Principles of Polymerization, Fourth Edition

Team DDU......Page 1
CONTENTS......Page 8
PREFACE......Page 26
1-1 Types of Polymers and Polymerizations......Page 28
1-1a Polymer Composition and Structure......Page 29
1-1b Polymerization Mechanism......Page 33
1-2 Nomenclature of Polymers......Page 36
1-2a Nomenclature Based on Source......Page 37
1-2c IUPAC Structure-Based Nomenclature System......Page 38
1-2d Trade Names and Nonnames......Page 43
1-3 Linear, Branched, and Crosslinked Polymers......Page 44
1-4 Molecular Weight......Page 46
1-5a Crystalline and Amorphous Behavior......Page 51
1-5b Determinants of Polymer Crystallinity......Page 54
1-5c Thermal Transitions......Page 56
1-6a Mechanical Properties......Page 59
1-6b Elastomers, Fibers, and Plastics......Page 62
References......Page 63
2 STEP POLYMERIZATION......Page 66
2-1a Basis for Analysis of Polymerization Kinetics......Page 67
2-1b Experimental Evidence......Page 68
2-1c Theoretical Considerations......Page 70
2-2 Kinetics of Step Polymerization......Page 71
2-2a Self-Catalyzed Polymerization......Page 73
2-2a-1 Experimental Observations......Page 74
2-2a-2 Reasons for Nonlinearity in Third-Order Plot......Page 75
2-2a-3 Molecular Weight of Polymer......Page 77
2-2b External Catalysis of Polymerization......Page 78
2-2c Step Polymerizations Other than Polyesterification: Catalyzed versus Uncatalyzed......Page 80
2-2d-1 Examples of Nonequivalence......Page 81
2-2d-2 Kinetics......Page 84
2-3 Accessibility of Functional Groups......Page 90
2-4a Closed System......Page 92
2-4b Open, Driven System......Page 94
2-5a Possible Cyclization Reactions......Page 96
2-5b Cyclization Tendency versus Ring Size......Page 97
2-5c Reaction Conditions......Page 99
2-5d Thermodynamic versus Kinetic Control......Page 100
2-6a Need for Stoichiometric Control......Page 101
2-6b Quantitative Aspects......Page 102
2-6c Kinetics of Nonstoichiometric Polymerization......Page 106
2-7a Derivation of Size Distributions......Page 107
2-7b Breadth of Molecular Weight Distribution......Page 109
2-7d Alternate Approaches for Molecular-Weight Distribution......Page 110
2-7e-3 Nonstoichiometry of Functional Groups......Page 113
2-8a Physical Nature of Polymerization Systems......Page 114
2-8b Different Reactant Systems......Page 116
2-8c-1 Description of Process......Page 117
2-8d Polyesters......Page 119
2-8e Polycarbonates......Page 123
2-8f Polyamides......Page 124
2-9a Branching......Page 128
2-9b Molecular Weight Distribution......Page 129
2-10 Crosslinking......Page 130
2-10a-1 Stoichiometric Amounts of Reactants......Page 132
2-10a-2 Extension to Nonstoichiometric Reactant Mixtures......Page 133
2-10b Statistical Approach to Gelation: Xw !1......Page 135
2-10c Experimental Gel Points......Page 138
2-10d Extensions of Statistical Approach......Page 139
2-11 Molecular Weight Distributions in Nonlinear Polymerizations......Page 141
2-12 Crosslinking Technology......Page 144
2-12a Polyesters, Unsaturated Polyesters, and Alkyds......Page 145
2-12b-1 Resole Phenolics......Page 147
2-12b-2 Novolac Phenolics......Page 151
2-12c Amino Plastics......Page 153
2-12d Epoxy Resins......Page 155
2-12e Polyurethanes......Page 157
2-12f Polysiloxanes......Page 159
2-12g Polysulfides......Page 161
2-13a Types of Copolymers......Page 162
2-13b-2 Alternating Copolymers......Page 165
