Handbook of Telechelic Polyesters, Polycarbonates, and Polyethers edited by Sophie M. Guillaume
Handbook of Telechelic Polyesters, Polycarbonates, and Polyethers
Handbook of Telechelic Polyesters Polycarbonates! and Polyethers edited by Sophie M. Guillaume! 1rrr PAN STANFORD PUBLISHING
Published by Pan Stanford Publishing Pte. Ltd. Penthouse Level, Suntec Tower 3 8 Temasek Boulevard Singapore 038988 Email: editorial@panstanford.com Web: www.panstanford.com British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library. Handbook of Telechelic Polyesters, Polycarbonates, and Polyethers Copyright 2017 by Pan Stanford Publishing Pte. Ltd. All rights reserved. This book, or parts thereof, may not be reproduced in any form or by any means, electronic or mechanical, including photocopying, recording or any information storage and retrieval system now known or to be invented, without written permission from the publisher. For photocopying of material in this volume, please pay a copying fee through the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, USA. In this case permission to photocopy is not required from the publisher. ISBN 978-981-4745-62-8 (Hardcover) ISBN 978-1-315-36446-9 (ebook) Printed in the USA
Contents Preface xiii 1. Basic Chemistry for the Synthesis of Telechelic Polyesters and Polycarbonates 1 Takeshi Endo and Atsushi Sudo 1.1 Introduction 1 1.2 Synthesis of Telechelic Polyesters and Polycarbonates by ROP: Fundamental Aspects 3 1.3 Cationic Ring-Opening Polymerization 5 1.4 Anionic and Coordination-Insertion Mechanisms 6 1.5 Activated Monomer Mechanism 12 1.6 Alternating Copolymerization of Epoxides with Other Compounds 15 1.7 Radical Ring-Opening Polymerization 17 1.8 Anionic Polymerization of Ketenes 22 1.9 Summary and Prospects 24 2. Telechelic Polyesters and Polycarbonates Prepared by Enzymatic Catalysis 29 Susana Torron, Mats K. G. Johansson, Eva Malmström, Linda Fogelström, Karl Hult, and Mats Martinelle 2.1 Synthesis of Telechelic Polyesters and Polycarbonates Using Enzyme Catalysis 29 2.1.1 Lipases in the Synthesis of Telechelic Polymers 31 2.2 Synthetic Strategies toward the Formation of Telechelic Polyesters and Polycarbonates by Enzyme Catalysis 34 2.2.1 Formation of Telechelic Polymers Using Enzyme Catalysis 36 2.2.1.1 Synthesis of telechelic polymers by enzymatic ring-opening polymerization (erop) 36
vi Contents 2.2.1.2 Synthesis of telechelic polymers by enzymatic polycondensation 42 2.2.1.3 Synthesis of telechelic polymers by enzymatic transacylation (scrambling) 44 2.2.2 The Importance of Appropriately Adjusted Reaction Conditions 45 2.2.2.1 Water as a nucleophile for hydrolytic enzymes 45 2.2.2.2 Effect of reaction temperature 45 2.2.2.3 Why is it challenging to obtain polymers of higher molar mass by enzyme catalysis? 46 2.2.3 End Capping of Polyesters and Polycarbonates 46 2.3 Some Illustrative Examples of Telechelic Polymers Using Enzyme Catalysis 47 2.3.1 Some Illustrative Examples of Telechelic Polyesters and Polycarbonates Obtained via erop 47 2.3.1.1 Hydroxyl end-functionalized telechelic polymers 47 2.3.1.2 Thiol end-functionalized telechelic polymers 49 2.3.1.3 Acrylate/methacrylate endfunctionalized telechelic polymers 51 2.3.2 Telechelic Polyesters and Polycarbonates Obtained by Enzymatic Polycondensation 53 2.3.3 Telechelic Polyesters and Polycarbonates Obtained by Combination of Enzymatic ROP and epc 54 2.4 Possible Applications of Telechelic Polyesters and Polycarbonates Synthesized Using Enzymes 55 2.5 Summary and Prospects 57
