T H I R D

E D I T I O N

POLYMER CHEMISTRY
A N INTRODUCTION

Malcolm P. Stevens
University of Hartford

New York
1999

Oxford

OXFORD UNIVERSITY PRESS

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, 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

15

1.8.1 1.8.2 1.8.3 1.8.4

Plastics, 25 Fibers, 27 Rubber (elastomers), 28 Coatings and adhesives, 29

30

1.9 Polymer recycling, References, 3 1 Review exercises, 32

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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 Viscometry, 50 Molecular weight distribution, 53

2.5 2.6

2.6.1 2.6.2 2.6.3 2.6.4

Gel permeation chromatography (GPC), 53 Fractional solution, 57 Fractional precipitation, 58 Thin-layer chromatography (TLC), 58
59

References, 58 Review exercises,

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 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, 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 5.5 X-ray, electron, and neutron scattering, 140 Characterization and analysis of polymer surfaces, 129

14 1

5.5.1 5.5.2 5.5.3 5.5.4 5.5.5 5.5.6

5.6

Scanning electron microscopy (SEM), ' 143 Attenuated total reflectance spectroscopy (ATR), 143 Photoacoustic spectroscopy (PAS), 1 44 Electron spectroscopy for chemical analysis (or applications) (ESCA) and AugCr electron spectroscopy (AES), l 4 5 Secondary-ion mass spectrometry (SIMS) and ion-scattering spectroscopy (ISS), 147 Atomic force microscopy (AFM), 148

Thermal analysis, l49 Differential scanning calorimetry (DSc) and differential 5.6.1 thermal analysis (DTA), 149

Contents

5.6.2 5.6.3 5.6.4 5.6.5

Thermomechanical analysis (TMA), l52 Thermogravimetric analysis (TGA), 1 52 Pyrolysis-gas chromatography (PGC), 1 5 3 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, 6.3.1 Bulk, 174 6.3.2 Suspension, 1 7 4 6.3.3 Solution, 174 6.3.4 Emulsion, 175 Kinetics and mechanism of polymerization, Stereochemistry of polymerization, 1 8 6 Polymerization of dienes, 188 6.6.1 Isolated dienes, 188 6.6.2 Conjugated dienes, 189 l73

6.4 6.5 6.6

176

6.7 Monomer reactivity, 19 1 6.8 Copolymerization, l 9 4 References, 20 1 Review exercises, 202

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7. Ionic polymerization, 205 7.1 Introduction, 205

7.2
Cationic polymerization, 7.2.1 7.2.2 7.2.3 7.2.4 7.2.5

205 Cationic initiators, 205

Mechanism, kinetics, and reactivity in cationic polymerization, 207 Stereochemistry of cationic polymerization, 2 1 3 Cationic copolymerization, 2 1 5 lsomerization in cationic polymerization, 2 17

7.3

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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 Group transfer polymerization, 227

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References, 230 Review exercises, 23 1

8. Vinyl polymerization with complex coordination catalysts, 8.1 Introduction, 234 8.2
Heterogeneous Ziegler-Natta polymerization, 8.2.1 8.2.2 8.2.3 8.2.4

234

236

Heterogeneouscatalysts, 236 Mechanism and reactivity in heterogeneous polymerization, 238 Stereochemistry of heterogeneous polymerization, Polymerization of dienes, 243

242

8.3

Homogeneous Ziegler-Natta polymerization, 8.3.1 8.3.2 8.3.3

245

Metallocene catalysts, 245 Mechanism and reactivity with metallocene catalysts, 246 Stereochemistry of metallocene-catalyzed polymerization, 248

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8.4 8.5 8.6 8.7

Ziegler-Natta copolymerization, 249 Supported metal oxide catalysts, 25 1 Alfin catalysts, 252 Metathesis polymerization, 252

xii

Contents

8.7.1 8.7.2

Ring-opening metathesis polymerization, Acyclic diene metathesis polymerization,

253 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 9.4 Ring-forming reactions, 263 Crosslinking, 265 9.4.1 9.4.2 9.4.3 9.4.4 9.4.5 9.5 9.5.1 9.5.2 Vulcanization, 265 Radiation crosslinking, 267 Photochemical crosslinking, 267 Crosslinking through labile functional groups, Ionic crosslinking, 272

27 1

Block and graft copolymer formation,

272

9.6

272 273 Polymer degradation, 276

Block copolymers, GraF copolymers, 9.6.1 9.6.2 9.6.3 Chemical degradation, 276 Thermal degradation, 277 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, 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

285

Conteizts

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10.8 Dendritic polymers, 30 1 10.9 Ring-opening polymerization, References, 306 Review exercises, 307 l l.l 1 1.2

304

I I . Polyethers, polysulfides, and related polymers, 309

Introduction, 309 Preparation of polyethers by chain-reaction and ring-opening polymerization, 309 11.2.1 11.2.2 11.2.3 11.2.4 1 1.3 Polymerization of carbonyl compounds, 309 Stereochemistry of aldehyde polymerization, 3 1 3 Polymerization of cyclic ethers, 3 1 4 Stereochemistry of epoxide polymerization, 320
1

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 Polysulfides, poly(alkylene polysulfide)~,and polysulfones, 11.4.1 Polysulfides, 329 11.4.2 Poly(alky1ene polysulfide)~, 33 1 11.4.3 Polysulfones, 332 329

1 1.4

References, 333 Review exercises, 334

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12. Polyesters, 338 12.1 Introduction, 338 12.2 Linear polyesters, 34 1

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12.2.1 12.2.2 12.2.3 12.2.4

Preparation of polyesters by polycondensation reactions, 3 4 1 Polycarbonates, 346 Preparation of polyesters by ring-opening polymerization, 348 Microbial polyesters, 352

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12.3 Hyperbranched polyesters, 353 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 13.2.2 13.2.3

Preparation of polyamides by polycondensation reactions, 366 Polymerization of lactams, 369 Miscellaneous methods of preparing polyamides, 374

372

13.3 Properties of polyamides, 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

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16. Inorganic and partially inorganic polymers, 16.1 Introduction, 425 16.2 Poly(sulfur nitride), 426 16.3 Polysiloxanes, 427 1 6.4 Polysilanes, 430 16.5 Polyphosphazenes, 43 1 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), 17.3.1 1 7.3.2 Poly(p-phenylene), 452 Poly(p-xylylene), 454 452

