containing diol and p-hydroxy benzoate
units, e.g., polyethylene-p-oxybenzoate, A-Tell TM)
PEEl Polyesteretherimide
PEEK Polyetheretherketone
PEG Polyethyleneglycol
PEH High density polyethylene (also HDPE)
PEl Polyetherimide
PEIE Polyetherimide ester copolymer
PEIm Polyetherimine
PEK Polyetherketone
PEKEKK Poly(ether-ketone-ether-ketone-ketone)
PEL Low density polyethylene (also LOPE)
PEM Medium density polyethylene; also MDPE
PEN,PENOC Poly(ethylene 2,6-naphthalene dicarboxylate), or
polyethylenenaphthalate
PENi Polyethemitrile
PEP Thermoplastic copolymer from ethylene and propylene
PEO Polyethylene glycol, usually PEG
PEOX Poly(2-ethyl-2-oxazoline)
PEPA Polyether-polyamide copolymer
PES Polyethersulfone [+~~ln
PESK Polyarylenethioetherketone
PEST Thermoplastic polyesters, (e.g., PBT, PET; also TPES)
PET,PETP Polyethyleneterephthalate
PETG Polyethyleneterephthalate glycol; copolymer with 66
mol % ethylene glycol and 34 mol % cyclohexylene
dimethanol
PEtI Polyethyleneimine
PEUR Polyetherurethane
PF Phenol-formaldehyde resin
PFA Polyfluoroalcoxyalkane; copolymer of tetrafluoroethylene and
perfluorinated alkyl Vinyl ethers
PFEP Copolymer from tetrafluoroethylene and hexafluoropropylene
(also FEP)
PFF Phenol-furfural resin
PG Poly-a-hydroxy acrylic acid
PGI Polyglutarimide
PH Phenolics
PHB Poly(p-hydroxybenzoic acid) (also POB)
PHBA Poly<.B-hydroxybutyric acid)
PHEMA Poly-2-hydroxyethyl methacrylate
PHIT Poly(hexylene-isophthalate-terephthalate)
PHMT Polyhexamethyleneterephthalate (also PHT)
PHP Physiological hydrophilic polymers
Appendix I 571
PhPS Poly(p-phenyl styrene)
PHT Polyhexamethyleneterephthalate (also PHMT)
PHZ Polyphosphazene
PI Polyimide, but also trans-1,4-polyisoprene, gutta-percha (UK)
PIAN Isoprene-acrylonitrile oil resistant elastomer
pm Polyisobutene
pmI Copolymer from isobutene and isoprene, Le., butyl rubber
(butyl, GR-I, IIR)
PIBO Polyisobuteneoxide
PIP Synthetic cis-1,4-polyisoprene (also CPI, IR)
PIPO Polyimidazipyrolone
PIR Polyisocyanurate (foam)
PIS Polyisobutylene
PISU Polyimidesulfone
PLA Polylactic acid
PMA Polymethylacrylate
PMAC Polymethoxy acetal
PMAN Polymethyl acrylonitrile
PMB Poly-p-methylenebenzoate
PMCA Polymethyl-a-ehloroacrylate
PMI Polymethacrylirnide
PMMA Polymethylmethacrylate
PMMA-MA Poly(methylmethacrylate-co-acrylic acid)
PMMI Polypyromellitimide
PMP Poly(4-methyl-1-pentene) (also TPX)
PMPPI Polymethylenepolyphenylene isocyanate; also PAPI
PMQ Silicone rubbers with methyl and phenyl substituents (see also
MPQ)
PMS Poly-a-methylstyrene
PpMS Poly-p-methylstyrene
PNA Polynuclear aromatics
PNF Polyfluoroalcoxyphosphazene
PNR Polynorbomene rubber
PO (1) Polyalkene; (2) elastomeric polypropylene oxide; (3) phenoxy
resin
POB Poly-p-hydroxy benzoate (also PHB)
POBI Polyoxadiazobenzimidazole
POCA Polyoxycyanoarylene
POD Polyoctadecene
PODZ Poly(p-phenylene-1,3,4-oxadiaxole)
POM Polyoxymethylene, polyformaldehyde, polyacetal or 'acetal
resin'
POMA Poly(oxetane methacrylate)
POP Polyoxypropylene (usually PPG)
POR Elastomeric copolymer from propylene oxide and allyl glycidyl
ether
POT Polyoctyl thiophene
PP Polypropylene, Le., oriented polypropylene (also OPP)
572 Appendix I
PP-MA Maleic anhydride-modified polypropylene
PPhA Polyphthalamide
PPA Polypropyleneadipate
PPAc Polypropylacrylate
PPBA Polyparabanic acid
PPC Chlorinated polypropylene
PPCA Poly(polycyclic (meth)acrylate)
PPD-T Poly(p-phenylene terephthalarnide), Kevlar™, (also PPTA)
PPE Poly(2,6-dimethyl-l,4-phenylene ether)
PPE-MA Maleic anhydride-modified poly(2,6-dimethyl-l,4-phenylene
ether)
PPG Polypropylene glycol
PPI Polymeric polyisocyanate
PPMS Poly(p-methyl styrene)
PPO GE Co. trade name for poly(2,6-dimethyl-l,4-phenylene ether)
(also PPE)
PPOEA Poly(phenoxyethoxyethyl acrylate)
PPOX,PPO Polypropylene glycol (usually PPG)
PPP Poly-p-phenylene
PPR Polypyrrole
PPS Polyphenylsulfide
PPSK, PKS Polyketonesulfide [-~S-</r-C0-1n
PPSS, PPS-S Polyphenylenesulfidesulfone, polythioethersulfone
PPSU Polyphenylene sulfone, Le., polysulfone (also PSF, PSO, PSU,
PSUL)
PPT,PPTP Polypropyleneterephthalate
PPTA Poly(l,4-phenylene terephthalarnide) (also PPD-T)
PPX Poly(p-xylylene)
PPy Polypyrrole
PPZ Polyorganophosphazene
PQ Elastomeric silicone with phenyl substituents
PS Polystyrene
PS-GMA Styrene-glycidyl methacrylate copolymer
PS-MA Styrene-maleic anhydrite copolymer
PSOX Styrene polymer having reactive (2-oxazoline) groups
PS-TSG Polystyrene foam, processed by injection (German literature)
PSAB Copolymer from styrene and butadiene (also SB, SIB)
PSAN Thermoplastic copolymer from styrene and acrylonitrile (also
AS,SAN)
PSB Styrene-butadiene rubber, also G5-R, SBR
PSBR Elastomeric terpolymer from vinyl pyridine, styrene, and
butadiene
PSF Polysulfone (also PSUL, PSU, PSO)
PSI Polymethyl phenyl siloxane
PSL Polysprrodilactone
PSO Polysulfone (also PSUL, PSU, PSF, PPSU)
PST Polystyrene fiber with at least 85% styrene units
PSU Polysulfone [+SCh-¢-0-¢C(CH3h+D-ln
Appendix I 573
PSUL Polysulfone (also PSF, PSU, PSO, PPSU)

PS-VPh Poly(styrene-b-vinyl phenol) block copolymer
PTA Polytetramethylene adipamide
PTF Polytetrafluoroethylene fiber
PTFE Polytetrafluoroethylene (also TFE)
PTHF Polytetrahydrofuran, also known as polybutylene glycol (PBG)
P1MA Polytetramethyleneadipate
PTMC Poly(trimethylene carbonate)
PTMEG Poly(tetramethylene ether glycol)
PTMG Polytetramethylene glycol
PTMT Poly(tetramethylene terephthalate), i.e.,
polybutyleneterephthalate (also PBI)
PTa Polytransoctanylene
PTR Polysulfide rubber
PU,PUR Polyurethane elastomer
PYA Polyvinyl acetal
PVAcorPVAC Polyvinyl acetate
PVAIor PVAL Polyvinyl alcohol (also PVOH)
PVBu Polyvinylbutyrate
PVBO Polyvinyl butyral
PVC Poly(vinyl chloride)
PVCA or PVCAc Copolymer from vinyl chloride and vinyl acetate
PVCC Chlorinated PVC (also CPVC, PeCe)
PVD Polyvinylidene chloride fiber with ~ 50 wt% vinylidene chloride
PVDC Polyvinylidene chloride (also PVC2)
PVDF Polyvinylidene fluoride (also PVF2)
PVF Polyvinyl fluoride
PVFMor PVFO Polyvinyl formal
PVI Poly(vinyl isobutyl ether)
PVID Polyvinylidenecyanide
PVIE Polyvinylisobutyl ether
PVK Poly-N-vinylcarbazole
PVM Copolymer from vinyl chloride and vinyl methyl ether
PVME Polyvinylmethylether
PVMQ Silicone rubber with methyl, phenyl, and vinyl substituents (see
als MPVQ)
PVOH Polyvinyl alcohol (also PVA, PVAI)
PVP Poly-N-vinylpyrrolidone
PVPH,PVPh Polyvinylphenol, poly(p-hydroxy styrene)
PVSI Polydimethyl siloxane with phenyl and vinyl substituents
PY Unsaturated polyester resins (also UP)
Q
Q Silicone elastomer
QA Quality assurance
QC Quality control
QDS Quality data statistics
QMC Quick molding change
574 Appendix I
AbbreviJ:ltion Description
R
RAM Restricted area molding
RCF Refractory ceramic fiber
REX Reactive extrusion
RF Resorcinol-formaldehyde resin
RH Relative humidity (in %)
RHB Reheat blow molding
RIM Reaction injection molding
RLM Reactive liquid polymer
RMPS Rubber-modified polystyrene
RP Reinforced plastics, reinforced thermoplastic (also RP IC, RTP)
RPBT Reinforced polybutyleneterephthalate
RPET Reinforced polyethyleneterephthalate
RPVC Rigid PVC film
RRIM Reinforced reaction injection molding
RID Residence time distribution
RTM Resin transfer molding
RTP Reinforced thermoplastic
RTPO Reactor-blended thermoplastic alkenic elastomer
RTS Reinforced thermoset
RTV Room temperature vulcanization (of silicone rubber)
RUC Chlorinated rubber
S
sPP Syndiotactic polypropylene
SAA Styrene-acrylic acid copolymer
SAMA Styrene-acrylonitrile-methacrylic acid copolymer
5-EPDM Sulfonated ethylene-propylene-diene terpolymer
5-PVC Suspension PVC
SAN Thermoplastic copolymer from styrene and acrylonitrile (also
AS, PSAN)
SANGMA Styrene-acrylonitrile-glycidyl methacrylate copolymer
SANMA Styrene-acrylonitrile-maleic anhydride copolymer
SB or SIB Thermoplastic copolymer from styrene and butadiene (also
PASB)
SBCL Styrene-butadiene-caprolactone copolymer
SBMA Styrene-butadiene-maleic anhydride copolymer
SBMI Styrene-butadiene-maleimide
SBP Styrene-butadiene polymer
SBR Styrene-butadiene elastomer
SB/BA Styrene-butadiene-butyl acrylate copolymer
SBS Styrene-butadiene-styrene triblock polymer
SCR Elastomeric copolymer from styrene and chloroprene
SEBS Styrene-ethylene/butylene-styrene triblock polymer
SEP Styrene-ethylene-propylene block copolymer
SF Structural foam
SFK Synthetic fiber reinforced plastic (German literature)
SFM Structural foam molding
Appendix I 575
SFP Scrapless forming process
SHIPS Super-high impact polystyrene
SI Thermoplastic silicone
SIN Simultaneous interpenetrating network or semi-interpenetrating
network
SIPN Sequential interpenetrating polymer network
SIR Elastomeric copolymer from styrene and isoprene
SIS Styrene-isoprene-styrene triblock polymer
SMA Copolymer from styrene and maleic anhydride
SMAA Copolymer from styrene and methacrylic acid
SMA-AA Styrene-maleic anhydride-acrylic acid copolymer
SMC Sheet molding compound
SMI Copolymer from styrene and maleimide
SMMorSMMA Styrene-methyl methacrylate copolymer
SMM-GM Styrene-methyl methacrylate-glycidyl methacrylate copolymer
SMM-MA Styrene-methyl methacrylate-maleic anhydride copolymer
SMS Copolymer from styrene and a-methylstyrene
SP Saturated polyester plastics
SPC Statistical process control
SPPF Solid-phase pressure forming
SPSF Solid-phase stretch forming
SR Synthetic rubber, polysulfide rubber
SRIM Structural reactive injection molding
SRP Styrene-rubber plastics
SSE Single-screw extruder
SVA Styrene-vinyl-acrylonitrile copolymer
SVPh Styrene-p-vinylphenolcopolymer
SWP Solvent welded plastics pipe
T
TA Cellulose triacetate (also CT, CTA)
TC Technically classified natural rubber
TDI Toluene di-isocyanate
TE Thermoplastic elastomer of any type
TEEE Thermoplastic elastomer, ether-ester
TEO Thermoplastic elastomer, alkenic
TES Thermoplastic elastomer, styrenic
TFE Polytetrafluoroethylene (also PTFE)
TGA Thermogravimetric analysis
TGIC Triglycidyl isocyanurate
TM Thioplasts, transfer molding
TMBA-PC Tetramethyl bisphenol-A polycarbonate (or TMPC)
TMC Thick molding compound
TMPC Tetramethyl bisphenol-A polycarbonate (or TMBPA-PC)
TOR trans-Polyoctenamer rubber
TP Thermoplastic
TPA l,5-trans-Polypentenamer (also TPR)
TPE Thermoplastic elastomer (also TPEL)
576 Appendix I
TPE-A Thennoplastic elastomer-amide
TPE-E Thennoplastic elastomer-ester
TPE-S Thennoplastic elastomer-polystyrene
TPES Thennoplastic polyesters, e.g., PBT, PET, see also PEST
TPI Thennoplastic polyimide
TPO Thennoplastic olefinic elastomer
TPR 1,5-trans-Polypentenamer (also TPA)
TPS Toughened PS (in the UK for HIPS)
TPU orTPUR Thennoplastic urethanes
TPV Thennoplastic vulcanizate
TPX Poly(4-methyl-1-pentene) (also PMP)
TR Thennoplastic elastomer or thio rubber (UK)
TREF Temperature rising elution fractionation
IS Thennoset
ISE Thennoset elastomer
ISI Thennoset polyimide
ISUR Thennoset polyurethane
U
UE Polyurethane elastomer
UF Urea-fonnaldehyde resin
UFS Urea-fonnaldehyde foam
UHMW-PE Ultrahigh-molecular-weight polyethylene (over 3 Mg/mol)
ULDPE Ultra low density polyethylene (::::: 900-915 kg/m3 )
UP Unsaturated polyester (also PY)
UP-G-G Prepreg from unsaturated polyesters and textile glass fibers
UP-G-M Prepreg from unsaturated polyesters and textile glass mats
UP-G-R Prepreg from unsaturated polyesters and textile glass rovings
UPVC Unplasticized PVC
UR Polyurethane elastomers (also UP)
V
VAc Vinylacetate
VAc-AN Copolymer from vinylacetate and acrylonitrile
VAcE Vinylacetate-ethylene copolymer
VC Vinylchloride (monomer)
VC/EorVCE Vinylchloride-ethylene copolymer
VCEMA Copolymer from vinyl chloride, ethylene and methyl acrylate (or
maleic anhydride)
VCEV Copolymer from vinyl chloride, ethylene and vinylacetate
VCMA Copolymer from vinyl chloride and methyl acrylate
VCMMA Copolymer from vinyl chloride and methylmethacrylate
VCOA Copolymer from vinyl chloride and octyl acrylate
VCVAc Copolymer from vinyl chloride and vinyl acetate
VCVDC Copolymer from vinyl chloride and vinylidene chloride
VCE Copolymer from ethylene and vinyl chloride
VCM Vinyl chloride (monomer) (also VC)
VDC Vinylidene chloride
Appendix I 577
VDC/AN Copolymer from vinylidene chloride and acrylonitrile

VF/HFP Copolymer from vinylidene fluoride and hexafluoropropylene
VLDPE Very low density polyethylene (~ 885 kg/m3)
VMQ Silicone rubber with methyl and vinyl substituents
Vex: Volatile organic compound
VPE Vulcanized (cross-linked) polyethylene (also XLPE)
VQ Elastomeric silicone with vinyl substituents
VSI Polydimethylsiloxane with vinyl groups
W
WR Woven rovings
X
XABS Acrylonitrile/butadiene/styrene/acidic monomer, an
elastomeric copolymer
XLPE Cross-linked polyethylene
XMC Extra-strength molding compound
XNBR Acrylonitrile/butadiene/acidic monomer; an elastomeric
copolymer
XPS Expandable or expanded PS
XSBR Butadiene/ styrene/ acidic monomer, an elastomeric copolymer
Y
YBPO Elastomeric polyetherester [( (CH2 k-D)n-e0-4>-CO-O-]m
YSBR Thermoplastic, elastomeric block copolymer from styrene and
butadiene
YXSBR Block copolymer from styrene and butadiene containing
carboxylic groups
Note: The list is based on the nomenclature proposed by diverse standards organizations, as
well as on the acronyms used in the technical literature, namely: American Society for Testing
Materials, Standard Terminology for Abbreviated Terms Relating to Plastics, ASTM D 141S-90,
ASTM D 1600-91a and there-referenced standards; British Standards, Schedule of common
names and abbreviations for plastics and rubbers, BS 3502-1978; Deutsches Institut fur Normung,
Plastics, symbols and codes for polymers and their special characteristics, DIN 7728 Tei! 1 01.88;
Symbols for reinforced plastics, DIN 7728 Tei! 2 03.80; Plastics molding materials DIN 7742 Tei! 1
01.88; Molding techniques for molding materials, definitions, DIN 16700 09.67; Association Fran~aise
de normalisation, Plastics, vocabulary, T 50-100 08.90; Plastics, symbols, T s0-050-1, T s0-050-2, T
s0-050-3 06.89; International Organization for Standardization, Plastics - symbols, ISO 1043-
1:1987, ISO 1043-2:1988, ISO 1043-3:1988; International Union for Pure and Applied Chemistry,
Pure App!. Chern. 18583 (1%9); 40, 473 (1974).
Appendix II
CO~RClALPOLYMERBLEND6
Blend name or Description Company

identity
A
A, AN PBT/ ABS alloys Teijin Chemical Ltd
ABS/PC 7901 PC/ABS alloys Diamond Polymers
ABSAlloys HAN-8654 is ABS/PA alloys Miwon Petrochemical
HBG-5700 is glass reinforced Corp.
ABS/PBT alloy
HAC-8200Z ABS/PC alloys for
automotive trim
Abson042 PVC/ABS alloys Abtec Chem./BF
Goodrich
Abstrene Acrylonitrile-butadiene-styrene Distillers
terpolymer, ABS
Accpro Polypropylene blends Amoco Chemical
Company
Acctuf Ethylene-propylene high impact Amoco Chemical
copolymers Company
Acculloy Polymer alloys Ado Compounders
Acpol Acrylic or thermoset polyesters; Freeman Chemical
Acrylic/urethane/styrene IPN Company
Acrylivin Polyvinylchloride/ acrylic alloys General Tire & Rubber
Company
Acryloid Poly(methylmethacrylate- Rohm & Haas
butadiene-styrene) (MBS, now Company
Paraloid™)
Adion Hydrophilic polymer blends with Asahi Chemical
either ABS or HIPS Industries
AdproAP Reactor alkenic thermoplastic Genesis Polymers
elastomers (RTPO)
Afcoryl Acrylonitrile-butadiene-styrene Pechiney-Saint-Gobain
terpolymer (ABS)
Appendix II 579

identity
Afcoryl Acrylonitrile-butadiene-styrene Pechiney-Saint-Gobain
terpolymer (ABS)
Aflas PTFE + PP + cure site monomer Asahi Glass
terpolymer
Akulon PA-6, PA-66 blends with PO, AI<ZO IDSM Plastics
reinforced or not
Akulon K228 PA blends with brominated PS DSM Plastics Int.
AkuloyJ Polyamide-66 with PP and 30% DSM Plastics Int.
glass fiber
AkuloyRM Polyamide-6 or -66 blends with DSM Plastics Int.
functionalized PP, glass fiber or
mineral filled, or not
Akuloy XT Polyamide-6 I thermoset elastomer DSM Plastics Int.
alloy
Albis Polyamide-6 I polyalkene (10%) Albis Plastics
blends
Alcryn Chlorinated alkene lEVAll DuPont
acrylate ester blends;
PVC I ethylene-Co-vinylchloride
copolymer (introduced in 1986)
Alloy 200 Polycarbonate blends with acrylics CyroCanada
Alphaloy PCI ABS alloys Kanegafuchi Chemicals
Alphaloy MPA PAl ABS alloys Kanegafuchi Chemicals
Alphaloy MPB PBT lABS alloys Kanegafuchi Chemicals
Alphaseal TPO elastomer for packaging Alpha Chemical &
Plastics
Alphatec TPE elastomer for medical Alpha Chemical &
products Plastics
Altuglas PUR/PMMA interpenetrating Elf Atochem
polymer networks
Amoron Polythioethersulfone, block Dainippon Ink &
copolymer of 53% PPS with Chemicals
polyphenylenesulfidesulfone,
filled with 0, 30 and 4Owt%
glass and PTFE
Apec Aromatic, 'high heat'; polyester- Bayer A.-G./Miles
carbonate (PEC)
Ardel PAr IPET blends Amoco Chemical
Company
Ardel D-24O Toughened blends of PAr with Amoco Corporation
either PET or PC
Ariloks Polyphenyleneether I HIPS; PPEI USSR
HIPS blends
Arloy Polycarbonate (PC) blends with Amoco Corporation
styrene-maleic anhydride
copolymer (SMA) and HIPS
580 Appendix II

identity
Arloy 1000 PC/SMA alloys ARCO Chemical
Company
Arloy 2000 SMA alloys with ARCO Chemical
polyethyleneterephthalate Company
(PET)
Amitel Thermoplastic ether-ester AI<ZO/DSM Plastics
elastomer (TPE) Int.
Arradur Acrylonitrile-butadiene-styrene Elf Atochem
terpolymer (ABS)
Artley PPE/PA alloys Sumitomo Chemical
Arylon Polyarylate (PAr) PET blends DuPont
Arylon PSF/ ABS alloys, introduced in Uniroyal Chemical Co.
1964 Inc.
Asahi PPS RE Polyphenylenesulfide, PPS alloy Asahi Glass
Aspect Thermoplastic polyester; PET- Phillips 66 Company
based blends
Astralon Rigid PVC formulations with I. G. Farbenindustrie
polyacrylic ester impact
modifier (introduced in 1937)
Aurum PI/LCP alloys (commercialized in Mitsui Toatsu
1990) Chemicals Inc.
AVP Engineering thermoplastic resins Polymerland Inc.
and blends
AX-500 Amorphous polyarylate/PA-6 Unitika Inc.
alloy + 40% glass
Azloy Toughened PC/PEST alloys AzdelInc.
B
BA PBT/ ABS alloys Dainippon Ink &
Chemicals
Baitaloy PC/AAS alloys Hitachi Chemical Co.
Inc.
Baitaloy VL PBT/ ABS alloys Hitachi Chemical Co.
Inc.
Bapolan 8445 Acrylonitrile-butadiene-styrene Bamberg Polymers
terpolymer (ABS)
Bayblend PC/ABS alloys, reinforced, flame Bayer A-G./Miles
retardant or not
Bayblend DP2 PC/ABS alloy for molding, Bayer A-G./Miles
structural foam
Bayblend T PC/ABS alloys Bayer A-G./Miles
Bayfol Films made of PC blends Bayer A-G./Miles
Bayfol CR PC/PBT blends Bayer A-G./Miles
Baymoflex Acrylonitrile-styrene-acrylic Bayer A-G./Miles
rubber blends
BCT 4201 Toughened PC/PEST alloys Toray Industries, Inc.
Appendix II 581
Blend 1Ulme or Description Company

identity
BE PPE/PEST/PC/elastomer alloys Dainippon Ink &
Chemicals
Benvic Blends of PVC with ABS, NBR, Solvay & Cie SA
MBS, CPE etc., reinforced or not
Bexel SAN/ acrylics alloys Bakelite Xylonite
Bexloy Polyester (PAr and/or PET) DuPont
blends
Bexloy C Toughened, amorphous DuPont
polyamide blends (PA)
Bexloy J Polybutyleneterephthalate (PBT) / DuPont
elastomer, blends
Bexloy K Reinforced PET blends Du Pont
Bexloy M Aromatic polyester blends DuPont
Bexloy V Thermoplastic copolyester DuPont
elastomer blends
Bexloy W Ionomer engineering blends DuPont
Bioform Acrylic-based IPN for artificial Dentsply International
teeth
BK891 TPO, PP/EPR blends Mitsui Toatsu
Chemicals Inc.
Blendex AB5-type modifier and processing GE Specialty Chemicals
aid for rigid PVC blends with PO
Blendur PU-based thermoset blends Bayer A.-G./Miles
Boltaron Polyvinylchloride/acrylic alloy GenCorp Polymer
sheets Prod.
BR Polyphenylenesulfide, PPS/PTFE Phillips 66 Company
blends
Brilion BT 40 Toughened polyamide alloys (PA) EMS/Emser Ind.
Bristrend Polyvinylchloride/ Polymers Inc.
polyvinylacetate
BU PBT/ acrylic elastomer blends Dainippon Ink &
Chemicals
BunaAP Thermoplastic elastomers; EPR or Bunawerke Hills
EPDM
Buna BL Styrene-butadiene block Polysar/Bayer A.-G.
copolymer, for impact modifi-
cation of PS, leading to HIPS
Buna EM Expandable SBR (E-SBR) Bunawerke Hills
Buna Hills butacryl Butadiene-acrylonitrile copolymer Plastugil, France
(NBR)
BunaN Poly(butadiene-co-acrylonitrile) Chemical Werke Hills
(NBR)
Bur-A-Loy PVC blends with nitrile rubber Mach-l Compounding
(NBR)
Butaprene Styrene-butadiene copolymers Firestone Synthetiz
Rubber Co.
582 Appendix II

identity
Buton Crosslinked butadiene-styrene Exxon, GB
copolymer
BX PBT/ acrylic elastomer blends Toray Industries Inc.
C
C,CN Toughened PET/PBT alloys Teijin Chemical Ltd
C-Flex Thermoplastic elastomers; SEBS/ Concept Polymer
PDMSblends
Cadon SMA and SMA/ABS elastomeric Monsanto Chemical
blends reinforced (with GF) or Company
not, since 1981
Calibre Polycarbonate (PC) and its blends Dow Chemical
Company
Calibre CR PC blended with PBT and PET Sumitomo Dow Ltd
Calibre 1M PC blended with elastomers Sumitomo Dow Ltd
Capron Toughened PA, i.e., polyamide-6, AlliedSignal Inc.
PA-6 and blends with PO or an
elastomer, reinforced or not
Capron AB Polyamide-6/elastomer, food- AlliedSignal Inc
grade barrier resin
Carlflex Styrene-butadiene block Shell Chemical
copolymer (5B) Company
Carll Polyphenyleneether (PPE) blends Shell Chemical
Company
Carllon Linear, alternating alkene/CO Shell Chemical Co.
copolymer (COPO) engineering
resin with good barrier
properties (based on Pd catalyst;
introduced in 1995)
Carloy Polyvinylchloride (PVC) blends Cary Chemical Inc.
with elastomers, e.g., NBR
Catalloy Polypropylene copolymer alloy Himont
Celanese Nylon 6 Polyarnide-6 (PA-6) impact Hoechst Celanese
modified Corporation.
Celanese Nylon 6/6 Polyamide-66 and polyamide-66/ Hoechst Celanese
TPU alloys reinforced (with Corporation
glass fibers) or not
Celanex Toughened PBT and/or PET Hoechst Celanese
alloys comprising elastomer, Corporation
reinforced or not
Celcon Co-polyoxymethylene (POM) Hoechst Celanese
glass-reinforced, impact- Corporation
modified POM/TPU alloys
Centrex Acrylonitrile-styrene-acrylate Monsanto Chemical
copolymers, ASA/AES rubber Co./Bayer
modified blends
Appendix II 583