Contents vii 3. Telechelic Polyhydroxyalkanoates/Polyhydroxybutyrates (PHAs/PHBs) 65 Abdulkadir Alli, Baki Hazer, Grażyna Adamus, and Marek Kowalczuk 3.1 Introduction 65 3.2 Natural PHAs/PHBs Derived from Various Bacteria 67 3.3 Synthetic Telechelic PHAs 71 3.3.1 Anionic ROP toward Synthetic Telechelic PHBs 73 3.3.2 Other ROP Approaches toward Synthetic Telechelic PHB Analogues 79 3.4 Chemical Modifications of Telechelic PHAs 80 3.5 Block and Graft Copolymers Derived from Telechelic PHAs 89 3.6 Summary and Prospects 102 4. Telechelic Poly(ε-Caprolactone)s: Synthesis and Applications 115 Timm Heek, Marc Behl, and Andreas Lendlein 4.1 Introduction 115 4.2 Synthesis of Telechelic PCLs 120 4.2.1 General Polymerization Methods 120 4.2.2 Postpolymerization Chemical Modification Methods 129 4.3 Applications of Telechelic PCLs 132 4.3.1 Telechelic PCLs for the Synthesis of Nanosized Drug Delivery Systems 132 4.3.1.1 Block copolymers 134 4.3.1.2 Stimuli-responsive block copolymers 137 4.3.1.3 Multiblock polyester(urea) urethanes 140 4.3.1.4 Supramolecular block copolymers based on noncovalent interactions 142 4.3.1.5 Inorganic hybrid polymer systems 144 4.3.1.6 Linear dendritic hybrid block copolymers 146
viii Contents 4.3.2 Telechelic PCLs for the Synthesis of Shape-Memory Polymers 147 4.3.2.1 Covalently crosslinked networks 149 4.3.2.2 Physically crosslinked networks 153 4.3.2.3 Reversible crosslinked polymer networks 157 4.4 Summary and Prospects 159 5. Telechelic Poly(Lactic Acid)s and Polylactides 185 Malgorzata Basko and Andrzej Duda 5.1 Introduction 185 5.2 Direct Synthesis of Telechelic Polylactides 188 5.2.1 Telechelic Polylactides from Polycondensation 188 5.2.2 Telechelic Polylactides from Ring-Opening Polymerization 192 5.2.2.1 Telechelic polylactides from metal-catalyzed polymerization 192 5.2.2.2 Telechelic polylactides from organocatalyzed polymerization 208 5.3 Telechelic Polylactides from Postpolymerization Chemical Modification of a Prepolymer 214 5.4 Summary and Prospects 219 6. Telechelic Polycarbonates 233 Sophie M. Guillaume 6.1 Introduction 233 6.2 Telechelic Bisphenol-A and Other Polycarbonates from Polycondensation 236 6.3 Telechelic Polycarbonates from Epoxides and Carbon Dioxide Copolymerization 239 6.3.1 Telechelic Polycarbonates from Propylene Oxide and Carbon Dioxide Copolymerization 242
Contents ix 6.3.2 Telechelic Polycarbonates from Cyclohexene Oxide and Carbon Dioxide Copolymerization 246 6.3.3 Telechelic Polycarbonates from Other Epoxides and Carbon Dioxide Copolymerization 251 6.3.4 Concluding Remarks on the Epoxide and Carbon Dioxide Copolymerization Synthesis of Telechelic Polycarbonates 253 6.4 Telechelic Polycarbonates from Enzyme-Catalyzed Polymerization 254 6.4.1 Telechelic Polycarbonates from Enzyme-Catalyzed Polycondensation 254 6.4.2 Telechelic Polycarbonates from Enzyme-Catalyzed Ring-Opening Polymerization 255 6.4.2.1 Telechelic poly(trimethylene carbonate) 256 6.4.2.2 Other telechelic polycarbonates 259 6.4.2.3 Telechelic carbonate copolymers 261 6.4.3 Concluding Remarks on the Enzyme-Catalyzed Synthesis of Telechelic Polycarbonates 266 6.5 Telechelic Polycarbonates from Metal-Catalyzed and Organocatalyzed Ring-Opening Polymerization 267 6.5.1 Hydroxy Telechelic Polycarbonates 268 6.5.1.1 Hydroxy telechelic polycarbonates from metal-based catalysts 268 6.5.1.2 Hydroxy telechelic polycarbonates from organic catalysts 280 6.5.2 Other Nonhydroxy Telechelic Polycarbonates 286 6.5.3 Concluding Remarks on the ROP Synthesis of Telechelic Polycarbonates 289
