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E-grāmata: RAFT Polymerization: Methods, Synthesis, and Applications

Edited by Graeme Moad (University of Adelaide, Australia), Edited by Ezio Rizzardo (University of New South Wales, Australia; University of Sydney, Australia)

Formāts: PDF+DRM
Izdošanas datums: 22-Oct-2021
Izdevniecība: Blackwell Verlag GmbH
Valoda: eng
ISBN-13: 9783527821341

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Formāts: PDF+DRM
Izdošanas datums: 22-Oct-2021
Izdevniecība: Blackwell Verlag GmbH
Valoda: eng
ISBN-13: 9783527821341

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Explore this one-stop resource for reversible addition-fragmentation chain transfer polymerization from a leading voice in chemistry 

RAFT Polymerization: Methods, Synthesis and Applications delivers a comprehensive and insightful analysis of reversible addition-fragmentation chain transfer polymerization (RAFT) and its applications to fields as diverse as material science, industrial chemistry, and medicine. This one-stop resource offers readers a detailed synopsis of the current state of RAFT polymerization.  

This text will inspire further research and continue the drive to an ever-increasing range of applications by synthesizing and explaining the more central existing literature on RAFT polymerization. It contains a beginner’s guide on how to do a RAFT polymerization before moving on to much more advanced techniques and concepts, like the kinetics and mechanisms of the RAFT process. The distinguished editors have also included resources covering the four major classes of RAFT agents and recent developments in processes for initiating RAFT polymerization. Readers will also benefit from the inclusion of: 

A thorough introduction to the mechanisms, theory, and mathematical modeling of RAFT 
Explorations of RAFT agent design and synthesis, dithioesters, dithiobenzoates, trithiocarbonates, xanthates, dithiocarbamates, macromonomer RAFT, and RAFT copolymerization 
Discussions of a variety of RAFT architectures, including multiblocks, combs, hyperbranched polymers, and stars 
Treatments of end group transformation, cationic RAFT, high-throughput RAFT, and RAFT in continuous flow 
An examination of sequence defined polymers by RAFT

Perfect for organic chemists, polymer chemists, and materials scientists, RAFT Polymerization: Methods, Synthesis and Applications will also earn a place in the libraries of chemical engineers seeking a one-stop reference for this method of controlled radical polymerization with a wide range of applications in multiple areas. 

Volume 1

Preface

Acknowledgements

xvii

1 Overview of RAFT Polymerization

(4)

Graeme Moad

Ezio Rizzardo

References

(10)

2 Terminology in Reversible Deactivation Radical Polymerization (RDRP) and Reversible Addition-Fragmentation Chain Transfer (RAFT) Polymerization

(10)

Graeme Moad

2.1 Terminology for Reversible Deactivation Radical Polymerization (RDRP)

(3)

2.2 Terminology in Reversible Addition-Fragmentation Chain Transfer (RAFT) Polymerization

(6)

2.3 Terminology That Is Not Ratified by IUPAC

(1)

References

(1)

3 How to Do a RAFT Polymerization

(34)

Almar Postma

Melissa Skidmore

3.1 Introduction

(4)

3.2 IP Landscape

(1)

3.3 General Experimental Conditions

(4)

3.3.1 Initiator

(1)

3.3.2 Solvent

(1)

3.3.3 Temperature

(1)

3.3.4 Pressure

(1)

3.4 RAFT Polymerization of Styrene

(4)

3.4.1 Experimental Procedures for the RAFT Polymerization of Styrene

(3)

3.5 RAFT Polymerization of Methacrylates and Acrylates

(6)

3.5.1 Methacrylates

(1)

3.5.2 Acrylates

(1)

3.5.3 Experimental Procedures for the RAFT Polymerization of Methacrylates

(2)

3.5.4 Experimental Procedures for the RAFT Polymerization of Acrylates

(2)

3.6 RAFT Polymerization of Acrylamides and Methacrylamides

(3)

3.6.1 Methacrylamides

(1)

3.6.2 Acrylamides

(1)

3.6.3 Experimental Procedures for the RAFT Polymerization of Acrylamides and Methacrylamides

(1)

3.7 RAFT Polymerization of Vinyl Esters and Vinyl Amides

(2)

3.7.1 Experimental Procedures for the RAFT Polymerization of Vinyl Esters and Vinyl Amides

(1)

3.8 Copolymers

(2)

3.8.1 Experimental Procedures for RAFT Copolymers

(1)

3.9 Block Copolymers

(3)

3.9.1 Experimental Procedures for RAFT Block Copolymers

(2)

3.10 Conclusion

(1)

References

(5)

4 Kinetics and Mechanism of RAFT Polymerizations

(36)

Michael Buback

4.1 Introduction

(1)

4.2 Ideal RAFT Polymerization Kinetics

(1)

4.3 Pulsed Laser Experiments in Conjunction with EPR Detection

(4)

4.4 Quantum Chemical Calculations of the RAFT Equilibrium

(1)

4.5 Xanthate-, Trithiocarbonate- and Dithiobenzoate-Mediated Polymerizations

(23)

4.5.1 General Aspects of Actual RAFT Polymerizations

(3)

4.5.2 Xanthates

(3)

4.5.3 Trithiocarbonates

(4)

4.5.4 Dithiobenzoates

(1)

4.5.5 The `Missing Step' Reaction

(8)

4.5.6 Kinetic Analysis of Dithiobenzoate-Mediated BA Polymerizations

(2)

4.5.7 Quantum Chemical Calculations for the CIP* -- CPDB Model System

(1)

4.5.8 Dithiobenzoate-Mediated MMA Polymerizations and Model Systems

(1)

4.6 Summary of Results and Concluding Remarks

(2)

