PRINCIPLES OF POLYMERIZATION FOURTH EDITIONPDF|Epub|txt|kindle电子书版本网盘下载

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1 INTRODUCTION1

1-1 Types of Polymers and Polymerizations1

1-1a Polymer Composition and Structure2

1-1b Polymerization Mechanism6

1-2 Nomenclature of Polymers9

1-2a Nomenclature Based on Source10

1-2b Nomenclature Based on Structure (Non-IUPAC)11

1-2c IUPAC Structure-Based Nomenclature System11

1-2d Trade Names and Nonnames16

1-3 Linear, Branched, and Crosslinked Polymers17

1-4 Molecular Weight19

1-5 Physical State24

1-5a Crystalline and Amorphous Behavior24

1-5b Determinants of Polymer Crystallinity27

1-5c Thermal Transitions29

1-6 Applications of Polymers32

1-6a Mechanical Properties32

1-6b Elastomers, Fibers, and Plastics35

References36

2 STEP POLYMERIZATION39

2-1 Reactivity of Functional Groups40

2-1a Basis for Analysis of Polymerization Kinetics40

2-1b Experimental Evidence41

2-1c Theoretical Considerations43

2-1d Equivalence of Groups in Bifunctional Reactants44

2-2 Kinetics of Step Polymerization44

2-2a Self-Catalyzed Polymerization46

2-2a-1 Experimental Observations47

2-2a-2 Reasons for Nonlinearity in Third-Order Plot48

2-2a-3 Molecular Weight of Polymer50

2-2b External Catalysis of Polymerization51

2-2c Step Polymerizations Other than Polyesterification:Catalyzed versus Uncatalyzed53

