T H I R D E D I T I O N

POLYMER j

CHEMISTRY
A N INTRODUCTION

Malcolm P. Stevens
University of Hartford

New York Oxford

OXFORD UNIVERSITY PRESS
1999
 CONTENTS

Preface, xvii

PART I POLYMER STRUCTURE AND PROPERTIES

I. Basic principles, 3
I. I Introduction and historical development, 3
1.2 Definitions, 6
1.3 Polymerization processes, 10
1.4 Step-reaction polymerization, 12
1.5 Chain-reaction polymerization, 1 3
1.6 Step-reaction addition and chain-reaction condensation, 15
1.7 Nomenclature, 1 6
1.7.1 Vinyl polymers, 1 7
1.7.2 Vinyl copolymers, 20
1.7.3 Nonvinyl polymers, 2 1
1.7.4 Nonvinyl copolymers, 24
1.7.5 End groups, 24
1.7.6 Abbreviations, 25
1.8 Industrial polymers, 25
1.8.1 Plastics, 25
1.8.2 Fibers, 27
1.8.3 Rubber (elastomers), 28
1.8.4 Coatings and adhesives, 29
1.9 Polymer recycling, 30
References, 3 1
Review exercises, 32
l

vii
viii Contents

2. Molecular weight and polymer solutions, 35

2.1 Number average and weight average molecular weight, 35
2.2 Polymer solutions, 37
2.3 Measurement of number average molecular weight, 42
2.3. l End-group analysis, 42
2.3.2 Membrane osmometry, 43
2.3.3 Cryoscopy and ebulliometry, 46
2.3.4 Vapor pressure osmometry, 46
2.3.5 Mass spectrometry, 46
2.3.6 Refractive index measurements, 48
2.4 Measurement of weight average molecular weight, 48
2.4.1 Light scattering, 48
2.4.2 Ulcentrifugation, 50
2.5 Viscometry, 50
2.6 Molecular weight distribution, 53
2.6.1 Gel permeation chromatography (GPC), 53
2.6.2 Fractional solution, 57
2.6.3 Fractional precipitation, 58
2.6.4 Thin-layer chromatography (TLC), 58
References, 58
Review exercises, 59

3. Chemical structure and polymer morphology, 6 1

3.1 Introduction, 6 1
3.2 Molecular weight and intermolecular forces,' 62
3.3 The amorphous state-rheology, 63
3.4 Glass transition temperature, 70
3.5 Stereochemistry, 74
3.6 Crystallinity, 79
3.7 Liquid crystallinity, 83
3.8 Chemical crosslinking, 85
3.9 Physical crosslinking, 86
3.10 Polymer blends, 87
References, 9 1
Review exercises, 93
 Contents

4. Chemical structure and polymer properties, 96

4.1 Introduction, 96
4.2 Fabrication methods, 96
4.3 Mechanical properties, 100
4.4 Thermal stability, 106
4.5 Flammability and flame resistance, 1 10
4.6 Chemical resistance, 1 12
I 4.7 Degradability, 1 14
4.8 Electrical conductivity, 1 17
4.9 Nonlinear optical properties, 120
4.10 Additives, 12 1
References, 124
Review exercises, 127

5. Evaluation, characterization, and analysis of polymers, 129

5.1 Introduction, 129
5.2 Chemical methods of analysis, 130
5.3 Spectroscopic methods of analysis, 130
5.3.1 Infrared, 13 1
5.3.2 Raman, 133
5.3.3 Nuclear magnetic resonance, 1 34
5.3.4 Electron spin resonance, 1 38
5.3.5 Ultraviolet (UV)-visible, 1 39
5.3.6 Fluorescence, 139
5.4 X-ray, electron, and neutron scattering, 140
5.5 Characterization and analysis of polymer surfaces, 14 1
5.5.1 Scanning electron microscopy (SEM), ' 143
5.5.2 Attenuated total reflectance spectroscopy (ATR), 143
5.5.3 Photoacoustic spectroscopy (PAS), 1 44
5.5.4 Electron spectroscopy for chemical analysis (or applications)
(ESCA) and AugCr electron spectroscopy (AES), l 4 5
5.5.5 Secondary-ion mass spectrometry (SIMS) and ion-scattering spec-
troscopy (ISS), 147
5.5.6 Atomic force microscopy (AFM), 148
5.6 Thermal analysis, l49
5.6.1 Differential scanning calorimetry (DSc) and differential
thermal analysis (DTA), 149
X Contents

5.6.2 Thermomechanical analysis (TMA), l52

5.6.3 Thermogravimetric analysis (TGA), 1 52
5.6.4 Pyrolysis-gas chromatography (PGC), 1 5 3
5.6.5 Flammabilitytesting, 154
5.7 Measurement of mechanical properties, 156
5.8 Evaluation of chemical resistance, 159
5.9 Evaluation of electrical properties, l 5 9
References, 160
Review exercises, 163

PART II VINYL POLYMERS

6. Free radical polymerization, 167

6.1 Introduction, 167
6.2 Free radical initiators, 169
6.2.1 Peroxides and hydroperoxides, 1 6 9
6.2.2 Azo compounds, 1 7 1
6.2.3 Redox initiators, 1 7 1
6.2.4 Photoinitiators, 1 7 2
6.2.5 Thermal polymerization, 1 7 2
6.2.6 Electrochemical polymerization, 1 73
6.3 Techniques o f free radical polymerization, l73
6.3.1 Bulk, 174
6.3.2 Suspension, 1 7 4
6.3.3 Solution, 174
6.3.4 Emulsion, 175
6.4 Kinetics and mechanism of polymerization, 176
6.5 Stereochemistry of polymerization, 1 8 6
6.6 Polymerization of dienes, 188
6.6.1 Isolated dienes, 188
6.6.2 Conjugated dienes, 189
6.7 Monomer reactivity, 19 1
6.8 Copolymerization, l 9 4
References, 20 1
Review exercises, 202
 I Contents

l
7. Ionic polymerization, 205
W 7.1 Introduction, 205
r
7.2 Cationic polymerization, 205
7.2.1 Cationic initiators, 205
7.2.2 Mechanism, kinetics, and reactivity in cationic
polymerization, 207
7.2.3 Stereochemistry of cationic polymerization, 2 1 3
7.2.4 Cationic copolymerization, 2 1 5
7.2.5 lsomerization in cationic polymerization, 2 17
6 7.3 Anionic polymerization, 2 17
7.3.1 Anionic initiators, 2 1 7
7.3.2 Mechanism, kinetics, and reactivity in anionic
polymerization, 2 1 9
7.3.3 Stereochemistry of anionic polymerization, 223
7.3.4 Anionic copolymerization, 225
1 7.4 Group transfer polymerization, 227
l
References, 230
I
Review exercises, 23 1
I

8. Vinyl polymerization with complex coordination catalysts, 234

I 8.1 Introduction, 234
8.2 Heterogeneous Ziegler-Natta polymerization, 236
8.2.1 Heterogeneouscatalysts, 236
8.2.2 Mechanism and reactivity in heterogeneous
polymerization, 238
8.2.3 Stereochemistry of heterogeneous polymerization, 242
8.2.4 Polymerization of dienes, 243
8.3 Homogeneous Ziegler-Natta polymerization, 245
8.3.1 Metallocene catalysts, 245
8.3.2 Mechanism and reactivity with metallocene
catalysts, 246
8.3.3 Stereochemistry of metallocene-catalyzed
polymerization, 248
1 8.4 Ziegler-Natta copolymerization, 249
8.5 Supported metal oxide catalysts, 25 1
l 8.6 Alfin catalysts, 252
8.7 Metathesis polymerization, 252
xii Contents

8.7.1 Ring-opening metathesis polymerization, 253

8.7.2 Acyclic diene metathesis polymerization, 25 5
References, 255
Review exercises, 257

9. Reactions of vinyl polymers, 259

9.1 Introduction, 259
9.2 Functional group reactions, 260
9.2.1 Introduction of new functional groups, 260
9.2.2 Conversion of functional groups, 26 1
9.3 Ring-forming reactions, 263
9.4 Crosslinking, 265
9.4.1 Vulcanization, 265
9.4.2 Radiation crosslinking, 267
9.4.3 Photochemical crosslinking, 267
9.4.4 Crosslinking through labile functional groups, 27 1
9.4.5 Ionic crosslinking, 272
9.5 Block and graft copolymer formation, 272
9.5.1 272
Block copolymers,
9.5.2 GraF copolymers,273
9.6 Polymer degradation, 276
9.6.1 Chemical degradation, 276
9.6.2 Thermal degradation, 277
9.6.3 Degradation by radiation, 278
References, 279
Review exercises, 28 1