References

(4)

5 RAFT Polymerization: Mechanistic Considerations

(44)

John F. Quinn

Graeme Moad

Christopher Barner-Kowollik

5.1 Introduction

(1)

5.2 Role of the R Group

(16)

5.2.1 Chain Transfer and Leaving Group Ability

(1)

5.2.2 Measurement of the Chain Transfer Constant

(6)

5.2.3 Mechanistic Implications for Block Copolymer Synthesis

103

(2)

5.2.4 Re-Initiation and Initialization

105

(4)

5.2.5 R Group Stability and Implications for Chain Transfer Kinetics

109

(1)

5.2.6 Differential Leaving Group Ability and Mechanistic Discrimination

109

(3)

5.3 Role of the Z Group

112

(18)

5.3.1 The Z Group and Radical Addition to the Thiocarbonyl

112

(2)

5.3.2 The Z-Group and Side Reactions

114

(2)

5.3.3 Manipulating Z to Dictate Reactivity: `Switchable' RAFT Agents

116

(2)

5.3.4 The Z-Group and Reaction Kinetics

118

(1)

5.3.5 Intermediate Radical Termination

119

(4)

5.3.6 Slow Fragmentation of the Intermediate Radical

123

(3)

5.3.7 Stability of the Z Group During Reaction

126

(4)

5.4 Light Effects on the Rate of Polymerization

130

(1)

5.5 Conclusion

131

(1)

References

132

(7)

6 Quantum Chemical Studies of RAFT Polymerization

139

(48)

Michelle L. Coote

6.1 Introduction

139

(1)

6.2 Methodology

140

(12)

6.2.1 Electronic Structure Calculations

140

(3)

6.2.2 Kinetics and Thermodynamics

143

(4)

6.2.3 Solvent Effects

147

(1)

6.2.4 Accuracy and Outstanding Challenges

147

(5)

6.3 Computational Modelling of RAFT Kinetics

152

(15)

6.3.1 Simplified Models for Theory and Experiment

153

(3)

6.3.2 Side Reactions

156

(3)

6.3.3 Computational Model Predictions

159

(6)

6.3.4 Ab initio Kinetic Modelling

165

(2)

6.4 Structure-Reactivity Studies

167

(13)

6.4.1 Fundamental Aspects

167

(4)

6.4.2 Structure-Reactivity in Practical RAFT Systems

171

(5)

6.4.3 RAFT Agent Design

176

(4)

6.5 Outlook

180

(1)

Abbreviations

180

(1)

References

181

(6)

7 Mathematical Modelling of RAFT Polymerization

187

(36)

Porfirio Lopez-Dominguez

Ivan Zapata-Gonzalez

Enrique Saldivar-Guerra

Eduardo Vivaldo-Lima

7.1 Introduction

187

(1)

7.2 Deterministic Modelling Techniques (DMTs)

188

(16)

7.2.1 Method of Moments (MM)

188

(2)

7.2.1.1 Homogeneous Systems

190

(4)

7.2.1.2 Heterogeneous Systems

194

(2)

7.2.2 Diffusion-Controlled or CL-Dependent Coefficients

196

(2)

7.2.3 Calculation of Full Molecular Weight Distributions

198

(1)

7.2.3.1 Explicit Integration Methods

199

(2)

7.2.3.2 Probability-Generating Function

201

(1)

7.2.3.3 Calculations Using the Predici® Software

201

(3)

7.3 Stochastic Modelling Techniques (SMTs)

204

(2)

7.3.1 Monte Carlo

204

(1)

7.3.1.1 Homogeneous Systems

205

(1)

7.3.1.2 Heterogeneous Systems

205

(1)

7.4 Hybrid Methods

206

(1)

7.5 Specific or Novel Polymerization Processes

206

(5)

7.5.1 Semibatch Polymerization

206

(2)

7.5.2 Polymerizations in CSTRs/PFR

208

(1)

7.5.3 Branched Copolymerizations

209

(1)

7.5.4 Microwave-Assisted (MA) RAFT Polymerization

210

(1)

7.6 Closing Remarks

211

(1)

Acknowledgments

212

(1)

References

212

(11)

8 Dithioesters in RAFT Polymerization

223

(136)

Graeme Moad

8.1 Introduction

223

(1)

8.2 Mechanism of RAFT Polymerization with Dithioester Mediators

224

(6)

8.2.1 Transfer Coefficients of Dithioesters

226

(4)

8.2.2 RAFT Equilibrium Coefficients with Dithioesters

230

(1)

8.3 Choice of RAFT Agents

230

(7)

8.3.1 Aromatic Dithioesters (Z = Aryl or Heteroaryl)

233

(2)

8.3.2 Functional Aromatic Dithioesters (Z = Aryl or Heteroaryl)

235

(1)

8.3.3 Bis-aromatic Dithioesters (Z = Aryl or Heteroaryl)

235

(1)

8.3.4 Aliphatic Dithioesters (Z = Alkyl or Aralkyl)

236

(1)

8.3.5 Bis-aliphatic Dithioesters (Z = Alkyl or Aralkyl)

237

(1)

8.4 Synthesis of Dithioester RAFT Agents

237

(2)

8.5 Monomers for Dithioester-Mediated RAFT Polymerization

239

(48)

8.5.1 1,1-Disubsituted Monomers

239

(1)

8.5.1.1 Methacrylates

239

(1)

8.5.1.2 Methacrylamides

240

(1)

8.5.1.3 Other 1,1-Disubsituted Monomers

240

(1)

8.5.2 Monosubstituted MAMs

240

(1)

8.5.2.1 Acrylates

240

(33)

8.5.2.2 Acrylamides

273

(2)

