Click Polymerization 1 0 0 P F 8- 0 1 0 1 0 8 8 7 1 8 7 9 9/ 3 0 1 0. 1 oi: d g | or c. s s.r b u p s:// p htt n o 8 1 0 2 st u g u A 8 2 n o d e h s bli u P View Online Polymer Chemistry Series Editor-in-chief: Ben Zhong Tang, The Hong Kong University of Science and Technology, Hong Kong, 1 China 0 0 P F 08- Series editors: 1 10 Alaa S. Abd-El-Aziz, University of Prince Edward Island, Canada 0 88 Jianhua Dong, National Natural Science Foundation of China, China 7 81 Jeremiah A. Johnson, Massachusetts Institute of Technology, USA 7 9/9 Toshio Masuda, Shanghai University, China 3 0 Christoph Weder, University of Fribourg, Switzerland 1 0. 1 doi: Titles in the series: g | 1: Renewable Resources for Functional Polymers and Biomaterials or c. 2: Molecular Design and Applications of Photofunctional Polymers and s bs.r Materials u ps://p 34:: FFuunncdtaimoneanl tPaolsl yomf Cerosn ftorro lNleadn/oLmiveindgic Rinaedical Polymerization htt n 5: Healable Polymer Systems o 8 6: Thiol-X Chemistries in Polymer and Materials Science 1 0 2 7: Natural Rubber Materials: Volume 1: Blends and IPNs ust 8: Natural Rubber Materials: Volume 2: Composites and Nanocomposites g u A 9: Conjugated Polymers: A Practical Guide to Synthesis 8 2 10: Polymeric Materials with Antimicrobial Activity: From Synthesis to n d o Applications e h 11: Phosphorus-Based Polymers: From Synthesis to Applications s bli 12: Poly(lactic acid) Science and Technology: Processing, Properties, u P Additives and Applications 13: Cationic Polymers in Regenerative Medicine 14: Electrospinning: Principles, Practice and Possibilities 15: Glycopolymer Code: Synthesis of Glycopolymers and their Applications 16: Hyperbranched Polymers: Macromolecules in-between Deterministic Linear Chains and Dendrimer Structures 17: Polymer Photovoltaics: Materials, Physics, and Device Engineering 18: Electrical Memory Materials and Devices 19: Nitroxide Mediated Polymerization: From Fundamentals to Applications in Materials Science 20: Polymers for Personal Care Products and Cosmetics View Online 21: Semiconducting Polymers: Controlled Synthesis and Microstructure 22: Bio-inspired Polymers 23: Fluorinated Polymers: Volume 1: Synthesis, Properties, Processing and Simulation 1 24: Fluorinated Polymers: Volume 2: Applications 0 P0 25: Miktoarm Star Polymers: From Basics of Branched Architecture to F 8- Synthesis, Self-assembly and Applications 0 1 0 26: Mechanochemistry in Materials 1 0 8 27: Macromolecules Incorporating Transition Metals: Tackling Global 8 7 1 Challenges 8 7 9 28: Molecularly Imprinted Polymers for Analytical Chemistry Applications 9/ 3 29: Photopolymerisation Initiating Systems 0 1 0. 30: Click Polymerization 1 oi: d g | or c. s s.r b u p s:// p htt n o 8 1 0 2 st u g u A 8 2 n o d e h s bli u P How to obtain future titles on publication: A standing order plan is available for this series. A standing order will bring delivery of each new volume immediately on publication. For further information please contact: Book Sales Department, Royal Society of Chemistry, Thomas Graham House, Science Park, Milton Road, Cambridge, CB4 0WF, UK Telephone: +44 (0)1223 420066, Fax: +44 (0)1223 420247 Email: [email protected] Visit our website at www.rsc.org/books View Online 1 0 0 P F 8- 0 1 0 1 0 8 8 7 1 8 7 9/9 3 0 1 0. 1 oi: d g | or c. s s.r b u p s:// p htt n o 8 1 0 2 st u g u A 8 2 n o d e h s bli u P View Online Click Polymerization 1 0 0 P F 8- Edited by 0 1 0 1 0 8 Anjun Qin 8 7 1 South China University of Technology, China 8 7 9 Email: [email protected] 9/ 3 0 1 0. and 1 oi: d g | Ben Zhong Tang or c. The Hong Kong University of Science and Technology, China s bs.r Email: [email protected] u p s:// p htt n o 8 1 0 2 st u g u A 8 2 n o d e h s bli u P View Online 1 0 0 P F 8- 0 1 0 1 0 8 8 7 1 8 7 Polymer Chemistry Series No. 30 9 9/ 3 0 Print ISBN: 978-1-78262-716-6 1 10. PDF ISBN: 978-1-78801-010-8 oi: EPUB ISBN: 978-1-78801-501-1 d g | Print ISSN: 2044-0790 c.or