T H I R D E D I T I O N POLYMER CHEMISTRY AN INTRODUCTION Malcolm P. Stevens University of Hartford New York Oxford OXFORD UNIVERSITY PRESS 1999
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T H I R D E D I T I O N
POLYMER CHEMISTRY
AN INTRODUCTION
Malcolm P. Stevens University of Hartford
New York Oxford
OXFORD UNIVERSITY PRESS
1999
CONTENTS
Preface, xvii
PART I POLYMER STRUCTURE A N D PROPERTIES
I. Basic principles, 3
1.1 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, 13
1.6 Step-reaction addition and chain-reaction condensation, 15
1.7 Nomenclature, 16
1.7.1 Vinyl polymers, 17 1.7.2 Vinyl copolymers, 20 1.7.3 Nonvinyl polymers, 21 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 fifaers, 27 1.8.3 Rubber (elastomers), 28 1.8.4 Coatings and adhesives, 29
1.9 Polymer recycling, 30
References, 31
Review exercises, 32
vii
Vll l 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
2.3.1 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 preäpitation, 58
2.6.4 Thin-layer chromatography (TLC), 58
References, 58
Review exercises, 59
3. Chemical structure and polymer morphology, 61
3.1 Introduction, 61
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, 91
Review exercises, 93
Contents ix
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, I 10
4.6 Chemical resistance, I 12
4.7 Degradability, I 14
4.8 Electrical conductivity, I 17
4.9 Nonlinear optical properties, 120
4.10 Additives, 121
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, 131 5.3.2 Raman, 133 5.3.3 Nuclear magnetic resonance, 134 5.3.4 Electron spin resonance, 138 5.3.5 Ultraviolet (UV)-visible, 139 5.3.6 Fluorescence, 139
5.4 X-ray, electron, and neutron scattering, 140
5.5 Characterization and analysis of polymer surfaces, 141
5.5.1 Scanning electron microscopy (SEM), 143 5.5.2 Attenuated total reflectance spectroscopy (ATR), 143 5.5.3 Photoacoustic spectroscopy (PAS), 144 5.5.4 Electron spectroscopy for chemical analysis (or applications)
(ESCA) and Auger electron spectroscopy (AES), 145 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, 149 5.6.1 Differential scanning calorimetry (DSC) and differential
thermal analysis (DTA), 149
X Contents
5.6.2 Thermomechanical analysis (TMA), 152 5.6.3 Thermogravimetric analysis (TGA), 152 5.6.4 Pyrolysis-gas chromatography (PGC), 153 5.6.5 Flammability testing, 154
5.7 Measurement of mechanical properties, 156
5.8 Evaluation of chemical resistance, 159
5.9 Evaluation of electrical properties, 159
References, 160
Review exercises, 163
PART II V INYL POLYMERS
6. Free radical polymerization, 167
6.1 Introduction, 167
6.2 Free radical initiators, 169
6.2.1 Peroxides and hydroperoxides, 169 6.2.2 Azo Compounds, 171 6.2.3 Redox initiators, 171 6.2.4 Photoinitiators, 172 6.2.5 Thermal polymerization, 172 6.2.6 Electrochemical polymerization, 173
6.3 Techniques of free radical polymerization, 173
6.3.1 Bulk, 174 6.3.2 Suspension, 174 6.3.3 Solution, 174 6.3.4 Emulsion, 175
6.4 Kinetics and mechanism of polymerization, 176
6.5 Stereochemistry of polymerization, 186
6.6 Polymerization of dienes, 188
6.6. / Isolated dienes, 188
6.6.2 Conjugated dienes, 189
6.7 Monomer reactivity, 191
6.8 Copolymerization, 194
References, 201
Review exercises, 202
Contents xi
7. lonic polymerization, 205
7.1 Introduction, 205
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, 21 3 7.2.4 Cationic copolymerization, 215 7.2.5 Isomerization in cationic polymerization, 217
7.3 Anionic polymerization, 217
7.3.1 Anionic initiators, 217 7.3.2 Mechanism, kinetics, and reactivity in anionic
polymerization, 219 7.3.3 Stereochemistry of anionic polymerization, 223 7.3.4 Anionic copolymerization, 225
7.4 Group transfer polymerization, 227
References, 230
Review exercises, 231
8. Vinyl polymerization with complex coordination catalysts, 234
8.1 Introduction, 234
8.2 Heterogeneous Ziegler-Natta polymerization, 236
8.2.1 Heterogeneous catalysts, 236 8.2.2 Mechanism and reactivity in heterogeneous