2-2d Nonequivalence of Functional Groups in Polyfunctional Reagents54

2-2d-1 Examples of Nonequivalence54

2-2d-2 Kinetics57

2-3 Accessibility of Functional Groups63

2-4 Equilibrium Considerations65

2-4a Closed System65

2-4b Open, Driven System67

2-4c Kinetics of Reversible Polymerization69

2-5 Cyclization versus Linear Polymerization69

2-5a Possible Cyclization Reactions69

2-5b Cyclization Tendency versus Ring Size70

2-5c Reaction Conditions72

2-5d Thermodynamic versus Kinetic Control73

2-5e Other Considerations74

2-6 Molecular Weight Control in Linear Polymerization74

2-6a Need for Stoichiometric Control74

2-6b Quantitative Aspects75

2-6c Kinetics of Nonstoichiometric Polymerization79

2-7 Molecular Weight Distribution in Linear Polymerization80

2-7a Derivation of Size Distributions80

2-7b Breadth of Molecular Weight Distribution82

2-7c Interchange Reactions83

2-7d Alternate Approaches for Molecular-Weight Distribution83

2-7e Effect of Reaction Variables on MWD86

2-7e-1 Unequal Reactivity of Functional Groups86

2-7e-2 Change in Reactivity on Reaction86

2-7e-3 Nonstoichiometry of Functional Groups86

2-8 Process Conditions87

2-8a Physical Nature of Polymerization Systems87

2-8b Different Reactant Systems89

2-8c Interfacial Polymerization90

2-8c-1 Description of Process90

2-8c-2 Utility92

2-8d Polyesters92

2-8e Polycarbonates96

2-8f Polyamides97

2-8g Historical Aspects101

2-9 Multichain Polymerization101

2-9a Branching101

2-9b Molecular Weight Distribution102

2-10 Crosslinking103

2-10a Carothers Equation: Xn → ∞105

2-10a-1 Stoichiometric Amounts of Reactants105

2-10a-2 Extension to Nonstoichiometric Reactant Mixtures106

2-10b Statistical Approach to Gelation: Xw → ∞108

2-10c Experimental Gel Points111

2-10d Extensions of Statistical Approach112

2-11 Molecular Weight Distributions in Nonlinear Polymerizations114

2-12 Crosslinking Technology117

2-12a Polyesters, Unsaturated Polyesters, and Alkyds118

2-12b Phenolic Polymers120

2-12b-1 Resole Phenolics120

2-12b-2 Novolac Phenolics124

2-12b-3 Applications126

2-12c Amino Plastics126

2-12d Epoxy Resins128

2-12e Polyurethanes130

2-12f Polysiloxanes132

2-12g Polysulfides134

2-13 Step Copolymerization135

2-13a Types of Copolymers135

2-13b Methods of Synthesizing Copolymers138

2-13b-1 Statistical Copolymers138

2-13b-2 Alternating Copolymers138

2-13b-3 Block Copolymers139

2-13c Utility of Copolymerization140

2-13c-1 Statistical Copolymers141

2-13c-2 Block Copolymers142

2-13c-3 Polymer Blends and Interpenetrating Polymer Networks143

2-13c-4 Constitutional Isomerism144

2-14 High-Performance Polymers144

2-14a Requirements for High-Temperature Polymers144

2-14b Aromatic Polyethers by Oxidative Coupling146

2-14c Aromatic Polyethers by Nucleophilic Substitution149

2-14d Aromatic Polysulfides151

2-14e Aromatic Polyimides151

2-14f Reactive Telechelic Oligomer Approach155

2-14g Liquid Crystal Polymers157

2-14h 5-Membered Ring Heterocyclic Polymers159

2-14i 6-Membered Ring Heterocyclic Polymers162

2-14j Conjugated Polymers163

2-14j-1 Oxidative Polymerization of Aniline165

2-14j-2 Poly(p-phenylene)166

2-14j-3 Poly(p-phenylene Vinylene)167

2-15 Inorganic and Organometallic Polymers168

2-15a Inorganic Polymers168

2-15a-1 Minerals168

2-15a-2 Glasses169

2-15a-3 Ceramics170

2-15b Organometallic Polymers172

2-15b-1 Polymerization via Reaction at Metal Bond172

2-15b-2 Polymerization without Reaction at Metal Bond173

2-15b-3 Polysilanes173

2-16 Dendritic (Highly Branched) Polymers174

2-16a Random Hyperbranched Polymers175

2-16b Dendrimers177

2-17 Miscellaneous Topics180

2-17a Enzymatic Polymerizations180

