Handbook of RAFT Polymerization

Handbook of RAFT Polymerization......Page 4
Contents......Page 8
List of Contributors......Page 12
1 Introduction......Page 16
2.1 Introduction......Page 20
2.2 Methodology......Page 22
2.3 Computational Modeling of RAFT Kinetics......Page 34
2.4 Structure–Reactivity Studies......Page 49
2.5 Abbreviations......Page 60
3.1 History......Page 66
3.2 Preequilibrium Kinetics and Mechanism......Page 74
3.3 Main Equilibrium Kinetics and Mechanism......Page 98
3.4 Mechanisms for Rate Retardation/Inhibition – Outstanding Questions......Page 105
3.5 RAFT Copolymerization: Block and Statistical Copolymers......Page 106
3.6 The Kinetics and Mechanism of Star and Graft Polymer Formation Processes......Page 109
3.7 Mechanism and Kinetics as a Guide for the Synthetic Polymer Chemist......Page 112
4.1 Introduction......Page 120
4.2 Chain-Length-Dependent Termination: A Brief Overview......Page 122
4.3 RAFT Chemistry as a Tool for Elucidating the Chain Length Dependence of k(t)......Page 124
4.4 Chain-Length-Dependent Propagation Rate Coefficients......Page 159
5.1 Historical Overview and Early Chemistry......Page 166
5.2 The Barton–McCombie Deoxygenation......Page 168
5.3 A Minor Mechanistic Controversy......Page 169
5.4 A New Degenerative Radical Process......Page 171
5.5 Synthetic Routes to Thiocarbonylthio Derivatives......Page 175
5.6 Some Synthetic Applications of the Degenerative Radical Transfer to Small Molecules......Page 183
5.7 Applications to Controlled Radical Polymerizations......Page 192
5.8 Concluding Remarks......Page 200
6.1 Introduction......Page 204
6.2 RAFT Agents......Page 207
6.3 RAFT Polymerization......Page 220
6.4 RAFT Polymerization Conditions......Page 237
6.5 Abbreviations......Page 240
7.1 Introduction......Page 250
7.2 Initiation Systems......Page 251
7.3 RAFT Agent Stability......Page 256
7.4 Suitable Monomers......Page 263
7.5 Examples of Experimental Procedures......Page 291
8.1 Introduction......Page 300
8.2 Effect of C(tr,RAFT) on M(n) and PDI in Homogeneous Systems......Page 307
8.3 Raft in Heterogeneous Systems......Page 308
8.4 Conclusion......Page 326
9.2 Block Copolymers......Page 330
9.3 Star Polymers via RAFT Polymerization......Page 358
9.4 Comb Polymers......Page 374
9.5 Other Complex Architectures......Page 379
9.6 Conclusions......Page 382
10.1 Introduction......Page 388
10.2 History of MADIX Polymerization......Page 389
10.3 Mechanism of MADIX Polymerization......Page 394
10.4 Kinetics of MADIX Polymerization......Page 398
10.5 Choice of MADIX Agents......Page 402
10.6 Synthesis of MADIX Agents......Page 405
10.7 Experimental Conditions in MADIX......Page 406
10.8 Monomers Polymerizable by MADIX......Page 408
10.9 MADIX Polymerization in Waterborne Dispersed Media......Page 414
10.10 Macromolecular Engineering by MADIX......Page 418
10.11 Methodologies to Remove the Dithiocarbonate End Groups......Page 427
10.12 Applications of MADIX (co)polymers......Page 429
11.1 Introduction......Page 438
11.2 Approach......Page 439
11.3 Properties......Page 459
11.4 Conclusions......Page 464
11.5 Abbreviations......Page 465
11.6 Acknowledgment......Page 466
12.1 Introduction......Page 470
12.2 Terminal Functionalities Introduced via the CTA......Page 471
12.3 RAFT in Combination with Other Polymerization Techniques......Page 482
12.4 Stability of the Thiocarbonylthio End Group and Its Modification Postpolymerization......Page 486
12.6 Abbreviations......Page 493
13.1 Introduction......Page 498
13.2 Bio-Related Applications......Page 500
13.3 Polymer-Based Materials for Various Applications......Page 523
13.4 Conclusions......Page 541
Subject Index......Page 552