identity
Chemigum TPE NBR blends with PVC, CPE, TPU Goodyear Tire &
and/or PA Rubber Company
Cladlux Acrylic/PVC alloys Richard Da1cman
Clariflex TR Styrene-butadiene-styrene Shell Chemical
copolymer (SBS) Company
Clear 01 PVC alloys with glutarimide Georgia Gulf
acrylic copolymer for hot-fill
bottles
Codabs ABS reinforced or not Codiplast
Comalloy 220 Reinforced ABS Comalloy Intl.
Corporation
Comalloy 832 ABS/PVC alloys Comalloy IntI.
Corporation
Condux 8000A Polyvinylch1oride/ABS alloys Advanced Dynamics
(PVC/ABS)
Contrex Acrylonitrile-styrene-acrylates Monsanto Europe SA
terpolymer (ASA)
Cortem Alloys Blends of low-melting point, Corning Incorporated
mixed alkali (Na, K, Li), zinc
phosphate glass with either
LCP or PEEK (introduced in
1994)
Crastin XMB Polybutyleneterephthalate/ABS DuPont
blends
Cycolac Acrylonitrile-butadiene-styrene GE Plastics
terpolymers (ABS)
Cycolac EHA ABS/PC alloys GE Plastics
Cycolac G ABS/PBT GE Plastics
Cycolac GCT/M ABS/PBT automotive blends GE Plastics
Cycolac SDB ABS/engineering polymer blends GE Plastics
Cycolac SDM ABS/electrostatic dissipation GE Plastics
polymer blends
Cycolin ABS/PBT or PC/ABS alloys GE Plastics
Cycoloy ABS/PC, ABS/PVC or ABS/TPU GE Plastics
blends
Cycoloy EHA PC/ABS alloys with varying PC GE Plastics
content
Cycoloy LG9000 PC/ABS alloys, having low gloss GE Plastics
Cycopac Acrylonitrile-butadiene-styrene GE Plastics
terpolymers (ABS)
Cycovin Acrylonitrile-butadiene-styrene BFGoodrich
terpolymers (ABS)
Cycovin K-29 PVC/ABS alloys The Geon Company
CycovinK2S PVC/ABS high impact strength BFGoodrich
alloys
CycovinKAB ABS/PVC alloys BFGoodrich
Cyrex SAN/PC opaque blends Cyro Industries
584 Appendix II
Blend nJlme or Description Company

identity
Cyrex 200 PMMA/PC opaque, high impact Cyro Industries
strength blends
Cyrolite Acrylic-based, impact modified Cyro Industries
highly transparent
multipolymer
D
D7 Acrylonitrile-butadiene-styrene Thermofil Inc.
terpolymer (ABS)
DB Styrene-acrylonitrile copolymer Thermofil Inc.
(SAN)
Dai EI PTFE/P~/PVDForPVDF/ Daikin/Chevassus
P~ elastomers
Daki Polistyren Styrene-butadiene copolymer INA
(SBR)
Decoloy Acrylic/PVC alloys Borg-Warner/Ube/GE
Plastics
Deflex TPO, PP/EPR blends A. Schulman
Defsan Toughened PC/PEST alloys Russia
Delrin Polyoxymethylene (Acetal) resins DuPont
(POM) POM/TPU alloys, some
grades contain PTFE
Delrin T, ST paM toughened by addition of DuPont
TPU elastomer
Denka HS Acrylonitrile-butadiene-styrene Denki Kagaku
terpolymerfPC
Denka LCS Polyvinylchloride, PVC/NBR Denki Kagaku/
blends Chevassus
Denka Taimelan Acrylonitrile-butadiene-styrene Denki Kagaku
terpolymer/PVC
Desmopan Polycarbonate (PC) with TPU Bayer A.-G./Miles
blends
Dexcarb Polycarbonate/polyamide (PC/ Dexter Corporation
PA) alloys (introduced in 1988)
Dexflex PO alloys Dexter Corporation
Dexlon Polyamide/polypropylene (PA/ Dexter Corporation
PP) alloys
Dexloy Customized alloys Dexter Corporation
Dexpro Polypropylene/polyamide (PP/ Dexter Corporation
PA) alloys
Dexter RPI lOlEP Polypropylene/polyalkene (PP/ Dexter Corporation
PO) alloys, reinforced or not
Dexter RPI 20lEP Acrylonitrile-butadiene-styrene Dexter Corporation
terpolymer (ABS)
Dexter RPI 207EP ABS/polycarbonate alloys Dexter Corporation
Dia Alloy ABS/PC alloys Mitsubishi Rayon
Diaaloy B PBT/ ABS alloys Mitsubishi Rayon
Appendix II 585

identity
DiaaloyN PA/ABS alloys Mitsubishi Rayon
Diacon PMMA, acrylic/elastomer blends ICI Advanced Materials
(powder)
Dialoy A PC/ASA alloys Mitsubishi Rayon
Dialoy C PC/ABS alloys Mitsubishi Rayon
Dialoy P Toughened PC/PEST alloys Mitsubishi Rayon
Dialoy X PPE/PEST/PC/elastomer Mitsubishi Rayon
alloys
Diarex Styrene-butadiene copolymer Mitsubishi Monsanto
(SBR)
Diarex HF55 Maleated polystyrene or SBR Mitsubishi
Petrochemical Ind.
DIC-PPS Polyphenylenesulfide, PPS, alloys Dainippon Ink &
with PPE (commerciallized in Chemicals
1982)
Dimension PPE/PA alloys (introduced in Allied Signal Inc.
1987)
DKE450 Polymethylmethacrylate/PVC DuPont
alloys
Dow ABS Acrylonitrile-butadiene-styrene Dow Chemical
terpolymer (ABS) Company
Duethan BC Elastomer modified PA-6 blends Bayer A-G./Miles
Duracryn TPE: ethylene interpolymers/PP DuPont
orPE
Dural 776/X6 Polyvinylchloride/ABS high Alpha Chemical &
impact alloys Plastics
Duralex Polyvinylchloride /PU /NBR Alpha Chemical &
alloys Plastics
Duraloy WOO Polyoxymethylene (POM) blended Hoechst Celanese
with elastomer Corporation
Duraloy 2000 Polybutyleneterephthalate (PBT) Hoechst Celanese
with elastomer Corporation
Duraloy POM/PBT or POM/TPU alloys Hoechst Celanese
Corporation
Duraloy/Vandar POM/TPU or PBT/elastomer Hoechst Celanese
blends Corporation
Durastrength Acrylic impact modifier for Elf Atochem
outdoor PVC siding and
window profiles
Durel Polyarylate (PAr) and PAr/PBT Hoechst Celanese
blends, reinforced (with glass Corporation
fiber) or not
Durethan PA-6 or PA-66 blended with PO or Bayer A-G./Miles Inc.
elastomer, modified and/or
reinforced
Durethan BC PA-6 blended with ethylene-butyl Bayer A-G./Miles Inc.
acrylate- acrylic acid
586 Appendix II

identity
DurethanRM PA-6 blended with methacrylate- Bayer A.-G./Miles Inc.
butyl acrylate- bisphenol-A co-
polymer, with glass fiber or not
Dutralene Thermoplastic elastomer (TPO) Himont/Montedison
Dylark SMA and its blends (e.g., with Arco Chemical
PBT, HIPS) Company
Dylene Polystyrene (PS): styrene- Arco Chemical
butadiene rubber (SBR) Company
Dynaflex TPOs: PP/EPR or EPDM/NBR JSR/Arco Chemical
blends Company
Dynyl Tough poly-block amides: PA-66- Rhone Poulenc
mb-PA-636
Dytron XL Polyalkene elastomer blends Monsanto Chemical
Company
E
Eastalloy DA Toughened PCTG/PC alloys Eastman Chemical
Company
Econit SHF-MR Polypropylene/nitrile rubber Resine Sintet. Adamoli
(PP/NBR)
Ecothene HDPE containing 28% post- Quantum Chemical
consumer resin Corporation
Edistir High impact polystyrene, HIPS ECP Enimont Polymeri
Editer Glass fiber reinforced ABS ECP Enimont Polymeri
Ektar MB DAOO3 PCTG/PC or SMA transparent Eastman Chemical
alloys Products
Ektar MB PC/SMA or toughened PCTG/PC Eastman Kodak
alloys
Elemid ABS/polyamide alloys (PA/ABS) GE Plastics
introduced in 1981 by Borg-
Warner
Elexar Triblock SEBS or SBS Shell Chemical
thermoplastic elastomers
Elix Polymer modifiers: elastomer with Monsanto Chemical
either PB, SAN, SMA, ASA or Company
MSAN
Elmit ZF PA/cyclic PO blends Mitsui Petrochemicals
EMC Toughened PET/PBT alloys Toyobo
EPMXFOO4 Ethylene-propylene impact Polysar-Miles
modifier for TPO
Epolan Acrylonitrile-butadiene-styrene Industrial Resistol
terpolymer (ABS)
Eref PA-6,6 or PA-rnXD,6 blends with Solvay SA
40-60% PP :S 50% glass fiber
Estane Thermoplastic polyurethanes BFGoodrich/
(TPU) and TPU/SAN or TPU/ Polyplastic
ABS blends
Appendix II 587

identity
ETA-Polymer PP/EPDM, TPO alloys, Republic Plastics
thennoplastic elastomers
Ethavin Alkenic/polyvinylchloride alloys Vichem Corporation
ETP Polyamide/acrylic thennoplastic DuPont
elastomer blends
Exceloy PC/ABS alloys JSR Corporation
Exxtral Reactor alkenic thennoplastic Exxon Chemical
elastomers (RTPO) Company
F
Ferro Flex TPO, Polypropylene, PP/EPDM Ferro Corporation
or EPM blends
Ferrolene TPO, PP/EPR blends Ferro Corporation
Ferrolene TPE lPN-type PP/EPDM blends Ferro Corporation
Fiberfil TN Polyamide-6,12 impact modified AKZO/DSM Plastics
blends containing PO, Int.
reinforced (with GF) or not
Fiberloc HTX PVC/acrylics blends The Geon Company
Finaclear SBS, linear poly(styrene-b- Fina Oil & Chemical
butadiene-b-styrene) with
75 wt % styrene, having a
lamellar structure
Flexloy PA-6/PP alloys Sumitomo Chemical
Flo-Well PP/PVC copolymer blends Air Products &
Chemical
Fluorel Thennoset fluoropolymers, 3M Industrial Chemical
PVDF/PHFP, blends for clear
PVC (impact strength
improvers)
Fonnaldefil Polyoxymethylene, POM/PTFE Wilson-Fiberfil
blends
Formion Ionomercompounds, PO/ A. Schulman Inc.
ionomer blends
Forprene Alkenic thennoplastic elastomers Ferro Corporation
(TPO)
Fosta Tuf-Flex Styrene-butadiene copolymer Hoechst A.-G.
(SBR)
FPC 75 Acrylonitrile-butadiene-styrene Federal Plastics
terpolymer (ABS)
Freshtuff Ionomer/ polyamide alloys American Can
Company
Fulton 404 POM lubricated with PTFE LNP Eng. Plastics
Fulton KL POM/TPU alloys LNP Corporation
G
Gafite PBT/ elastomer alloys, reinforced GAF Corporation
or not
588 Appendix II

identity
Gaflex TPU, ester/ether thermoplastic GAF Corporation
elastomer
Gaftuf High impact PBT/ elastomer GAF Corporation
alloys
Gapex PP/PA-6 or PA-66 compatibilized Ferro-Eurostar
alloys, reinforced or not
Garaprene Thermoplastic elastomeric alloys Evode Plastics Ltd./
Ferro Corp.
Garaprene E Thermoplastic elastomers Ferro Corporation
Garaprene 0 TPO for wire and cable Ferro Corporation
applications
Gary PVC PVC compounds for cables Evode Plastics Ltd
GECET PPE/PSfoams GE Plastics
Geloy GYl220 ASA/PVC alloys in pellet form GE Plastics
Geloy sec 1320 ASA/polymethylmethacrylate GE Plastics
(PMMA) blends
Geloy XP 2003 ASA/polyvinylchloride (PVC) GE Plastics
alloys
Geloy XP 4001/4025 ASA/polycarbonate (PC) blends GE Plastics
for automobile
Gemax Polyphenylene ether blends with GE Plastics
PBT, PPE/PBT PPE/PEST/PC/
elastomer alloys - can be
reinforced
Geolast Thermoplastic elastomer blends, Monsanto/Adanced
either NBR/EPDM or PP/NBR Elastomer Systems
blends
Geon Polyvinylchloride and its blends, BFGoodrich Company
e.g., PVC/NBR
Geon Polyblends PVC mechanically blended with BFGoodrich Company
50-90 wt % NBR elastomeric,
ozone-resistant cable insulator,
introduced in 1947
GeonHTX Polyvinylchloride-based high BFGoodrich Company
performance alloys
Geon/Hycar PVC/NBR blends BFGoodrich Company
Georgia-Gulf Polyvinylchloride (PVC) resins Georgia-Gulf
and alloys
Gepax PPE/crystalline PS alloys GE Plastics
Grilon PA-6 or PA-612 blended with PB EMS-American Grilon
or EPR
Grilon A Polyamide-6 (PA-6) with PB or Emser Industries
EPR, filled or not
Grilon BT PA-6/aromatic-aliphatic EMS-American Grilon
polyamide, PA alloys
Grilon XE3404 Polyamide-polyethylene blends EM5-Chemie A.-G.
GX~200 ASA/polycarbonate (PC) alloys GE Plastics
Appendix II 589

identity
H
Haibulen PVC/acrylics blends Nippon Zeon
HannamABS Acrylonitrile-butadiene-styrene Hannam
terpolymer (ABS)
Hevea-Plus NR/PMMA interpenetrating Malaysia
polymer networks
HF-2230 Polyvinylchloride (PVC) blends Georgia Gulf
with ABS
Hicond-2000 HDPE/PP electrically conductive United Composites
alloys
HiFax Reactor alkenic thermoplastic Montell Polyolefins
elastomers (RTPO) PP/EPR or
EPDM blends
HimodPUGL Thermoplastic polyurethane Polymer Composites
(TPU) alloys Inc.
Hivalloy PS/PP alloys Montell Polyolefins
HMS -1000 Conductive styrenic alloys HMS Compounds Inc.
Hostadur X PBT/PET alloys Hoechst Celanese
Corporation
HostaformC POM/TPU alloys Hoechst Celanese
Corporation
Hostaform S POM/TPU alloys Hoechst Celanese
Corporation
Hostalen PP TPO, PP/EPR blends Hoechst Celanese
Corporation
Hostalit Z High impact strength PVC/CPE Hoechst Celanese
blends Corporation
Hostalloy 731 Polyolefin alloys with high Hoechst Celanese
abrasion resistance Corporation
Hostyren Polystyrene, PS, and its toughened Hoechst Celanese
PS/PB blends Corporation
Hycar PVC with nitrile rubber (PVC/ BFGoodrich Company
NBR)
Hycar PA Modified acrylic elastomers BFGoodrich Company
Hydrin Polyepichlorohydrin elastomer, Zeon Chemicals Inc.
can be blended with any elasto-
mer, sulfur or peroxide curable
Hyperlite Toughened PEST/PC alloys Kanegafuchi Chemicals
Hytrel HA Copolyester/ polyacrylate/PET DuPont
I
Idemitsu SC PC/ABS, PES blends Idemitsu
Petrochemicals
Idemitsu SC-150 PC/elastomer blends Idemitsu
Petrochemicals
Idemitsu SC 600 Toughened PC/PEST alloys Idemitsu
Petrochemicals
590 Appendix II

identity
men Polybutyleneterephthalate (PBT) / Dr. llling GmbH
elastomer blends
Impact Toughened PEST/PC alloys AlliedSignai Inc.
Implex High impact acrylic blends Rohm& Haas
Company
Innovex PE blends with O.01-5.0wt% LCP, British Petroleum
for good processability Company
(available since 1993)
Insite Ethylene/octene copolymers Dow Plastics
prepared using the constrained-
geometry metallocene catalyst
IPCL JSA1986 TPO, PP/EPR blends IPCL
IPN-Compound Interpenetrating polymer ABB Polymer Compo
ITP Polyester-type PU/ polystyrene ICI Polyurethanes
IPN Group
lupi-ace PPE/PEST/PC/elastomer or Mitsubishi Gas
PPE/PPS alloys Chemical Co.
lupilon MB PC/ABS alloys Mitsubishi Gas
Chemical Co.
lupilon PA/PC alloys Mitsubishi Gas
Chemical Co.
lupilon Polym. All. Polycarbonate/ABS alloys Mitsubishi Gas
Chemical Co.
luptal-FL Polyoxymethylene (POM) Mitsubishi Gas Chern.
fluoropolymer blends Co./Franklin
luptal-FU Polyoxymethylene (POM) Mitsubishi Gas Chern.
elastomer blends Co./Franklin
J
J-Plast. Thermoplastic elastomer (TPE) J. Von
Jet-Flex Acrylonitrile-ethylene/ propylene- Multibase Inc.
styrene copolymer blends, AES
orAXS
JSR Excelloy CB ABS alloys with polycarbonate JSR Corporation
(ABS/PC)
JSR Excelloy GE Polycarbonate/AES alloys JSR Corporation
JSRNE NBR/EPDM blends JSR Corporation
JSRNV Polyvinylchloride blended JSR Corporation
with nitrile rubber (NBR/PVq
alloys
K
K-Resin Butadiene-styrene copolymer, SB Phillips Chemicals
orSBR
K-Resin SB Plastic Styrene-butadiene copolymer (SB) Phillips 66 Company
Kadon ABS/SMA blends Monsanto Chern. Co./
Bayer A.-G.
Appendix II 591

identity
Kalrez Perfluoro elastomer parts, TFE/ DuPont
PVME blends
Kane-Ace PVC/acrylics blends Kanegafuchi Chemicals
Kane Ace B Methacrylate-butadiene-styrene Kanegafuchi Chemicals
(MBS) modifiers
Kane Ace PA Acrylic processing aids Kanegafuchi Chemicals
KaneAceMUH PA/ABS alloys Kanegafuchi Chemicals
Kane Ace-FM Acrylic low gloss impact modifiers Kanegafuchi Chemicals
for PVC
Kaneka Teralloy, HDT modifiers for PVC Kanegafuchi Chemicals
Kaneka Enplex ABS/PVC alloys compatibilized Kanegafuchi Chemicals
with a-methyl styrene- methyl
methacrylate copolymer
KC 1257 PVC alloy with glutarimide Keysor-Century
acrylic copolymer for hot-fill
bottles
Kel-F PVDF/PCTFE blends 3M Company
Kelburon Reactor blended PP/EPDM, or DSM Polymers Int.
RTPO, for self-supporting car
bumpers
Kelprox Thermoplastic alkenic elastomers DSM Polymers Int.
(TPO)
Keltan Thermoplastic elastomers (EPDM, DSM Polymers Int.
PP/EPDM)
Keltlan TP PP/EPDM blends with fillers DSM Polymers Int.
Kibisan PN Acrylonitrile-styrene-acrylates Chi Mei Ind. Company
copolymer (ASA) Ltd
Koblend Polycarbonate/AES and PC/ABS ECP Enimont Polymeri
alloys
Koblend PCA Polycarbonate/ABS blends Montedipe Milano
Kodar PETG Thermoplastic copolyester of 1,4 Eastman Chemicals
cyclohexylene glycol and
mixture of isophthelic and
terephthalia acids
Koroseal Polyvinylfluoride (PVF) blends BFGoodrich Company
Korton Thermoplastic fluoropolymer Norton Perform. Plast.
alloy
Kostil BV Styrene-acrylonitrile copolymer Montepolimeri
(SAN) reinforced
Kralastic Acrylonitrile-butadiene-styrene Uniroyal Chemical Co.
terpolymers, ABS Inc.
Kralastic FVM ABS/polyvinylchloride alloys Uniroyal/Sumitomo
Kralastic PVC/ABS alloys Uniroyal/Sumitomo
Kraton D1101 SBS three block thermoplastic Shell Chemical
elastomer Company
Kraton D1107 SIS three-block thermoplastic Shell Chemical
elastomer Company
592 Appendix II
Blend IUlme or Description Company

identity
Kraton Dl116 (SB)n multiblock thermoplastic Shell Chemical
elastomer Company
Kraton D1320X (SI)n multiblock thermoplastic Shell Chemical
elastomer Company
Kraton D2103 SBS/HIPS alloys Shell Chemical
Company
Kraton FG SEBS functionalized with maleic Shell Chemical
or succinic anhydride (PA Company
impact modifier)
Kraton G SEBS blends Shell Chemical
Company
Kraton G1650 SEBS three-block thermoplastic Shell Chemical
elastomer Company
Kraton G1701 SEP three-block thermoplastic Shell Chemical
elastomer Company
Krynac NY NBR/polyvinylchloride alloys Polysar/Miles/Bayer
(34% AN) A.-G.
Kydene Polyvinylchloride/ R6hm & Haas
polymethylmethacrylate alloys Company
Kydex PVC/acrylics blends Rohm & Haas
Kydex 100 Polyvinylchloride/acrylic sheets Kleerdex Company
PVC/PMMA
L
Laril Modified polyphenyleneether Lati Eng. Thermoplast.
(mPPE) alloys
Lastiflex Polyvinylchloride/ terpolymer Lati Eng. Thermoplast.
alloys
Lastilac ABS, reinforced or not Lati Eng. Thermoplast.
Lastilac 09-11 ABS/polycarbonate alloy Lati Eng. Thermoplast.
Latamid 66 PA blends with brominated Lati Eng. Thermoplast.
PS
Latene EP Impact modified polypropylene Lati Eng. Thermoplast.
(PP)
LAX 23 PA-6/PP alloys Ube Industries Ltd
Lexan Polycarbonate resins or blends GE Plastics
toughened by PO or elastomers,
reinforced or not
Lexan PPC Polyphthalate-earbonate resins or GE Plastics
blends (PPC)
Limera Styrenic blends with a variety of Dainippon Ink &
polymers: PS, PVC, PMMA, Chemicals
ABS or PPE, reinforced or not
Limera R PS/PB blends Dainippon Ink &
Chemicals
Lomod Copolyetherimide esters GE Plastics
elastomer blends (PBT/SBS)
Appendix II 593

identity
Lubricomp A ABS/PTFE or POMS with 0-30% ICI/LNP Eng. Plastics
glass fiber
Lubricomp Fulton/ POM + 0-25% PTFE, 0-2% POMS, ICI/LNP Eng. Plastics
K filler
Lucalen Ethylene/acrylic acid/acrylate BASF Plastics
copolymers (EAA)
Lucky ABS Acrylonitrile-butadiene-styrene Standard Polymers
terpolymer (ABS)
Lucobit Ethylene copolymer/bitumen BASF Plastics
blends
Lumax PBT/ ABS alloys Lucky Company Ltd.
Lupolen 0 250 LOPE/PIB alloys BASF A.-G.
Lupoy ABS alloys S.P.c.l.
Luran Styrene-acrylonitrile copolymers BASF Plastics
and blends
Luran S SAN blended with grafted acrylic BASF Plastics
ester elastomer, ASA and its
blends
Luranyl PPE/styrene-butadiene BASF Plastics
copolymer blends, reinforced
with up to 30 wt% GF, or not
Lustran ABS 860 PVC/ABS alloys Monsanto Chemical
Company
Lustran ABS Acrylonitrile-butadiene-styrene Monsanto Chemical
terpolymer (ABS) high gloss, Company
general purpose
Lustran Elite Acrylonitrile-butadiene-styrene Monsanto Chemical
terpolymer (ABS) low gloss, Company
high flow
Lustran FRABS Acrylonitrile-butadiene-styrene Monsanto Chemical
terpolymer (ABS) flame- Company
retardant grades
Lustran Ultra Acrylonitrile-butadiene-styrene Monsanto Chemical
terpolymer (ABS) for injection Company
molding
Lustropak Acrylonitrile-butadiene-styrene Monsanto Chemical
terpolymers (ABS) Company
Lycra Diisocyanates/ polyether DuPont
elastomeric fibers
Lynex A PPE/PA alloys Asahi Chemical
Industries
Lynex B PC/ABS alloys Asahi Chemical
Industries
Lynex PPE/polyamide blends Asahi Chemical
Industries
Lynex T POM/PBT alloys Asahi Chemical
Industries
594 Appendix II

identity
M
M-511, M-521 MBS modifiers for PC, PEST, Kaneka
PVC
Mablex ABS/polycarbonate alloys, ABS/ Mazzucchelli Cell.
PC
Macroblend PBT/ elastomer blends Bayer A-G./Miles
Inc.
Macslloy A ABS/PA alloys with high JSR Corporation
moldability and chemical
resistance, available since
1995
Macslloy B ABS/PBT alloys, having chemical JSR Corporation
resistance and superior fatigue
performance characteristics
Macslloy H ABS/PA alloys with permanent JSR Corporation
antistatic properties, available
since 1995
Macslloy K ABS/PA/AES alloys with good JSR Corporation
weatherability and resistance to
heat and chemicals
Magnum ABS/elastomer blends Dow Chemical
Company
Makroblend Toughened PC/PEST alloys Bayer A-G./Miles
Inc.
Makroblend DP PC/PET/HDPE general purpose Bayer A-G./Miles Inc.
alloys
Makroblend EC 900 PVC/elastomer, high impact Bayer A-G./Miles Inc.
blends
Makroblend PR Polycarbonate/PBT or PET Bayer A-G./Miles Inc.
alloys
Makroblend UT Toughened PEST/PC alloys, filled Bayer A-G./Miles Inc.
or not
Makrofol Polycarbonate (PC) films or Bayer A-G./Miles Inc.
PC/PVF
Makrolon Impact modified PC, with Bayer A-G./Miles Inc.
< 6% butylacrylate-
methacrylate elastomer,
reinforced or not
Makrolon T-78 PC/elastomer blends Bayer A-G./Miles
Inc.
Malecca SMI blends with ABS or PBT Denki Kagaku Kogyo
Malecca A SMI/SAN alloys Denka Kagaku Kogyo
Malecca B PBT/ ABS alloys Denka Kagaku Kogyo
Malecca K SMI/ABS alloys Denka Kagaku Kogyo
Malecca N SMI/PA alloys Denka Kagaku Kogyo
Malecca P PCI ABS alloys Denka Kagaku Kogyo
Malecca S PA/ABS alloys Denki Kagaku Kogyo
Appendix II 595