PART Ill N O N V I N Y L POLYMERS

10. Step-reaction and ring-opening polymerization, 285

10. I Introduction, 285
10.2 Step-reaction polymerization-kinetics, 285
10.3 Stoichiometric imbalance, 290
10.4 Molecular weight distribution, 292
10.5 Network step polymerization, 295
10.6 Step-reaction copolymerization, 297
10.7 Step polymerization techniques, 298
 Conteizts xiii

10.8 Dendritic polymers, 30 1

ia
10.9 Ring-opening polymerization, 304
References, 306
Review exercises, 307
I I . Polyethers, polysulfides, and related polymers, 309
l l.l Introduction, 309 1

1 1.2 Preparation of polyethers by chain-reaction and ring-opening

polymerization, 309
11.2.1 Polymerization of carbonyl compounds, 309
11.2.2 Stereochemistry of aldehyde polymerization, 3 1 3
11.2.3 Polymerization of cyclic ethers, 3 1 4
11.2.4 Stereochemistry of epoxide polymerization, 320
1 1.3 Preparation of polyethers by step-reaction polymerization, 3 2 1
11.3.1 Synthesis of polyethers from glycols and bisphenols, 32 1
11.3.2 Polyacetals and polyketals, 322
11.3.3 Poly(pheny1ene oxide)^, 324
11.3.4 Epoxy resins, 326
1 1.4 Polysulfides, poly(alkylene polysulfide)~,and polysulfones, 329
11.4.1 Polysulfides, 329
11.4.2 Poly(alky1ene polysulfide)~, 33 1
11.4.3 Polysulfones, 332
References, 333
Review exercises, 334
<
12. Polyesters, 338
EI 12.1 Introduction, 338
12.2 Linear polyesters, 34 1
12.2.1 Preparation of polyesters by polycondensation reactions, 3 4 1
l
I
l
12.2.2 Polycarbonates, 346
12.2.3 Preparation of polyesters by ring-opening polymerization, 348
12.2.4 Microbial polyesters, 352
l
, 12.3 Hyperbranched polyesters, 353
l
I 12.4 Crosslinked polyesters, 354
12.4.1 Saturated polyester resins, 354
12.4.2 Unsaturated polyesters, 356
References, 359
Review exercises, 360
xiv Contents

13. Polyamides and related polymers, 364

13.1 Introduction, 364
13.2 Polyamides, 366
13.2.1 Preparation of polyamides by polycondensation
reactions, 366 I

13.2.2 Polymerization of lactams, 369

13.2.3 Miscellaneous methods of preparing polyamides, 372
13.3 Properties of polyamides, 374
13.4 Polyureas, 377
13.5 Polyurethanes, 378
13.6 Polyhydrazides, 382
13.7 Polyimides, 382
References, 388
Review exercises, 390

14. Phenol-, urea-, and melamine-formaldehyde polymers, 395

14.1 Introduction, 395
14.2 Phenol-formaldehyde polymers: resoles, 396
14.3 Phenol-formaldehyde polymers: novolacs, 399
14.4 Chemical modifications of phenolic resins, 402
14.5 Urea-formaldehyde polymers, 404
14.6 Melamine-formaldehyde polymers, 406
References, 407
Review exercises, 408

15. Heterocyclic polymers, 409

15.1 Introduction, 409
15.2 Polypyrrole, polyfuran, and polythiophene, 4 12
15.3 Polycyanurate and polyphthalocyanine resins, 4 1 3
15.4 Heterocyclic polymers formed from precursor polymers, 4 14
15.5 Heterocyclic polymers formed from polyfunctional monomers, 4 15
15.5.1 Polybenzimidazoles, 4 1 5
15.5.2 Polybenzoxazoles and polybenzothiazoles, 4 1 7
15.5.3 Polyhydantoins, 4 1 8
15.5.4 Poly(parabanic acid)^, 4 1 8
15.5.5 Polyquinoxalines and polypyrazines, 4 1 9
15.5.6 Polypyrazoles and polyimidazoles, 4 1 9
15.5.7 Poly(as-triazine)~and polytriazolines, 420
 Contents

)I 15.5.8 Polyquinolines and polyanthrazolines, 42 1

References, 42 1
Review exercises, 422
9
16. Inorganic and partially inorganic polymers,

1
'I
16.1 Introduction, 425
16.2 Poly(sulfur nitride), 426
16.3 Polysiloxanes, 427
i 1 6.4 Polysilanes, 430
16.5 Polyphosphazenes, 43 1
r 16.6 Carborane polymers, 434
16.7 Organometallic polymers, 436
16.8 Coordination polymers, 438
References, 442
Review exercises, 444

17. Miscellaneous organic polymers, 447

17.1 Introduction, 447
17.2 Miscellaneous unsaturated polymers, 447
1 7.2.1 Polycarbodiimides, 447
17.2.2 Polyimines, 449
17.2.3 Polymers containing carbon-carbon double bonds, 450
17.2.4 Azo polymers, 450
1 7.2.5 Polymers containing carbon-carbon triple bonds, 45 1
17.3 Poly(p-phenylene) and poly(p-xylylene), 452
17.3.1 Poly(p-phenylene), 452
1 7.3.2 Poly(p-xylylene), 454
17.4 Friedel-Crafts polymers, 455
17.5 Cycloaddition polymerization, 456
1 7.5.1 Diels-Alder polymerization, 456
1 7.5.2 +
2 2 Cycloaddition polymerization, 459
17.6 Polyanhydrides, 460
17.7 Polyamines, 46 1
1 7.8 Charge-transfer polymers, 464
17.9 Ionic polymers, 467
References, 469
Review exercises, 47 1
xvi Contents

18. Natural polymers, 476

18.1 Introduction, 476
18.2 Miscellaneous natural polymers, 476
18.2.1 Rubber, 476
18.2.2 Lignin, humus, coal, and kerogen, 479
18.2.3 Asphaltenes, 48 1
18.2.4 Shellac, 48 1
18.2.5 Amber, 482
18.2.6 Tall oil-derived polymers, 482
18.3 Polysaccharides, 484
18.3.1 Cellulose, 484
18.3.2 Regenerated cellulose, 485
18.3.3 Derivatives of cellulose, 486
18.3.4 Starch, 489
18.3.5 Derivatives of starch, 490
18.3.6 Other polysaccharides, 49 1
18.4 Proteins, 492
18.4.1 Amino acids, polypeptides, and proteins, 492
18.4.2 Protein structure, 495
18.4.3 Synthesis of polypeptides and proteins, 498
18.4.4 Wool, silk, collagen, and regenerated protein, 500
18.5 Nucleic acids, 502
18.5.1 Nucleic acid structure, 502
I 8.5.2 Nucleic acid synthesis, 507
18.6 Conclusion, 5 10
References, 5 10
Review exercises, 5 1 3

Appendix A Commonly used polymer abbreviations, 5 15

Appendix B Polymer literature, 5 17
Appendix C Sources of laboratory experiments
in polymer chemistry, 526
Index, 535
 INDEX

A-stage, definition of, 327 Alpha helix, 496-97

ABA block copolymers, 206 Alpha olefins, 234
Abbreviations, 25 Alternating copolymer, definition of, 7
Abrasion resistance, 101, 159 Alternating copolymerization,mechanism of,
M S . See Acrylonitrile-butadiene-styrene 199-201
copolymer Amber, 482
Acetal polymer. See Polyoxymethylene Amino acids, 492-95
Acetate rayon, 487 C-terminal, 493
Acid number, 43 N-terminal, 493
Acrylonitrile-butadienecopolymer, 168 Amorphous state, 63-70
Acrylonitrile-butadiene-styrene copolymer, 168 AMP. See Adenosine 5'-monophosphate
Acrylonitrile-vinyl chloride copolymer, 168 Amylopectin, 489-90
Acyclic diene metathesis polymerization, 255 Amylose, 489
Addition polymerization, definition of, 10 Anionic polymerization, 217-27
Addition polymers, definition of, 10 chain transfer in, 220-21
Additives, 121-24 copolymerization, 225-27
Adenine, 504 epoxides, 3 17-18
Adenosine, 504 initiators, 217-19
Adenosine diphosphate, 504-5 kinetics and mechanism of, 219-23
Adenosine monophosphate, 504-5 of lactams, 370
Adenosine triphosphate, 504-5 rate constants for, 222
Adhesives, 29-30 stereochemistry of, 223-25
ADMET. See Acyclic diene metathesis poly- Annealing, 79
merization Antiblocking agents. See Additives
ADP. See Adenosine diphosphate Antifogging agents. See Additives
AES. See Augkr electron spectroscopy Antioxidants. See Additives
Aesthetic property modifiers. See Additives Antistatic agents. See Additives
AFM. See Atomic force microscopy Araban, 492
Agar, 491-92 Arachin, 502
Alfin catalysts, 252 Ararnids, 368
Alginic acid, 491 properties of, 106
Alkali cellulose, 485 Arc resistance, 160
Alkyds. See Crossliied polyesters Aromatic polyamides. See Aramids
Alkyleneimines, polymerization of, 46364 Asphaltenes, 481
Ally1 resins, 168, 189 Atactic, definition of, 74
2-Allylphenol, 403 Atom transfer radical polymerization, 184
536 Index