x Contents 6.6 Telechelic Polycarbonates as Precursors to Polyurethanes 289 6.7 Summary and Prospects 293 7. Telechelic Polyethers by Living Polymerizations and Precise Macromolecular Engineering 309 Pierre J. Lutz, Bruno Ameduri, and Frédéric Peruch 7.1 Introduction 309 7.2 From Monofunctional to Multifunctional Telechelic PEOs via AROP 312 7.2.1 General Considerations on AROP of Ethylene Oxide 312 7.2.2 Linear Telechelic PEOs via AROP of Ethylene Oxide 314 7.2.3 Multifunctional Telechelic PEOs via AROP of Ethylene Oxide 315 7.3 Polyether Telechelics and Macromonomers 317 7.3.1 General Considerations of Macromonomers 317 7.3.2 PEO Macromonomers Prepared by Initiation 317 7.3.3 PEO Macromonomers Prepared by Deactivation 322 7.3.4 Heterobifunctional PEO Macromonomers 325 7.4 Graft Copolymers 328 7.4.1 General Considerations on PEO Graft Copolymers 328 7.4.2 The Grafting-onto Process 330 7.4.2.1 Grafting-onto via AROP 330 7.4.2.2 Grafting-onto via telechelic PEOs 331 7.4.2.3 Noncovalent grafting-onto 334 7.4.3 The Grafting-from Process 335 7.4.3.1 General remarks on grafting-from processes 335 7.4.3.2 Grafting-from via AROP of EO 336 7.4.3.3 Grafting-from hydrophilic PEO-based copolymers 337
Contents xi 7.4.4 Grafting-through Processes: A Macromonomer Approach 337 7.4.4.1 General considerations on the grafting-through process 337 7.4.4.2 PEO graft copolymers via the macromonomer-based grafting-through method 339 7.5 Amphiphilic Telechelic PEOs 343 7.5.1 General Considerations on the Water Solubilty of (Amphiphilic) Telechelic PEOs 343 7.5.2 Linear Amphiphilic PEOs End-Modified with Short Alkanes 344 7.5.3 Branched Amphiphilic PEOS End-Capped with Short Alkanes 346 7.5.4 Amphiphilic Telechelic PEOs and POSS 347 7.5.4.1 General remarks on polyoctahedral silsesquioxanes 347 7.5.4.2 PEO-grafted POSS structures 348 7.6 Fluorinated Telechelic Polyethers 351 7.6.1 General Considerations and Interest of Fluorinated Telechelic Polyethers 351 7.6.2 Synthesis of Fluorinated Telechelic Polyethers 353 7.7 Telechelic Polytetrahydrofuran 362 7.7.1 General Considerations 362 7.7.2 Telechelic PTHF Synthesis and Their Applications 366 7.7.2.1 PTHF macromonomers synthesis and their use 366 7.7.2.2 Other telechelic polymers 366 7.7.2.3 Macromolecular architectures 369 7.8 Telechelic Poly(Oxymethylene) 372 7.9 Summary and Prospects 373 Index 401
Preface Telechelic polymers are defined, according to the IUPAC, as polymeric molecules capable of entering into further polymerization or other reactions through their reactive end groups. Such polymers have garnered a great deal of scientific interest due to their reactive chain-end functions, enabling them to enter the composition of more sophisticated polymeric materials. Endfunctional polymers can react selectively with other chemically different monomers, thus acting as macroinitiators, to afford ABor ABA-type block copolymers otherwise inaccessible. Also, upon reaction of such telechelic building blocks with other functional (macro)molecules featuring a complementary antagonist reactive group, polymer networks become accessible. One famous example with a major commercial market are the polyurethanes prepared from hydroxy telechelic polymers and difunctional isocyanates. The development of telechelic polymers has benefited from advances in the design and synthesis of well-defined tailormade polymers through living and controlled polymerization techniques. Telechelic polymers can thus be directly synthesized with reactive end groups arising from the initiating moiety, the terminating or chain transfer agent used in chain polymerizations. Alternatively, postpolymerization chemical functionalization also enables to access end-functional polymers. Telechelic polymers are thus a highly valuable tool to access functional polymeric materials with tunable physical properties matching industrial requirements and needs. Handbook of Telechelic Polyesters, Polycarbonates, and Polyethers evidences the high significance of telechelic polymers in the field of polymeric materials commonly referred to as plastics whose annual world production is currently estimated at over 300 million metric tons and that are spread all over our modern lives. This comprehensive book compiles and details basic principles and cutting-edge research in telechelic polyesters, polycarbonates, and polyethers, ranging from synthesis to practical applications. Each chapter is an authoritative account on an explicit topic and