17.4 Friedel-Crafts polymers, 455 17.5 Cycloaddition polymerization, 456

1 7.5.1 1 7.5.2

Diels-Alder polymerization, 456 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,

476 479

18.2.1 18.2.2 18.2.3 18.2.4 18.2.5 18.2.6 18.3

Rubber, 476 Lignin, humus, coal, and kerogen, Asphaltenes, 48 1 Shellac, 48 1 Amber, 482 Tall oil-derived polymers, 482

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 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 Nucleic acids, 502 18.5.1 Nucleic acid structure, I 8.5.2 Nucleic acid synthesis,

18.4

18.5

502 507

18.6 Conclusion, 5 10 References, 5 10 Review exercises, 5 1 3

Appendix A Appendix B Appendix C Index, Commonly used polymer abbreviations, 5 15 Polymer literature, 5 17 Sources of laboratory experiments in polymer chemistry, 526

535

INDEX

A-stage, definition of, 327 ABA block copolymers, 206 Abbreviations, 25 Abrasion resistance, 101, 159 M S . See Acrylonitrile-butadiene-styrene copolymer Acetal polymer. See Polyoxymethylene Acetate rayon, 487 Acid number, 43 Acrylonitrile-butadienecopolymer, 168 Acrylonitrile-butadiene-styrene copolymer, 168 Acrylonitrile-vinyl chloride copolymer, 168 Acyclic diene metathesis polymerization, 255 Addition polymerization, definition of, 10 Addition polymers, definition of, 10 Additives, 121-24 Adenine, 504 Adenosine, 504 Adenosine diphosphate, 504-5 Adenosine monophosphate, 504-5 Adenosine triphosphate, 504-5 Adhesives, 29-30 ADMET. See Acyclic diene metathesis polymerization ADP. See Adenosine diphosphate AES. See Augkr electron spectroscopy Aesthetic property modifiers. See Additives AFM. See Atomic force microscopy Agar, 491-92 Alfin catalysts, 252 Alginic acid, 491 Alkali cellulose, 485 Alkyds. See Crossliied polyesters Alkyleneimines, polymerization of, 46364 Ally1 resins, 168, 189 2-Allylphenol, 403

Alpha helix, 496-97 Alpha olefins, 234 Alternating copolymer, definition of, 7 Alternating copolymerization,mechanism of, 199-201 Amber, 482 Amino acids, 492-95 C-terminal, 493 N-terminal, 493 Amorphous state, 63-70 AMP. See Adenosine 5'-monophosphate Amylopectin, 489-90 Amylose, 489 Anionic polymerization, 217-27 chain transfer in, 220-21 copolymerization, 225-27 epoxides, 3 17-18 initiators, 217-19 kinetics and mechanism of, 219-23 of lactams, 370 rate constants for, 222 stereochemistry of, 223-25 Annealing, 79 Antiblocking agents. See Additives Antifogging agents. See Additives Antioxidants. See Additives Antistatic agents. See Additives Araban, 492 Arachin, 502 Ararnids, 368 properties of, 106 Arc resistance, 160 Aromatic polyamides. See Aramids Asphaltenes, 481 Atactic, definition of, 74 Atom transfer radical polymerization, 184

536
Atomic force microscopy, 148-49 ATP. See Adenosine triphosphate ATR. See Attenuated total reflectance spectroscopy Attenuated total reflectance spectroscopy,

Index
Bulk polymerization, 174, 299 1,3-Butadiene, 18 Butyl rubber, 206,216 Butyrolactam, polymerization of, 3 7 1

143-44
Augir electron spectroscopy, 145-47 Autoacceleration, 174 Autoionization, 207 Average functionality, 295-96 Azeotropic polymerization, 197 Aziridines. See Alkyleneimines Azo compounds, 1 7 1 Azo polymers, 450-51 Azomethine polymers. See Polyimines Cage effect, 169 Calendering, 99 Caoutchouc. See Natural rubber Caprolactam, polymerization of, 369 Capryllactam, polymerization of, 3 7 1 Carbon fiber, 263-64 Carbon nanotubes, 263 Carborane polymers, 434-36 Carborane-siloxane polymers, 435 Carboxymethyl cellulose, 488 Cardanol. See Cashew nut shell liquid Cardo polymers, 108 Carothers equation, 13,286,289-92 Carothers, Wallace Hume, 5,460 Carrageenin, 491-92 Casein, 502 Cashew nut shell liquid, 403 Casting, 98 Cationic polymerization, 205-17 aldehydes, 312 chain transfer in, 208-12 copolymerization, 215-17 cyclic ethers, 315-17 initiators, 205-7 isomerism in, 217 kinetics and mechanism of, 207-15 lactams, 369-70 rate constants for, 212 stereochemistry of,.213-15 Ceiling temperature, 193-94 of aliphatic polysulfones, 332 Cellophane, 486 Celluloid. See Cellulose nitrate Cellulose, 484-89 crosslinked, 488-89 derivatives of, 486-89 fibers, 485 graft copolymers of, 488 native, 484 regenerated, 485-86 solvents for, 485 Cellulose acetate, 487 Cellulose butyrate, 487

Backbiting, 1 8 1 Baekeland, Leo, 5 Bagasse, 479 Bakelite. See Phenol-formaldehyde polymers Balata, 478-79 Barcol test. See Hardness Base unit, definition of, 7 Benzophenone-3,3',4,4'-tetracarboxylic dianhydride, polyimide from, 385 Benzoyl peroxide, 169-70 Berzelius, 5 Beta arrangement. See Pleated sheet Bimetallic mechanism, 238-40 Bingham Newtonian fluid, 65-66 Bis(hydroxyethy1) terephthalate, 341 Bismaleimides, polyimides from, 385-86 Bisnadimides, polyimides from, 3 8 6 8 7 Bisphenol A, 72 in epoxy resins, 326 Bisphenol A-furfural resins, 403 Bisphenol A-propylene oxide derivative,

112-13
Biturnens. See Asphaltenes Block copolymers, 272-73 definition of, 7 Blowing agent, 99.See also Additives Bodying. See Oil-modified alkyds Boron nitride, 425-26 Branched polymer, definition of, 8 Bridged ferrocenes, thermal polymerization of,