2-13b-3 Block Copolymers......Page 166
2-13c Utility of Copolymerization......Page 167
2-13c-1 Statistical Copolymers......Page 168
2-13c-2 Block Copolymers......Page 169
2-13c-3 Polymer Blends and Interpenetrating Polymer Networks......Page 170
2-14a Requirements for High-Temperature Polymers......Page 171
2-14b Aromatic Polyethers by Oxidative Coupling......Page 173
2-14c Aromatic Polyethers by Nucleophilic Substitution......Page 176
2-14e Aromatic Polyimides......Page 178
2-14f Reactive Telechelic Oligomer Approach......Page 182
2-14g Liquid Crystal Polymers......Page 184
2-14h 5-Membered Ring Heterocyclic Polymers......Page 186
2-14i 6-Membered Ring Heterocyclic Polymers......Page 189
2-14j Conjugated Polymers......Page 190
2-14j-1 Oxidative Polymerization of Aniline......Page 192
2-14j-2 Poly(p-phenylene)......Page 193
2-14j-3 Poly(p-phenylene Vinylene)......Page 194
2-15a-1 Minerals......Page 195
2-15a-2 Glasses......Page 196
2-15a-3 Ceramics......Page 197
2-15b-1 Polymerization via Reaction at Metal Bond......Page 199
2-15b-3 Polysilanes......Page 200
2-16 Dendritic (Highly Branched) Polymers......Page 201
2-16a Random Hyperbranched Polymers......Page 202
2-16b Dendrimers......Page 204
2-17a-1 In Vivo (within Living Cells)......Page 207
2-17a-2 In Vitro (outside Living Cells)......Page 208
2-17c Cycloaddition (Four-Center) Polymerization......Page 210
2-17e Pseudopolyrotoxanes and Polyrotoxanes......Page 211
References......Page 212
3 RADICAL CHAIN POLYMERIZATION......Page 225
3-1b-1 General Considerations of Polymerizability......Page 226
3-1b-2 Effects of Substituents......Page 227
3-2a Possible Modes of Propagation......Page 229
3-2b Experimental Evidence......Page 230
3-3a Sequence of Events......Page 231
3-3b Rate Expression......Page 233
3-3c-2 Chemical and Spectroscopic Analysis......Page 235
3-4a-1 Types of Initiators......Page 236
3-4a-3 Dependence of Polymerization Rate on Initiator......Page 239
3-4a-4 Dependence of Polymerization Rate on Monomer......Page 241
3-4b-1 Types of Redox Initiators......Page 243
3-4b-2 Rate of Redox Polymerization......Page 244
3-4c Photochemical Initiation......Page 245
3-4c-1 Bulk Monomer......Page 246
3-4c-2 Irradiation of Thermal and Redox Initiators......Page 247
3-4c-3 Rate of Photopolymerization......Page 248
3-4d Initiation by Ionizing Radiation......Page 251
3-4e Pure Thermal Initiation......Page 253
3-4f Other Methods of Initiation......Page 254
3-4g-2 Mechanism of f<1: Cage Effect......Page 255
3-4g-3 Experimental Determination of f......Page 259
3-4h Other Aspects of Initiation......Page 262
3-5b Mode of Termination......Page 263
3-6a Effect of Chain Transfer......Page 265
3-6b-1 Determination of CM and CI......Page 267
3-6b-2 Monomer Transfer Constants......Page 268
3-6b-3 Initiator Transfer Constants......Page 271
3-6c-1 Determination of CS......Page 272
3-6c-2 Structure and Reactivity......Page 273
3-6c-3 Practical Utility of Mayo Equation......Page 276
3-6d Chain Transfer to Polymer......Page 277
3-6e Catalytic Chain Transfer......Page 281
3-7 Inhibition and Retardation......Page 282
3-7a Kinetics of Inhibition or Retardation......Page 283
3-7b Types of Inhibitors and Retarders......Page 286
3-7c Autoinhibition of Allylic Monomers......Page 290
3-8a Non-Steady-State Kinetics......Page 291
3-8b Rotating Sector Method......Page 292
3-8c PLP-SEC Method......Page 294
