Introduction to Polymer Science and Chemistry A Problem Solving Approach Manas ChandaPunt in 2006 by ‘por & race Goep = 000 Broken Sound Pray NW, Sut 300 Boca Raton, FL 334872742 1 2006 by Talo & Francs Gro, LLC (Cm Presi ing of Tylor & Fels Crop No cls ail U.S. Government works Pred inthe United Sts of Amerie om ace paper wosTes4szl TeurtsionlStandd Book Number 10 02493.7384.0(Hadcov) Themaional Stunard Bock Nuner-13 S75.08488-7384 (Hadzoven) “Tis book coins infomation oben rom ate aad ily regarded sures. Rept mattis “Good it poson and sores rine, A wide varity f references ae lied. Resomable ors eS bere alae we pobln eel dam and infrmation, bot the aor andthe pulser cao sun responsi forthe ay of all mato for he consequences of ei se, 1 pat of is book my be pine repaid, tansnited,o ized in any form by any elect, ‘Recines ot otter means now known bear imeted ecg pooropying, oii, a ‘Trdg cin ay ifort storage o evel rye, witout writen pemison Som th publisher Fe prison opetocopy ox we mses letra fom hs work, plete aces ww coprghicom (tnpurwwncopyHeitcon? ce contact he Cope Chrce Cente, Ine, (CCC) 222 Rosewood Dev ‘Damen, MA 01928, 978 750-840, CCC 8 ot for gro ogaizaion at proves Brees and reseuton fr wniey of aren oregon hake boon gran phorcopy Tense bythe CCC 9 spate ‘ate of payment as bee range “Trademark Notice: Pott or crprt ns may be ademas oc gisred ademas, ol a wed oly {cries nxn witotinet nog Library of Congress Gataloying-in-Publcation Data ‘Cnlog reso aval rom the Library of Congress informa =sss2-"" “Bylo rai and the CRC Press Website at inte hie cinamapic. — RepuiwwwrcrepresscomBeings reper Dedicated to the memory of my beloved father and mentor Narayan Chandra ChandaPreface Generally speaking, polymer science isthe science of polymers in all is aspects and itis beyond the scope of a single textbook. In writing a polymer science book the author therefore has to be very selective, keeping in view the reader ship he wants to reach out to. The present book, which has been written keeping in mind the student with chemistry knowledge af atleast undergraduate level, is, designed to serve primarily as the text fora senior-level undergraduate ora begin- ning graduate-leyel course in polymers dealing with basic aspects of polymer sci- ence and polymer chemistry with an emphasis on polymerization kinetics. Those ‘opics have been discussed that may lay the foundation of polymer science and chemistry built on organic chemistry and physical chemistry from which all as- pecs ofthe subject are developed. The book also keeps in view the needs of many students, researchers, and professionals, who enter the field of polymers with ttle background in polymer science and need to educate themselves by self-study in its basic principles and methodologies. My experience in teaching the subject over several decades has taught me the importance of making questions and answers an integral part of discussion on any topic. A question asked during the discussion, oF even ahead of it, excites the learner's mind and rouses his eagemess to probe, thus making the process of learning more thorough. It is this conviction that motivated me to adopt the un- usual approach of lacing up the polymer text with questions and answers at every step of the development of a theory or concept. My experience in teaching bas also taught me the great value of dealing with numbers to deepen the understand ing. Therefore, most of the problems with which the text is studded are chosen to be of numerical type. The same is true for many exercise problems appended at the end of each chapter. Each such problem is also provided with numerical answers for the reader to compare with his own, ‘The book has ten chapters in all and these fall into two distinct groups — the fist four chapters comprising one group introduce the reader to polymers and their basic characteristics, both in solid state and in solution, and the next six chapters ‘comprising the second group are all concerned with various polymerization eac-tions, mechanisms, and kinetics. This division is, however, notional and isnot ‘made explicit by numbering the two groups of chapters se Convenience a single sequence of numbers is sed throughew we Chapter | is devoted to intoductory cone and dfn, eae Chapter 2 deals with physical and molecular aspects of polymers, than tins tno smolectar shape and siz, distinctive characteristics, conformation wa enti tational behaviog, tut fests, morpholony, thermal wanuert hen ena, and relaxation properties, Chapter 3 discusses polymer solutes aheros the emphasis being on thermodynamics, phase equilibria, solubility, swctiee ie tional properties, and viscosity. Molecular Weight determination sane ee af the ist steps of polymer characterisation nd central pone oto, mer scence, mostly imvoves analysis of polymers in solution, Tie a tote is therefore devoted to polymer molecular Weithts with ogy gute ent le tals of molecular weight stasis and methods of measurermeny than gigi, and significance. The chemistry part ofthe book focusing 0 polymer anisms, and kinetics stars with Chapter 5. Five main types of neteneten, sac annie Sep feral i) oa RODIN (chain), and sing opening — mania ee in five essentially self- contained chapters. Copolymerization that may involve any of qhewe polymer tention mechanisms is included in respective chapters, an ence eee pe radical chain copolymerization which, in view of ts great praca importance tnd considerable theoretical development tat hasten ince rare been accorded the space of one full chapter. While polymerizaticn tnnacines been characterized onthe basis of mechanisms and kinetic fequsey capo een placed on understanding te ection prams why eens as twolling polymerization rates, degree of polymerization, and structural features, such as branching and crosslinking. " Tn wing his book, Ihave received much nspition and yqlyle glance from the following wellknown polymer texts listed alphateratyy“aleeek, H.R. and Lampe, F. W., Contemporary Polymer Chenisiny: Perce Hall Be, alevood Cf, New Jersey, 199; Bllmeyes Ie, EW. Text op Pobmer Science, John Wiley, Now York, 1994; Cowie JMG. Poigae coe Pobmer Pos of Moder Materials, Blackie, SEW and Londo gh nt Principles of Polymer Chemistry, Corel University Press, hace i985; Ghosh, B, Polymer Science and Tecnology of Plastics and Rubbers ne esac nak, New Det, 1990; Hiemenz,P,Pobymer Chemin, Maret Bela ons Nak, B, Inroductionto Macromolecular Scene, oba Wiley, New aor aoe te G., Principles of Polymerization, Yon Wiley. New York, 1991" Romer, P and Meri, E. W., Polymer Synthesis, Huthig & Wepf, Basel, 1936. Rodriguez, Fy Principles of Polymer Systems, Tata Mer Hil, New Det Renee k Parately, Instead, for ation reactions, mech-The Blements of Polymer Science and Engineering, Academic Press, Orlando, Florida, 1982; Seymour, R. B. and Carraher, Je, C. E., Polymer Chemistry: An Introduction, Marcel Dekker, New York, 1992; Williams, D.J., Polymer Science ‘and Engineering, Prentice-Hall, Englewood Cliffs, New Jersey, 1971; and Young, RJ. and Lovell, P. A. dntroduction to Polymers, Chapman & Hall, London, 1990. However, I should make a particular mention of Odian’s Principles of Polymer- ‘zation, te first edition (MeGraw-Hill, New York, 1970) of which appeared when 1 was sila student and it made a marked impression on me, Another book which influenced me greatly was Rudin's The Elements of Polymer Science and Engi- neering, a prescribed text at the University of Waterloo, Canada, where I taught ‘during a sabbatical year (1985-1986) ‘There may be a question: why another book on polymer science and polymer ‘chemistry when there ae so many’? There are two reasons. During my teaching ‘of polymer science and chemistry over the past three decades involving extensive interaction with students, I have always felt that learning becomes much easier, ‘especially for self-study, if problem solving is integrated with the text. Such an effort has been made in the present book. The second reason is the advent of 1 number of new concepts over the past two decades, some of them being very recent, which have enriched polymer science considerably. The present book pro- Vides an opportunity to include some ofthese, such as supramolecular polymer- ization (Chapter 1), hyperbranching (Chapter 5), photoemulsion polymerization (Chapter 6), “zrafting from” polymerization and polymer brushes (Chapter 6), Living/controlled radical polymerization (Chapter 6), metallocene-based Ziegler- [Natta catalysts (Chapter 9), ironobilized metallocene catalysts (Chapter 9), and oscillating metallocene catalysts (Chapter 9), ‘While SI units are being used increasingly in all branches of science, non-SI units like the older ces system are stil in common use. This is particularly true of polymer science: In this book, therefore, both SI and non-SI units have been used However, in most places where non-ST units have been used, equivalent values are given in SI terms, A suitable conversion table is also provided as an appendix. ‘To move in tune with time, [took up the onerous task of preparing the en- tire book electronically. While I myself dial the tex) typesetting, formating, and page designing, I received valuable help from several students and colleagues (Ajay Karmarkar, Uma Badrachalam, and B. G. Girija) who prepared computer graphics for all diagrams, chemical structures, and chemical formula-based equa- tions. {thank all of them. I am deeply indebted to Dr. P, Sunthar, an acknowl- edged software expert on te campus, for guiding me patiently inthe use of word processing softwares during this difficult venture. In writing this book, I have been helped, directly or indiecty, by many aca- demicians. Among them I would like to mention Prof. K. F. O'Driscoll, Prof. G. L. Rempel, and Prof. Alfred Rudin, all ofthe University of Waterloo, Waterloo,‘Ontario (Canada), Prof. Kenneth J. Wynne of the Virginia Commonweelth Uni- versity, Richmond, Vieginia (USA), Prof. Premamoy Ghosh of the Univeristy of Calcutta, Calcuta (Indi, and Prof. S. Ramakrishnan and Prof. M. Giridhar, both of the Indian Institute of Science, Bangalore (India). [express my gratitude to all of them. Interaction with students whom I met over the years during my long academic career, both in India and abroad, contributed greatly to the evolution of the book to its present form featuring a unique problem solving approach. Itis not possible to thank them individually asthe number is too large. However, I should mention, ‘gratefully, two of my students, Dr. Amitava Sarkar and Dr. Deepyaman Seth, ‘who were closely associated with me during my last service year atthe Institute and still have continued to help me from abroad by sending current literature in polymer science and chemistry. This has helped me in no small measure in the preparation of the book, Finally, « word of appreciation and gratitude is due to my wife Mridule and daughter Amrita, who sacrificed their share of my time for the sake ofthis book. ANAS CHANDA.Contents Preface 1 Introductory Concepts LL Basic Definitions LLL Polymer 1:12 Monomer 1.13 Molecular Weight and Molar Mass 1.14 End Groups ‘i 1.15 Degree of Polymerization 1.16 Copolymers 2 Polymerization and Functionality 1.3. Polymerization Processes 13.1 Addition or Chain Polymerization 13.2. Step Polymerization 1.3.3 Supramolecular Polymerization 1.4 Molecular Architecture 15 Classification of Polymers 15.1 Thermoplastics and Thermosets 1.6 Plastics, Fibers, and Elastomers 17 Polymer Nomenclature REFERENCES EXERCISES 2. Chain Dimensions, Structures, and Transitional Phenomena 21 Introduction 22. Polymer Chains: Structures and Dimensions 22.1 Conformational Changes 2.2.11 Polyethylene 2.2.12 Polyisobutylene 31 37 37 38 39 412.2.13. Polypropylene 2.2.2 Polymer Conformations in Crystals 22.3. Polymer Size in the Amorphous State 2.2.3.1 Freely Jointed Chains 2.2.32 Real Polymer Chains 23. Constitutional and Configurational Isomerism 2.3.1 Constitutional Isomerisim 2.3.2 Configurational omerism 23.2.1 Geometrical somerism 23.22 _ Stereoisomerism Optical Activity in Polymers ‘Tactcity in Polymers Meso- and Racemic Placements NMR Measurement of Tactcity 2.4 Crystallinity in Polymers 24,1 Structure of Bulk Polymers 241.1 Spherulites 25. Thermal Transitions in Polymers 25.1 TyandT 2.5.2. Fist- and Second-Order Transitions 2.6 Regions of Viscoelastic Behavior 2.7 Factors Affecting T, 28 Factors Affecting Tr, 29. Relation Between Ty and 7; 2.10 Theoretical Treatment of Glass Transition 2.10.1 Quantitative Effects of Factors on Tz 2.11 Chain Movements in Amorphous State 2.11.1 The Reptation Model 2.12 Thermodynamics of Rubber Elasticity 2.121 Stress-Strain Behavior of Crosslinked Elastomers 2.12.2. Nonideal Networks 2.12.2.1 Network Defects 2.12.2.2 Elastically Active Chain Sections REFERENCES EXERCISES Polymers in Solution 3.1 Tatroduction 3.2. Thermodynamics of Liquid Mixtuces 3.2.1 Low-Molecular-Weight Mixtures: van Laar Mode! 3.22. Polymer-Solvent Mixtures: Flory-Huggins Model a 43 45 41 31 31 54 34 55 35 56 37 61 6 68 68 0 0 " B 6 83 89 91 3 95 101 101 101 103 loa nt ml. nL 14 usContents 3.2.2.1 Flory-Huggins Expressions for Thermodynamic Fanctions : 3.2.2.2 Colligative Properties and Interaction Parame- tery ae Relative Vapor Pressure and y Osmotic Pressure and 3.2.2.3 Vial Coefficients Virial Coefficient and y . a 3.2.2.4. Modification of Flory-Huggins Theory Significance of wand « . ‘Methods to Determine Theta Solvents 32.2.5 Flory-Krighaum Theory 3.2.2.6 Excluded Volume Theory Expansion Factor 3.3 Phase Equilibria in Poor Solvents . 3.3.1 Upper and Lower Critical Solution Temperatures 3.4. Solubility Behavior of Polymers 35. Swelling of Crossslinked Polymers . 3.5.1 Determination ofy from Swelling 3.6 Frictional Properties of Polymer Molecules in Dilute Solution 3.6.1 Viscosity of Dilute Polymer Solutions 3.6.11 Determination of Polymer Molecular Dimen- sions from Viscosity REFERENCES EXERCISES, Polymer Molecular Weights 4.1 Introduction 4.2. Molecular Weight Averages 42.1 Arithmetic Mean 422 Number-Average Molecular Weight 42.3 Weight-Average Molecular Weight 43° Molecular Weights in Terms of Moments. 43.1 Ratio of First and Zeroth Moments 432 _ Ratios of Higher Moments 44 Molecular Weight Determination 44.1 End-Group Analysis 442 Colligative Property Measurement 442.1 Ebulliometry Boiling Point Elevation) 442.2 Cryoscopy (Freezing Point Depression) m2 124 1s rr 129 130 BI 132 133 133 134 136 139 143 144 153 157 159 160 164 168, 169) a 7 178 178 178 180 181 183 184 185 186 188 188 138xi Contents 4423 Membrane Osmometry 189 Virial Equations 192 Practical Aspects of Osmmometry 193 44.2.4 VaporPhase Osmometry . 17 Practical Aspects - : 198 4.4.3. Light-Scatering Method 200 443.1 Rayleigh Ratio . 200 4.43.2 Turbidity and Rayleigh Ratio 202 4433 Turbidity and Molecular Weight of Polymer . . 204, 4434 Dissymmetry of Seattering 208 Intrapartcle Interference 208 Scattering Factor au 4435. ZimmPlos 21 44.4 Dilute Solution Viscometry 214 4441 - Calibration of the Ma Houwink-SakradsEaua- tion 217 4442 Measurement of Intrinsic Viscosity 218 44.3 Gel Permeation Chromatography m2 445.1 _ Data Interpretation and Calibration 224 REFERENCES, 7 209 EXERCISES 230 5 Condensation (Step-Growth) Polymerization 235 5.1 Introduction : 235 5.2. Rates of Polycondensation Reactions ie a96 5.2.1 Irreversible Polycondensation Kinetics 237 5.2.2 Reversible Polycondensation Kinetics 245 5.3. Number-Average Degree of Polymerization 247 5.4 Control of Molecular Weight 250 S41 Quantitative Effect of Stoichiometric imbalance - 252 5.5 Molecular Weight Distribution (MWD) : 256 5.5.1 Breadth of MWD as 5.6 Nonlinear Step Polymerization... . 266 56.1 Branching - . 266 5.62 Crosslinking and Gelation 261 | "Average Functionality Approsch =. = 269 | 562.1 Statistical Approach : am ‘Systems with one type of branch unit. . 2 am ‘Systems with different types of branch units. . . 