437
B-stage, 97-98,327,358

dex
Cellulose esters, 486-87 Cellulose ethers, 487-88 Cellulose nitrate, 486-87 Cellulose propionate, 487 Ceramers, 430 Chain transfer, 180-83,208-12 Chain transfer agents, 175 Chain transfer constants, 183 Chain transfer grafting, 273-74 Chain-growth polymerization. See Chainreaction polymerization Chain-reaction polymerization, 13-15 definition of, 11 Charge transfer complexes, 200-1 Charge-transfer polymers, 464-67 Chemical analysis, 130 Chemical blends, 88 Chemical degradation, 276-77 Chemical property modifiers. See Additives Chemical resistance, 112-14 evaluation of, 159 Chicle, 478-79 chitin, 49 1 Chitosan, 491 Chlorendic anhydride, 328 Chloroprene, 190 CNSL. See Cashew nut shell liquid Coal, 479-80 Coatings, 29-30 COC. See Cycloolefin copolymers Cohesive energy density, 38 Cold flow. See Creep Collagen, 495,502 Comb polymers, definition of, 8-9 Commodity plastics, definition of, 26 Compatibilizers, 9 1 Complex coordination polymerization, 234-55 catalysts for, 236-38, 245-46 chain transfer in, 240-41 copolymerization, 249-51 dienes, 24345 epoxides, 3 18-20 mechanism and reactivity in, 23842, 246-48 stereochemistry of, 242-43, 248-49 Compression molding, 97-98 Compressive strength, 101-5 Compton scattering. See X-ray scattering Condensation polymerization, definition of, 10

537
Condensation polymers, definition of, 10 Conductivity. See Electrical conductivity Cone-plate rotational viscometer, 69-70 Conjugated dienes, polymerization of, 189-9 1 Conjugated proteins, 495 Controlled release, 115-17 Convergent synthesis. See Dendrimers Coordination polymers, 4 3 8 4 2 Copolymer, definition of, 7 Copolymer composition equation. See Copolymer equation Copolymer equation, 195 Copolymerization anionic, 225-27 cationic, 215-17 free radical, 194-201 step-reaction, 297-98 Ziegler-Natta, 249-5 1 Copper, conductivity of, 119 Cotton, properties of, 106 Coparone-indene resins, 206 Counterions. See Ionic polymerization Coupling agents. See Additives Crazing, 159 Crease-resistance. See Cellulose, crosslinked Creep, 104 Crepe, 479 Crick, Francis, 505 Critical reaction conversion, 296 Cross-polarization. See Nuclear magnetic resonance spectroscopy Crosslink density, 86 Crosslinked polyesters, 354-56 Crosslinking, 85-87,268-72 definition of, 10 ionic, 272 pho.tochemical, 267-70 through labile functional groups, 271 vinyl polymers, 265-72 with radiation, 267 Crosslinking agents. See Additives Cryoscopy, 46 Crystalline melting point, 81-83 Crystallinity, 79-83 Crystallites, 79-80 stag& definition of, 327 Cumyl hydroperoxide, 170 Cupramrnonium process, 486 Curing. See Crosslinking

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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 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

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

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 copolymer Epichlorohydrin, 326 Episulfides, polymerization of, 330 Epitaxial morphology, 8 1 EPM. See Ethylene-propylene copolymer

In,dex
Epoxidized linseed oil, 123 Epoxidized oils, 327 Epoxidized soya oil, 123 Epoxy resins, 326-29 B-stage, 327 curing of, 327-28 grafting of, 329 EPR. See Electron paramagnetic resonance. See also Ethylene-propylene rubber Erythvo structures, 76-78 ESCA. See Electron spectroscopy for chemical analysis ESI-MS. See Electrospray ionization mass spectrometry ESR. See Electron spin resonance spectroscopy Ester gums, 483 Ethylcellulose, 487 Ethylene-l-allcene copolymer. See Linear lowdensity polyethylene Ethylene oxide, polymerization of, 14, 3 15 Ethylene, polymerization of, 13-14 Ethylene-propylene block copolymers, 236, 25 1 Ethylene-propylene copolymers, 236, 249 Ethylene-propylene-diene copolymer, 236, 249-50 Ethylene-propylene rubber, 249 Ethylene-vinyl acetate copolymer, 168 EVA. See Ethylene-vinyl acetate copolymer Exiplexes. See Fluorescence spectroscopy Expansion factor, 40-41 Extended-chain crystals, 80 Extrusion, 98

539
Flammability. See Flame resistance Flammability testing, 154-56 Flash pyrolysis. See Pyrolysis gas chromatography Flexible spacers, 85 Flexural strength, 101-5 Flory, Paul, 6 Flory-Fox equation, 41 Flory temperature. See Theta temperature Fluorescence spectroscopy, 139-40 Foams, 99 Folded-chain lamella model, 80 Fractional precipitation, 58 Fractional solution, 57-58 Franklin, Rosalind, 505 Free radical initiators, 169-73 azo compounds, 173 electrochemical polymerization, 173 peroxides and hydroperoxides, 169-71 photoinitiators, 172 redox, 171 thermal polymerization, 172 Free radical polymerization, 167-201 chain transfer, 180-83 constants for propagation and termination, 180 copolymerization, 194-201 dienes, 188-91 ketene acetals, 351 kinetic chain length, 179-80 kinetics and mechanism of, 176-86 living, 184-85 monomer reactivity, 191-94 primary radical termination, 177 stereochemistry of, 186-88 techniques of, 173-76 Friedel-Crafts polymers, 455-56 Fringed micelle model, 79-80 FTIR. See Infrared spectroscopy Fulvic acid. See Humus Furan resins, 402 Furfural, 402 Furfuryl alcohol, 402-3 Furnace chamber pyrolysis. See Pyrolysis gas chromatography

Fabrication of polymers, 96-100 Fatigue, 101, 157 FD-MS. See Field desorption mass spectrometry Ferrocenylmethyl acrylate, 436 Fiber-reinforced plastic, 5, 98 Fibers, 27-28 Fibroin, 495 Field desorption mass spectrometry, 47 Filament winding, 99 First-order transition temperature. See Crystalline melting point Flame resistance, 110-12 Flame retardants. See Additives

Galactans, 492 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 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 resonance spectroscopy

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

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 '