8.5.2.3 Styrenics

275

(3)

8.5.2.4 Diene Monomers

278

(1)

8.5.3 1,2-Disubstituted MAMs

279

(1)

8.5.4 Monosubstituted IAMs and LAMs

279

(1)

8.5.5 Monomers with Reactive Functionality

279

(1)

8.5.6 Macromonomers

280

(7)

8.6 Cyclopolymerization

287

(1)

8.7 Ring-Opening Polymerization

287

(1)

8.8 RAFT Crosslinking Polymerization

288

(4)

8.9 RAFT Self-condensing Vinyl Polymerization

292

(1)

8.10 RAFT-Single-Unit Monomer Insertion (RAFT-SUMI) into Dithioesters

292

(3)

8.11 Dithioesters in Mechanism-Transformation Processes

295

(3)

8.11.1 Ring-Opening Polymerization (ROP)

295

(1)

8.11.2 Ring-Opening Metathesis Polymerization (ROMP)

296

(1)

8.11.3 Atom Transfer Radical Polymerization (ATRP)

296

(1)

8.11.4 Nitroxide-Mediated Polymerization (NMP)

297

(1)

8.12 Thermally Initiated RAFT Polymerization with Dithioesters

298

(1)

8.13 Photoinitiated RAFT with Dithioesters

299

(1)

8.14 Redox-Initiated RAFT with Dithioesters

300

(1)

8.15 Reaction Conditions and Side Reactions of Dithioesters

300

(1)

8.16 RAFT Emulsion/Miniemulsion Polymerization Mediated by Dithioesters

301

(1)

8.17 Dithioester Group Removal/Transformation

302

(11)

8.17.1 Dithioester Group Removal by Reaction with Nucleophiles

302

(1)

8.17.2 Dithioester Group Removal by Radical-Induced Reactions

303

(1)

8.17.2.1 Radical-Induced Coupling/Disproportionation

303

(3)

8.17.2.2 Radical-Induced Reduction

306

(1)

8.17.3 Dithioester Group Removal by Oxidation

306

(3)

8.17.4 Dithioester Group Removal by Thermolysis

309

(1)

8.17.5 Electrocyclic Reactions of Dithioesters

310

(1)

8.17.6 Boronic Acid Cross-Coupling

311

(1)

8.17.7 Conclusions and Outlook

311

(2)

Abbreviations

313

(5)

References

318

(41)

9 Trithiocarbonates in RAFT Polymerization

359

(134)

Graeme Moad

9.1 Introduction

359

(1)

9.2 Mechanism of RAFT Polymerization with Trithiocarbonate Mediators

359

(8)

9.2.1 Transfer Coefficients for Trithiocarbonates in RAFT Polymerization

362

(5)

9.2.2 RAFT Equilibrium Coefficients for Trithiocarbonates

367

(1)

9.3 Choice of Homolytic Leaving Group R for Trithiocarbonate RAFT Agents

367

(3)

9.3.1 Homolytic Leaving Group `R' for 1,1-Disubsituted MAMs

368

(1)

9.3.2 Homolytic Leaving Group `R' for Monosubstituted MAMs

369

(1)

9.3.3 Homolytic Leaving Group `R' for IAMs and LAMs

369

(1)

9.3.4 Macro-leaving Group `R' for Block Copolymer Synthesis

369

(1)

9.4 Choice of Activating Group `Z' for Trithiocarbonate RAFT Agents

370

(1)

9.5 Symmetric Trithiocarbonates

370

(8)

9.5.1 Bis-trithiocarbonates

370

(8)

9.6 Non-symmetric Trithiocarbonates

378

(1)

9.7 Functional Trithiocarbonates

379

(29)

9.8 Synthesis of Trithiocarbonates

408

(1)

9.9 Polymer Syntheses with Trithiocarbonates

409

(17)

9.9.1 Methacrylates

409

(15)

9.9.2 Methacrylamides

424

(1)

9.9.3 Other 1,1-Disubstituted Monomers

424

(1)

9.9.4 Acrylates

424

(1)

9.9.5 Acrylamides

424

(1)

9.9.6 Styrenics

425

(1)

9.9.7 Diene Monomers

425

(1)

9.9.8 Other Monosubstituted Monomers (MAMs, IAMs, LAMs), Vinyl Monomers

425

(1)

9.9.9 Monomers with Reactive Functionality

426

(1)

9.10 Macromonomers

426

(1)

9.11 Cyclopolymerization

426

(2)

9.12 Radical Ring-Opening Polymerization

428

(1)

9.13 RAFT Crosslinking Polymerization

428

(2)

9.14 RAFT Self-condensing Vinyl Polymerization

430

(1)

9.15 RAFT-Single-Unit Monomer Insertion (RAFT-SUMI) into Trithiocarbonates

430

(3)

9.16 Trithiocarbonates in Mechanism Transformation Processes

433

(3)

9.16.1 Ring-Opening Polymerization (ROP)

434

(1)

9.16.2 Ring-Opening Metathesis Polymerization (ROMP)

434

(1)

9.16.3 Ring-Opening Opening Alkyne Metathesis Polymerization (ROAMP)

435

(1)

9.16.4 Cationic Polymerization

435

(1)

9.16.5 Anionic Polymerization

435

(1)

9.16.6 Nitroxide Mediated Polymerization (NMP)

435

(1)

9.16.7 Atom Transfer Radical Polymerization (ATRP)

435

(1)

9.17 Photoinitiated RAFT with Trithiocarbonates

436

(1)

9.18 Redox-Initiated RAFT with Trithiocarbonates

436

(1)

9.19 RAFT Emulsion/Miniemulsion/Dispersion Polymerization Mediated by Trithiocarbonates

437

(1)