276 5.62.2 Model for Gelation Process 280 5.62.3 Molecular Size Distribution 5 » 280Contents 5.62.4 Post-gel Relations 5.7 Recursive Approach for Average Properties 57.1 Linear Step-Growth Polymerization 5.1.2 Nonlinear Step-Growth Polymerization 57.21 Polymerization of Ay (f > 2) 5.7.22 Polymerization of Ay (f >2)+ Bo 5.723 Polymerization of A; + EB 573° Postgel Properties... . — 5.73.1, Polymerization of Ay Gel-point Conversion Weight Fraction Solubles and Crosslink Density 5.73.2 Polymerization of Ay + Bo 5.8 Polycondensation of A (n+ m)-mer ‘occur equally. Thus, at any stage the product consists of molecules of varying sizes, giving a range of molecular weights. The average molecular weight builds tp slowly in the step polymerization process, ad a high-molecular-weight prod- tet is formed only after a sufficiently long reaction time when the conversion is more than 98% [see Fig, 1.2(a)}. In contrast, polymerization by chain mechanism proceeds very fast, a full-sized polymer molecule being formed almost instanta~ reously aftr a chain i initiated; the polymer size is thus independent of reaction time (Fig, 1.2(b)). In certain ionic chain polymerizations, which feature a fast initiation process Coupled with the absence of reactions that terminate the propa- ‘ating reactive centers, molecular weight increases linearly with conversion [Fi 120 ‘Since most (though not all) ofthe step polymerization processes involve poly- ‘condensation (repeated condensation) reactions the terms “step polymerization” tnd “condensation polymerization” are often used synonymously. Consider, for example, the synthesis of a polyamide, ic, a polymer with amide (-CONH-) as the characteristic linkage. If we stat with, say, hexamethylenediamine and adipic cid as reactants, the fist step inthe formation of the polymer (nylon) isthe fol- Towing reaction producing a monosmide HN-LCI}ENH, + HO-CACH Ae f-OH ° HNC ie NPA CH EOF + HAO ° 08) MonsuiseTawodvtory Concepts 2B ‘The reaction continues step-by-step to give the polyamide nylon-6,6. The overall reaction may thus be represented as MUN-ACH)e- Nh + mHO-EECH IZ E-OFL Oo BENCH I NH Cte OH +“ GrdthO 3 ay Poly(hexametiyleneadipamide) ‘We see that the composition of the repeating unit (enclosed in square brack- es) equals that of two monomer molecules minus two molecules of water. Thus a condensation polymer may be defined as one whose synthesis involves elimina tion of small molecules or whose repeating unit lacks certain atoms present in the ‘monomer(s) Problem 14 _Poly(hexamethylene adipamide) (Nylon-6,6) was synthesized by conden- sation polymerization of hexamethylenediamine and adipic acid in 1:1 mole ratio, Caleu- late the acid equivalent of the polymer whose average DP is 40, Anower: 0 ° Former: Exch NEO 8 n= 440 Molar mass. of repeating unit = 226 gimol Average molar mass = 440%226 + 18 or 99,458 ghmol ‘We of polymer (in grams) containing ‘one acid equivalent = 99,458, With the development of polymer science and the synthesis of new polymers, the previous definition of condensation polymer is inadequate. For example, in polyurethanes (Table 1.2), which are classified as condensation polymers, the re- peating unit has the same net composition asthe two monomers (i..,a diol and a isocyanate), which react without eliminating any small molecule. To overcome such problems, chemists have introduced a definition which describes condensa- tion polymers as consisting of structural units joined by internal functional groups“ Qhapter 1 such as a Coole ep ssside (—F NH), imide (—N.), } ‘cO- o | ° urethane (O—C—NHL), sulfide ( ater 0) i cabnteGO—G-—0), sa sime (A) nas $ $ A pgmer staying ite oc hf te oe fos s cai sci tr ane uisn tie E te et ee aes poe tiog wh er sg eae ae es a es ylvnen cpa bypobroncion se felhae ci ee wwe 0. nyc-cittc, —e fow,-g oh oy (1.10) or e-caprotactam a (afin —> Barter} -cok, | proceed ether by chain or step mechanisms, depending onthe particular monomer, reaction conditions, and initiator employed. However, the polymers produced in Eqs. (110) and (111) will be structurally clasified as condensation polymers, since they contain functional groups (@.., ether, amide) in the polymer chain, ‘Such polymerizations thus point out very clearly that one must distinguish be- ‘ween the classification based on polymerization mechanism and that based on polymer structure, The two classifications cannot always be used interchange- ably. Both structure and mechanism are usually needed in order to clearly classify a polymer, 13.3 Supramolecular Polymerization Supramolecular polymers are a relatively new class of polymers in which mono- ‘meric repeating units are held together with directional and reversible (noncova- lent) secondary interactions (Lehn, 2000), unlike conventional macromolecular species in which repetition of monomeric units is mainly governed by covalent ‘bonding. A schematic comparison of a covalent polymer and a supramolecular polymer is shown in Fig, 13.Introduetory Concepts ee ee ee ve ebayer = fmm ott ee ‘uauiAjog HonesuapH0D IGA, TT SRL so setChapter 1 = on a0 LQOHOF ~-O7 Or Om ox HL OLOd — Orr 7Or gees BOLO ~ op eOL Oyun raed amas EMC) — seer oCpo — Sanemete owas sapenarenneg ‘es STN pe oT Trauikjog wonesuapucD aoumEO} RAL SUIS ET AKL,Inuoductory Concepts ” Figure 13 Schematic representation of (a) covalent polymer and. (b) 4 supramolecular polymer (After Brunsveld et al. 2001.) @ °. NH o ‘O=C=N-R* a R som * 1= Bod OY Figure 14 Syotess of « monofunetona 2-urito-4{1H}-pyimidinone (UP3) CD and 10° M~? in CHCls) by self-complimentary quadrupole (array of, our) hydrogen bonding (2 in Fig. 1.4) prompted them to use this functionality as the associating end group in reversible self-assembling polymer systems. ‘A difunctional UPy compound, 4 in Fig. 1.5, possessing two UPy units can be easily made in a one step procedure, from commercially available compounds, ‘methylisocytosine (R = CHs) and hexyldiisocyanate (R” = CHa). The com: pound forms very stable and long polymer chains (S in Fig. 1.5) in solution as Figure LS. Prepasation of (a) UPy possessing an isocyanate functional group (3) and (b) ‘8 difunetional UPy compound (4) which forms a supramolecular polymer by hydrogen bonding (ef, Fig. 1.4). (After Folmer etl, 2000; Brunsveld et ,2001.)Introductory Concepts 9 Dee + Qr | oe Gr Oa-Bry Figure 1.6 Schematic representation ofthe formation of supramolecular polymer (0) by chain exension of resctve teléchelic oligomer with UPy. (After Folmer el, 2000,) ‘well as in the bulk (Brunsveld et al, 2001). Dissolving a small amount of the compound in chloroform gives solutions with high viscosities, while calculations show that polymers with molecular weights ofthe order of 108 can be formed. De- liberate addition of small amounts of monofunctional compounds (Lin Fig. 14) results in @ sharp drop in viscosity, proving that linkages between the building blocks are reversible and unidirectional and thatthe monofunctional compounds act as chain stoppers. For the same reason, the supramolecular polymers show polymer-like viscoelastic behavior in bulk and solution, whereas at elevated tem- peratures they exhibit liquid-like properties (Brunsveld etal, 2001). The quadrupole hydrogen-bonded unit can be employed in the chain exten sion of telecheli oligomers such as polysiloxanes, polyethers, polyesters, and polyacrbonates (Folmer et a., 2000), Thus the electrophilic isocyanate group (NCO) of ‘synthon” @ in Fig. 1.5) can be reacted with common nucleophilic end groups (-OH or -NHz) of telechelic oligomers, resulting in supramalecu- lar polymers by chain extension (Fig. 1.6). ‘Thus the material properties of telechelic polymers have been shown to improve dramatically upon functional- ization with synthon, and materials have been obtained that combine many of the mechanical properties of conventional macromolecules with the low melt vs cosity of oligomers (Brunsveld et al, 2001). In contrast to conventional high- molecular-weight polymers, supramolecular (reversible) polymers with a high “virtual” molecular weight show excellent processability due to the strong temper- ature dependency of the melt viscosity Folmer etal, 2000). Moreover, hybrids between blocks of covalent macromolecules and supramolecular polymers can be easily made. 1.4 Molecular Architecture Polymers can be classified, based on structural shape of polymer molecules, as near, branched, or network (cross-linked). Schematic representations are given in Fig. 1.7.2 Chapeer 1 3 tie (0 sted COtometectd (Cnt Figure 1.7. Scematic represea- tan of various types of polymer won mrlecules The branch pins {hu juneton points indicted by — heavy dos Linear polymers have repeating units linked together in a continuous length [Fig. 1.7(a)}. Ina linear polymer each repeating unit is therefore linked only t0 two others. When branches protrude from the main polymer chain at irregular intervals (Fig. 1.7(b)), the polymer is termed a branched polymer. Branches may be short, forming a comblike structure Fig. 1.7(b)] or may be long and divergent [Fig. 1.1()]. Branched polymers ae thus those in which the repeating units are not linked solely in linear way. ‘Branched polymers may be formed either because at least one ofthe monomers has functionality greater than 2 oF because the polymerization process itself cre~ ‘ates branching points on the polymer chain, An example of the firs type is the polymer made, for instance, from styrene and a very small amount of divinyl benzene (VIII. A segment of such a macromolecule might look like (X) So oo Qua eg O Oe “2 ~ ‘A good example of the second type of branched polymer is the polyethylene that is made by free radical polymerization at high temperatures (100-300°C) and pressures (1,000-3,000 atm). The extent of branching varies considerably de~ pending on reaction conditions and may reach as high as 30 branches per 500Introductory Coneepes a ‘monomer ini. Branches in polyethylene are mainly short branches (thy and butyl) andre beloved to est from intramolecular chain taster during poly ‘merization (described later in Chapter 6). This branched polyethylene lo called low-density polyetiylene (LDPE), difers from linear polyethylene (high-density polyethylene, HDPE) of slow-pressre proces o mich so thatthe two materials fe generally not used forthe same aplication. The term branched commonly implies that the polymer molecules ae ds- crete, which means tht they ean generally be dissolved in 8 solvent snd their sizes canbe measured by some of the methods described in Chapter 4 ‘A network polymer [Fig. 17] on the other hand, canbe described as an interconnected branched polymer. Forexample, a thre-imensional or space net- wore stricture wl develop instead ofthe branched structure (8) if styrene i copolymerized with higher concentrations of divinyl benzene, Ins network src= tir, al polymer chains ae linked o form one giant molecule and the molecular vveight is “infinite” in the sense that itis too high to be meased by standard tectniques (gee Problem 1.5. Because oftheir network structure such polymers cannot be dissolved in solvent and cannot be te by heat strong heating only cases decomposition Problem 15 Fora network polymer sample in the form ofa sphere of 1 cm diame ‘er with a density of L0 glem®, estimate the molecular weight assuming thatthe sample constitutes a single molecule. (Avogadro number = 62x10 molecules/nal, Male mus = (MEE) arog mb) Ci of phe XDemip argu me) (3.14)(1.0 cmy> a (1.0 gem") (602x10% mot“) = 3.15«10% g mol"! Molecular weight = 3.15x10% Ifthe average functionality ofa mixture of monomers is greater than , copoly- merization reaction to sfcintly high conversion yields netvork stactures (Gee Chapter 5). Network polymers can also be made by chemically linking al- ready formed linear or branched polymers and the proces is called crosslinting Vulcanizaron isan equivalent term that is commonly used for rubbers. Sulfur crosslinks are intoduced into a rubber by heating it with sulfur (1-2% by weight) and accelerating agents. Sulfur reacts with the double-bonded carbon atom to produce a network structure, 8 shown schematically in Fig, 1.82 Chapter 1 Problem 1.6 Assuming tha each crosslink produced by vulcanization (Fig. 1.8(6) con- {sins an average of two sulfur atoms, calculate the sulfur content of vulcanized natral rubber thats 50% crosslinked, (Neglect sulfur ater than tha is part of te crosslink) Answer: “Molar mass of isoprene (Fig. 1.8(@)], CsHg = 5x12 + 8x1 = 68 gimol. According to representation in Fig. 1.8(b), each sulfide crosslink joins two isoprene units. With x =2, ‘one sulfur atom, onthe average, is required for crosslinking per isoprene repeating unit Therefore, 051328) Sulfur content = 03X28) 109 = 19% Uae + ew Problem 7 rubber contains 60% butadiene, 30% isoprene, 5% sulfur, and 5% car- ton black. If each sulfide erosslnk contains an average of two sulfur atoms, what faction ‘of possible crosslinks are joined by vlcanization? (Assume tha al the sulfur is present in crosslinks) Answer: “Molar mass of butadiene (CyHs) = 54 glmol. Molar mass of isoprene (C3Hs) = 68 g/l Since one sulfur atom, on the average, is required for croslinking per repeating unit (f Problem 1.6), Fraction of cross-links (6 9/22 mot) (60 @)AS4 g mol") + (30 g)/68 gmol) O11 or 101%, ‘A ladder polymer consists of two parallel strands with regular rosslinks (Fig, 1.7) in between, asin polybenzimidszopyrrolone (XD). This polymer is made by polycondensation of pyromelltic dianhydride (XID) and 1,2,4,5-tetraminobenzene (XID. The polymer is nearly as resistant as pyrolytic graphite to high tempera- tures and high energy radiation. It does not burn or melt when heated but forms carbon char without much weight oss. nn Ad «xy — ‘pW we xm . 5 om °Figure 18_‘eatn f mt See ereie Ro Sees -ovfionavtonovontzonfion-or lise speed - ‘vulcanization with sulfur. The nurn- moat ae sme Salant in sat ‘sean em my ~ ‘as high as 8 under conditions where ‘yaw oor arr rnin reat Te it chelate aber Fa ns Sr pat Te io nar sea onontonrg=0- Oh tr Peo @ {A ladder (or two-strand) structure, as shown above, is one that has an unin termupted sequence of rings joined one to another at two connecting atoms. A semiladder stactare, onthe other hand, i one in which there are single bonds in- terconnecting some ofthe rings. Polyimide (XIV) obtained by polycondensation of pyromelitic anhydride (XIE) and m-phenylenediamine (XY) i an example of is a polyurethane, and 4R-SO23—~ isa polysulfone Inthe common naming system, condensation polymers are named by analogy with the Iower-molecular-eightproducts produced by condensation. Thus, since allesters are named by adding the suflix ‘ae’ to the name ofthe parent acid (e., ethyl acetate), polymer (I is named polyethylene terephthalate) according © the parent acid, terephthalic acid, which is a para acid. The word “ethylene” here implis ‘ethylene glyco!” because te alcohol used must be a glycol ifthe polymer isto be linear. Similar reasoning is ls followed in naming polyamides. Thus, the word ‘hexamethylene’ in poly(hexamethylene adipamie) obviously implies hex- amethylene diamine because the polymeric suucture could be made by the con- KT there wll be preference forthe rans state 22.11 Polyethylene ‘The potential energy diagram for polyethylene -C-CHo~CH-),~ will be expected {o be very similar to that for butane shown above, since the conformations can be ‘obtained simply by substituting the ~CH groups on C2 and C3 in Fig. 2.1 by two segments of the polymer chain adjoining the bond of rotation. The distribution of40 Chapter? ners wae Hess goer ene sh UK a a " ‘Figure 24. Newnan pojesions ofthe clipe and staggered confrmatons of e-buane lel. {Alter Young ad Lael 1950) trans (¢) and gauche (g) _ states along a chain will be a function of the temper- ‘ture and the relative stability of these states. Consequently, there is an unequal distribution of each (see Problem 2.1). ee Problem 2.1 For polyethylene the energy difference between the gauche and mans ‘Sats is about 3.34 Klimol, Calculate the ratio ofthe number of ans and gauche states slong a cain at 100,200 and 300°K. Answer: ac ae 334K mol! k= 138x109 77 (9.34% 108 J mot") /(602% 10 molecules mol!) 0.55% 10° J molecule)" From Ea. (2.1) gin, = Dexpl(-0.55%10)/(L.98% 10 x79} r 100°K 200K 300°K yin; 0036 0.264 0.524 ‘Atlow temperatures, rans states are ths preponderant a ‘ince the backbone of polyethylene molecule is composed of a chain of tetra- hhedral carbon atoms, the molecule in all-rans conformation has a linear zigzag structure (like corrugated sheets) shown in (I). (The dotted lines denote bonds ‘below and the wedge signifies bonds above the plane of the page.)(Chain Dimensions, Seuctures, and Transitional Phenoment 4 Solos w Ca al it we ART ue Nay ne ms ee saute Figure 25 (a) Schematic isgram showing wo cen cabons, Cy stl Cn the main hn of polysobutyere, ( Newzon projestns of tagaeredconfrmatons of wcent carton inthe aa Linear polyethylene is thus capable of close-packing into tight unit cell and is highly crystalline, despite its low cohesive energy. The all-rans zigzag form is the shape of the molecule in crystalline regions of polyethylene. Hawever, at hhigher temperature the /n, ratio increases (see Problem 2.1) showing that the ‘chain becomes less extended and more coiled as the temperature increases. 