1 INTRODUCTION 1
1-1 Types of Polymers and Polymerizations 1
1-1a Polymer Composition and Structure 2
1-1b Polymerization Mechanism 6
1-2 Nomenclature of Polymers 9
1-2a Nomenclature Based on Source 10
1-2b Nomenclature Based on Structure （Non-IUPAC） 11
1-2c IUPAC Structure-Based Nomenclature System 11
1-2d Trade Names and Nonnames 16
1-3 Linear，Branched，and Crosslinked Polymers 17
1-4 Molecular Weight 19
1-5 Physical State 24
1-5a Crystalline and Amorphous Behavior 24
1-5b Determinants of Polymer Crystallinity 27
1-5c Thermal Transitions 29
1-6 Applications of Polymers 32
1-6a Mechanical Properties 32
1-6b Elastomers，Fibers，and Plastics 35
References 36
2 STEP POLYMERIZATION 39
2-1 Reactivity of Functional Groups 40
2-1a Basis for Analysis of Polymerization Kinetics 40
2-1b Experimental Evidence 41
2-1c Theoretical Considerations 43
2-1d Equivalence of Groups in Bifunctional Reactants 44
2-2 Kinetics of Step Polymerization 44
2-2a Self-Catalyzed Polymerization 46
2-2a-1 Experimental Observations 47
2-2a-2 Reasons for Nonlinearity in Third-Order Plot 48
2-2a-3 Molecular Weight of Polymer 50
2-2b External Catalysis of Polymerization 51
2-2c Step Polymerizations Other than Polyesterification：Catalyzed versus Uncatalyzed 53
2-2d Nonequivalence of Functional Groups in Polyfunctional Reagents 54
2-2d-1 Examples of Nonequivalence 54
2-2d-2 Kinetics 57
2-3 Accessibility of Functional Groups 63
2-4 Equilibrium Considerations 65
2-4a Closed System 65
2-4b Open，Driven System 67
2-4c Kinetics of Reversible Polymerization 69
2-5 Cyclization versus Linear Polymerization 69
2-5a Possible Cyclization Reactions 69
2-5b Cyclization Tendency versus Ring Size 70
2-5c Reaction Conditions 72
2-5d Thermodynamic versus Kinetic Control 73
2-5e Other Considerations 74
2-6 Molecular Weight Control in Linear Polymerization 74
2-6a Need for Stoichiometric Control 74
2-6b Quantitative Aspects 75
2-6c Kinetics of Nonstoichiometric Polymerization 79
2-7 Molecular Weight Distribution in Linear Polymerization 80
2-7a Derivation of Size Distributions 80
2-7b Breadth of Molecular Weight Distribution 82
2-7c Interchange Reactions 83
2-7d Alternate Approaches for Molecular-Weight Distribution 83
2-7e Effect of Reaction Variables on MWD 86
2-7e-1 Unequal Reactivity of Functional Groups 86
2-7e-2 Change in Reactivity on Reaction 86
2-7e-3 Nonstoichiometry of Functional Groups 86
2-8 Process Conditions 87
2-8a Physical Nature of Polymerization Systems 87
2-8b Different Reactant Systems 89
2-8c Interfacial Polymerization 90
2-8c-1 Description of Process 90
2-8c-2 Utility 92
2-8d Polyesters 92
2-8e Polycarbonates 96
2-8f Polyamides 97
2-8g Historical Aspects 101
2-9 Multichain Polymerization 101
2-9a Branching 101
2-9b Molecular Weight Distribution 102
2-10 Crosslinking 103
2-10a Carothers Equation：Xn→∞ 105
2-10a-1 Stoichiometric Amounts of Reactants 105
2-10a-2 Extension to Nonstoichiometric Reactant Mixtures 106
2-10b Statistical Approach to Gelation：Xw→∞ 108
2-10c Experimental Gel Points 111
2-10d Extensions of Statistical Approach 112
2-11 Molecular Weight Distributions in Nonlinear Polymerizations 114
2-12 Crosslinking Technology 117
2-12a Polyesters，Unsaturated Polyesters，and Alkyds 118
2-12b Phenolic Polymers 120
2-12b-1 Resole Phenolics 120
2-12b-2 Novolac Phenolics 124
2-12b-3 Applications 126
2-12c Amino Plastics 126
