Professional Documents
Culture Documents
Commercial Polymer Blends Book
Commercial Polymer Blends Book
Commercial
Polymer Blends
L. A. Utracki
National Research Council of Canada,
Industrial Materials Institute,
and
Department of Chemical Engineering,
McGill University,
Montreal, QC,
Canada
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
Part Two
Technical and Economic Rationality for Polymer Blending 83
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
Part Three
Commodity Resin Blends 137
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
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
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
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.
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.
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.
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.
...........................:. : .
. ..
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).
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.
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
Early period: 1800-1945 17
ago (namely the use of UV-crosslinkable resins for embalming or molding of every-
day objects, or of crosslinkable albumin in mortar).
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.
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
Early period: 1800-1945 21
clear, glass-like abrasion-resistant resins were initially used exclusively for surface
coatings, and later also as molding powders.
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
Early period: 1800-1945 23
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.
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).
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).
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-
10"
-e:.
( II
(/)
:h~
::>
Cl
0
~
....J
~102
::>
><
w
....J
U.
10'
860 900 940 980
3
DENSITY (kg/m )
~~ ------- -----
120 - - - -- - - 120
--~
I-
Z 100 100
~
C>
z
5w 80 80
~
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).
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
Growth period: post 1945 35
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.
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.
Growth period: post 1945 37
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
Growth period: post 1945 39
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.
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
Growth period: post 1945 41
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
Growth period: post 1945 43
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.
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).
Growth period: post 1945 47
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-<I>-O--<I>-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.
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
Growth period: post 1945 51
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
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
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).
56 Development of polymer processing
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.
3.8 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.
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
68 Development of polymer science
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).
Early polymers and polymerization reactions 69
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.
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
Early polymers and polymerization reactions 71
(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
72 Development of polymer science
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).
R-CH-X
I
R CH 2
\ /
/ ,,
/ \ ,, ,,
/
Ti AI CH 2=CHX Ti AI
,, ,
\ ,,
\
~
/ /
/
/
R /
R
@ CH 3
I
Zr + -( -AI-O -) -
"CI
n
@
Structure 4.2 Mettalocene catalyst
Early polymers and polymerization reactions 75
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).
76 Development of polymer science
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(P<I>3hCh catalyst leads to living telechelic poly-
mers that can be used for block copolymerization and diverse end-eapping.
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
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
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.
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:
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
88 Reasons for, benefits and problems of blending
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
Figure 6.1 Density profile across the interface, defining the thickness of the interphase (after
Helfand and Tagami, 1971).
90 Reasons for, benefits and problems of blending
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.
92 Reasons for, benefits and problems of blending
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.
Table 6.2 Chemical processes for interchain copolymer formation during reactive
blending
(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).
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).
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).
Flow-imposed morphology 101
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)
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.
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).
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.
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)
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.
(8.4)
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
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.
1.5
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
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)
(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)
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):
:
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).
8.12 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
• 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.
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
122 Development of polymer blends
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.
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
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
126 Development of polymer blends
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.
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
132 Development of polymer blends
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-
Outline of polymer alloys and blends evolution 133
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
134 Development of polymer blends
UNI'l'ED STATES PATENT OFFICE.
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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.
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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).
10.3.1 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
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polyalkene blends (Morrow et al., 1994).
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-
ABS and its blends 159
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.
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-
166 Styrenics: polystyrene and styrene copolymers
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.
ABS and its blends 167
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.
168 Styrenics: polystyrene and styrene copolymers
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
178 Styrenics: polystyrene and styrene copolymers
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
SBS block copolymer blends 179
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
180 Styrenics: polystyrene and styrene copolymers
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
SBS block copolymer blends 181
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).
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
182 Styrenics: polystyrene and styrene copolymers
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).
SBS block copolymer blends 183
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).
184 Styrenics: polystyrene and styrene copolymers
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).
SBS block copolymer blends 185
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).
186 Styrenics: polystyrene and styrene copolymers
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
SBS block copolymer blends 187
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
~
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).
188 Styrenics: polystyrene and styrene copolymers
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).
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.
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).
198 Polyvinylchloride
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).
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.
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).
214 Polyvinylchloride
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).
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.
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.
•
14.1.2 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).
~~
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).
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).
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
250 Polyethylene blends
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).
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).
465
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).
PPIEPR blends
7
l
5
o 40 80
w (wt % EPR)
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).
30 1.5
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0 COMPATIBILIZERS 0.9
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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».
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
PP/engineering resin blends 275
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).
15.13 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).
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.,
290 Polyamide blends
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
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
294 Polyamide blends
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).
PA/commodity resin blends 295
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).
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
(Asahi-Dow Ltd., 1981).
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
PNcommodity resin blends 299
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.
300 Polyamide blends
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
PNcommodity resin blends 301
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).
302 Polyamide blends
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
PA/commodity resin blends 303
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).
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).
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).
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
(Asahi-Dow Ltd., 1981).
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
312 Polyamide blends
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).
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
328 Polyamide blends
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).
PNengineering resin blends 329
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).
330 Polyamide blends
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).
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).
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
350 Polyester blends
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
PEST blends with commodity resins 351
(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).
352 Polyester blends
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).
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).
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.
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).
432 Specialty resin 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).
21.4 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
444 Specialty resin blends
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).
446 Specialty resin blends
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).
21.6 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.
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.
21.9.1 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.
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
472 Recycling and biodegradable blends
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.
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,
480 Recycling and biodegradable blends
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).
22.2.1 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.
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).
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Appendix I
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
Abbreviation Description
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
Abbreviation Description
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
Abbreviation Description
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
Abbreviation Description
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
Abbreviation Description
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
Abbreviation Description
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
Abbreviation Description
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 [-<I>-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
Abbreviation Description
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
Abbreviation Description
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
Abbreviation Description
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
Abbreviation Description
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
Abbreviation Description
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
Abbreviation Description
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
Abbreviation Description
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
Abbreviation Description
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
dimensional stability,
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
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
dimensional stability,
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
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
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.