2212. Polyisobutylene ‘To describe the effects of steric restrictions in another polymer, polyisobutylene, consider the Newman projections ofthe staggered conformations of two adjacent carbons in its repeat unit, as shown in Fig. 2.5. Here the chain substituent on the rear carbon is either between a methyl group and polymer chain or between two methyl groups on the front carbon, There is no significant energy difference between the conformers. Since no conformation is favored, polyisobutylene will, tend to form both a helix (gauche conformers) and a zigzag (I), thereby assum- 1g highly flexible random coil formation, The polymer thus exhibits rubbery Properties at room temperaturea Chapter 2 " 4 4 " Hye HH Ho Hae 4 ‘ 8 1 2 a " ¥ H 4 # cs TEL, aL, 4 4 4 5 5 He eh BMH YH PH WE Se in fa On oy 2.2.13 Polypropylene Considering again two adjacent carbons in the main chain of the polymes, six ‘conformations are now possible because of the presence of an asymmetrically Substituted carbon atom, as shown in Fig. 2.6. Forms 1 and 6 can be neglected for steric reasons; so four different conformations are sil possible for the poly- ‘met, Atactic polypropylene (see Stereoisomerism) has two trans forms (2 and 8) In the fully extended state (IIT) and so, unlike polyisobutylene, is incapable of crystallizing upon being stretched. Isotactic polypropylene, however, having all the methyl groups on one side, crystallizes easily. mae BE A BE AS i NN SY fin fin On On Ow a(Chain Dimensions, Structures, and Transitional Phenomena a Figure 2.7. Mouel of the packing of polymer chaine in the crystal stuctare of polyethylene in which a= 7.41 A, b = 4.94 A, and successive pendant atoms are 2.55 A apart along the chain axis, 2.2.2 Polymer Conformations in Crystals ‘The conformation of a polymeriin its erystal will generally be that with the lowest ‘energy consistent with regular placement of structural units in the unit cell. Heli- cal conformations occur frequently in polymer crystals. Helices are characterized bby a number f; where / is the number of monomer units per j number of com- plete turns ofthe helix. Thus, polyethylene could be characterized as a1 helix in its unit cell wth an all-trans conformation. The arrangement of the molecules in the polyethylene crystal structure is illustrated in Fig. 2.7. Totactic polypropylene crystallizes as @ 3; helix because the bulky methyl substituents on every second carbon atom in the polymer backbone force the. ‘molecule from an all-trans conformation into a rransigauchelimansigauche... = quence with angles of rotation of O"(rrans) followed by a 120°(gaueke) twist. In syndiotactic polymers (see Stereoisomerism) the substituents are farther apart be- cause the configurations of successive asymmetric carbons altemate and so the ‘ransitransitrans... planar zigzag conformation is generally the lowest energy form, This conformation is observed in syndiotactic poly(vinyl chloride) and 1,2- polybutadiene. Syndiotactic polypropylene can also crystallize inthis confornta- tion but a rransltrans/gauche/gauicke... sequence forming @ 2; helix is slightly favored energetically. In polymers having polar groups, intermolecular electrostatic attractions exert strong influence on chain conformation in ther crystals. In polyamides, hydrogen bonds form between the carbonyls and NH groups of neighboring chains (Fig 2.8) and influence the crystallization of the polymer in the form of sheets, with the macromolecules themselves packed in planar zigzag conformations [see Fig. 2.800)4“ Chapter 2 « Figure 28. (@) Hydrogen bonds between neighboring chins of polyamide. (6) Alignment of chains in hydrogen-bonded sheets in the crystal structure of ayloa-6,6. (After Holmes et al, 1955) wo Problem 2.2 Explain the fact chat conversion ofthe amide groups ~-CONH— in ny- Jon to metilot groups -CON(CH;OH)- by reaction with formaldehyde, followed by ‘methylation to ether groups ~-CON(CH;OCHs)~ rests nthe transformation ofthe fer to arubbery product with low modulus and high elasticity. Answer: Replacing the -NH- hydrogen in polyamides by an ether group cutals the intermolee:- lar hydrogen bonding. Hence at ow degrees of substitution the modulus is reduced and ‘more elastic bers obtained, As the substitution increases, te crystallinity is Gommpletly destroyed and rubbery property appears. ‘Our discussion above on polymer conformations in single chains and in erys- tals has assumed regularity of macromolecular structure. However, iregularities such as inversions of monomer placements (head-to-head instead of head-to-tail), branches, and changes in configuration may occur. These irregularities, which are considered ina later section, may inhibit crystallization and have a profound cffect on polymer properties.Chain Dimensions, Suactures, and Transitional Phenomens 6 See WEP oe a igure 29 Skeletal representation of polyethy lene chain in planar zigzag frm, 2.2.3 Polymer Size in the Amorphous State ‘The development of the random coil by H. F. Mark and many further develop ments by PJ. Flory led to # description ofthe conformation of chains inthe bulk amorphous state. Neutron scattering studies revealed that the conformation in the bullcis close to that found in solution in ©-solvents (see Chapter 3) thus strength- cing the random coil model. On the other hand, some workers suggested thatthe chains have various degrees of either local or long range order, Using the concept of free rotation of the carbon-carbon bond, Guth and Marke (Guth and Mark, 1934) developed the idea of the “random walk” or “random flight” ofthe polymer chain, which eventually led to the famous relationship be- ‘ween the end-to-end distance ofthe main chain and the square root ofthe molec- ular weight, described below. 223.1 Freely Jointed Chains A simple measure of chain dimensions is the length ofthe chain along its back- bone. It is known as the contour length. For a chain consisting of n backbone bonds each of length /, this contour length is nl. However, because of the fixed bond angle (109.5" of carbon, the maximum end-to-end distance of the polymer chain will be somewhat less than nl (see Fig. 2.9 and Problem 2,3), For linear flexible chains that are more like random coils, the distance separating the chain tends, ie, the end-to-end distance r (Fig. 2.10), will be even considerably less than nl Problem2.3 For a linear molecule of polyethylene of molecular weight L4x10° what ‘would be the end-to-end distance of the polymer molecule inthe extended all-trans) state, as compared to the contour length ofthe molecule? Anower: : ‘The polyethylene molecule may be represented skeletal ina planar grag form as shown, in Fig. 29, where = 0.154 nm and 9 = 108.5°. In order to perform te calculation, the46 Chapter 2 umber m of backbone bonds is required, It can be obtained from the molar mass of the Mulecul since there is only one mettylene group per backbone bond (neglecting chain ‘Tigo which make an insignificant contrition to molecular weight fo lng chains) n= 1ax108/4 = 10,000 “The contour length is the length ofthe molecule along Contourlength = nf-= 10,000(0.154 nm) = 1540nm ts backbone and sos given by ‘Since each bond in the fully extended molecule has a projection of {si(/2), the end-to- fend distance ris given by 1 = (10,000) (0.154 nm) sin (109.572) = 1258 nm (Magnified «milion times, the chain could be represented bya piece of wire 1.26 m long ‘and 0.3 mm in diameter.) For an isolated polymer molecule it is not possible to assign a unique value ‘ofr because the chain conformation (and hence r) changes continuously due to rotation of backbone bonds. Since the single polymer chain can take any of an Infinite aumber of conformations, an average magnitude of r over all possible onformations is therefore computed from the mean of the squares of end-to- tnd distances and is called the roor mean square (RMS) end-to-end distance, fepresented by (7°)"2, where () means thatthe quantity is averaged over time It is piven by a rather simple equation (see Appendix 2.1) QPP = nl 02 ihre he subscript f indicates thatthe results fo fet jointed chain uation (22) eeveas tat (2)! is actor of! smaller than the contour reat Since is large, hs highlights the highly coed nate of eb polymer tains The dneion of polymer molecules ae also deserted often in tems ofthe [RMS uistnce of chain segment fom the center of mass of he molecule. Its Teta the square oot the average squared distance fall th repeating units fine nlecte rom ts centr of mass an is known simply a8 the RMS radius of gyration, (S)'. Ivis thus given by (Orfino, 1961) (5) = (im Ys) 3) here s is the vector distance from the center of mass tothe ih unit of the chin jn one particular conformation of the molecule and is the total numberof units ‘The angular brackets denote a linear average over all possible conformations of the molecular chain.(Chain Dimensions, Structures, and Transitional Phenomena a ‘The radius of gyration has the advantage that it also canbe used to characterize the dimensions of branched macromolecules (with more than two chain end) and @ > 90°, cosé is negative and (r*) is greater than nl? of the freely jointed chain model [Eq. (2.2)]. For polymers having C-C backbone bonds with @ = 109.5for which cos6 = ~§, the equation becomes (?Pijq = nl? 26) ‘Thus for polymers such as linear polyethylene, bond angle restrictions cause the RMS end-to-end distance to increase by a factor of ‘2 from that ofthe freely- jointed chain,6 Chapter 2 ——————————— Proton 34 Fors armas of poles of nec weght 1-10 what ee RMS cate nance acorn toe aoe snl adel as cmpaed caae edn ome tel jomed chain mel and headend stance of fall aaa sser Commeat onthe rales Obie, infeing wich one a more ‘leat of inden. nave: Lengthofeach bond = 0.154 Ge Fig 29) umber of ond, x = 10000 (ee Foe 23) End toend dstace oly extended molecule = 1258 ee rblem 23) “Te RMS endivend dstnce, acorn tes ined can mol is bined som 2 (2) = 0000)! 154 am) = 154m ‘The RMS end-to-end distance according to valence angle mode is obtained from Eq 2.) 12 ast am {1 = seectonseyy! (PvE = cn ast am (1 = S20} = 218m Carmen: “The wot ei of he ore te ema of ini ies i ha cree ge nce mage na Taobao ait alg of be a eae arte es ela es ‘The valence angle model, though more realistic than the freely jointed model, sil underestimates the tue dimensions of polymer molecules, because it ignores restrictions upon bond rotation arising from short-range steric interactions. Such restrictions are, however, more difficult to quantify theoretically. A simpler pro- cedure isto assume that the conformations of each sequence of three backbone bonds are restricted to the rotational isomeric states that correspond to the poten tial energy minima such as those shown for n-butane in Fig. 2.3. For the simplest ‘case of polyethylene and for Vinylidene-type polymers, the application of the ro- tational isomeric state theory yields the following equation (l= cos8)(1 + Se *(SeM(iS3 ] an where the subscript indicates thatthe result is fra polymer chain with hindered Totation about fixed bond angle, The quantity eos represents the average value Sreoe where ¢ isthe angle of bond rotation a defined for n-butane (se Figs. 33 and 2.4), Ifthe bond tation is fee or unrestricted, ll values of ar equally Pra(Chain Dimensions, Stuctures, and Transitional Phenomena 0 probable causing the postive and negative values of cose to cancel each other out, 80 that 20s = O and Eq. (2.7) then reduces t0 Eq, (2.5. However, duc to short-range steric restrictions, values of || < 90" are more probable which means that C054 is positive and (7*)y is greater than ()jq, Moreover, if bulky side groups occur on the polymer chain, ., phenyl group in polystyrene, there wil bbe additional steric interactions due wo side groups, producing further hindrance to bond rotation, Since these effects are difficult to evaluate theoretically, Eqn. (2.7) is usually writen i a semi-empirical form (Young and Lovell, 1990) 3s y= nr ‘where ois a steric parameter and is the factor by which (77)}/? exceeds {r2)¥. It ‘is usualy evaluated from values of (7)! measured experimentally (he subscript «indicating tat the results observed and no caleulated) and typically has values beeen 15 and 2.5, One can obtain an idea ofthe stiffness of a polymer chain from the ratio (PYPHAYP, thats, the square 100 ofthe rio, Co = (72, / m2, called the characteristic ratio (Young and Lovell, 1990). The value of Cl? indicates how much greater the RMS end-to-end distance of areal polymer chain is, compared (o that ofthe freely jointed chain ws) 17 cos6, oe Problem 2.5 A:ealpolymer chain consisting ofn bonds each of length! may be usefully represented by an equivalent freely jointed chain of links each of length b such that it will have the same end-o-end distance and the same contour length. Obtain Nand & in terms of the characteristic ratio Cu of the polymer chain. dae ifsc het ene on sans en Wy = NP (P2.5.1) Ashe ae comma hen mea ws) om 25 a 232, eeue 2 ms wt = P25.) é ) When an average end-to-end distance of macromolecular coi is (-)!2 as, given by Eq, (2.7) or more generally (7)! as given by Bq. (2.8), the polymer is30 Chapter 2 said to bein its “unperturbed” state (See below). Henceforth the subscript will ‘be used to indicate the unperturbed sate ofa polymer molecule. "The model considered above does not impose any restriction on the relative positions of the bonds widely separated in the chain, or, in other words, does not prevent parts of the chain occupying the same space. Ina real situation, however, this cannot happen as each part of an isolated polymer molecule excludes other tore remotely connected parts from its volume, Because of these long-range Sere interactions, the trae RMS end-to-end distance, 72)", is greater than the “unperturbed dimension (72). These effects are usually considered in terms of an txcluded volume (see Chapter 3) and the extent to which unperturbed dimensions fe perturbed in eal chains is dfined by an expansion factor a such that (Py = aly? 29 Pesturbations in chain dimensions are slso caused by interactions ofthe chain with its molecular environment, e.g, with solvent molecules or other polymer molecules, The effects of these interactions are also reffected in the expansion parameter a. In a theta solvent (see Chapter 3), cis reduced to unity and the fnd-to-end distance of a polymer chain is then the same as it would be in bulk polymer at the same temperature. Ee Problem 2.6 Assuming that the RMS end-fo-end distance isan approximation to the ameter ofthe spheriel, coiled polymer in dilute solution, calculate the volume occu pied by one molecule of polystyrene (molecular weight 108) ina theta solvent at 25°C. {(Carbon-carbon bond length = 1.54%10° em, tetrahedral bond angle = 109%; sere parameter, for polystyrene at 25°C = 2.3) Answer: Molar mass of styrene = 104g mot“! Degree of polymerization = (10% gmét)/(104 gmol"!) = 9615 [Number of beckbone C-C bonds = 2x9615 = 19230 roms. 28) (2 = o@n (S22) stxi0-8 em, @= 109.5", cos = 1/3. 19230, ‘Therefore, Phe (2.377 (19230K1.54% 10% em)*2) 24x10" em? Volume ina theta solvent (ie,@= 1) = (xj6)(24x 10°" em?)¥ 44x10" em? _— ——————Chain Dimensions, Stuctues, and Transitional Phenomena 3 2.3. Constitutional and Configurational Isomerism If different isomers of a molecule have different configurations, that is, spatial ‘arrangements that cannot be interchanged (without atleast momentary breaking ‘of bonds), them itis referred to as configurational isomerism. Another type of isomerism, which involves constitutional variations of a molecule, is veferred to as constcurional isomerism. 2.3.1 Constitutional Isomerism Except in monomers like ethylene and tetrfluoroethylene where the substituents ‘on the two carbons are identical, the two carbons of the double bond in a vinyl type monomer are distinguishable, One of them can be arbitrarily labeled the head and the other the sail of the monomer, as shown below for vinyl chloride (IV), ‘During polymerization, the monomer in principle can be joined by head-to-tail or hhead-to-head/tail-to-tal (V) additions, as shown by Eqs. (P2.7.1) and (P2.7.2), respectively. However, head-to-tail enchainmet is the predominant constitution ‘of most vinyl monomers (see Problem 2.7). Problem 2.7 — Explain the fat that inal polymerizatons the head-o-til addition i su ally the predominant mode of propagation. Answer: Vinyl monomers polymerize by attack of an active center (VI) onthe double bond. Equa- tion (P27.1) shows the propagation step in head-to-tail enchainment and Eq, (P2.7.2) that in head-to-head or ail-totail enchainment 27.) 272)2 Chapter 2 ‘The active center involved inthe propagation reaction may be a free-radical, om, oF metal-carbon bond (see Chapters 6-10). A propagating species will be more stable ifthe Impaired electron or ionic charge a the end of the chain can be delocalized across either tr both substituents X and ¥. Such resonance stabilization is possible in (VEN but not in (VII), Moreover when X andor Y is bulky there will be more steric hindrance in reaction (STEq, (P2.72) than in the reaction of Eq, (P27.1). So in general, head-to-tail addition as {nq (2.71) is considered tobe the predominant mode of propagation in all polymesi2a- Problem 2.8 chemical method of determining head-o-hesd stractures in poly(vinyt aleohal) is by means ofthe following difference in dol reactions (For. 1950): cf rt mK 4 HO, ee fr + HO, + HO bu bu 2D) # se HO, cttw 20+ so racon ox bx (3 Dit) Poly(viny! acetate) of number-average molecular weight 250,000 is hydrolyzed by base- ‘catlyzed tansesteification with methanol to yield poly(vinyl aleobol). Oxidation of the Tater with periodic acid yields a poly(vinyl lcohol) with number-average degree of poly merization 485, Calculate the percentages of head-to-tail and head-to-head linkages in poly(vinyl acetate). Answer: Repeat unt of poly(vinyl acetate): -ECHy-CH(OCOCHS)+- ‘Molar mass of repet unit = 86 g molt ‘Assume that poly(vinyl acetate) is completely hydrolyzed so tht Fy of the resulting poly (ny! alcoho) is also 2907, The fact that is educed from 2907 to 485 upon treatment with periodic acid means that each poly(vinyl leobol) molecule is, onthe average, cleaved to yisld 29074485 or 6 smaller molecules each of Z, = 485 and so the number of cleavages w= 5. Therefore, te average polymer molecule has 5 head-to-head linkages out of ‘total of 2907 ~ | = 2906 linkages inthe polymer chain. . 