9.20 Reaction Conditions and Side Reactions of Trithiocarbonates

438

(1)

9.21 Trithiocarbonate Group Removal/Transformation

439

(7)

9.21.1 Trithiocarbonate Group Removal by Radical-Induced Coupling

439

(3)

9.21.2 Trithiocarbonate Group Removal by Radical-Induced Disproportionation

442

(1)

9.21.3 Trithiocarbonate Group Removal by Radical-Induced Reduction

443

(1)

9.21.4 Trithiocarbonate Group Removal by Reaction with Nucleophiles

444

(1)

9.21.5 Trithiocarbonate Group Removal by Thermolysis

444

(2)

9.21.6 Trithiocarbonate Group Removal by Oxidation

446

(1)

9.22 Conclusions and Outlook

446

(1)

Abbreviations

447

(5)

References

452

(41)

10 Xanthates in RAFT Polymerization

493

(56)

Mingxi Wang

Jean-Daniel Marty

Mathias Destarac

10.1 Introduction

493

(1)

10.2 Synthesis of RAFT/MADIX Agents

493

(11)

10.2.1 Reaction of a Xanthate Salt with an Alkylating Agent

500

(1)

10.2.2 Reaction with Xanthogen Disulfides

500

(1)

10.2.3 Xanthates Used as Precursors to Provide New Xanthates

500

(4)

10.3 Experimental Conditions

504

(3)

10.3.1 Initiation

504

(1)

10.3.1.1 Thermal Initiators

504

(1)

10.3.1.2 UV or Visible Light

504

(1)

10.3.1.3 60Co γ-ray Irradiation

505

(1)

10.3.1.4 Redox Initiation

505

(1)

10.3.2 Polymerization Conditions

506

(1)

10.3.2.1 High-Pressure Polymerization

506

(1)

10.3.2.2 Heterogeneous Polymerizations

506

(1)

10.4 Kinetics

507

(1)

10.5 Monomers

508

(6)

10.5.1 Styrenics

508

(1)

10.5.2 Acrylates and Acrylamides

508

(1)

10.5.3 Methacrylates

509

(1)

10.5.4 Vinyl Esters

510

(1)

10.5.5 S-Vinyl Monomers

510

(1)

10.5.6 Vinyl Phosphonic Acid

511

(1)

10.5.7 N-Vinyl Monomers

511

(1)

10.5.8 Halo-olefins

512

(1)

10.5.9 Ethylene

513

(1)

10.5.10 Cyclic Ketene Acetals (CKAs)

513

(1)

10.5.11 Diallyl Monomers

514

(1)

10.6 Macromolecular Architectures

514

(11)

10.6.1 End-Functional Homopolymers/Statistical Copolymers

515

(1)

10.6.2 Block Copolymers

516

(3)

10.6.3 Gradient Copolymers

519

(1)

10.6.4 Cyclic Copolymers

519

(1)

10.6.5 Graft/Comb/Brush Copolymers

520

(1)

10.6.6 Star Polymers

521

(3)

10.6.7 Hyperbranched Polymers/Polymer Gels

524

(1)

10.7 Methodologies for Xanthate End-Group Removal

525

(4)

10.7.1 Nucleophilic Reaction (Aminolysis/Hydrolysis/Ionic Reduction)

525

(1)

10.7.2 Oxidation

526

(1)

10.7.3 Thermolysis

527

(1)

10.7.4 Radical-Induced Reduction

528

(1)

10.8 Industrial Applications of RAFT/MADIX Polymerization

529

(1)

10.9 Conclusion

530

(1)

References

531

(18)

11 Dithiocarbamates in RAFT Polymerization

549

(62)

Graeme Moad

11.1 Introduction

549

(3)

11.2 Dithiocarbamate Transfer Constants

552

(2)

11.3 Dithiocarbamates and RAFT Polymerization

554

(1)

11.4 Monomers for RAFT Polymerization

555

(20)

11.4.1 1,1-Disubstituted MAMs (Methacrylates)

555

(17)

11.4.2 Monosubstituted MAMs (Acrylates, Acrylamides, Styrenes)

572

(1)

11.4.3 LAMs, IAMs (Vinyl Monomers)

572

(3)

11.5 Synthesis of Dithiocarbamate RAFT Agents

575

(5)

11.5.1 Method A -- Reaction of a Carbodithioate Anion with an Alkylating Agent

575

(2)

11.5.2 Method B -- Reaction of a Dithiochloroformate or a Thiocarbonyl-bis-imidazole with a Nucleophile

577

(1)

11.5.3 Method C -- Addition of a Dithioic Acid Across an Olefinic Double Bond

578

(1)

11.5.4 Method D -- Radical-induced Decomposition of a Thiuram Disulfide

578

(2)

11.5.5 Method E -- Ketoform Reaction

580

(1)

11.5.6 Method F -- Other Methods

580

(1)

11.5.7 Method G -- Commercially Available

580

(1)

11.6 Activity of Dithiocarbamate RAFT Agents

580

(7)

11.6.1 Dithiocarbamate RAFT Agents with Balanced Activity

582

(1)

11.6.2 Switchable Dithiocarbamate RAFT Agents

583

(2)

11.6.3 Dithiocarbamates as Mediators of Cationic Polymerization

585

(1)

11.6.4 Dithiocarbamate R Substituents

585

(1)

11.6.5 Prediction of Dithiocarbamate Activity

585

(2)

11.7 Dithiocarbamates in RAFT Emulsion Polymerization

587

(1)

11.8 Dithiocarbamates in Mechanism-Transformation Processes

587

(1)

11.8.1 Ring-Opening Polymerization (ROP)

587

(1)