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Inverse emulsion. See Emulsion polymerization Ion-exchange resins, 468 Ion-scattering spectroscopy, 147-48 Ionenes, 467-68 Ionic crosslinking, 272 Ionic polymerization, 205-30 anionic, 217-27 cationic, 205-17 Ionic polymers, 46769 Ionomers, 272 IF'N. See Interpenetrating polymer networks Isobutylene-cyclopentadienecopolymer, 206 Isobutylene-isoprene copolymer, 206 Isolated dienes, polymerization of, 188-89 Isomerization polymerization, 217 Isotactic, definition of, 74 Isothermal TGS. See Thermogravimetric analysis ISS. See Ion-scattering spectroscopy Izod impact test, 157

Limiting oxygen index, 155-56 Limiting viscosity number. See Intrinsic viscosity Linear low-density polyethylene, 234 commercial uses for, 236 Linear polymer, definition of, 8 Liquid crystallinity, 83-85 Living polymers anionic, 221-22 cationic, 211 free radical, 184-85 polyether, 312, 317, 320 LLDPE. See Linear low-density polyethylene Logarithmic viscosity number. See Inherent viscosity LOI. See Limiting oxygen index Low-profile additives. See Additives Lubricants. See Additives

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Kendrew, John, 498 Keratin, 495, 501 Kerogen, 481 Ketene aminal, polymerization of, 373 Kevlar. See Poly(p-phenylene terephthalamide), 84 Kinetic chain length, 179-80

Lactarns, polymerization of, 369-72 Ladder polymers, 417 definition of, 9 Ladder pyrrones. See Polyirnidazopyrrolones Laser desorption mass spectrometry, 47 ' Laser pyrolysis. See Pyrolysis gas chromatography Latex blends, 88 Lauryllactarn, polymerization of, 371 LD-MS. See Laser desorption mass spectrometry LDPE. See Polyethylene, low-density Light scattering, determination of molecular weight by, 4 5 4 9 Light stability, 114 Lignin, 4034,479-80

Macromers. See Macromonomers Macromolecule, definition of, 3 Macromonomers, definition of, 9 Magic angle spinning. See Nuclear magnetic resonance spectroscopy MALDI-MS. See Matrix-assisted laser desorption ionization mass spectrometry MALDI-TOF. See Matrix-assisted laser desorption ionization mass spectrometry MAO. See Methylalumoxanes Mark-Houwink-Sakurada equation, 4 1 4 2 , 52-53,55,68 Marvel, Carl, 5, 108, 415 Mass spectrometry, molecular weight determination by, 46 Matrix-assisted laser desorption ionization mass spectrometry, 47 MDPE. See Polyethylene, medium-density Mechanical blends, 88 Mechanical properties, 100-106 measurement of, 156-59 Mechanical property modifiers. See Additives Mechanochemical blends, 88 Melamine, 395,406 Melamine-formaldehyde polymers, 406-7 Membrane osmometry, 43-45 Membrane-controlled release devices, 116-17

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542 Mercaptoethylcellulose, 488 Mercerization, 485 Merrifield, Bruce, 6, 498 Merrifield solid-phase peptide synthesis, 498-500 Meso structures, 75 Mesogens, definition of, 85 Mesophase, definition of, 83 Messenger RNA. See Nucleic acids Metaldehyde, 3 11 Metallocene catalysts, 245-46 Metathesis polymerization, 252-55 Methylalumoxanes, 245 Methylcellulose, 487-88 5'-Methylcytosine, 504 MF. See Melamine-formaldehyde polymers Microbial polyesters, 352-53 Microgels, 86 MIR. See Multiple internal reflection Model compounds. See Infrared spectroscopy Modulus, 102-5 Molecular sieving. See Gel permeation chromatography Molecular weight, determination of, 42-53 Molecular weight distribution, 53-58, 292-95 determination of, 53-58 in step-reaction polymerization, 292-95 Molecular wires, 120 Molecule-induced homolysis. See Thermal polymerization Monomer, definition of, 3 Monomer reactivity, 191-94 Monomeric unit, definition of, 7 Monometallic mechanism, 238-39 Multiblock copolymer, definition of, 7 Multiple internal reflection, 143 Myosin, 495

Index Neighboring group effect, 259-60 Neoprene rubber. See Polychloroprene Network polymer, definition of, 8 Network step polymerization, 295-97 Neutron scattering, 141 Newtonian fluid, 65-66 Nitrile rubber. See Acry1onitrile-butadiene copolymer Nitrocellulose. See Cellulose nitrate NLO. See Nonlinear optical properties NMR. See Nuclear Magnetic Resonance spectroscopy Nomenclature, 16-24 end groups, 24 IUPAC, 18 nonvinyl copolymers, 24 nonvinyl'polymers, 21-24 source-based, 16 vinyl copolymers, 20-21 vinyl polymers, 17-19 Nonchain scission. See Thermal degradation Nonisothermal TGA. See Thermogravimetric analysis Nonlinear optical properties, 120-21 Norbomene polymer. See Poly(l,3-cyclopentenylenevinylene) Nomsh type II reactions, 115 Noms-Smith effect. See Trommsdorff effect Noryl. See Poly(pheny1ene oxide) Novolacs, 399-402 Nuclear magnetic resonance spectroscopy, 134-38 Nucleating agents. See Additives Nucleation, 8 1 Nucleic acids, 502-1 0 base pairing, 505-7 cyclic, 505, 507 primary structure, 507 replication of, 505-6 synthesis of, 507-10 Nucleoside, definition of, 503 Nucleotide, definition of, 503 Number average molecular weight, 35-37 Number average molecular weight, determination of, 42-48 cryoscopy and ebulliometry, 46 end-group analysis, 42-43 mass spectrometry, 46-48 membrane osmometry, 43-45

Nadic methyl anhydride, 328 Native cellulose, 484 Natta, Giulio, 6, 74, 234 Natural polymers, 476-510 commercial uses for, 477 Natural rubber, 476-79 from guayule, 478 Naval stores, 482 N-Carboxy-m-amino acid anhydrides, polymerization of, 371-72

Index
refractive index measurement, 48 vapor pressure osmometry, 46 Nylon 1, derivatives of, 373-74 Nylon 2,371-72 Nylon 3,373-74 Nylon 4, 371 Nylon 5, 371 Nylon 6, 365, 369 Nylon 7, 365, 367 Nylon 8, 365, 371 Nylon 9, 365, 367 Nylon 11, 365, 367 Nylon 12, 365, 371 Nylon 46, 365, 367 Nylon 66, 365, 367 Nylon 69, 365 Nylon 610, 365 Nylon 612, 365 Nylons, mechanical properties of, 105-6