6100 72906 Sheadtotail = 100-02 = 99.8%. . Fehead-to-bead = = 020%(Chain Dimensions, Suuctures, and Transitional Phenomena 3 Problem 2.9 Polymers of dienes (hydrocarbons contining two carbon-carbon double bonds), such as butadiene and isoprene, have the potential for head-o-tail and hesd-0- head isomerism and variations in double-bond postion as wll. How many constitutional isomers can form in the polymerization of (a) polybutadiene and (0) plyisoprene ? Answer: ‘The conjugated diene butadiene can polymerize to produce 1,4 and 1,2 products (Ruskin, 1982): head-to-head 1.2-polybutadtene WE ~feuy-tat-cn ‘L-polybutadiene ‘Thus, there are thee posible constitutional isomers and, in addition, there isthe possibility of mixed structures. Note tha there is no 3,4 polybutadiene because itis intial with 12 polybutadiene. This isnot the case with 2 substituted conjugated butacienes like isoprene ‘and chloroprene. Thus, 3s shown below, there ae six possible constitutional isomers of isoprene or chloroprene, o say nothing ofthe potential for mixed structures (Rudin, 1982) R } [testa sot, wdac, teat 12 paiymer hyd ¥ end-oseas Caet—e=cn, T= tcc a toe ek estou &, corn: Ret, 3pm Chg: Rect bu reateorbead tot atc) aos esti Elestomeric behavior is shown by 1-pol)mer, particulary ifthe polymer structure is cis about the residual double bond (ee Section 2.3.21),e Chapeor 2 2.3.2. Configurational Isomerism “The configuration of a molecule specifics the relative spatial arrangement of bonds in the molecule (of given constitution) irrespective of the changes in molecular shape which can arse because of rotations about single bonds. A given config- ‘uation can thus be changed only by breaking and reforming of chemical bonds, "There are two types of configurational isomerism in polymers and these are anal- ‘ogous to geometrical and optical isomerisms in micromolecular chemistry. 23.2.1 Geometrical Isomerism ‘Since rotation cannot take place about a double bond between two carbon ators, two nonsuperimposable configurations (geometrical isomers) are possible if the tovo substituents on each carbon differ from each other. For example, the two monomers maleic acid (IX) and fumaric acid (X) are geometrical isomers, desig nated cis and trans resnectively H—C—CooHt H—¢—CooH H—C—cooH HOOC—C—H ax) ® In solid, the molecules of trans isomers pack more closely and crystallize more readily than those of ci isomers. This is reflected in the fact thatthe melting point of fumaric aid is about 160°C higher than that of of maleic acid. Similarly, the differences in the properties of cis and trans isomers of polymers are also significant, as shown below withthe example of poly(soprene) ‘Natural rabberis | 4-polyisoprene and the polymer configuration is cis at each double bond in the chain, as shows in (XI). Consequently, the polymer molecule thas a bent and less symmetrical structure. Natural rubber does not ciystallize at room temperature and is amorphous and elastomeric. Balata (guttapercha) is also 1L4-polyisaprene, but the polymer configurations erans at the double bond (XID ‘The molecule is more extended and has symmetrical structure. The trans isomer is thus a nonelastic, hard, and crystalline polymer. Is used as a thermoplastic eer Fe v_/ \_/ ri cn | if ‘oiaspe any cm)(Chain Dimensions, Structures, and Transitional Phenoment 55 232.2 Stereoisomerism Optical Activity in Polymers Stereoisomerism in polymers is formally similar 1 the optical isomerism of organic chemistry. In a vinyl polymer with the general structure shown in (XII every other carbon atom in the chain, labeled C*, is a site of steric isomerism, because it has four different substituents, namely, X, Y, and two sections of the main chain that differ in length (Rudin, 1982), oe ta Act Le oy cx) Problem 2.10 Explain why polypropylene of relatively high molecular weight is opt cally inactive despite having an asymmetic center at every other carbon, while, onthe other hand, poly(propylene oxide is optically active. ‘Answer: Optical activity is influenced only by the frst few stoms around an asyrmettic carbon (C*), For the two sections of the main chain, these willbe identical regardless of the Length of the whole polymer chain, The carbons marked C* in (XII) are thus not teuly asymmetric and ae termed pseudoasymmenic or peudoehirel carbons. Only those CC* centers near the ends of a polymer molecule willbe wuly asymumettc, but sie there se too few chain ends ina high molecular-weight polymer such centers do nt confer any significant optical activity oa the molecule as 2 whole, Polypropylene is thus optically inactive. 2 Inpoly(propylene oxide), E-CHC*(H(CH)O}., the Cis eve asymmetric conte, as itis surrounded by -H, ~CHs, ~CHp, and -O-, ‘The polymer is therefore optclly I is easy to see that there are two distinet configurational arrangements of the repeat unit of (XID, viz., (XEV) and (XY), where the wedge and the dotted lines denote bonds which are extending above and below the plane of the paper, respectively. These two stereoisomers of the repeat unit eannot be interchanged by bond rotation and they exist because the substituted carbon atom, labeled C”, is attached to four different groups. Thus, every C* may have one or other ofthe two configurations, One of the configurations is designated as D (or d) and the ‘other as L (or). The configuration is fixed when the polymer molecule is formed ‘and is independent of any rotations of the main chain carbons about the single bonds connecting ther,56 Chapter 2 igure 2.11, Diagrams of (@)isotactc, (6) syndionse- tie, and (¢) atactic conig- rations of {CH2-CXY3- polymer. The correspond- ing Fisher projections are shown on the right. ‘Tacticity in Polymers As explained above, the C* atoms in (KILN) are pseu ‘dochiral and hence do not give rise to optical activity; the two mirror image con figurations remain distinguishable, however. The different possible configurations or spatial arrangements that occur as a consequence are called the acticity ofthe polymer (Rudin, 1982; Cowie, 1991). "The usual way to picture the configurational nature of a vinyl polymer is to ‘consider the polymer backbone stretched out so thatthe bonds between the main chain carbons form a planar zigzag patter inthe plane ofthe paper and the X and YY substituents on successive pseudoasymmettic or pseudochiral carbons le either above or below the plane of the backbone, as shown in Fig. 2.11. Tf the substituents, say X, are then all above or all below the plane (Fi 2.11(a)], the configurations of successive pseudoasymmetric carbons ar the same; the polymer is termed isoractic and designated as dda... or 1... If, however, ‘piven substituent appears alternately above and below the reference plane in the planar zigzag conformation (Fig. 2.11(b)] the polymer is termed syndiotacric and(Chain Dimensions, Sauctures, and Transitional Phenomena 7 designated as ddl. or ld... In both cases, configurations of successive pseu dochiral carbons are regular, and the polymer is sid tobe stereoregular or saci ‘When the configurations of pseudoasymmetic carbons are more or less random (Fig. 2.11(0)], the polymer is not steeoregular and is said to be atacri. Those polymerization that yield tactic polymers are ealed stereospecific. Is useful at {his point to reiterate that stereoisomerism does not exist ifthe substituents X and Y are the same. Stereoreglarity in vinyl polymers has a profound influence on the crystal lizabilty of the material. Polymer chains with stereoregulartyaze beter abe to pack together ina regula manner and erytallize. The inerease in crystallinity is reflected in higher melting point, greater rigidity, and less solubility compared to amorphous species with the same conatitatio. A striking example is provided by polypropylene. Isotactic polypropylene has aerystal meting point of 176°C and is widely used as fiber and filament and in automotive, furniture, and appliance applications while the stactic polymer i @subbery amorphous material that finds no important use. Syndiotactic polymers, as we have seen above, are stereoreg- ular and so are erystallizable. They, however, do not have the same mechanical properties as isotacti polymers. Thus mast ofthe highly stereoregular polymers of commercial importance are isotactc, and relatively few syndiotactie polymers are made (Rudin, 1982) Itis important to note at this point that completely tactic and completely atse- tic polymers represent extremes of steeoisomerism and polymers often possess intermediate degrees of tctcty. The most powerful tol for measuring the ex tent of stereoregularity in polymers is nuclear magnetic resonance (NMR) spec- troscopy (see below). ‘Meso- and Racemic Placements The Fisher projections in Fig, 2.11 show that placement ofthe groups in isotactic structures corresponds to & meso (same) or lacement of a pair of consecutive pseudochiral centers, whereas the syadio- tactic structure corresponds to a racemic (opposite) or r-placement of the corre- sponding pair of pseudochiral centers. Its important to note here that the m orr notation refers to the configuration of one pseudochiral center rlative to its neigh- bot. Thus, the meso dyad is designated m, and the racemic dyad r. The system ‘of nomenclature can be extended to sequences of any length. Thus, an isotacic ‘wiad is mm, a heterotactic triad is mr, and a syndiotactc triad rr. Several such configurational sequences are illustrated in Table 2.1, Each of these, and even ‘more complicated combinations, can be designated through NMR studies. ‘Letus assume thatthe probability of generating a meso sequence when a new ‘monomer unit is added atthe end of a growing chain can be denoted by a singleChapter 2 58 | i. woo | pepe Pome wen o outee | Pp | tora HE ws ava | EEE) une esves tH] ow pena drovte | PH pH] aus trie tat aus Jewel Tp] ae fe | bubeaet | ae wen | There Jeaeutae | Tb | OPS peu eo [oot | cae oon | F-¥ | | co va | eee | oe |" a l |muroaes et Son0gh seouanbog jeuonnsyvoD TZ AIAN,(Chain Dimensions, Sructures, and Transitional Phenomena ” parameter, Py (and similarly P; for a racemic sequence). Implied init is an as- sumption that the polymer obeys Bernoullian statistics, that is, the probability of forming an m orr sequence is independent ofthe stereochemical configuration of the chain already formed. Since addition can be only m or r type, itis obvious that Pp + Pe ‘A triad sequence involves two monomer additions. Thus the Bernoullian prob abilities of mm, mr, and rr are P2, 2Pq(l ~ Py) and (I~ Pq), respectively. A plot of these relations is shown in Fig 2.12, It wll be noted thatthe proportion of mr, that is, heterotactic units, rises to @ maximum at Py, =0.5, corresponding to ran dom propagation. For «random polymer (Pm =0.5) the proportion mm: mir:rr will be 1:2: The Pa values of 0 and I correspond to completely syndioiactic and isotactic polymers, respectively. Problem 2.11 Derive the Bernoulian probabilities for triad sequences in terms ofthe parameter Py. Anower: “ Denoting the rates of meso and racemic dyad placements by Ry and R,, respectively the probabilities Py and P, canbe defined by Pa = Radin +R), Pe = Rel(Rn +R Pat P Since Py and P, are synonymous with iotactic and syndiotactic dyad fractions me and r, respectively, probabilities for iotactic, syndiotatc, and heteroactic iad sequences will be given by mm = Fly rr = PP = 1— Pa), mr = 2Py(l ~ Pad ‘The cooffcient of 2 forthe heterotatc triad arses fom the fact thatthe eterotacti rad «can be produced in two ways (as mr and rm). For any given polymer following simple Bemnoullian statistics, the mm, mr, rr sequence frequencies, as estimated from the relative areas of the appropriate peaks in NMR spectra (see below), should li on a single vertical line in Fig 2.12, ‘corresponding to a single value of , (see Problem below). If this is not the ‘case, then the polymer's configurational sequence deviates from the Bernoullian statistics, Plots such as Fig. 2.12 can be made (Bovey and Tiers, 1960) for tetrad and ‘other higher order probabilities (or fractions) as a function of Pp using the rela- tionships given in Table 2.1. These are useful for peak assignments in NMR spec- tra, aided by certain necessary relationships (Bovey, 1969) among the frequencies ‘of occurrences of sequences, which must hold regardless of the configurational statisties (Bemnoullian or not),6 Chapter 2 Figure 2.12 The probabilities (or fractions) of isotactic (mo), heterotac- tie (mr), and syndiotaetic (rr) triads asa function of Py, the probability of isctactic monomer placement during 0 02 04 06 08 10 ‘propagation, Bovey and Tiers, 1960.) », Normalized id oo pape ee me =. ‘Mainly syndiotactic; (6) 2 So eee a tia sift em figuration, (Bovey, 1969) oe Ne oy Ke \ et ond Syndiotctc Figure 2.14 tsotactic, syndiotatc, and heterctactc triad coniguation for polymethyl methacrylate)Chain Dimensions, Seuctures, and Transitional Phenomena 61 NMR Measurement of Tacticity High resolution NMR spectroscopy makes the ‘quantitative measurement of sequence distribution feasible (see Problem below) and allows one to compare actual polymer chains with theoretical predictions Problem 212 ‘Two typical spectra of polymethyl methacrylate) samples (Bovey, 1969), ‘known tobe predominantly isotactc and syndiotactic, ae shown in Fig. 2.13. Justify the assignment of various peaks in these spectra, Answer: Since the thee protons in an a-methy] group ae equivalent, they will absorb radiation at singe frequency, but tis frequency willbe different fr each of the thee types of triads, ‘because the environment of a-methyl groups in each is differeat (See Fig. 2.14). The a ‘methyl groups give the set of three peaks at 8.78r, 895r, and 9.09r. For e sample that is mainly isotactic, te peak at 8.78r is much larger than the ater to. So itis assigned tothe a-methyl groups which are flanked on each side by a monomer unit with similar configuration (See Fig. 214). Such a group of tree units constitutes an isotaetic (mo) ‘iad, Fora manly syndiotacti sample the peak aC8.09r is the most prominent of the three peaks. It is assigned to a-methyl protons in the middle of syndiotactc (7) triads. ‘The remaining peak at 8.95r is therefore atributed to the a-metyl group inthe mide of heterotsctic (my) triads. The numbers of isotsctic, heterotactc, and syndiotactic triads in any particular sample, and hence mm, mr, and 7, are proportional tothe areas under the appropriate peas. ‘The method of identifying streoregular suuctures by NMR can also be ap- plied to polymers that are not predominantly stereoregular; to obtain information bout the probability py that a monomer adding on to the end ofa growing cha will have the same configuration as the unit itis joining. ‘The faction of each configuration — mm, rr, and mr — is measured from the isotatic, syndiotct and heterotactic peak areas, respectively in the NM spectra. The resulis are then fied othe probability curves by placing one of them, say the faction rad on the curve and letting the other fractions, vz., mm and mr, fall where they may. If the later fractions also fll satisfactorily close to the calculated curves, then the configurational statistics is Bemnoulian and can be described by a single value of Pro Problem 2.13 Determination ofthe individual peak ares in the a-methyl region ofthe [NMI spectra of ply(methyl methacrylate) shown in Fig. 2.13 yielded the following values Bovey and Tiers, 1960):2 Chapter? Anas Polymer No. _ Polymerization conditions Iso_Heiero _Syndio “T Benzoyl peroxide in bulk, O'S 86 375539 2 Buin toluene, ~62°C 6 8 Determine whether the polymerization in each case canbe determined by a single value of Pp in agreement with Bemoullian statistics. Answer: ‘We might test for Bernollian Siting by placing the (mm), (mr), and (rr) triad intensities (thats, the factional areas representing polymer fractions in so, hetero, and syndio con- figurations, respectively) on the probability curves of Fig. 2.12. This is done in Fig. 2.15, fr polymer 1 by placing the syndiotactic (7) point (0.54) on the curve to obtain the cor- responding Py Value (0.27) and then letting the otber two points fall where they may on the vertical line a this Py. Tes observed thatthe factions of mr (heteotactic) and mm (Gsotactic) units fl satisfactorily close to the calculated curves. This may be interpreted indicating thatthe free radial propagation inthe given case is Bernoulian and can be eserbed bya singe value of Pq (= 0.27), For polymer 2, made by anionic polymerization, the results are fted similarly to the probability curves in Fig. 2.15 by placing the (mm) point onthe curve and leting the otber points fll where they may. tis observed thatthe (mr) and (rr) points are significantly ‘vay from the ealulated curves, an indication that the polyner is non-Bemoullian. Thus the anionic pol)meriation mechanism inthe given case cannot be described by a single value of Py. Figure 215 Test of Bemoullian ‘model wih data for polymer 1 and polymer 2 of Problem 2.13. 