3-8d Typical Values of Reaction Parameters......Page 296
3-9a Activation Energy and Frequency Factor......Page 298
3-9a-1 Rate of Polymerization......Page 299
3-9a-2 Degree of Polymerization......Page 301
3-9b-1 Significance of 
G, 
H, and 
S......Page 302
3-9b-2 Effect of Monomer Structure......Page 303
3-9b-3 Polymerization of 1,2-Disubstituted Ethylenes......Page 304
3-9c-1 Ceiling Temperature......Page 306
3-10a Course of Polymerization......Page 309
3-10b Diffusion-Controlled Termination......Page 310
3-10c Effect of Reaction Conditions......Page 313
3-10d-2 Template Polymerization......Page 314
3-10e Dependence of Polymerization Rate on Initiator and Monomer......Page 315
3-11a Low-Conversion Polymerization......Page 316
3-12 Effect of Pressure......Page 319
3-12a-1 Volume of Activation......Page 320
3-12a-2 Rate of Polymerization......Page 321
3-12a-3 Degree of Polymerization......Page 322
3-13 Process Conditions......Page 323
3-13c Heterogeneous Polymerization......Page 324
3-13d Other Processes; Self-Assembly and Nanostructures......Page 326
3-14a Polyethylene......Page 327
3-14b Polystyrene......Page 329
3-14c-1 Poly(vinyl chloride)......Page 331
3-14c-2 Other Members of Vinyl Family......Page 333
3-14d-1 Acrylate and Methacrylate Products......Page 334
3-14d-3 Other Members of Acrylic Family......Page 335
3-14e Fluoropolymers......Page 336
3-14f Polymerization of Dienes......Page 337
3-14g-1 Poly(p-xylylene)......Page 338
3-15a General Considerations......Page 340
3-15b-1 Polymerization Mechanism......Page 343
3-15b-2 Effects of Components of Reaction System......Page 346
3-15b-3 Complex Kinetics......Page 348
3-15b-4 Block Copolymers......Page 349
3-15b-5 Other Polymer Architectures......Page 351
3-15c Stable Free-Radical Polymerization (SFRP)......Page 352
3-15d Radical Addition-Fragmentation Transfer (RAFT)......Page 355
3-16b Functional Polymers......Page 357
References......Page 359
4-1a Utility......Page 377
4-1b-1 Components and Their Locations......Page 378
4-1b-2 Site of Polymerization......Page 380
4-1b-3 Progress of Polymerization......Page 381
4-2a Rate of Polymerization......Page 383
4-2b Degree of Polymerization......Page 387
4-2c Number of Polymer Particles......Page 389
4-3b Surfactants......Page 390
4-3d Propagation and Termination Rate Constants......Page 391
4-3f Molecular Weight and Particle Size Distributions......Page 392
4-3g Surfactant-Free Emulsion Polymerization......Page 393
4-3h Other Emulsion Polymerization Systems......Page 394
4-3i Living Radical Polymerization......Page 395
References......Page 396
5-1 Comparison of Radical and Ionic Polymerizations......Page 399
5-2a-1 Protonic Acids......Page 401
5-2a-2 Lewis Acids......Page 402
5-2a-4 Photoinitiation by Onium Salts......Page 406
5-2a-5 Electroinitiation......Page 407
5-2a-6 Ionizing Radiation......Page 408
5-2b Propagation......Page 409
5-2c-1 b-Proton Transfer......Page 411
5-2c-2 Combination with Counterion......Page 413
5-2c-4 Other Transfer and Termination Reactions......Page 414
5-2d-1 Different Kinetic Situations......Page 415
5-2d-3 Molecular Weight Distribution......Page 418
5-2e-1 Experimental Methods......Page 419
5-2e-2 Difficulty in Interpreting Rate Constants......Page 421
5-2e-3 Comparison of Rate Constants......Page 423
5-2e-4 CM and CS Values......Page 425
5-2f-1 Propagation by Covalent Species; Pseudocationic Polymerization......Page 426