identity
Maranyl Impact modified PA-66 or ICI Advanced Materials
PA-6/elastomer blends,
mineral filled
Marvalloy Acrylic-modified polystyrene MarvalIndustries
Marvyloy ABS/ polyvinylchloride alloys DSM Plastics Int.
Mater-Bi Starch based biodegradable Novamont
thermoplastics
Maxloy A PA/ABS alloys JSR Corporation
Maxloy B PBT/ ABS alloys JSR Corporation
MB3500 Toughened PEST/PC alloys Mitsubishi Gas
Chemical Co.
MB4300 Toughened PC/PEST alloys Mitsubishi Gas
Chemical Co.
MCX-Q PA-6/PP alloys Mitsui Petrochemical
Ind.
Merion Polycarbonate (PC) blends, Bayer A.-G./Miles Inc.
e.g., PC/PO
Mertex TPU blends Bayer A.-G./Miles Inc.
Metablen Poly(styrene-co-AN-co-MMA-g- Mitsubishi Rayon Co.
butyl acrylate-g-MMA) impact
modifier for PVC, PC, PEST,
PPS, etc., introduced in 1972
Metablen P-522 Acrylic processing aid for PVC Mitsubishi Rayon Co.
blow molding
Metablen P-570 Acrylic processing aid for PVC Mitsubishi Rayon Co.
sidings
Metamarble Polycarbonate/PMMA alloys Teijin Chemical Ltd
Milastomer TPO, PP/EPR blends Mitsui Petrochemical
Ind.
Milkon PPS/PTFE blends Tribol Ind. Inc.
Mindel Polysulfone based blends, Amoco Chemical
reinforced or not Company
Mindel A Polysulfone/ ABS blends, Amoco Chemical
Mindel B Polysulfone/PET blends, Amoco Chemical
MinIon PA-66 or PA-66/ionomer alloy DuPont
+ mineral/glass
Modylen TPO, PP copolymer/EPR or Tiszai Vegyi Komb.
EPDM blends
Moldex A ABS/polycarbonate alloys Anic
Monkalloy N PAlABS alloys Monsanto-Kasei
Company
Monkalloy P PC/ABS alloys with glass fibers Monsanto-Kasei
Company
Moplen SP TPO, PP/EPR blends Montell Polyolefins
MPPE PA/PPE alloys Asahi Chemical
Industries
596 Appendix II

identity
Multi-Flex SEBS (Kraton-G) based Multibase Inc.
compounds
Multibase ABS Acrylonitrile-butadiene-styrene Multibase Inc.
copolymers
Multilon Polycarbonates, and PC/ABS Teijin Chemical Ltd
alloys
Multilon PX PC/ABS alloys Teijin Chemical Ltd
MX-5350 Polystyrene/elastomer blends Mobil
N
N5 PAlABS alloys Thermofil Inc.
NB PA-6/PP alloys Toyobo
Neopolen PE/Polypropylene foams BASF Plastics
Neopolen Polystyrene/ polyethylene BASF Plastics
(PS/PE) blends
Nipeon AL ABS/Polyvinylchloride (50%) Zeon Kasei Company
alloy
Nipol NBR/PVC blends Nippon Zeon
Nipol Polyblends NBR/PVC (30-50%) elastomeric Nippon Zeon Company
alloys plasticized or not Ltd
Nipol Terpolymer Acrylonitrile-butadiene-isoprene Nippon Zeon Company
elastomers; grade DN-224 Ltd
contains 50% DOP
NitrifIex Acrylonitrile-butadiene-styrene A. Schulman Inc.
copolymer, ABS
Nitrilene Polyvinylchloride/BR/ABS alloys Rhein-ehemie
Nitrovin Nitrile or polyurethane rubber / Vichem Corporation
PVC, alloys
Noryl PPE/styrenics thermoplastic GE Plastics
alloys, reinforced or not,
commercialized in 1965
Noryl APS PPE/PPS alloys GE Plastics
Noryl BN PPE/HIPS alloys, reinforced or GE Plastics
not
Noryl FN Foamable PPE/HIPS alloys GE Plastics
NorylGFN Glass fiber filled PPE/HIPS GE Plastics
alloys
Noryl GTX PA/PPE(30%) blends, reinforced GE Plastics
or not, commercialized in 1983
Noryl Plus PPE/HIPS/PA alloys GE Plastics
Novablend 4510 PVC alloys with glutarimide Novatech Plastics &
acrylic copolymer used for hot- Chemical
fill bottles
Novablend PVC rigid blends Novatech Plastics &
Chemical
Novadol Toughened PBT or PC/acrylic Mitsubishi Chemical
elastomer alloys
Appendix II 597

identity
Novadur ST520 Polybutyleneterephthalate with Mitsubishi Chemical
20% acrylic rubber PBT/MBA
Novalar Elastomeric grafting copolymer Nova Polymers Inc.
for use in ABS, PVC, PC, PBT,
TPU, EP, acrylics, etc., for
improvement of impact strength
and ductility
Novalast Thermoplastic alkenes (TPE) Nova Polymers Inc.
Novalene RF TPO/TPE impact modifier for PE Nova Polymers Inc.
orPP
Novalene TPO compound from recycled PE Nova Polymers Inc.
or PP, 50-90 Shore A durometer
Novalloy 9000 Polyvinylchloride/ABS alloys Novatech Plastics &
(PVC/ABS) Chemical
Novalloy-A PA-6 or PA-66 blends with ABS Daicel Chemical Ind.
Ltd.
Novalloy-B PBT blends with ABS, reinforced Daicel Chemical Ind.
or not Ltd.
Novalloy-S ABS/polycarbonate blends, Daicel Chemical Ind.
reinforced or not Ltd.
NovamateA AAS blends with polycarbonate, Mitsubishi Chemical
Novamate B ABS/PC blends Mitsubishi Chemical
Novamid AC PA-6/PP alloys Mitsubishi Chemical
Novamid ST220 Polyamide/elastomer blends Mitsubishi Chemical
NovarexAM PC/elastomer blends (with glass Mitsubishi Chemical
fiber or not)
Novodur Acrylonirrile-butadiene-styrene Bayer A.-G./Miles
terpolymer (ABS)
Novolen Rubber modified PP/PE blends BASF Plastics
Novolen KR Polypropylene/EPR blends BASF Plastics
Novon Biodegradable polymers based on Warner-Lambert
starch, for extrusion, injection Company
molding or thermoforming
NX-7000 PPE/PA-6 alloys for automobile Mitsubishi Gas
applications Chemical Company
NX-9000 PPE/polyamide-66 alloys Mitsubishi Gas
Chemical Company
Nybex Polyamides (PA-6 and PA-66) Ferro Corporation
impact modified
Nycoa Toughened PA Nylon Corporation of
America
Nycoa 1485 Polyamide-6 with PE toughened Nylon Corporation of
blends America
Nycoa 2084 Polyamide-6 with EEA toughened Nylon Corporation of
blends America
Nycoa 7551 Polyamide-6 with EPR toughened Nylon Corporation of
blends America
598 Appendix II

identity
Nydur Polyamide, PA/PO blends, fiber Bayer A.-G./Miles Inc.
reinforced or not
Nylafil Toughened PA Wilson-Fiberfil
Nylafil G Polyamide-6/elastomer, glass or AI<ZO/DSM/Wilson-
carbon fibers Fiberfil
Nylafil J-l Polyamide-66/elastomer, glass or AI<ZO/DSM/Wilson-
carbon fibers Fiberfil
Nylafil J-2 Polyamide-610/elastomer blends, AKZO/DSM/Wilson-
glass fibers Fiberfil
Nylon Toughened PA Celanese Engineering
Resins
Nylon 7000 Polyamide/elastomer blends Hoechst Celanese
Corporation
0
Oleflex TPO blends of PE, PP and with Showa Denko K. K.
a-alkene random copolymer,
LLDPE
Oleflex TPO, PP/EPR blends Showa Denko K. K.
Ontex ABX, APE PP/EPDM, elastomeric binder Dexter Corporation.
blends
OppanolO Isobutylene-styrene copolymer BASF Plastics
(9:1)
Optum Polypropylene/TPO alloys; Ferro Corporation
reinforced
Optum TPO, PP/EPR blends Ferro Corporation
Orgablend PA/PP recycled alloys Elf Atochem
Orgalloy R-6 PA-6/PP alloys Elf Atochem
Orgalloy R 60ES Polypropylene/polyamide-6, C~ Elf Atochem
and H20 barrier compatibilized
with PA-co-PP
Orgalloy R 6000 Polypropylene/ polyamide-6 Elf Atochem
alloys (PP/PA-6) with up to
30 wt % glass fibers
Orgalloy R 6600 Polypropylene/ polyamide-66 Elf Atochem
alloys (PP/PA-66)
Orgater PBT, PBT/EVA/PEBA alloys, Elf Atochem
introduced in 1983
Oxyblend Polyvinylchloride (PVC) Occidental Chemical
elastomer blends Corporation
Oxyblend PVC/NBR blends OxyChem
Oxyclear 4190 PVC alloy with glutarimide acrylic Occidental Chemical
copolymer for hot-fill bottles Corporation
Oxytuf Polyvinylchloride, PVC/EPDM Occidental Chemical
blends Corporation
P
Palapreg SMC/BMC resins BASF Plastics
Appendix II 599

identity
Pantalast Polyvinylchloride, PVC/EVAc Pantasote Inc.
alloys
Paracril AZO Nitrile rubber, NBR alloys with Uniroyal Chemical Co.
PVC Inc.
Paracril OZO NBR/PVC blends Uniroyal Chemical Co.
Inc.
Paraloid Poly(methylrnethacrylate- Rohm & Haas
butadiene-styrene) Company
(MBS; old Acryloid™)
Paraloid EXL - 3361 Acrylic impact modifier for PC Rohm & Haas
and its blends Company
Paraloid EXL - 3657 MBS impact modifier for PC and Rohm & Haas
its blends Company
Paraloid EXL - 4151 Polyglutarimide for alloying PC Rohm & Haas
with PA Company
Paraloid HT-510 Polyacrylic-imide modifier for Rohm & Haas
PVC bottles Company
Parastyren Styrene-butadiene copolymer (SBR) Paraisten Kalkki Oy
Pax Plus HDPE/polyisobutylene blends AlliedSignal
Corporation
Pax-Plus LDPE/PIB alloys Paxon Polymer
Company
Paxon Polyethylene/ polyisobutylene Allied Signal
(PE/PIB) blends Corporation
Paxon Pax Plus PElelastomer blends Allied Signal
Corporation
PBF-300 Polybutyleneterephthalate, glass Polyfil Inc.
filled (PBT)
Pebar Blends of polyalkenes (HDPE, PP) BP Chemicals
with high-nitrile resin, Barex™
Pensrene EN IPN of polyphenylenesulfide and Dinippon Ink &
TS resin Chemical
Perbunan N Latex Anionic latices of nitrile rubber Polysar/Bayer A.-G.
(NBR) 45-50% solids;
AN = 18-48%
PermaStat 2500 Polycarbonate/ABS alloys RTPCompany
Petsar PETfPC/acrylic blends with Polysar/Novacor
30 % glass fiber Chemicals Inc.
Phenoxy Bisphenol-A/epichlorohydrin Amoco Chemical
copolymer Company
Philprene Styrene-butadiene thermoplastic Phillips 66 Company
copolymer (SBR)
Pibiter PBT homopolymers or blends, Montepolimeri
filled or not
Pibiter HI PBT/ elastomer blends Montedipe
Plaslube AC Polyoxymethylene with 15% AKZO/DSM Plastics
fluorocarbon (POM) Int.
600 Appendix II

identity
Plastalloy Polysulfone alloys with short glass AKZO/DSM Plastics
fiber (PSU) Int.
Plexalloy PMMA/ABS alloys R6hm & Haas
Company
Plexiglas Acrylic, methacrylic resins and Roehm GmbH
blends
Poean Toughened PC/PEST alloys Bayer A-G./Miles Inc.
Poean 7913 PBT/PC/elastomer alloys Bayer A-G./Miles Inc.
Poean-S PBT/ elastomer blends Bayer A-G./Miles Inc.
Poliblend NH Polypropylene/polyamide alloys Poliresins SA
(PA-6/PP) reinforced or not
Polycast Polyvinylidenefluoride/ Royalite
polymethylmethacrylate
(PVDF/PMMA) miscible blends
for electrets
Polycomp PPS, PAr or PET/PTFE blends LNP Corporation
Polydene Polymethylmethacrylate/PVC A Schulman Inc.
alloys
Polylac Acrylonitrile-butadiene-styrene Chi Mei Industrial
Polyloy PA-6 or PA-66 blends with either Dr. filing GmbH
PO or TPO
Polyman ABS/PVC compounds A Schulman Inc.
Polyman 500 PVC/ABS alloys A Schulman Inc.
Polyman 506, 509 Polyvinylchloride/ABS high A Schulman Inc.
temperature alloys
Polyman552 SAN/PO blends A Schulman Inc.
Polymer XE 3055 Polyamide blends, PA Ems Chemie A-G.
Polysar EPDM EPDM rubbers with ethylene: Polysar/Bayer A-G.
propylene ratio varying from
58:42 to 75:25
Polysar PS/PB blends Bayer A-G./Miles Inc.
Polysar S Emulsion SBR with 23.5% bound Polysar/Bayer A-G.
styrene
Polysar SS Emulsion SBR with 64% bound Polysar/Bayer A-G.
styrene
Polystyrol Polystyrene/ polybutadiene BASF Plastics
alloys (PS/PB) blends, Le.,
HIPS; styrene-butadiene
copolymer (SBR), etc.
Polytrope TPO, PP/EPR blends A Schulman Inc.
Polytrope TPP TPO alloys, PP/EPDM A Schulman Inc.
Prevail TPU/ ABS blends, available since Dow Chemical
1990 Company
Prevex PPE-eopolymer/ styrenics alloys GE Plastics
(introduced in 1982 by Borg-
Warner Chemicals)
Appendix II 601

identity
Prevex P2A, V3A PA/PPE copolymer blends with GE Plastics
glass fiber
Prevex PMA, PQA PPE copolymer based blends with GE Plastics
HIPS
Prevex 533 Polyamide/PPE copolymer alloys GE Plastics
Pro-Fax Polypropylene and PP/EPR Hirnont Canada
blends
Proloy ABS/polycarbonate alloys GE Plastics
Proloy/Lexan PC/ABS alloys GE Plastics
Propathene TPO, polypropylene (PP), ICI Materials - Plast.
toughened PP/EPR
PU-21713 Polypropylene, PP/EPR, rubber Ferro-Eurostar
modified alloys
Pulse Polycarbonate/ABS (30%) alloy Sumitomo Dow Ltd
R
R2-9000 Toughened PC/PEST alloys Thermofil Inc.
R2-9900 Polycarbonate, PC/PBT alloy Thermofil Inc.
R4-9900 Polycarbonate, PC/SMA alloy Thermofil Inc.
Radlite Glass fiber reinforced PC/PBT Azdel Inc.
blends
Ravikral Acrylonitrile-butadiene-styrene Enichem
terpolymer (ABS)
RDZ Acrylics/PC opaque blends Cyro Industries
Reichold TPR Thermoplastic elastomers: POI Reichold Chemical Inc.
EPDM blends
Remaloy PPE/PA alloys Mitsubishi
Petrochemical Co.
Ren-Hex Thermoplastic elastomers, TPO, Dexter Corporation
PP/EPDM
Reo-alloy PSF/PA alloys Riken Vinyl
Retain ABS containing 25 wt % recycles Dow Plastics
Rex Hex-D Thermoplastic elastomers, filled or Dexter Corporation
not (TPO)
Rhodopas Styrene-butadiene copolymer Rh6ne-Poulenc
(SBR)
Rigidex PE blends with O.Ol-5.0wt% LCP British Petroleum
for good processability Company
(available since 1993)
Rilsan A Polyamide-12 (PA-12) or blends Elf Atochem
with PEBA
Rimplast Compatibilization of siloxanes Petrarch Systems
with other thermoplastics (e.g.,
PA-66 or PA-6), moisture cross-
linking (introduced in 1982)
Riteflex Thermoplastic elastomer and Hoechst Celanese
blends Corporation
602 Appendix II

identity
Riteflex BP Polybutyleneterephthalate (PBT) Hoechst Celanese
alloys with a thermoplastic Corporation
elastomer
Ronfalin Acrylonitrile-butadiene-styrene/ DSM Plastics Int.
PC
Ronfaloy E Acrylonitrile-butadiene-styrene/ DSM Plastics Int.
EPDM alloy
Ronfaloy P Acrylonitrile-butadiene-styrene/ DSM Plastics Int.
PET alloy
Ronfaloy V Acrylonitrile-butadiene-styrene/ DSM Plastics Int.
PVC
Ropet Polyethyleneterephthalate, PET/ R6hm & Haas
PMMAalloys Company
Rovel Styrene-acrylonitrile copolymer Uniroyal/Dow
(SAN) blended with saturated Chemical Co.
al1<anic elastomer, EPR
Rovel747 Polycarbonate, PC/AES blends Dow Chemical
Company
Royalite Acrylonitrile-butadiene-styrene Uniroyal Chemical Co.,
terpolymers (ABS)/ Inc.
polyvinylchloride alloys
Royalite R 11 Polycarbonate/ABS alloys Uniroyal Chemical Co.
Inc.
Royaltherm EPDM modified with silicone Uniroyal Chemical Co.
Inc.
Royaltuf Modified EPDM Uniroyal Chemical Co.
Inc.
Royaltuf 372 EPDM grafted with SAN Uniroyal Chemical Co.
Inc.
Royaltuf 46S EPDM functionalized with maleic Uniroyal Chemical Co.
anhydride Inc.
Royaltuf XN6G EPDM grafted with polyamide-6 Uniroyal Chemical Co.
Inc.
RPI 504 EP Polycarbonate-based alloys Research Polymers Inti.
RPI 507 EP Polypropylene/EPDM type TPO Dexter Corporation
blends
RPI 602 EP Polyamide-66 based alloys Research Polymers Inti.
RPI Polyalkene, PO/EPDM blends Dexter Corporation
RTA-Polymer Rigid TP alloys Republic
Plast.Company
RID Impact-modified acrylics Cyro Industries
RTP 200 TFE Polyamide-66/PTFE/PDMS, filled RTPCompany
or not
RTP 200c Polyamide-ll/PTFE (20%), filled RTPCompany
or not
RTP200D Polyamide-612/PTFE ($ 20%), RTPCompany
filled or not
Appendix II 603

identity
RTP200H Polyamide/PTFE (::; 20%), filled RTPCompany
or not
RTP 300 TFE Po~cMbonare/PTFE/PDMS, RTPCompany
filled or not
RTP 600 ABS/PTFE or PDMS, filled or not RTPCompany
RTP 800 POM/TPU PTFE or PDMS, filled RTPCompany
or not
RTP 900 PSF/PTFE (15%), filled or not RTPCompany
RTP 1000 PBT/PTFE (15%), filled or not RTPCompany
RTP 1300 PPS/PTFE e20%), filled or not RTPCompany
RX Acrylonitrile-butadiene-styrene Resin Exchange
copolymer (ABS)
RX Polyphenylenesulfide, PPS/PTFE IntI. Polym.
blends Corporation
RxLoy Polyalkene alloys for medical Ferro Corporation
applications, TPO, PP/EPR
blends
Rynite PBT Polybutyleneterephthalate/ DuPont
elastomer alloys
Rynite Polyethyleneterephthalate/ DuPont
elastomer with up to 35 wt %
mica and glass fibers
Rynite SST Polyethyleneterephthalate/ DuPont
elastomer alloys
Ryulex PC/ABS alloys Dainippon Ink &
Chemicals
Ryulex C Polycarbonate / acrylonitrile- Dainippon Ink &
butadiene-styrene Chemicals
S
Sabre Toughened PC/PEST alloys Dow Chemical
Company
Sabre 1600 Toughened PEST/PC alloys Dow Chemical
Company
Santoprene Polypropylene/EPDM or EPM, Monsanto Chemical
dynamically vulcanized Company
Sapedur Polyvinylchloride compounds Saplast
(PVC)
Saranex Polyvinylidenechloride (PVDC) Dow Chemical
Company
Sarlink TPO, PP/EPR blends DSM/Novacor
Sarlink 1000 TPE, oil resistant PP/PB blends DSM Plastics Int./
Novacor
Sarlink 2000 TPE; low permeability PP/BR DSM Plastics Int./
blends Novacor
Sarlink 3000 TPE; multipurpose PP/EPDM DSM Plastics Int. /
Novacor
604 Appendix II

identity
SC Toughened PEST/PC alloys Idemitsu Petrochem.
SCl50 PET/ elastomer alloys Idemitsu Petrochem.
SC200 PC/PS blends Idemitsu Petrochem.
SC250 PC/ABS alloys Idemitsu Petrochem.
SC 720 PA/PC alloys Idemitsu Petrochem.
Schulman ABS Acrylonitrile-butadiene-styrene A. Schulman Inc.
copolymer (ABS)
Sclar Polyamide/polyalken (PA/PO) DuPont Canada
blends
Sconatex Acrylonitrile-butadiene-styrene Buna A.-G.
copolymer (ABS)
Selar Barrier Resin Polyamide blends (introduced in DuPont
1982)
Selar OH EVAl resins for oxygen barrier DuPont
film (blends)
Selar PA Amorphous PA for oxygen barrier DuPont
film (blends)
Selar PT Polyethyleneterephthalate (PET) DuPont
blends
Selar RB PA/HDPE concentrates for 02 DuPont
barrier PO films
Shinko-Lac GH Acrylonitrile-butadiene-styrene Mitsubishi, Rayon
copolymer (ABS) Company
Shore Polyester elastomers (TPE)
Shuman 700 Acrylonitrile-butadiene-styrene Philip Shuman & Sons
copolymers (ABS)
Shuman 780 Polyviny1chloride/ ABS alloy Philip Shuman & Sons
(PVC/ABS)
ShumanSP Polyphenyleneether (PPE) alloys Philip Shuman & Sons
Shutane Polyviny1chloride/TPU alloys Reichold Chemical Inc.
Shuvinite Polyviny1chloride/ABS alloys Reichold Chemical Inc.
Sicoflex Acrylonitrile-butadiene-styrene Sic Plastics
copolymers (ABS)
Siltem Siloxane-etherimide copolymers GE Plastics
and blends
Sinkral Acrylonitrile-butadiene-styrene ECP Enimont Polymeri
copolymers (ABS)
Snialoy AP06 Polyamide-66 with PP toughened Nylon Corporation of
blends America
Snialoy BP06 Polyamide-6 with PP toughened Nylon Corporation of
blends America
Snialoy PA-6/PP alloys Nylon Corporation of
America
Snissan Acrylonitrile-butadiene-styrene Snia Tecnopolimeri
copolymer (ABS) SpA
Sol T SBS & SIS block copolymers Enarco Elastomers
Company
Appendix II 605

identity
Solprene Branched (SB)n or (SI)n block Phillips Petrol.
copolymers
Somel TPO thermoplastic elastomer Colonial
(PP/EPDM)
ST-801 Polyamide elastomer blends DuPont
ST-Nylon Polyamide/ ionomer(?) blends Toray Industries Inc.
Staloy N Acrylonitrile-butadiene-styrene/ DSM Polymer Int.
PA alloys
Stanuloy ST Polyethyleneterephthalate (PET) MRC Polymers Inc.
modified or blended with
polycarbonate (PC)
Stanyl Polyamide-4,6 and its blends DSM Polymer Int.
(PA-46)
Stapron Rubber modified amorphous DSM Polymer Int.
polymers
Stapron C Polycarbonate / acrylonitrile- DSM Polymer Int.
butadiene-styrene
Stapron E Polycarbonate/PET or PBT with DSM Polymer Int.
PB as impact-modifier, for
interior automobile door panels
Stapron N Polyamide-6 (PA-6) alloys with DSM Polymer Int.
ABS
Stapron S Rubber modified amorphous SMA DSM Polymer Int.
with glass-fiber reinforcements
or not
Star Reinforced thermoplastics, Ferro-Eurostar
e.g., ABS, SAN
Star X PA-6, PA-46 or PA-66 with an Ferro-Eurostar
impact modifier, toughened
PA, glass fiber reinforced or
not
Starflam ABS ABS/SMA blends, flame retarded, Ferro-Eurostar
reinforced with glass fibers or
not
Starflam PA6 PA blends with brominated PS, Ferro Plastics
impact modified, glass or
mineral reinforced or not
Starflam PA66 PA blends with brominated PS, Ferro Plastics
impact modified, glass or
mineral reinforced or not
Starflam PBT PBT blends, flame retarded, glass Ferro-Eurostar
reinforced
Stilon Acrylonitrile-butadiene-styrene/ USSR
polycarbonate
Styroblend PS/PB blends BASF A.-G.
Styron Impact modified polystyrene, Dow Chemical
HIPS Company
606 Appendix II

identity
Styroplus Polystyrene (PS) blends with BASF Plastics
polybutadiene (PB)
Styropol Styrene-butadiene copolymer Carl Gordon Ind.
(SBR)
Sumiploy PES, PES/PEEK-modified blends Sumitomo Chemical
Company
Sumiploy EK PEEK/LCP alloys Sumitomo Chemical Co.
Sumiploy SK PEEK/PES alloys Sumitomo Chemical Co.
Sumitomo TPE TPO, PP/EPR blends Sumitomo Chemical Co.
Sunloid Acrylonitrile-butadiene-styrene Tsutsunaka Plastics
terpolymers (ABS)
Sunloid KD Polyvinylchloride/ acrylics alloys Tsutsunaka Plastics
Sunprene PVC-based elastomers Mitsubishi Kasei/ A.
Schulman Inc.
Supec Polyphenylenesulfide (PPS) and GE Plastics
blends with PEl, PPE, reinforced
with glass fibers
Supec CTX540 PPS/PEI blends with 40% GF GE Plastics
Supec W331 PPS/PTFE blends with 30% GF GE Plastics
Superec P ABS/PC family of alloys Mitsubishi-Monsanto
Superex Compatibilized blends of PET with Polymer Inc./Foster-
1o-15wt% LCP (non- Miller
transparent, not-white;
introduced in 1994)
Superohm Ethylene-propylene copolymer A. Schulman Inc.
(EPR)
Suprel Styrene-acrylonitrile grafted on Vista Chemical
PVC (SAN/PVC) alloys Company
Suprel SVA Polyvinylchloride/a-methyl Vista Chemical
styrene-ABS Company
Surlyn PO/ionomer resin DuPont
SX PA/ABS alloys Toray Industries Inc.
Synergy Polyamide-6/PPE blends AlliedSignallnc.
Syntewax Acrylonitrile-butadiene-styrene Comiel SpA
terpolymer (ABS)
Systemer S Polypropylene/ polyarnides Showa Denko K. K.
(PA-6/PP) alloys, reinforced
or not
T
Taflite Polystyrene, PS-g-EPDM blends Mitsui Toatsu
Chemicals Inc.
Tafmer A Metallocene-made linear low Mitsui Petrochemical
density polyalkene with 1% Industries Inc.
acidic groups, used for
compatibilization
Appendix II 607

