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Book Details
Abstract
Nitroxide-mediated polymerization is an important branch of controlled radical polymerization, which has revolutionised the preparation of polymer architectures and compositions. This is the first book dedicated to the topic and covers the history and development of nitroxide-mediated polymerization, as well as current techniques of academic and industrial interest. Nitroxide-Mediated Polymerization gathers together and comprehensively discusses all aspects of nitroxide-mediated polymerization, from fundamental principles through to industrial applications. A specific focus will be dedicated to the principle of the technique, its kinetics aspects, the synthesis of the controlling agents, the range of polymerizable monomers, its potential for preparation of advanced organic and hybrid materials and its status at the industrial stage. The book details all stages of the field, with chapters detailing the history, recent developments and novel materials in this fast developing area. Edited and written by expert researchers working in the field and academia this book focuses on highlighting the kinetic aspects of nitroxide-mediated polymerization, providing insight into the kinetics that can sometimes be hard to follow in published papers. The book will be of interest to polymer chemists and materials scientists at graduate level and above.
Table of Contents
| Section Title | Page | Action | Price |
|---|---|---|---|
| Cover | Cover | ||
| Contents | vii | ||
| Preface | v | ||
| Chapter 1 The History of Nitroxide-mediated Polymerization | 1 | ||
| 1.1 Introduction | 1 | ||
| 1.2 Radical Polymerization | 2 | ||
| 1.3 Initiation Mechanisms in Radical Polymerization by Radical Trapping | 5 | ||
| 1.4 First Examples of Nitroxide-mediated Polymerization | 8 | ||
| 1.4.1 Homopolymer Synthesis | 8 | ||
| 1.4.2 Block Copolymer Synthesis | 14 | ||
| 1.4.3 Graft Copolymer Synthesis | 16 | ||
| 1.4.4 Effects of Alkoxyamine Structure and Polymerization Conditions on Homolysis Rates | 16 | ||
| 1.4.5 End-group Removal | 20 | ||
| 1.5 Developments in NMP 1993-2000 | 21 | ||
| 1.5.1 Xerox Group | 21 | ||
| 1.5.2 Hawker Group | 26 | ||
| 1.5.3 Fukuda Group | 27 | ||
| 1.5.4 Fischer Group | 27 | ||
| 1.5.5 Other Groups | 28 | ||
| 1.6 Conclusions | 29 | ||
| References | 30 | ||
| Chapter 2 Kinetic Aspects of Nitroxide Mediated Polymerization | 45 | ||
| 2.1 Nitroxide Mediated Polymerization (NMP) and Key Reactions that Determine its Kinetics | 45 | ||
| 2.1.1 Persistent Radical Effect (PRE) and its Application for NMP | 48 | ||
| 2.1.2 Equations for NMP and the Phase Diagram Approach | 51 | ||
| 2.1.3 Evidence of the Occurrence of PRE in NMP | 53 | ||
| 2.1.4 Importance of kc | 53 | ||
| 2.1.5 Importance of kd | 57 | ||
| 2.1.6 Importance of the Initiation Stage | 59 | ||
| 2.1.7 Importance of the Side-reactions on the Fate of NMP | 63 | ||
| 2.2 Recombination of Nitroxides and Alkyl Radicals | 66 | ||
| 2.2.1 Techniques and Methods of Determination | 66 | ||
| 2.2.2 Arrhénius Parameters\r | 70 | ||