2-12d Epoxy Resins 128
2-12e Polyurethanes 130
2-12f Polysiloxanes 132
2-12g Polysulfides 134
2-13 Step Copolymerization 135
2-13a Types of Copolymers 135
2-13b Methods of Synthesizing Copolymers 138
2-13b-1 Statistical Copolymers 138
2-13b-2 Alternating Copolymers 138
2-13b-3 Block Copolymers 139
2-13c Utility of Copolymerization 140
2-13c-1 Statistical Copolymers 141
2-13c-2 Block Copolymers 142
2-13c-3 Polymer Blends and Interpenetrating Polymer Networks 143
2-13c-4 Constitutional Isomerism 144
2-14 High-Performance Polymers 144
2-14a Requirements for High-Temperature Polymers 144
2-14b Aromatic Polyethers by Oxidative Coupling 146
2-14c Aromatic Polyethers by Nucleophilic Substitution 149
2-14d Aromatic Polysulfides 151
2-14e Aromatic Polyimides 151
2-14f Reactive Telechelic Oligomer Approach 155
2-14g Liquid Crystal Polymers 157
2-14h 5-Membered Ring Heterocyclic Polymers 159
2-14i 6-Membered Ring Heterocyclic Polymers 162
2-14j Conjugated Polymers 163
2-14j-1 Oxidative Polymerization of Aniline 165
2-14j-2 Poly（p-phenylene） 166
2-14j-3 Poly（p-phenylene Vinylene） 167
2-15 Inorganic and Organometallic Polymers 168
2-15a Inorganic Polymers 168
2-15a-1 Minerals 168
2-15a-2 Glasses 169
2-15a-3 Ceramics 170
2-15b Organometallic Polymers 172
2-15b-1 Polymerization via Reaction at Metal Bond 172
2-15b-2 Polymerization without Reaction at Metal Bond 173
2-15b-3 Polysilanes 173
2-16 Dendritic （Highly Branched） Polymers 174
2-16a Random Hyperbranched Polymers 175
2-16b Dendrimers 177
2-17 Miscellaneous Topics 180
2-17a Enzymatic Polymerizations 180
2-17a-1 In Vivo （within Living Cells） 180
2-17a-2 In Vitro （outside Living Cells） 181
2-17b Polymerization in Supercritical Carbon Dioxide 183
2-17c Cycloaddition （Four-Center） Polymerization 183
2-17d Spiro Polymers 184
2-17e Pseudopolyrotoxanes and Polyrotoxanes 184
References 185
3 RADICAL CHAIN POLYMERIZATION 198
3-1 Nature of Radical Chain Polymerization 199
3-1a Comparison of Chain and Step Polymerizations 199
3-1b Radical versus Ionic Chain Polymerizations 199
3-1b-1 General Considerations of Polymerizability 199
3-1b-2 Effects of Substituents 200
3-2 Structural Arrangement of Monomer Units 202
3-2a Possible Modes of Propagation 202
3-2b Experimental Evidence 203
3-2c Synthesis of Head-to-Head Polymers 204
3-3 Rate of Radical Chain Polymerization 204
3-3a Sequence of Events 204
3-3b Rate Expression 206
3-3c Experimental Determination of Rp 208
3-3c-1 Physical Separation and Isolation of ReactionProduct 208
3-3c-2 Chemical and Spectroscopic Analysis 208
3-3c-3 Other Techniques 209
3-4 Initiation 209
3-4a Thermal Decomposition of Initiators 209
3-4a-1 Types of Initiators 209
3-4a-2 Kinetics of Initiation and Polymerization 212
3-4a-3 Dependence of Polymerization Rate on Initiator 212
3-4a-4 Dependence of Polymerization Rate on Monomer 214
3-4b Redox Initiation 216
3-4b-1 Types of Redox Initiators 216
3-4b-2 Rate of Redox Polymerization 217
3-4c Photochemical Initiation 218
3-4c-1 Bulk Monomer 219
3-4c-2 Irradiation of Thermal and Redox Initiators 220
3-4c-3 Rate of Photopolymerization 221
3-4d Initiation by Ionizing Radiation 224
3-4e Pure Thermal Initiation 226
3-4f Other Methods of Initiation 227
3-4g Initiator Efficiency 228
3-4g-1 Definition off 228
3-4g-2 Mechanism off ＜ 1：Cage Effect 228
3-4g-3 Experimental Determination off 232
3-4h Other Aspects of Initiation 235