identity
Taitalac Acrylonitrile-butadiene-styrene Taita Chemical
TC POM/TPU alloys Polyplastics
Techniace TA Polyamide I ABS, PAl ABS, alloys Sumitomo Dow Ltd.
Techniace TB Polybutyleneterephthalatel ABSI Sumitomo Dow Ltd.
AE5-GMA alloys
(commercialized in 1990)
Techniace TC ABS/polycarbonate alloys: Sumitomo Dow Ltd.
T series are heat & impact resist
H series are high heat & impact
resist W series are weather &
impact resist F series are flame
& impact resistant
Techniace TV Thermoplastic polyurethane I ABS Sumitomo Dow Ltd.
alloys (commercialized in 1992)
Technyl Toughened PA Rhone Poulenc
Technyl A Polyamide-661 elastomer, with Rhone Poulenc
filler or not
TechnylB Polyamide-66,6/elastomer, with Rhone Poulenc
filler or not
Technyl C Polyamide-61 elastomer, with filler Rhone Poulenc
or not
Technyl D Polyamide-610 I elastomer, with Rhone Poulenc
filler or not
Techster Polyesters: PBT or PET and their Rhone Poulenc
blends
Techster T Polybutyleneterephthalatel Rhone Poulenc
elastomer blends
Tecnoflon Auoro elastomers: PVDF IPHFP Enimont
blends
Telcar PP IEPDM, TPO elastomeric blends Teknor Apex
Telcothene Polyethylene (PE) blends with ICI
polyisobutylene (pm),
manufactured in 1937 for
submarine cables
Temprene Polyvinylchloride I nitrile rubber Piltec Group
(15-40 phr)
Tenneco Polyvinylchloride/EVA blends Tenneco Polymers
Terblend B ABS/polycarbonate (PC) blends BASF Plastics
Terblend S ASA/polycarbonate (PC) blends BASF Plastics
Terblend Styrene copolymer blends BASF Plastics
Terluran Acrylonitrile-butadiene-styrene BASF Plastics
terpolymers (ABS) and their
blends with acrylic rubber
Terlux Clear methyl methacrylate-acry- BASF Plastics
lonitrile-butadiene-styrene
(MABS)
608 Appendix II

identity
Texin 3000 Polycarbonate/polyester-PU (PC I Bayer A-G./Miles Inc.
TPU)alloys(availablesince 1961)
Texin 4000 Polyester-PU alloys with PC Bayer A-G./Miles Inc.
(manufactured since 1961)
Thermalloy Acrylonitrile-butadiene-styrene CdFChimie
(ABS) blends
Thermocomp PA-6/PP, POM/TPU, etc., alloys LNP Corporation
Thermocomp DL Polycarbonate, PC/PTFE 13%1 LNP Corporation
silicone 2%
Thermocomp PDX PEEK/PTFE (20%) alloys LNP Corporation
Thermocomp RFL Polyamide-66/silicone 5% blends LNP Corporation
Thermocomp RL Polyamide-66/PTFE 13%1 LNP Corporation
Rimplast
Thermolan 2000 TPO, polypropylene/EPDM, PP I Mitsubishi
EPR blends Petrochemical Co.
Thermolan 3000 EPDM/polypropylene blends Mitsubishi
Petrochemical Co.
Toplex PolycarbonatelABS alloy Multibase Inc.
TorIon Polyamideimide (PAl) modified- Amoco Chemical
PAl with PTFE, for electrical Company
connectors, valves, bushings,
parts etc.
TorIon 4000 Polyamideimide + PTFE + Amoco Chemical
graphite Company
TorIon 7000 Polyamideimide + PTFE + glass I Amoco Chemical
graphite fiber Company
Total Plast Thermoplastic elastomers: Total Chimie.
EPDM/PO blends, etc.
Toyarac Acrylonitrile-butadiene-styrene Toray Industries Inc.
(ABS)
Toyolac Alloy PAl ABS alloys Toray Industries Inc.
TP0900 TPO, polypropylene/EPDM, PP I Reichold Chemical Inc.
EPR blends
TPP 10GB Polypropylene alloys with talc, Ferro Corporation
paintable
Trefsin Thermoplastic elastomers (TPR) Advanced Elastomer
PP/BR Systems
Triax 1000 PAl ABS alloys (introduced 1987) Monsanto Chemical
Company I
Bayer A-G.
Triax 1120 Polyamide-61 ABS blends Monsanto Chemical
Company I
Bayer A-G.
Triax 1125 Polyamide-66 I ABS = 1:1 blends Monsanto Chemical
Company I
Bayer A-G.
Triax 1180 Polyamide-6,66 I acrylonitrile- Monsanto Chemical
butadiene-styrene Company I
Bayer A-G.
Appendix II 609

identity
Triax 2000 PC/ acrylonitrile-butadiene-styrene Monsanto Chemical
(ABS) (available since 1983) Company/Bayer A.-G.
Triax 4000 PBT/ ABS alloys Monsanto Chemical
Company/Bayer A.-G.
Triax CBE PVC/a-methyl styrene-ABS alloys Monsanto Chemical
(discontinued) Company/Bayer A.-G.
Triax XP40 ABS/PETfPC experimental blends Monsanto Chemical
(available since 1993) Company/Bayer A.-G.
Tribolon Polyimide/poly- Rogers Corporation
tetrafluoroethylene (PI/PTFE)
Tribolon XT Polyphenylenesulfide/ Rogers Corporation
polytetrafluoroethylene
Troluloid Rigid PVC formulations with poly- I. G. Farbenindustrie
acrylic ester, impact modifier
Trovidur Rigid PVC formulations with I. G. Farbenindustrie
polyacrylic ester, impact
modifier
Trivin Polyvinylchloride alloys (PVC) Vichem
Tufprene Triblock SBS thermoplastic Asahi Chemical Co. Ltd
elastomer
Tufrex VB ABS/PVC alloys Mitsubishi-Monsanto
Tybrene Acrylonitrile-butadiene-styrene Dow Chemical Company
terpolymers
Tylac Polyvinylchloride, PVC/BR blends Standard Brands
Chemicals
U
U-8OOO Toughened blends of PAr with Unitikau Inc.
either PET or PC
Ube 3000 Polyamide-12, modified (PA-12) Ube Industries Ltd.
Ube Alloy CA700 Polypropylene/ polyamide, Ube Industries Ltd.
PP/PA blends
Ube Nylon Polyamide-6 or -66, modified Ube Industries Ltd.
(PA-6, PA-66)
Ucardel P4174 Polysulfone/SAN blends Amoco Chemical
Company
Udel P-1700 PSF + 10% anhydride terminated Amoco Chemical
PSF + 50% PA-6 (or PA-66), with Company
PA being the matrix
Udel-X PSU/PA-6 or PA-66 experimental Amoco Chemical
alloys, with lOwt% anhydride- Company
terminated PSU
Ugikral Acrylonitrile-butadiene-styrene GE Plastics
copolymer (ABS)
Ultem Polyetherimide and blends, e.g., GE Plastics
with PC, PPE, PPS etc.
Ultem 8000 Polyetherimide/ polycarbonate GE Plastics
alloy (PEl/PC)
610 Appendix II

identity
Ultem LTX PEl/PC alloys (available since GE Plastics
1990)
Ultem LTX200B PEl/PC blends (unreinforced) GE Plastics
Ultrablend KR Toughened PET or PBT/PC/ BASF Plastics
elastomer blends
Ultrablend S PBT/SAN, ABS or ASA blends BASF Plastics
with up to 30 wt % glass fiber
Ultradur B Polybutyleneterephthalate (PBT) BASF Plastics
and impact-modified PB
Ultradur KR PBT/ elastomer blends BASF A-G.
Ultraform Polyoxymethylene/ thermoplastic BASF Plastics
polyurethane (POM/TPU)
alloys, with ID-30wt% TPU
Ultramid Toughened PA-6, PA-66, PA-610 BASF Plastics
PA blends with ABS, reinforced
Ultramid A Polyamide-66, PA-66/elastomer BASF Plastics
with glass fibers, mineral fillers
or not
Ultramid A3X PA blends with brominated PS BASF A-G.
Ultramid B Polyamide-6, PA-6/elastomers BASF Plastics
with glass fiber, mineral filler or
not
Ultramid C Copolyamide-6/66, PA-6,66/ BASF Plastics
elastomer 15-30 wt % mineral
filled
Ultramid KR PA-6/PP alloys BASF A-G.
Ultramid Lurans Polyamide, PA-66/ASA alloys BASF Plastics
Ultramid T Semi-aromatic PA-6/66, PA-66T BASF Plastics
or PARA with elastomer,
30 wt % GF or mineral filled
Ultramid Terluran Polyamide, PA-66/ABS alloys BASF Plastics
Ultranyl PA-66/PPE alloys, reinforced or BASF Plastics
not
Ultrason Polyethersulfone (PES) alloys BASF Plastics
Ultrastyr OSA SAN-EPDM/ABS or PC alloys ECP Enimont Polymeri
UP Polyarylate/poly- Unitika Inc.
ethyleneterephthalate blends
Uravin TPU/PVC alloy Vichem
Urtal Acrylonitrile-butadiene-styrene Montepolimeri
copolymer (ABS)
UTX PA-6/PP alloys Unitika Inc.
V
Valox Toughened PBT or PET or PCT, GE Plastics
resins or blends
Valox 500 PBT/PET alloys; glass reinforced GE Plastics
Valox 800 Polybutyleneterephthalate alloys, GE Plastics
glass reinforced
Appendix II 611

identity
Valox 815 PBT/PET alloys; with glass fiber GE Plastics
or not
Valox HV7000 Polybutyleneterephthalate alloys, GE Plastics
mineral filled
Valox vcr PBT or PET toughened with GE Plastics
elastomer
Valtra 7023 Rubber-modified styrenic blends Chevron Chemicals
Vandar PBT/ acrylic elastomer, reinforced Hoechst Celanese
or not Corporation
Vector 6000 SB, SBS, Sl and SIS block Dexco Polymers
copolymers
Vectra VI40 LCP/PPS blends for electrical! Hoechst Celanese
electronic parts Corporation
Vectra- PC with LCP fibers (length = Polyplastics Co.
Supercomposite 100 /-L m; diameter = 0.5-2 /-Lm)
with excellent processability
and strength (introduced
1995)
Verton PPE/styrenics alloys Hills A-G.
Vespel ST Super-tough polyimide with high DuPont
impact strength
Vestamid Polyamide-12, Polyamide-6,12 Hills A-G.
(PA-12) elastomer
Vestenamer trans-Polyoctenamer, Hills A-G.
thermoplastic elastomer
Vestoblend Polyamide/PPE alloys, reinforced Hills/Nuodex Inc.
or not
Vestolen EM EPR or EPDM modified Hills A-G.
polypropylene (PP) containing
or not: talc, CaC03 , GF, mineral
fillers etc.
Vestolen EM TPO, PP/EPR blends Hills A-G.
Vestolit Rigid PVC formulations with 1. G. Farbenindustrie
polyacrylic ester impact
modifier
Vestoplast Amorphous alkene copolymers Hills A-G.
(TPO)
Vestopren Polyalkene impact modifier (PO) Hills A-G.
Vestoran 1900 PPE/styrenics alloys Hills-Nuodex
Vestoran 2000 PPE blends with HIPS and Hills A-G.
elastomer
Victrex Polyethersulfone (PES) PES/PEEK lCI Materials - Plast.
blends
Victrex VKT Polyetheretherketone, PEEK/ ICI Materials - Plast.
PTFE blends
Victrex VST Polyethersulfone, PES/PTFE ICI Materials - Plast.
blends
612 Appendix II

identity
Vifnen VN AAS/Polyvinylchloride (PVC) Hitachi Chemical
alloys
Vinidur Polyvinylchloride (PVC)/ acrylics BASF Plastics
blends: impact-modified PVC
with 5-15wt% acrylate-graft
copolymer
Vinika Polyvinylchloride-based A. Schulman Inc.
elastomers, PVC
Viniproz Polyvinylchloride/PMMA alloys USSR
Vinuran MBS modifier for BASF Plastics
polyvinylchloride
Viton A Vinylidenefluoride/ DuPont
fluoridehexafluoropropylene
Viton B PTFE/PHFP/PVDF DuPont
Volara EVA/PP or PE blends, vulcanized Seiksui/Voltek
thermoplastic elastomers (TPO)
VX PBT/ ABS alloys Toray Industries Inc.
Vydyne Toughened PA Monsanto Chemical
Vynite PVC/NBR blends Alpha Chemical!
Dexter Corp.
Vyram PP/ diene elastomer blends Monsanto Chemical
Company
Vythene PVC/TPU alloy Dexter Corporation
W
Wellamid 22 L Toughened PA Wellman Inc.
Wellamid 22 LHI Polyamide-66/ elastomer Wellman Inc.
(PA-66) blends
Wellamid MR Polyamide-66/polyamide-6 Wellman Inc.
(PA-6) alloys with acrylonitrile-
butadiene-styrene (ABS) and up
to 30 wt % glass fibers
X
Xenoy PC/PBT/MBA alloys, reinforced GE Plastics
or not (introduced in 1982)
Xenoy 1000, 5000 Polycarbonate, PC:PBT = 1:1 GE Plastics
toughened alloys
Xenoy 2000 Toughened PEST/PC/MBA alloys GE Plastics
Xenoy 3000 Polycarbonate (PC)/TPE alloys GE Plastics
Xenoy 6125 PET/PC, impact modified with GE Plastics
0-30 wt % glass fibers
Xenoy DX6302 Polycarbonate/ polyester alloys GE Plastics
with carbon fibers
XT 3055 Polyamide alloys (PA) EMS-American Grilon
XT Acrylic-based multipolymer Cyro Industries
blends
Appendix II 613

identity
XT Polymer Acrylic-based transparent, high Cyro Industries
impact blends
XTPL NFR-6000 Thermoplastic elastomers (TPE) DuPont
XU TPU/ acrylonitrile-butadiene- Dow Chemical
styrene (ABS) alloys Company
Xycon TPEs/TPU alloys Amoco Chemical
Company
Xyron 200 Polyphenyleneether (PPE)/HIPS Asahi Chemical
alloys (introduced in 1979 by Industries
Asahi-Dow Limited)
XyronA Polyamide/PPE alloys, reinforced Asahi Chemical
or not Industries
XyronG Polyamide/ polyphenyleneether Asahi Chemical
(PPE) alloys Industries
Z
Zerlon Polystyrene, PS/PMMA alloys Dow Chemical
Company
Zetpol Hydrogenated nitrile elastomer Nippon Zeon Company
(HNBR), highly saturated for Ltd.
fuel & solvent resistance
Zetpol PBZ HNBR/PVC blends Nippon Zeon Company
Ltd.
Zylar ST SAN/polybutadiene alloys with Novacor Chemicals Inc.
high transparency and impact
strength (introduced in 1991)
Zytel71G Polyamide-66/ionomer, PA-66 DuPont
alloys
Zytel77G Polyamide-6,12/ionomer, PA-612 DuPont
alloys
Zytel 300, 400 Polyamide-6,6/ionomer, DuPont
toughened PA-66 alloys
Zyte13100 Polyamide-6/polyamide-66 alloys DuPont
Zytel FN Flexible polyamide alloys DuPont
Zytel FR PA blends with brominated PS DuPont
Zytel ST Impact modified PA-6 or PA-66 DuPont
(introduced in 1975)
Zytel ST-350 Polyamide-612/elastomer, PA-612 DuPont
alloys
Appendix III
EXAMPLES OF THE MAJOR TYPES OF POLYMER BLENDS

(Note: Polymer abbreviations are listed in Appendix I)
No. Polymer Name Supplier Comments

A B
1. PS PB Hostyren Hoechst The blends are

(BR) Limera R Dainippon Ink & formulated for
or Chemicals extrusion, injection
PE Polysar Bayer Miles and blow molding.
Polystyrol BASF A-G. Excellent
Styroblend BASF A-G. processability, low
Styroplus BASF A-G. moisture absorption
and shrinkage, and
improved impact
strength. Composition-
dependent modulus,
toughness, ductility,
transparency and
gloss.
2. ABS Elasto- Cadon (yV. SMA) Monsanto Chern. Blends of ABS or ASA
or mer Centrex Monsanto Chern. with either acrylic
ASA or SMA Luran S BASF A-G. rubber or PB
Magnum Dow Chern. Co. formulated for
Rovel Uniroyal extrusion,
Starflam ABS Ferro Plastics thermoforming,
Terluran BASF A-G. injection and blow
molding. Excellent
processability,
weatherability, impact
strength, HOT, scratch
resistance, paintability
and plateability.
Appendix III 615

A B
3. TPU ABS Prevail Dow Chern. Co. The blends can be
Techniace TV Sumitomo Dow injection molded,
extruded, blow or
thermoformed.
Transfer or
compression molding,
calendering and
solid state may also
be used. They show
hardness between
that of TPU and ABS;
they have superb
toughness, chemical
resistance and
appearance.
4. LDPE PIB Lupolen 0 250 BASF A.-G. The 1:1 blends are
Pax-Plus Paxon Polymer Co. flexible, resistant to
cracking under stress,
show good water-
vapor properties.
The blends are
formulated for
extrusion,injection
and blow molding.
The weld-line
strength, resistance to
warpage and
shrinkage depend on
processing conditions.
5. NBR EPDM or Geolast Monsanto Blends are for
CPE or (W. EPDM) extrusion, calendering,
PVC JSRNE JSR Corporation injection and blow
(W. EPDM) molding. Either
Chemigum TPE Goodyear Tire & cocontinuous or
(W. EPDM) Rubber Co. dispersed
morphology. Good
Krynac NV Polysar Inc. processability, ozone,
Nipol Nippon Zeon oil and heat resistance,
Paracril OZO Uniroyal Chemical low compression set,
low- temperature
flexibility, nearly
total elastic recovery
and excellent weather
resistance. For
automotive weather
stripping, interior
616 Appendix III

A B
moldings, tubings,
hoses, seals, gaskets,
expansion joints, cable
sheathUngs,conveying
belts, roofing, pond
liners, geomembranes,
floorings etc.
6. PP TPOor BK891 Mitsui Chemical For injection molding,
EPRor Deflex A. Schulman but they can also be
EPDM Dynaflex JSR extruded, thermo-
Ferrolene Ferro Plastics formed or vacuum
Ferro Flex Ferro Plastics formed compression
HiFax Montell Polyolefines or transfer molded,
Hostalen PP Hoechst A.-G. calendered and blow
IPCL JSAI986 IPCL molded. Several are
Kelburon, Keltan
DSM Polymer dynamically
TP International vulcanized, showing
Milastomer Mitsui Petrochem. toughness, and
Modylen Tiszagi Vergi Kom. composition-
Moplen SP Montell Polyolefines dependent ( S 30 wt %
Oleflex Showa Denko Co. EPR) properties, such
Optum Ferro Plastics as hardness and heat
Polytrope A. Schulman Inc. resistance. Some
Propathene ICI blends are reactor
PU-21713 Ferro Plastics made. Reinforced and
RPI 507 EP Research Polym. filled grades (W. glass
RxLoy Ferro Plastics fiber, talc, CaC03 or
Santoprene Monsanto mineral filler) are
Sarlink Novacor available. Show good
Sumitomo TPE Sumirnoto Chemical processability, low-
Co. temperature modulus
Thermolan 2000 Mitsubishi, and impact strength,
Petrochem. dimensional stability,
TP0900 Reichold Chemical low shrinkage, good
Vestolen EM Hills A.-G. mechanical properties
at temperatures from
-40 to 150 °C, ozone
resistance, dynamic
fatigue and abrasion
resistance, as well as
high good weatherab-
ility (especially carbon
black filled grades)
tear strength and
potability. Over 200
applications have been
found for these
materials.
Appendix III 617

A B
7. PVC Acrylics Acrylivin Gen. Tire & Rub. Suspension PVC

Cladux R. Daleman modified by 5-15
Decoloy GE Plastics wt% acrylic elastomer.
Fiberloc HTX The Goon Company For extrusion,
Haibulen Nippon Zeon injection and blow
Kane-ace Kanegafuchi Chern molding, vacuum
Kydex Rohm& Haas or thermoforming
Metabulen Mitsubishi Rayon and calendering.
Polycast Royalite Show high impact
Sunloid KD Tsusunaka strength, rigidity,
Vinidur BASF A.-G. resilience, dimensional
stability, flame
retardancy, excellent
outdoor performance,
good flame, abrasion,
electrical, chemicals
and solvent resistance.
Used in industrial,
commercial,
consumer, medical,
food or beverage
equipment, aircraft
or mass transit
interior components,
and in applications
requiring good
resistance to
weathering.
8. PVC NBR Carloy Cary Chern. Inc. Blends (containing
Geon/Hycar BFGoodrich 3O-6Owt% PVC)
Denka LCS Showa Denko Co. are formulated
JSRNY JSRCorp. mainly for extrusion
Krynac NY Miles-Polysar and calendering,
Nipol Nippon Zeon but injection, blow,
Oxyblend OxyChem compression and
Paracril OZO Uniroyal Chern. transfer molding
Vynite Alpha Gary Corp. can also be used.
Good processability,
fast calendering
and extrusion, impact
and tear strength,
oil, fuel, improved
chemical,
abrasion,weathering,
ozone, antistatic, flame
and moisture
resistance.
Applications include
618 Appendix III

A B
cables and hoses,

printing plates and
rollers, shoe soles,
bottles for cosmetics
and edible oils,
profiles etc.
9. PVC ABS Abson 042 Abtec Chern. Co. Blends for injection
or Cycovin K-29 The Geon Co. molding, extrusion,
ASA Denka Taimel. Denka Kagaku and thermo or vacuum
Geloy XP2oo3 GE Plastics. forming, but
Kaneka Enplex Kanegafuchi Corp. calendering can also
Kralastic Uniroyal/Sumitomo be used. They show
Lustran ABS 860 Monsanto Chern. superior
Nipeon AL Zeon Kasei Co. processability, impact
Polyman 500 A. Schulman Inc. strength, flame
Ronfaloy V DSM retardancy, chemical
Tufrex VB Mitsubishi resistance, flame
Triax CBE (dis- retardance and
continued) Monsanto Chern. cost-to-performance
ratio. The blends with
ASA show superior
weatherability,
whereas those
containing SMA have
high HDT. The main
use is for business
machines, electrical
and electronic
housings, automotive
swimming pool
feetings, irrigation,
etc.
10. PA-6 Other Grilon BT EM5-Chemie Miscible blends
PA Wellamid MR Wellman Inc. show improved
Zytel3100 DuPont processability, solvent
resistance, elongation,
low-temperature
impact and tensile
strength.
11. PA PP AkuloyRM DSM Eng. Plast. Blends mainly for
Dexpro, Dexlon Dexter Corp. injection molding
Eref Solvay and extrusion. PA-6,
Aexloy Sumitomo Chern. PA-66, PA-mXD6 or
Gapex Ferro Plastics PARA are used. In
LAX 23 Ube, Inc. most blends PAis
MCX-Q Mitsui Petrochem. the matrix phase.
NB Toyobo The blends show
Novamid AC Mitsubishi Chern. good processability,
Appendix III 619

A B
Orgalloy R-6 Elf-Atochem reduced water

Poliblend NH Poliresins SA absorption,
Snialoy Nyltech Company dimensional stability,
Systemer S Showa Denlm Co. low density, low
Thermocomp LNP liquid and vapor
Ube Alloy CA Ube Inc. permeability,
Ultramid KR BASF A-G. moderate impact
UTI< Unitika strength, good
resistance to
alcohols, glycols and
gasohol, improved
heat aging, primer-less
paintability and
resistance to
cracking when
exposed to metal
halides (e.g. CaCh).
Some grades are
reinforced. Blends
are used for
appliances,
automotive, tools,
building, furniture
and industrial
applications.
12. PA-6, PE, Albis Albis Plastics For extrusion, co-
PA- EPR, Bexloy C DuPont extrusion, injection,
66, Acrylic Brilion BT-40 Emser Ind. compression, transfer
PARA Elas- Capron AlliedSignal and blow molding.
or tomers, Durethan Bayer A-G. They can also be
PA- or Dynyl Rhone Powenc thermoformed.
666 ionomers Fiberfil TN DSM Eng. Plast. Grades containing
Grilon A EM5-Chem. A-G. up to40wt%
Maranyl ICI mineral or glass
Minlon DuPont fibers are available.
Nybex Ferro Plastics Some may contain
Nycoa Nyltech Co. PTFE. They have good
Nydur Bayer A-G. processability, low
Nylafil Wilson-Fiberfillnt. temperature impact
Nylon Celanese Eng. Res. strength, rigidity,
Star X Ferro Plastics stiffness, high heat
Technyl A & B Rhone Powenc resistance and lower
Ultramid A, B, C BASF A-G. service temperature.
& T Monsanto Chern. The molded articles
Vydyne Wellman Inc. can suppress
Wellamid 22 L DuPont vibration, even when
Zytel ST dry and at sub-zero
temperatures. The
620 Appendix III

A B
blends find use in a

broad range of
applications:
automotive (stone &
splash guards, under-
the-hood moldings,
seals, hoses, tubes,
clips, fasteners, fuel
doors, gears),
appliances, sport (e.g.
ski bindings, roller
skates), business
equipment, consumer
products (office chair
seats, housings,
casters, wheels, rollers,
pulleys, gears), etc.
13. PA-66Bromin- Akulon 1<228 DSM These fire-resistant
or ated PS Latamid 66 Lati unreinforced blends,
PA-6 Starflam PA6 Ferro Plastics designed for injection
Starflam PA66 Ferro Plastics molding or extrusion,
Ultramid A3X DuPont are used in automotive
Zytel FR and electrical
applications. They
show good flame
retardance, mechanical
properties and
dimensional stability.
14. PA-6 ABS Alphaloy MPA Kanegafuchi Chern The compatibilized
or Elemid GE Plastics blends (with either PA
PA-66 Diaaloy N Mitsubishi Rayon as matrix or co-
Kane ace MUH Kanegafuchi Chern continuity of both
Malecca S Denki Kagaku phases) are formulated
Maxloy A JSR Corporation for injection molding,
Monkalloy N Monsanto Kasei extrusion and
N5 Thermofillnc. thermoforming, but
Novaloy-A Daicel Chern. Ind. blow and compression
Stapron N DSM molding also can be
SX Toray Industries Inc. used. They show good
Techniace TA Sumitomo Dow processability and
Toyolac Alloy Toray Industries Inc. flow, high heat and
Triax 1000 Monsanto chemical resistance,
Ultramid BASF A.-G. high resistance to oil,
wear and abrasion,
dimensional stability,
low temperature
impact strength,
reduced moisture
Appendix III 621