| 2.2.3 Effects Influencing kc | 71 | ||
| 2.3 The C-ON Bond Homolysis of Alkoxyamines | 84 | ||
| 2.3.1 Techniques and Methods of Determination | 85 | ||
| 2.3.2 Arrhénius Parameters\r | 86 | ||
| 2.3.3 Effects Influencing kd | 88 | ||
| 2.3.4 Other Types of Activation | 101 | ||
| 2.4 Conclusion and Outlook | 102 | ||
| Acknowledgments | 102 | ||
| References | 103 | ||
| Chapter 3 Synthesis of Nitroxides and Alkoxyamines | 114 | ||
| 3.1 Introduction | 114 | ||
| 3.1.1 General Considerations | 115 | ||
| 3.1.2 Nitroxide Preparation | 117 | ||
| 3.1.3 Nitroxide Design | 123 | ||
| 3.2 Synthesis of Alkoxyamines | 135 | ||
| 3.2.1 General Considerations | 135 | ||
| 3.2.2 Alkoxyamine Preparation | 138 | ||
| 3.3 Conclusions | 145 | ||
| References | 146 | ||
| Chapter 4 NMP Under Homogenous Conditions in Bulk, Organic Solvents and Aqueous Systems | 153 | ||
| 4.1 Introduction | 153 | ||
| 4.2 Bulk NMP | 153 | ||
| 4.2.1 Homopolymerizations by Bulk NMP with TEMPO | 155 | ||
| 4.2.2 Bulk NMP with TEMPO-derived Initiators | 166 | ||
| 4.2.3 Bulk NMP with TIPNO | 166 | ||
| 4.2.4 Bulk NMP with SG1 | 172 | ||
| 4.3 NMP in Organic Solvents | 176 | ||
| 4.3.1 NMP with TEMPO in Organic Solvents | 176 | ||
| 4.3.2 NMP with TIPNO in Organic Solvents | 178 | ||
| 4.3.3 NMP with SG1 in Organic Solvents | 180 | ||
| 4.4 NMP in Aqueous Solutions | 181 | ||
| 4.5 Conclusions and Outlook | 184 | ||
| References | 184 | ||
| Chapter 5 Nitroxide-mediated Polymerization in Dispersed Media | 199 | ||
| 5.1 Introduction | 199 | ||
| 5.2 Nitroxide-mediated (Mini)Emulsion Polymerization | 201 | ||
| 5.2.1 Brief Account of Free-radical Polymerization in Miniemulsion and Emulsion | 201 | ||
| 5.2.2 Challenges to Overcome | 205 | ||
| 5.2.3 NMP in Miniemulsion | 206 | ||
| 5.2.4 NMP in Emulsion | 226 | ||
| 5.2.5 NMP in Microemulsion | 242 | ||
| 5.2.6 Compartmentalization Effects | 245 | ||
| 5.3 Nitroxide-mediated Dispersion Polymerization | 246 | ||
| 5.3.1 Dispersion Polymerization in Common Solvents | 247 | ||
| 5.3.2 Dispersion Polymerization in Supercritical Carbon Dioxide (scCO2) | 251 | ||
| 5.4 Nitroxide-mediated Precipitation Polymerization | 253 | ||
| 5.5 Nitroxide-mediated Suspension Polymerization | 255 | ||
| 5.6 Conclusion | 256 | ||
| References | 257 | ||
| Chapter 6 Recent Developments in Nitroxide Mediated Polymerization | 264 | ||
| 6.1 Introduction | 264 | ||
| 6.2 Nitrone Spin Trapping Methods | 265 | ||
| 6.2.1 Spin Trapping in Radical Polymerization | 265 | ||
| 6.2.2 Enhanced Spin Capturing Polymerization | 266 | ||
| 6.2.3 Nitrone-mediated Radical Coupling | 272 | ||
| 6.2.4 Block Copolymer Formation Based on ESCP and NMRC Polymers | 273 | ||
| 6.2.5 Complex Macromolecular Architectures Based on ESCP/NMRC | 275 | ||
| 6.3 In Situ Nitroxide Mediated Polymerization | 281 | ||
| 6.4 Light-sensitive Alkoxyamines: Towards Nitroxide Mediated Photopolymerization (NMP2) | 285 | ||
| 6.4.1 Light-sensitive Alkoxyamines | 288 | ||
| 6.4.2 Towards Nitroxide Mediated Photopolymerization: NMP2 | 292 | ||
| References | 300 | ||
| Chapter 7 NMP of Methacrylic Esters: How to Circumvent a Long-time Obstacle | 305 | ||
