The chemistry of radical polymerization / Graeme Moad and David H. Solomon.

Format:

Book

Author/Creator:

Moad, Graeme.

Contributor:

Solomon, D. H. (David Henry)

Moad, Graeme.

Language:

English

Subjects (All):

Polymerization.

Radicals (Chemistry).

Physical Description:

xxvi, 639 pages : illustrations ; 25 cm

Edition:

Second fully revised edition.

Place of Publication:

Amsterdam ; Boston : Elsevier, 2006.

Contents:

2 Radical Reactions 11

2.2 Properties of Radicals 12

2.2.1 Structures of Radicals 12

2.2.2 Stabilities of Radicals 14

2.2.3 Detection of Radicals 14

2.3 Addition to Carbon-Carbon Double Bonds 16

2.3.1 Steric Factors 19

2.3.2 Polar Factors 21

2.3.3 Bond Strengths 22

2.3.4 Stereoelectronic Factors 23

2.3.5 Entropic Considerations 24

2.3.6 Reaction Conditions 24

2.3.7 Theoretical Treatments 26

2.4 Hydrogen Atom Transfer 29

2.4.1 Bond Dissociation Energies 30

2.4.2 Steric Factors 30

2.4.3 Polar Factors 31

2.4.4 Stereoelectronic Factors 32

2.4.5 Reaction Conditions 33

2.4.6 Abstraction vs Addition 34

2.5 Radical-Radical Reactions 36

2.5.1 Pathways for Combination 37

2.5.2 Pathways for Disproportionation 38

2.5.3 Combination vs Disproportionation 39

3 Initiation 49

3.2 The Initiation Process 50

3.2.1 Reaction with Monomer 51

3.2.2 Fragmentation 54

3.2.3 Reaction with Solvents, Additives, or Impurities 55

3.2.4 Effects of Temperature and Reaction Medium on Radical Reactivity 55

3.2.5 Reaction with Oxygen 56

3.2.6 Initiator Efficiency in Thermal Initiation 57

3.2.7 Photoinitiation 58

3.2.8 Cage Reaction and Initiator-Derived Byproducts 60

3.2.9 Primary Radical Termination 61

3.2.10 Transfer to Initiator 62

3.2.11 Initiation in Heterogeneous Polymerization 63

3.3 The Initiators 64

3.3.1 Azo-Compounds 68

3.3.2 Peroxides 79

3.3.3 Multifunctional Initiators 96

3.3.4 Photochemical Initiators 98

3.3.5 Redox Initiators 104

3.3.6 Thermal Initiation 106

3.4 The Radicals 111

3.4.1 Carbon-Centered Radicals 112

3.4.2 Oxygen-Centered Radicals 118

3.4.3 Other Heteroatom-Centered Radicals 131

3.5 Techniques 133

3.5.1 Kinetic Studies 133

3.5.2 Radical Trapping 133

3.5.3 Direct Detection of End Groups 141

3.5.4 Labeling Techniques 145

4 Propagation 167

4.2 Stereosequence Isomerism - Tacticity 168

4.2.1 Terminology and Mechanisms 168

4.2.2 Experimental Methods for Determining Tacticity 173

4.2.3 Tacticities of Polymers 173

4.3 Regiosequence Isomerism - Head vs Tail Addition 176

4.3.1 Monoene Polymers 176

4.3.2 Conjugated Diene Polymers 182

4.4 Structural Isomerism - Rearrangement 185

4.4.1 Cyclopolymerization 185

4.4.2 Ring-Opening Polymerization 194

4.4.3 Intramolecular Atom Transfer 208

4.5 Propagation Kinetics and Thermodynamics 213

4.5.1 Polymerization Thermodynamics 213

4.5.2 Measurement of Propagation Rate Constants 216

4.5.3 Dependence of Propagation Rate Constant on Monomer Structure 218

4.5.4 Chain Length Dependence of Propagation Rate Constants 220

5 Termination 233

5.2 Radical-Radical Termination 234

5.2.1 Termination Kinetics 235

5.2.2 Disproportionation vs Combination 251

5.3 Inhibition and Retardation 264

5.3.1 'Stable' Radicals 267

5.3.2 Oxygen 268

5.3.3 Monomers 269

5.3.4 Phenols 270

5.3.5 Quinones 271

5.3.6 Phenothiazine 272

5.3.7 Nitrones, Nitro- and Nitroso-Compounds 272

5.3.8 Transition Metal Salts 273

6 Chain Transfer 279

6.2 Chain Transfer 279

6.2.1 Measurement of Transfer Constants 283

6.2.2 Homolytic Substitution Chain Transfer Agents 289

6.2.3 Addition-Fragmentation Chain Transfer Agents 296

6.2.4 Abstraction-Fragmentation Chain Transfer 309

6.2.5 Catalytic Chain Transfer 310

6.2.6 Transfer to Monomer 316

6.2.7 Transfer to Polymer 320

6.2.8 Transfer to Initiator 325

7 Copolymerization 333