3-5 Molecular Weight 236
3-5a Kinetic Chain Length 236
3-5b Mode of Termination 236
3-6 Chain Transfer 238
3-6a Effect of Chain Transfer 238
3-6b Transfer to Monomer and Initiator 240
3-6b-1 Determination of CM and Cl 240
3-6b-2 Monomer Transfer Constants 241
3-6b-3 Initiator Transfer Constants 244
3-6c Transfer to Chain-Transfer Agent 245
3-6c-1 Determination of Cs 245
3-6c-2 Structure and Reactivity 246
3-6c-3 Practical Utility of Mayo Equation 249
3-6d Chain Transfer to Polymer 250
3-6e Catalytic Chain Transfer 254
3-7 Inhibition and Retardation 255
3-7a Kinetics of Inhibition or Retardation 256
3-7b Types of Inhibitors and Retarders 259
3-7c Autoinhibition of Allylic Monomers 263
3-8 Determination of Absolute Rate Constants 264
3-8a Non-Steady-State Kinetics 264
3-8b Rotating Sector Method 265
3-8c PLP-SEC Method 267
3-8d Typical Values of Reaction Parameters 269
3-9 Energetic Characteristics 271
3-9a Activation Energy and Frequency Factor 271
3-9a-1 Rate of Polymerization 272
3-9a-2 Degree of Polymerization 274
3-9b Thermodynamics of Polymerization 275
3-9b-1 Significance of △G，△H，and △S 275
3-9b-2 Effect of Monomer Structure 276
3-9b-3 Polymerization of 1，2-Disubstituted Ethylenes 277
3-9c Polymerization-Depolymerization Equilibria 279
3-9c-1 Ceiling Temperature 279
3-9c-2 Floor Temperature 282
3-10 Autoacceleration 282
3-10a Course of Polymerization 282
3-10b Diffusion-Controlled Termination 283
3-10c Effect of Reaction Conditions 286
3-10d Related Phenomena 287
3-10d-1 Occlusion （Heterogeneous） Polymerization 287
3-10d-2 Template Polymerization 287
3-10e Dependence of Polymerization Rate on Initiator and Monomer 288
3-10f Other Accelerative Phenomena 289
3-11 Molecular Weight Distribution 289
3-11a Low-Conversion Polymerization 289
3-11b High-Conversion Polymerization 292
3-12 Effect of Pressure 292
3-12a Effect on Rate Constants 293
3-12a-1 Volume of Activation 293
3-12a-2 Rate of Polymerization 294
3-12a-3 Degree of Polymerization 295
3-12b Thermodynamics of Polymerization 296
3-12c Other Effects of Pressure 296
3-13 Process Conditions 296
3-13a Bulk （Mass） Polymerization 297
3-13b Solution Polymerization 297
3-13c Heterogeneous Polymerization 297
3-13d Other Processes； Self-Assembly and Nanostructures 299
3-14 Specific Commercial Polymers 300
3-14a Polyethylene 300
3-14b Polystyrene 302
3-14c Vinyl Family 304
3-14c-1 Poly（vinyl chloride） 304
3-14c-2 Other Members of Vinyl Family 306
3-14d Acrylic Family 307
3-14d-1 Acrylate and Methacrylate Products 307
3-14d-2 Polyacrylonitrile 308
3-14d-3 Other Members of Acrylic Family 308
3-14e Fluoropolymers 309
3-14f Polymerization of Dienes 310
3-14g Miscellaneous Polymers 311
3-14g-1 Poly（p-xylylene） 311
3-14g-2 Poly（N-vinylcarbazole） 313
3-14g-3 Poly（N-vinylpyrrolidinone） 313
3-15 Living Radical Polymerization 313
3-15a General Considerations 313
3-15b Atom Transfer Radical Polymerization （ATRP） 316
3-15b-1 Polymerization Mechanism 316
3-15b-2 Effects of Components of Reaction System 319
3-15b-3 Complex Kinetics 321
3-15b-4 Block Copolymers 322
3-15b-5 Other Polymer Architectures 324
3-15c Stable Free-Radical Polymerization （SFRP） 325
3-15d Radical Addition-Fragmentation Transfer （RAFT） 328
3-15e Other Living Radical Polymerizations 330
3-16 Other Polymerizations 330
3-16a Organometallic Polymers 330
3-16b Functional Polymers 330