2-17a-1 In Vivo (within Living Cells)180

2-17a-2 In Vitro (outside Living Cells)181

2-17b Polymerization in Supercritical Carbon Dioxide183

2-17c Cycloaddition (Four-Center) Polymerization183

2-17d Spiro Polymers184

2-17e Pseudopolyrotoxanes and Polyrotoxanes184

References185

3 RADICAL CHAIN POLYMERIZATION198

3-1 Nature of Radical Chain Polymerization199

3-1a Comparison of Chain and Step Polymerizations199

3-1b Radical versus Ionic Chain Polymerizations199

3-1b-1 General Considerations of Polymerizability199

3-1b-2 Effects of Substituents200

3-2 Structural Arrangement of Monomer Units202

3-2a Possible Modes of Propagation202

3-2b Experimental Evidence203

3-2c Synthesis of Head-to-Head Polymers204

3-3 Rate of Radical Chain Polymerization204

3-3a Sequence of Events204

3-3b Rate Expression206

3-3c Experimental Determination of Rp208

3-3c-1 Physical Separation and Isolation of Reaction Product208

3-3c-2 Chemical and Spectroscopic Analysis208

3-3c-3 Other Techniques209

3-4 Initiation209

3-4a Thermal Decomposition of Initiators209

3-4a-1 Types of Initiators209

3-4a-2 Kinetics of Initiation and Polymerization212

3-4a-3 Dependence of Polymerization Rate on Initiator212

3-4a-4 Dependence of Polymerization Rate on Monomer214

3-4b Redox Initiation216

3-4b-1 Types of Redox Initiators216

3-4b-2 Rate of Redox Polymerization217

3-4c Photochemical Initiation218

3-4c-1 Bulk Monomer219

3-4c-2 Irradiation of Thermal and Redox Initiators220

3-4c-3 Rate of Photopolymerization221

3-4d Initiation by Ionizing Radiation224

3-4e Pure Thermal Initiation226

3-4f Other Methods of Initiation227

3-4g Initiator Efficiency228

3-4g-1 Definition off228

3-4g-2 Mechanism off < 1: Cage Effect228

3-4g-3 Experimental Determination off232

3-4h Other Aspects of Initiation235

3-5 Molecular Weight236

3-5a Kinetic Chain Length236

3-5b Mode of Termination236

3-6 Chain Transfer238

3-6a Effect of Chain Transfer238

3-6b Transfer to Monomer and Initiator240

3-6b-1 Determination of CM and Cl240

3-6b-2 Monomer Transfer Constants241

3-6b-3 Initiator Transfer Constants244

3-6c Transfer to Chain-Transfer Agent245

3-6c-1 Determination of Cs245

3-6c-2 Structure and Reactivity246

3-6c-3 Practical Utility of Mayo Equation249

3-6d Chain Transfer to Polymer250

3-6e Catalytic Chain Transfer254

3-7 Inhibition and Retardation255

3-7a Kinetics of Inhibition or Retardation256

3-7b Types of Inhibitors and Retarders259

3-7c Autoinhibition of Allylic Monomers263

3-8 Determination of Absolute Rate Constants264

3-8a Non-Steady-State Kinetics264

3-8b Rotating Sector Method265

3-8c PLP-SEC Method267

3-8d Typical Values of Reaction Parameters269

3-9 Energetic Characteristics271

3-9a Activation Energy and Frequency Factor271

3-9a-1 Rate of Polymerization272

3-9a-2 Degree of Polymerization274

3-9b Thermodynamics of Polymerization275

3-9b-1 Significance of △G, △H, and △S275

3-9b-2 Effect of Monomer Structure276

3-9b-3 Polymerization of 1,2-Disubstituted Ethylenes277

3-9c Polymerization-Depolymerization Equilibria279

3-9c-1 Ceiling Temperature279

3-9c-2 Floor Temperature282

3-10 Autoacceleration282

3-10a Course of Polymerization282

3-10b Diffusion-Controlled Termination283

3-10c Effect of Reaction Conditions286

3-10d Related Phenomena287

3-10d-1 Occlusion (Heterogeneous) Polymerization287

3-10d-2 Template Polymerization287

3-10e Dependence of Polymerization Rate on Initiator and Monomer288

3-10f Other Accelerative Phenomena289

3-11 Molecular Weight Distribution289

3-11a Low-Conversion Polymerization289

3-11b High-Conversion Polymerization292

3-12 Effect of Pressure292

3-12a Effect on Rate Constants293

3-12a-1 Volume of Activation293