11.8.2 Ring-Opening Metathesis Polymerization (ROMP)

587

(1)

11.8.3 Atom Transfer Radical Polymerization (ATRP)

588

(1)

11.9 Dithiocarbamate Group Removal/Transformation

588

(3)

11.9.1 Dithiocarbamate Group Removal by Radical-Induced Coupling

588

(1)

11.9.2 Dithiocarbamate Group Removal by Radical-Induced Disproportionation

588

(1)

11.9.3 Dithiocarbamate Group Removal by Radical-Induced Reduction

589

(1)

11.9.4 Dithiocarbamate Group Removal by Reaction with Nucleophiles

589

(1)

11.9.5 Dithiocarbamate Group Removal by Thermolysis

590

(1)

11.9.6 Dithiocarbamate Group Removal by Oxidation

591

(1)

11.9.7 Dithiocarbamate Group Removal by Other Methods

591

(1)

11.10 Dithiocarbamate Z'Z"NC(=S)S groups

591

(2)

11.11 Conclusions

593

(1)

Acknowledgements

593

(1)

Abbreviations

593

(2)

References

595

(16)

12 Photo RAFT Polymerization

611

(36)

Robert Chapman

Kenward Jung

Cyrille Boyer

12.1 Introduction

611

(1)

12.2 Photoinitiation

612

(1)

12.3 Photoiniferter Polymerizations

613

(12)

12.3.1 Catalyst-Free Photoiniferter

614

(3)

12.3.2 Photoredox Catalysis

617

(1)

12.3.2.1 PET-RAFT with Ir/Ru

618

(1)

12.3.2.2 PET-RAFT with Porphyrins

619

(3)

12.3.2.3 Metal-Free Photocatalysts

622

(3)

12.4 Applications

625

(10)

12.4.1 Single Unit Monomer Insertion (SUMI)

625

(3)

12.4.2 Wavelength Orthogonal Polymerization

628

(1)

12.4.3 High-Throughput Polymer Libraries

629

(4)

12.4.4 Hydrogels and 3D Printing

633

(1)

12.4.5 Live Cell Graft Polymerizations

634

(1)

12.5 Conclusions and Outlook

635

(1)

References

636

(11)

Volume 2

13 Redox-Initiated RAFT Polymerization and (Electro)chemical Activation of RAFT Agents

647

(32)

Francesco Lorandi

Marco Fantin

Krzysztof Matyjaszewski

13.1 Introduction

647

(1)

13.2 Redox Initiation

648

(8)

13.3 Chemical Activation of RAFT Agents

656

(4)

13.4 Electrochemical Activation of RAFT Agents

660

(10)

13.4.1 Electrochemistry of RAFT Agents

661

(4)

13.4.2 Direct and Mediated Electro-reduction of RAFT Agents

665

(2)

13.4.2.1 Organic Mediators for cRAFT Polymerizations

667

(1)

13.4.2.2 Activation of RAFT Agents via Electro-reduction of ATRP Catalysts

668

(2)

13.5 Electro-reduction of Radical Initiators

670

(3)

13.6 Conclusions and Perspectives

673

(1)

Acknowledgement

673

(1)

References

673

(6)

14 Considerations for and Applications of Aqueous RAFT Polymerization

679

(28)

Alexander W. Fortenberry

Charles L. McCormick

Adam E. Smith

14.1 Introduction

679

(1)

14.2 Chain Transfer Agents

679

(5)

14.2.1 Hydrolysis of the CTA

680

(1)

14.2.2 Aminolysis

681

(3)

14.3 Initiation

684

(6)

14.3.1 Initiation via Azo-containing Species

684

(1)

14.3.2 Photochemical Initiation

685

(1)

14.3.2.1 Externally Initiated aRAFT Photopolymerization

685

(1)

14.3.2.2 Initiator-Free aRAFT Photopolymerization

686

(2)

14.3.2.3 PET-RAFT Photopolymerizations

688

(2)

14.4 Deoxygenation Methods

690

(6)

14.4.1 PET-RAFT

690

(1)

14.4.2 Enzyme-Catalyzed Deoxygenation

691

(1)

14.4.2.1 Initiation by Thermal Initiation

691

(2)

14.4.2.2 Enzymatic Initiation Systems

693

(3)

14.5 Polymerization-Induced Self-assembly

696

(3)

14.6 Grafting from Biomolecules

699

(2)

References

701

(6)

15 RAFT-Mediated Polymerization-Induced Self-Assembly (PISA)

707

(46)

Franck D'Agosto

Muriel Lansalot

Jutta Rieger

15.1 Introduction

707

(2)

15.2 History/Origin of PISA

709

(1)

15.3 PISA Process

710

(6)

15.3.1 Emulsion, Dispersion, and Precipitation Polymerizations: The Reference Processes

710

(2)

15.3.2 Main Parameters at Play for a Successful PISA at a Glance

712

(1)

15.3.2.1 MacroRAFT Type

712

(1)

15.3.2.2 Initiation in RAFT-PISA

712

(1)

15.3.2.3 Chemical Nature of the Blocks

713

(1)

15.3.3 PITSA, PICA, PIESA, and PIHSA: Different Acronyms However All Boiling Down to PISA

714

(1)

15.3.4 PISA-Inspired Synthesis of Surfactant-Free Latexes

715

(1)

15.4 Reactive/Functional Nano-objects

716

(10)

15.4.1 Via the RAFT Agent: Functionalization of the a-End of the Shell Polymer

717

(1)

15.4.2 Via the Solvophilic Block: Functionalization Along the Shell Polymer

718

(1)

15.4.2.1 A Variety of Functions

718

(1)

