The Chemistry of Radical Polymerization, Second Edition

Graeme Moad, D.H. Solomon9780080442884, 0080442889

Книга The Chemistry of Radical Polymerization, Second Edition The Chemistry of Radical Polymerization, Second EditionКниги Химия Автор: Graeme Moad, David H. Solomon Год издания: 2005 Формат: pdf Издат.:Elsevier Science Страниц: 665 Размер: 23,5 ISBN: 0080442889 Язык: Английский0 (голосов: 0) Оценка:In the ten years since the first edition appeared the renaissance in Free Radical Polymerization has continued to gain momentum. In this second revised edition, the authors critically evaluate the findings of the last decade, where necessary reinterpreting earlier work in the light of these ideas, and point to the areas where current and future research is being directed. The overall aim is to provide a framework for further extending our understanding of free radical polymerization and create a definable link between synthesis conditions and polymer structure and properties.The authors have updated all chapters, and added many new references and two new chapters to reflect the significant advances made in radical polymerization. One new chapter has been devoted tothe area of living radical polymerization which is now responsible for a very substantial fraction of the papers in the field. In addition to offering polymers with unique compositions and properties not achievable with other methodologies, living radical polymerization has also been combined with otherprocesses and mechanisms to give structures and architectures that were not previously thought possible.The developments are seen to have great application particularly in the emerging areas of electronics, biotechnology and nanotechnology.* An excellent text suitable for graduates in polymer chemistry and a reference source for researchers and practitioners in radical polymerization* Seven chapters revised and updated with eight years of new research* A new chapter devoted to the growing field of living radical polymerization

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Table of contents :
Cover……Page 1
Title Page……Page 4
ISBN: 0080442889……Page 5
2 RADICAL REACTIONS……Page 6
3 INITIATION……Page 7
4 PROPAGATION……Page 9
5 TERMINATION……Page 10
6 CHAIN TRANSFER……Page 11
Poly(methacrylonitrile-co- styrene)……Page 12
8 CONTROLLING POLYMERIZATION……Page 13
9 LIVING RADICAL POLYMERIZATION……Page 14
Index to Tables (with page links)……Page 17
Index to Figures (with page links)……Page 21
Preface to the First Edition……Page 24
Preface to the Second Edition……Page 26
Acknowledgments……Page 27
1 INTRODUCTION……Page 28
References……Page 35
Introduction……Page 38
Structures of Radicals……Page 39
Detection of Radicals……Page 41
Addition to Carbon-Carbon Double Bonds……Page 43
Steric Factors……Page 46
Polar Factors……Page 48
Bond Strengths……Page 49
Stereoelectronic Factors……Page 50
Temperature……Page 51
Solvent……Page 52
Theoretical Treatments……Page 53
Summary……Page 55
Hydrogen Atom Transfer……Page 56
Steric Factors……Page 57
Polar Factors……Page 58
Stereoelectronic Factors……Page 59
Reaction Conditions……Page 60
Abstraction TO Addition……Page 61
Radical-Radical Reactions……Page 63
Pathways for Combination……Page 64
Pathways for Disproportionation……Page 65
Statistical factors……Page 66
Steric factors……Page 67
Stereoelectronic and other factors……Page 68
Reaction conditions……Page 69
Summary……Page 70
References……Page 71
Introduction……Page 76
The Initiation Process……Page 77
Reaction with Monomer……Page 78
Fragmentation……Page 81
Effects of Temperature and Reaction Medium on Radical Reactivity……Page 82
Reaction with Oxygen……Page 83
Initiator Efficiency in Thermal Initiation……Page 84
Photoinitiation……Page 85
Cage Reaction and Initiator-Derived Byproducts……Page 87
Primary Radical Termination……Page 88
Transfer to Initiator……Page 89
Initiation in Heterogeneous Polymerization……Page 90
The Initiators……Page 91
Dialkyldiazenes……Page 95
Thermal decomposition……Page 99
Initiator efficiency……Page 101
Transfer to initiator……Page 104
Hyponitrites……Page 105
Peroxides……Page 106
Thermal decomposition……Page 109
Photochemical decomposition……Page 110
Initiator efficiency……Page 111
Redox reactions……Page 112
Dialkyl peroxydicarbonates……Page 114
Thermal decomposition……Page 115
Dialkyl peroxides……Page 117
Alkyl hydroperoxides……Page 119
Inorganic peroxides……Page 120
Persulfate……Page 121
Multifunctional Initiators……Page 123
Non-concerted decomposition……Page 124
Aromatic carbonyl compounds……Page 125
Benzoin and related compounds……Page 126
Carbonyl compound-tertiary amine systems……Page 129