3-12a-2 Rate of Polymerization294

3-12a-3 Degree of Polymerization295

3-12b Thermodynamics of Polymerization296

3-12c Other Effects of Pressure296

3-13 Process Conditions296

3-13a Bulk (Mass) Polymerization297

3-13b Solution Polymerization297

3-13c Heterogeneous Polymerization297

3-13d Other Processes; Self-Assembly and Nanostructures299

3-14 Specific Commercial Polymers300

3-14a Polyethylene300

3-14b Polystyrene302

3-14c Vinyl Family304

3-14c-1 Poly(vinyl chloride)304

3-14c-2 Other Members of Vinyl Family306

3-14d Acrylic Family307

3-14d-1 Acrylate and Methacrylate Products307

3-14d-2 Polyacrylonitrile308

3-14d-3 Other Members of Acrylic Family308

3-14e Fluoropolymers309

3-14f Polymerization of Dienes310

3-14g Miscellaneous Polymers311

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 Polymerization313

3-15a General Considerations313

3-15b Atom Transfer Radical Polymerization (ATRP)316

3-15b-1 Polymerization Mechanism316

3-15b-2 Effects of Components of Reaction System319

3-15b-3 Complex Kinetics321

3-15b-4 Block Copolymers322

3-15b-5 Other Polymer Architectures324

3-15c Stable Free-Radical Polymerization (SFRP)325

3-15d Radical Addition-Fragmentation Transfer (RAFT)328

3-15e Other Living Radical Polymerizations330

3-16 Other Polymerizations330

3-16a Organometallic Polymers330

3-16b Functional Polymers330

3-16c Acetylenic Monomers332

References332

4 EMULSION POLYMERIZATION350

4-1 Description of Process350

4-1a Utility350

4-1b Qualitative Picture351

4-1b-1 Components and Their Locations351

4-1b-2 Site of Polymerization353

4-1b-3 Progress of Polymerization354

4-2 Quantitative Aspects356

4-2a Rate of Polymerization356

4-2b Degree of Polymerization360

4-2c Number of Polymer Particles362

4-3 Other Characteristics of Emulsion Polymerization363

4-3a Initiators363

4-3b Surfactants363

4-3c Other Components364

4-3d Propagation and Termination Rate Constants364

4-3e Energetics365

4-3f Molecular Weight and Particle Size Distributions365

4-3g Surfactant-Free Emulsion Polymerization366

4-3h Other Emulsion Polymerization Systems367

4-3i Living Radical Polymerization368

References369

5 IONIC CHAIN POLYMERIZATION372

5-1 Comparison of Radical and Ionic Polymerizations372

5-2 Cationic Polymerization of the Carbon-Carbon Double Bond374

5-2a Initiation374

5-2a-1 Protonic Acids374

5-2a-2 Lewis Acids375

5-2a-3 Halogen379

5-2a-4 Photoinitiation by Onium Salts379

5-2a-5 Electroinitiation380

5-2a-6 Ionizing Radiation381

5-2b Propagation382

5-2c Chain Transfer and Termination384

5-2c-1 β-Proton Transfer384

5-2c-2 Combination with Counterion386

5-2c-3 Chain Transfer to Polymer387

5-2c-4 Other Transfer and Termination Reactions387

5-2d Kinetics388

5-2d-1 Different Kinetic Situations388

5-2d-2 Validity of Steady-State Assumption391

5-2d-3 Molecular Weight Distribution391

5-2e Absolute Rate Constants392

5-2e-1 Experimental Methods392

5-2e-2 Diffculty in Interpreting Rate Constants394

5-2e-3 Comparison of Rate Constants396

5-2e-4 CM and Cs Values398

5-2f Effect of Reaction Medium399

5-2f-1 Propagation by Covalent Species;Pseudocationic Polymerization399

5-2f-2 Solvent Effects401

5-2f-3 Counterion Effects403

5-2g Living Cationic Polymerization403

5-2g-1 General Requirements404

5-2g-2 Rate and Degree of Polymerization405

5-2g-3 Specific Living Cationic Polymerization Systems406

5-2h Energetics408

5-2i Commercial Applications of Cationic Polymerization410

5-2i-1 Polyisobutylene Products410

5-2i-2 Other Products411

5-3 Anionic Polymerization of the Carbon-Carbon Double Bond412

5-3a Initiation412

5-3a-1 Nucleophilic Initiators412

5-3a-2 Electron Transfer414