543
PBT. See Poly(buty1ene terephthalate) PC. See Polycarbonate PEEK. See Polyetheretherketone PEI. See Polyetherimide PEK. See Polyetherketone PEN. See Poly(ethy1ene naphthalene-2,Uicarboxylate) Permanence, 123 Peroxides, 169-7 1 Perutz, Max, 498 PET. See Poly(ethy1ene terephthalate) PETE. See Poly(ethy1ene terephthalate) PF. See Phenol-formaldehyde polymers PGC. See Pyrolysis-gas chromatography Phase-transfer catalysis, 300-301, 322 PHB. See Poly(3-hydroxybutyrate) PHBV. See Poly(3-hydroxybutyrate-valerate) Phenol, 395 Phenol-formaldehyde polymers, 396-404 chemical modifications of, 402-4 novolacs, 399-402 resoles, 396-99 Phenolic resins. See Phenol-formaldehyde polymers Phillips catalyst, 25 1 Phosphonitrilic chloride trimer. See Hexachlorocyclotriphosphazene Phosphonitrilic polymers. See Polyphosphazenes Phosphorylation, 367 Photoacoustic spectroscopy, 144 Photochemical crosslinking, 267-70 Photocrosslinking. See. Photochemical crosslinking Photocycloaddition polymerization. See Photopolymerization Photoinitiators, 172 Photonics. See Nonlinear optical properties Photopolymerization, 459-60 PI. See Polyimide Pigments. See Additives a-Piperidone. See Valerolactarn Plasma polymerization, 169 Plasticizers, 121-24 Plastics, 25-27 Pleated sheet, 496 PMR. See Bisnadimides Poled polymer. See Nonlinear optical properties

Odorants. See Additives Oil-in-water emulsion. See Emulsion polymerization Oil length. See Oil-modified alkyds Oil-modified alkyds, 355-56 Olefin metathesis, 252 Oligomer, definition of, 6 Optical rotatory dispersion, 139 ORD. See Optical rotatory dispersion Ordered copolyamides, 375 Organometallic polymers, 436-38 2-Oxazolines, polymerization of, 464 Oxetane, 315 Oxirane, 3 15 Ozone, resistance, 114, 250 Ozonolysis of polyacetylene, 130 Ozonolysis of rubber, 130

PAI. See Polyamideimide PAMAM. See Polyamidoamine Paper chromatography, 58 Paraformaldehyde, 3 12 Paraldehyde, 3 11 PAS. See Photoacoustic spectroscopy Pauling, Linus, 496 PBI. See Polybenzimidazole PBO. See Polybenzoxazoles

544

Index
Polyblend. See Polymer blends 2 0 6 Polybutadiene, 189-90, commercial uses for, 2 3 6 glass transition temperature of, 74, 82 limiting oxygen index of, 1 5 6 Poly(1-butene), 2 3 5 3 6 Poly(buty1ene terephthalate), 3 3 9 Polycaprolactarn. See Nylon 6 Polycaprolactone, 340, 350 Polycapryllactam. See Nylon 8 Polycarbamate. See Polyurethanes Polycarbodiimides, 447-49 Polycarbonates, 340,346-48 charge-transfer type, 4 6 5 6 6 from cyclic oligomers, 351-52 glass transition temperature of, 72-73,

Polyacetals, 322-24 Polyacetone, 117-18,3 1 3 Polyacetylene, 1 1 7 1 9 conductivity of, 1 1 9 metathesis polymerization synthesis, 254-55 precursor polymer synthesis, 277-78 Polyacetylenes, 451-52 aromatic polymers from, 452 Polyacrolein, 31 3 Polyacrylamide, 168, 262 Polyacrylates, 3 4 1 4 2 Poly(acry1ic acid), 17,1 6 8 Polyacrylonitrile, 1 6 8 Poly(alky1ene polysulfide)~, 3 31 3 2 commercial uses of, 31 0 Poly(alky1ene sulfide)~. See Polysulfides Polyallomers. See Ethylene-propylene block copolymers Poly(allyl acetate), 1 7 6 Poly(amic acid), 384 Polyamidehydrazides, 382 Polyamides, 364-78 biodegradable, 3 7 6 commercially important, 36566 from diisocyanates, 372-73 from ketene arninals, 3 7 3 from lactams, 369-72 from polycondensation reactions, 366-69 polyureas, 3 7 7 7 8 properties of, 374-76 Polyamidines, 449 Polyamidoamine, 301-2 Polyamines, 461-64 Polyampholytes, 469 Polyanhydrides, 4 6 0 6 1 Polyaniline, 462 conductivity of, 11 9 Polyanthrazolines, 4 2 1 Polyarylsulfone, 332 Polyaspartirnides, 3 8 6 Polyaziridenes, 463-64 Polybenzimidazole, 415-16 glass transition temperature of, 7 2 7 3 thermal stability of, 1 0 7 8 Polybenzothiazoles, 417 Polybenzoxazoles, 417 Poly(bispheno1 A isophthalate), 342 Poly(bispheno1 A terephthalate/isophthalate),

346-47
limiting oxygen index of, 1 5 6 mechanical properties of, 1 0 5 Polycarbophosphazene, 434 Polycarboranesiloxanes, commercial uses of,

426
Pclycatenanes, definition of, 9 Polychloral, 31 2 1 3 Polychloroprene, l 9 0 commercial uses for, 1 6 8 crystalline melting temperature of, 82 glass transition temperature of, 74,82 Poly(p-ch1orostyrene)-graft-polyacrylonitrile,

274
Polycyanoacrylate, 2 0 6 Polycyanurates, 413 Poly(l,3~yclohexadiene),453 Poly(l,4-cyclohexylenedimethylene suberamide), 3 6 5 Poly(l,3-cyclopentenylenevinylene), 236, 254 Polydichlorophosphazene, 431-32 Polydicyclopentadiene, 254 Poly(l,4-dihydroxymethylcyclohexyl terephthalate), 340 Polydispersity index, 37, 294-95 Polydithiahydrazide, 414 Polyelectrolytes, 120, 468-69 Polyester resins. See Crosslinked polyesters Polyesters, 338-58 block copolymers of, 343-44 by polycondensation, 3 4 1 4 8 commercially available, 339-40 crosslinked, 354-58