0 02 04 06 08 10 P,(Chain Dimensions, Structures, and Transitional Phenomena 6 24 Crystallinity in Polymers Polymers crystallized from melt are never completely crystalline. This is be- cause there are extensive chain entanglements in the melt making it impossible for the polymer chains to be fully. aligned t0 form a 100% crystalline polymer ‘Region II (cto d) in Fig. 2.21 is described asthe rubbery plateau region. The ‘modulus after a sharp drop, as described above, again becomes nearly constant in this region with typical values of 2x10" dynelcm? (2x10* Pa) and polymers exhibit significant rubber like elasticity. In region Il (c to) of Fig. 2.21, three eases can be distinguished: (1) If the polymer is linear, the solid line is followed with the modulus decreasing slowly With increasing temperature and the length of the plateau depends significantly ‘on the molecular weight of the polymer, i.e., the higher the molecular weight, the longer the plateau. (2) Ifthe polymer is semicrystalline, the dotted line in Fig. 2.21 is followed and the height of the plateau (i.e, the modulus) depends. ‘on the degree of crystallinity. (3) If the polymer is crosslinked, the dashed line in Fig, 2.21 is followed, improved rubber elasticity is observed with the creep portion suppressed (a common example being the ordinary rubber band at room temperature), and the region II remains in effect at higher temperatures upto the decomposition temperature. For cross-linked polymers, therefore, regions IV and YV (described below) do not occur. Region IV is the rubbery flow region, which is exhibited by un-crosslinked linear polymers when heated past the rubbery plateau region, In this region, the polymer exhibits both rubber elasticity and flow properties depending on the time scale of the experiment. When subjected to stress for a short time, the entangle ‘ments of polymer chains are not able to relax and the material still shows rubbery ‘behavior, ut over a longer duration under stress atthe increased temperature, the chains can move, resulting in a visible flow. Region V (¢ tof) in Fig. 2.21 is the liquid low region, which is reached at still higher temperatures where the increased kinetic energy ofthe chains permits them to wriggle out through entanglements rapidly and move as individual molecules,2 Chaper 2 often producing highly viscous flow. This is the melting temperature and it is always above the glass transition temperature. se Problem 2.18 A new polymer is reported to soften at 60°C. Describe «very simple cxpeviment to determine whether his softening isa glass transition ora melting point. Answer: 160°C is glass transition, then heating the polymer slowly past 60°C. would ake itt the rubbery plateau region (tegion I in Fig, 221), where the modulus E, and hence hardness, ‘would emain fast constant with increase of temperature. Fora meting transition, how ‘rer, the modulas would drop rapid and the polymer would become increasingly softer ina similar experiment (Sperling, 1986). “The penetration ofa weighted needle into the polymer asthe temperature is raised can ‘be used asa very simple test. Problem 2.19 Show schematically the results that would be expected from te folowing texperimenis With the new polymer of Problem 218 if the reported softening temperature {G0°C) is indeed a melting transition (Spering, 1986) (@) Specific volume (0) asa function of temperature (7) (&) Diserenial scanning calorimetry (@) Young's modulus (E) a a function of temperature (T. (@ Xray difracton “The experiments are carted out inthe temperature range 50°C-10°C Answer: (@) The specific volume would show a fiat oer ansion, However () DSC would show an endother- sons explined eatlier, the melting trn- HC Pea. sition for polymers usually occurs over @ range of temperature. 1CQ) :Chain Dimensions, Seuctures, and Transitional Phenomens B (OA plotoflogé versus T would show a (@) If the polymer has a high de sharp downturn at about 60°C. ree of crystallinity, x-ray diffraction a1 50°C sould show sharp lines but ‘only diftse rings or halo at 70°C, 19] Problem 2.20 What type of results would be obtained ifthe reported softening tempee- ture (60°C) for the polymer in Problem 218 wore glass transition (Sperling, 1986) ? log E 70 Ancwer: (@) The specif volume would show a second order transition, Tee & () Hea capacity of the material changes at the glass transition, 7, ie taken asthe temper. sture at which one-half of the change in heat capacity ACy has occured. | ~~ Be Endo Exo i { +a 0 a7 ae) TEC) (@) A pass i 4 nti tat has fost (©) J quasistatic measuemen's, ost of ts dtiy bt has me changed maximum rate of decrease of the otherwise on cooling; on the basis of x- mols ous a ‘ay diffacton it wil be indsingush 28 fom the coresponding rbber on the oterside of, [oo 30 log% Chapter 2 2.7 Factors Affecting Ty, [As T, marks the onset of molecular motion, a numberof factors that affect rotation about links (necessary fr movement of polymer chains) wil also influence the Ty ot polymer, These include (a) chain flexibility, (b) molecular structure (steric effects), (c) molecular weight, and (@) branching and crosslinking. “The flexibility ofthe chain may be considered to be the most important fac~ tor that influences the T, ofa polymer. Ifthe chain i highly exible, Ty will generally below and if the chain is rigid, the Ty value wil be high. The cain flexibility epends onthe rotation or torsion of skeletal bonds. Chains made up of| bbond sequences which are able to rotate easily are flexible, and hence polymers ‘containing +-CH>~CH)-}, ~CHz~O-CH2+, or --Si-O-Si}- links will have correspondingly low values of T,. For example, poly(dimethyl siloxane), which has Si-O bonds inthe backbone chain, has one of the lowest T, values known (123°C). ‘The value of J; increases markedly with the insertion of groups that stiffen the chain by impeding rotation, since more thermal energy is then required to set the chain in motion, Paticlary effective in this respect isthe p-phenylene ring, Some examples of such polymers are_poly(xylylene), On 7 =-280°C and poly(phenylene oxide), —Or-O, Tq = 83C, a8 ‘compared to polyethylene - Gar Bonlh * Te to8 Chapter 2 Here B is a constant for the pair of monomers. With the assumption that B, whicl is never far from unity, is exactly unity, Eq. (2.45) reduces to the very simple, but nonlinear form Liwim 7a’ (2.46) ‘This isthe familiar Fox equation (Fox, 1956). This equation predicts the typically convex relationship obtained when 7; i plotted against wy or w>. “Equation (2.45) ean be rearranged to a more convenient form: will ~ Tya) + ball + Tea) = 0 ean where k = B(T,/T2). Ths is known as the Wood equation, which fits data for many copolymers very well ‘Though Eqs. (2.44) to (2.47) are derived for random copolymers, these are also applicable to those cases of polymer blending and plasticization with low ‘molecular weight compounds where phase separation does not take place and one phase is retained. [002 04 06 08 10 489_458_431_ 413394378 asimate the value of 7 fora PPOPS blend with PS weight faction of 03. Answer: ‘The T, values of the PPOIPS blends ae pled against the weight fraction my of PPO in Fig, 225, The curves forthe linea equation (244), the Fox equation (2.46) andthe Wood ‘equation (2.47 ae drawn on the same graph, Best ft is seen to be obtained forthe Wood. ‘equation with k= 0.679. From Eq. (247) ay = Tat boty = ne 13, 2 =0.7, Tyt =378°K, Tyo =489°K, 03x (378 °K) + 0.6790.7 (489 °K) as 03 + 0679x07 cen Problem 233 low much of a low molecular weight plasticizer with Ty should beaded toa lm of nylon6,6 inorder that Ti reduced from 50°C to 25°C? Answer: ‘Assuming that single phase is retained on plastiization, equations derived for random polymers ean be used .(Chain Dimensions, Structures, and Transitional Phenomena 89 Tp = 50°C= 323 °K, Typ =~ 80 From Eq, (2.44) (298°K) = (1 92}23°K) + w9(193"K) = wp = 019 From Eq, (2.46) ae em ie Bry” oH * BH ‘The difference is due to higher Ty value predicted by the linear equation, =m =017 2.11 Chain Movements in Amorphous State ‘The random chain arrangements in amorphous or molten polymer create extra ‘empty space, called the free volume, which essentially consists of holes in the matrix. When sufficient thermal energy is available, the vibrations can cause a segment to jump into a hole by cooperative bid rotation and a series of such jumps can result inthe polymer chain eventually changing its position. However, the complete movement of a chain cannot remain unaffected by the surrounding. ‘chains since considerable entanglement exists in the melt and any motion will be retarded by other chains. ‘According to Bueche (1962), the polymer molecule may drag along several ‘others during flow, causing energy dissipation due to friction. The length of the polymer chains in the sample would thus be expected to play a significant role in ‘determining the friction and resistance to flow. The effect of chain length on melt viscosity (7), measured at low shear rates to ensure Newtonian flow, is lustrated 9 oH toma sof Fobect £ cot nol Figure 225 Plo of Tagine com- positon for PPOIPS bends accord od eattaaam ing (the incareqation, 0 the eee ‘Fox equation, and (c) the Wood eque- 3704 r tion, Circles represent experimental ara ae as 10 7 points (ata of Problem 2.32),90 Chapter 2 in Fig. 2.26. The plot (Fox and Flory, 1951) shows the dependence of melt viscosity on chain length Z defined asthe weight average number of chain atoms in the polymer molecules. (For vinyl polymers Z is twice and for diene polymers ‘our times the weight-average degree of polymerization.) Below the critical chain length Z. the melt viscosity is given by n= Kzi® 2.48) and above Z., the melt viscosity is given by n= Kaz 2.49) where Ki and Kiy ate constants for low and high degrees of polymerization, They are temperature dependent ‘While the 1.0 power dependence in Eq. (2-48) represents the simple increase in viscosity a the chain gets longer, the dependence of the viscosity on the 3.4 power of the chain length as shown in Eq, (2.49) arises from entanglement and {itfuson considerations. Thus the extical chain length Z may be looked upon 4s the threshold below which the chains are too short to cause significant increase in viscosity by entanglementeffects and above which the chains are large enough to cause entanglement, larg increase in viscosity and retard melt flow. A few ap- proximate Z. values (Sperling, 1986) ate: polyisobutylene 610, polystyrene 730, poly(dimethyl siloxane) 950, and poly(decamethylene adipate) 290, Relatively flexible polymer chains have a high Z., while more rigid-chain polymers have a relatively low Ze Problem 2.34 A plastics extruder is known to work best at @ melt viscosity of sbout 20,000 poises. ‘The vinyl polymer of DP = 750 and T, = 80°C, earlier used with the ‘extruder, ha this visosity at 150°C. However, a batch of the same poljmer received subsequently has DP, = $00, At what temperature should the extruder now be run so that the optimam melt viscasity for processing is achieved (Spering, 1986)? Anewer: Fora vinyl polymer, Z =2(DP,). Since bot samples have Z > 700, Eq (2.49) ‘canbe tsed fr both For plyme with BPy, = 750 and at 150°C, 2x10 = Ky (2x75) Ky = 318x107? at 150°C For polymer with DP = 500, 1 = 318x107 (2x500)9* = 6023 Poise at 150°C ‘The WLF equation (ef Eg (2.32) can be writen as 17a = %) aes -%) :Chain Dimensions, Structures, and Transitional Phenomena 3 Since at high molecular weight Tj is esentilly constant, both the polymer samples may be assumed to have the same T,. Terefore, eam _-1744(150 - 80 ae aa = Ses sa) ~~ SOI Re Applying te WL equation agin a TAA — 80) Solving, T = 142°C "8S 6x1019 ~ 51.6 +r 80) 2.11.1 The Reptation Model Since inependeat chin mobility is not possible for polymer chains longer than Z. because of the onset of entanglement, a modified model is required to account ior the ability of lng chains to translate an diffs through the polymer matrix ‘The reptarion model of De Gennes consists of a single polymeric cain, tapped inside thee dimensional network of entangled chains, which ay be considered to const a set of fixed obstacles, as shownrin Fg. 2.27. The chain is not allowed to eros any of the obstacles, but it may move in a snake fashion Among them. This snakes motion i called repttion Tn the De Gennes approach the polymer chain s assumed to be contin in a hypothetical tbe (Fig. 228(a], the contours of which ae defined by the position of the entanglement points in te network. Mechanistic, repation an be viewed asthe movement of a kink inthe chain along its length [fe Fig 225(b] unl reaches the end ofthe chain and leaves it. Successive mekions of Figure 226 Plot of melt viseos- lity versus chain length Z for ply- a {isobutylene fractions at 217°C, (AE {er Fox and Flory 1951.)92 Chapter 2 Figure 227, A model for rptation. The poly: ter chain moves among fixed obstacles, but can not cross any of them. (After De Gennes, 1971; Specling, 1986) igure 2.28 (a) Schematic representation of a polymer chain confined in a hypothetical tube ae ‘comoured by fxed obstacles, (b) Movement of © 2S 4 "kink" along the chai. (After Cowie, 1991) this kind translate the chain through the tube and eventually take it completely out ‘of the tube. Using scaling concepts, de Gennes (1971) found that the diffusion co- efficient, D, ofa chain in the entangled polymer matrix depends on the molecular weight Af as ® Dem (2.50) Polyethylene of molecular weight 10,000 has a value of D near 10-* em?/s at 176°C and polystyrene of molecular Weight 100,000 has a D value of about 10-1? cem2/s at 175°C (Tirell, 1984), ‘When two blocks of the same polymer are pressed together at @ temperature above the J; for a relatively short time ¢, interdiffusion of polymer chains takes place (by reptation) across the interface to produce a significant number of entan- ‘glements, thereby joining the blocks together (Sperling, 1986). The-strength of the junction formed will, however, depend on time Problem 235 Mills etal. (1984) related the difusion coefficient of polystyrene at 170°C to the weight-average molecular weight by the equation D = 8x10702,)"? emis In the welding of polystyrene (My = 108) ata temperature of 170°C, calculate the ux of polymer molecules across the interface for diffusion over a 100 A distance, (Density of polystyrene = 1.0 elem?) Answer: (1.0 gem") ae eery = ate Bulk concentration of polymer =(Chain Dimensions, Structures, and Transitional Phenomena 93 ‘Concentration gradient over 100 A or 10° em distance from the bulk concentration to 3 zero concentration = [(10-S ~ 0) mol em™3]/(10"S em) = 10 mol cm* D = 8x10? x10" = 81073 en? st Flux = (x10 \10 mol em™4X6% 107° molecules mot!) = 48x10"! molecules em” ¢ In one second, 48x10"? molecules will diffuse through @L-em? area ofthe interface 2.12 Thermodynamics of Rubber Elasticity Elastomer deformation is particularly amenable to analysis using thermodynamics since an ideal elastomer behaves essentially as an ‘entropy spring’, resembling, an ‘deal gas inthis respect. In the following we shall derive relationships for internal energy (U/} and entropy(S) changes accompanying deformation of an elastomer, ‘More particularly, we shall be concerned with derivation of relationships between UW and S and the state variables — force (/),léfeth (2), and temperature (7) — from the first and second laws of thermodynamics and use the analogy of an ideal elastomer and an ideal gas since both can be considered as entropy springs. ‘The first law of thermodynamics states thatthe change in internal energy (AU) of an isolated system is equal to the total heat (Q) absorbed by the system less the work (W) done by the system: oe Au =0-W (@st In differential form, du = dQ-aw (252) ‘If the work is done on the system, such as when a gas is compressed or an elas-- ‘omer is deformed by applying foree, the corresponding equation is du = do+aw (2.53) According tothe second law of thermodynamics, the heat absorbed by the system 40 at temperature Pi related tothe increment of entropy dS by ds = aor a.s4) Fora reversible process, Eqs. (2.53) and (2.54) thus yield au = Tds + aw 255) Ifthe length of an elastic specimen is increased a small amount dl by tensile force f then the amount of work fal will be done gn the system (i.e. the spec- men). There is also a change in volume dV during elastic deformation. So if hydrostatic pressure P is acting in addition to the tensile force f, the work PaV is done by the system against the pressure, P. The total work done on the system is {herefore aw = sat ~ Pav (2.56)“ Chapter 2 (One experimental observation which allows the analysis to be simplified is thatthe deformation of elastomers takes place approximately at constant volume, ise. the deformation is nearly isovolume. For such a deformation at ambient pres- sure (P= I atm), the contribution of PaV to dW’ will be small and so the work done on the system in creating an elongation is aw = fal sn Substitution in Bq, (2.55) gives au = fal + Tas 258) ‘A useful thermodynamic quantity to characterize changes at constant volume of the working substance is Helmholtz free energy. Its defined as AsU-TS (2.59) Differentiating at constant temperature, aA = dU ~TaS (2.60) From a comparison of Eqs. (2.58) and (2.60), GA = fal (constant T ) 61 ‘Therefore, f= @Alat yr (2.62) Combining Eqs. (2.60) and (2.62), the force f can be expressed as, f= (@U/AL)p ~ T@SIAt yr (2.63) "The first term in Eq, (2.63) refers to the change in intemal energy with extension ‘and the second to the change in entropy with extension. Thus the contribution to the total force consists of an intemal energy component and an entropy compo- nent. While the internal energy term is dominant inthe case of most materials, for W = @SBKS)I = 4.177 Problem 239 Foran deal aber sip (20 cmlong, emi, nd om wide}, 20 Jo Work scapoded in stething itt vies gh 25°. Calls he nds in elon! Answer: Energy/volume = 203/40 cm? = 0.5 Jem? nergyivolume = [Zouk = (aR N) [PAR — (0.5 Fom™}(10" erg J!) So, Vi ee = 2x10 mol om” (8.37 10? erg mot 298") - z Fata] = eri) -(Chin Dimensions, Seuctures, and Transitional Phenomens vw” Problem 240 Ina sample ofaturl ruber (cts-palysoprene) vleanizate about one of very 200 chain carbon stoms is crosslinked. Estimate che Young’ modulus ofthe sample at low extensions. (Density of vuleanizate = 094 giem? at 25°C; gus constant R= 8.3«107 ergs mol! “K-1 = 1.987 eal mot“! "K-) Answer: ‘There are 200 carbon atoms between crosslinks onthe average This corresponds to 20044 = 50 monomer units between eosslinks (ee Fig. 1.8 in Chapter 1). Since the formula ‘weigh of isoprene monomer (CsHe) = 68 g mol“, Mz = 0x68 = 2400 g mol! 40.99 gem™)(8.3 10? dyne.cm mol! *K"!