5-3b Termination416

5-3b-1 Polymerizations without Termination416

5-3b-2 Termination by Impurities and Deliberately Added Transfer Agents416

5-3b-3 Spontaneous Termination417

5-3b-4 Termination and Side Reactions of Polar Monomers418

5-3c Group Transfer Polymerization420

5-3d Kinetics of Living Polymerization422

5-3d-1 Polymerization Rate422

5-3d-2 Effects of Reaction Media423

5-3d-3 Degree of Polymerization428

5-3d-4 Energetics: Solvent-Separated and Contact Ion Pairs429

5-3d-5 Association Phenomena in Alkyllithium433

5-3d-6 Other Phenomena435

5-4 Block and Other Polymer Architectures436

5-4a Sequential Monomer Addition436

5-4b Telechelic (End-Functionalized) Polymers439

5-4c Coupling Reactions441

5-4d Transformation Reactions443

5-5 Distinguishing Between Radical, Cationic, and Anionic Polymerizations443

5-6 Carbonyl Polymerization444

5-6a Anionic Polymerization445

5-6a-1 Formaldehyde445

5-6a-2 Other Carbonyl Monomers446

5-6b Cationic Polymerization447

5-6c Radical Polymerization447

5-6d End Capping448

5-7 Miscellaneous Polymerizations449

5-7a Monomers with Two Different Polymerizable Groups449

5-7b Hydrogen-Transfer Polymerization of Acrylamide450

5-7c Polymerization and Cyclotrimerization of Isocyanates451

5-7d Monomers with Triple Bonds451

References452

6 CHAIN COPOLYMERIZATION464

6-1 General Considerations465

6-1a Importance of Chain Copolymerization465

6-1b Types of Copolymers465

6-2 Copolymer Composition466

6-2a Terminal Model; Monomer Reactivity Ratios466

6-2b Statistical Derivation of Copolymerization Equation469

6-2c Range of Applicability of Copolymerization Equation470

6-2d Types of Copolymerization Behavior471

6-2d-1 Ideal Copolymerization: r1 r2=1471

6-2d-2 Alternating Copolymerization: r1 r2=0473

6-2d-3 Block Copolymerization: r1 > 1, r2>1475

6-2e Variation of Copolymer Composition with Conversion475

6-2f Experimental Evaluation of Monomer Reactivity Ratios480

6-2g Microstructure of Copolymers481

6-2g-1 Sequence Length Distribution481

6-2g-2 Copolymer Compositions of Different Molecules484

6-2h Multicomponent Copolymerization485

6-3 Radical Copolymerization487

6-3a Effect of Reaction Conditions487

6-3a-1 Reaction Medium487

6-3a-2 Temperature489

6-3a-3 Pressure490

6-3b Reactivity490

6-3b-1 Resonance Effects490

6-3b-2 Steric Effects496

6-3b-3 Alternation; Polar Effects and Complex Participation497

6-3b-4 Q-e Scheme500

6-3b-5 Patterns of Reactivity Scheme503

6-3b-6 Other Quantitative Approaches to Reactivity505

6-3c Terminal Model for Rate of Radical Copolymerization505

6-4 Ionic Copolymerization506

6-4a Cationic Copolymerization507

6-4a-1 Reactivity507

6-4a-2 Effect of Solvent and Counterion508

6-4a-3 Effect of Temperature510

6-4b Anionic Copolymerization510

6-4b-1 Reactivity510

6-4b-2 Effects of Solvent and Counterion511

6-4b-3 Effect of Temperature512

6-5 Deviations from Terminal Copolymerization Model512

6-5a Kinetic Penultimate Behavior513

6-5b Depropagation during Copolymerization515

6-5c Copolymerization with Complex Participation518

6-5d Discrimination between Models521

6-6 Copolymerizations Involving Dienes521

6-6a Crosslinking521

6-6b Alternating Intra/intermolecular Polymerization;Cyclopolymerization524

6-6c Interpenetrating Polymer Networks527

6-7 Other Copolymerizations528

6-7a Miscellaneous Copolymerizations of Alkenes528

6-7b Copolymerization of Carbonyl Monomers528

6-8 Applications of Copolymerization529

6-8a Styrene529

6-8b Ethylene530

6-8c Unsaturated Polyesters531

6-8d Allyl Resins532

6-8e Other Copolymers532

References533

7 RING-OPENING POLYMERIZATION544

7-1 General Characteristics545