A B
sensitivity and
economy. Used in
automotive/chemic~,
electric~, consumer
and sport industries.
Some grades are glass
fiber reinforced. The
material has been also
used in antivibration
damping structures.
15. PA Cyclic ElmitZF Mitsui Processability/impact
PO Petrochemicals strength and moisture
insensitivity.
16. PA PC Dexcarb 0& S Plast. Processability, HOT>
Iupilon Mitsubishi Gas 200 °C/ impact
SC 720 Idemitsu strength, low mold
Petrochemicals shrinkage, solvent and
moisture sensitivity.
17. PC TPU Texin 3000 Bayer A.-G./Miles PC blends with
Texin 4000 polyester-urethane
were designed for
extrusion or molding
articles used in
automotive and
consumer goods
industries.
18. PC Elasto- Idemitsu SC-150 Idemitsu The blends for
mer Petrochemicals extrusion or injection
Makrolon T-78 Bayer A.-G./Miles molding contain
NovarexAM Mitsubishi Chem. < 6 wt % elastomer,
thus are opaque. They
show low temperature
toughness, high
impact strength/good
weld-line strength and
HOT.
19. PC ABS Alphaloy Kanegafuchi Chem Formulated for
(and SAN Bayblend T Bayer A.-G./Miles injection molding,
in some Cycoloy GE Plastics extrusion and thermo-
blends) Denka HS Denka Kagaku or vacuum forming,
Dialoy C Mitsubishi Rayon but they can also be
Exceloy JSR Corporation compression or
Iupilon MB Mitsubishi Gas transfer molded. Good
Lynex B Asahi Chem. processability,
Malecca P Denka Kagaku excellent plating, HOT
Multilon PX Teijin Chem. Ltd. and impact strength,
Novaloy-S Oaicel Chem. Ind. high stiffness and
Proloy /Lexan GE Plastics strength, dimension~
622 Appendix III

A B
Pulse Dow Chern. Co. stability, toughness,
Ronfalin DSM delamination
Royalite Rll Uniroyal resistance, low-
Ryulex Dainippon temperature impact
SC250 Idemitsu Petrochem. strength, good weld-
Techniace TC Sumitomo Dow line strength, solvent
Toplex Multibase Inc. and chemical
Terblend B BASF A.-G. resistance. These are
Triax 2000 Monsanto Chern. three-phase blends,
ABS/PC 7901 Diamond Polymers with 3Q.-.65 wt % PC
usually being the
matrix. Grades with
glass fiber
reinforcement are
available. The blends
are used for housings
of computers, business
machines and
electrical appliances,
electrical and
electronic parts,
connectors, carriages,
switches, fans, power
and agricultural,
garden and lawn
tools, cameras,
optical
instruments, exterior
automotive
components, electronic
or telecommunication.
20. PC ASA Baitaloy Hitachi Chern. High impact strength,
or (W. AAS) Mitsubishi Rayon thermal stability,
AAS Dialoy A GE Plastics improved resistance to
Geloy XP4001 BASF A.-G. high temperature
Terblend S aging and UV
degradation, excellent
weatherability, rigidity
and dimensional
stability. The blends
are formulated mainly
for extrusion, injection
molding and
thermoforming.
21. PC PS Novadol Mitsubishi Chern. Impact strength,
SC200 Idemitsu thermal stability and
Petrochemicals weatherability.
Appendix III 623

A B
22. PC SMA Arloy 1000 ARca Chern. Co. For extrusion,

Ektar MB Eastman Kodak thermoforming or
R49900 Thermofil Inc. injection molding.
Excellent
processability,
toughness and heat
resistance.
23. PC PBT Azloy Azdel Inc. Formulated for
or BCT 4201 Toray injection molding,
PET Defsan Russia extrusion and blow
or Dialoy P Mitsubishi Rayon molding, but they
PCTG Ektar MB, Eastman Chemical can be transfer or
(and Eastalloy DA Company compression
10-20 (PCTG) molded, formed in the
wt % Idemitsu SC 600 Idemitsu Petrochem. solid state, or
impact Makroblend Bayer A.-G. thermoformed. In
modifier) MB4300 Mitsubishi Gas most blends PC is
Novadol Mitsubishi Chern. the matrix. The
Pocan Bayer A.-G. impact modifier
R2-9000 Thermofil Inc. can be PE, ABS or
Sabre Dow acrylic copolymer,
Stapron E DSM Polymer Int. e.g., MBS. The
Ultrablend KR BASF A.-G. blends show good
Valox GE Plastics processability,
Xenoy 1000 GE Plastics heat resistance,
ductility, HDT, high
modulus, impact,
tensile and flexural
strength over a wide
temperature range,
good adhesion,
solvent, chemical and
UV resistance. They
can be painted, hot
stamped, metallized
and plated. Some
blends (W.PB) may
have poor
weatherability. The
blends are mainly used
in the automotive
industry.
24, PET Elasto- Arloy 2000 ARca Chern. Co. For extrusion,
mer Celanex Hoechst Celanese injection, compression,
or Rynite DuPont blow, and transfer
SMA SC-150 Idemitsu molding. The blends
Petrochemicals contain ~ 35wt%
glass fiber. They show
624 Appendix III

A B
good processability,
rigidity, impact and
tensile strength, as
well as excellent
weatherability.
25. PET PC Ektar MB Eastman These blends can be
or (and Hyperlite Kanegafuchi Chern injection molded or
PCTGl5-20 Impact AlliedSignal extruded. They are
wt% Makroblend UT Mobay partially miscible, with
impact MB3500 Mitsubishi Gas cocontinuous
modifier) Petsar Polysar morphology showing
Sabre 1600 Dow improved
SC Idemitsu processability, solvent
Petrochemicals resistance, elongation,
Xenoy 2000 GE Plastics low-temperature
impact and tensile
strength. Ektar resins
are based on
poly(cyclohexane-
terephthalate-glycol)
mixed with PC and/or
with SMA. Used in
business machines,
appliances, consumer
goods, garden tooffi,
lightning, automotive,
sports equipment,
fluid handling, etc.
26. PBT PET C,CN Teijin Good surface
Celanex Hoechst Celanese properties, HDT,
EMC Toyobo impact strength,
Valox GE Plastics dimensional stability
and economy.
27. PBT Acrylic BU Dai Nippon Ink Improved
rubber BX Toray processability and
Novadol Mitsubishi Chern. impact resistance.
Vandar Hoechst A-G.
28. PBT Elasto- Bexloy J DuPont These impact-
mer Celanex Hoechst Celanese modified PBT blends
Gafite GAF are formulated for
Macroblend Bayer A-G. Miles injection molding, but
Inc. they can also be
Pibiter HI Montedipe extruded and
Starflam PBT Ferro Plastics thermoformed. Good
Techster T Rhone Poulenc processability,
Ultradur KR BASF A-G. electrical properties,
high stiffness and
strength, HDT,
Appendix III 625

A B
impact strength,
solvent and chemical
resistance.
29. PBT ABS A, AN Teijin The blends contain
or Alphaloy MPB Kanegafuchi Chern 0-30 wt % glass fiber or
AAS BA Oai Nippon Ink mineral fillers. They
Baitaloy VL Hitachi Chern. are formulated for
Cycolin GE Plastics injection molding, but
Diaaloy B Mitsubishi Rayon can be extruded,
Lumax Lucky Co. Ltd thermoformed or solid
Malecca B Denka Kagaku state formed. Excellent
Maxloy B JSR Corporation processability, high
Novaloy-B Oaicel Chern. Ind. gloss, stiffness at high
Techniace TB Sumitomo Dow temperature, good
Triax 4000 Monsanto electrical properties,
Ultrablend S BASF A.-G. thermal stability,
VX Toray mechanical strength,
HOT, low shrinkage,
good dimensional
stability, impact
strength, as well as
solvent and chemical
resistance. Used in
electronics,
automotive and
electrical industries,
as well as office, sports
and household
equipment.
30. PAr PET ArdeI0-240 Amoco Corp. Processability, high
or PC U-8OO0 Unitika HOT, tough, high
impact strength
31. POM PBT Duraloy Hoechst Celanese HOT, toughness,
Lynex T Asahi Chern. softness, high impact
strength.
32. POM TPU Celcon Hoechst Celanese Formulated for
Delrin DuPont extrusion, injection,
Duraloy Hoechst Celanese compression, blow
Formaldafil Wilson-Fiberfil and transfer molding.
Fulton KL LNPCorp. Excellent
Hostaform S Hoechst A.-G. processability, rigidity,
RTP800 RTPCorp. high impact strength,
TC Polyplastics high fatigue, flexural
Thermocomp LNP and tensile strength,
Ultraform BASF A.-G. high toughness, low
water absorbency,
gloss and resistance to
626 Appendix III

A B
chemicals. In most
blends POM is impact
modified with
10-30wt% TPu. Some
grades contain PTFE.
Co-continuous
morphology gives
especially good
performance. These
blends find use in
sports equipment,
plumbing, electronic
and mechanical parts,
automotive parts,
appliances, hinges etc.
33. PPE PS Gepax GE Plastics These blends, with
(HIPS, Luranyl BASF A-G. 25--60 wt % PPE, were
SBS, Noryl GE Plastics designed for injection
SEBS, Prevex GE Plastics or blow molding,
ABS, Verton Hiils A-G. calendering,
SB, etc.) Vestoran 1900 Hiils-Nuodex thermoforming,
and 2000 extrusion. Some
Xyron 200 Asahi grades are reinforced
with < 30wt% glass
fibers. They show
good processability,
HOT = 90-150°C,
toughness, good
resistance to hot water,
flame retardance, low
density, cost/
performance ratio and
moisture absorption.
34. PPE PA Artley Sumitomo Chern. For extrusion,
Dimension AlliedSignal thermoforming, or
Lynex A Asahi Chern. Ind. injection molding.
NorylGTX GE Plastics They are
Remaloy Mitsubishi compatibilized, with
Petrochemicals 40-60wt% PA,
Ultranyl BASF A-G. showing moderate
Vestoblend Hiils A-G. processability and
XyronA & G Asahi Chern. Ind. impactstrength,good
tensile and flexural
strength, high
temperature creep,
solvent, and chemical
resistance with low
Appendix III 627

A B
moisture absorption.
They are
dimensionally stable,
paintable and platable.
35. PPE PBT (+ Dialoy X Mitsubishi Rayon Excellent
PC + BE Oai Nippon Ink processability, high
impact Gemax GE Plastics solvent and
modifier) Iupi-ace Mitsubishi Gas temperature resistance
and good dimensional
stability.
36. PPE PPS DlC PPS Oainippon Ink & For injection molding,
Chemicals but extrusion,
Iupi-ace Mitsubishi Gas compression molding
Noryl APS GE Plastics or thermoforming can
also be used. They are
compatibilized and
contain up to 40 wt %
glass fibers. Good
processability,
reduced flash,
toughness, and high
heat resistance.
37. PVDF PMMA Polycast Royalite Used for electrets or as
outdoor films with
good clarity, chemical
and UV stability.
38. PSF ABS Arylon Uniroyal The blends can be
Mindel A Amoco Corp. either extruded or
injection molded.
They show good
processability,
toughness,
high HOT, hot water
resistance, plateability,
and paintability. Used
in plumbing, food
service, fiber optics
controlled system.
39. PSF PET Mindel B Amoco Corp. Either extruded or
injection molded.
Improved
processability and
impact strength, low
shrinkage and
warpage, high HOT,
good stress crack
chemical and solvent
628 Appendix III

A B
resistance and good

economy. Used for
molded electrical
parts, such as
connectors, relays,
switches, motor
starters, control
housings, etc.
40. PSF PA Reo-alloy Riken Vinyl Processability, low
viscosity and low
water absorption.
41. SMI SAN Malecca A Denka Kagaku High heat and impact
resistance.
42. SMI ABS Malecca K Denka Kagaku High heat and impact
resistance.
43. SMI PA Malecca N Denka Kagaku High heat, solvent and
impact resistance.
44. PEEK PES Sumiploy SK Sumitomo Chern. For injection molding,
but extrusion,
compression molding
or thermoforming can
also be used. The SK
1660 contains glass
fibers. Good
processability,
excellent high
temperature, chemical
and hot water
resistance.
45. PEEK LCP Sumiploy EK Sumitomo Chern. For injection molding,
but extrusion,
compression molding
or thermoforming can
also be used. Good
processability, high
strength, modulus and
HDT.
46. PEl PC Ultem LTX GE Plastics For injection molding
and extrusion.
Properties are
processability, HDT,
flexural, tensile and
impact strength, flame
retardancy, long term
hydrolytic
Appendix III 629

A B
stability, stain and

chemical resistance,
lower cost than PEl.
47. PI LCP Aurum Mitsui Toatsu Good processability,
low viscosity, HDT
and low water
absorption.
48. ABS Hydro- Adion Asahi Chemical Pennanent antistatic
or philic Toray properties.
HIPS polymer
Appendix IV
POLYMER BLEND DISCOVERIES AND DEVELOPMENTS
Year Content Reference

1846 First patenting of polymer blend: natural Parkes, Alexander, of
rubber (NR) was blended with gutta Birmingham, Artist, Brit.
percha (GP). Pat., 1,147.
1865 Nitrocellulose (NC) was blended with Parkes, Alexander, of
either GP or NR and camphor to Birmingham, Brit. Pat.,
produce flexible Parkesine. 1,313.
1910 First patent on simultaneous Aylsworth, Jonas W., of East
interpenetrating polymer networks: Orange, New Jersey, US
vulcanized India rubber or gutta percha, Pat. 1,111,284 to Condensite
NR, with phenol-formaldehyde, PF. Co.
1911 First patent on dissolution of styrene in Matthews, F., K, Brit. Pat.,
rubber, then polymerization into SBR. 016,278.
1925 High impact polystyrene (HIPS) Ostromislensky, Iwan I., of
produced by dissolution of 1-10wt% of New York, N.Y., US Pat.,
an elastomer in styrene, then 1,613,620, to Naugatuck
polymerizing. Chern. Co., CT.
1928 Blend of PVC/PVAc = 60/40, was Voss, W. and Dickhauser, K,
compatibilized by poly(vinylchloride- Ger. Pat. 579,048, to I.G.
co-vinylacetate) (PVCAc). Farben.
1930 Latex blending of vinyl and acrylic I. G. Farbenin., Brit. Pat.,
(co)polymers. 353,866.
1936 Polyvinylchloride, PVC, was blended Fikentscher, H. and Schmidt,
with an acrylic impact modifier for F., Ger. Pat. 636,014, to I. G.
cable covering. Farbenindustrie.
1937 Toughening of polyalkenes with MW = Standard Oil Development
800-500000 by addition of rubber. Co., Fr. Pat. 812,490.
1938 PVC, was blended with 50-90 % nitrile Badum, E., US Pat. 2,297,194,
rubber (NBR) for cable insulators with to Bergisch-Gladbach.
ozone resistance.
1941 Plasticized PVC, was blended with CR as B. F. Goodrich Co., Brit. Pat.
Neoprene, then vulcanized, to give 539,834.
insensitive-to-oil blends.
Appendix IV 631

1942 LDPE, was blended with cyclo-rubber, for Child, C. L./ Clarke, R. B. F. F.
bonding polyethylene to metal. and Habgood, B. J./ Brit.
Pat., 544,359.
1946 Mechanical mixing of NBR, with SAN Daly, L. E., US Pat., 2/439/202/
generated AB5-type A, commercialized to Naugatuck Chern.
as Royalite™.
1948 Blends of maleated polyamide (PA-66) Hoover, F. W./ US Pat.,
with PVAc for improvemed mechanical 2/448/978/ to DuPont
properties.
1950 Emulsion polymerization of AB5-type G. Vanderbilt, B. M. and Bascom
Commercialized in 1955 as Novodur. F., US Pat., 2/527/162/ to
Standard Oil.
1951 PVC/ABS, blends developed for the Parker, C. L./ US Pat.,
manufacture of artificial leathers, and 2/539/385/ to Radio
phonographic records (blends of ABS/ Corporation of America.
PVC were commercialized by Borg-
Warner as Cycovin™ in 1969).
1956 Blends of PVC with chlorinated Frey, H. H., Ger. Pat.,
polyethylene (CPE) as Hostalit™ Z 1/111,383/ to Hoechst A.-G.
were introduced.
1958 PA-66, was blended with either PA-6 or Stott/ L. L. and Hervey, L. R.
PA-610, for compression molding B., Brit. Pat., 792/954/ to
stress-free articles. Polymer Corp.
1958 Blending of LDPE with LLDPE improved Canterino, P. J. and
stiffness, abrasion resistance and Martinovich, R. J./ US Pat.,
reduced water permeability. 3/086/958/ to Phillips.
1958 PA/PO blends for sheets, films, fibers or Mesrobian, R. B. and
bottles; has good processability and Amrnondson, C. J./ Brit.
permeability. Pat., 889,354. to CCc.
1960 Miscibility of polyphenyleneether (PPE) Boldebuck, E. M., US Pat.,
with PS. Blends were commercialized in 3/063/851/ to General
1965 as NoryiTM. Electric Co.
1960 PP blends with either ethylene-propylene Schilling, W. M., US Pat.,
rubbers, 1~% EPR, or with 5-70% 3/200/173/ to Hercules
LLDPE, for low temperature impact. Powder Co.; Holzer, R. and
Mehnert, K./ Ger. Pat.,
1/145/792/ to Hoechst A.-G.
1960 Easy moldable polycarbonates (PC) Grabowski, T. 5./ US Pat.,
were prepared by blending with 5-49% 3/130/177/ to Borg-Warner.
ABS.
1961 Polycaprolactam (PA-6) with 1~% ABS Grabowski, T. 5./ US Pat.,
had good moldability, strength, 3/134/746/ to Borg-Warner.
elongation and hardness.
1963 Polyarnides, PA-6, PA-66 or PA-6lO, were Halliwell, R. H., Fr. Pat.,
blended with ::; 99% ionomers. 1/411/274/ to DuPont.
1963 High impact strength PVC blends were Bimei, S./ Takine, M. and
obtained by blending with 5-30% Akita, K./ Jap. Pat., 000,949,
ABSM. to Kanegafuchi.
632 Appendix IV

1964 In 1964, polysulfone (PSF) blends with Ingulli, A F. and Alter, H. L.,
ABS were introduced by Uniroyal Inc. So. Afr. Pat., 6,806,262, to
as ArylonTM. Uniroyal Inc.
1964 PBT blends with poly(hexylene- Wiener, M. V., US Pat.,
isophthalate-terephthalate) (40% PAr) 3,466,348, to Goodyear.
for electrical insulation.
1965 Polyaryether sulfone (PAES) blends with Union Carbide Corp., Neth.
1-99%PC, for elongation, impact and Pat. Appl., 6,604,731.
tensile strength.
1965 PET was blended with 05--50% Surlyn™ Cope, O. J., US Pat., 3,435,093,
ionomer, to give high toughness and to DuPont.
low mold shrinkage.
1965 Acetal, paM, was blended with 1-25% Celanese Corp., Neth. Pat.
PVAc, to improve surface properties Appl., 6,613,086.
and paintability.
1966 PMMA, blends with PVDF, for use as Koblitz, F. F., Petrella, R. G.,
outdoor films with better chemical & Dukert, A A and
UV stability, and clarity. Christofas, A, US Pat.,
3,253,060, to Pennwalt
Chern.
1966 PC blended 1-5wt% PET had improved Cziesla, M. and Bottenbruch,
stress corrosion resistance in boiling L., Ger. Pat., 1,694,124, to
water. Bayer A-G.
1967 PET with either 0.05-10% EVAc or Brinkmann, L., Cherdron, H.,
0.5-10% PEA or PBA gave good Herwig, W., So. Afric Pat.,
hardness, abrasion, solvent resistance, 04, 541, to Farbwerke
and impact strength. Hoechst A-G.
1967 PP blends with 20% SBS or SIS showed Japan Synthetic Chern. Ind.,
good impact strength, without Fr. Pat., 2,000,728.
decreasing other properties.
1967 Polysulfone (PSF) was blended with Ingulli, A F. and Alter, H. L.,
40-52% ABS for moldability, HDT, So. Afr. Pat., 6,806,262, to
impact and flame resistance Uniroyal Inc.
(commercialized as Arylon™ in 1964).
1968 For high impact and tear resistance, Reimschussel, H. K. and
PETjPA-6 was compatibilized with Dege, G. J., Ger. Pat.,
dimethylolpropionic acid. 1,918,499, to Allied.
1968 Blends of semicrystalline PA with Dynamit Nobel A-G., Fr. Pat.,
amorphous, aromatic PARA for high 2,004,607.
mechanical performance.
1969 PET was blended with 25% PC for high Horiuchi, K. and Kamiya, T.,
impact resistance without decrease of Jpn. Pat., 001,639, to Teijin
crystallinity and Tm. Chemicals.
1969 Elasticity of paM was improved by McAndrew, F. 8., Ger. Pat.,
blending it with thermoplastic 2,051,028, to Celanese Corp.
polyurethanes (40-60% TPU).
1969 Dynamic vulcanization of PPjEPDM in Coran, A Y. and Patel, R., Ger.
1969 led to introduction of Santoprene™ Pat., 2,757,430, to
by Monsanto. Monsanto.
Appendix IV 633

1969 Caprolactam was polymerized in the Bottenbruch, L., Michael, D.
presence of EVAl into blends with high and Nielinger, W., Ger. Pat.,
mechanical properties. 1,920,043, to Bayer A-G.
1970 Polyethersulfone (PES) was blended with Nield, E., Ger. Pats, 2,122,735,
PA-ll, PE, PP, EPR or EPDM for high 2,122,734, to ICI.
flow and impact.
1970 ABS blends with PES and 10-50% PC gave Weaver, E. P., Ger. Pat.,
alloys with good processability, HOT 2,154,445, to Uniroyal Inc.
and impact strength.
1971 Polyarylates (PAr) were blended with Koshimo, A, Sakata, H.,
ABS, polyacrylate rubber, PP, EVAc or Okamoto, T. and Hasegawa,
PE, for processability and impact H., lpn. Pats., 025,053,
strength improvement. 051,94s-8, to Unitika Co.
1971 PPE was modified by blending with Komoto, H., lpn. Pat., 020,243,
1-20% PA-12, for processability, impact to Asahi Chemical Industry
and solvent resistance. Co.
1972 POM was blended with 4-40% PPE for Ishida, S. and Masamoto, J.,
improved processability and lpn. Pat., 018,144, to Asahi
mechanical properties. Chemical Industry Co.
1972 PBT was blended with 27-47.5% PC and Nakamura, Y, Hasegawa, R.
5-20% MBS, for moldability, chemical and Kubota, H., Ger. Pat.,
and impact resistance. 2,343,609, to Teijin
Chemicals. Ltd.
1972 PA/PP blend with 0.5% maleated PP gave Davis, J. H., Brit. Pat.,
improved strain at break and notched 1,403,797, to ICI.
impact strength.
1974 PC/PA-12 was blended with PSF, PPE or Okuzono, T., Kifune, M., Jpn.
PET, to enhance moldability and Pats., 116,541, 030,255 and
mechanical performance. 030,256 to Mitsubishi Gas
Chemical Co. Inc.
1974 PC with 5-95% PPS or PAr for Miyanishi, K. and Manabe Y,
moldability, HDT, tensile and impact lpn. Pat., 047,043, to Teijin
strength. Chern. Ltd.
1974 To improve abrasion resistance of PC, it Kishimoto, T., lpn. Pat.,
was blended with 2% PP and 3.5% 059,952, to Mitsui Petro
PTFE. chemical Industries Ltd.
1974 POM was blended with 4% PARA, for Fukuma, N., Kusunose, T.
significant improvement over the du and Ugajin, I., lpn. Pat.,
Pont patent claims. 017,972, to Asahi.
1974 PP was reactor blended with PE and EPR, Strametz, H., Leuering, H. J.,
to give high impact strength, especially Rust, K. and Engelmann,
at low temperature. M., Ger. Offen, 2,417,093, to
Hoechst A-G.
1975 PBT, blended with TPU and 25% PBT-co- Baron, A L., Bailey, J. V., Ger.
TPU, had good impact resistance to Pat., 2,646,647, to Mobay
-70°C, ductility and hardness. Chern.
1975 PPS, blended with 25% PSF, PPE or PC, Bailey, F. W., US Pat.,
showed improved physical properties. 4,021,596, to Phillips
Petroleum.
634 Appendix IV

1976 PAr was blended with 40% PET and PA-6 Asahara, H., Asai, Y./ Yasue,
for transparent, impact resistant resins. K. and Okabayashi, Y./ Ipn.
Pats./100, 552 and 100/553/
to Unitika Ltd.
1976 Polyarylate (PAr) was blended with Matsunaga, H., Uemura, Y./
polyphe-nylenesulfide (1-99% PPS). Saito, T. and Ishida, H., Ipn.
The blend had good processability, Pat., 057/255/ to Sumitomo
impact strength, fire and abrasion Chemical Co. Ltd.
resistance.
1976 Introduction of PET/PBT blends (Valox™ J. A Vaccarl, Product Eng., 39/
800 series) by General Electric Co. Feb (1976).
1976 Polyphenylenesulfide (PPS) was Alvarez, R. T, US Pat.,
introduced in 1973. Ryton TM blends with 4/017,555.
polyimide (60% PI) gave specimens
with HDT = 276°C, low friction and
good mechanical properties.
1976 Hydrogenated block copolymers, 5% Davison, S. and Gergen, W.
SEBS, were blended with PA, PE, PBT, P., Ger. Pat., 2/725,663, 15
PC, PES, POM, TPU, PMP/ fluoro- Dec 1977; US Pat., 4,041,103,
polymers and acrylonitrile copolymers, 9 Aug 1977/ to Shell·Oil Co.
to obtain good toughening effects.
1977 Polyamide (20-80% PA-6) was blended Kyo, K. and Asai, y., Ipn. Pat.,
with polysulfone (80-20% PSF), for 129,248, to Unitika Ltd.
good processability and mechanical
properties.
1977 PC was blended at a ratio 1:1 with Fava, R. A, US Pat., 4,160,792/
styrene-maleimide (SMI) to get high toARCO.
HDT, stiffness and tensile strength.
1977 Polyarylsulfone (PSF) was blended with Binsack, R./ Reese, E. and
polycarbonate (20% PC, linear or Wank J., Ger. Pat., 2,735,092/
branched), to give mechanical Ger. Pat., 2,755,025/6 to
properties similar to those of PSF, but Bayer A-G.
better solvent resistance than either one
of the components.
1977 Fluoro rubber was blended with 2 70% Watanabe, S., Murao, K. and
ethylene glycol-epichlorohydrin co- Isoda, M., Ipn. Pat., 003,865,
polymer, to give blends with improved to Hitachi Cable Ltd.
crack resistance in oxidized gasoline.
1978 Thermoplastic polyurethane (1-99% TPU) Aitken, R. R., Brown, J. P. and
was blended with an ABS, to produce Lord, D. M., Brit. Pats., 2,021,
blends with high moldability and low 600; 2,021,603, to ICI.
temperature impact strength.
1979 Probably the earliest patent application Hergenrother, W. L., Matlock,
for the use of maleic anhydride adducts M. G. and Ambrose, R. J.,
with SEBS (10-50%) as impact US Pat., 4,427,828, to
improvers for polyamides. Excellent Firestone Tire & Rubber Co.
impact strength improvement was
noted.
Appendix IV 635