5-2f-2 Solvent Effects......Page 428
5-2g Living Cationic Polymerization......Page 430
5-2g-1 General Requirements......Page 431
5-2g-2 Rate and Degree of Polymerization......Page 432
5-2g-3 Specific Living Cationic Polymerization Systems......Page 433
5-2h Energetics......Page 435
5-2i-1 Polyisobutylene Products......Page 437
5-2i-2 Other Products......Page 438
5-3a-1 Nucleophilic Initiators......Page 439
5-3a-2 Electron Transfer......Page 441
5-3b-2 Termination by Impurities and Deliberately Added Transfer Agents......Page 443
5-3b-3 Spontaneous Termination......Page 444
5-3b-4 Termination and Side Reactions of Polar Monomers......Page 445
5-3c Group Transfer Polymerization......Page 447
5-3d-1 Polymerization Rate......Page 449
5-3d-2 Effects of Reaction Media......Page 450
5-3d-3 Degree of Polymerization......Page 455
5-3d-4 Energetics: Solvent-Separated and Contact Ion Pairs......Page 456
5-3d-5 Association Phenomena in Alkyllithium......Page 460
5-3d-6 Other Phenomena......Page 462
5-4a Sequential Monomer Addition......Page 463
5-4b Telechelic (End-Functionalized) Polymers......Page 466
5-4c Coupling Reactions......Page 468
5-5 Distinguishing Between Radical, Cationic, and Anionic Polymerizations......Page 470
5-6 Carbonyl Polymerization......Page 471
5-6a-1 Formaldehyde......Page 472
5-6a-2 Other Carbonyl Monomers......Page 473
5-6c Radical Polymerization......Page 474
5-6d End Capping......Page 475
5-7a Monomers with Two Different Polymerizable Groups......Page 476
5-7b Hydrogen-Transfer Polymerization of Acrylamide......Page 477
5-7d Monomers with Triple Bonds......Page 478
References......Page 479
6 CHAIN COPOLYMERIZATION......Page 491
6-1b Types of Copolymers......Page 492
6-2a Terminal Model; Monomer Reactivity Ratios......Page 493
6-2b Statistical Derivation of Copolymerization Equation......Page 496
6-2c Range of Applicability of Copolymerization Equation......Page 497
6-2d-1 Ideal Copolymerization: r1 r2 ?1......Page 498
6-2d-2 Alternating Copolymerization: r1 r2 ?0......Page 500
6-2e Variation of Copolymer Composition with Conversion......Page 502
6-2f Experimental Evaluation of Monomer Reactivity Ratios......Page 507
6-2g-1 Sequence Length Distribution......Page 508
6-2g-2 Copolymer Compositions of Different Molecules......Page 511
6-2h Multicomponent Copolymerization......Page 512
6-3a-1 Reaction Medium......Page 514
6-3a-2 Temperature......Page 516
6-3b-1 Resonance Effects......Page 517
6-3b-2 Steric Effects......Page 523
6-3b-3 Alternation; Polar Effects and Complex Participation......Page 524
6-3b-4 Q杄 Scheme......Page 527
6-3b-5 Patterns of Reactivity Scheme......Page 530
6-3c Terminal Model for Rate of Radical Copolymerization......Page 532
6-4 Ionic Copolymerization......Page 533
6-4a-1 Reactivity......Page 534
6-4a-2 Effect of Solvent and Counterion......Page 535
6-4b-1 Reactivity......Page 537
6-4b-2 Effects of Solvent and Counterion......Page 538
6-5 Deviations from Terminal Copolymerization Model......Page 539
6-5a Kinetic Penultimate Behavior......Page 540
6-5b Depropagation during Copolymerization......Page 542
6-5c Copolymerization with Complex Participation......Page 545
6-6a Crosslinking......Page 548
6-6b Alternating Intra/intermolecular Polymerization; Cyclopolymerization......Page 551
6-6c Interpenetrating Polymer Networks......Page 554
6-7b Copolymerization of Carbonyl Monomers......Page 555