3-16c Acetylenic Monomers 332
References 332
4 EMULSION POLYMERIZATION 350
4-1 Description of Process 350
4-1a Utility 350
4-1b Qualitative Picture 351
4-1b-1 Components and Their Locations 351
4-1b-2 Site of Polymerization 353
4-1b-3 Progress of Polymerization 354
4-2 Quantitative Aspects 356
4-2a Rate of Polymerization 356
4-2b Degree of Polymerization 360
4-2c Number of Polymer Particles 362
4-3 Other Characteristics of Emulsion Polymerization 363
4-3a Initiators 363
4-3b Surfactants 363
4-3c Other Components 364
4-3d Propagation and Termination Rate Constants 364
4-3e Energetics 365
4-3f Molecular Weight and Particle Size Distributions 365
4-3g Surfactant-Free Emulsion Polymerization 366
4-3h Other Emulsion Polymerization Systems 367
4-3i Living Radical Polymerization 368
References 369
5 IONIC CHAIN POLYMERIZATION 372
5-1 Comparison of Radical and Ionic Polymerizations 372
5-2 Cationic Polymerization of the Carbon-Carbon Double Bond 374
5-2a Initiation 374
5-2a-1 Protonic Acids 374
5-2a-2 Lewis Acids 375
5-2a-3 Halogen 379
5-2a-4 Photoinitiation by Onium Salts 379
5-2a-5 Electroinitiation 380
5-2a-6 Ionizing Radiation 381
5-2b Propagation 382
5-2c Chain Transfer and Termination 384
5-2c-1 β-Proton Transfer 384
5-2c-2 Combination with Counterion 386
5-2c-3 Chain Transfer to Polymer 387
5-2c-4 Other Transfer and Termination Reactions 387
5-2d Kinetics 388
5-2d-1 Different Kinetic Situations 388
5-2d-2 Validity of Steady-State Assumption 391
5-2d-3 Molecular Weight Distribution 391
5-2e Absolute Rate Constants 392
5-2e-1 Experimental Methods 392
5-2e-2 Difficulty in Interpreting Rate Constants 394
5-2e-3 Comparison of Rate Constants 396
5-2e-4 CM and Cs Values 398
5-2f Effect of Reaction Medium 399
5-2f-1 Propagation by Covalent Species；Pseudocationic Polymerization 399
5-2f-2 Solvent Effects 401
5-2f-3 Counterion Effects 403
5-2g Living Cationic Polymerization 403
5-2g-1 General Requirements 404
5-2g-2 Rate and Degree of Polymerization 405
5-2g-3 Specific Living Cationic Polymerization Systems 406
5-2h Energetics 408
5-2i Commercial Applications of Cationic Polymerization 410
5-2i-1 Polyisobutylene Products 410
5-2i-2 Other Products 411
5-3 Anionic Polymerization of the Carbon-Carbon Double Bond 412
5-3a Initiation 412
5-3a-1 Nucleophilic Initiators 412
5-3a-2 Electron Transfer 414
5-3b Termination 416
5-3b-1 Polymerizations without Termination 416
5-3b-2 Termination by Impurities and Deliberately Added Transfer Agents 416
5-3b-3 Spontaneous Termination 417
5-3b-4 Termination and Side Reactions of Polar Monomers 418
5-3c Group Transfer Polymerization 420
5-3d Kinetics of Living Polymerization 422
5-3d-1 Polymerization Rate 422
5-3d-2 Effects of Reaction Media 423
5-3d-3 Degree of Polymerization 428
5-3d-4 Energetics：Solvent-Separated and Contact Ion Pairs 429
5-3d-5 Association Phenomena in Alkyllithium 433
5-3d-6 Other Phenomena 435
5-4 Block and Other Polymer Architectures 436
5-4a Sequential Monomer Addition 436
5-4b Telechelic （End-Functionalized） Polymers 439
5-4c Coupling Reactions 441
5-4d Transformation Reactions 443
5-5 Distinguishing Between Radical，Cationic，and Anionic Polymerizations 443
5-6 Carbonyl Polymerization 444
5-6a Anionic Polymerization 445
5-6a-1 Formaldehyde 445
5-6a-2 Other Carbonyl Monomers 446
5-6b Cationic Polymerization 447
5-6c Radical Polymerization 447