15.4.2.2 Surface Functionalization by Sugar Moieties and Amino Acids

719

(1)

15.4.2.3 Fluorinated Shells

720

(1)

15.4.2.4 PISA and CO2

721

(1)

15.4.3 Via the Solvophobic Block: Core Functionalization

722

(1)

15.4.3.1 Fluoroparticles

722

(1)

15.4.3.2 Core-crosslinking

723

(2)

15.4.3.3 Adding a Function Allowing Degradation of the Particle Core

725

(1)

15.4.3.4 CO2-sensitive Particles

725

(1)

15.5 Control over the Particle Morphology

726

(12)

15.5.1 From Spherical to Anisotropic Block Copolymer Particles

726

(2)

15.5.2 Main Parameters that Impact the Particle Morphology

728

(1)

15.5.2.1 Varying the Molar Mass

729

(1)

15.5.2.2 Varying the Chemical Nature of the Solvophobic Block

729

(1)

15.5.2.3 Varying the Topology of the Shell or the Core

730

(1)

15.5.2.4 Varying the Solvent Quality

731

(1)

15.5.2.5 PISA in Aqueous Media: Varying pH and/or Ionic Strength

731

(1)

15.5.2.6 Varying the Block Copolymer Architecture via the RAFT Agent

732

(1)

15.5.3 Strategies to Stir Specific Morphologies

733

(1)

15.5.3.1 Using PICA

733

(1)

15.5.3.2 Using Mesogenic Monomers (PIHSA)

733

(1)

15.5.3.3 Using Ionic Complexes (PIESA) and Hydrogen-Bonding Units

734

(1)

15.5.3.4 Hierarchical Assembly Between Particles

735

(1)

15.5.4 Post-polymerization Morphological Transitions/Chain Reorganization

735

(1)

15.5.4.1 Temperature

735

(1)

15.5.4.2 Ph

736

(1)

15.5.4.3 `Reactive' Groups

736

(1)

15.5.4.4 Light

737

(1)

15.5.4.5 Oxygen

738

(1)

15.6 Applications

738

(2)

15.7 Conclusions

740

(1)

Acknowledgements

741

(1)

Abbreviations

741

(1)

References

742

(11)

16 RAFT-Functional End Groups: Installation and Transformation

753

(52)

Andrew B. Lowe

Elena Dallerba

16.1 Introduction

753

(4)

16.2 Functionalization and Transformation of RAFT Polymers via the R-group

757

(5)

16.3 Thiocarbonylthio End Group Removal and Transformation

762

(31)

16.3.1 Desulfurization of RAFT (Co)Polymers

763

(1)

16.3.1.1 Thermolysis

763

(2)

16.3.1.2 Radical-Mediated Reduction

765

(1)

16.3.1.3 Addition--Fragmentation Coupling

766

(2)

16.3.1.4 Radical-Induced Oxidation

768

(1)

16.3.2 Heteroatom Diels--Alder Chemistry

769

(3)

16.3.3 Generation and Application of Macromolecular Thiols

772

(3)

16.3.3.1 Radical Thiol--Ene Reaction

775

(1)

16.3.3.2 Radical Thiol--Yne Reaction

776

(1)

16.3.3.3 Catalyzed Thiol-Michael Additions

777

(3)

16.3.3.4 Thiol-Isocyanate Modification

780

(2)

16.3.3.5 Thiol-Epoxy Ring Opening

782

(1)

16.3.3.6 Thiol-Halo Substitution

783

(4)

16.3.3.7 Disulfide Reactions

787

(3)

16.3.3.8 Miscellaneous Examples of End Group Transformation and Applications

790

(3)

16.4 Summary

793

(1)

References

794

(11)

17 Sequence-Encoded RAFT Oligomers and Polymers

805

(24)

Joris J. Haven

Jeroen De Neve

Tanja Junkers

References

825

(4)

18 Synthesis and Application of Reactive Polymers via RAFT Polymerization

829

(44)

Martin Gauthier-Jaques

Hatice Mutlu

Heba Gaballa

Patrick Theato

18.1 Introduction

829

(1)

18.2 N-Hydroxysuccinimide (NHS)

830

(2)

18.3 Pentafluorophenyl (PFP) Ester and Its Derivatives

832

(3)

18.4 p-Nitrophenyl Esters and Their Derivatives

835

(1)

18.5 Miscellaneous Activated Ester Functional Group Transformations

836

(1)

18.6 Acetone Oxime (AO)

836

(1)

18.7 Salicylic Acid (SA)

837

(1)

18.8 p-Dialkylsulfonium Phenoxy Ester (DASPE)

837

(1)

18.9 1,1,1,3,33-Hexafluoroisopropanol(HFIP)

838

(1)

18.10 Di(Boc)-Acrylamide (DBAm)

838

(1)

18.11 Acyl Chloride

839

(1)

18.12 AlkylHalide

839

(1)

18.13 Trichlorotriazine (TCT)

840

(1)

18.14 Isocyanate (NCO)

840

(2)

18.15 Azlactone

842

(1)

18.16 Anhydride

842

(1)

18.17 Thiolactone

843

(1)

18.18 Thiol Exchange (Disulphide)/Michael Addition/Thiol-Ene

843

(1)

18.19 Epoxide

843

(2)

18.20 Diels--Alder Cycloaddition

845

(1)

18.21 Triazolinedione

845

(1)

18.22 Carbonyl Groups and their Derivatives

846

(1)

18.23 Copper-Catalysed Azide--Alkyne Cycloaddition (CuAAC)

847

(1)

18.24 Strain-Promoted Azide--Alkyne Cycloaddition (SPAAC)

848

(1)