Atomic force microscopy, 148-49 Bulk polymerization, 174,299

ATP. See Adenosine triphosphate 1,3-Butadiene, 18
ATR. See Attenuated total reflectance spec- Butyl rubber, 206,216
troscopy Butyrolactam, polymerization of, 371
Attenuated total reflectance spectroscopy,
143-44
Augir electron spectroscopy, 145-47 Cage effect, 169
Autoacceleration, 174 Calendering, 99
Autoionization, 207 Caoutchouc. See Natural rubber
Average functionality, 295-96 Caprolactam, polymerization of, 369
Azeotropic polymerization, 197 Capryllactam, polymerization of, 371
Aziridines. See Alkyleneimines Carbon fiber, 263-64
Azo compounds, 171 Carbon nanotubes, 263
Azo polymers, 450-51 Carborane polymers, 434-36
Azomethine polymers. See Polyimines Carborane-siloxane polymers, 435
Carboxymethyl cellulose, 488
Cardanol. See Cashew nut shell liquid
Backbiting, 181 Cardo polymers, 108
Baekeland, Leo, 5 Carothers equation, 13,286,289-92
Bagasse, 479 Carothers, Wallace Hume, 5,460
Bakelite. See Phenol-formaldehyde polymers Carrageenin, 491-92
Balata, 478-79 Casein, 502
Barcol test. See Hardness Cashew nut shell liquid, 403
Base unit, definition of, 7 Casting, 98
Benzophenone-3,3',4,4'-tetracarboxylic dian- Cationic polymerization, 205-17
hydride, polyimide from, 385 aldehydes, 312
Benzoyl peroxide, 169-70 chain transfer in, 208-12
Berzelius, 5 copolymerization, 215-17
Beta arrangement. See Pleated sheet cyclic ethers, 315-17
Bimetallic mechanism, 238-40 initiators, 205-7
Bingham Newtonian fluid, 65-66 isomerism in, 217
Bis(hydroxyethy1) terephthalate, 341 kinetics and mechanism of, 207-15
Bismaleimides, polyimides from, 385-86 lactams, 369-70
Bisnadimides, polyimides from, 386-87 rate constants for, 212
Bisphenol A, 72 stereochemistry of,.213-15
in epoxy resins, 326 Ceiling temperature, 193-94
Bisphenol A-furfural resins, 403 of aliphatic polysulfones, 332
Bisphenol A-propylene oxide derivative, Cellophane, 486
112-13 Celluloid. See Cellulose nitrate
Biturnens. See Asphaltenes Cellulose, 484-89
Block copolymers, 272-73 crosslinked, 488-89
definition of, 7 derivatives of, 486-89
Blowing agent, 99.See also Additives fibers, 485
Bodying. See Oil-modified alkyds graft copolymers of, 488
Boron nitride, 425-26 native, 484
Branched polymer, definition of, 8 regenerated, 485-86
Bridged ferrocenes, thermal polymerization of, solvents for, 485
437 Cellulose acetate, 487
B-stage, 97-98,327,358 Cellulose butyrate, 487
 dex 537 /
l

Cellulose esters, 486-87 Condensation polymers, definition of, 10

Cellulose ethers, 487-88 Conductivity. See Electrical conductivity I
l
Cellulose nitrate, 486-87 Cone-plate rotational viscometer, 69-70
Cellulose propionate, 487 I
Conjugated dienes, polymerization of, 189-9 1
Ceramers, 430 Conjugated proteins, 495 I

Chain transfer, 180-83,208-12 Controlled release, 115-17 l

Chain transfer agents, 175 Convergent synthesis. See Dendrimers
l1
11
Chain transfer constants, 183 Coordination polymers, 4 3 8 4 2 ( 1 1
Chain transfer grafting, 273-74 Copolymer, definition of, 7 1I 1 I
Chain-growth polymerization. See Chain- Copolymer composition equation. See I I I
reaction polymerization Copolymer equation Ill l
Chain-reaction polymerization, 13-15 Copolymer equation, 195 II
definition of, 11 Copolymerization
Charge transfer complexes, 200-1 anionic, 225-27 1
l
Charge-transfer polymers, 464-67 cationic, 215-17 1 l

Chemical analysis, 130 free radical, 194-201 I I

Chemical blends, 88 step-reaction, 297-98

Chemical degradation, 276-77 Ziegler-Natta, 249-5 1
l
Chemical property modifiers. See Additives Copper, conductivity of, 119
Chemical resistance, 112-14 Cotton, properties of, 106 I I
evaluation of, 159 Coparone-indene resins, 206 I l l
l 1 I
Chicle, 478-79 Counterions. See Ionic polymerization 1 1 ~
chitin, 49 1 Coupling agents. See Additives I
Chitosan, 491 Crazing, 159
Chlorendic anhydride, 328 Crease-resistance. See Cellulose, crosslinked
il 1

1 I
Chloroprene, 190 Creep, 104
CNSL. See Cashew nut shell liquid Crepe, 479 I

Coal, 479-80 Crick, Francis, 505 I /

l
Coatings, 29-30 Critical reaction conversion, 296
1
COC. See Cycloolefin copolymers Cross-polarization. See Nuclear magnetic reso- l
Cohesive energy density, 38 nance spectroscopy ll II l
Cold flow. See Creep Crosslink density, 86 l
l l I
Collagen, 495,502 Crosslinked polyesters, 354-56
Comb polymers, definition of, 8-9 Crosslinking, 85-87,268-72 1 l I
Ill l
Commodity plastics, definition of, 26 definition of, 10
Compatibilizers, 9 1 ionic, 272 l
Complex coordination polymerization, 234-55 pho.tochemical, 267-70 1111 1
catalysts for, 236-38, 245-46 through labile functional groups, 271 1 1 I
chain transfer in, 240-41 vinyl polymers, 265-72
copolymerization, 249-51 with radiation, 267 l l 1
dienes, 24345 Crosslinking agents. See Additives
epoxides, 3 18-20 Cryoscopy, 46 l ;
1 l
1
mechanism and reactivity in, 23842, Crystalline melting point, 81-83 11 l
246-48 Crystallinity, 79-83 I I
stereochemistry of, 242-43, 248-49 Crystallites, 79-80
Compression molding, 97-98 stag& definition of, 327 l~ l 1
Compressive strength, 101-5 Cumyl hydroperoxide, 170 1 I
Compton scattering. See X-ray scattering Cupramrnonium process, 486
,l 1
l 1
Condensation polymerization, definition of, 10 Curing. See Crosslinking l
l
 Index
Cyclic ethers, polymerization of, 314-20
Cyclic oligomers, 351-52
Cycloaddition polymerization, 456-60
Cycloolefin copolymers, 251
Cyclopolymerization, 188-89
Cytidine, 504
Cytosine, 504
Defoaming agents. See Additives
Degradability, 114-17
Degradation of polymers, 276-79
Degree of polymerization, definition of, 7
Dendrimers, 301-3
definition of, 9
Dendritic polymers. See Dendrimers
Deodorants. See Additives
Deoxyadenosine, 504
Deoxycytidine, 504
Deoxyguanosine, 504
Deoxyribonucleic acids. See Nucleic acids
Deoxythymidine, 504
Depolymerization by ADMET, 255
Depropagation. See Thermal degradation
3,3-Di(chloromethyl)oxacyclobutane, polymel
ization of, 315
Di-2-ethylhexyl adipate, 121, 123
Di-2-ethylhexyl phthalate, 123
Di-2-ethylhexyl sebacate, 123
Di-i-decyl phthalate, 123
Di-n-octyl phthalate, 123
Di-n-tridecyl phthalate, 123
Di-n-undecyl phthalate, 123
Di-t-butyl peroxide, 170
Diacetyl peroxide, 170
Diallyl phthalate, 189
Diblock copolymer, definition of, 7
Dicyclopentadiene dioxide, in epoxy resins,
327
Die swell, 64, 67
Dielectric constant, 160
Dielectric strength, 160
Diels-Alder polymerization, 456-59
Diene polymerization, 188-91, 243-45
Diethylene glycol bis(ally1 carbonate), 189
Differential scanning calorirnetry, 149-52
Differential thermal analysis, 149-52
Dimer acids, 483
Divergent synthesis. See Dendrimers
DNA. See Nucleic acids
Dodecenylsuccinic anhydride, 328
Dopants, 117-18
Dragline silk, 500
Drawing, 79, 102
Drawn fibrillar morphology, 81
Dry spinning, 99
Drying. See Oil-modified akyds
Drying Oils. See Oil-modified akyds
DSc. See Differential scanning c a l o r i m e ~
DTA. See Differential thermal analysis
Durable press. See Cellulose, crosslinked
Durham route, 278-79
Dyes. See Additives
Dynamic equilibrium method. See Membrane
osmometry
Ebulliometry, 46
Elastomers, 28-29
Electrical conductivity, 117-20
Electrical properties, evaluation of, 159-60
Electrochemical polymerization, 173
Electron paramagnetic resonance. See Electron
spin resonance spectroscopy
ElectTon scattering, 140-41
Electron spectroscopy for chemical analysis,
145-47
Electron spin resonance spectroscopy, 138-39
Electrospray ionization mass spectrometry, 47
Ellagic acid, 403-4
Elongation. See Tensile strength
Emaraldine salt. See Polyaniline
Emulsifiers. See Additives
Emulsion polymerization, 175-76
kinetics of, 185-86
End group analysis, 42-43
End group modification, 113
End groups
definition of, 7
nomenclature of, 24
Engineering plastics, definition of, 26
EPDM. See Ethylene-propylene-diene copoly-
mer
Epichlorohydrin, 326
Episulfides, polymerization of, 330
Epitaxial morphology, 8 1
EPM. See Ethylene-propylene copolymer
 In,dex 539 ,