7-1a Scope; Polymerizability545

7-1b Polymerization Mechanism and Kinetics546

7-2 Cyclic Ethers548

7-2a Anionic Polymerization of Epoxides548

7-2a-1 Reaction Characteristics548

7-2a-2 Exchange Reactions551

7-2a-3 Chain Transfer to Monomer553

7-2b Cationic Polymerization554

7-2b-1 Propagation554

7-2b-2 Initiation555

7-2b-3 Termination and Transfer Processes556

7-2b-4 Cyclic Acetals559

7-2b-5 Kinetics of Reversible ROP562

7-2b-6 Energetic Characteristics565

7-2b-7 Commercial Applications568

7-3 Lactams569

7-3a Cationic Polymerization570

7-3b Hydrolytic Polymerization572

7-3c Anionic Polymerization573

7-3c-1 Use of Strong Base Alone573

7-3c-2 Addition of N-Acyllactam575

7-3d Reactivity577

7-4 N-Carboxy-α-Amino Acid Anhydrides578

7-4a Polymerization by Bases578

7-4b Polymerization by Transition Metal Complexes580

7-5 Lactones581

7-5a Anionic Polymerization581

7-5b Cationic Polymerization583

7-5c Enzymatic Polymerization584

7-5d Other Cyclic Esters585

7-6 Nitrogen Heterocyclics586

7-6a Cyclic Amines586

7-6b Other Nitrogen Heterocyclics587

7-7 Sulfur Heterocyclics588

7-8 Cycloalkenes589

7-9 Miscellaneous Oxygen Heterocyclics592

7-10 Other Ring-Opening Polymerizations594

7-11 Inorganic and Partially Inorganic Polymers595

7-11a Cyclosiloxanes595

7-11b Cyclotriphosphazenes597

7-11c Metallocenophanes599

7-11d Phosphorus-Containing Cyclic Esters599

7-11e Sulfur and Sulfur Nitride Polymers600

7-12 Copolymerization600

7-12a Monomers with Same Functional Group601

7-12b Monomers with Different Functional Groups603

7-12c Block Copolymers604

7-12d Zwitterion Polymerization605

References606

8 STEREOCHEMISTRY OF POLYMERIZATION619

8-1 Types of Stereoisomerism in Polymers620

8-1a Monosubstituted Ethylenes621

8-1a-1 Site of Steric Isomerism621

8-1a-2 Tacticity622

8-1b Disubstituted Ethylenes624

8-1b-1 1,1-Disubstituted Ethylenes624

8-1b-2 1,2-Disubstituted Ethylenes624

8-1c Carbonyl and Ring-Opening Polymerizations626

8-1d 1,3-Butadiene and 2-Substituted 1,3-Butadienes627

8-1d-1 1,2- and 3,4-Polymerizations627

8-1d-2 1,4-Polymerization628

8-1e 1-Substituted and 1,4-Disubstituted 1,3-Butadienes629

8-1e-1 1,2- and 3,4-Polymerizations629

8-1e-2 1,4-Polymerization630

8-1f Other Polymers631

8-2 Properties of Stereoregular Polymers633

8-2a Significance of Stereoregularity633

8-2a-1 Isotactic, Syndiotactic, and Atactic Polypropenes633

8-2a-2 Cis- and Trans- 1,4-Poly-1,3-Dienes633

8-2a-3 Cellulose and Amylose634

8-2b Analysis of Stereoregularity635

8-3 Forces of Stereoregulation in Alkene Polymerizations637

8-3a Radical Polymerization637

8-3b Ionic and Coordination Polymerizations640

8-3b-1 Effect of Coordination640

8-3b-2 Mechanism of Stereoselective Placement641

8-4 Traditional Ziegler-Natta Polymerization of Nonpolar Alkene Monomers644

8-4a Historical Development of Ziegler-Natta Initiators644

8-4b Chemical Nature of Propagating Species645

8-4c Primary versus Secondary Insertion; Regioselectivity646

8-4d Propagation at Carbon-Transition Metal Bond647

8-4e Mechanism of Isoselective Propagation647

8-4f Mechanism of Syndioselective Propagation652

8-4g Direction of Double-Bond Opening654

8-4h Effects of Components of Ziegler-Natta Initiator655

8-4h-1 Transition Metal Component656

8-4h-2 Group Ⅰ-Ⅲ Metal Component657

8-4h-3 Third Component: Electron Donor (Lewis Base)658

8-4i Kinetics658

8-4i-1 Observed Rate Behavior658

8-4i-2 Termination659

8-4i-3 Rate and Degree of Polymerization661

8-4i-4 Values of Kinetic Parameters662

8-4j Transition Metal Oxide Initiators664

8-5 Metallocene Polymerization of Nonpolar Alkene Monomers665

8-5a Metallocene Symmetry666

8-5b C2v-Symmetric Metallocenes668