18.25 Nitrone-- and Nitrile Oxide--Alkyne Cycloadditions (SPANOC/SPANC)

848

(1)

18.26 Cross-coupling Reactions

848

(1)

18.27 Boronic Acid/Diol Condensation

849

(1)

18.28 Multicomponent Reactions (MCR)

849

(1)

18.29 Metal-Ligand Coordination

850

(1)

18.30 Bioapplications of Reactive Polymers

850

(1)

18.31 Drug Delivery

851

(4)

18.32 Bio-conjugation

855

(4)

18.33 Surface/Particle Modification

859

(5)

18.34 Conclusion and Outlook

864

(1)

References

864

(9)

19 RAFT Crosslinking Polymerization

873

(60)

Patricia Perez-Salinas

Porfirio Lopez-Dominguez

Alberto Rosas-Aburto

Julio Cesar Hernandez-Ortiz

Eduardo Vivaldo-Lima

19.1 Introduction

873

(2)

19.2 Structure and Characteristics of Polymer Networks

875

(1)

19.3 RAFT Crosslinking Polymerization

876

(22)

19.3.1 Synthesis Pathways to Obtain Polymer Networks

877

(2)

19.3.2 RAFT Controllers Used in the Synthesis of Polymer Networks

879

(19)

19.4 Synthesis of Polymer Networks by RAFT Copolymerization of Vinyl/Multivinyl Monomers in Supercritical Carbon Dioxide as Green Solvent

898

(6)

19.5 Modelling of Polymer Network Formation

904

(14)

19.5.1 Background on Modelling of Crosslinking and RAFT

906

(1)

19.5.2 Trifunctional Polymer Molecule Modelling Approach

907

(3)

19.5.3 Multifunctional Polymer Molecule Modelling Approach

910

(5)

19.5.4 Kinetic Random Branching Theory (KRBT)

915

(3)

19.6 Closing Remarks

918

(1)

Acknowledgements

918

(1)

References

918

(15)

20 Complex Polymeric Architectures Synthesized through RAFT Polymerization

933

(50)

Thomas G. Floyd

Satu Hakkinen

Matthias Hartlieb

Andrew Kerr

Sebastien Perrier

20.1 Introduction

933

(1)

20.2 RAFT Synthesis of Block Copolymers

933

(15)

20.2.1 Block Copolymer by Sequential Polymerization Steps

934

(1)

20.2.1.1 Choice of CTA

935

(2)

20.2.1.2 Block Order

937

(1)

20.2.1.3 Polymer Livingness

938

(3)

20.2.1.4 Initiation System

941

(1)

20.2.1.5 Further Considerations

942

(1)

20.2.1.6 Multiblock Copolymers

942

(1)

20.2.2 Block Copolymers by Chain Extension of a Pre-functionalized MacroCTA

943

(1)

20.2.3 Block Copolymers by Conjugation of Two Polymeric Chains

944

(1)

20.2.3.1 Block Copolymer Synthesis Through Click Chemistry

945

(2)

20.2.3.2 Supramolecular Block Copolymers

947

(1)

20.2.4 General Guidelines

948

(1)

20.3 Gradient Copolymers

948

(1)

20.4 Cyclic Polymers

949

(1)

20.5 Star-Shaped Polymers

950

(6)

20.5.1 Methods to Produce Star-Shaped Copolymers

950

(1)

20.5.1.1 Divergent Synthesis of Star (Co)Polymers

950

(3)

20.5.1.2 Convergent Synthesis of Star Polymers by RAFT Polymerization

953

(2)

20.5.2 Classification by Composition

955

(1)

20.6 Graft Polymers

956

(8)

20.6.1 Grafting Through

958

(1)

20.6.2 Grafting Onto

959

(1)

20.6.3 Grafting From

960

(3)

20.6.4 General Guidelines

963

(1)

20.7 Hyperbranched Polymers

964

(4)

20.7.1 Self-condensing Vinyl Polymerization

964

(2)

20.7.2 Copolymerization of Multifunctional Monomers

966

(1)

20.7.3 Alternative Methods of Hyperbranched Synthesis

967

(1)

20.7.4 General Guidelines

968

(1)

20.8 Conclusion

968

(1)

Acknowledgements

968

(1)

References

969

(14)

21 Star Polymers by RAFT Polymerization

983

(34)

Stephanie Allison-Logan

Fatemeh Karimi

Mitchell D. Nothling

Greg G. Qiao

21.1 Star Polymers

983

(2)

21.2 Synthesis of Star Polymers via RAFT Polymerization

985

(17)

21.2.1 Core-first Approach

985

(2)

21.2.1.1 Z-group Approach

987

(1)

21.2.1.2 R-group Approach

988

(3)

21.2.1.3 Developments in Synthesis

991

(3)

21.2.2 Arm-first Approach

994

(2)

21.2.2.1 Developments in Synthesis

996

(6)

21.2.3 Grafting-to Approach

1002

(1)

21.3 Application of Star polymers

1002

(8)

21.3.1 Star Polymers in Biomedical Applications

1003

(1)

21.3.2 Star Polymers in Other Applications

1004

(2)

21.3.2.1 Emulsion Stabilization

1006

(1)

21.3.2.2 Advanced Materials

1007

(3)

21.4 Conclusion

1010

(1)

References

1010

(7)

22 Surface and Particle Modification via RAFT Polymerization: An Update

1017

(34)

Julia Pribyl

Brian C. Benicewicz

22.1 Introduction

1017

(3)

22.2 Complex Brush Architectures

1020

(7)

22.3 Bioconjugation and Stimuli-responsive Polymer Brushes

1027

(3)

22.4 Advanced Composites

1030

(9)