340

Index
from cyclic monomers, 348-52 glass transition temperature of, 7 2 7 3 hyperbranched, 353-54 ionomers, 467 linear, 341-53 melting points of, 344-45 microbial, 3 5 2 5 3 polycarbonates, 34648 properties of, 1 0 6 unsaturated, 356-58 Polyetheretherketone, 321-22 Polyetherimide, 321-22 Polyetherketone, 3 2 1 Polyethers, 3 0 9 2 9 by chain-reaction polymerization, 3 0 9 1 3 by ring-opening polymerization, 314-20 by step-reaction polymerization, 3 2 1 2 9 commercial uses for, 310 epoxy resins, 326-29 from aldehydes, 3 0 9 1 3 from glycols and bisphenols, 321-22 polyacetals and polyketals, 322-24 poly(pheny1ene oxide)^, 324-25 stereochemistry of, 313-14 Polyethersulfone, 332 Poly(ethy1 acrylate), 1 6 8 Polyethylene, 1 7 glass transition temperature of, 71-72 limiting oxygen index of, 1 5 6 mechanical properties of, 1 0 5 6 Polyethylene, high-density, 26, 234-35 commercial uses for, 235 pyrogram of, 1 5 5 Polyethylene, low-density, 26,1 8 1 commercial uses for, 1 6 8 Polyethylene, medium-density, 2 6 Polyethylene, ultrahigh-molecular-weight, 235 Poly(ethy1ene adipate), crystalline melting temperature of, 82 Poly[ethylene-CO-(vinyl acetate)], 1 5 4 Poly(ethy1ene glycol), 5 Poly(ethy1ene naphthalene-2,6-dicarboxylate),

545
Poly(ferrocenylethylene), 437 Poly(ferrocenylsilane)s, 437 Polyfomal. See Polyoxymethylene Polyformaldehyde. See Polyoxymethylene Polyfuran, 412 Polyglutaraldehyde, 3 1 3 Poly(glycolic acid), 340,343, 350-51 Polyglycolide. See Poly(glyco1ic acid) Poly(7-heptanamide). See Nylon 7 Poly[hexafluoropropylene-CO-(vinylidenefluo3 ride)], 1 1 Poly(hexamethy1ene adipamide). See Nylon 66 Poly(hexamethy1ene azelamide). See Nylon 69 Poly(hexamethy1ene dodecane@amide). See Nylon 612 Poly(hexamethy1ene phosphonamide), 368-69 Poly(hexamethy1ene sebacarnide). See Nylon 610 Poly(hexamethy1ene-m-benzenedisulfonarnide),

368
Polyhydantoins, 418 Polyhydrazides, 382,414 Poly(4-hydroxybenzoate), 339, 341-42 Poly(3-hydroxybutyrate), 352 Poly(3-hydroxybutyrate-valerate), 340,3 5 3 Polyimidazoles, 4 19-20 Poly(l,3-imidazolidine-2,4,5-trione)~. See Poly(parabanic acids)s Polyimidazopyrrolones, 417 Polyimides, 382-87 addition type, 385-87 condensation type, 3 8 3 8 5 from bismaleirnides, 3 8 5 8 6 from bisnadimides, 386-87 thermal stability of, ' 1 0 7 Polyirnidesulfone, 3 8 5 Polyimines, 449 Polyisobutylene, 2 0 6 Polyisocyanides, 449 Polyisocyanurates, 3 8 1 Polyisoprene, 189-90,2 0 6 commercial uses for, 2 3 6 crystalline melting temperature of, 82 glass transition temperature of, 74, 82 hydroboration of, 262 Polyketals, 322-24 Poly(1actic acid), 340, 3 5 0 51 Polylactide. See Poly(1actic acid) 2 Polylauryllactam. See Nylon 1 Polymer, definition of, 3

339-40
Poly(ethy1ene oxide), limiting oxygen index of, 1 5 6 Poly(ethy1ene succinate), 5 Poly(ethy1ene terephthalate), 339-42 crystalline melting temperature of, 82 mechanical properties of, 1 0 5

Index

Polymer alloys. See Polymer blends Polymer blends, 87-91 Polymer degradation, 276-79 Polymer solutions, 37-42 Polymeric chelates, 438, 4 4 1 4 2 Polymeric sulfur, 425 Polymerization, defition of, 3 Polymers, history of, 5-6 Poly (methacrylic acid), 168, 262 Poly(methy1 acrylate), 168 Poly(methy1ene-4,4'-dicyclohexylenedodecanediamide), 365 Poly(methy1 methacrylate), 19 ceiling temperature of, 193 commercial uses for, 168 depropagation, 278 glass transition temperature of, 79 limiting oxygen index of, 156 mechanical properties of, 105 N M R spectra of, 134-36 stereochemistry of, 187, 223-24 Poly(4-methyl-l -pentene), 235-36 Poly(a-methylstyrene), 17 Poly(p-methylstyrene), 168 Poly(methy1 vinyl ether), melting temperature of, 82 Poly(N-acylamidrazone),414-15 Poly(N-isopropylacrylamide), 117 Poly(9-nonanamide). See Nylon 9 Polynucleotides. See Nucleic acids Poly(N-vinylcarbazole), 117 Polyoctenamer. See Poly(1-octenylene) Poly(1-octenylene), 236, 254 Polyolefins, definition of, 16 Poly(l,3,4-oxadiazole)~, 414-15 Polyoxazole, thermal stability of, 107 Poly(oxy-2,6-dimethyl-1,4-phenylene). See Poly(pheny1ene oxide) Polyoxymethylene, 31 1-12 limiting oxygen index of, 156 Poly@arabanic acids)~, 418 Polypentenamer, hydroformylation of, 262 Poly(1-pentene), 17 Polypeptides. See Proteins Poly(p-phenylene), 452-54, 458 conductivity of, 119 from precursor polymers, 453 thermal stability of, 107 Poly(m-phenylene isophthalamide), 365, 368