Epoxidized linseed oil, 123 Flammability. See Flame resistance

Epoxidized oils, 327 Flammability testing, 154-56
Epoxidized soya oil, 123 Flash pyrolysis. See Pyrolysis gas chromatog-
Epoxy resins, 326-29 raphy
B-stage, 327 Flexible spacers, 85
curing of, 327-28 Flexural strength, 101-5
grafting of, 329 Flory, Paul, 6
EPR. See Electron paramagnetic resonance. Flory-Fox equation, 41
See also Ethylene-propylene rubber Flory temperature. See Theta temperature
Erythvo structures, 76-78 Fluorescence spectroscopy, 139-40
ESCA. See Electron spectroscopy for chemical Foams, 99
analysis Folded-chain lamella model, 80
ESI-MS. See Electrospray ionization mass Fractional precipitation, 58
spectrometry Fractional solution, 57-58
ESR. See Electron spin resonance spectroscopy Franklin, Rosalind, 505
Ester gums, 483 Free radical initiators, 169-73
Ethylcellulose, 487 azo compounds, 173
Ethylene-l-allcene copolymer. See Linear low- electrochemical polymerization, 173
density polyethylene peroxides and hydroperoxides, 169-71
Ethylene oxide, polymerization of, 14, 3 15 photoinitiators, 172
Ethylene, polymerization of, 13-14 redox, 171
Ethylene-propylene block copolymers, 236, thermal polymerization, 172
25 1 Free radical polymerization, 167-201
Ethylene-propylene copolymers, 236, 249 chain transfer, 180-83
Ethylene-propylene-diene copolymer, 236, constants for propagation and termination,
249-50 180
Ethylene-propylene rubber, 249 copolymerization, 194-201
Ethylene-vinyl acetate copolymer, 168 dienes, 188-91
EVA. See Ethylene-vinyl acetate copolymer ketene acetals, 351
Exiplexes. See Fluorescence spectroscopy kinetic chain length, 179-80
Expansion factor, 40-41 kinetics and mechanism of, 176-86
Extended-chain crystals, 80 living, 184-85
Extrusion, 98 monomer reactivity, 191-94
primary radical termination, 177
stereochemistry of, 186-88
Fabrication of polymers, 96-100 techniques of, 173-76
Fatigue, 101, 157 Friedel-Crafts polymers, 455-56
FD-MS. See Field desorption mass spectrome- Fringed micelle model, 79-80
try FTIR. See Infrared spectroscopy
Ferrocenylmethyl acrylate, 436 Fulvic acid. See Humus
Fiber-reinforced plastic, 5, 98 Furan resins, 402
Fibers, 27-28 Furfural, 402
Fibroin, 495 Furfuryl alcohol, 402-3
Field desorption mass spectrometry, 47 Furnace chamber pyrolysis. See Pyrolysis gas
Filament winding, 99 chromatography
First-order transition temperature. See
Crystalline melting point
Flame resistance, 110-12 Galactans, 492
Flame retardants. See Additives Gallic acid, 403-4
 Index
Gas-phase polymerization, 173
Gegenions. See Ionic polymerization
Gel effect. See Trornrnsdorff effect
Gel filtration chromatography, 54
Gel permeation chromatography, 53-57
Gel point, 295
Gel-spinning, 105
Gelatin, 502
GFC. See Gel filtration chromatography
Glass, properties of, 106
Glass transition temperature, 70-74
Glycidyl ether, definition of, 326
Glycinin, 502
Glycogen, 492
Glycolide, polyester from, 350
Glyptal, 354-55
Gold, conductivity of, 119
Goodyear, Charles, 266
GPC. See Gel permeation chromatography
Graft copolymer, definition of, 7
Graft copolymers, 273-76
of cellulose, 488
of epoxy resins, 329
Graphite fiber. See Carbon fiber
Group molar attraction constants, 38-39
Group transfer polymerization, 227-30
GTP. See Group transfer polymerization
Guanine, 504
Guanosine, 504
Guayule, 478
Gum arabic, 492
Gum tragacanth, 492
Guncotton. See Cellulose nitrate
Gutta percha, 478-79
Halatopolymers, 468
Hardness, 101, 158
HDPE. See Polyethylene, high-density
Head-to-tail polymerization, 74, 176
Heat stabilizers. See Additives
Hemicelluloses, 492
Hemitactic, definition of, 78
Heterochain polymer, definition of, 7
Heterocyclic polymers, 409-21
from precursor polymers, 414-15
from polyfunctional monomers, 405-21
Heterogeneous catalysts, 236-388
Heterotactic. See Atactic
Hevea. See Natural rubber
Hexachlorocyclotriphosphazene,431
Hexafluoropropylene oxide, polymerization
315
Hexamethylenetetrarnine, 401-2
High-mileage catalysts, 238
Homochain polymer, definition of, 7
Homopolymer, defmition of, 7
Humic acid. See Humus
Humin. See Humus
Humus, 479-80
Hydrocarbon resins, 206
Hydrolytic polymerization, 371
Hydroperoxides, 169-7 1
Hydroxyethyl cellulose, 488
Hydroxymethylfurfural, 402-3
Hydroxypropyl cellulose, 488
Hyperbranched polyesters, 353-54
Hyperbranched polymers, 303, 353-54
definition of, 9
Hyperfine splitting. See Electron spin reso-
nance spectroscopy
IEN. See Interpenetrating elastomeric networks
Immortal polymers, 320
Impact modifiers. See Additives
Impact strength, 101, 105
Industrial polymers, 25-30
Infrared spectroscopy, 131-33
Inherent viscosity, 5 1
Inifer, 210
Initiating system, 207
Initiator efficiency, 178
Injection molding, 97-98
Inorganic polymers, 425-27
Inorganic-organic polymers, 427-42
Insulation resistance, 160
Interaction spectnun. See Infrared spectroscopy
Interfacial polymerization, 299-300
Intermolecular forces, 62
Internal reflection spectroscopy. See
Attenuated total reflectance spectroscopy
Interpenetrating elastomeric networks, 88
Interpenetrating polymer networks, 88
1n&sic viscosity, 5 1-52
Gtumescent flame retardants, 112
 Index
1 ' 1 ' ; '

Inverse emulsion. See Emulsion polymeriza- Limiting oxygen index, 155-56 ' 1 ,
I 8

tion Limiting viscosity number. See Intrinsic vis- I,

1
115

Ion-exchange resins, 468 cosity 11, ;

Ion-scattering spectroscopy, 147-48 Linear low-density polyethylene, 234
Ionenes, 467-68 commercial uses for, 236 l
~l
, 8'

