Principles of Polymerization, 4th Edition

Preface xxiii

1 Introduction 1

1-1 Types of Polymers and Polymerizations 1

1-2 Nomenclature of Polymers 9

1-3 Linear, Branched, and Crosslinked Polymers 17

1-4 Molecular Weight 19

1-5 Physical State 24

1-6 Applications of Polymers 32

References 36

2 Step Polymerization 39

2-1 Reactivity of Functional Groups 40

2-2 Kinetics of Step Polymerization 44

2-3 Accessibility of Functional Groups 63

2-4 Equilibrium Considerations 65

2-5 Cyclization versus Linear Polymerization 69

2-6 Molecular Weight Control in Linear Polymerization 74

2-7 Molecular Weight Distribution in Linear Polymerization 80

2-8 Process Conditions 87

2-9 Multichain Polymerization 101

2-10 Crosslinking 103

2-11 Molecular Weight Distributions in Nonlinear Polymerizations 114

2-12 Crosslinking Technology 117

2-13 Step Copolymerization 135

2-14 High-Performance Polymers 144

2-15 Inorganic and Organometallic Polymers 168

2-16 Dendritic (Highly Branched) Polymers 174

2-17 Miscellaneous Topics 180

References 185

3 Radical Chain Polymerization 198

3-1 Nature of Radical Chain Polymerization 199

3-2 Structural Arrangement of Monomer Units 202

3-3 Rate of Radical Chain Polymerization 204

3-4 Initiation 209

3-5 Molecular Weight 236

3-6 Chain Transfer 238

3-7 Inhibition and Retardation 255

3-8 Determination of Absolute Rate Constants 264

3-9 Energetic Characteristics 271

3-10 Autoacceleration 282

3-11 Molecular Weight Distribution 289

3-12 Effect of Pressure 292

3-13 Process Conditions 296

3-14 Specific Commercial Polymers 300

3-15 Living Radical Polymerization 313

3-16 Other Polymerizations 330

References 332

4 Emulsion Polymerization 350

4-1 Description of Process 350

4-2 Quantitative Aspects 356

4-3 Other Characteristics of Emulsion Polymerization 363

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

5-3 Anionic Polymerization of the Carbon–Carbon Double Bond 412

5-4 Block and Other Polymer Architectures 436

5-5 Distinguishing Between Radical, Cationic, and Anionic Polymerizations 443

5-6 Carbonyl Polymerization 444

5-7 Miscellaneous Polymerizations 449

References 452

6 Chain Copolymerization 464

6-1 General Considerations 465

6-2 Copolymer Composition 466

6-3 Radical Copolymerization 487

6-4 Ionic Copolymerization 506

6-5 Deviations from Terminal Copolymerization Model 512

6-6 Copolymerizations Involving Dienes 521

6-7 Other Copolymerizations 528

6-8 Applications of Copolymerization 529

References 533

7 Ring-Opening Polymerization 544

7-1 General Characteristics 545

7-2 Cyclic Ethers 548

7-3 Lactams 569

7-4 N-Carboxy-a-Amino Acid Anhydrides 578

7-5 Lactones 581

7-6 Nitrogen Heterocyclics 586

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

7-12 Copolymerization 600

References 606

8 Stereochemistry of Polymerization 619

8-1 Types of Stereoisomerism in Polymers 620

8-2 Properties of Stereoregular Polymers 633

8-3 Forces of Stereoregulation in Alkene Polymerizations 637

8-4 Traditional Ziegler–Natta Polymerization of Nonpolar Alkene Monomers 644

8-5 Metallocene Polymerization of Nonpolar Alkene Monomers 665

8-6 Other Hydrocarbon Monomers 682

8-7 Copolymerization 684

8-8 Postmetallocene: Chelate Initiators 685

8-9 Living Polymerization 689

8-10 Polymerization of 1,3-Dienes 689

8-11 Commerical Applications 695

8-12 Polymerization of Polar Vinyl Monomers 699

8-13 Aldehydes 703

8-14 Optical Activity in Polymers 704

8-15 Ring-Opening Polymerization 707

8-16 Statistical Models of Propagation 708

References 713

9 Reactions of Polymers 729

9-1 Principles of Polymer Reactivity 729

9-2 Crosslinking 737

9-3 Reactions of Cellulose 745

9-4 Reactions of Poly(vinyl acetate) 748

9-5 Halogenation 748

9-6 Aromatic Substitution 750

9-7 Cyclization 751

9-8 Other Reactions 752

9-9 Graft Copolymers 752

9-10 Block Copolymers 759

9-11 Polymers as Carriers or Supports 760

9-12 Polymer Reagents 765

9-13 Polymer Catalysts 768

9-14 Polymer Substrates 771

References 777

Index 789