(298°K) (6400 g mol") 20x10" dynecm"® = 20x10 Nm (ldyne em"? =0.1 Nm? =0.1 Pay From Ea. 2.79): E = 2MPa) Problem 241 Suessstrain measurements on a lightly vulcanized natural ubber sample Yielded a value of 19x10" dyme/em? for Young's moss at low extensions. (a) Calculate the molecular weight ofan averoge chain length between crosslinks. (b) Assuming ideal network structure obtain an estimate of the crosslinked isoprene unis in the vulcanized rubber Answer: (@) From Eg, (2.79) Be = 3pRT/E 310.94 g em9)(8.3% 10" dynecm mol"! °K"H(298 °K) : 19x10" dyne en? = 3671 gma () Molar mass of isoprene (CsHs) = 68 g mal! ‘According to the idealized strcture shown in Fig. 1.4 (Chapter units crosslinked = (68 g mol“/(3671 g mol!) = 0.02 fraction of isoprene ‘ny bere nt (27 ade oe eek. Te ac chore crs ned Susana borer towe mace cath the Mooney-Rivlin equation (Mooney, 1948; Rivlin, 1948): +0 = Sot. intr! 20 ‘where C; and C2 are empirical constants. Equation (2.80) is sometimes written in a form similar to Eq. (2.77) as © = CC) + 2GyA)Q — 19) sl)100 Chapter 2 eth Bab Got Sout 8 Figure231_ A Mooney-Rivn plot with sole titi the data of Problem 242. (After Sper @02 Ga 0608 10 ting, 1986) a thas been shown that 2C} is related tothe degree of crosslinking (1/M.), to 8 fsic approximation, by 2C, = pRT/M. (2.82) ‘The parameter C is rganded a a factor coneting forthe oversimplifcation ofthe elastic theory model ‘According to Eq. (2.77), the reduced stress o{(A ~ 1/2 ) should be a constant. uation (281), on the other and prec tha this quantity depends on 2. Plos ‘of ofA — 1/A2 ) versus 1/A are, in fact, found to be linear, especially at low elongation and tis allow forthe determination of both Cy and Cs (Ge Problem 24) “The parameter Ce may be considered to bean approximate measure ofthe departures from the ideal behavior. The magnitude of this parameter is large in dry and lightly swollen rubbers but decreases o zero a high degresof swelling {ce also "Thory of Sweling” in Chaper 3). Ahighly swollen rubber thus obeys the eal ubber Eq, (2.7) more closely. Problem 242 Consider the following stress-strain data (Sperling, 1986) for @ rubber band subjected to increasing load at 25°C: 7 Tse) Pr | 3653719 1 a “Make a Mooney Rivlin plot and determine the constants C; and C, Obtain an extimat of te degree of rosslnkng ofthe rubber ban. (Density of rubberband = 1.09 gfe.) Answer: Extension Lis calculated from stein ey the elation fq. (2.72): 2 = 1 + € and oth 12 is poted again 1/2 Fg. 231). The uptar inthe curve thigh extensions Ges low 1/2) would be atibuted t non-Gaussian behavior and limited extensibility of(Chain Dimensions, Stuctues, and Transitional Phenomens 101 the chain molecules, The values of2C; and 2C3 are obtined from the intercept and slope, respectively, ofthe linear portion ofthe plot at low extesions. This yields Cy = L.Axl0® Pa = L.1xl0® dynelem? and Cy = 14x10? Pa = LAxl0® dynelem From Eg (2.82): ae 201-1210 dyno cm”) C08 gem) (8.31% 10 erg mor KHOI) 8.1% 10° mot 2.12.2, Nonideal Networks 2.2.2.1 Network Defects ‘The elastic properties ofa vulcanizate is largely influenced by the initial molecu- lar weight of the raw rubber, Le, before vulcanization. This is because the number of chain ends depends on the molecular weight and each chain end constitutes a flaw in the final network structure. The portion-of a molecule from one end to its first crosslinkage along its path, such as the chain AB in Fig. 2.32), makes no contribution toward sustaining a suess as itis always free to assume any confor- ‘mation whatever, as the end A is free. Similarly, the two chains EC and CF of molecule EF are inactive, and so the crosslinkage at Cis nota point of constraint on the chain BD. The portion ofthe network from B to Dis thus to be considered single (active) chain, as ifthe crosslinkage at C were not present, The crosslink junctions B and D are elastically active, while Cis not. 1 follows from the above discussion that a junction is elastically active if st least three paths leading away from it are independently attached tothe network. AA polymer chain segment, also called a strand, is elastically active if itis bound at each end by elastically active junctions. Loops in the network structure [Fi 2.32(0)] do not contribute to the elasticity of the network as they have the wo ends of a chain segment connected tothe network at the same point, 2.12.22 Blastieally Active Chain Sections [As explained above, a number of chsin sections, such as loops and chain ends, do not contribute to the elasticity ofthe network. It is therefore necessary to develop an expression forthe number n of ative chain sections in areal structure containing a total number of both active and inactive chain sections Suppose that the material consisted orginally of N individual molecules of| average molecular weight M, per unit volume. The minimum numberof links Per nit volume which would be required to create a continuous system forming a giant molecule is N'— 1, Ie would be incorrect o call ita network, inasmuch as it contains no net-like structure, it possesses no eieuitous connections within its structure. As additional crosslinks ae added, the structure acquires the character102 Chapter? 8 @ § F Figure 2.32 (a) Effect of ends of molecules fon network structure. (b) Network structure 3 and defects: * erasslinks; © terminus of 7 ‘molecule; (1) elastically active chin; (2) 2 i inactive loop: (@) inactive loose end. An arrow (—») signifies contiauation of the net ‘work srvture. (After Flory, 1944) ‘of a network, Only connections in excess of (N ~ 1) effectively fx the structure 80 that it responds elastically to deformation. ‘The number of crosslinks per unit volume in a perfect network will be (n/2) (see Fig,2.30). The effective number of ‘crosslinks per unit volume in areal structure is therefore given by 2 in which 1 has been neglected as being small compared with N. Now N may be expressed by B= f-Ww-n~ f-N 283) N= pNw/My (2.84) ce (eten\(y 2M “+ Get ass “This expression for ne should be substituted for» in Eq, (2.75). The combination (of Eqs. (2.75) and (2.85) yields v= Gilt at- 2 2) 23 fark, + 0.85 289 etc 056 2.7, Be ee wks aha mmactc et st eset asain is Dae ae hes accurately measuring or controlling Me. In practice, M, may also change during Sout lain eof nea eg Problem 243 Given rubber that has Wy = 100,000 g/mol before crosslinking. After crosslinking, tis stretched o 2 times its unstretched length at 25°C supporting a stress of (0.84 MINimé. Ager aging 10 days in airat 125°C, the stress at 2 times its unstretched length {25°C is only 048 MNm?, (a) Calculate the degree of crosslinking of the rubber before(Chain Dimensions, Structures, and Transitional Phenomena 103 aging. (b) What fraction of crosslinks are lot on aging ? The density ofthe crosslinked rubber (without filler is 0.98 glen. Answer: (T= 298K, 2 Prom Bq. 2.86) (64108 dyne om) 84 MN ay 4108 dyne em” (0.98 geom”)(8.37% 107 erg molt *K-1298°%) Solving, We= 4621 g mot", QNote that use of Eq. (2.77) gives Bf = $092 g mol!) Degree of csslinking = fe)" = 4621 g mol!) = 22x10 mol (©) After aging, = 048MNm? = 484108 dyne em? at T = 25°C 298°K). From Eq, (286), Mz = 7563 gmol“!. Since (.)" is proportional tothe number of crosslinks, (4621 g mol“!)“L > (1563 g moly (G@2I gor 139 06 39% loss of eroslinks on aging = REFERENCES Alkonis, 1.3, J. Chem, Ec, 58(11), 892 (1981). Beamea, R.G, J. Polym. Sci, 9,470 (1952). Bovey, F. A,*Polymer Conformation and Configuration”, Academic Press, New York, 1969. Bovey, FA. and Tets, GV. D.,J- Poly. Sei. 4, 173 (1960), Boyer, RB, J. Appl Phys, 25,825 (1954). ‘Boeche, F, “Physical Properties of Polymers", Interscience Publishers, New York, 1962 Cowie, J. M. G. “Polymers: Chemistry and Physics and Modem Materials”, Blackie, Giasgow, 1991. De Gennes, PG. J. Chem. Phys, 85, $72 (1971). Eyring, HL, J. Chem. Phys. 4, 283 (1936), Flory, PJ, Cher. Rev.,35, 51 (1948). Flory, P 1, “Principles of Polymer Chemistry", Come Uni. Pres, Ithaca, N.Y, 1953, Flory, P.1- and Leutner,F S.J. Polym. Se, 3,880 (1948); 8,267 (1950). For, T.G., Bull. Am. Phys, Soc 1,123 (1956). Fox, T.G. and Flory, P.J.,J- Appl. Pips, 21, $81 (1950). Fox, T.G. and Flory, P. JJ. Phys. Chem. 85,221 (1951) For, T.G. and Flory, PJ. J. Poly, Sci. 14, 315 (1988), Guth, B. end Mark, H, Monarch. Chem 65,93 (1934).104 Chapter 2 Hay, JN. Brit Pom. J 3,74 (1971). Holmes, B.R., Bunn, C. W,, and Smith, D. J, J. Polym, Sei 17, 139 (1953). Kelley, FN. and Bueche, FJ. Poly. Sct, 80, 549 (1961), Koenig, 5 L., “Chemical Mieostrcture of Polymer Chins", chaps. 68, Wiley Inter science, New York, 1980, Mandelkern, T., Mastin, G. M.,and Quinn, F.A., J. Res. Nal. Bur. Stan, 88,137 (1957). Mills, P.1., Green, PE, Palmstrom, C. S., Mayer, J. W. and Kramer, EJ, Appl. Phy. Lett, 88(9), 957 (1984). ‘Mooney, M. J. Apal. Phys. 19, 434 (1948). ‘Odian, G., “Principles of Polymerization" 34 ed. John Wiley, New York, 1991 Ono, A., Polymer, 2, 305 (1961). Price FP. in B, H, Doremus, B. W. Roberts, and Turnbull D,, Eds. “Growth and Perec tion in Crystals p. 466, Wiley, New York, 1958 Rivlin, R.S., Trans. Roy, Soe. (Lond, A2A1, 379 (1948) Rudin, A., “The Elements of Polymer Science and Enginecring", Academic Press, Or lando, 1982. ‘Sharma, .C., Mandelker,L., ad Stebling, F.C J Py. Sc, B10, 345 (1972). Sima, Rand Boyer, R.FJ- Chem. Phys, 37, 1003 (1962). Sperling, L. HL, “Introduction to Physical Polymer Science", Wile-Interscience, New York, 1986, ‘Tne, M, Rubber Chem. Tech. 51,523 (1984). Wiliams, ML, Landel, RF and Ferry J... J. Am. Chem. Soe. 77,3701 (195). ‘Young, RJ. and Lovell, PA. “Inrodaction to Polymers”, Chapman and Hall, London, 1560, cee EXERCISES 2.1 (@) Calculate the root mean square end-to-end distance and the radius of gyration for ‘ molecule in molten polypropylene of molecular weight 10°. (Data: carbon-carbon bond length = 1.54X10- cm; tevaedal bond angle = 109.5"; steric parameter, wii6at 140°C, (b) How extensible is the molecule? (Hint: Calculate the ratio of the extended chain length to the aerage chain end separation.) [Ans (@) 24x10°® em 9.8107 cm, (6) 24 times) 2.2. Assuming thatthe RMS end-to-end distance isan approximate measure ofthe diam ‘er ofthe spherical, coiled polymer molecule in dilute solution, compare the volume ‘occupied by one molecule of polyisoburylene of molecular weight 10° (a) In solid at 30°C (density = 0.92 gem?) () ine herasolvent ‘Take the value ofthe steric parameter o forthe polymer as 2.0 and the carbon-carbon bond length as 1.5410" cm. [Ans @) L8b0° A; (b) 292x108 A)Chain Dimensions, Structures, and Transitional Phenomena 105 23. The RMS end-to-end distance is 2.01y/m A for eis-plyisoprene and 2.90 A for trans-polysoprene,n being the taal numberof bonds in each rel etn, Compare the chain sttiness ofthe two polymers. (Ans. Trans-polyisoprene is 14 times sifer than cis-polysoprene) 24 From the data given above calculate the values of @ and Cy for ci and tans polysopeene, given tat the length af an isoprene repeating unit is 4.6010", Ans, Cis-polyisoprene: c= 1.2; Cup = 3.1. Trans-poyisoprene: © = L.8; Cou = 64] 225 Given that the RMS end-to-end distance < 72>)? i (290/R)10"* em for ras polyisoprene, where isthe total numberof bonds inthe real chain, and the length of am isoprene repeating uit is 4.60%10°® em, caleult the numberof monomer wis ‘Lrrans-polyisoprene molecule has per equivalent random (feelyjonted) chain ink, (Ans. 159] 26 The a-methyl resonance in poly(a-methyl styrene) is found to be split into three peaks which are assigned to isotacti,heterotactic, and syndiotasc triads. Fractions ‘ofthe polymers inthe three coafiguratons deterpined bythe area ofthese peaks ae ven belo for poly(a-mety styrene) prepared with two different catalysts [Brown stein, ., Bywater, Sand Worsfold, DJ, Makromol. Cher, 48, 127 (1961): Polymer | Caiajat Fraction of polymer (cero _ Syndlo 1 BF; - oll 089 2 | NaNapithenide | 013 048 039 Determine the probability Py and west for consistency with Bemoullian statistics.“ ‘What do the values of Py obtained in the two cases signify ? [Ans Polymer I: Py = 006; Polymer 2: Py = 0.4] 27. The density of ensaline poyetyen is 0.996 gfeu?, while the density of amor phous polyethylene i 0.866 jem’. Calculate the percentage of crystallinity in a sample of linear polyeylene of density 0.970 glen? and in e sample of branched pyetylene of easy 0.917. Why do the two samples have considerably diferent ceysalliites? {dns 426%: 82.1%) 28 Chemically both wax and polyethylene canbe described as polyethylene an ep sented by-¢CH but while the farmers abit solid the ars a tough plastic ‘What ae the reasoas for his iference in mechanical behavior? 29. Draw alogE versus temperature plot for lnear, amorphous polymer and indicate the poition and name the five regions of viscoelastic behavior How isthe curve changed if (the polymer is semierystalline, (b) the polymer i eosslinked, and (6) the experiment is run faster?106 Chapter 2 2.10 To be a useful plastic, an amorphous polymer must be below its fy atthe ambient temperature, while crystalline polymers may be either above oF below their Z's why? 2.11. Explain the following {@) By dipping into liquid nitrogen, an adhesive tape loses its stickiness (0) A bollow rubber ball when cooled in liquid nitrogen and thrown hard against the wall breaks into pieces. (Gia dinner bel Goated with latex paint and kept ina freezer makes louder noise than the one costed and kept at room temperature. {G) Molding ox extrusion of plastics too close to, can result in a stiffening ofthe materiel (@) The Ty ofa semicrystalline polymer is often higher than the same polymer in & ‘completely amorphous sate {B In emulsion polymerization of styrene, often carried out at 80°C, the reaction does not proceed quite to 100% conversion. {When nylon shirts are warbed and hung up to dripy, reas srighten out by themselves (b) The postage stamp, which is coated with linear polyvinyl sleobol) adhesive, needs to be moistened with water (or saliva) before applying, 12.12 When polyethylene is chloritated, chlorine replaces hydrogen at random. The soft- ‘ning point ofthis chlorinated product depends onthe chlorine content. Ts found that small amounts of ehlorine (10 to 50 wi CI) lowers the softening pont while Jarge amounts (~ 70%) raise the softening point. Rationalize this observation on the basis of intermolecular forces. 12.13 Account for the fat thatthe coeicent of volume expansion below 7p is smaller than that above T,. Why is it ssi that in the glassy state the polymer is nt ina true thermodynamic equilibrium ? 