Poly(pheny1ene oxide), 90, 324-25 limiting oxygen index of, 156 thermal stability of, 107 Polyphenylenes, 453 Poly(p-phenylene sulfide), 329 thermal stability of, 107 Poly(p-phenylene terephthalamide), 365, 368 Poly(p-phenylenevinylene), conductivity of, 119 Polyphenylsilsequioxane, 429 Polyphosphazenes, 113,431-34 commercial uses for, 426 Polyphosphonamides, 368-69 Polyphthalocyanines, 413 Polypropylene, 19 commercial uses for, 235-36 glass transition temperature of, 71-72 herniisotactic, 248 limiting oxygen index of, 156 mechanical properties of, 105-6 Polypyrazines, 419 Polypyrazoles, 419-20, 452 Polypynrole, 412, 452 conductivity of, 119 Polyquinolines, 421 Polyquinoxaline, 4 19 thermal stability of, 107-9 Polyrotaxanes, definition of, 9 Polysaccharides, 484-92 cellulose, 484-89 starch, 489-90 Polysilanes, 430-31 commercial uses for, 426 Polysilastyrene, 43 1 Polysiloxanes, 427-30 . commercial uses for, 426 limiting oxygen index of, 156 Polystannanes, 43 1 Polystyrene, 17 commercial uses for, 168, 235 ceiling temperature of, 193 chloromethylation of, 261 crosslinked, 456 crystalline melting temperature of, 82 glass transition temperature of, 71-72 limiting oxygen index of, 156 mechanical properties of, 105 oxazoline-substituted, 275-76 thermal polymerization of, 372

Index
Polysulfides, 329-3 1 Polysulfonamides, 368, 371-72 Polysulfones, 321122, 332 commercial uses for, 3 11 Poly(su1fur nitride), 117, 426-27 conductivity of, 119 Polyterpene resins, 206 Polytetrafluoroethylene, 17, 113 commercial uses for, 168 limiting oxygen index of, 156 mechanical properties of, 105 Poly(tetramethy1ene adipamide). See Nylon 46 Poly(l,3,4-thiadiazole),414 thermal stability of, 107 Polythiazoles, TGA thermograms of, 153 Polythiazyl. See Poly(sulfur nitride) Polythioacetals, 330-3 1 Polythiocarbonates, 348 Poly(thiocarbony1 fluoride), 330 Polythioketals, 330-3 1 Polythiophene, 412-13,452 conductivity of, 119 Polythiophosphazenes, 434 Poly(as-triazines), 420 Poly(l,2,4-triazole), 414-15 Polytriazolines, 420 Polytnchloroacetaldehyde.See Polychloral Polytrichl~rofluoroethylene, 168 Poly(trimethy1ene terephthalate), 339-40 Poly(2,4,4-trimethylhexamethyleneterephthalamide), 366, 369 Poly(2,4,6-triphenylbenzylmethacrylate), 188 Poly(1 l-undecanamide). See Nylon 11 Polyurea ionomers, 467 Polyureas, 377-78 Polyurethanes, 378-8 1 coatings, 381 elastomeric fibers, 379 foams, 380-81 self-extinguishing, 38 1 ionomers, 467 Poly(viny1 acetate), 168 P ~ l y ( ~ i nalcohol), yl 261-62 degradation of, 130 glass transition temperature of, 71-72, 82 limiting oxygen index of, 156 synthesis of, 261-62 Poly(viny1 alcohol-graft-polyethylene), 274 Poly(viny1 amine), 262

547

Poly(4'-vinylbenzo-18-crown-6), 441 Poly(viny1 bromide), head-to-head, 262 Poly(viny1 butyral), 264-65 Poly(viny1 chloride), 19 commercial uses for, 168 crystalline melting temperature of, 82 ' dehydrochlorination of, 262 glass transition temperature of, 71-72 limiting oxygen index of, 156 mechanical properties of, 105 thermogram of, 151 Poly(viny1 et hers)^, 206 Polyvinylfemocene, 436 Poly(viny1 fluoride), 168, 176 Poly(viny1idene chloride), 168 limiting oxygen index of, 156 Poly(viny1idene cyanide), 217-1 8 Poly(viny1idene fluoride), 113, 168, 176 Poly(2-vinylnaphthalene), glass transition temperature of, 71-72 Poly(p-xylylene), 454-55 POM. See Polyoxymethylene Popcorn polymerization, 174 PP. See Polypropylene PPO. See Poly(pheny1ene oxide) PPS. See Poly(pheny1ene sulfide) Preform, 98 Prepreg. See Preform Priestley, Joseph, 478 Primary radical termination, 177 Processing modifiers. See Additives Promoter, 170, 317 Promoters. See Additives P-Propiolactone, polymerization of, 349-50 Propiosultam, polymerization of, 371-72 Propylene oxide, polymerization of, 3 15 Prosthetic group, 495 Proteins, 492-502 amino acids from, 492-95 classification of, 495 conjugated, 495 crosslinking of, 502 primary structure, 495 quaternary structure, 498 regenerated, 502 secondary structure, 496 synthesis of, 498-500 tertiary structure, 496, 498 Proton trap, 209-10

548

Inde 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 polymerization Rosin, 483 RRIM. See Reinforced reaction injection molding RTV rubber. See Polysiloxanes Rubber, 28-29,476-79

PS. See Polystyrene Pseudobisdienes. See Diels-Alder polymerization 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 degradation 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 osmometry 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

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 OSmometry 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 marphology

Index
Silicone oils, 428 Silicone rubber, 428-29 Silicone-ether block copolymers, 429-30 Silicones. See Polysiloxanes Silk, 500-502 modification of, 501-2 Simple rule of mixtures, 89 SIMS. See Secondary-ion mass spectrometry Simultaneous interpenetrating polymer networks, 88 SIN. See Simultaneous interpenetrating polymer networks Single-site catalysts. See Metallocene catalysts Size exclusion chromatography. See Gel permeation chromatography Slip agents. See Additives SMA. See Styrene-maleic anhydride copolymer Smart polymers, 117 Smith-Ewart kinetics, 185-86 Soda cellulose. See Alkali cellulose Sol-gel process, 430 Solid phase synthesis, 261, 498-500, 508510 Solitons, l l 8 Solubility parameter, 38 Solution blends, 88 Solution polymerization, 174 Solvent gradient chromatography. See Fractional solution Solvent polymerization, 299 Sparging, 299 Specific refractive increment. See Light scattering Specific viscosity, 5 1 Spectroscopic analysis, 130-40 Sphemlites, definition of, 81 Spherulitic morphology, 8 1 Spinneret. See Spinning Spinning, 99-100 Spiro polymers, 323, 331 Star-block copolymers, 227 Starburst polymers. See Dendrimers Starch, 489-90 derivatives of, 490 Star polymers, definition of, 8 Static equilibrium method. See Membrane osmometry