5-6d End Capping 448
5-7 Miscellaneous Polymerizations 449
5-7a Monomers with Two Different Polymerizable Groups 449
5-7b Hydrogen-Transfer Polymerization of Acrylamide 450
5-7c Polymerization and Cyclotrimerization of Isocyanates 451
5-7d Monomers with Triple Bonds 451
References 452
6 CHAIN COPOLYMERIZATION 464
6-1 General Considerations 465
6-1a Importance of Chain Copolymerization 465
6-1b Types of Copolymers 465
6-2 Copolymer Composition 466
6-2a Terminal Model； Monomer Reactivity Ratios 466
6-2b Statistical Derivation of Copolymerization Equation 469
6-2c Range of Applicability of Copolymerization Equation 470
6-2d Types of Copolymerization Behavior 471
6-2d-1 Ideal Copolymerization：r1 r2 = 1 471
6-2d-2 Alternating Copolymerization：r1 r2 = 0 473
6-2d-3 Block Copolymerization：r1 ＞ 1，r2 ＞ 1 475
6-2e Variation of Copolymer Composition with Conversion 475
6-2f Experimental Evaluation of Monomer Reactivity Ratios 480
6-2g Microstructure of Copolymers 481
6-2g-1 Sequence Length Distribution 481
6-2g-2 Copolymer Compositions of Different Molecules 484
6-2h Multicomponent Copolymerization 485
6-3 Radical Copolymerization 487
6-3a Effect of Reaction Conditions 487
6-3a-1 Reaction Medium 487
6-3a-2 Temperature 489
6-3a-3 Pressure 490
6-3b Reactivity 490
6-3b-1 Resonance Effects 490
6-3b-2 Steric Effects 496
6-3b-3 Alternation； Polar Effects and Complex Participation 497
6-3b-4 Q-e Scheme 500
6-3b-5 Patterns of Reactivity Scheme 503
6-3b-6 Other Quantitative Approaches to Reactivity 505
6-3c Terminal Model for Rate of Radical Copolymerization 505
6-4 Ionic Copolymerization 506
6-4a Cationic Copolymerization 507
6-4a-1 Reactivity 507
6-4a-2 Effect of Solvent and Counterion 508
6-4a-3 Effect of Temperature 510
6-4b Anionic Copolymerization 510
6-4b-1 Reactivity 510
6-4b-2 Effects of Solvent and Counterion 511
6-4b-3 Effect of Temperature 512
6-5 Deviations from Terminal Copolymerization Model 512
6-5a Kinetic Penultimate Behavior 513
6-5b Depropagation during Copolymerization 515
6-5c Copolymerization with Complex Participation 518
6-5d Discrimination between Models 521
6-6 Copolymerizations Involving Dienes 521
6-6a Crosslinking 521
6-6b Alternating Intra/intermolecular Polymerization；Cyclopolymerization 524
6-6c Interpenetrating Polymer Networks 527
6-7 Other Copolymerizations 528
6-7a Miscellaneous Copolymerizations of Alkenes 528
6-7b Copolymerization of Carbonyl Monomers 528
6-8 Applications of Copolymerization 529
6-8a Styrene 529
6-8b Ethylene 530
6-8c Unsaturated Polyesters 531
6-8d Allyl Resins 532
6-8e Other Copolymers 532
References 533
7 RING-OPENING POLYMERIZATION 544
7-1 General Characteristics 545
7-1a Scope； Polymerizability 545
7-1b Polymerization Mechanism and Kinetics 546
7-2 Cyclic Ethers 548
7-2a Anionic Polymerization of Epoxides 548
7-2a-1 Reaction Characteristics 548
7-2a-2 Exchange Reactions 551
7-2a-3 Chain Transfer to Monomer 553
7-2b Cationic Polymerization 554
7-2b-1 Propagation 554
7-2b-2 Initiation 555
7-2b-3 Termination and Transfer Processes 556
7-2b-4 Cyclic Acetals 559
7-2b-5 Kinetics of Reversible ROP 562
7-2b-6 Energetic Characteristics 565
7-2b-7 Commercial Applications 568
7-3 Lactams 569
7-3a Cationic Polymerization 570
7-3b Hydrolytic Polymerization 572
7-3c Anionic Polymerization 573
7-3c-1 Use of Strong Base Alone 573
7-3c-2 Addition of N-Acyllactam 575