6-8a Styrene......Page 556
6-8b Ethylene......Page 557
6-8c Unsaturated Polyesters......Page 558
6-8e Other Copolymers......Page 559
References......Page 560
7 RING-OPENING POLYMERIZATION......Page 571
7-1a Scope; Polymerizability......Page 572
7-1b Polymerization Mechanism and Kinetics......Page 573
7-2a-1 Reaction Characteristics......Page 575
7-2a-2 Exchange Reactions......Page 578
7-2a-3 Chain Transfer to Monomer......Page 580
7-2b-1 Propagation......Page 581
7-2b-2 Initiation......Page 582
7-2b-3 Termination and Transfer Processes......Page 583
7-2b-4 Cyclic Acetals......Page 586
7-2b-5 Kinetics of Reversible ROP......Page 589
7-2b-6 Energetic Characteristics......Page 592
7-2b-7 Commercial Applications......Page 595
7-3 Lactams......Page 596
7-3a Cationic Polymerization......Page 597
7-3b Hydrolytic Polymerization......Page 599
7-3c-1 Use of Strong Base Alone......Page 600
7-3c-2 Addition of N-Acyllactam......Page 602
7-3d Reactivity......Page 604
7-4a Polymerization by Bases......Page 605
7-4b Polymerization by Transition Metal Complexes......Page 607
7-5a Anionic Polymerization......Page 608
7-5b Cationic Polymerization......Page 610
7-5c Enzymatic Polymerization......Page 611
7-5d Other Cyclic Esters......Page 612
7-6a Cyclic Amines......Page 613
7-6b Other Nitrogen Heterocyclics......Page 614
7-7 Sulfur Heterocyclics......Page 615
7-8 Cycloalkenes......Page 616
7-9 Miscellaneous Oxygen Heterocyclics......Page 619
7-10 Other Ring-Opening Polymerizations......Page 621
7-11a Cyclosiloxanes......Page 622
7-11b Cyclotriphosphazenes......Page 624
7-11d Phosphorus-Containing Cyclic Esters......Page 626
7-12 Copolymerization......Page 627
7-12a Monomers with Same Functional Group......Page 628
7-12b Monomers with Different Functional Groups......Page 630
7-12c Block Copolymers......Page 631
7-12d Zwitterion Polymerization......Page 632
References......Page 633
8 STEREOCHEMISTRY OF POLYMERIZATION......Page 646
8-1 Types of Stereoisomerism in Polymers......Page 647
8-1a-1 Site of Steric Isomerism......Page 648
8-1a-2 Tacticity......Page 649
8-1b-2 1,2-Disubstituted Ethylenes......Page 651
8-1c Carbonyl and Ring-Opening Polymerizations......Page 653
8-1d-1 1,2- and 3,4-Polymerizations......Page 654
8-1d-2 1,4-Polymerization......Page 655
8-1e-1 1,2- and 3,4-Polymerizations......Page 656
8-1e-2 1,4-Polymerization......Page 657
8-1f Other Polymers......Page 658
8-2a-2 Cis- and Trans-1,4-Poly-1,3-Dienes......Page 660
8-2a-3 Cellulose and Amylose......Page 661
8-2b Analysis of Stereoregularity......Page 662
8-3a Radical Polymerization......Page 664
8-3b-1 Effect of Coordination......Page 667
8-3b-2 Mechanism of Stereoselective Placement......Page 668
8-4a Historical Development of Ziegler-Natta Initiators......Page 671
8-4b Chemical Nature of Propagating Species......Page 672
8-4c Primary versus Secondary Insertion; Regioselectivity......Page 673
8-4e Mechanism of Isoselective Propagation......Page 674
8-4f Mechanism of Syndioselective Propagation......Page 679
8-4g Direction of Double-Bond Opening......Page 681
8-4h Effects of Components of Ziegler-Natta Initiator......Page 682
8-4h-1 Transition Metal Component......Page 683
8-4h-2 Group I-III Metal Component......Page 684
8-4i-1 Observed Rate Behavior......Page 685
8-4i-2 Termination......Page 686
8-4i-3 Rate and Degree of Polymerization......Page 688