2.14 A newly prepared thermoplastic polymer has a Ty of 110°C and « melt viscosity of ‘2c! poise at 140°C, The polymer, however, degrades above 160°C. Can this polymer be processed with an extraer which performs best when the melt viscosity fe about 2x10" poses” If no, what canbe done to make the polymer processable [ans Cannot be used as nygpc. > 7108 processability. Plsticier may be added] 12.15 The following data were obtained (L, Mandelkern, G, M. Matin, and F.A. Quinn, J ‘Res, Nat. Bur. Sian, $8,137 (1957) forte pass transition temperature T, of the copalymers of vinylidene fuoride and chlororluoroetiylene, as a fonction ofthe ‘weight faction wy ofthe frst comonomer. rn Teo| 19 3 8 1538 ‘What would be the Ty of «copolymer with w = 0.75? [ans 28°C] 2.16 Two polystyrene standards (monodisperse) of molecular weights 8106 and | 6x10* have T, values of 105.9°C. and 108,7°C, respectively. Calculate the Tp value of 2 highly polydsperse polystyrene made up of four low polydisperse components 3s shown below: .(Chain Dimensions, Structures, and Transitional Phenomena 107 Component We frscton(w) _My 0 T 0.05 T 2 oat 2am 3 039 2x10 4 ous spa! Tas 083°C 2.17 A new polymer with a weight average degree of polymerization of 1400 and five ‘toms inthe repeating wait has a melt viscosity of 1500 poses at 190°C. What will be the viscosity atthe same temperature if its molecular Weight is dovbled ? Ans. 15854 poise} 2.18 A vinyl polymer with a Z value of 200 has a met viscosity of 100 poises. What ‘would the viscosity ofthis polymer be if Z = 800°? (Ans. 798 poise) 2.19 Apolymer with aT, of 105°C and a Z value of 400 is found to have a melt viscosity (of 500 poises at 170°C. Whar will be the melt viscosity at 150°C if Z = 800? ‘Assume Z- = 600. (Hint: Combine the DP dependence with the WLF equation.) [ans. 7.510? poise] “ 2.20 Account forthe fact that if strip of rubber is bought into contact with the tempera ‘ure-senstve lips nd stretched rapidly, an instantaneous warming ofthe stip can be cally perceived 2.21 A polysoprene rubber has 2.5% ofits epeating units crosslinked by sulfur vuleaniza- sion. Estimate the modulus ofthe sample at low extensions. (Deasity of vulcanizate =0.94 glom? 825°C.) [Ans. 27 MN m-? (= 2.7510" dyne om”)] 2.22 A synthetic rubber containing 60% butadiene and 40% isoprene by weight was vl ‘canized with 56 (w/w) sulfur. Stessstrain measurements on ths vulcanizate at low extensions yielded a value of 28x10" dynefem for Young's modulus. (2) Calculate ‘the molecular weight ofthe chain lengths between crosslinks. (b) Assuming that all slurs used in crosslinking, determine how mmsny sulfur toms on average are used ineach crosslink. (Density of vulcanizate = 0.99 glem® at 25°C.) (Ans. (a) 2464 g mol“!; (&) 38), 2.23 The synthetic rubber in the above problem was vulcanized such that 1.2% of the monomer units in the polymer were crosslinked. (a) Calculate the stress at 25% longation ofthe vulcanizate (b) What would be the coresponding stres if 2.4% ‘ofthe uit ae crosslinked ? Assume random disebution of both monomers inthe chain, Density of vuleanizate =0.93 glen? at 25°C.) (Ans: 0293108 N mr? (=0.29 MPa); (6) 0.59108 Nm? (=0.59 MPa] 2.24 Aminteresting experiment vas described (6. V. Henderson, D. 0. Cambell, V. Kuzmicz, and L. HL Specing, Chem. Bd. 62,269 (1985)] to determine the extent of hydrogen bonding in gelled gelatin by observing the depth of indentation of a sphere ino the surface ofthe gl. Ina typical experiment 22g gelatin was dissolved in 600 ml water and allowed to set in refrigerator at 5"C. A ste ball em in diameter and weighing108 225 226 Chapter 2 1262 g made an indentation 1.20 em deep when placed on the gelled gelatin. Assum- ing a molecular weight of 30,000 forthe gelatin, calulate the number of hydrogen bonde per molecule ‘Youngs modulus (E) may be determined from indentation by using the equation 0A Be grr vere F represents the force of sphere against the gelatin surface (= mg dyes), epresents the depth of indentation of sphere (em), sth radius of sphere (em), is the gravity constant, and is posson's ato (may be assumed tobe 0.5). (Ans. 0.46] 'A 60cm long rubberband is stretched to 15.0 em. Its found that o keep the rubber ‘band at this length when the temperature i raised from 27°C to 32°C, an atonal stress of 15x10° Pa isto be applied. Calculate the modulus of this robber at 1% tlongaton at 27°C. (Neglect any changes in volume with temperate) Ans. 114 MPa] “Two idecicl rubber bands, A and B, each 10 em long, are ted together at their ends and sreched ta total length of 30 cm. The rubber bands A and B are at 25°C. and 140°C, respectively, Calculate the distance ofthe knot from the untied end of A. {Ans. 16cm)(Chain Dimensions, Structures, and Transitional Phenomena 109 APPENDIX 2.1 End-to-End Distance of a Freely Jointed Chain ‘The simplest mathematical model ofa polymer chain isthe fesly oid chin. 1 has ‘nlinks, each of length 2 joined ina linear sequence with no restriction on the angles ‘between successive bonds. The length ofthe chain along is backbone is known as the contour length and is given by nl. However, for linear exible chain i is more realistic to consider its dimensions in tems ofthe distance between the two chain ends, that i the end-to-end distance 7 (Fig. A210] ‘The analysis ofthis model is similar to that of the well-known rondom-walk model which was fst developed to describe the random movement of molecules in an ideal gs ‘The ony difference now i tha forthe feey joined chain, each step is of equal length 4. To analyze the model one end of the chain may be fixed atthe origin O of a tuee- imensional rectangular coordinate system, a shown in Fig. A2.1¢), andthe probability, 'PG.3.2) of finding the other end within a small volume element di-dyz at & patialar point with coordinates (2) may be calculated, Such calculation lads ro an equation of ‘he fom (Young and Lavell, 1950) Popa) = Woxyeddndyde (a2. where W(x) is the probability densi function, i, probability per wit volume. When ‘nip large and r nl, W(sy.2) i given by Wena) = Bie! expl- pe? +? +2) a2) where = [3/2n)1", Since r? = 32-+y2-+ 22, Ba, (A2.2) simplifies Wore) = BaP ex 6) (323) ‘The value of W6.:2) comesponds to an end-to-end distance rin a particular dretion specified by the set of coordinates (2). However, here may be many such coordinates cach of which gives rise othe same end-to-end distance rutin different diection. The probability of finding out chain end a a distance r in any direction from the other chain nd located at the origin is equal to the probability Wir of Sing the chain end in a sperical shell of thickness dr at araial distance rfrom the ign. Since the volume ofthe spherical shell is 4nr2dr and the probability density funtion is W.32, the protabilicy ‘Wendi given by Wonder = Woy2)4P dr ana) ‘Substitution of W942) from Bq, (42.3) then gives the Following expression forthe radia dsribtion fntion Wi) Wer) = AaB) exp— 9) (2s) ‘This fonction hes a maximum value ata cerita value of r I can be shown by simple ferentiation that this maximum occurs atr = 1/8. Its also possible to show that Wir)110 Chapter 2 D Figure AZ (a) Schematic represen tation of & coved polymer molecule ‘ sowing te endto-end distance.) Diagram showing a cold polymer rnolecule of endoand dance rin recaaglar coordina system with one 7: fia end Sed a he origin. Afr a is ‘Yung snd Lovell, 1980.) sormalizes oni, Gwindr=t 26 “The meen square end-to-end distance, , isthe second moment of the radial isibution funtion and sis defined by the inepral (Young and Lovell, 1990)

(Amer «ann Susttuing for Wr Eg (A2.) ad imegrting ee Problem A2.1) lead 0 <7? 323/069 cas) ‘Since f* = 3/(2ni”), the RMS end-to-end distance is given by

smaller than te contour length nf by 8 factor cof nl, The value of being large, this difference is considerable and it indicates the ight coiled ate of flexible polymer chains. A polymer chain in dite solution can thas be picned a col, commonly altering its shape an size duet conformations changes under the action of random thermal moons. The angular brackets of < 72 > denote averaging ove al possible conformational ies evalabe to polymer molecules of the same molecular weight Sie diferences become more sinifian fo polymer samples vii are plydspere and contin chains of wie variety of chain lengths. This eal for ‘nother averaging, Chsin dimensions of polysperse near polymers are thas given bythe teraye RMS endtocnd distance <7? >!, where the bar indicates averaging de to chain polydispersity, whereas !? without bar epresets the RMS end-o-nd distance of & Single chain or monodisperse polymer sampleChapter 3 Polymers in Solution 3.1 Introduction ‘A number of important characteristics of polymers, such as molecular weight, chain length, branching, and chain stiffness, can be explored when the individual ‘molecules are separated from each other. Such studies therefore employ dilute solutions of polymers. However, the dissolution of a polymer also brings with it many new problems. For a correct interpretation of the behavior of polymer solutions it is essential to understand the thermodynamics of polymer-solvent in- teraction, We will therefore explore some of the basic underlying thermodynamic principles of polymer solutions in this chapter. A major part of the chapter will be concerned with methods of studying polymer solutions that deal with equilib- ria and can be fully described by thermodynamic relations. These include vapor “ pressure, osmotic pressure, and phase separation in polymer-solvent systems 3.2 Thermodynamics of Liquid Mixtures ee ee ee ate ae ey ce ee polymer solutions aze partial molar volume V; and partial molar Gibbs fee energy 1G. The later quantity is of special significance since itis identical to te quantity Coe i 1 (Foray Se ee ee ey =G en am12 Chapter 3 {lis evidently equal tothe molar Gibbs free energy G} of pure component iat the same temperature and pressure. ‘The chemical potentials ae the key partial molar quantities. The 4's deter mine reaction and phase equilibrium. Moreover al other partial molar properties and all thermodynamic properties ofthe solution ean be found from the p's if we ‘know the chemical potentials as functions of 7, P, and composition. “The free energy of mixing in the formation of a solution, AGrsix, i given by Ga = G- YG? ea where Gis the free energy characterizing the state of the solution and G7 repre- sents the free energies ofthe individual (pure) components forming the solution. Recognizing that chemical potential is equal to the partial molar Gibbs free energy, as shown by Eq, (31), and that the chemical potential of pure component i, nit is equal to simply the molar Gibbs free energy of pure component i.e, Gf atthe pressure and temperature of the system, itis easy to show from Eq, (3.2) that Ba LS “The partial derivative on the right hand side of Eq. (3.3) is the partial molar Gibbs _free energy change, denoted by BG; (Young and Lovell, 1990). ‘Tt may be noted that all known thermodynamic relations are also valid forthe pattial molar functions. Thus, the relation G =H ~ 7S in terms of partial molar functions is 6) ‘Therefore, from Bq, (3.3) mi = BG, = BA; ~ TAS; G3) For ideal solutions that form with a zero heat effect, BFZ; = 0. Hence for ideal solutions wih = BG, = -THS, (ex) {will be shown late that ideal entropy of mixing of two components, say, | and 2, is given by z Six Where nj and x; ate, respectively, number of moles and mole fractions of com- ‘ponent i. Partial ideal entropies of mixing can be obtained by differentiating Eq. (G7), Thus for component i, in general, =-R(mlnx: + malnm) en BS eee? Rinx, G8) Substituting in Eq. 6.6), ena = Ring, 6%Polymers in Soltion 13 “Thus, the change in chemical potential of the th component in n ideal solution depends only onthe mole fraction ofthat component in solution Inthe case ofa real solution, : » sh = Rind 6.10) where py and pf ae the pata vapor pressures ofthe ith component above the solution and above the pure component, respectively. Since fora themodynam cally stable solution p< pit follows fom Ea, (3.10) that pz < 0 oF j= ic. the chemical potential of ech component inthe solution i salle than that of the pure component Comparing Eqs. (39) and (3.10) we obtain, fran ies solution, pildh = 3 Gay Relation (3.11) was obtained empirically by Raoult and is called Raoult's law. Hence in idea solutions Raoult’ law hold ovr the entice range of compositions, this being represented by a straight line inthe vapor pressure composition curve (Fig. 3.1). In reality, most solutions do not obey Eqs. (3.9) and (3.11). Such solutions ae called nonideal or rea. Polymer solutions charactristiely display Sharp negative deviations from ideality, a canbe seen in Fig. 3. 'A method of estimating the deviation of solutions from ideality, suggested by Lewis, consists in substituting a certain function elled activity forthe mole fractions in all thermodynamic equations which are not valid fr real solutions. ‘Thus, instead of Eqs. (3.9) and (3.11) we may write ‘i wen = Su = RT Ina; G.12) = pip = a G13), ‘Theoretical procedures for deriving expressions for AGruix usually start with the construction of a model of the mixture. The most popular Flory-Hugeins theory, which was developed in the early 1940s, is based on the pseudolattice ‘model and many approximations (Flory, 1953). Though extremely simple, the theory explains correctly (atleast qualitatively) a large number of experimental ‘observations, and serves asa basis for other more sophisticated theories. Flory-Huggins theory is based.on splitting AGaix into an enthalpy term and an entropy term according to Eq. (3.14) and evaluating these two terms separately AGniz = AHpix ~ TASaix G14) ‘The entropy of mixing ASqiz is computed from the number of possible ar- rangements of the molecules on a lattice, while the enthalpy of mixing, Anis, is calculated from the change in interaction energies among molecular surfaces uring the process of mixing. Before turning to Flory-Huggins theory, itis con- venient to develop firs the theory for mixtures of low molecular weight solvents to gota better grasp of the principles involved.4a Chapter 3 Figure 3.1 Dependence of vapor pres- sure over a polymer solution on mote {action of components. 3.2.1 Low-Molecular-Weight Mixtures: van Laar Model Letus considera mixture of to substances A and B satisfying the conditions that molecules of A and B are identical n size and shape and (i) the energies of ike Ge, A-A or B-B) and unlike (.e., A-B) molecular interactions are equal. Such mixtures form deal solutions. Condition i leads to athermal mixing (i. AH (0), which also means that there are no changes in the rotational, vibrational, and vansatonal entropies and in the entropy of intermolecular interetions ofthe Components upon mixing. Thus, MSaix depends only upon the configurational (er combinatorial entropy change, ASant, whichis positive because the mimber odstngushable spatial arangements ofthe molecules increases when they are mixed. Hence SGux of Eq, (14) is negative and formation ofan ideal solution is favorable. “The methods of statistical mechanics can be used to derive an equation for Swat by assuming tha the molecules are placed randomly into eels that are of molecular size and are arranged inte form of thee-cimensional tice (rep- fesented in two dimensions in Fig. 32(a). The entropy $ of an‘assembly of Inolecues andthe total mmber {1 of distinguishable degenerate (ie. of equal nergy arrangements of the molecules are related by the well-known Boltzmann uation: = S = kind ei ‘where kis the Boltzmann constant. Since ASaix is equal to ASzo. applying Fa (3.15) the formation ofan ideal soltion one obtains AScost = KIN mig ~ Cn + InMs)] G16) where M4, 0g, and Opis are, respectively, the total numbers of distinguishable spatial arrangements ofthe molecules in the pure substance A, pure substance B, and the ideal mixture. All the molecules ofa pure substance being identical, there ccan be only one distinguishable spatial arrangement of them, thats, of placing NVPolymers in Solution ns eo[o[e[se[oje] + [OJoyo 3] ofefelofofofefo] —|ofojo| ) ofojolofefe|oje| joletet oO} e@[ole[ojojolelo} [olelo o ofelolelefolojo| folete alo e[ololojofe|ole| | fojofeojojetelo olole|e|o[o|o} ololeterete|6o olelololefofelo| —[ojofojojojofojo @ © Figure 32 Schematic representation of quasicystalline latice model for salutons. (2) Simple solution: mixture of molecules of equa siz, white circles representing the solvent ‘molecules and filed ctces the solute molecules. It is assume that solvent molecules can ‘exchange sites with solute molecules. Tis results in an increas in the number of Ways they ‘canbe arranged, and hence in an increase in entopy, £0) Polymer solution: mixture of solvent molecules (unfilled cirles) wit a polymer molecule composed of chain segments {ach segment represented by a filled circle) tied with chemical bons. Its assumed that solvent molecules can exchange sites with polymer chain segments, This results in an increase in entropy. (After Flory, 1953) indistinguishable molecules in a latice containing N cells. Thus 4 = 1 and Og and Eq, G16) reduces Swot = EnDnis Gun) The total number of distinguishable spatial arrangements of Ng molecules of and Ny molecules of B in a lattice of (Na +Np) cells is equal to the number of permutations of (V4 +Na) objects consisting of Na identical objects oftype A and Np identical object of type B, thet is, ia Na So = Na Substitution of a, (18) into Bg, 3.17) gives ae ‘(Na + Np)! A = Hn tA on) Applying Siting’ approximation lant = wiaw = 9 220 (Gor large N), Eq. G.19) leads to sa = nla Seg) + eine }] oan6 Chapter 3 Itis more convenient to deal with equations in terms of numbers of moles, m, and mole fractions, x. Inthe present case, these are given by na = MalNav, mp = NaiNay, m= m4 + Mw 822) xa = naling +a), 2p = malta + na) 623) “where Nay is Avogadro's number, Thus, Eq. (3.21) takes a simple form AScost = —RUnalnzy + nalnzs] 24) in which R(= KNay) is the universal gas constant. (It may be noted that since the configurational entopy of unmixed components is 270, Sais infact exeal to San ofthe mix) Since forthe formation of nidealslition, Six = ASwut and Hix = 0, 4, 6.14) becomes Gis = RT toalnsy + plas) 25) uation (3.25) provides the bass for deivation of standard thermodynamic relationships for del solution (©, Raoult lav). To make it more genealy “pleas this equation has to be andi for nonidealty of solution when tuning is nonathermal (Le. Aff # 9) de to nonequivalent intermolecular in- teractions caused by the socalled dispersion forces. The decrease in eneay due to imeractions is called the interaction energy. This energy 8 larger for poet molecules than for nonpolar mlecules Inthe liquid late defied above, each molecule as z contact points, 2 being the coordination number ofthe lates, In «mixture of A and B there are three ‘oper of contact namely, A-A. B-Band A-B ith interaction energies xa 55 fit a, respectively. (The tmodel implies that all contact points ofa molecule areequivalent) The enthalpy of mixing is ven by Adis = H - Ha - He 326) where H, Ha, and Hy represent the contributions of the contact energy to the ‘enthalpies ofthe mixture, pure component A, and pure component B, respectively Hand Hp can be calculated (Munk, 1989) from Hy = wNaernal 2 Hy = Waess/? 