7.2 Copolymer Depiction 335

7.3 Propagation in Statistical Copolymerization 335

7.3.1 Propagation Mechanisms in Copolymerization 337

7.3.2 Chain Statistics 354

7.3.3 Estimation of Reactivity Ratios 359

7.3.4 Prediction of Reactivity Ratios 363

7.4 Termination in Statistical Copolymerization 366

7.4.1 Chemical Control Model 366

7.4.2 Diffusion Control Models 368

7.4.3 Combination and Disproportionation during Copolymerization 370

7.5 Functional and End-Functional Polymers 374

7.5.1 Functional Initiators 375

7.5.2 Functional Transfer Agents 377

7.5.3 Thiol-ene Polymerization 378

7.5.4 Functional Monomers 379

7.5.5 Functional Inhibitors 381

7.5.6 Compositional Heterogeneity in Functional Copolymers 381

7.6 Block & Graft Copolymerization 384

7.6.1 Polymeric and Multifunctional Initiators 385

7.6.2 Transformation Reactions 387

7.6.3 Radiation-Induced Grafting Processes 389

7.6.4 Radical-Induced Grafting Processes 390

7.6.5 Polymerization and Copolymerization of Macromonomers 400

8 Controlling Polymerization 413

8.2 Controlling Structural Irregularities 414

8.2.1 "Defect Structures" in Polystyrene 414

8.2.2 "Defect Structures" in Poly(methyl methacrylate) 417

8.2.3 "Defect Structures" in Poly(vinyl chloride) 420

8.3 Controlling Propagation 421

8.3.1 Organic Solvents and Water 425

8.3.2 Supercritical Carbon Dioxide 432

8.3.3 Ionic liquids 432

8.3.4 Lewis Acids and Inorganics 433

8.3.5 Template Polymerization 437

8.3.6 Enzyme Mediated Polymerization 440

8.3.7 Topological Radical Polymerization 441

9 Living Radical Polymerization 451

9.1.1 Living? Controlled? Mediated? 451

9.1.2 Tests for Living (Radical) Polymerization 452

9.2 Agents Providing Reversible Deactivation 454

9.3 Deactivation by Reversible Coupling and Unimolecular Activation 457

9.3.1 Kinetics and Mechanism 457

9.3.2 Sulfur-Centered Radical Mediated Polymerization 461

9.3.3 Selenium-Centered Radical Mediated Polymerization 466

9.3.4 Carbon-Centered Radical Mediated Polymerization 467

9.3.5 Reversible Addition-Fragmentation 470

9.3.6 Nitroxide Mediated Polymerization 471

9.3.7 Other Oxygen-Centered Radical Mediated Polymerization 483

9.3.8 Nitrogen-Centered Radical Mediated Polymerization 483

9.3.9 Metal Complex-Mediated Radical Polymerization 484

9.4 Atom Transfer Radical Polymerization 486

9.4.1 Initiators 488

9.4.2 Catalysts 492

9.4.3 Monomers and Reaction Conditions 497

9.5 Reversible Chain Transfer 498

9.5.1 Molecular Weights and Distributions 499

9.5.2 Macromonomer RAFT 501

9.5.3 Thiocarbonylthio RAFT 502

9.5.4 Iodine-Transfer Polymerization 521

9.5.5 Telluride-Mediated Polymerization 522

9.5.6 Stibine-Mediated Polymerization 524

9.6 Living Radical Copolymerization 525

9.6.1 Reactivity Ratios 525

9.6.2 Gradient Copolymers 526

9.6.3 NMP 527

9.6.4 ATRP 528

9.6.5 RAFT 529

9.7 End-Functional Polymers 531

9.7.1 NMP 531

9.7.2 ATRP 533

9.7.3 RAFT 538

9.8 Block Copolymers 540

9.8.1 Direct Diblock Synthesis 541

9.8.2 Transformation Reactions 544

9.8.3 Triblock Copolymers 546

9.8.4 Segmented Block Copolymers 547

9.9 Star Polymers 548

9.9.1 Core-first Star Synthesis 549

9.9.2 Arm-first Star Synthesis 554

9.9.3 Hyperbranched Polymers 555

9.10 Graft Copolymers/Polymer Brushes 558

9.10.1 Grafting Through - Copolymerization of Macromonomers 558

9.10.2 Grafting From - Surface Initiated Polymerization 560

9.10.3 Grafting To - Use of End-Functional Polymers 563

9.11 Outlook for Living Radical Polymerization 563.

Notes:

Rev. ed. of: The chemistry of free radical polymerization. 1st ed. 1995.

Includes bibliographical references and index.

Related Work:

Moad, Graeme. Chemistry of free radical polymerization.

ISBN:

0080442889

0080442862

OCLC:

62282371

Publisher Number:

9780080442884

9780080442860