Electronic ISSN: 2044-0804 s s.r b A catalogue record for this book is available from the British Library u p ps:// © The Royal Society of Chemistry 2018 htt on All rights reserved 8 1 0 2 Apart from fair dealing for the purposes of research for non-commercial purposes or for ust private study, criticism or review, as permitted under the Copyright, Designs and Patents g Au Act 1988 and the Copyright and Related Rights Regulations 2003, this publication may 8 not be reproduced, stored or transmitted, in any form or by any means, without the prior 2 on permission in writing of The Royal Society of Chemistry, or in the case of reproduction in ed accordance with the terms of licences issued by the Copyright Licensing Agency in the UK, h blis or in accordance with the terms of the licences issued by the appropriate Reproduction Pu Rights Organization outside the UK. Enquiries concerning reproduction outside the terms stated here should be sent to The Royal Society of Chemistry at the address printed on this page. Whilst this material has been produced with all due care, The Royal Society of Chemistry cannot be held responsible or liable for its accuracy and completeness, nor for any consequences arising from any errors or the use of the information contained in this publication. The publication of advertisements does not constitute any endorsement by The Royal Society of Chemistry or Authors of any products advertised. The views and opinions advanced by contributors do not necessarily reflect those of The Royal Society of Chemistry which shall not be liable for any resulting loss or damage arising as a result of reliance upon this material. The Royal Society of Chemistry is a charity, registered in England and Wales, Number 207890, and a company incorporated in England by Royal Charter (Registered No. RC000524), registered office: Burlington House, Piccadilly, London W1J 0BA, UK, Telephone: +44 (0) 207 4378 6556. For further information see our web site at www.rsc.org Printed in the United Kingdom by CPI Group (UK) Ltd, Croydon, CR0 4YY, UK 7 0 0 P F 8- 0 Preface 1 0 1 0 8 8 7 1 8 7 9 9/ 3 0 1 10. Click chemistry, conceptually coined by Sharpless and colleagues in 2001, oi: refers to a class of elegant reactions with such wonderful advantages as d g | high efficiency, regio- and/or stereospecificity, atom economy, and no or c. offensive by-product. In 2002, the first click reaction, Cu(i)-catalyzed s s.r azide–alkyne cycloaddition (CuAAC), was reported. Attracted by its fantas- b u p tic click merits, polymer scientists embarked on developing CuAAC into a ps:// click polymerization. As a result, Cu(i)-catalyzed azide–alkyne click polym- n htt erization (CuAACP) was successfully established and applied in preparing o 8 a number of functional polymers with linear and hyperbranched struc- 1 20 tures. Inspired by the great success of CuAACP and thanks to the rapid ust development of new click reactions of small molecules, such as thiol-ene/ g Au yne, Diels–Alder, and amino-yne click reactions, polymer scientists have 28 also successfully developed these reactions into new kinds of click polym- n o erizations, i.e. thiol-ene/yne, Diels–Alder, and amino-yne click polymeriza- d he tions, and so on. s bli Thanks to the kind invitation from the editors of the Royal Society of u P Chemistry (RSC), we embarked on the preparation of this book, which is specifically dedicated to the research of click polymerization. We invited a group of active polymer scientists in the area to contribute to this book on topics including transition metal-catalyzed and metal-free azide–alkyne click polymerizations, catalyst-free click polymerization based on nitrile N-oxides, thiol-yne click polymerization, proton transfer polymerization through thiol- epoxy and amine-epoxy ‘click’ reactions and multicomponent polymeriza- tion mediated by click chemistry. This book is aimed at providing a valuable reference for readers who are interested