polymerization, 238 8.2.3 Stereochemistry of heterogeneous polymerization, 242 8.2.4 Polymerization ofdienes, 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
8.4 Ziegler-Natta copolymerization, 249
8.5 Supported metal oxide catalysts, 251
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, 255
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, 261
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, 271 9.4.5 lonic crosslinking, 272
9.5 Block and graft copolymer formation, 272
9.5.1 Block copolymers, 272 9.5.2 Graft 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, 281
PART III N O N V I N Y L POLYMERS
10. Step-reaction and ring-opening polymerization, 285
10.1 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
Contents
10.8 Dendritic polymers, 301
10.9 Ring-opening polymerization, 304
References, 306
Review exercises, 307
11. Polyethers, polysulfides, and related polymers, 309
l l . l Introduction, 309
I 1.2 Preparation of polyethers by chain-reaction and ring-opening polymerization, 309
11.2.1 Polymerization of carbonyl Compounds, 309 /1.2.2 Stereochemistry ofaldehyde polymerization, 313 /1.2.3 Polymerization ofcyclic ethers, 3 14 /1.2.4 Stereochemistry of epoxide polymerization, 320
11.3 Preparation of polyethers by step-reaction polymerization, 321
/1.3.1 Synthesis of polyethers from glycols and bisphenols, 321 11.3.2 Polyacetals and polyketals, 322 11.3.3 Poly(phenylene oxide)s, 324 /1.3.4 Epoxy resins, 326
11.4 Polysulfides, poly(alkylene polysulfide)s, and polysulfones, 329
11.4.1 Polysulfides, 329 11.4.2 Poly(alkylene polysulfide)s, 331 /1.4.3 Polysulfones, 332
References, 333
Review exercises, 334
12. Polyesters, 338
12.1 Introduction, 338
12.2 Linear polyesters, 341
12.2.1 Preparation of polyesters by polycondensation reactions, 341 12.2.2 Polycarbonates, 346 / 2.2.3 Preparation of polyesters by ring-opening polymerizavon, 348 12.2.4 Microbial polyesters, 352
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 Preparation ofpolyamides by polycondensation reactions, 366
13.2.2 Polymerization oflactams, 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, 412
15.3 Polycyanurate and polyphthalocyanine resins, 413
15.4 Heterocyclic polymers formed from precursor polymers, 414
15.5 Heterocyclic polymers formed from polyfunctional monomers, 415
15.5.1 Polybenzimidazoles, 415 15.5.2 Polybenzoxazoles and polybenzothiazoles, 417 15.5.3 Polyhydantoins, 418 15.5.4 Poly(parabanic aäd)s, 418 15.5.5 Polyquinoxalines and polypyrazines, 419 15.5.6 Polypyrazoles and polyimidazoles, 419 15.5.7 Poly(as-triazine)s and polytriazolines, 420
Contents
15.5.8 Polyquinolines and polyanthrazolines, 421
References, 421
Review exercises, 422
16. Inorganic and partially inorganic polymers, 425
16.1 Introduction, 425
16.2 Poly(sulfur nitride), 426
16.3 Polysiloxanes, 427
16.4 Polysilanes, 430
16.5 Polyphosphazenes, 431
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
/ 7.2.1 Polycarbodiimides, 447 / 7.2.2 Polyimines, 449 / 7.2.3 Polymers containing carbon-carbon double bonds, 450 / 7.2.4 Azo polymers, 450 / 7.2.5 Polymers containing carbon-carbon triple bonds, 451
17.3 Poly(p-phenylene) and poly(p-xylylene), 452
/ 7.3.1 Poly(p-phenylene), 452 / 7.3.2 Poly(p-xylylene), 454
17.4 Friedel-Crafts polymers, 455
17.5 Cycloaddition polymerization, 456
/ 7.5.1 Diels-Alder polymerization, 456 / 7.5.2 2 + 2 Cycloaddition polymerization, 459
17.6 Polyanhydrides, 460
17.7 Polyamines, 461
17.8 Charge-transfer polymers, 464
17.9 lonic polymers, 467
References, 469
Review exercises, 471
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, 481 18.2.4 Shellac, 481 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, 491
184 Proteins, 492 / 8.4.1 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 18.5.2 Nucleic acid synthesis, 507
18.6 Conclusion, 510
References, 510
Review exercises, 513
Appendix A Commonly used polymer abbreviations, 515
Appendix B Polymer literature, 517
Appendix C Sources of laboratory experiments in polymer chemistry, 526
Index, 535
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