1979 Polyamideimide (PAl) was blended 1:1 Maresca, L. M., Matzner, M.
with polyetherimide (PEl) showing and Robeson, L. M., US
good mechanical properties and Pat., 4,250,279, to Union
excellent environmental stress crack Carbide Corp.
resistance.
1979 Polyethylene (70% PE), 20% PA-66 and 3% Subramanian, P. M., Eur. Pat.
of ethylene-g-fumaric acid copolymer, Appl., 015,556, to DuPont;
were mixed to reduce moisture "Selar™ Barrier Resins,"
permeation and to improve impact Bulletins E73971, E73973,
stre~. In 1982 DuPont introduced E73974 by du Pont.
Selar , PA blends to be used as an
additive to polyalkene to reduce
permeability.
1979 First patent on reactor-blended thermo- Morita, Y. and Kashiwa, N.,
plastic alkenic elastomer (R-TPO) was Eur. Pat. Appl., 022,376, to
disclosed in 1979. PE was polymerized Mitsui Petrochemical
in the presence of an active catalyst and Industries Ltd.
already polymerized alkenic copolymer
(e.g., ethylene-l-butene copolymer) or
the sequence was reversed.
1979 Thermoplastic polyurethane (TPU) was Megna, I. S., US Pat., 4,238,
blended with ethylene-earboxylic acid 574, to American Cyanamid
copolymers (10% ionomer) for Co.
improved melt strength.
1979 Polyphenylene ether (44% PPE) was Ueno, K. and Maruyama, T.,
blended with 44% PA-66 and 12% SBR, Eur. Pat. Appl., 024,120,
to give good solvent and impact to Sumitomo Chemical Co.
resistance. Ltd.
1979 PET was reactively blended with lida, H., Kometani, K. and
ethylene-glycidyl methacrylate Yangi, M., Jpn. Pat., 017,942,
copolymer (EGMA) to give blends with to Toray Industries Inc.
good moldability, toughness, resistance
to moisture and heat.
1979 Polybutyleneterephthalate (PBT) and/or Dieck, R. L., Ger. Offen.,
polyethyleneterephthalate (PET) blends 3,002,985, 7 Aug 1980; US
with PC and an impact modifier, MBS, Pat., 4,280,948, to General
showed high impact and high Electric Co.; M. D.
deformation properties. Bertollucci and D. E.
In 1979 General Electric introduced DeLaney, Soc. Plast. Eng.
XenoyTM, an impact modified blend of NATEC, Sept. 20-27, 1983.
PC with PBT and/or PET.
1979 Addition of liquid crystal polymers (LCP) Cogswell, F. N., Griffin, 8. P.
to polysulfones, polyethers, and Rose, J. 8., Eur. Pat.
polycarbonates, polyesters, Appl, 030,417, to ICI.
polyphenylene ethers etc., improved
flowability and processing.
1979 Impact-resistant blends comprised PAr, Robeson, L. M., Eur. Pat. Appl.
PET and a polymer selected from TPU, 024,245, to Union Carbide
Corp.
636 Appendix IV

PVC, poly~l ether, polyesterether,
Acryloid or Phenoxy were described.
In 1983 Ardel™ D-240 (PAr/PET
blends) were introduced by Union
Carbide Corp.
1980 Blend of 30% PET, with anisotropic Celanese Corp., Fr. Demand,
aromatic polyester, 25-80% LCP, 2,484,430; US Pat.,
showed good processability, 4,489,190.
mechanical properties, HDT = 167°C,
and economy.
1980 In 1980, toughened blends of Celanex™ - Thermoplastic
polybutylene-terefbthalate (PBT) with Polyester, Bulletin IIA,
elastomer Celanex ,and poly- Celanese Corp., Feb 1984.
oxymethylene (POM) with elastomer
Celcon™, were introduced by Celanese.
1980 Polyetherarnide (PEA) was blended with Hitachi Chemical Co. Ltd,lpn.
styrene-butyl acrylate copolymer (SBA) Pat., 115,337; lpn. Pat.,
giving excellent processability, impact 057,717.
and heat resistance.
1980 Blends of styrene-grafted PPE (80% PPE- Izawa, S., Sugiyama, J. and
S) with SBR and SB showed good Kosaka, N., Can. Pat.,
processability, high gloss and impact 1,144,680, to Asahi-Dow,
strength. In the Oainippon patent, 50 Ltd; Oainippon Ink &
parts PPS was blended at 280 °C with 50 Chemicals Inc., lpn. Pat.,
parts PPE-S and 5 parts polyetherester 209,956.
rubber (Pelprene™), for good
toughness, impact and tensile strength.
1980 In 1980 Union Carbide introduced Mater. Eng., 94(1), 16 (1981).
Mindel™, a blend of ABS and
polysulfone (PSF) with good
processability (first ABS/PSF, Arylon,
was introduced by Uniroyal in 1964).
1980 Polyarylenesulfide, 5-95% PPS, blended Froix, M. F., US Pat.,
with wholly aromatic polyester (LCP) 4,276,397, to Celanese Corp.
had good processability and physical
properties.
1980 Polyarylamideimide (PAl) Torlon™, was Toray Industries Inc., lpn.
blended with PE to improve Pat., 151,756.
moldability and surface smoothness.
1980 PVC was blended with polyimide (30% Kopchik, R. M., US Pat.,
PI) and 50% MBS, to give high HOT, 4,255,322, to Rohm and
impact strength and clarity. Haas Co.
1981 Polyarylenesulfide (10-90% PPS, Ryton TM) Robeson, L. M., Eur. Pat. App!.,
blends with polyarylketone (PEEK) had 062,830, to Union Carbide
good processability, synergistically Corp.
high tensile, flexural strength and
impact resistance.
Appendix IV 637

1981 PSF was blend with 70% aromatic Hitachi Chemical Co. Ltd,lpn.
polyetheramide, PEA, to give products Pat., 052,348.
with good mechanical properties and
HDT.
1981 Styrene-maleimide copolymer (SMI) Denki Kagaku Kogyo K. K.,
was blended with 25% ABS, and 10% lpn. Pats., 125,241 and
SAN, for high heat and impact 125,242.
resistance.
1981 PPE, was blended with ABS, and either Asahi-Dow Ltd, lpn. Pat.,
polyamide (PA) and SMA Dylark™, or 165,448; Mitsubishi
with glycidylo-carbonyl-propyl Petrochemical Co. Ltd, lpn.
phosphate polymer. The blends had Pat., 195,147.
high resistance to boiling water, heat,
solvents, fire and impact.
1981 PC was reactively blended with 65% SMA Bourland, L. G., US Pat.,
Dylark™, and 5% PCL, to give high 4,388,443, to Atlantic
impact strength moldable resins. Richfield.
1982 PC was blended with PET and MBS to Allen, R. B., Giles, H. F., Jr.,
show good processability, high notched Heuschen, J. M. H. and
impact strength and weatherability. Wiercinski, R. A, Eur. Pat.
Office, 107,048, to General
Electric Co.
1982 Polyetherimide (PEl) blends with poly Giles, H. F., Jr. and White, D.
(carbonate-b-siloxane), EPDM, ABS, M., US Pats., 4,387,193,
MBS and acrylate copolymers (e.g., 4,390,665, 4,393,168 and
MBS, MMBA), PP, PSF, PEC, PAr, 4,395,518; Giles, H. F., Jr.
ternary blends with PC and polyesters, and Schlicht, W. R., US
polyacrylate elastomers, PA, etc., were Pats., 4,430,484 and
patented. The blends showed good 4,427,830, to General
processability, as well as improved Electric Co.
flexural and impact strength.
1982 PEl, was blended with PA-6, and with Robeson, L. M. and Matzner,
PEI-PA block copolymer, for M., Eur. Pat. Appl., 104,659,
improved moldability and impact to Union Carbide Corp.
strength.
1982 PA-6, PA-66 or PA-61O, blended with Coran, A. Y., Patel, R.
cured, millable polyurethane rubber Williams, D., US Pat.,
(PU) showed high strength, elongation, 4,419,499, to Monsanto Co.
toughness and impact strength.
1982 PAr was blended with PS and PAr-PS Unitika Ltd, lpn. Pat., 157,844;
copolymer, to give semitransparent lpn. Pat., 011,354.
blends with good moldability, and
mechanical properties. In the later
patent, PAr was blended with PA-6 and
PET, to give moldings with excellent
processability, gloss, chemical,
638 Appendix IV

mechanical, electrical properties and
HDT.
1983 PA was blended with polyester (e.g., 15% Chiba, K. and Tanaka, S., Jpn.
PET), to give good moldability, rigidity, Pat., 204,264, to Toray
strength and fire resistance. Industries, Inc.
1983 In 1983 General Electric Co. introduced Chem. Week, Nov 27, 1985,
Noryl GT™, the first blend in a new p.108; Eur. Plast. News,
family of high performance GEC 1984(10), p. 52.
blends, Noryl Plus™. The blend of PPE
with PA had high impact and heat
resistance (to 190°C).
1983 Atochem introduced two blends based on Jacquemin, J. P. and Deleens,
their proprietary-re0lyether-block-amide G., Fr. Pat, 2,591, 607;
(PEBA). Orgater blend with PBT and Couchoud, J. J., Glotin, M.,
EVA, and RilsanTM blend with PA and Guerin, B. and Parmeland,
5-50% ABS, MBS, NBR, SBR or EPDM. G., Fr. Pat, 2,592,388, to
The blends showed good low Atochem SA
temperature impact strength.
1983 In 1984 Mobay Chemicals Corp. intro- Plast. Buss. News, April 23,
duced Macroblend, PC/PBT or PET/ 1984, p. 6.
elastomer blend, for automobile use.
1984 Polyoxymethylene (PaM) blends with Nakagawa, M., US Pat.,
maleated EPR, had good processability, 4,526,921, to Mitsui
heat resistance, moldability, lack of Petrochemical Ind., Ltd;
delamination, rigidity, toughness, Burg, K., Cherdron, H.,
tensile and impact strength. In the Kloos, F. and Schlaf, H., Ger.
Hoechst patent, paM was mixed with Pat., 3,505,524, to Hoechst
either MBS, or methyl methacrylate- A-G.
grafted polybutadiene, to give high
impact strength.
1984 Blend of PES with PEEK had high tensile Harris, J. E. and Robeson, L.
modulus, HDT = 155°C, good stress M., Eur. Pat. Appl., 176,989,
cracking and impact resistance. to Union Carbide Corp.
1984 Borg-Warner introduced ABS/PA blend Plast. Focus, March 11, 1985, p.
Elemid™, Mobay Chemicals C0%.t 3; J. Commerce, June 13,
introduced PC/TPU blend Texin , for 1985, p. 2113.
the use in automobile industry.
1984 PPE blended with HIPS and Jadamus, H., Ribbing, W.,
poly(trans-octanylene) (PTa) led to Feinauer, R. and Schaefer,
excellent prosessability, and high termal W., Ger. Offen., 3,442,273;
stability. In later patents, HIPS was Ger. Offen., 3,518,277, to
found to be not only unnecessary but Chemische Werke Hiils
detrimental- it lowered HDT. Thus PPE A-G.
with a wide range of PTa content (and
other ingredients, such as PA, PEST,
fillers, flame retardants, etc.) had a
processing temperature of 260 °C, high
impact strength and HDT = 194°C.
Appendix IV 639
1984 PA-46 was blended with 5-50% PPS. The Chiba, K., PCT Int. Appl,
blend had good physical properties, 003,212, to Stamicarbon BV.
heat and chemical resistance, and
moldability.
1984 PEl was blended with polyester (PET) and Quinn, c. B. and Holub, F. F.,
polyestercarbonate (PEe). The material Eur. Pat. Appl., 187,416, to
has good processability and impact General Electric Co.
strength similar to PEl.
1985 PPE blended with polytransoctenylene Droescher, M., Bartmann, M.,
(PTO) and PA, was prepared in two Burzin, K., Feinauer, R,
steps. First, PPE with 40-2% PTO and Gerth, c., Neugebauer, W.,
0.1- 5% maleic anhydride was blended. Jadamus, H., Ribbing, W.
Next, the blend was mixed with PA-12. and Lohmar, J., Eur. Pat.
The resulting alloy had good App!., 205,816, to
prosessability, high impact strength, Chemische Werke Huls
solvent resistance and HDT = 156 0c. A.-G.
1985 PES was blended with 2:: 5% PEEK and Rostami, S., Eur. Pat. App!.,
2:: 10% PEl (e.g., 20% PES, 60% PEEK 211,604, to ICI.
and 20% PEl) and was found to have
good compatibility, and high heat
resistance.
1985 Polysulfone/polysulfide (PSF/PPS) Hashimoto, M., Jpn. Pat.,
blended with PSF-PPS block copolymer 246,755, to Dainippon Ink
was reported to have improved impact and Chemicals Inc.
strength, uniformity and cohesion.
1985 Blends with good compatibility, Kita, M. and Hashimoto, K.,
containing (PP) and Jpn. Pat., 131,043, to Daicel
polytransoctanamer (PTO) gave high Huels Ltd.
Izod impact strength at -40 to 23 0c.
1985 In 1985, BASF Plastics introduced Terblend- Plast. World, Dec 1985, p. 66;
S, a blend of PC with poly(acrylate-co- Plast. Technol., April 1986, p.
styrene-eo-acrylonitrile) (ASA); Dow 103.
Chemical Co. introduced Pulse™, PC/
AB5-type blends. Both used for
automotive application.
1985 PPE reactively blended with SBS and Van der Meer, R. and Yates, J.
maleic anhydride gave functionalized B. III., PCT Int. Appl.,
mPPE. That resin, mixed with either PA 000,540, to General Electric
or polyester, in turn produced materials Co.
with high impact strength and chemical
resistance.
1986 Maleated polyphenylene ether (mPPE) was Togo, S., Amagai. A., Kondo,
reactively blended with maleated-PP SBR, Y. and Yamada, T., Eur. Pat.
glycidyl methacrylate copolymer and/or Appl., 268,486, to Mitsubishi
phenylenediamine binder, to give excellent Gas Chemical Co.
solvent resistance, moldability, impact and
mechanical properties.
640 Appendix IV
1986 PA-6 or PA-66 were toughened by Grant, T. S. and Howe, D. V.,

blending with maleic anhydride- US Pats., 4,496,690 and
modified ABS (AB5-MA) to give alloys 4,740,552, to Borg-Warner;
with high impact resistance. In 1987 Lavengood, R. E., Harris, A
Monsanto introduced its successful F. and Padwa, A R. US Pat.,
Triax™ 1000 = PAl AB5-MA blends 4,777,211, to Monsanto Co.
with cocontinuous morphology.
1986 Miscible blends of PC/PMMA with a Kambour, R. P., Eur. Pat.
lower solubility temperature, > 140°C, Appl., 263,378, to General
were obtained. After modification of PC Electric Co.
chain ends the LCST increased to
300 0e. The blends are useful for glazing
materials and optical disks.
1987 PA blends with functionalized PPE, were Akkapeddi, M. K., van
found to have high elongation and Buskirk, B. and Brown, A
impact strength. The functionalization B., PCT. Int. Appl., 008,433;
and subsequent blending were done in US. Pat., 5,162,440, to
reactive extrusion, using maleic Allied-Signal Inc.
anhydride or fumaric acid. In 1991
Allied Signal introduced PPE/PA-6 as
Dimension™ D9000.
1987 PPE was blended with 25-75% PBT (or Yates, J. B., ill, PCT Int. Appl.,
PET), 8-25% SEBS and 5-40% PC. The 005,311; US Pat., 4,831,087,
blend, Gemax™, had good impact and to General Electric Co.
solvent resistance, surface finish and
low coefficient of thermal expansion.
1987 Polyetherimide (PEl) was blended with Peters, E. N. and Rock, J. A,
polycarbonate (PC) and with phenyl Eur. Pat. Appl., 325,719, to
phosphate stabilizer for ascertaining General Electric Co.;
melt stability. In 1992 Ultem LTX™, Modern Plast. Inti., Sep 1992,
blends were introduced by GEe. p.147.
1988 PPS was blended with PPE, and styrene- Nishiyama, M., Ohtsuki, K.,
glycidyl methacrylate copolymer Nakakita, Y. and Ozawa,
(SGMA). Fine dispersion of PPE in a PPS H., Eur. Pat. Appl., 360,544,
matrix resulted in excellent mechanical, to Ube Industries Ltd.
impact and thermal properties.
1988 Processability, thermal and mechanical Koning, e. E., Kingma, J. A J.
properties of ester-based LCP, were and Prinsen, L., Eur. Pat.
improved by blending with either Appl., 365,101, to
Phenoxy or ester-amide-based LCP. Stamicarbon BV.
1988 PA, was blended with PAr, using PA-co- Dean, B. D., US Pat., 4,937,297,
PAras compatibilizer, giving good to Amoco Corp.
processability, mechanical properties,
UV stability, heat, solvent and stress-
crack resistance.
Appendix IV 641

1988 Alternating carbon monoxide-alkene Gergen, W. P. and Lutz, R. G.,
copolymers (COPO) were blended with US Pat., 4,818,786;
PVDF, polyester rubbers, 4,839,435, to Shell Oil Co.
polyvinylpyridine, poly-2-oxazoline or
polysulfone. The blends were
toughened by incorporation of ethylene-
propylene copolymers EPR and EPDM.
1988 In 1988 Dexer introduced Dexcarb™, Perron, P. J., US Pat.,
PC/PA/poly-esteramide blends, with 4,782,114, to Dexer Corp.
elastomer and maleated polyalkenes.
1989 PA blends with PPS were compatibilized Sakazume, S. and Orikasa, Y,
with styrene-glycidylmethacrylate Eur. Pat. Appl, 423,767, to
(PSGMA). The blends had high heat Nippon Petrochemicals.
and impact resistance.
1989 Polycarbonate (PC) was blended with Skochdopole, R. E. and
polyurethane (TPU) for mechanical Wright, D. L., US Pat.,
strength, solvent, environmental stress 4,912,177, to Dow Chemical
cracking and impact resistance. Co.
1990 POM was blended with 20% TPU, then Flexman, E. D., Jr., Eur. Pat.
20% of a third component (selected App!., 464,512, to DuPont.
from PA, LLDPE, PP, PBT or PET) was
incorporated. The blend showed
excellent toughness, impact strength,
elongation and recyclability.
1990 Polyoxymethylene (POM) was found Machado, J. M. and French, R.
miscible with polyvinylphenol (PVPH; N., US Pat., 5,079,301, to
poly-p-hydroxy styrene). Shell Oil Co.
1990 PA-46 was blended in a twin-screw Koning, C. E. and Vroomans,
extruder with polyethersulfone (PES) H. J., Eur. Pat. Appl.,
then injection molded, to give excellent 463,238, to Stamicarbon BV.
balance of mechanical and thermal
properties.
1990 Polyetheramide, (~ 95% PEA), as Brown, S. B., Lowry, R. c.,
PEBAX™, when blended with PPE and Avakian, R. W., Bailly, C. M.
0-3% triglycidyl isocyanurate showed E. and Dehaye, F. J. L., Eur.
nondelaminating behavior and good Pat. Appl., 476,368, to
mechanical properties. General Electric.
1990 PPS with better chemical resistance, Serizawa, H., Kubota, M. and
toughness and impact strength was Sano, H., Eur. Pat. Appl.,
prepared by blending with 40% PBT 468,772, to Polyplastics Co.
and aminopropyl-ethylsilane. In the Ltd; Koshirai, A., Nakata,
Mitsubishi patent, PPS toughening was A., and Yamamoto, N., Eur.
accomplished by addition of PDMS Pat. App!., 468,772, to
acrylate grafted rubber latex with Mitsubishi Rayon Co. Ltd.
particle diameters ~ 0.2 JLm.
642 Appendix IV

1990 Polyphenylenesulphidesulfone (5-95% Ishio, A and Kobayashi, A
PPSS) was blended with a resin, Eur. Pat. Appl., 463,738, to
selected from PA-6, PA-66, PET or PBT, Toray Industries Inc.
for good mechanical properties, HDT,
dimensional stability and chemical
resistance.
1990 Liquid c~stalline polyesters (LCP) as Dekkers, M. E. J., Yoshimura,
Vectra ,were reactively blended with D. K. and Laughner, M. P.,
50-95% PBT Valox™, in the presence of US Pat., 5,171,778, to
0.05-25% triglycidyl isocyanurate General Electric Co.
(TGIC) Araldite™. The blends were
found to have increased stiffness and
improved drip characteristics.
1991 In 1992 Toray Industries introduced Toray- lpn. Chem. Week, 1992.11.06,
PC™, a PC blended with 30% p.5.
polyaramid (PARA). The material with
high strength at break and HDT, found
use in electronic and information
industries.
1991 Engineering polymers were blended with Bahn, W. A, Beal, G. H.,
low temperature inorganic glass or Ference, J., Monahan,
ceramic glass. The resins were PEK, Quinn, c. J. and Roussel, P.
PEEK, PPS, PEl, LCP, PC, PET, PBT and 5., US Pat., 5,043,369, to
fluorinated polymers. The glasses had Corning Inc.; Bahn, W. A
sufficiently low glass transition and Quinn, C. J., SPE Techn.
temperature, < 300 °C, and ability to Papers, 37, 2370 (1991).
interact with the polymer.
1991 Polymethylpentene (75-99.5% PMP) was Boudreaux, E., Jr., PCT Int.
blended with PPS, for high heat and Appl., 016,586, to Phillips
flame resistance. The blend was used Petroleum Co.
for moldings with high strength.
1991 PPS as Fortron was blended with PC, PPE, Orikasa, Y. and Sakazume, 5.,
AB5-type polymer and a Eur. Pat. Appl., 506,006, to
compatibilizing graft copolymer. The Nippon Petrochemicals Co.
blends showing good processability, Ltd.
impact strength, heat resistance, and
appearance were used for manufacture
of automobile, electrical or electronic
parts.
1991 PSF as Udel™ was blended with 40% PET EI-Hibiri, M. J., Jack, G. 5.,
CleartuffTM, to obtain flame-retardant Kelly, W. E. and Patel, S. R.,
blends. US Pat., 5,151,462, to
Amoco Corp.
Appendix IV 643
1994 PET was blended with LCP (Xydar™ or Bonis, L. J., Schuler, P. S. and
Vectra™) and at least one Adur, A. M., PCT Int. Appl.,
compatibilizer selected from a WO 96/00752, to Foster-
copolyester elastomer (Hytrel™ Miller, Inc.
HTR-6108), ethylene-maleic anhydride
(Polybond™ 3009), an acrylate
copolymer (SP-2205™, DS1328/60™,
Lotader™ 2400, Escor™ ATX-320,
Escor™ ATX-325 or Escor™ VX-ll.04),
or an acrylic rubber (Vamac™ Gl). The
alloys were prepared by melt blending,
e.g., 89wt% PET with 4.7wt% DS, then
adding through the vent 9.3wt% Vectra
with 2wt% Polybond. The yield stress,
modulus and oxygen barrier were
significantly improved.
Index
Note: Polymer names appear in full; polymer blends are shown in abbreviated form.
Abrasion resistance 21, 85,161,168,171,173, weatherable 156-7