in click polymerization. Although we have tried our best to make the book comprehensive, some important work may have been omitted, due   Polymer Chemistry Series No. 30 Click Polymerization Edited by Anjun Qin and Ben Zhong Tang © The Royal Society of Chemistry 2018 Published by the Royal Society of Chemistry, www.rsc.org vii View Online viii Preface to the limited space of the book and the rapid development in the area. Thus, we hope that the readers will provide us with constructive comments, so that we may modify the book in its next edition. We would like to thank all of the authors of this book for their enthusias- 7 tic contributions. We also appreciate the Royal Society of Chemistry editors, 0 P0 Mr Connor Sheppard, Dr Leanne Marle and Dr Robin Driscoll for their F 8- enthusiastic encouragement and technical support. We hope this book will 0 1 0 stimulate new efforts, trigger new ideas, and encourage more scientists to 1 0 8 devote themselves to further developing click polymerization. 8 7 1 78 Anjun Qin 9 9/ Center for Aggregation-Induced Emission 3 10 State Key Laboratory of Luminescent Materials and Devices 0. 1 South China University of Technology oi: d g | Ben Zhong Tang c.or Department of Chemistry s s.r The Hong Kong University of Science & Technology b u p s:// p htt n o 8 1 0 2 st u g u A 8 2 n o d e h s bli u P 9 0 0 P F 8- 0 Contents 1 0 1 0 8 8 7 1 8 7 9 9/ 3 0 1 10. Chapter 1 Overview of Click Polymerization 1 oi: Die Huang, Anjun Qin and Ben Zhong Tang d g | or c. 1.1 Introduction 1 s s.r 1.2 CuAACPs 3 b u p 1.3 Ru(ii)-Catalyzed Azide–Alkyne Click ps:// Polymerization (RuAACP) 7 n htt 1.4 Metal-free Click Polymerization (MFCP) of o 8 Azides and Alkynes 9 1 20 1.5 Organobase-mediated AACP 10 ust 1.6 Thiol-ene Click Polymerization 11 g Au 1.7 Thiol-yne Click Polymerization 12 28 1.7.1 Photo-/Thermo-initiated Thiol-yne n o Click Polymerization 12 d he 1.7.2 Amine-mediated Thiol-yne Click s bli Polymerization 15 u P 1.7.3 Transition Metal-catalyzed Thiol-yne Click Polymerization 16 1.7.4 Spontaneous Thiol-yne Click Polymerization 17 1.8 Diels–Alder Click Polymerization 17 1.9 Other Click Polymerizations 19 1.10 Conclusion and Perspective 21 Acknowledgements 22 References 23   Polymer Chemistry Series No. 30 Click Polymerization Edited by Anjun Qin and Ben Zhong Tang © The Royal Society of Chemistry 2018 Published by the Royal Society of Chemistry, www.rsc.org ix View Online x Contents Chapter 2 Transition Metal-catalyzed Click Polymerization 36 Die Huang, Anjun Qin and Ben Zhong Tang 2.1 Introduction 36 9 2.2 CuAACPs 37 0 P0 2.2.1 Mechanism of CuAAC 37 F 8- 2.2.2 CuSO /SA-catalyzed AACP 38 0 4 1 0 2.2.3 Photoinitiated CuAACP 51 1 0 8 2.2.4 CuX-catalyzed AACP 53 8 7 1 2.2.5 Cu(i) Complex-catalyzed AACP 60 8 7 9 2.2.6 Supported Cu(i)-catalyzed AACP 69 9/ 3 2.3 Ru(ii)-catalyzed AACP 74 0 1 0. 2.4 Conclusion and Perspective 77 1 oi: Acknowledgements 78 d g | References 78 or c. s s.r Chapter 3 Metal-free Azide–Alkyne Click Polymerization 86 b pu Baixue Li, Anjun Qin and Ben Zhong Tang s:// p htt 3.1 Introduction 86 n 8 o 3.2 MFCP of Aroylacetylenes and Azides 87 1 0 3.3 MFCP of Propiolates and Azides 94 2 st 3.4 MFCP of Activated Azides and Alkynes 104 u g u 3.5 Organobase-mediated MFCP of Azides and A 8 Alkynes 111 2 on 3.6 Summary and Outlook 113 d e References 114 h s bli u P Chapter 4 Catalyst-free Click Polymerization Using Nitrile N-Oxides Applicable to Various Dipolarophiles 122 T. Takata, Y. Koyama and H. Sogawa 4.1 Introduction 122 4.2 Preparation Methods for Nitrile N-Oxides 126 4.3 Reactions of Nitrile N-Oxides 128 4.4 Aromatic Nitrile N-Oxides 132 4.4.1 Syntheses of Homoditopic Aromatic Nitrile N-Oxides 132 4.4.2 Click Polymerization Using Aromatic Nitrile N-Oxides 136 4.5 Aliphatic Nitrile N-Oxides 147 4.5.1 Syntheses, Structures and Reactions of Aliphatic Nitrile N-Oxides 148 4.5.2 Click Polymerization and Cross-linking Using Aliphatic Nitrile N-oxides 156 4.6 Conclusion 162