549
Staudinger, Hermann, 5 Steel, properties of, 106 Step-growth polymerization. See Step-reaction polymerization Step-ladder polymer. See Semiladder polymer Step-reaction addition polymerization, $5 Step-reaction copolymerization, 297-98 Step-reaction polymerization, 12-13, 285309 copolymerization, 297-98 definition of, 11 dendrimers, 301-3 kinetics of, 285-90 molecular weight distribution, 292-95 network polymerization, 295-97 stoichiometric imbalance, 290-92 techniques of, 298-301 Stereoblock, definition of, 74 Stereochemistry of polymerization aldehyde polymerization, 313-14 anionic, 223-25 cationic, 213-15 epoxides, 320 free radical, 186-88 heterogeneous Ziegler-Natta, 242-45 homogeneous Ziegler-Natta, 248-49 with metallocene catalysts, 248-49 Stereochemistry of vinyl polymers, 7 4 7 9 STM. See Scanning tunneling microscopy Stoichiometric imbalance, 290-92 Stress relaxation, 104 Styrenated alkyds, 356 Styrene-acrylonitrile copolymer, 168 Styrene-butadiene block copolymers, 206 Styrene-butadiene copolymer, emulsion polymerization, 175 Styrene-butadiene rubber, 168, 206 Styrene-maleic anhydride copolymer, 168 Succinite. See Amber Sulfur, 425 Supported metal oxide catalysts, 251 Supramolecular assembly, definition of, 9 Surface analysis, 141-49 Surface property modifiers. See Additives Surface resistivity, 159-60 Suspension polymerization, 174 Syndiotactic, definition of, 74 Synthetic natural rubber, 224-25

550 T,. See Ceiling temperature T,. See Glass transition temperature T,. See Crystalline melting point Tactic dyad, 75-76 Tactic placement. See Tactic dyad Tactic triad, 75-76 Tall oil-derived polymers, 482-83 Tall oil fatty acids, 483 Tangential stress. See Shear stress Tannin, 403-4 Tear resistance, 101, 159 Telechelic polymer, 263 definition of, 7 Telomerization, 183 Telomers, 183 Tenacity, 106 Tensile strength, 101-6 Tetrahydrofuran, polymerization of, 315 TGA. See Thermogravimetric analysis Thermal analysis, 149-56 Thermal degradation, 277-78 Thermal gradient turbidimetry. See Fractional precipitation Thermal polymerization, 172 Thermal stability, 106-10 Thermogravimetric analysis, 152-53 Thermomechanical analysis, 152 Thermoplastic elastomers, 28,87-88 Thermosetting, definition of, 10 Theta state, 41 Theta temperature, 41 Thickening agents. See Additives Thin-layer chromatography, molecular weight distribution by, 58 Thiokol rubbers. See Poly(alky1ene polysulfide)s Thixotropy, 66 Threo structures, 76-78 Thymine, 504 TLC. See Thin-layer chromatography TMA. See Thermomechanical analysis Topological bonding, 90-91 TPE. See Thermoplastic elastomer Transdermal patches, 117 Transfer RNA. See Nucleic acids Tn-2-ethylhexyl trimellitate. See Plasticizers Triblock copolymer, definition of, 7 Trimer acids, 483

Index

2,2,4-Trimethylpentane-1,3-diol, 112-13 Trioxane, 309,311 polymerization of, 314-15 Trommsdorff effect, 180 Turbidimetry. See Fractional precipitation
W. See Urea-formaldehyde polymers UHMWPE. See Polyethylene, ultrahighmolecular-weight Ultracentrifugation, 50 Ultraviolet stabilizers. See Additives Ultraviolet-visible spectroscopy, 139 Universal calibration parameter, 55-57 Unperturbed dimension, 4041 Unsaturated polyesters, 356-58 recycling of, 358 Uracil, 504 Urea, 395 Urea-formaldehyde polymers, 404-6 Uridine, 504

Vapor pressure osmometry, 46 Velocity gradient. See Shear rate Vinylcylohexene dioxide, in epoxy resins, 327 Vinylferrocene, 436 Vinylidene, definition of, 16 Vinyl polymers block and graft copolymers of, 272-76 chlorination of, 260 chlorosulfonation of, 260-61 crosslinking of, 265-72 definition of, 16 degradation of, 276-79 fluorination of, 261 ' functional group reactions in, 260-63 reactions of, 259-79 ring-forming reactions of, 263-65 Vinylruthenocene, 436 Viscoelasticity. See Rheology Viscometry, 50-53, 69 Viscose process. See Xanthate process Viscose rayon, 486 Viscosity average molecular weight, 52-53 Viscosity number. See Reduced viscosity Viscosity ratio. See Relative viscosity Vitrification, 63

Index Vitrinite, 480 Volume resistivity, 159 Vulcanization, 265-67

551
Xanthate process, 485-86 XPS. See Electron spectroscopy for chemical analysis X-ray diffraction. See X-ray scattering X-ray photoelectron spectroscopy. See Electron spectroscopy for chemical analysis X-ray scattering, 140-41 Xylan, 492

Water-in-oil emulsion. See Emulsion polymerization Watson, James, 505 WAXS. See X-ray scattering Weatherability, 159 Weight average molecular weight, 35-37 determination of, 48-50 by ultracentrifugation, 50 by light scattering, 48 Wet spinning, 99 Wetting agents. See Additives Wilkins, Maurice, 505 Wittig reaction, unsaturated polymers by, 450 Wood flour. See Additives Wool, 500-502 modification of, 501-502 tensile strength of, 106

Zein, 502 Ziegler, Karl, 6, 74, 234 Ziegler-Natta catalysts, 236-38, 245-46 heterogeneous, 236-38 homogeneous, 245-46 Ziegler-Natta polymerization, 2 3 6 5 1 copolymerization, 249-5 1 epoxides, 318-20 heterogeneous, 236-45 homogeneous, 245-49 Zirnm plots, 49