8-5c C2-Symmetric Metallocenes668

8-5c-1 Effect of Initiator Structure669

8-5c-2 Effect of Reaction Variables671

8-5d Cs-Symmetric Metallocenes672

8-5e Cl-Symmetric Metallocenes673

8-5f Oscillating Metallocenes675

8-5g Coinitiators676

8-5g-1 Methylaluminoxane (MAO)676

8-5g-2 Boron-Containing Coinitiators677

8-5h Kinetics678

8-5h-1 Rate of Polymerization678

8-5h-2 Degree of Polymerization680

8-5h-3 Supported Metallocenes681

8-5i Branching in Metallocene Polymerizations682

8-6 Other Hydrocarbon Monomers682

8-6a 1,2-Disubstituted Alkenes; Cycloalkenes682

8-6b Styrene683

8-6c Alkynes684

8-7 Copolymerization684

8-8 Postmetallocene: Chelate Initiators685

8-8a ansa-Cyclopentadienyl-Amido Initiators685

8-8b α-Diimine Chelates of Late Transition Metals686

8-8c Phenoxy-Imine Chelates688

8-9 Living Polymerization689

8-10 Polymerization of 1,3-Dienes689

8-10a Radical Polymerization689

8-10b Anionic Polymerization691

8-10c Cationic Polymerization694

8-10d Other Polymerizations695

8-11 Commerical Applications695

8-11a Process Conditions695

8-11b High-Density Polyethylene696

8-11c Linear Low-Density Polyethylene697

8-11d Polypropene697

8-11e Ethylene-Propene Elastomers698

8-11f Other Polymers698

8-11g Polymers from 1,3-Dienes699

8-12 Polymerization of Polar Vinyl Monomers699

8-12a Methyl Methacrylate699

8-12b Vinyl Ethers703

8-13 Aldehydes703

8-14 Optical Activity in Polymers704

8-14a Optically Active Monomers704

8-14b Chiral Conformation704

8-14c Enantiomer-Differentiating Polymerization705

8-14d Asymmetric Induction707

8-15 Ring-Opening Polymerization707

8-16 Statistical Models of Propagation708

8-16a Polymer Chain End Control708

8-16a-1 Bernoullian Model708

8-16a-2 First-Order Markov Model709

8-16b Catalyst (Initiator) Site Control711

8-16c Application of Propagation Statistics712

References713

9 REACTIONS OF POLYMERS729

9-1 Principles of Polymer Reactivity729

9-1a Yield730

9-1b Isolation of Functional Groups730

9-1c Concentration730

9-1d Crystallinity731

9-1e Change in Solubility731

9-1f Crosslinking732

9-1g Steric Effects732

9-1h Electrostatic Effects733

9-1i Neighboring-Group Effects735

9-1j Hydrophobic Interactions735

9-1k Other Considerations736

9-2 Crosslinking737

9-2a Alkyds737

9-2b Elastomers Based on 1,3-Dienes738

9-2b-1 Sulfur Alone739

9-2b-2 Accelerated Sulfur Vulcanization740

9-2b-3 Other Vulcanizations742

9-2c Peroxide and Radiation Crosslinking742

9-2d Other Crosslinking Processes744

9-3 Reactions of Cellulose745

9-3a Dissolution of Cellulose745

9-3b Esterification of Cellulose747

9-3c Etherification of Cellulose747

9-3d Chitin748

9-4 Reactions of Poly(vinyl acetate)748

9-5 Halogenation748

9-5a Natural Rubber748

9-5b Saturated Hydrocarbon Polymers749

9-6 Aromatic Substitution750

9-7 Cyclization751

9-8 Other Reactions752

9-9 Graft Copolymers752

9-9a Radical Graft Polymerization753

9-9a-1 Vinyl Macromonomers753

9-9a-2 Chain Transfer and Copolymerization754

9-9a-3 Ionizing Radiation755

9-9a-4 Redox Initiation756

9-9a-5 Living Radical Polymerization756

9-9b Anionic Graft Polymerization757

9-9c Cationic Graft Polymerization758

9-9d Other Approaches to Graft Copolymers758

9-10 Block Copolymers759

9-11 Polymers as Carriers or Supports760

9-11a Synthesis761

9-11a-1 Functionalization of Polymer761

9-11a-2 Functionalization of Monomer763

9-11a-3 Comparison of the Two Approaches763

9-11b Advantages of Polymer Reagents, Catalysts, and Substrates764

9-12 Polymer Reagents765

9-13 Polymer Catalysts768

9-14 Polymer Substrates771

9-14a Solid-Phase Synthesis of Polypeptides772

9-14b Other Applications776

References777

INDEX789