' ,
Ionic crosslinking, 272 Linear polymer, definition of, 8
:l,
Ionic polymerization, 205-30 Liquid crystallinity, 83-85
anionic, 217-27 Living polymers ( l l
cationic, 205-17 anionic, 221-22 I l l

Ionic polymers, 46769 cationic, 211 I , i

Ionomers, 272 free radical, 184-85 11, l 1
IF'N. See Interpenetrating polymer networks polyether, 312, 317, 320 l
Isobutylene-cyclopentadienecopolymer, 206
11 ' 1
LLDPE. See Linear low-density polyethylene
Isobutylene-isoprene copolymer, 206 Logarithmic viscosity number. See Inherent
'1',

Isolated dienes, polymerization of, 188-89 viscosity

' ! l8 l
l', 1
1
Isomerization polymerization, 217 LOI. See Limiting oxygen index !
Isotactic, definition of, 74 Low-profile additives. See Additives I ',

Isothermal TGS. See Thermogravimetric analy- Lubricants. See Additives l1 8

sis
ISS. See Ion-scattering spectroscopy
,l
8

~ l1
,,I j
Izod impact test, 157
Macromers. See Macromonomers
Ill 1
Macromolecule, definition of, 3 l,, l
Kendrew, John, 498 Macromonomers, definition of, 9 1111 l
'l
Keratin, 495, 501 Magic angle spinning. See Nuclear magnetic l I
Kerogen, 481 resonance spectroscopy ,', 1
Ketene aminal, polymerization of, 373 MALDI-MS. See Matrix-assisted laser desorp- l
Kevlar. See Poly(p-phenylene terephthal- tion ionization mass spectrometry i l
amide), 84 MALDI-TOF. See Matrix-assisted laser de- l1
111,' l
l
Kinetic chain length, 179-80 sorption ionization mass spectrometry /I
MAO. See Methylalumoxanes 'l il l
Mark-Houwink-Sakurada equation, 4 1 4 2 , '~ 1
Lactarns, polymerization of, 369-72 52-53,55,68 ,, 11

Ladder polymers, 417 Marvel, Carl, 5, 108, 415 ' 1

: l
definition of, 9 Mass spectrometry, molecular weight determi- l;1, l
Ladder pyrrones. See Polyirnidazopyrrolones nation by, 46 'il 1
Laser desorption mass spectrometry, 47
' Laser pyrolysis. See Pyrolysis gas chromatog-
Matrix-assisted laser desorption ionization
mass spectrometry, 47
'1 ~i 1
V'( l
raphy MDPE. See Polyethylene, medium-density l
1
I

Latex blends, 88 Mechanical blends, 88 'l!,l

Lauryllactarn, polymerization of, 371 Mechanical properties, 100-106 l ,l
LD-MS. See Laser desorption mass spectrome- measurement of, 156-59 l
try
LDPE. See Polyethylene, low-density
Mechanical property modifiers. See Additives
Mechanochemical blends, 88
#I8 i
!
1
Light scattering, determination of molecular Melamine, 395,406 ,l', l 1
weight by, 4 5 4 9 Melamine-formaldehyde polymers, 406-7 'l !

Light stability, 114 Membrane osmometry, 43-45

:' l
!' ,
Lignin, 4034,479-80 Membrane-controlled release devices, 116-17 Ill 1
i l
542 Index

Mercaptoethylcellulose, 488 Neighboring group effect, 259-60

Mercerization, 485 Neoprene rubber. See Polychloroprene
Merrifield, Bruce, 6, 498 Network polymer, definition of, 8
Merrifield solid-phase peptide synthesis, Network step polymerization, 295-97
498-500 Neutron scattering, 141
Meso structures, 75 Newtonian fluid, 65-66
Mesogens, definition of, 85 Nitrile rubber. See Acry1onitrile-butadiene
Mesophase, definition of, 83 copolymer
Messenger RNA. See Nucleic acids Nitrocellulose. See Cellulose nitrate
Metaldehyde, 3 11 NLO. See Nonlinear optical properties
Metallocene catalysts, 245-46 NMR. See Nuclear Magnetic Resonance spec-
Metathesis polymerization, 252-55 troscopy
Methylalumoxanes, 245 Nomenclature, 16-24
Methylcellulose, 487-88 end groups, 24
5'-Methylcytosine, 504 IUPAC, 18
MF. See Melamine-formaldehyde polymers nonvinyl copolymers, 24
Microbial polyesters, 352-53 nonvinyl'polymers, 21-24
Microgels, 86 source-based, 16
MIR. See Multiple internal reflection vinyl copolymers, 20-21
Model compounds. See Infrared spectroscopy vinyl polymers, 17-19
Modulus, 102-5 Nonchain scission. See Thermal degradation
Molecular sieving. See Gel permeation chro- Nonisothermal TGA. See Thermogravimetric
matography analysis
Molecular weight, determination of, 42-53 Nonlinear optical properties, 120-21
Molecular weight distribution, 53-58, 292-95 Norbomene polymer. See Poly(l,3-cyclopen-
determination of, 53-58 tenylenevinylene)
in step-reaction polymerization, 292-95 Nomsh type II reactions, 115
Molecular wires, 120 Noms-Smith effect. See Trommsdorff effect
Molecule-induced homolysis. See Thermal Noryl. See Poly(pheny1ene oxide)
polymerization Novolacs, 399-402
Monomer, definition of, 3 Nuclear magnetic resonance spectroscopy,
Monomer reactivity, 191-94 134-38
Monomeric unit, definition of, 7 Nucleating agents. See Additives
Monometallic mechanism, 238-39 Nucleation, 8 1
Multiblock copolymer, definition of, 7 Nucleic acids, 502-1 0
Multiple internal reflection, 143 base pairing, 505-7
Myosin, 495 cyclic, 505, 507
primary structure, 507
replication of, 505-6
Nadic methyl anhydride, 328 synthesis of, 507-10
Native cellulose, 484 Nucleoside, definition of, 503
Natta, Giulio, 6, 74, 234 Nucleotide, definition of, 503
Natural polymers, 476-510 Number average molecular weight, 35-37
commercial uses for, 477 Number average molecular weight, determina-
Natural rubber, 476-79 tion of, 42-48
from guayule, 478 cryoscopy and ebulliometry, 46
Naval stores, 482 end-group analysis, 42-43
N-Carboxy-m-amino acid anhydrides, polymer- mass spectrometry, 46-48
ization of, 371-72 membrane osmometry, 43-45
 Index 543

refractive index measurement, 48 PBT. See Poly(buty1ene terephthalate)

vapor pressure osmometry, 46 PC. See Polycarbonate
Nylon 1, derivatives of, 373-74 PEEK. See Polyetheretherketone
Nylon 2,371-72 PEI. See Polyetherimide
Nylon 3,373-74 PEK. See Polyetherketone
Nylon 4, 371 PEN. See Poly(ethy1ene naphthalene-2,Uicar-
Nylon 5, 371 boxylate)
Nylon 6, 365, 369 Permanence, 123
Nylon 7, 365, 367 Peroxides, 169-7 1
Nylon 8, 365, 371 Perutz, Max, 498
Nylon 9, 365, 367 PET. See Poly(ethy1ene terephthalate)
Nylon 11, 365, 367 PETE. See Poly(ethy1ene terephthalate)
Nylon 12, 365, 371 PF. See Phenol-formaldehyde polymers
Nylon 46, 365, 367 PGC. See Pyrolysis-gas chromatography
Nylon 66, 365, 367 Phase-transfer catalysis, 300-301, 322
Nylon 69, 365 PHB. See Poly(3-hydroxybutyrate)
Nylon 610, 365 PHBV. See Poly(3-hydroxybutyrate-valerate)
Nylon 612, 365 Phenol, 395
Nylons, mechanical properties of, 105-6 Phenol-formaldehyde polymers, 396-404
chemical modifications of, 402-4
novolacs, 399-402
Odorants. See Additives resoles, 396-99
Oil-in-water emulsion. See Emulsion polymer- Phenolic resins. See Phenol-formaldehyde
ization polymers
Oil length. See Oil-modified alkyds Phillips catalyst, 25 1
Oil-modified alkyds, 355-56 Phosphonitrilic chloride trimer. See
Olefin metathesis, 252 Hexachlorocyclotriphosphazene
Oligomer, definition of, 6 Phosphonitrilic polymers. See
Optical rotatory dispersion, 139 Polyphosphazenes
ORD. See Optical rotatory dispersion Phosphorylation, 367
Ordered copolyamides, 375 Photoacoustic spectroscopy, 144
Organometallic polymers, 436-38 Photochemical crosslinking, 267-70
2-Oxazolines, polymerization of, 464 Photocrosslinking. See. Photochemical
Oxetane, 315 crosslinking
Oxirane, 3 15 Photocycloaddition polymerization. See
Ozone, resistance, 114, 250 Photopolymerization
Ozonolysis of polyacetylene, 130 Photoinitiators, 172
Ozonolysis of rubber, 130 Photonics. See Nonlinear optical properties
Photopolymerization, 459-60
PI. See Polyimide
PAI. See Polyamideimide Pigments. See Additives
PAMAM. See Polyamidoamine a-Piperidone. See Valerolactarn
Paper chromatography, 58 Plasma polymerization, 169
Paraformaldehyde, 3 12 Plasticizers, 121-24
Paraldehyde, 3 11 Plastics, 25-27
PAS. See Photoacoustic spectroscopy Pleated sheet, 496
Pauling, Linus, 496 PMR. See Bisnadimides
PBI. See Polybenzimidazole Poled polymer. See Nonlinear optical proper-
PBO. See Polybenzoxazoles ties
544 Index