197,207,219,225,228,236,242,252,262, Acrylonitrile-butadiene-styrene-glycidyl
276,325,338,340,368,379,390,396,402, methacrylate (AB5-GMA)
405, 430, 449, copolymers 158
ABS/Eo-ECH. See Electrostatic dissipating Acrylonitrile-butadiene-styrene-
blends (ESD) methylmethacrylate copolymer
ABS/PA blends 168-70,286,298--9,310 (ABSM) 270
ABS/PBT blends 170-2,352--<i Acrylonitrile-butadiene-vinylch1oride
ABS/PC blends 161-7,386-7 copolymer (ABVC) 209
ABS/PC/EO-CHR. See Electrostatic Acrylonitrile-ethylene rubber-styrene (AES)
dissipating blends (ESD) terpolymer 148, 154
ABS/PEST blends 170-2, 352--<i Acrylonitrile-methylmethacrylate copolymer
ABS/PET/PC blends 171 (AMMA) 143,200,210,220
ABS/PSF blends 173-5,436 Acrylonitrile-styrene-acrylate terpolymers
ABS/PVC blends 159--<i1, 211 (ASA, AAS) 36, 157
ABS/SMA blends 175 Actylonitrile-styrene-EPDM-glycidyl
ABS/TPU blends 172-3 methacrylate copolymer (AE5-
Acrylic elastomers 23, 157 GMA) 172
Acrylic impact modifiers (MBA) 194,249 Advanced Elastomer System 18
Acrylics 22-3,357--<iO,387,400-1 AE5-GMA/PEST blends 172,344,354
Acrylivin 201 Affinity resins 32, 75
Acryloid (now Paraloid) 22,214,220,249, Aflas 45
251,347 Akulon 309
KM330 358 Aliphatic polyketone. See Poly(carbon
KM611 364 monoxide-eo-polyolefin) or (CaPO)
KM660 359 Alkali cellulose 1~16
Acrylonitrile 18, 21 Alketh 25
Acrylonitrile-acrylate rubber (ACM) 353 Alkyd resins 20
Acrylonitrile-butadiene-styrene copolymer Alphalux 407
(ABS) 11-2,21,28,36-9,41,95,115,119, Arnide-ester exchange reactions 97, 327, 365
126,128--32,153-8,220,266,287,298--9, Amodel 48, 280
310,354,465 Amoroon 47
applications 154 Amorphous aromatic polyarnides. See
blends 159-75, 286-99, 352--<i, 386-7 Aromatic polyarnides (PARA)
high heat 155--<i Amorphous polyhexamethylene
impact modifiers 347 isophthalarnide-eo-terephthalarnide
preparation 65, 153-4 (PA-6IT6) 310
reactively acidified (AB5-MA or Analysis 63-4
AB5-GMA) 157-8 Aniline-formaldehyde (AF) 20
type-A 11, 21 Anionic polymerization 73
Index 645
Antistatic properties 465--7 Also see Carboxy-terminated nitrile rubber
Electrostatic dissipating blends (ESD) (CTBN) 291, 303
Araldite 20 Carilon (COPO) 51, 211-2. See also
Ardel 338, 340, 438 poly(carbon monoxide-co-polyolefin)
Arloy 2000 356 Carloy 202
Aromatic polyamides (PARA) 41,48,97, Carodel 42
248,280,288,308,332,334,430-1, Carothers, Wallace Hume xiii, 18, 25-7, 65,
447-8 69,72-3,447
Armenius rule of mixing 104 Casein 16
Arylon 42, 48, 437 Casson equation 105
ASA/PMMA/PC blends 166 Catalin 19
Astralon 24 CaVity transfer mixer (CTM) 121
Astrel 47, 394 Celanex 41, 337
Atactic polypropylene (aPP) 259 Cellophane 16
Atactic PP blends 232 Celluloid 10, 24
Aurum 442, 463 Cellulose acetate (CA) 16, 224
Aylsworth, Jonas W. 133-4 Cellulose acetate-butyrate (CAB) 16
Cellulose butyrate (CB) 16
Badum, Ernst 195-6 Cellulose ethers and esters 16
Baekeland, Leo 19,58-9,133 Cellulose nitrate (NC) 24
Bakelite 19 Cellulosies 10-15
Bakelite Polysulfone 394 Chlorinated butyl rubber (CBR) 260
Barrier properties. See Permeability reduction Chlorinated ethylene-propylene-diene
Beetle 19 terpolymer (C-EPDM) 204
Biodegradable blends 246-7,270,317,440, Chlorinated HDPE (CPE) 203-7
4&}-3 Chlorinated polyethylene (CPE) 95,194,
Biopolymers, 246, 4&}-2 266
early use 4-5 Chlorinated PVC (CPVC) 203, 224
modified 10-17 Chlorinated SBR (C-SBR) 204
Bisoxazoline 348 Chlorobutyl rubber (CR; Chloroprene) 18,
Bisphenol-A 42 269
Bisphenol-A polycarbonate. See Chlorosulfonated polyethylene (CSR,
Polycarbonate (PC) CSM) 204-5,232-3,265-6
Blending strategy 118-21 Chlorotrifluoroethylene 45
Blends, blending. See Polymer blends Cibanite 20
Block copolymers 90,91,93,96,97, 142-3, Cladux 201
235 Co-continuous morphology 18, 36, 82,
Blow molding 60-1 98-100,123,125,135,146-7,159,162,165,
Boltzman theory 71 168-70,176,179-80,185,139,191,203,
Branch pOints 78 213,231,241,248,257-8,263,268,288,
Branched copolymer 79 297-8,301,308,310,331-2,339,353,355,
Branched structures 3 367,379,385,402,474
Brittle resins 125 Coalescence 88,93-4,100,102,107-8
Buna 11,17-8,21,154,262 Collodion 10
Buna-N 11, 18, 24, 72 Colloids 66, 68
Buna-S 11, 18, 21, 72, 139 Comb macromolecule 78
Butadiene 18, 21 Commercialization dates of selected
Butadiene-acrylonitrile rubber. See Nitrile polymers 11-15
rubber (NBR) Commodity resins 28-39,46,134-5
Butadiene-b-isoprene-b-styrene (SEP) 94 blends 137-282,287-317,340--61,384-8,
Butadiene-b-styrene (SEB) 94 400-3,409-15
Butadiene-methylmethacrylate-vinyl Compatibilization 94-7,101-2, 120, 135, 136,
pyridine terpolymer 148 149,186,203,257,273,470-2
Butadiene-styrene rubber (SBR) 260 by addition of copolymers 93-4
Butyl acrylate 46 definitions, methods and principles 86-9,
Butyl rubber 18 effects on flow 112-13,
reactive. See Reactive compatibilization.
Capillarity number 106-7 Compounding 36,53,55,57,85-6,94-5,
Carbon black (CB) 373 117-8,120-1
646 Index
Compression molding 53, 57 Denka Taimel 211
Computational methods 136 Denkovinyl 209
Computer integrated manufacturing (CIM) Devolatilization 59, 479
technology 55 Dexcarb 332
Concentration dependence of viscosity Diarex 328
108-9 Dimensional stability - polymers and their
Condensite 133 blends
Conex 41 ABS 158-9, 161, 167-70, 386, 388, 403
Constitutional repeating units (CRU) 78 PA 168-70,185,188,248,272,288,298-9,
Constrained geometry catalyst technology 306,309,312,320,324,331,334,416
(CGCT) 31 PAl 51
Continuous use temperature, CUT 47, SO, PC 161, 167, 331, 368, 370, 373, 386, 388,
429-30 390,394
Continuum mechanics 110 PEA 382
COPO See Poly(carbon monoxide-co- PEl 50, 336, 443
polyolefin) or Aliphatic polyketone PEST 41-2,171-2,252,277,337,339-41,
Copolyamide (CPA) 101 345, 348-9, 353-4, 361, 363, 368, 370,
Copolymerization 18, 25, 194 373-4,382-3,390,418
Copolymers 78-9 PMMA 222, 224
nomenclature 80 POM 252, 403-4
Core-shell copolymer 86-8,125,157,160--1, PP 261-3,272, 277
169, 171, 173, 179, 184, 200, 210, 220, PPE 44, 191, 374-5, 320, 322, 379, 407,
222-4,243,274,292-3,298,300-2,311, 410-1,413,416,418,426
319,344-7,350-1,353,356,358-9,363, PPS 334,379
369-70,372,377,387-8,391,393,396, PSF 394,436
399-400,421,437 PVC 159,388
Corfam 27 SEBS 185, 241, 248, 298, 353
Cortem Alloys 436 sPS 75
Cost of polymer blends 117 Dimethylformamide (DMF) 23
Couette flow 116 Diskpack extruder 56
Critical capillarity number 107 Dispersion 102
Critical micelle concentration (CMC) 91 Dispersoids 68
Crosslinked copolymer 79 Doolittle's equation 104
Crosslinked structures 3 Dry powder blending 194
Crosslinking agent 20 Duprene 18
Crosslinking point 78 Duralex 207
Crystallinity 73 Durel 48
effects of blending 49, 87, 97, 234-5, 256, Dylark 308
261,273,282,304,306-7,328,367-8,385, Dynamic (oscillatory) shear flow 109-12,
389,435,453,458,461,471 114-5
enhanced of PA 327, 366, 389 Dynamic vulcanization or curing 10,14,
enhanced of PP 275 33,36,232,243,260,263-4,269,336,
of PC 331 441,445
of PET 251,326-7,340-2,349,351,360-1,
363,365,370,417 Ebonite 10
ofPOM 378 Economy of blending 117
of PVC 195, EKF 76
of sPS 37-8, 139-40, 184, Ekkcel 41
shrinkage 170 Ektar 426
Crystalloids 66 Elastic or Maxwell's, melt extruder 55
CTBN /PA blends 303 Elasticity 38-9,70,72,74,102,106,113,115,
Cyclomer 43 121, 145-6, 166, 176-7,247,281,286,402,
Cyclopentene-vinylchloride copolymer 446,463
203 Elasticity of polymer blends 115
Cycovin 211 Electrically conductive polymer blends
(ECPB) 126-7, 245-6, 271, 464-8
Dacron 41 Electrically conductive polymers (ECP)
Decoloy 201 467-8
Dendritic polymers 76 Electromagnetic interference (EMI) 246
Index 647
Electrostatic dissipating (ESO) blends Ethylene-acetoxybicycloheptene
126-7,151-3,465-7 copolymer 262
with epihalohydrin 13, 126-7, 185, 191, Ethylene-acrylate 46
278,288,322,376,395,412,415,459, Ethylene-acrylic acid (EAA) 97, 301
466-7 Ethylene-acrylic acid-butyl acrylate
Ellis model 323-4 copolymer (EBA-AA) 301
Elmit 288 Ethylene-butyl acrylate-co-glycidyl
Elongational flows 115-16,121-2 methacrylate (EBA-GMA) 172
Elongational Flow Mixer (EFM) See Ethylene-carbonate (ECA) 301
Extensional flow mixer Ethylene-co-glycidyl methacrylate copolymer
Elvaeel 24 (EGMA) 253, 308, 348
Emulsion polymerization. See Polymerization Ethylene-ethylacrylate (EEA) 269,301
Encapsulation, flow-induced 102-3 Ethylene-ethylacrylate-glycidyl methacrylate
Engineering resins 39-44, copolymer (EEA-GMA) 292, 345
blends 39,119,181,211-14,218,271-9, Ethylene-glycidyl methacrylate
287,317-33,361-79,389-94,403-5 (EGMA) 343, 347
Enplex 201 Ethylene-methylmethacrylate (EMMA) 226,
Entrance-exit pressure drop in capillary 301
flow 113 Ethylene-propylene rubber (EPR) 30, 35, 46,
Environmental stress crack resistance 142,234,261,274,295-7
(ESCR) 239,288,335,381,444 Ethylene-propylene-I, 4-hexadiene
EPOM 13,35-6,119,128-32, 142, 150, 153-4, (EPOM) 35, 234
156-7, 161, 165, 172, 174, 181-2, 189, 194, Ethylene-propylene-dicyclopentadiene 263
218, 221, 227, 246, 253, 335-6, 444, 449, Ethylene-propylene-diene copolymers
466,475,482 (EPOM) 18,46, 142, 234, 261-5, 275,
NBR blends 18, 242 295-7,349
PA blends 95,186,248,288,292-8,302-3, Ethylene-propylene-diene elastomer,
305,308,322-3,325 maleated (EPOM-MA) 95, 302
PC blends 250,275,332,385,389,398 Ethylene-propylene-diene terpolymer,
PE blends 30,232,234-7 chlorinated (C-EPOM) 194
PEST blends 341,343-50,352-4,365, Ethylene-propylene-ethylidene-
371-2,374,378 norbomene 263
PP blends 33,36, 121, 239, 254-{;, 26(H;, Ethylene-tetrafiuoroethylene copolymer
271-2,274-7 (ETFE) 396
PPE blends 408,410,414 Ethylene-vinyl acetate (EVAc) 25, 163, 231,
PPS blends 46, 334, 428 269,289,300,301,465
PVC blends 39,202,205,208 Ethylene-vinyl acetate-carbon monoxide
Epoxy resins (EP) 20 copolymer (EVAc-CO) 200, 208
EPR 13,35-6, 119, 128-32, 142, 153, 156, 168, Ethylene-vinyl acetate-glycidyl methacrylate
170, 172, 180, 182, 204, 218, 224, 227, 242, copolymer (EVAc-GMA) 175
246, 253, 399, 436, 465, 468, 472, 475, 477, Ethylene-vinyl acetate-vinylchloride
481-2 terpolymer (EVAc-VC) 224
PA blends 186,248,288,292,295-9,305, E~ylene-vinyl alcohol (EVAl) 231,245,269,
307-8,317,320,322,325 275,314-17
PC blends 250,332,385,389,393,397-8 Ethylene-vinylchloride copolymer
PE blends 29-30, 234-7, 242, 244 (VCE) 270
PEST blends 252,343-9,252,254,258-9, EVAc/PMA blends 219
363,365,371,373-4,376,378 EVAc/PP blends 269-70
PP blends 33, 35-6, 216, 254-65, 267, EVAc/PVC blends 200, 207-9
270-7 EVAI/PA blends 314-7
PPE blends 410, 415, 417-8, 420 Extensional flow mixer (EFM) 121-2
PPS blends 46, 428 Extensional or elongational viscosity 110,
Equilibrium deformation 107 113,115-6
Equilibrium drop diameter 108 Extrudate swell parameter 112
Equilibrium morphology 98 Extruders 5, 24, 44, 53-7, 61, 97, 120, 136,
Erinoid 16 145,148,197,236,295-6,321
Estane 27 disk 55
Ester-amide exchange reactions 97 elastic melt 55
Ethyl 209 Patfoort 95, 144,472-3
648 Index
Extruders (Cant.) spectrum 110
ram 53 Gutta-percha (GP) 10, 95, 127, 132
single-screw (SSE) 54, 150, 233, 396, 424,
454,459 HOPE 12, 28-9, 33-4, 55, 61, 73, 88, 230,472,
twin-screw (TSE) 39, 54-7, 61, 95-6, 102, 475
144, 188-9, 211, 223, 225, 247, 252, 272, HOPE blends 234-5, 250-2, 343, 367
275,278,281-2,294,302,307,309,316, with other PEs 116, 130, 236-9, 476
319,327,332-3,346,350-1,361,365-6, with PA 100,102,248,274,290,296,312
374,376,381,393,397,413,420,426, with PP 232, 255-8, 269
430,432,435,452,460,464,466,476,479 with PS or styrenics 98, 143, 146, 178-80,
Extrusion 53-7,95,120-1,144 241-2,266,268,474,478
Exxpol 32 with PVC' 203-4, 206, 244
Heat distortion temperature (HOT) 24, 42,
Ferilon 41 118, 142, 148, 155, 157-67, 169, 173-5,
Fibrillation 99, 101-2, 455 182-4,186,188-93,199,202-6,209-10,
effect of compatibilizer 101-2 212-4, 220, 222-3, 226-7, 248, 251, 270,
Flame-resistance 42, 213, 321, 349 277-8,290,292-3,296-8,301,310-1,
Flory, Paul J. 4,69-72 318-20,324-5,329,332-4,339-40,345-8,
Flow 354-7,361-2,364-5,368,370,373,375,
behavior 104-16 377-83,390-5,397-8,404,408,410-11,
encapsulation 102 413,415,420,422-6,430-2,437-42,446-9,
imposed morphology 99-103 451-2,456-7,459,461,463,465,482
induced coalescence 102 Helfand-Tagami lattice theory 90
induced dispersion 100-1 Hexamethylene-diamine 324
induced encapsulation 102-3 High density polyethylene. See HOPE
shear-induced segregation 102 High impact polystyrene. See HIPS
Fluorocarbon polymers 45 High melt strength PP 35
Formaldehyde 16 High performance materials 76
Formica 19 High pressure low-density polyethylene. See
Fracture mechanics 87, 120, 122-6, 136, 148, HPPE;LPDE
170,176,287-8,295,365 High resolution transmission electron
Crazing-and-eracking 122, 254, 473 microscopy (TEM) 196
Shear banding 122,144,410 High temperature polymers 46-7
Free radical polymerization 22 HIPS 21,36-7,95, 124, 125, 139, 140-3,
Free volume 69-7 1794lO, 220, 250, 321, 397, 426,
HIPS 179
Galalith 16 with block copolymers 142-3
Geloy XP2003 211 with EPR 142
Gemax 392 Historical milestones for polymer blends
Geolast 18 (table) 128-32
Geon 196, 197 Hoechst HMA 451
Glass transition temperature (Tg ) 22,37, Homogeneous blends 150
41-52,71, 75, 114, 139, 144, 150, 161-2, Hostaflon 396, 434
167,176,191,197-8,206,208-9,213, Hostalit 204, 209
216-7,220,223,225,243,254,259,265-6, Hostalit H and HM 201
273, 278-9, 300, 302, 313, 316, 325, 329, HPPE 25
333-5,349-50,356,364,367,373,382-3, Huggins, Maurice L. 67, 70, 78-9
396-7,407-8,410,420,422,428,430,432, Hycar 198
434,436,446,448,462-3,483 Hydrazine 248
Glycidyl methacrylate (GMA) 164, 252, 312 Hydroxypropyl-starch/PA or PEST. See
Glycidyl methacrylate grafted ethylene- Biodegradable blends
propylene-diene copolymer (EPDM- Hylar 45
GMA) 344 Hytrel 336
Glyptal 20
Grafted copolymers 79 Igamid U 27
Grilamid 335-6 Immiscible blends 104, 105
Grillon A 288 Impact-modified blends 285-6
Gross frequency relaxation Impact-resistant blends 329
function 111 Impact-resistant polyamides (PA-6) 295
Index 649
Injection molding 21,59-60,165 oriented 68
Innovex 253 with commodity resins 281-2,454-5
Inorganic glasses 382-3 with engineering resins 336, 382, 398, 424,
Insite 31, 32, 75 435,455-60
Interchain copolymer formation 96 with inorganic, low temperature glass
Interface. See Interphase 463
Interlayer slip 100, 102, 109, 112 with PA 455,336
Internal mixers 53 with PC 455-6, 398
International Union of Pure and Applied with PEl 460-1
Chemistry (IUPAC) 78 with PEST 456-9, 382
Interpenetrating polymer network with PEST/PC blends 457
(IPN) 117,178,465 with PI commercial blends 236
Interphase 87-94,97,100--1,105,113,125,136 with PP 102-3,281-2
definitions 82 with PPE 102,281-2,424-5,459
fundamentals 89-90 with PPS 435, 461
interfacial polymerization 40, 43, 88 with PSF 462
interfacial tension coefficient 86-8, 90-4, with specialty resins 460-64
101, 106-8, 112, 117 LCST. See Lower critical solution temperature
interfacial thickness 82, 89-90, 92-3 LOPE 25,28-9, 116, 230, 233, 234
spreading coefficient 88 LOPE/HOPE blends 238-9
Intrinsic viscosity ([7)]) 67,76,99, 105, 113, LOPE/LLOPE blends 236-7
264,330,408,426 Lew~ acids 285
Ionomer 233-4, 267 Lexan 249, 438
blends with PA 290-3 Lin's fluidity relation 109
blends with PE 233-4 Linear copolymer 3, 78
Iridescence 163, 190, 225-6, 353, 357-8 Linear homopolymeric macromolecule 3
Irradiation Linear low density polyethylene. See LLOPE
crosslinking 174 Linear polyuretharie (TPU) 194
sbbiltzation 33,82,87,256,315,426,471 Liquid ambar orienblis 21
res~bnceto 51,211,246,250,258,360,480 Liquid crystal polymers (LCP) 14, 41, ~9,
Isoplast 351 103,134,28(}-2,336,361-2,382,398,
Isoprene 17,18 424-5,430,435,436,440,442,449,452-64
Isoractic PMMA (i-PMMA) 223 blends See LCP blends
!zod impact strength 125 LLOPE 28-33, 116, 134, 145, 177, 179, 188,
230,232-5,248,249,251,384
Kaminsky's catalyst 74-5 LLOPE/HOPE blends 238-9
Kancace 200,201,208,359 LLOPE/LLOPE blends 237-8
Kaneka Enplex 211 Log-additivity rule 108
Ke-F 45 Loop-reactor technology 195
Kevlar 41 Lobder 252, 274-5, 308, 366
Kodapak 426 Low density polyethylene. See LOPE
Kralastic 211 Low haze transparent blends (see also
Kraton 38,250,274,308,322,392,465 Transparent blends) 179,221
Krene 209 Low molecular weight polyamides
Krynac 197 (LMW-PA) 294
Kydene 201 Low temperature (inorganic) glasses
(LTC) 382,435-6,462
Lamellar blend structures 117, 123, 178, Lower critical solution temperature
244-5,314-5 (LCST) 100, 149,223,225,387
Langmuir-Blodgett monolayers 76 Lutofan 209
Laroflex 209
Lastiflex 211 MABS 354
Latamid 309 Macromolecular assemblies 68, 81
Latex blending 72, 117, 128, 143, 153-4, 156, Macromolecules 78
163,194-7,199,205,208,216,220 Makroblend 391
LCP 14, 41, ~9, 103, 134, 28(}-2, 336, 361-2, Maleated acrylonitriIe-bubdiene-styrene
382,398,424-5,430,435,436,440,442, copolymer (AB5-MA) 165, 349
449,452-64 Maleated ethylene-propylene copolymer
blends 68,102-3,119,130-2,452-62 (EPR-MA) 349
650 Index
Maleated hydrogenated styrene-butadiene of PO 235--6,238-9,250-1,256,258-9,269
block polymer (SEB5-MA) 180 of PMMA 217-20, 222-5, 227,
Maleated polyethylene (PE-MA) 248, 289 ofPOM 405
Maleated polypropylene (PP-MA) 248, 269, ofPPE 408-9,412-3,415,417--s,425-7
271,280 of PS 148-51, 191
Mark, Herman 4, fr.7, 25, 64, 6fr.70, 72, 78 of PSF 438-9
Mark-Houwink-Sakurada equation 67 of PVC 195-9,206,208-9,211,213
Mastication 9-10, 132 Mixing 53, 120-1
.Mathematical models 94, 107, 136 Molecular colloids 68
Matthews, Francis Edward 139-40 Molecular composites (MC) 449-52
Mechanical behavior of polymer blends Molecular weight (MW) 63
122--6 determination 67-9
Mechano-chemical distribution, MWD 31-3,35,63,71,73-4,
blending 86, 88 82,86,97
degradation 100 Moplen 34
Melamine-formaldehyde (MF) 20 Morphology 86,88,98-103,125,135,148
Melt strength 33, 35, 42 Multicomponent blends 330
Mercerized cellulose 15
Mers 3 Natta, Giulio 29
Mesodyad 34 Natural polymers. See Biopolymers
Meta-marble 163 Natural rubber (NR) 4, 9, 10, 95, 127, 132
Metabulen 201 Negatively deviating blends (NOB) 96, 108,
Metallocene catalysis 6,29-35,37,51, 74--6, 109,113
136 Negatively-positively deviating blends
Methacrylate-Butadiene-Styrene copolymers (NPDB) 108
(MBS) 119, 126, 128-31 Neoprene 18, 202
Methacrylate-grafted polybutadiene Newtonian liquids 105-7, 116
(MBA) 400 Nipeon 211
Methyl alumino oxane (MAO) 74, 75 Nipol 197
Methyl methacrylate (MM) 220 Nitrile rubber (NBR) 21,95, 127, 143, 194,
Methyl methacrylate-butadiene-styrene 195,220,260,297
polymer (MBS) 158, 175, 194, 213, 220, Nitrocellulose (NC) 10, 15, 127
270 Nomenclature of polymeric systems 7B--s2
Methyl methacrylate-butyl acrylate-styrene for Non-Linear Macromolecules 81
copolymer (MBS) 354-5 for Polymer Blends 81-2
Methyl methacrylate-grafted styrene- for Copolymers 78
butadiene rubber (MBS) 400 traditional 78
Methyl methacrylate-vinyl acetate-acrylic Non-linear macromolecules 81
acid copolymer (MMVAc-AA) 221 Noryl 44, 407, 408, 438
Micellar colloids 68 Notation. See Nomenclature
Microrheology 100, 10fr.8, 136 NovalIoy 309
deformability parameter 1Ofr.7 NPDB 108
dispersion 86-7, 93, 98, 100, 112 Nylon (PA) 26
drop breakup 107
Mindel 437 Oleflex 262
Miscibility 38, 52, 70, 75, 86, 88, 93, 100, 104, Oprum 262
117, 119, 132, 136 OrgalIoy 306
definition 82 Organil 209
flow of 104,110-1,114-5 Organosilicone polymers 28
Miscible blends 104, 110, 155, 159--61, 163, Organosols 39
175,179,181,461,483. See also Molecular Orgater 335
composites Oropon 22
of PA 288,304-5,315,320,322-4,329, Ostromislensky, Ivan I. 18,23,72, 140-1
332-3,336 Ostwald ripening 107
ofPAES 130 OxyBlend 202
of PARA 447-9 OxyClear 202
of PC 387--s,3%,398
of PEST 354-5,359,361-2,367,373,377, PA. See Polyarnides
380 PA-1/PA-2 blends 286,323-4
Index 651
PA-12 97 PAr/PPS blends 449
PA-6 26,95,97,102,295,304,338 PARA blends 248,280,288,308,332,334,
PA-66 26,40,95,97,304,338 430-1,447-8
PA-ll 97 PARA. See Aromatic polyamides
PA/ABS blends 169-70,286,298-9,310 PARA/ABS blends 299
PA/COPO elastomeric blends 304 Paracril 197
PA/CfBN elastomer blends 303 Paraloid. See Acryloid
PA/elastomer blends 274-5,295-304 Parkes, Alexander 132-3
PA/EPDM blends 295-7 Parkesine 10
PA/EPR blends 295-7 Particular rheological composition
PA/EVAI blends 314 (PRC) 100
PA/GMA-eontaining copolymer blends 312 Patfoort extruder 95, 144,472-3
PA/ionomer blends 290-3 PBI miscible blends (molecular
PA/LCP blends 336 composites) 449-52
PA/PAI blends 336 PBI/PEEK blends 451-2
PA/PAr blends 329 PBT/ ABS blends 171
PA/PARA blends 324-5 PBT /MMMA for pearl-like luster 226
PA/PBT blends 328-9,366 PBT/PC blends 172,353,362, 371, 391
PA/PC blends 330-3,389 PBT/PCI blends 362
PA/PDMS Rimplast elastomeric blends 304 PBT/PET blends 339,361
PA/PEA blends 335-6 PBT/PHT blends 361
PA/PEG 285,317 PC/ ABS blends 163-7, 3~7
PA/PEI blends 336 PC/acrylics blends 387
PA/PEST blends 32~33, 327-9, 365-7 PClfluoropolymer blends 3%
multicomponent 330 PC/LCP blends 398
PA/Phenoxy blends 334-5 PC/PA blends 96,389
PA/PO blends 286,289-90 PC/PAl antistatic blends 397
PA/PO rigid blends 272-3,304-9 PC/PAr blends 370
PA/PO-MA blends 293 PC/PBT blends 87, 372
PA/POM blends 325-6,365 PC/PDMS homogenous film 394
PA/PP rigid blends 272-3 PC/PEl blends 397-8
PA/PPE blends 317-23, 41~17 PC/PEST blends 339,367-74,389-91,393
PA/PPS blends 333-4 PC/PET blends 371, 372, 374, 393
PA/PSF blends 333 PC/PMMA blends 225, 387
PA/PVAI blends 314-7 PC/PO blends 275-6, 384-5
PA/PVDF blends 335 PC/polyimide blends 39~7
PA/SB-block copolymers blends 310--11 PC/polysulfone copolymer (PC-PSF) 195
PA/SBS blends 297-8 PC/POM blends 393-4
PA/SEBS blends 297--8 PC/PP blends 275-6
PA/SMA blends 189,311 PC/PPE blends 391-3
PA/Specialty Polymer Blends 333-6 PC/PS blends 385
PA/Starch - biodegradable 317, ~2 PC/PSF blends 394-6
PA/styrenics blends 309-12 PC/PTFE 396
PA/TPU blends 313-14 PC/PVC blends 388
PA/vinyls blends 313 PC/SEBS blends 188
PAES/PEEK blends 441 PC/siloxane resin blends 394
PAES/PO for high flow 282 PC/styrenics blends 385-7
PAI/PA blends 336 PC/TPU blends 388
PAI/PE for moldability 253 PCT/PPE blends 427
PAI/PPS blends 432 PE/acrylic blends 242-3
PAI/PSF blends 438 PE/CSR crosslinkable blends 232-3
Palieme theory 112 PE/elastomer blends 231-4
PANI conductive blends 467--8 PE/EPDM blends 234-5
PAr/PA blends 329 PE/EPR blends 234-5
PAr/PARA blends 367 PE/ionomer blends 233-4
PAr/PC blends 370 PE/LCP for high flow 253
PAr/PEST blends 340, 364 PE/PA blends 247-8
PAr/PET blends 364 PE/PC blends 248-50
PAr/PMB miscible blends 362 PE/PE blends 235-6
652 Index
PE/PEST blends 251-2 PHB biodegradable blends 480, 483
PE/pm blends 25,233 Phenol-formaldehyde (PF) 9,64,133
PE/POM blends 252 Phenolics 19
PE/PP blends 232, 239-40 Phenoxy (Polyhydroxyether of bisphenol-
PE/PPE blends 250-1 A) 250, 334-5, 358, 440, 462
PE/PS blends 94, 2~1 PIILCP blends 442
PE/SAN for crack resistance 241 Plaseon 19
PE/Specialty resin blends 253 Plasticization 24,39, 194
PE/styrenics blends 241-2 Plastics
PEA/PSF 440 consumption 6
Pebax 336 production 6, 40
PEEK/PAES blends 441 world production 3, 5
PEEK/PSF blends 439 Plastisols 39
PEl/PBI 381 Plastomer 75, 260
PEl/PC blends 397-8 Plateau modulus 72, 123
Pelprene 361 Plexiglas (PMMA) 22,219
Perlon 26,27,40 Plexigum 22
Permeability reduction 244--5, 314-7 PMA/PVAc blends 219
PES blends 436-40, 448 PMMA biodegradable blends 482-3
PEST. See Thermoplastic polyesters (PEST) PMMA/acrylics blends 219-23
PEST/poly (p-methoxy phenyl methacrylate) PMMA/elastomer blends 224-5
- miscible blends 359 PMMA/EVAc-VC transparent & tough
PEST. See Thermoplastic polyesters (PEST) blends 222
PEST/ ABS or AAS blends 352~ PMMA/PA blends 227-8
PEST/acrylics blends 357~ PMMA/PC blends 225-6
PEST/ elastomer blends 345-52 PMMA/PEST blends 226-7
PEST/inorganic glass blends 382-3 PMMA/PGI for automobile 223
PEST/LCP blends 382 PMMA/PO blends 224
PEST/PA blends 365-7 PMMA/poly(meth)acrylates blends 221-3
PEST/PAr blends 364-5 PMMA/POM blends 228
PEST/PC blends 338,367-74,389-91 PMMA/PPE blends 227
PEST/PEA blends 382 PMMA/PVC blends 223--4
PEST/polyimide blends 381-2 PMMA/PVDF blends 218, 228-9
PEST/polysulfide blends 379-80 PMMA/SAN blends 221
PEST/ polysulfone blends 380-1 PNDB 108
PEST/POM blends 37S-9 PO/PA blends 96
PEST/PP blends 276-8 PO/PS blends 146
PEST/PPE blends 374-8 PO/PTOblends 232
PEST/PPS blends 379 PO/PVAI for antistatic properties 245,465--{)
PEST/PSF blends 437 Poiseuille flow 116
PEST/SEBS blends 186 Poly(l, 4-cyclohexylene dimethylene
PEST/styrenics blends 352--{) terephthalate) (PCT) 345
PEST/vinyl blends 360-1 Poly(2,5, (6')-benzothiazole) (PBZ) 450
PET 97,146,350 Poly(2,6-dimethyl-l,4-phenylene ether)
blends with other PEST resins 361-3 (PPE) 465
PET/elastomer blends 339 Poly(2-eyano-5-norbomene) (PCN) 160, 210
PET/PA blends 366 Poly(butylene cyclohexane dicarboxylate)
PET/PAr 364 (PBCD) 350
PET/PBT blends 172, 338, 361, 362 Poly(butylene-naphthalene-dicarboxylate)
PET/PC blends 372, 391 (PBNDC) 338
PET /PCT blends 363 Poly(cyclohexanedimethylene terephthalate)
PET/PEN 338 (PeT) 351
PET/PHT blends 361 Poly(ethylene-2, 6-naphthalene
PET/PO blends 340-2 dicarboxylate) (PEN) 42, 337, 338
PET/SMA blends 356-7 Poly(ethylene-alt-cyclo-pentene) 76
Phase Poly(ethylene-eo-chloro-trifluoroethylene)
cocontinuity 98. See also Cocontinuous (ECTFE) 45
morphology Poly(ethylene-eo-vinyl acetate) (EVAc) 208
inversion 98 Poly(meta-phenylene isophthalamide) ~1
Index 653
Poly(methylmethacrylate-<:o-styrene) blends with engineering resins 389
(SMMA) 392 blends with specialty resins 394-8
Poly(vinylchloride-co-vinylacetate) Polycarbonate-polydimethylsiloxane
copolymer (PVCAc) 25,194,202,208 copolymer (PC-POMS) 39
Poly-3-octy1 thiophene (POn 245 Poly(carbon monoxide-<:o-polyolefin)
Poly-a-methylstyrene 149 (COPO) 15, 51, 129-32, 151, 186-7, 198,
Poly-f-eaprolactam 40 211-12,304,335,405,483
Poly-p-methylenebenzoate (pMB) 52 Polycast 201, 218
Poly-p-methylstyrene 145 Polychloroprene (CR) 207
Polyacetylene (PAc) 245 Polychlorotrifluoroethylene (PCTFE) 396,
Polyacrylic ester imide (PAEI) 52 434
Polyacrylonitrile (PAN) 23 Polycycloalkene (PCO) 52, 235
Polyalkene plastomers (POP) 32 Poly-1,4-
Polyalkenes (PO) 304-9, 384-5 cylcohexylendimethanoleterephthalate
blends 180-1 (Pen 337, 426
recycling 475-6 Polydimethyl-diphenyl siloxane
Polyalkyl methacrylates 220 (POMDPhS) 321
Polyalkyloxazolines 331 Polydimethylsiloxane (POMS) 46, 264, 352,
Polyamideimides (PAl) SO, 51, 336, 3%, 431, 394,405,433
432 Polydiphenylsiloxane (POPS) 407
Polyamides (PA) 26,39-41,247-8,274 Polyester (PESn blends 337-83
biodegradable or recyclable blends 317 Polyester-earbonates (PEC) 277
biodegradable polymer blends 476-7 Polyester-polyamide 39
blends 185-6, 285-336 Polyester-polyether 39
early blends (up to 1970) 285-7 Polyesteramides (PEA) 366, 382
recycling 476-7 Polyether sulfone (PAES) 253,282
with engineering resins 287 Polyetheramide (PEA) 335-6
blends with reduced permeability Polyetheretherketone (PEEK) 48, 103, 432,
314-17 436,~3
commodity resin blends 287-317 Polyetherimide (PEl) ~1, 282, 336, 381-2,
elastomeric blends 303 431,438,443-7
engineering resin blends 317-33 Polyetherimine (PElm) universal
reactively-toughened blends 293-5 compatibilizer 471
specialty polymer blends 333-6 Polyethersulfide 207
toughened blends 288-95 Polyethersulfone (PES) 47, 163, 394
Polyaniline (PANt) 245,467-8 Polyethylacrylate (PEA) 302
Polyarylamideimide (PAl) 253 Polyethyleneimine (PEtI) for odor
Polyarylate (PAr) blends 42,47-8,329,337, elimination 476
340,364-7,370,448-9 Polyethylenenaphthate (PEN) 42
Polyarylates (polyarylphthalates) (PAr) 364 Polyethylenes (PE) 25-6, 28--33, 230-53,
Polyarylene sulfide (PPS) 46-7, 428--36 255-8
Polyaryletherketone (PAEK) 48, 424 biodegradable blends 246-7
Polyarylethersulfone (PAES) 47, 394, 424, !:>lends with other commodity
436,441 polymers 243-4
Polyarylsulfone (PSF) 436 blends with reduced permeability 244-5
Polybenzimidazoles (PBI) 52, 450 commercialization 12
Polybismalcimide (PBMI) 52 electrically conductive blends 245
Polybisphenol-A-terephthalate (PAr) 42 evolution 25-6, 28--33
Polybutadiene rubber 21 impact properties 257
Polybutylene naphthalate (PBN) 337 market share 28, 40
Polybutylene terephthalate (PBn 39,41-2, Polyethyleneterephthalate (PEn 27, 41, 42,
186,251,277,327-9,337,342-5,348--50, 49, 97, 146, 186,226,251,277,327,337,
378 350
Polybutylene terephthalate-isophthalate Polyethyleneterephthalate glycol (PETG) 97,
(PBT /1) 337 468
Polycaprolactone (PCL) 127, 325, 348 Polyethyleneterephthalate-isophthalate
Polycarbonate of bisphenol-A (PC) 39, (PET/I) 337
42-3,46,186-8,203,330-3,384-98 Polyethyloxazoline (PEOX) 269, 331
blends with commodity resins 384-8 Polyglutarimide (PGI) 314
654 Index
Polyglycolides 440 Polymeric modifiers 194
Polyhexanethyleneterephthalate (PHT) 337, Polymeric systems, nomenclature of 78--82
361 Polymerization 3, 17, 18,29,66-79, 140, 141,
Polyhydroxybenzoate (PETHB) 49 213
Polyimidazipyrolone (PIPO) 52 anionic 73
Polyimides (PI) 49-50, 213, 297, 396-7 beginnings 63
Polyimidesulfones (PISO, PISU) 50, 52, 3%, condensation 3, 25-7, 42-3, 47-9, 51, 65-6,
431 68--9,72,78,133
Polyisobutylene (PIB) 202, 207, 233, 2~9 developments 63-76
Polyisoprene (PI) 207 emulsion 18,21-24,37,72, 194
isomers 95 new methods 76
Polymer alloy. See Polymer blends interfacial 40, 43, 88
Polymer blends 121 metallocene 6, 29-35, 37, 51, 7~, 136
benefits and problems of blending 85-97 of ethylene 37
commercial development 118--22 of HIPS 21
commercial names or identity 577-612 radical 72
cost of 117 reactions 66-77
definitions 81-2 Ziegler-Natta 73-4
development 117-36 Polymethylacrylate (PMA) 22,219
discoveries and developments Polymethylmethacrylate (PMMA) 22, 93,
chronology 63Q--43 150, 195,200, 203, 210, 219-29
economy of blending 117 Polynorbornene 76
clasticity of 115 Polyol 295
evolution 127-36 Polyoxydiazobenzimidazole (POBI) 52
examples of major types 613-29 Polyoxycyanoarylene (FOCA) 253
history 128--32 Polyoxymethylene (POM) 39,43-4, 101, 213,
performance 122-7 252,325-6,378,399-406,419
procedure for blends' development blends with commodity resins 400-3
117-22 blends with engineering resins 403-5
reasons for blending 85 blends with specialty resins 405-6
terminology 81-2 Polyparaphenylenes (PPP) 245
Polymer Poly-p-methylenebenzoate (PMB) 52
commercialization dates 11-15 Polyphenylene benzobisthiazole (PBZT) 450
compensation of properties 120 Polyphenylene ether, or poly(2, 6-dimethyl-l,
consumption 3, 5 4-phenylene other) (PPE) 6, 39, 44, 46,
definitions 3-4 181-4,250-1,278--9,317-23,373,391-3,
early developments 66-77 407-27,465
early discoveries 64-5 blends with commodity resins 409-15,
history ~, 64 416-20
bookson 6-7 blends with fluorinated polymers 422
industry 8--52 blends with semicrystalline polymers 409
early period: 180(H945 8--28 blends with specialty polymers 420-5
growth period: post-1945 28--52 blends with specialty resins 420-2
international abbreviations 559-76 miscible blends 425-7
market share of different resin 28 Polyphenylene sulfide (PPS) 253, 333-4, 437
modification of properties by blends with fluoropolymers 434
blending 119-20 blends with inorganic glass 435-6
networks, definitions 78--82 blends with polysiloxanes 433
new types 76-7 blends with semicrystalline polymers 409
processing 10, 69, 78, 79, 118, 129 blends with styrenics 354
development 53-62 Polyphenylene sulfide sulfone (PPSS) 379
production 3,5,40 Polyphenylene terephthalarnide (PPTA) 450
science Polyphenylethersulfone (PPSP) 47
as special discipline 66 Polyphthalarnide (PPM) 48, 52
beginnings 63-4 Polypropylene (PP) 34-5,180,239-40,254-82
development 63-77 amorphous (aPP) 254
history 63 biodegradable blends 270
systematic names 80 blends with other commodity resins 270
traditional names 78, 80 blends with other polyalkenes 259-i)(}
Index 655
electrically conductive blends 271 with PPE 404-5
engineering resin blends 271-9 Positively deviating blends (POB) 96, 104,
high melt strength 35 108, 109, 113
isotactic 254 Positive-negative deviating blends
specialty polymer blends 279-82 (PNDB) 108
syndiotactic (sPP) 6, 15, 34-5, 74, 76, 254, Positron annihilation 71
265,269 PP/ acrylic elastomer blends 267--8
toughened blends 271 PP/ chlorinated elastomer blends 265-6
Polypropylene terephthalate (PPT) 337 PP/ elastomer blends 260--8
Polypyrrole (PPy) 127, 245, 467 PP/EPOM blends 261-5
Polysaccharide blends, biodegradable PP/EPR blends 258,261-5
480-2 PP/EVAc blends 269-70
Polysiloxanes 194,433 PP/HDPE blends 257
Polystyrene (PS) 21. 36-8, 64, 93, 139-93,240 PP/LCP blends 102,281-2
syndiotactic (sPS) 15, 37--8, 75-6, 139-40, PP/LLOPE blends 25S--S
475 PP/PA blends 258,271
Polysulfide elastomers (Thiokol) 18 PP/PARA blends 280
Polysulfone (PSF) 46,47, 163, 277, 333, 422-3 PP/PC blends 275-6
blends with fluoropolymers 439 PP/PE blends 25S--S
diverse blends 440 PP/PEST blends 276--8
Polysulfone-POMS 39 PP/Pffi blends 258-9
Polytetrafluoroethylene (PTFE) 45, 280, 434 PP/POM blends 279
Polytetramethyleneterephthalate (P1MT) 41 PP/PPE blends 278-9
Polythioethersulfone or PP/PS blends 268
polyphenylenesulfide-sulfone (PTES, PP/PVC blends 270
PPSS) 52, 379, 421, 430 PP/rubber blends 260
Polytiophenes 245 PP/SBR blends 267
Polytransoctanamer (PTO) 232, 320 PP/ styrenic elastomer blends 266-7
Polyureas 18 PPE/HIPS 193
Polyurethane ether-ester type 39 PPE/LCP blends 424-5
Polyurethanes (PU) 27 PPE/PA blends 96,185,318-19,320-3,
Polyvinyl acetal (pVA) 221 416-17
Polyvinyl acetate (PVAc) 24, 194, 315 PPE/PBT/PC/SEBS/blends 96
Polyvinyl alcohol (PVAI) 24, 95, 285, 300 PPE/PC blends 419
Polyvinyl bromide (PVB) 64 PPE/PE blends 414
Polyvinyl butyral (PVBO) 25 PPE/PEOA blends 425
Polyvinyl chloride (PVC) 23, 39, 64, 127, PPE/PEST blends 374--8,391. 392, 417-19
194-214 PPE/PET/PC/EGMA blends 96
Polyvinyl formal (PVFO) 25 PPE/PI blends 423--4
Polyvinyl halides 23--5, 45 PPE/PMMA blends 414
Polyvinylidene chloride (PVOC) 24, 215-18, PPE/polysiloxane blends 425
224,315 PPE/POM blends 419-20
Polyvinylidene fluoride (PVDF) 24, 45, PPE/PP blends 415
216-17,228-9,315,335,434 PPE/PPS blends 420-2
Polyvinylphenol (PVPh) 361, 405 PPE/PS blends 191-3,408-14,425
Polyvinylpyrrolidone (PVP) blends 214 PPE/PSF blends 422-3
POM Blends with PPE/PTO blends 320
commodity resins PPE/styrenics blends 354
with acrylics 400-1 PPE/vinyl resin blends 415
with EGMA 114 PPS Blends with Polysiloxanes 433
with PMMA 114 PPS Commercial blends 428-9
with PP 279 PPS/fluoropolymer blends 434
with PS 189, 400 PPS/inorganic glass blends 435-6
with TPU 401-3 PPS/LCP blends 435, 461
engineering resins PPS/PAI blends 432
withPA 326 PPS/PAr blends 430
with PC 393--4 PPS/PARA blends 430-1
with PEST 399 PPS/PEK blends 432
with POM 399,403--4 PPS/PEST blends 380
656 Index
PPS/PI blends 431 PVC/PMMA blends 201
PPS/PSF blends 429-30 PVC/PO blends 203
PPS/SEBS moldable alloys 193 PVC/polyurethane blends 207
PPSS/PA 379 PVC/POM blends 213
PPSS/PEST 379 PVC/PVP blends 214
PPTA/PA -E molecular composites 450 PVC/TPU blends 207
Prevex 44, 408 PVDF/acrylics blends 217-18
Processing, equipment 53-62 PVDF/ engineering resin blends 218
Production of plastics 3, 5 PVDF/LCP for oriented films 216
Proteins 16-17 PVDF/PA blends 218
PS/acrylics blends 148 PVDF/PMMA blends 217
PS/EVAc recyclable blends 146
PS/modified PE blends 144-8 Q-film 42
PS/PA blends 189
PS/PC blends 189-90, 385 R-TPO 36,235
PS/PDMS 39 Radel 47
PS/PE blends 126, 144-8, 190-1 Radical polymerization 72-3
recycling 473-5 Radius of gyration 71, 92
PS/PEMA blend 150 Rayon 16
PS/PEST blends 190-1 Rayton 333, 420
PS/PMMA blends 94 Reactive compatibilization (or blending)
PS/PO blends 126, 147 94-7, 136, 186
PS/POM blends 189 Reactive extrusion 95
PS/PPE blends 191-3,410-11 Reactive injection molding (RIM) 41,60
PS/PPS blends 193 Reactive processing 293
PSF Blends 173-4,333,380-1,394-6,422-3, Reactor blending 136, 257
436-40 Reactor-type thermoplastic polyalkene. See
PSF Blends with fluoropolymers 439 R-TPO
PSF Blends with PAl, PI, or PEl 438-9 Recyclability 88
PSF Blends with PEK 430-40 Recyclable blends 317
PSF 47-8 Recycling 146-8,469-80
PSF/ ABS blends 436, 437 PA blends 476-7
PSF/LCP blends 462 PS/PE 473-5
PSF/PAI blends 438 Reinforced reaction injection molding
PSFfPC blends 394-6 (RRIM) 60
PSF/PEA blends 440 Relaxation spectrum 110-1,154
PSF/PEEK blends 439 Rheology 104-16
PSF/PEI blends 438 Rigid formulations 24
PSF/PEST blends 437 Rigid PA/PO blends 304-8
PSF/PI blends 438 Rigid PVC 24
PSF/PPS blends 439 Rigid-rod macromolecules 67
PSF/PTFE blends 439 Rigidex 253
PSIPE blends 144-8,190-1 Rilsan 335
PTFE 103, 289 Rimplast 304
PTFE/PSF 439 Ronfaloy 211
PVC blends 194-214 Rotational molding 61-2
PVC/ ABS blends 159-60,209-11 Royalite 153
pvc/capo blends 21 Roylar 27
PVC/CPE blends 203-7 Rubber blends 231-2
PVC/CSR blends 203-7 Rubber-milling technology 194
PVC/elastomer blends 202 Rubbers 4
PVC/engineering resin blends 211-14 Ryton 431
PVC/EVAc blends 200, 207-9
PVC/EVAc-VC blends 207-9 Santoprene 36, 263
PVC/MABS for enhanced miscibility 154, Saran 198
160 SBS block copolymer blends 176-89
PVC/NBR blends 195-8 SBS/SEBS blends 177
PVC/PC blends 212-13 with engineering resins 181-8
PVC/PI blends 213-14 with specialty resins 188-9
Index 657
Sdairtech 30 (SEBS) 176, 241, 247-8, 250, 266, 275,
Selar 244,314 297-8,353
Shear-induced interiayer slip 102 Styrene-g-polybutadiene 220
Shellac 4, 54 Styrene-isobutylene copolymer (psm) 285
Shellvis 251 Styrene-isoprene-butadiene (SmR) 143
Side chains 78 Styrene-maleic anhydride copolymer
Silicone resins (POMS) 27-8, 46 (SMA) 97, 175, 274, 308, 311, 347
Sirnha Robert 67,70,105 Styrene-methyl methacrylate copolymer
Simultaneous interpenetrating polymer (SMMA) 143, 148, 355
network (SIN) 133 Styrene-methyl methacrylate-glycidyl
Single-screw extruder (SSE) 12~1 methacrylate (SMMA-GMA) 165,
Single-site metallocene catalysts 6, 31, 74--6 295
SMA/ABS 175-6 Styrene-methyl methacrylate-maleic
SMA/PMMA for HOT & dimensional anhydride copolymer (SMMA
stability 150, 155 MA) 165,295
Solutions 68 Styrene-a-methylstyrene-acrylonitrile
Solvic 209 (MSAN) 163
Specialty resins and blends 44-5,188-9,253, Styrenics 21,38-9,139-93,241-2,266-7,
279-82,333-6,379-83,394-8,405-6, 309-12,352-6,385-7
422-5,428-83 Sumikasuper LCP E6000 440
Spirodilactone (SOL) 356 Sumilite 47
sPP, syndiotactic polypropylene 6, 15, 34-5, Sumiploy 440
74,76,254,265,269 Sunloid 201
Sprigg's theory 115 SUPEC 45
sPS syndiotactic polystyrene 15, 37-8, 75-6, Superex 458
139-40,475 Surlyn Ionomers 228, 338, 340, 347
Stabilization Suspensions 68
chemical 195,326,402,472-3 Syndiotactic PMMA (sPMMA) 223
of commingled polymers 147-8,246,472 Syndiotactic poly (p-phenyl styrene)
of morphology 82,87-8,180,305,319,375, (sPhPS) 75
391,419,471 Syndiotactic polypropylene (sPP) 34, 265
Stapron 309 Synergistic effects 77, 153, 168, 181, 241, 306,
Star macromolecule 78 344,351,355,371,373,380,410,432,441
Starflam 309 Synthetic polymers 4, 133
Static dissipation 465-7 biodegradable blends 482-3
Staudinger Hermann 6, 25, 43, 66-8 Synthetic rubbers 17-18
Steady state flow 114, 15 Synthetic thermoplastic polymers 21-8
Sterically hindered amines (HALS) 261 Synthetic thermosetting polymers 19-21
Storax officinalis 21
Strain (form) recovery 112 Tafmer 32,74,466
Strain hardening (SH) 115 Tafmer A20090 359
Stress-induced fibrillation 101 Talpa 47
Styrene 21, 34 Tang-Huang equation 91
Styrene copolymers 139-93 Techniace 309
Styrene-acrylic acid copolymer (SAA) 148 Telcothene 25
Styrene-acrylonitrile (SAN) 21, 36, 93, 97, Tenite 41
148,160,209,465 Tensile strength 118
Styrene-butadiene elastomer (SBR) 139,141, Terylene (PET) 337, 447
143-4,266,297 Tetracarboxylic dianhydride (BTDA) 50
Styrene-butadiene graft copolymer Tetraethylsilane 27
(SBR) 141 Texin 388
Styrene-butadiene rubber (SEBS) 266 Thermoforming 62
Styrene-butadiene-styrene three-block Thermoplastic alkenic elastomers (TPO)
copolymers (SBS) 36, 297-8 35-6,39,260
Styrene-diene block copolymers (SBS, Thermoplastic elastomer (TPE) 39
SIS) 266 Thermoplastic polyamides 304
Styrene-ethylene bulk copolymer (SER) 144 Thermoplastic polyesters (PEST) 2fr-7, 39,
Styrene-ethylene/butylene-styrene 41-2,97,186,276-8,327,356
hydrogenated block copolymer blends with commodity resins 340--57
658 Index
blends with engineering resins 361-79 Uitrason E 47
blends with specialty resins 379--B3 Upper critical solution temperature
Thermoplastic polyurethane (TPU) 27, 228, (UCST) 149
313-14,351,356,388,401-3 Urea-formaldehyde resins (UF) 19
Thermoplastics 4 Utracki-Shi equation 91
Thermoset polyesters 20-1
Thermosets 4 Valox 41
Thiokol 18 Varnes 303
Thiourea-formaldehyde 20 Varlen 209
Time-temperature superposition 114 Vectra 454, 464
Torlon 253 Very low density polyethylene. See VLOPE
TPO 18, 39, 46, 47, 48, 51, 162 Vestolen 262
TPU/ ABS blends 173 Vestoran 426
Tradlac 438 Victrex 48, 438
Tradlon 438 Victrex PEK 220P 442
Trans amide-ester reactions 97, 327-8, Vinidur 201, 209
341-2,36!H> Vinnol 209
Transesterification 27, 42-3, 49, 87-8, 97, Vinylidene chloride-acrylonitrile copolymers
120,329,361,367-9,373,389-92,456 (VDC/ AN) 204
Transfer molding 57-8 Vinylon 20
Transparent blends 141-2,145,150,154,158, Vinyl polymer blends 177,360-1
160,170,178-9,198-200,202,204,208-11, Viscoelasticity 71-2, 104
213,217,220-3,225-6,228,231,233,238, development of theory 71
241,265,310,314-5,317,324-5,329,333, time-temperature principle 106
351,353,364,369,377,380,394,398,407, (WLF) time-temperature shift factor 92
439,447-9,458,477 Viscosity 108
Triax 309 concentration dependence of 108-9
Triglycidyl isocyanurate (TGIC) 348 ratio 104
Trogamid 41,48,448 Viton 45
Trolitul 18, 21 VLOPE 30, 33, 234
Trolitur 139 Vulcanization 10
Troluloid 24 Vynaprene 202
Tufrex 211 Vynite 197
Twin-screw extruder (TSE) 121. See also
Extruders Xenoy 367
Two roll mill, see Compounding Xydar SRT-500 442
Two-dimensional deuteron NMR 114 Xylenols 192
Two-phase systems 105 Xylonite 10
Xyron 44, 408
U-Polymer 42, 48, 338
Udel 47, 394, 438 Yield stress 112. See also Rheology
Uitem (PEl) 50, 397
Ultra-high molecular weight HOPE Ziegler, Karl 29
(UHMWPE) 29, 287 Ziegler-Natta
Ultra-low density polyethylene (ULOPE) 30, catalysts 6, 29, 34, 37, 73, 230, 234, 235
33,177,233 anionic polymerization 73
Ultramid 288, 289, 309 Zytel 288,300,309, 288