7-3d Reactivity 577
7-4 N-Carboxy-α-Amino Acid Anhydrides 578
7-4a Polymerization by Bases 578
7-4b Polymerization by Transition Metal Complexes 580
7-5 Lactones 581
7-5a Anionic Polymerization 581
7-5b Cationic Polymerization 583
7-5c Enzymatic Polymerization 584
7-5d Other Cyclic Esters 585
7-6 Nitrogen Heterocyclics 586
7-6a Cyclic Amines 586
7-6b Other Nitrogen Heterocyclics 587
7-7 Sulfur Heterocyclics 588
7-8 Cycloalkenes 589
7-9 Miscellaneous Oxygen Heterocyclics 592
7-10 Other Ring-Opening Polymerizations 594
7-11 Inorganic and Partially Inorganic Polymers 595
7-11a Cyclosiloxanes 595
7-11b Cyclotriphosphazenes 597
7-11c Metal locenophanes 599
7-11d Phosphorus-Containing Cyclic Esters 599
7-11e Sulfur and Sulfur Nitride Polymers 600
7-12 Copolymerization 600
7-12a Monomers with Same Functional Group 601
7-12b Monomers with Different Functional Groups 603
7-12c Block Copolymers 604
7-12d Zwitterion Polymerization 605
References 606
8 STEREOCHEMISTRY OF POLYMERIZATION 619
8-1 Types of Stereoisomerism in Polymers 620
8-1a Monosubstituted Ethylenes 621
8-1a-1 Site of Steric Isomerism 621
8-1a-2 Tacticity 622
8-1b Disubstituted Ethylenes 624
8-1b-1 1，1-Disubstituted Ethylenes 624
8-1b-2 1，2-Disubstituted Ethylenes 624
8-1c Carbonyl and Ring-Opening Polymerizations 626
8-1d 1，3-Butadiene and 2-Substituted 1，3-Butadienes 627
8-1d-1 1，2- and 3，4-Polymerizations 627
8-1d-2 1，4-Polymerization 628
8-1e 1-Substituted and 1，4-Disubstituted 1，3-Butadienes 629
8-1e-1 1，2- and 3，4-Polymerizations 629
8-1e-2 1，4-Polymerization 630
8-1f Other Polymers 631
8-2 Properties of Stereoregular Polymers 633
8-2a Significance of Stereoregularity 633
8-2a-1 Isotactic，Syndiotactic，and Atactic Polypropenes 633
8-2a-2 Cis- and Trans- 1，4-Poly- 1，3-Dienes 633
8-2a-3 Cellulose and Amylose 634
8-2b Analysis of Stereoregularity 635
8-3 Forces of Stereoregulation in Alkene Polymerizations 637
8-3a Radical Polymerization 637
8-3b Ionic and Coordination Polymerizations 640
8-3b-1 Effect of Coordination 640
8-3b-2 Mechanism of Stereoselective Placement 641
8-4 Traditional Ziegler-Natta Polymerization of Nonpolar Alkene Monomers 644
8-4a Historical Development of Ziegler-Natta Initiators 644
8-4b Chemical Nature of Propagating Species 645
8-4c Primary versus Secondary Insertion； Regioselectivity 646
8-4d Propagation at Carbon-Transition Metal Bond 647
8-4e Mechanism of Isoselective Propagation 647
8-4f Mechanism of Syndioselective Propagation 652
8-4g Direction of Double-Bond Opening 654
8-4h Effects of Components of Ziegler-Natta Initiator 655
8-4h-1 Transition Metal Component 656
8-4h-2 Group Ⅰ-Ⅲ Metal Component 657
8-4h-3 Third Component：Electron Donor （Lewis Base） 658
8-4i Kinetics 658
8-4i-1 Observed Rate Behavior 658
8-4i-2 Termination 659
8-4i-3 Rate and Degree of Polymerization 661
8-4i-4 Values of Kinetic Parameters 662
8-4j Transition Metal Oxide Initiators 664
8-5 Metallocene Polymerization of Nonpolar Alkene Monomers 665
8-5a Metallocene Symmetry 666
8-5b C2v-Symmetric Metallocenes 668
8-5c C2-Symmetric Metallocenes 668
8-5c-1 Effect of Initiator Structure 669
8-5c-2 Effect of Reaction Variables 671
8-5d Cs-Symmetric Metallocenes 672
8-5e C1-Symmetric Metallocenes 673
8-5f Oscillating Metallocenes 675
8-5g Coinitiators 676
8-5g-1 Methylaluminoxane （MAO） 676
8-5g-2 Boron-Containing Coinitiators 677
8-5h Kinetics 678