8-4i-4 Values of Kinetic Parameters......Page 689
8-4j Transition Metal Oxide Initiators......Page 691
8-5 Metallocene Polymerization of Nonpolar Alkene Monomers......Page 692
8-5a Metallocene Symmetry......Page 693
8-5c C2-Symmetric Metallocenes......Page 695
8-5c-1 Effect of Initiator Structure......Page 696
8-5c-2 Effect of Reaction Variables......Page 698
8-5d CS-Symmetric Metallocenes......Page 699
8-5e C1-Symmetric Metallocenes......Page 700
8-5f Oscillating Metallocenes......Page 702
8-5g-1 Methylaluminoxane (MAO)......Page 703
8-5g-2 Boron-Containing Coinitiators......Page 704
8-5h-1 Rate of Polymerization......Page 705
8-5h-2 Degree of Polymerization......Page 707
8-5h-3 Supported Metallocenes......Page 708
8-6a 1,2-Disubstituted Alkenes; Cycloalkenes......Page 709
8-6b Styrene......Page 710
8-7 Copolymerization......Page 711
8-8a ansa-Cyclopentadienyl-Amido Initiators......Page 712
8-8b a-Diimine Chelates of Late Transition Metals......Page 713
8-8c Phenoxy-Imine Chelates......Page 715
8-10a Radical Polymerization......Page 716
8-10b Anionic Polymerization......Page 718
8-10c Cationic Polymerization......Page 721
8-11a Process Conditions......Page 722
8-11b High-Density Polyethylene......Page 723
8-11d Polypropene......Page 724
8-11f Other Polymers......Page 725
8-12a Methyl Methacrylate......Page 726
8-13 Aldehydes......Page 730
8-14b Chiral Conformation......Page 731
8-14c Enantiomer-Differentiating Polymerization......Page 732
8-15 Ring-Opening Polymerization......Page 734
8-16a-1 Bernoullian Model......Page 735
8-16a-2 First-Order Markov Model......Page 736
8-16b Catalyst (Initiator) Site Control......Page 738
8-16c Application of Propagation Statistics......Page 739
References......Page 740
9-1 Principles of Polymer Reactivity......Page 756
9-1c Concentration......Page 757
9-1e Change in Solubility......Page 758
9-1g Steric Effects......Page 759
9-1h Electrostatic Effects......Page 760
9-1j Hydrophobic Interactions......Page 762
9-1k Other Considerations......Page 763
9-2a Alkyds......Page 764
9-2b Elastomers Based on 1,3-Dienes......Page 765
9-2b-1 Sulfur Alone......Page 766
9-2b-2 Accelerated Sulfur Vulcanization......Page 767
9-2c Peroxide and Radiation Crosslinking......Page 769
9-2d Other Crosslinking Processes......Page 771
9-3a Dissolution of Cellulose......Page 772
9-3c Etherification of Cellulose......Page 774
9-5a Natural Rubber......Page 775
9-5b Saturated Hydrocarbon Polymers......Page 776
9-6 Aromatic Substitution......Page 777
9-7 Cyclization......Page 778
9-9 Graft Copolymers......Page 779
9-9a-1 Vinyl Macromonomers......Page 780
9-9a-2 Chain Transfer and Copolymerization......Page 781
9-9a-3 Ionizing Radiation......Page 782
9-9a-5 Living Radical Polymerization......Page 783
9-9b Anionic Graft Polymerization......Page 784
9-9d Other Approaches to Graft Copolymers......Page 785
9-10 Block Copolymers......Page 786
9-11 Polymers as Carriers or Supports......Page 787
9-11a-1 Functionalization of Polymer......Page 788
9-11a-3 Comparison of the Two Approaches......Page 790
9-11b Advantages of Polymer Reagents, Catalysts, and Substrates......Page 791
9-12 Polymer Reagents......Page 792
9-13 Polymer Catalysts......Page 795
9-14 Polymer Substrates......Page 798
9-14a Solid-Phase Synthesis of Polypeptides......Page 799
9-14b Other Applications......Page 803
References......Page 804
INDEX......Page 816