Polyacetals, 322-24 Polyblend. See Polymer blends

Polyacetone, 117-18,313 Polybutadiene, 189-90,206
Polyacetylene, 1 17-19 commercial uses for, 236
conductivity of, 119 glass transition temperature of, 74,82
metathesis polymerization synthesis, 254-55 limiting oxygen index of, 156
precursor polymer synthesis, 277-78 Poly(1-butene), 235-36
Polyacetylenes, 451-52 Poly(buty1ene terephthalate), 339
aromatic polymers from, 452 Polycaprolactarn. See Nylon 6
Polyacrolein, 313 Polycaprolactone, 340,350
Polyacrylamide, 168,262 Polycapryllactam. See Nylon 8
Polyacrylates, 341-42 Polycarbamate. See Polyurethanes
Poly(acry1ic acid), 17,168 Polycarbodiimides, 447-49
Polyacrylonitrile, 168 Polycarbonates, 340,346-48
Poly(alky1ene polysulfide)~,331-32 charge-transfer type, 465-66
commercial uses of, 310 from cyclic oligomers, 351-52
Poly(alky1ene sulfide)~.See Polysulfides glass transition temperature of, 72-73,
Polyallomers. See Ethylene-propylene block 346-47
copolymers limiting oxygen index of, 156
Poly(allyl acetate), 176 mechanical properties of, 105
Poly(amic acid), 384 Polycarbophosphazene, 434
Polyamidehydrazides, 382 Polycarboranesiloxanes, commercial uses of,
Polyamides, 364-78 426
biodegradable, 376 Pclycatenanes, definition of, 9
commercially important, 36566 Polychloral, 312-13
from diisocyanates, 372-73 Polychloroprene, l90
from ketene arninals, 373 commercial uses for, 168
from lactams, 369-72 crystalline melting temperature of, 82
from polycondensation reactions, 366-69 glass transition temperature of, 74,82
polyureas, 377-78 Poly(p-ch1orostyrene)-graft-polyacrylonitrile,
properties of, 374-76 274
Polyamidines, 449 Polycyanoacrylate, 206
Polyamidoamine, 301-2 Polycyanurates, 413
Polyamines, 461-64 Poly(l,3~yclohexadiene),453
Polyampholytes, 469 Poly(l,4-cyclohexylenedimethylene
Polyanhydrides, 460-61 suberamide), 365
Polyaniline, 462 Poly(l,3-cyclopentenylenevinylene), 236,254
conductivity of, 119 Polydichlorophosphazene, 431-32
Polyanthrazolines, 421 Polydicyclopentadiene, 254
Polyarylsulfone, 332 Poly(l,4-dihydroxymethylcyclohexyl tereph-
Polyaspartirnides, 386 thalate), 340
Polyaziridenes, 463-64 Polydispersity index, 37,294-95
Polybenzimidazole, 415-16 Polydithiahydrazide, 414
glass transition temperature of, 72-73 Polyelectrolytes, 120,468-69
thermal stability of, 107-8 Polyester resins. See Crosslinked polyesters
Polybenzothiazoles, 417 Polyesters, 338-58
Polybenzoxazoles, 417 block copolymers of, 343-44
Poly(bispheno1 A isophthalate), 342 by polycondensation, 341-48
Poly(bispheno1 A terephthalate/isophthalate), commercially available, 339-40
340 crosslinked, 354-58
 Index 545

from cyclic monomers, 348-52 Poly(ferrocenylethylene), 437

glass transition temperature of, 72-73 Poly(ferrocenylsilane)s, 437
hyperbranched, 353-54 Polyfomal. See Polyoxymethylene
ionomers, 467 Polyformaldehyde. See Polyoxymethylene
linear, 341-53 Polyfuran, 412
melting points of, 344-45 Polyglutaraldehyde, 313
microbial, 352-53 Poly(glycolic acid), 340,343,350-51
polycarbonates, 34648 Polyglycolide. See Poly(glyco1ic acid)
properties of, 106 Poly(7-heptanamide). See Nylon 7
unsaturated, 356-58 Poly[hexafluoropropylene-CO-(vinylidenefluo-
Polyetheretherketone, 321-22 ride)], 1 13
Polyetherimide, 321-22 Poly(hexamethy1ene adipamide). See Nylon 66
Polyetherketone, 321 Poly(hexamethy1ene azelamide). See Nylon 69
Polyethers, 309-29 Poly(hexamethy1ene dodecane@amide). See
by chain-reaction polymerization, 309-13 Nylon 612
by ring-opening polymerization, 314-20 Poly(hexamethy1ene phosphonamide), 368-69
by step-reaction polymerization, 321-29 Poly(hexamethy1ene sebacarnide). See Nylon 610
commercial uses for, 310 Poly(hexamethy1ene-m-benzenedisulfonarnide),
epoxy resins, 326-29 368
from aldehydes, 309-13 Polyhydantoins, 418
from glycols and bisphenols, 321-22 Polyhydrazides, 382,414
polyacetals and polyketals, 322-24 Poly(4-hydroxybenzoate), 339,341-42
poly(pheny1ene oxide)^, 324-25 Poly(3-hydroxybutyrate), 352
stereochemistry of, 313-14 Poly(3-hydroxybutyrate-valerate), 340,353
Polyethersulfone, 332 Polyimidazoles, 419-20
Poly(ethy1 acrylate), 168 Poly(l,3-imidazolidine-2,4,5-trione)~. See
Polyethylene, 17 Poly(parabanic acids)s
glass transition temperature of, 71-72 Polyimidazopyrrolones, 417
limiting oxygen index of, 156 Polyimides, 382-87
mechanical properties of, 105-6 addition type, 385-87
Polyethylene, high-density, 26, 234-35 condensation type, 383-85
commercial uses for, 235 from bismaleirnides, 385-86
pyrogram of, 155 from bisnadimides, 386-87
Polyethylene, low-density, 26,181 thermal stability of, '107
commercial uses for, 168 Polyirnidesulfone, 385
Polyethylene, medium-density, 26 Polyimines, 449
Polyethylene, ultrahigh-molecular-weight, 235 Polyisobutylene, 206
Poly(ethy1ene adipate), crystalline melting tem- Polyisocyanides, 449
perature of, 82 Polyisocyanurates, 381
Poly[ethylene-CO-(vinylacetate)], 154 Polyisoprene, 189-90,206
Poly(ethy1ene glycol), 5 commercial uses for, 236
Poly(ethy1ene naphthalene-2,6-dicarboxylate), crystalline melting temperature of, 82
339-40 glass transition temperature of, 74, 82
Poly(ethy1ene oxide), limiting oxygen index hydroboration of, 262
of, 156 Polyketals, 322-24
Poly(ethy1ene succinate), 5 Poly(1actic acid), 340,350-51
Poly(ethy1ene terephthalate), 339-42 Polylactide. See Poly(1actic acid)
crystalline melting temperature of, 82 Polylauryllactam. See Nylon 12
mechanical properties of, 105 Polymer, definition of, 3
 Index

