Principles of Polymerization Fourth EditionPDF电子书下载

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