Sulfur compounds……Page 130
Metal complex-organic halide redox systems……Page 131
Ceric ion systems……Page 132
Thermal Initiation……Page 133
Styrene homopolymerization……Page 134
Acrylate homopolymerization……Page 136
Copolymerization……Page 137
The Radicals……Page 138
Alkyl radicals……Page 139
a-Cyanoalkyl radicals……Page 140
Acyl radicals……Page 144
Alkoxy radical……Page 145
t-Butoxy radicals……Page 146
Other f-alkoxy radicals……Page 151
Acyloxy and alkoxycarbonyloxy radicals……Page 152
Benzoyloxy radicals……Page 153
Alkoxycarbonyloxy radicals……Page 154
Hydroxy radicals……Page 155
Sulfate radical anion……Page 156
Alkylperoxy radicals……Page 157
Silicon-centered radicals……Page 158
Phosphorus-centered radicals……Page 159
Radical Trapping……Page 160
Spin traps……Page 161
Transition metal salts……Page 163
Metal hydrides……Page 164
Nitroxides……Page 165
a-Methystyrene dimer……Page 167
Infra-red and UV-visible spectroscopy……Page 168
Nuclear magnetic resonance spectroscopy……Page 169
Mass spectrometry……Page 170
Chemical methods……Page 171
Radiolabeling……Page 172
Stable isotopes and nuclear magnetic resonance……Page 173
References……Page 176
Introduction……Page 194
Terminology and Mechanisms……Page 195
Tacticities of Polymers……Page 200
Monoene Polymers……Page 203
Poly(vinyl acetate)……Page 205
Poly(vinyl chloride)……Page 206
Fluoro-olefin polymers……Page 207
Allyl polymers……Page 208
Conjugated Diene Polymers……Page 209
Polychloroprene, polyisoprene……Page 211
Cyclopolymerization……Page 212
1,6-Dienes……Page 213
Triene monomers……Page 218
1,4- and 1,5-dienes……Page 219
1,7- and higher l,n-dienes……Page 220
Ring-Opening Polymerization……Page 221
Vinyl substituted cyclic compounds……Page 223
Methylene substituted cyclic compounds……Page 226
Double ring-opening polymerization……Page 232
Polyethylene and copolymers……Page 235
Acrylate esters and other monosubstituted monomers……Page 238
Addition-abstraction polymerization……Page 239
Polymerization Thermodynamics……Page 240
Measurement of Propagation Rate Constants……Page 243
Dependence of Propagation Rate Constant on Monomer Structure……Page 245
Chain Length Dependence of Propagation Rate Constants……Page 247
References……Page 248
Introduction……Page 260
Radical-Radical Termination……Page 261
Classical kinetics……Page 262
Molecular weights and molecular weight averages……Page 265
Molecular weight distributions……Page 267
Diffusion controlled termination……Page 269
Termination at low conversion……Page 271
Termination at medium to high conversions……Page 275
Termination in heterogeneous polymerization……Page 276
Termination during living radical polymerization……Page 277
Disproportionation TO Combination……Page 278
Model studies……Page 279
Polystyrene and derivatives……Page 280
Poly(alkyl methacrylates)……Page 282
Poly(methacrylonitrile)……Page 283
Polymerization……Page 285
Polystyrene……Page 287
Poly(alkyl methacrylates)……Page 288
Poly(acrylonitrile)……Page 289
Summary……Page 290
Inhibition and Retardation……Page 291
Stable’Radicals……Page 294
Oxygen……Page 295
Monomers……Page 296
Phenols……Page 297
Quinones……Page 298
Nitrones, Nitro- and Nitroso-Compounds……Page 299
References……Page 300
Chain Transfer……Page 306
Measurement of Transfer Constants……Page 310
Addition-fragmentation……Page 314
Reversible chain transfer……Page 315
Homolytic Substitution Chain Transfer Agents……Page 316
Thiols……Page 317
Disulfides……Page 318
Monosulfides……Page 319
Halocarbons……Page 320
Solvents and other reagents……Page 321
Addition-Fragmentation Chain Transfer Agents……Page 323
Vinyl ethers……Page 325
Allyl sulfides, sulfonates, halides, phosphonates, silanes……Page 326
Allyl peroxides……Page 330
Macromonomers……Page 332
Thionoester and related transfer agents……Page 335
Abstraction-Fragmentation Chain Transfer……Page 336
Mechanism……Page 337
Cobalt (II) cobaloximes……Page 340
Cobalt (III) cobaloximes……Page 341
Reaction conditions……Page 342
Transfer to Monomer……Page 343
Styrene……Page 344
Vinyl chloride……Page 345
Allyl monomers……Page 346
Transfer to Polymer……Page 347
Poly(alkyl methacrylates)……Page 348
Poly(alkyl acrylates)……Page 349
Poly (vinyl acetate)……Page 350
References……Page 352
Introduction……Page 360
Propagation in Statistical Copolymerization……Page 362
Terminal model……Page 364
Model description……Page 369
Remote substituent effects on radical addition……Page 371
MMA-S copolymerization……Page 374
Other copolymerizations……Page 375
Origin of penultimate unit effects……Page 376
Models involving monomer complexes……Page 377
Copolymerization with depropagation……Page 380
Binary copolymerization according to the terminal model……Page 381