22.5 Shaped Polymer-Grafted Particles

1039

(3)

22.6 Conclusion

1042

(1)

Acknowledgements

1042

(1)

References

1043

(8)

23 High-Throughput/High-Output Experimentation in RAFT Polymer Synthesis

1051

(26)

Carlos Guerrero-Sanchez

Roberto Yanez-Macias

Miguel Rosales-Guzman

Marco A. De Jesus-Tellez

Claudia Pinon-Balderrama

Joris J. Haven

Graeme Moad

Tanja Junkers

Ulrich S. Schubert

23.1 Introduction

1051

(1)

23.2 Fundamental Experimentation and Limitations of HT/HO-E in RAFT Polymer Synthesis

1052

(1)

23.3 HT/HO-E Kinetic Investigations

1053

(3)

23.4 Utilization of HT/HO-E for the RAFT Synthesis of Polymer Libraries

1056

(3)

23.5 Applications of RAFT Polymer Libraries in Nanomedicine and Drug Delivery Systems

1059

(6)

23.5.1 Applications of RAFT Polymer Libraries as Antimicrobial Agents

1064

(1)

23.6 Conclusions

1065

(2)

Abbreviations

1067

(2)

Acknowledgements

1069

(1)

References

1069

(8)

24 An Industrial History of RAFT Polymerization

1077

(94)

Graeme Moad

24.1 Introduction

1077

(1)

24.2 Macromonomer RAFT Polymerization

1077

(5)

24.3 Thiocarbonylthio-RAFT Polymerization

1082

(59)

24.3.1 Development of RAFT Polymerization

1086

(11)

24.3.2 RAFT Emulsion Polymerization

1097

(40)

24.3.3 Synthesis of Stars and Nano- or Microgels by RAFT Polymerization

1137

(1)

24.3.4 RAFT Applications

1137

(1)

24.3.5 RAFT Thiocarbonylthio-End-Group Removal/Transformation

1137

(4)

Abbreviations

1141

(1)

References

1141

(30)

25 Cationic RAFT Polymerization

1171

(13)

Mineto Uchiyama

Kotaro Satoh

Masami Kamigaito

25.1 Introduction

1171

(1)

25.2 Background and Overview of Cationic RAFT Polymerizations

1172

(3)

25.2.1 Living Cationic Polymerization and Mechanism

1172

(1)

25.2.2 Overview of Cationic RAFT Polymerizations and Comparison to Radical RAFT Polymerizations

1173

(2)

25.3 Design of Cationic RAFT or DT Polymerizations

1175

(9)

25.3.1 RAFT or DT Agents for Cationic Polymerizations

1175

(4)

25.3.2 Initiators, Cationogens, or Catalysts for Cationic RAFT or DT Polymerizations

1179

(3)

25.3.3 Monomers for Cationic RAFT or DT Polymerizations

1182

(2)

25 A Design of Well-Defined Polymers by Cationic RAFT or DT Polymerizations

1184

(11)

25.4.1 End-Functionalized Polymers

1184

(1)

25.4.2 Block Copolymers

1185

(4)

25.4.3 Star Polymers

1189

(1)

25.5 Summary and Outlook for Cationic RAFT or DT Polymerizations

1190

(1)

Abbreviations

1191

(1)

References

1191

(4)

Index

1195

Graeme Moad obtained his BSc (Hons, First Class, 1974) and PhD (1978) from the University of Adelaide in organic free radical chemistry. Between 1977 and 1979, he undertook post-doctoral research at Pennsylvania State University. He joined CSIRO in 1979 where he currently holds the position of CSIRO fellow. Dr Moad is (co)author of over 200 publications, co-inventor on 38 patent families (17 relate to RAFT) and co-author of the book The Chemistry of Radical Polymerization (3rd edition in preparation). His research interests lie in the fields of polymerization mechanisms, and polymer design and synthesis. In recognition of his work Dr Moad was awarded a CSIRO medal in 2003, the RACIs Battaerd-Jordan Polymer Medal in 2012, a Clunies Ross Award and a Thomson-Reuters' Citation Laureate in 2014, a Warwick University IAS Fellowship, a CSIRO Newton-Turner award and Thomson-Reuters' Highly Cited List in 2015 and the Australian Academy of Science's David Craig Medal for outstanding achievement in the field of Chemistry in 2020. In 2014 he was added to Clarivate Analytics' Hall of Citation Laureates. Dr Moad is currently also an adjunct professor at Monash University, and an honorary professor at the Beijing University of Chemical Technology. He is an Associate Member of the IUPAC Polymer Division and the Division representative on the International Committee for Terminology, Nomenclature and Standards (ICTNS). He is a Fellow of the Royal Australian Chemical Institute and the Australian Academy of Science.

Ezio Rizzardo holds a BSc with First Class Honours in Applied Chemistry from the University of New South Wales (1965) and a PhD in Organic Chemistry from the University of Sydney (1969). Following post-doctoral research in organic synthesis at Rice University (Houston), the Research Institute for Medicine and Chemistry (Boston), and the Australian National University (Canberra), he was appointed in 1976 at the Commonwealth Scientific and Industrial Research Organisation (Melbourne) to explore polymer chemistry. At CSIRO, he has led teams who have devised and developed, among others: radical trapping with nitroxides, nitroxide mediated polymerization (NMP), chain transfer by radical addition-fragmentation, and its reversible version, RAFT polymerization. In recognition of his many achievements, Dr Rizzardo has been awarded Australias highest scientific honour; the Prime Ministers Prize for Science, and the highest civic honour; Companion of the Order of Australia (AC). He is also a Fellow of Australias Scientific Academies (FAA, FTSE) and a Fellow of the Royal Society of London (FRS).

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