8-5h-1 Rate of Polymerization 678
8-5h-2 Degree of Polymerization 680
8-5h-3 Supported Metallocenes 681
8-5i Branching in Metallocene Polymerizations 682
8-6 Other Hydrocarbon Monomers 682
8-6a 1，2-Disubstituted Alkenes； Cycloalkenes 682
8-6b Styrene 683
8-6c Alkynes 684
8-7 Copolymerization 684
8-8 Postmetallocene：Chelate Initiators 685
8-8a ansa-Cyclopentadienyl-Amido Initiators 685
8-8b α-Diimine Chelates of Late Transition Metals 686
8-8c Phenoxy-Imine Chelates 688
8-9 Living Polymerization 689
8-10 Polymerization of 1，3-Dienes 689
8-10a Radical Polymerization 689
8-10b Anionic Polymerization 691
8-10c Cationic Polymerization 694
8-10d Other Polymerizations 695
8-11 Commerical Applications 695
8-11a Process Conditions 695
8-11b High-Density Polyethylene 696
8-11c Linear Low-Density Polyethylene 697
8-11d Polypropene 697
8-11e Ethylene-Propene Elastomers 698
8-11f Other Polymers 698
8-11g Polymers from 1，3-Dienes 699
8-12 Polymerization of Polar Vinyl Monomers 699
8-12a Methyl Methacrylate 699
8-12b Vinyl Ethers 703
8-13 Aldehydes 703
8-14 Optical Activity in Polymers 704
8-14a Optically Active Monomers 704
8-14b Chiral Conformation 704
8-14c Enantiomer-Differentiating Polymerization 705
8-14d Asymmetric Induction 707
8-15 Ring-Opening Polymerization 707
8-16 Statistical Models of Propagation 708
8-16a Polymer Chain End Control 708
8-16a-1 Bernoullian Model 708
8-16a-2 First-Order Markov Model 709
8-16b Catalyst （Initiator） Site Control 711
8-16c Application of Propagation Statistics 712
References 713
9 REACTIONS OF POLYMERS 729
9-1 Principles of Polymer Reactivity 729
9-1a Yield 730
9-1b Isolation of Functional Groups 730
9-1c Concentration 730
9-1d Crystallinity 731
9-1e Change in Solubility 731
9-1f Crosslinking 732
9-1g Steric Effects 732
9-1h Electrostatic Effects 733
9-1i Neighboring-Group Effects 735
9-1j Hydrophobic Interactions 735
9-1k Other Considerations 736
9-2 Crosslinking 737
9-2a Alkyds 737
9-2b Elastomers Based on 1，3-Dienes 738
9-2b-1 Sulfur Alone 739
9-2b-2 Accelerated Sulfur Vulcanization 740
9-2b-3 Other Vulcanizations 742
9-2c Peroxide and Radiation Crosslinking 742
9-2d Other Crosslinking Processes 744
9-3 Reactions of Cellulose 745
9-3a Dissolution of Cellulose 745
9-3b Esterification of Cellulose 747
9-3c Etherification of Cellulose 747
9-3d Chitin 748
9-4 Reactions of Poly（vinyl acetate） 748
9-5 Halogenation 748
9-5a Natural Rubber 748
9-5b Saturated Hydrocarbon Polymers 749
9-6 Aromatic Substitution 750
9-7 Cyclization 751
9-8 Other Reactions 752
9-9 Graft Copolymers 752
9-9a Radical Graft Polymerization 753
9-9a-1 Vinyl Macromonomers 753
9-9a-2 Chain Transfer and Copolymerization 754
9-9a-3 Ionizing Radiation 755
9-9a-4 Redox Initiation 756
9-9a-5 Living Radical Polymerization 756
9-9b Anionic Graft Polymerization 757
9-9c Cationic Graft Polymerization 758
9-9d Other Approaches to Graft Copolymers 758
9-10 Block Copolymers 759
9-11 Polymers as Carriers or Supports 760
9-11a Synthesis 761
9-11a-1 Functionalization of Polymer 761
9-11a-2 Functionalization of Monomer 763
9-11a-3 Comparison of the Two Approaches 763
9-11b Advantages of Polymer Reagents，Catalysts，and Substrates 764
9-12 Polymer Reagents 765
9-13 Polymer Catalysts 768
9-14 Polymer Substrates 771
9-14a Solid-Phase Synthesis of Polypeptides 772
9-14b Other Applications 776
References 777
INDEX 789