6.28) Where the factor 2 accounts for the fact that each contact involves two contact points. ‘Assuming that the number of heterogeneous contacts is Nag, we can thus write (Munk, 1989) for H = Napwas + (Na ~ Nasbona/2 + (Na ~ Nan )ons/2 (3-28) Substtation of Hy, Hp, and H from Eqs. (3.27)-(3.29) into Eg. (3.26) then yields Adlnix = Naslwas ~ (4a + nn)/2] = Nason -° (3.30)Polymers in Solution 7 where Awxe = Was — (waa + wap), representing the change in energy for the formation of an AB contact, is the excess contact energy of an AB contact. ‘The numberof heterogeneous contacts Nap can be easly estimated. I is equal to the number of contact points associated with A molecules multiplied by the probability pp that a neighbor of molecule A is molecule B (Munk, 1989), that is, Nap = Napa 63) For simplicity, pg is assumed to be the probability that any molecule (not necessarily a neighbor of molecule A) in the solution is a molecule B. This letter probability is equal to the mole fraction of component B in the mixture. Its use is justified only when the arrangement of molecules on the lattice is completely random, Combining Eqs. (3.30) and (3.31) and replacing pe by the mole fraction x5 of component B, which is equal to Np/(Na + Np), one obtains Adaix = Naxezhuns 632) Substitution of Nj from Eq, (3.22) then yield, AHinix = xanaNwzhons 633) ‘The product Nqy2Aw,p has a physical meaning. It represents an enthalpy change for the transfer of 1 mol of A (or B) from its pure state to an infinitely dilute solution in B (or A). Combining Eqs. (3.14), (3.24), and (3.33), and noting that Swix one obtains ao Scant RY (nly + mplnzg + nqxpNayzhenss/RT) (3.34) ‘The last term in this expression is commonly simplified by introducing the interaction parameter Xap, defined (Munk, 1989) as Yaa = Navchwgg/RT = Beogy/hT 635) According to the model, 4p is thus inversely proportionalto temperature, whereas ‘Awan is assumed to be independent of temperature, Note that Aus, and hence _xAp, can be either postive or negative, Combination of Eq. (3.34) with Bq. (3.35) yields Gig = RE (nglnay + mplnxy + naxayas) 3:36) Equation (3.36) describes the vn Laar model of solvent mixtures and i appli- cable only to mixtures of low-molecular-weight components with approximately the same molar volume. ‘The van Laar model fails to give realistic predictions of the thermodynamic properties of polymer solutions. This arises from the assumption made in this ‘model that the solvent and solute molecules ate identical in size. Flory (1942) and. Huggins (1942) proposed, independently, a modified lattice theory that takes into account the large differences in size between solvent and polymer molecules, in addition to intermolecular interactions.us Chapter 3 3.2.2 Polymer-Solvent Mixtures: Flory-Huggins Model In order to place both the solvent molecules and polymer molecules onto the same pseudolattice, it becomes necessary to consider the polymer molecules to be ‘chains of segments, each segment being equal in size to a solvent molecule. Tae ‘umber, ofthese segments in the chain defines the size of a polymer molecule and is given by the ratio of molar volumes V/V; (from now on we will assign the Subscript Ito the solvent and 2 tothe polymer solute). Hence o is not necessarily ‘equal tothe degree of polymerization, ‘The model assumes that each lattice cell is occupied by either a solvent molecule or a chain segment, and each polymer ‘molecule is placed in the latice so that its chain segments occupy a continuous sequence of cells (as indicated in Fig. 3.2(b). ——————eE Problem 31 Calulte, in terms of the ltce model ofthe Flo-Huggins theory. the umber of segments per polysiyrene motel of molecular weight 290,00 solved in {a)taluene and () metyl ety ketone (MEK) at 25°C, (Data: polymer density = 1.083 fem fa tolvene and L091 glem? in MK, calculated onthe assumption of aivity of Solumes toluene density = 0.861 gem; MEK density =0.799 glen all a 25°C] Answer: (@ Polysyrenatoluene Mz _ 290x108 got! n 085 80 Vi = (2gmoty(0:861 gear) Ye _ 2678x108 en? mo = 2.678% 10% cm? mot % 106,852 em? mot” 4) e gx 0% ca) Hi * “068s2@n8 mor = 78 (Pye MEK: : aa010% gmat ee pp = 290210 mY 9.6510 en! ma A ae ad rpm = sot ent matt 079960) (2.658108 cm? mol!) (0.1 ex? mor) In comparison, the degre of polymerization ofthe polymer = (2.90%10° g ma-"V(Q04 g = 7950 Inthe first stage, the Flory-Huggins theory derives an expression for ASzix ‘when AMfaix = 0. This involves the application of Eq. (3.16), but this time withPolymers in Solution ug ‘M > | because each molecule can adopt many different conformations (ue. dis- tinguishable spatial arangements of the sequence of segments). Hence for poly ‘mer solutions (considering the configurational entropy change ASyeq to be the only source of AS) one can write ASpie = kla(O2/ 02) 37) ‘The evaluation of 2, 92, and AS of Eq. (3:37) is rather complex. The cal- culations, considered in outline below, are based on the formation of a polymer solution by mixing N2 polymer molecules, each comprising segments in the chain, with Nj solvent molecules in a lattice containing N, + o> (= N) cals, ‘The polymer molecules are added tothe lattice one-by-one before adding the sol- vent molecules. ‘When adding a polymer molecule tis assumed, using s mean feld approxima ‘fon, that the segments ofthe previously added polymer molecule are distributed uniformly in the latice. The N; solvent molecules are added to the lattice after the addition of Np polymer molecules. However, since the solvent molecules are identical, there is only one distinguishable spatial arrangement of them obtained by placing one solvent molecule in each of the remaining empty cells. Consider- ing further the fact thatthe Np polymer molecules are identical, the total number ‘of distinguishable spatil arrangements of the mixture is given by On = WMD TEY we 338) ‘here 1 is the total number of possible conformations of the polymer molecule i and [Tis the symbol for a continuous product, which inthis ease is uy up us x ug ++ ay. The expression for yp given in 2 useful form by Flory is ao = for EPI al] 0m ‘The product of the quantities in the frst two pair of square brackets of Eq, (3.39) represents Mand s0 Eq. (3.37) takes the form ee ke Sux = ~K{Ni In) + NoIngo) Gan where ) and gare the volume fractions of solvent and polymer given by the fractions of the total number of lattice points occupied by solvent molecules and polymer segments, respectively OL = MIM +O) and gy = eNA/N +02) 3.42)120 Chapter 3 Tn terms of number of moles, Eq. (3.41) becomes Snax = ~Rfn Ing + n2lnds) (3.43) ‘This expression for polymer solutions is seen to be very similar to the comrespond- ing expression for ideal mixing of small molecules, ie., Eq. (3.24). The only difference is that in place of the mole fractions in Eq. (3.24) we now use the cor- responding volume fractions. It should be noted that Eq. (3.43) reduces to Eq (3.24) when Problem 3.2 Using te entropy change equation ofthe lattice model, calculate the change inentropy when equal amounts (100 g) of two components are mixed foreach ofthe fol- Towing systems: (a) toluene and meth] ethyl ketone (MEK); (0) toluene and polystyrene ‘of molecular weight 1.210%; and (2) polystyrene and poly(methy! methacrylate) each of molecular weight 10,000. Take the density ofeach component as 1.0 gem. Comment on the comparative entropy changes of mixing forthe thee systems. Answer: (@) Tose Bq, (2.24) let A and B cepresent toluene and MEK, respectively, Molar masses of A and B: Ma (CyHs)=92 gmol"!; Mp (C4Hg0)=72 g mot? (200 =) 400 @) Moles of AsndB: nq = 108) 1.087 mol, np = 0°08 — = 1.389 mol Sgmor} emo} 561 ‘Mole factions of A and B: x4 = 1.087(.087 1.389) = 0.439, x5 = 1-0.439) Spc = —(8314 J mol! K-"((.087 mol) in0.439 + (1.389 mot) In0.561) 4K (0) Ea, (643) is used for calculating Sais of polymer solution. 1m, = mq = 1.087 mal; mz = (100 g)/(1-2x10° g mol!) = 833%10-* mol “The polymer consists of segments, cdch of which can displace a single solvent molecule fron alatice sit. Thus, = Ms /(exV4), where Ma isthe molecular weight ofthe polymer that would have density pp in the coresponding amorphous state at the solution tempers- ture and V9 isthe molar volume ofthe solvent Using aproprite data the calculated values are (4.2%10° gmat!) 0x10? (O2gme) gens) EBC) coven | tore] (1.087 mot) = 1 = TroeTmoh + 130x105 eI IO man] ~ °° 62 = 10-050 = 050 Sn = ~(8.314 Jmol“! °K (1.087 mol) In 0.50 + (8.33%10~ mol in'0.50]Polymers in Solution oy (6) Ba, (343) applies also if ewe polymers are being mixed. In this cas, the number of segmens inte th component ofthe mixture is eleulated from a; = M/piV- where Y; is now a reference volume equal to the molar volume ofthe smallest polymer repeating ‘unit in the mixture. The corresponding volume fraction is = mi! Zr, For the given problem, my = np = (100 (10000 ¢ mol!) = 001 mol. The mola volume cof metiyl methacrylate repeating Unit ( = CsHy02) i aken a the reference volume (V). ‘Thus, yy = MCstaO "= Dens (10000 g mot!) an (1.0 gem-)(100 em® mot) 01% 100 * = Goretoo-+oorxiag “0% #2 = 25 Six = ~(8:314 J mol“ *K-Y[(0.01 mol) 205 + (0.01 mol) in0.5] ork ” ‘Comment: The entropy of mixing of polymers with solvent is small compared to that of micromolecules because there are fewer possible arrangements of solvent molecules and polymer segments than there would be ifthe segments were nos connected to each oer The entropy gain per unit of mixture is futher reduced drastically if two polymers are ‘mixed than if one of the component is #low-mmolecular-weight solvent, beeause both m and mare very small inthe former case. Having obtained an expression for AS, the second stage inthe development . of Flory-Huggins theory is to derive an expression for the enthalpy change, AFfnix. {or the polymer solution. This follows almost exactly the outline depicted for low. ‘molecular-weight mixtures in Eas. (3.26)-(3.33). The only difference now is in probability pz {ie., pa in Eq. (3.31)) that a given lattice point is occupied by 4 polymer segment. In this case, the probability must be approximated by the volume fraction go, instead of mole fraction ra. Thus, for a polymer solution the expression for AFigix reads [ef. Eqs, (3.33) and (3.35)] Alinix = midaNavzher = RTmérx ra G44) where x2 is the Flory-Huggins interaction parameter defined by Eq. (3.38). The interaction parameter y plays a very important role inthe theory of polymer solu- tions. Ifollows from Bq, (3.44) that y12 isa dimensionless parameter equal the ratio of the energy of interaction of the polymer with the solvent molecules to the kinetic energy RT, which should not depend on the concentration of a solution, ‘However, a more rigorous derivation reveals that y2 should be concentration de- ‘pendent. This dependence is a slowly varying function and the absolute value of 1x12 increases with increasing é,m2 Chapter 5 ‘A combination ofthe entropy term of Eq, (3.43) and the enthalpy term of Ea. (3.44) according to Eq, (3-14) gives the following expression for AGaix Gmix = RT (mynd + malng2 + mgzxia) G45) “This remarkably simple expression is the famous Flory-Huggins equation forthe Gibbs free energy of mixing, It has remained as the comerstone of polymer ther- ‘modynamics for more than six decades, Using Flory-Huggins theory its possible to account for the equilibrium thermodynamic properties of polymer solutions. However, the theory is only able to predict general tends and fails to achieve precise agreement with experimental data Tn dilute polymer solutions, the polymer molecules are isolated from each other by regions of pure solvent, ie, the polymer segments are not uniformly tistibuted in the lattice, Tn view ofthis, he Flory-Huggins theory is least satis factory for dilute polymer solutions and only applies to concentrated solutions or mixtures, Furthermore, the interaction parameter introduced to account for the f- fects of polymer-solvent contact interactions is nota simple parameter and should contain both enthalpy and entropy contributions, Additionally, as noted carir, it hhas also been shown to be dependent on the solution concentration, 3.2.2.1 Plory-Huggins Expressions for Thermodynamic Functions Once the analytical expression for AGnix is known, the calculation of chemi- cal potentials and other thermodynamic functions (activities, activity coefficients, vVrial coefficients, et.) is straightforward. For polymer solutions, we must apply Eq, (3.3) to Flory-Huggins equation (3.45), keeping in mind that volume fractions (are functions of the number of moles, as given by 6 = mln +072) 3.46) 2 = om|(m + o7m2) Gan [These relations result from Eqs. (3.42) by dividing numerator and denominator by the Avogadro number Nay.] Thus partial differentiation of Eq. (3.45) with respect to ny (note that both g and gz are functions of m) leads to the following relation for the solvent (see Problem 3.3): 1 : mii = BG, = RT lings + (1-5 be + x0 48) and partial differentiation of Eq, (3.45) with respect to ny similarly leads to the following relation for the polymer o-18, = BO, = RT (ing +(l-oi+ox’G] G49) A= x Gxn/3bder (350) X= xn + Oxn/dbder GSI) wherePolymers in Salation 13 Problem 33 Stating from Flory Hugains equation (3.45) show that forthe formation ofa soltion from a monodisperse polymer the partial molar Cibbs free energy of mixing ‘BG, forthe solvent is given by Ea, (3.48). Answer: ‘The Flory-Huggins equation (3.45) Gag = RT (nm ln6 + myIngs + migoxiad /ASGen) em Sins = mil, +m) ad 8 = hy + om andfrom Ea. G0: BG = = a BG, = er (sr tectnmy ~ mtaem + omy) a + pp alam ~ manny + m)) RG _ om my an ae any — In(rr + om) rom m =H 1 eee om GS ome ay + omy) + mma dee be Gi tomy des dn, Simplifying and substiating for da/dny, Ra 14D, yy [tt mt om Br tA Geaay tome gmm_ den _-om Gert oma) dey tas + om Rg pM EOM=M gy alt Ge 7 be + ESM oa — 68( 2) ts + [I +e (2 3 = wre where x 41 (0x12/6))mm Chapter 3 tn the simplest form ofthe Flory-Huggins theory, te parameter yi is inde- pendent of concentration, and doesnt depend onda Consequently, te Perefone vine ada equal and they are usually represented by the same Symbol. Frter replacing be factor by a = Vuh 52) where Vand V are the molar volumes of solvent and slut (polyme) respec Uvely Eqs, O48) and G49) are rewsiten as . vi 7 mi = Rtgs + (1B) +0] @s3) arlnes+(t-Z2}u «(pel 059 ree pains e ie wit Fy (12) 9 btn fe corresponding activities ofthe components. For example, the activity of the sol vent is given by ob mah er te can be shown hain the limit of extremely small volume fictions, the sighthand side of Eq, (35) sequal fo hy and Eq. (58) dhs reduces to the aon va for ideal solutions with actives aegul to ol fractions w na, = tc +(I- Pe tx G59) 3.222. Colligative Properties and Interaction Parameter x “Thermodynamic equations relating yy and ay to various colligative properties are found in any textbook on thermodynamics. The following relationships are ob tained on using the expression for wet Hatt = na 56 wat Ds om ee a os my na ox Inthese equations, AA; and AH are the latent heats of freezing and vaporization; Ty and Ty are the boiling and freezing points of the solution; 7s and 7 are the boiling and freezing points of the pure solvent; AT, (= Tp 7s) is the elevation inthe boiling point; AT (= 1j~T3) isthe depression in the freezing point; 1 is