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Commercial Polymer Blends

runt SPRINGER-SCIENCE+BUSINESS MEDIA, B.V.

Thomson Science is a division of International Thomson Publishing

3 Development of polymer processing S3

4 Development of polymer science 63

5 Nomenclature of polymeric systems 78

6 Reasons for, benefits and problems of blending 85

9 Development of polymer blends 117

10 Styrenics: polystyrene and styrene copolymers 139

12 Polyvinylidene halide blends 215

13 Poly(methyl)methacrylate, PMA and PMMA, Blends 219

14 Polyethylene blends 230

16 Polyamide blends 285

17 Polyester blends 337

18 Polycarbonate blends 384

18.3.2 PC/PSF blends 394

19 Polyoxymethylene (acetal resins) 399

21 Specialty resin blends 428

22 Recycling and biodegradable blends 469

Montreal, November 1996

In the Appendices, the following abbreviations will be used:

Table 1.1 World production of steel and plastics for 1992

Table 1.2 Early use of natural polymers

Thousand years BC Polymer use

WORLD PLASTICS PRODUCTION 1990 - 1990

poirits - data; lin~ - population growth eq.

1900 1920 1940 1960 1980 2000

2.1 EARLY PERIOD: 1800-1945

2.1.1 Modified natural polymers

Year Acronym Polymer Producer

Year Acronym Polymer Producer

1958 UHMWPE ultra high molecular weight Hoechst A-G./Himont

Year Acronym Polymer Producer

Cellulose ethers and esters

2.1.2. Synthetic rubbers

Polyureas and polysulfides

2.1.4 Synthetic thermoplastic polymers

Vinyl and Vinylidene Halides

Thermoplastic polyesters (PEST)

2.2 GROWTH PERIOD: POST 1945

2.2.1 Commodity resins

Table 2.2 World market share by resin type in 1992

No. Resin type Market share (%)

Figure 2.1 Flexural modulus versus density of polyethylenes.

Multi-site catalyzed LLDPE

Single-site catalyzed LLDPE

The newest, single-site metallocene catalysts (e.g., the constrained geometry

Thermoplastic olefin elastomers (TPO)

2.2.2 Engineering resins

Table 2.3 Plastics production for 1988 (kilotons, kt)

Resin Canada USA Europe Japan

2.2.3 Specialty polymers

Liquid crystal polymers

To convert the diverse polymeric materials into marketable products, an entirely

Table 3.1 Development of mixing and extrusion technology

Technology Year Event

3.3 COMPRESSION MOLDING

3.4 TRANSFER MOLDING