| 7.1 Introduction | 305 | ||
| 7.2 Reasons for the Failure of the NMP of MMA | 306 | ||
| 7.3 Development of Dedicated Nitroxides | 316 | ||
| 7.4 The Copolymerization Approach | 325 | ||
| 7.5 New NMP Alternatives to Control Methacrylic Esters | 331 | ||
| 7.6 PMMA-based Materials Prepared by NMP | 336 | ||
| 7.7 Conclusion | 343 | ||
| References | 343 | ||
| Chapter 8 Complex Macromolecular Architectures Prepared by NMP | 349 | ||
| 8.1 Introduction | 349 | ||
| 8.2 General Considerations | 350 | ||
| 8.3 Linear Topologies by Unimolecular or Bimolecular Initiation | 352 | ||
| 8.3.1 Styrene-based Copolymers | 352 | ||
| 8.3.2 Acrylate-based Copolymers | 355 | ||
| 8.3.3 Methacrylate-based Copolymers | 358 | ||
| 8.3.4 Acrylamide-based Copolymers | 358 | ||
| 8.3.5 Acrylonitrile and Acrylic Acid-based Copolymers | 360 | ||
| 8.3.6 Diene-based Copolymers | 360 | ||
| 8.4 Linear Topologies by Combination of NMP with Other Polymerization Methods | 361 | ||
| 8.5 Non-linear Topologies | 361 | ||
| 8.5.1 Grafted Copolymers | 361 | ||
| 8.5.2 Star Copolymers | 370 | ||
| 8.5.3 Hyperbranched Copolymers | 373 | ||
| 8.5.4 Cyclic Polymers | 373 | ||
| 8.6 Conclusion | 375 | ||
| References | 375 | ||
| Chapter 9 NMP-derived Materials for Biomedical Applications | 383 | ||
| 9.1 Introduction | 383 | ||
| 9.2 Glycopolymers | 384 | ||
| 9.3 Bioconjugates | 387 | ||
| 9.4 Polymer Nanocomposites and Biocompatible Surfaces | 394 | ||
| 9.5 Polymeric Nanoparticles | 397 | ||
| 9.6 Conclusion | 401 | ||
| References | 401 | ||
| Chapter 10 Surface-initiated Nitroxide-mediated Polymerization | 406 | ||
| 10.1 Scope | 406 | ||
| 10.2 Introduction | 407 | ||
| 10.2.1 Polymer Brushes | 408 | ||
| 10.2.2 Controlling Systems | 415 | ||
| 10.3 SI-NMP on Different Substrates | 420 | ||
| 10.3.1 Silicon Wafers | 420 | ||
| 10.3.2 Silica Particles (Dense and Mesoporous) | 423 | ||
| 10.3.3 Other Inorganic Surfaces | 426 | ||
| 10.3.4 Organic Surfaces | 431 | ||
| 10.4 Perspective on Future Research Opportunities | 433 | ||
| Acknowledgments | 436 | ||
| References | 436 | ||
| Chapter 11 Novel Materials: From Nanoporous Materials to Micro-Electronics | 441 | ||
| 11.1 Introduction | 441 | ||
| 11.2 Photoresists/Imprint Lithography | 443 | ||
| 11.2.1 Photoresists Using Copolymers Synthesized by NMP | 444 | ||
| 11.3 Polymer Templating and Nanoporous Membranes | 447 | ||
| 11.3.1 Nanoporous Thin Films | 448 | ||
| 11.3.2 Breath Figure (BF) Technique | 451 | ||
| 11.3.3 Inorganic Templating | 452 | ||
| 11.4 Proton Exchange Membrane and Ionic Polymers | 455 | ||
| 11.4.1 Styrene Sulfonate Containing Polymers | 455 | ||
| 11.4.2 Polymer Ionic Liquids | 457 | ||
| 11.5 Organic Electronics | 460 | ||
| 11.5.1 Organic Photovoltaic (OPV) Devices | 461 | ||
| 11.5.2 Polymer Organic Light-emitting Diodes (PLEDs or Polymer OLEDs) | 472 | ||
| 11.5.3 Memory Device Applications | 478 | ||
| 11.6 Materials Property Enhancement and Industrial Implementation | 480 | ||
| 11.7 Conclusion and Perspective | 482 | ||
| References | 483 | ||
| Subject Index | 494 |