Polymer alloys. See Polymer blends Poly(pheny1ene oxide), 90, 324-25

Polymer blends, 87-91 limiting oxygen index of, 156
Polymer degradation, 276-79 thermal stability of, 107
Polymer solutions, 37-42 Polyphenylenes, 453
Polymeric chelates, 438, 4 4 1 4 2 Poly(p-phenylene sulfide), 329
Polymeric sulfur, 425 thermal stability of, 107
Polymerization, defition of, 3 Poly(p-phenylene terephthalamide), 365, 368
Polymers, history of, 5-6 Poly(p-phenylenevinylene), conductivity of,
Poly (methacrylic acid), 168, 262 119
Poly(methy1 acrylate), 168 Polyphenylsilsequioxane, 429
Poly(methy1ene-4,4'-dicyclohexylenedode- Polyphosphazenes, 113,431-34
canediamide), 365 commercial uses for, 426
Poly(methy1 methacrylate), 19 Polyphosphonamides, 368-69
ceiling temperature of, 193 Polyphthalocyanines, 413
commercial uses for, 168 Polypropylene, 19
depropagation, 278 commercial uses for, 235-36
glass transition temperature of, 79 glass transition temperature of, 71-72
limiting oxygen index of, 156 herniisotactic, 248
mechanical properties of, 105 limiting oxygen index of, 156
N M R spectra of, 134-36 mechanical properties of, 105-6
stereochemistry of, 187, 223-24 Polypyrazines, 419
Poly(4-methyl-l -pentene), 235-36 Polypyrazoles, 419-20, 452
Poly(a-methylstyrene), 17 Polypynrole, 412, 452
Poly(p-methylstyrene), 168 conductivity of, 119
Poly(methy1 vinyl ether), melting temperature Polyquinolines, 421
of, 82 Polyquinoxaline, 4 19
Poly(N-acylamidrazone),414-15 thermal stability of, 107-9
Poly(N-isopropylacrylamide), 117 Polyrotaxanes, definition of, 9
Poly(9-nonanamide). See Nylon 9 Polysaccharides, 484-92
Polynucleotides. See Nucleic acids cellulose, 484-89
Poly(N-vinylcarbazole), 117 starch, 489-90
Polyoctenamer. See Poly(1-octenylene) Polysilanes, 430-31
Poly(1-octenylene), 236, 254 commercial uses for, 426
Polyolefins, definition of, 16 Polysilastyrene, 43 1
Poly(l,3,4-oxadiazole)~,414-15 Polysiloxanes, 427-30 .
Polyoxazole, thermal stability of, 107 commercial uses for, 426
Poly(oxy-2,6-dimethyl-1,4-phenylene). See limiting oxygen index of, 156
Poly(pheny1ene oxide) Polystannanes, 43 1
Polyoxymethylene, 31 1-12 Polystyrene, 17
limiting oxygen index of, 156 commercial uses for, 168, 235
Poly@arabanic acids)~,418 ceiling temperature of, 193
Polypentenamer, hydroformylation of, 262 chloromethylation of, 261
Poly(1-pentene), 17 crosslinked, 456
Polypeptides. See Proteins crystalline melting temperature of, 82
Poly(p-phenylene), 452-54, 458 glass transition temperature of, 71-72
conductivity of, 119 limiting oxygen index of, 156
from precursor polymers, 453 mechanical properties of, 105
thermal stability of, 107 oxazoline-substituted, 275-76
Poly(m-phenylene isophthalamide), 365, 368 thermal polymerization of, 372
 Index 547

Polysulfides, 329-3 1 Poly(4'-vinylbenzo-18-crown-6),441

Polysulfonamides, 368, 371-72 Poly(viny1 bromide), head-to-head, 262
Polysulfones, 321122, 332 Poly(viny1 butyral), 264-65
commercial uses for, 3 11 Poly(viny1 chloride), 19
Poly(su1fur nitride), 117, 426-27 commercial uses for, 168
conductivity of, 119 crystalline melting temperature of, 82 '
Polyterpene resins, 206 dehydrochlorination of, 262
Polytetrafluoroethylene, 17, 113 glass transition temperature of, 71-72
commercial uses for, 168 limiting oxygen index of, 156
limiting oxygen index of, 156 mechanical properties of, 105
mechanical properties of, 105 thermogram of, 151
Poly(tetramethy1ene adipamide). See Nylon 46 Poly(viny1 et hers)^, 206
Poly(l,3,4-thiadiazole),414 Polyvinylfemocene, 436
thermal stability of, 107 Poly(viny1 fluoride), 168, 176
Polythiazoles, TGA thermograms of, 153 Poly(viny1idene chloride), 168
Polythiazyl. See Poly(sulfur nitride) limiting oxygen index of, 156
Polythioacetals, 330-3 1 Poly(viny1idene cyanide), 217-1 8
Polythiocarbonates, 348 Poly(viny1idene fluoride), 113, 168, 176
Poly(thiocarbony1 fluoride), 330 Poly(2-vinylnaphthalene), glass transition tem-
Polythioketals, 330-3 1 perature of, 71-72
Polythiophene, 412-13,452 Poly(p-xylylene), 454-55
conductivity of, 119 POM. See Polyoxymethylene
Polythiophosphazenes, 434 Popcorn polymerization, 174
Poly(as-triazines), 420 PP. See Polypropylene
Poly(l,2,4-triazole), 414-15 PPO. See Poly(pheny1ene oxide)
Polytriazolines, 420 PPS. See Poly(pheny1ene sulfide)
Polytnchloroacetaldehyde.See Polychloral Preform, 98
Polytrichl~rofluoroethylene,168 Prepreg. See Preform
Poly(trimethy1ene terephthalate), 339-40 Priestley, Joseph, 478
Poly(2,4,4-trimethylhexamethyleneterephthala- Primary radical termination, 177
mide), 366, 369 Processing modifiers. See Additives
Poly(2,4,6-triphenylbenzylmethacrylate), 188 Promoter, 170, 317
Poly(1 l-undecanamide). See Nylon 11 Promoters. See Additives
Polyurea ionomers, 467 P-Propiolactone, polymerization of, 349-50
Polyureas, 377-78 Propiosultam, polymerization of, 371-72
Polyurethanes, 378-8 1 Propylene oxide, polymerization of, 3 15
coatings, 381 Prosthetic group, 495
elastomeric fibers, 379 Proteins, 492-502
foams, 380-81 amino acids from, 492-95
self-extinguishing, 38 1 classification of, 495
ionomers, 467 conjugated, 495
Poly(viny1 acetate), 168 crosslinking of, 502
P ~ l y ( ~ i nalcohol),
yl 261-62 primary structure, 495
degradation of, 130 quaternary structure, 498
glass transition temperature of, 71-72, 82 regenerated, 502
limiting oxygen index of, 156 secondary structure, 496
synthesis of, 261-62 synthesis of, 498-500
Poly(viny1 alcohol-graft-polyethylene), 274 tertiary structure, 496, 498
Poly(viny1 amine), 262 Proton trap, 209-10
548 Inde
PS. See Polystyrene
Pseudobisdienes. See Diels-Alder polymeriza-
tion
Pseudocationic polymerization, 210
Purine, 504
PVC. See Poly(viny1 chloride)
Pyrimidine, 504
Pyrogallol, 403-4
Pyrolysis-gas chromatography, 153-54
Pyromellitic dianhydride, 328
polyimides from, 383-85
2-Pyrrolidone. See Butyrolactam
Q-e scheme, 198-99
Racemic structures, 75
Radial copolymers. See Star-block copolymers
Radiation crosslinking, 267
Raman spectroscopy, 133-34
Random chain scission. See Thermal degrada-
tion
Random copolymer, definition of, 7
Rayon, 486-87
Reaction injection molding, 98, 254, 380
Reactive end groups, 109-10
Reactive oligomer, definition of, 7
Reactivity ratios, 195-99, 215-16, 226,
249-5 1
Recycling of polymers, 30-31
Redox initiators, 171
Reduced osmotic pressure. See Membrane os-
mometry
Reduced viscosity, 5 1
Refractive index, determination of molecular
weight by, 48
Regenerated cellulose, 485-86
Regenerated protein, 502
Reinforced reaction injection molding, 98
Reinforcing fillers. See Additives
Relative viscosity, 51
Repeating unit, definition of, 7
Resist technology, 114-15
Resite. See Phenol formaldehyde polymers
Resoles. See Phenol-formaldehyde polymers
Resorcinol, 403
Reversible crosslinking, 271
Rheology, 63-70
Ribonucleic acid. See Nucleic acids
Ribosomal RNA. See Nucleic acids
RIM. See Reaction injection molding
Ring-forming reactions, 263-65
Ring-opening metathesis polymerization,
253-55
Ring-opening polymerization, 11, 304-6
RNA. See Nucleic acids
Rockwell test. See Hardness
ROMP. See Ring-opening metathesis polymer-
ization
Rosin, 483
RRIM. See Reinforced reaction injection molding
RTV rubber. See Polysiloxanes
Rubber, 28-29,476-79
SAN. See Styrene-acrylonitrile copolymer
Saturated polyester resins, 354-56
SAXS. See X-ray scattering
SBR. See Styrene-butadiene rubber
Scanning electron microscopy, 143
Scanning force microscopy. See Atomic force
microscopy
Scanning tunneling microscopy, 148
Schiff base polymers. See Polyimines
Schweitzer's reagent, 485-86
SEC. See Gel permeation chromatography
Secondary-ion mass spectrometry, 1 4 7 4 8
Second-order transition temperature. See Glass
transition temperature
Self-extinguishing, definition of, 110
SEM. See Scanning electron microscopy
Semi-interpenetrating .polymer networks, 88
Semiladder polymer, definition of, 9
Semipermeable membrane. See Membrane OS-
mometry
SFM. See Atomic force microscopy
Shear modulus, 65-66
Shear rate, 65-66
Shear strain, 65-66
Shear stress, 64-65
Shear thickening, 66
Shear thinning, 66-67
Shellac, 48 1-82
Shish kebab morphology. See Epitaxial mar-
phology
 Index 549