Binary copolymerization according to the penultimate model……Page 382
Binary copolymerization according to other models……Page 383
Terpolymerization……Page 384
Estimation of Reactivity Ratios……Page 386
Composition data……Page 387
Monomer sequence distribution……Page 389
Q-e scheme……Page 390
Patterns of reactivity scheme……Page 392
Chemical Control Model……Page 393
Diffusion Control Models……Page 395
Combination and Disproportionation during Copolymerization……Page 397
Poly(methyl methacrylate-co-styrene)……Page 398
Functional and End-Functional Polymers……Page 401
Functional Initiators……Page 402
Functional Transfer Agents……Page 404
Thiol-ene Polymerization……Page 405
Functional Monomers……Page 406
Compositional Heterogeneity in Functional Copolymers……Page 408
Block & Graft Copolymerization……Page 411
Polymeric and Multifunctional Initiators……Page 412
Transformation Reactions……Page 414
Radiation-Induced Grafting Processes……Page 416
Radical-Induced Grafting Processes……Page 417
Maleic anhydride graft polyolefins……Page 419
Maleate ester and maleimide graft polyolefins……Page 423
(Meth)acrylate graft polyolefins……Page 424
Vinylsilane graft polyolefins……Page 426
Polymerization and Copolymerization of Macromonomers……Page 427
References……Page 428
Introduction……Page 440
“Defect Structures” in Polystyrene……Page 441
“Defect Structures” in Poly(methyl methacrylate)……Page 444
“Defect Structures” in Poly(vinyl chloride)……Page 447
Controlling Propagation……Page 448
Organic Solvents and Water……Page 452
Homopolymerization……Page 453
Copolymerization……Page 456
Ionic liquids……Page 459
Homopolymerization……Page 460
Copolymerization……Page 462
Non-covalently bonded templates……Page 464
Covalently bonded templates……Page 465
Enzyme Mediated Polymerization……Page 467
Topological Radical Polymerization……Page 468
References……Page 470
Living? Controlled? Mediated?……Page 478
Tests for Living (Radical) Polymerization……Page 479
Agents Providing Reversible Deactivation……Page 481
Initiators, iniferters, initers……Page 484
Molecular weights and distributions……Page 485
Polymerization kinetics……Page 487
Disulfide initiators……Page 488
Monosulfide initiators……Page 490
Monomers, mechanism, side reactions……Page 492
Selenium-Centered Radical Mediated Polymerization……Page 493
Carbon-Centered Radical Mediated Polymerization……Page 494
Monomers, mechanism, side reactions……Page 496
Reversible Addition-Fragmentation……Page 497
Nitroxide Mediated Polymerization……Page 498
Nitroxides……Page 499
Initiation……Page 502
Side reactions……Page 505
Rate enhancement……Page 506
Acrylates……Page 507
Heterogeneous polymerization……Page 508
Nitrogen-Centered Radical Mediated Polymerization……Page 510
Metal Complex-Mediated Radical Polymerization……Page 511
Atom Transfer Radical Polymerization……Page 513
Initiators……Page 515
Molecular weights and distributions……Page 517
Reverse ATRP……Page 518
Catalysts……Page 519
Copper complexes……Page 520
Ruthenium complexes……Page 522
Nickel complexes……Page 523
Heterogeneous polymerization……Page 524
Reversible Chain Transfer……Page 525
Molecular Weights and Distributions……Page 526
Macromonomer RAFT……Page 528
Thiocarbonylthio RAFT……Page 529
Mechanism……Page 530
RAFT agents……Page 532
RAFT agent synthesis……Page 542
Side Reactions……Page 544
Reaction conditions……Page 545
Heterogeneous polymerization……Page 547
Iodine-Transfer Polymerization……Page 548
Telluride-Mediated Polymerization……Page 549
Stibine-Mediated Polymerization……Page 551
Reactivity Ratios……Page 552
Gradient Copolymers……Page 553
NMP……Page 554
ATRP……Page 555
RAFT……Page 556
omega-Functionalization……Page 558
omega-Functionalization……Page 560
alpha-Functionalization……Page 563
omega-Functionalization……Page 565
alpha-Functionalization……Page 566
Block Copolymers……Page 567
ATRP……Page 568
RAFT……Page 570
Transformation Reactions……Page 571
Second step ATRP……Page 572
Triblock Copolymers……Page 573
Segmented Block Copolymers……Page 574
Star Polymers……Page 575
Core-first Star Synthesis……Page 576
Arm-first Star Synthesis……Page 581
Self-condensing vinyl polymerization……Page 582
Dendritic polymers……Page 583
Grafting Through – Copolymerization of Macromonomers……Page 585
Grafting from polymer surfaces……Page 587
Grafting from inorganic surfaces……Page 589
Outlook for Living Radical Polymerization……Page 590
References……Page 591
ABBREVIATIONS……Page 614
A……Page 618
B……Page 623
C……Page 626
D……Page 632
E……Page 636
F……Page 637
G……Page 638
H……Page 639
I……Page 641
J,K……Page 642
L……Page 643
M……Page 644
N……Page 648
O……Page 649
P……Page 650
Q,R……Page 654
S……Page 658
T……Page 661
V……Page 665
X,Z……Page 666