xiv Preface can be read on its own. The general strategies toward telechelic polymers are first discussed in Chapter 1, centered on fundamental aspects of polycondensation reactions, of cationic, anionic, coordination-insertion, radical, and activated monomer mechanisms of the metal-, enzyme-, or otherwise organocatalyzed ring-opening polymerization of cyclic monomers, and of postpolymerization chemical modification methods of polymer precursors. Telechelic polyesters and polycarbonates prepared by enzymatic catalysis are especially highlighted in Chapter 2. For the ease of reading, all main classes of polymers are then covered separately in Chapters 3 6, comprising natural and synthetic polyhydroxyalkanoates and polyhydroxybutyrates, poly(e-caprolactone)s, poly(lactic acid)s, and polylactides, and polycarbonates, such as bisphenol-a polycarbonate, poly(propylene carbonate), poly(trimethylene carbonate), and poly(cyclohexene carbonate), and also including synthetic approaches as well as some illustrative current examples and uses. Chapter 7 similarly addresses polyethers, such as poly(ethylene oxide), poly(tetrahydrofuran), and fluorinated polyethers. Chemical modification of prepolymers into telechelic analogues, applications of hydroxyl-, thiol-, amino-, or acrylate/methacrylate end-capped polymers as starting materials for the preparation of diverse polymer architectures, ranging from block, graft, and star-shaped copolymers and micelles to precursors for ATRP macroinitiators, polyurethane copolymers, shape-memory polymers, or nanosized drug delivery systems, are also discussed. The rationale of this book is to provide up-to-date accounts of research and development activities on telechelic polyesters, polycarbonates, and polyethers. Hopefully, it will also contribute to their further development. This practical and user-friendly book can be adopted for introductory courses in polymer science and chemistry. Therefore, it is intended for students, professors, and researchers in macromolecular science, especially those with an interest in functional and reactive polymers, and it will appeal to any polymer chemists in academia and industry. This book is the product of several combined expertises, from internationally renowned leaders in their fields of polymer science. It would not have been possible without their collective efforts. Grateful thanks to all the contributing authors for their greatly appreciated contribution!
Preface xv Finally, I would like to dedicate this book to Professor Andrzej Duda, who passed away soon after completing his contribution to the chapter, Telechelic Poly(lactic acid)s and Polylactides (PLAs). Andrzej was a full professor of chemistry, a title conferred by the president of the Republic of Poland, at the Department of Polymer Chemistry, Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Lodz, in Poland. His major research interests included the study of kinetics and thermodynamics of polymerization, ring-opening polymerization, and stereocontrolled polymerization, as well as macromolecular engineering, focusing on the valorization of renewable resources toward the elaboration of biocompatible and (bio)degradable polymers such as PLA. He (co) authored more than 90 scientific papers (including 5 book chapters), published mostly in the highest-impact factor polymer journals, and 50 contributions to international symposia. We will remember him not only for his expertise in polymer science but also as a friendly, peaceful, and very nice colleague. He will be missed. Sophie M. Guillaume Rennes, France