Silicone oils, 428 Staudinger, Hermann, 5

Silicone rubber, 428-29 Steel, properties of, 106
Silicone-ether block copolymers, 429-30 Step-growth polymerization. See Step-reaction
Silicones. See Polysiloxanes polymerization
Silk, 500-502 Step-ladder polymer. See Semiladder polymer
modification of, 501-2 Step-reaction addition polymerization, $5
Simple rule of mixtures, 89 Step-reaction copolymerization, 297-98
SIMS. See Secondary-ion mass spectrometry Step-reaction polymerization, 12-13, 285-
Simultaneous interpenetrating polymer net- 309
works, 88 copolymerization, 297-98
SIN. See Simultaneous interpenetrating poly- definition of, 11
mer networks dendrimers, 301-3
Single-site catalysts. See Metallocene catalysts kinetics of, 285-90
Size exclusion chromatography. See Gel per- molecular weight distribution, 292-95
meation chromatography network polymerization, 295-97
Slip agents. See Additives stoichiometric imbalance, 290-92
SMA. See Styrene-maleic anhydride copoly- techniques of, 298-301
mer Stereoblock, definition of, 74
Smart polymers, 117 Stereochemistry of polymerization
Smith-Ewart kinetics, 185-86 aldehyde polymerization, 313-14
Soda cellulose. See Alkali cellulose anionic, 223-25
Sol-gel process, 430 cationic, 213-15
Solid phase synthesis, 261, 498-500, 508- epoxides, 320
510 free radical, 186-88
Solitons, l l 8 heterogeneous Ziegler-Natta, 242-45
Solubility parameter, 38 homogeneous Ziegler-Natta, 248-49
Solution blends, 88 with metallocene catalysts, 248-49
Solution polymerization, 174 Stereochemistry of vinyl polymers, 7 4 7 9
Solvent gradient chromatography. See STM. See Scanning tunneling microscopy
Fractional solution Stoichiometric imbalance, 290-92
Solvent polymerization, 299 Stress relaxation, 104
Sparging, 299 Styrenated alkyds, 356
Specific refractive increment. See Light scat- Styrene-acrylonitrile copolymer, 168
tering Styrene-butadiene block copolymers, 206
Specific viscosity, 5 1 Styrene-butadiene copolymer, emulsion poly-
Spectroscopic analysis, 130-40 merization, 175
Sphemlites, definition of, 81 Styrene-butadiene rubber, 168, 206
Spherulitic morphology, 8 1 Styrene-maleic anhydride copolymer, 168
Spinneret. See Spinning Succinite. See Amber
Spinning, 99-100 Sulfur, 425
Spiro polymers, 323, 331 Supported metal oxide catalysts, 251
Star-block copolymers, 227 Supramolecular assembly, definition of, 9
Starburst polymers. See Dendrimers Surface analysis, 141-49
Starch, 489-90 Surface property modifiers. See Additives
derivatives of, 490 Surface resistivity, 159-60
Star polymers, definition of, 8 Suspension polymerization, 174
Static equilibrium method. See Membrane os- Syndiotactic, definition of, 74
mometry Synthetic natural rubber, 224-25
550 Index

T,. See Ceiling temperature 2,2,4-Trimethylpentane-1,3-diol, 112-13

T,. See Glass transition temperature Trioxane, 309,311
T,. See Crystalline melting point polymerization of, 314-15
Tactic dyad, 75-76 Trommsdorff effect, 180
Tactic placement. See Tactic dyad Turbidimetry. See Fractional precipitation
Tactic triad, 75-76
Tall oil-derived polymers, 482-83
Tall oil fatty acids, 483 W. See Urea-formaldehyde polymers
Tangential stress. See Shear stress UHMWPE. See Polyethylene, ultrahigh-
Tannin, 403-4 molecular-weight
Tear resistance, 101, 159 Ultracentrifugation, 50
Telechelic polymer, 263 Ultraviolet stabilizers. See Additives
definition of, 7 Ultraviolet-visible spectroscopy, 139
Telomerization, 183 Universal calibration parameter, 55-57
Telomers, 183 Unperturbed dimension, 4041
Tenacity, 106 Unsaturated polyesters, 356-58
Tensile strength, 101-6 recycling of, 358
Tetrahydrofuran, polymerization of, 315 Uracil, 504
TGA. See Thermogravimetric analysis Urea, 395
Thermal analysis, 149-56 Urea-formaldehyde polymers, 404-6
Thermal degradation, 277-78 Uridine, 504
Thermal gradient turbidimetry. See Fractional
precipitation
Thermal polymerization, 172 Vapor pressure osmometry, 46
Thermal stability, 106-10 Velocity gradient. See Shear rate
Thermogravimetric analysis, 152-53 Vinylcylohexene dioxide, in epoxy resins, 327
Thermomechanical analysis, 152 Vinylferrocene, 436
Thermoplastic elastomers, 28,87-88 Vinylidene, definition of, 16
Thermosetting, definition of, 10 Vinyl polymers
Theta state, 41 block and graft copolymers of, 272-76
Theta temperature, 41 chlorination of, 260
Thickening agents. See Additives chlorosulfonation of, 260-61
Thin-layer chromatography, molecular weight crosslinking of, 265-72
distribution by, 58 definition of, 16
Thiokol rubbers. See Poly(alky1ene polysul- degradation of, 276-79
fide)s fluorination of, 261 '
Thixotropy, 66 functional group reactions in, 260-63
Threo structures, 76-78 reactions of, 259-79
Thymine, 504 ring-forming reactions of, 263-65
TLC. See Thin-layer chromatography Vinylruthenocene, 436
TMA. See Thermomechanical analysis Viscoelasticity. See Rheology
Topological bonding, 90-91 Viscometry, 50-53, 69
TPE. See Thermoplastic elastomer Viscose process. See Xanthate process
Transdermal patches, 117 Viscose rayon, 486
Transfer RNA. See Nucleic acids Viscosity average molecular weight, 52-53
Tn-2-ethylhexyl trimellitate. See Plasticizers Viscosity number. See Reduced viscosity
Triblock copolymer, definition of, 7 Viscosity ratio. See Relative viscosity
Trimer acids, 483 Vitrification, 63
 Index 551

Vitrinite, 480 Xanthate process, 485-86

Volume resistivity, 159 XPS. See Electron spectroscopy for chemical
Vulcanization, 265-67 analysis
X-ray diffraction. See X-ray scattering
X-ray photoelectron spectroscopy. See
Water-in-oil emulsion. See Emulsion polymer- Electron spectroscopy for chemical
ization analysis
Watson, James, 505 X-ray scattering, 140-41
WAXS. See X-ray scattering Xylan, 492
Weatherability, 159
Weight average molecular weight, 35-37
determination of, 48-50 Zein, 502
by ultracentrifugation, 50 Ziegler, Karl, 6, 74, 234
by light scattering, 48 Ziegler-Natta catalysts, 236-38, 245-46
Wet spinning, 99 heterogeneous, 236-38
Wetting agents. See Additives homogeneous, 245-46
Wilkins, Maurice, 505 Ziegler-Natta polymerization, 2 3 6 5 1
Wittig reaction, unsaturated polymers by, 450 copolymerization, 249-5 1
Wood flour. See Additives epoxides, 318-20
Wool, 500-502 heterogeneous, 236-45
modification of, 501-502 homogeneous, 245-49
tensile strength of, 106 Zirnm plots, 49