Handbook of. Telechelic Polyesters, Polycarbonates, and Polyethers. Sophie M. Guillaume. edited by

Transcription

1 Handbook of Telechelic Polyesters, Polycarbonates, and Polyethers edited by Sophie M. Guillaume

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3 Handbook of Telechelic Polyesters, Polycarbonates, and Polyethers

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5 Handbook of Telechelic Polyesters Polycarbonates! and Polyethers edited by Sophie M. Guillaume! 1rrr PAN STANFORD PUBLISHING

6 Published by Pan Stanford Publishing Pte. Ltd. Penthouse Level, Suntec Tower 3 8 Temasek Boulevard Singapore editorial@panstanford.com Web: 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 (Hardcover) ISBN (ebook) Printed in the USA

7 Contents Preface xiii 1. Basic Chemistry for the Synthesis of Telechelic Polyesters and Polycarbonates 1 Takeshi Endo and Atsushi Sudo 1.1 Introduction Synthesis of Telechelic Polyesters and Polycarbonates by ROP: Fundamental Aspects Cationic Ring-Opening Polymerization Anionic and Coordination-Insertion Mechanisms Activated Monomer Mechanism Alternating Copolymerization of Epoxides with Other Compounds Radical Ring-Opening Polymerization Anionic Polymerization of Ketenes Summary and Prospects 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 Lipases in the Synthesis of Telechelic Polymers Synthetic Strategies toward the Formation of Telechelic Polyesters and Polycarbonates by Enzyme Catalysis Formation of Telechelic Polymers Using Enzyme Catalysis Synthesis of telechelic polymers by enzymatic ring-opening polymerization (erop) 36

8 vi Contents Synthesis of telechelic polymers by enzymatic polycondensation Synthesis of telechelic polymers by enzymatic transacylation (scrambling) The Importance of Appropriately Adjusted Reaction Conditions Water as a nucleophile for hydrolytic enzymes Effect of reaction temperature Why is it challenging to obtain polymers of higher molar mass by enzyme catalysis? End Capping of Polyesters and Polycarbonates Some Illustrative Examples of Telechelic Polymers Using Enzyme Catalysis Some Illustrative Examples of Telechelic Polyesters and Polycarbonates Obtained via erop Hydroxyl end-functionalized telechelic polymers Thiol end-functionalized telechelic polymers Acrylate/methacrylate endfunctionalized telechelic polymers Telechelic Polyesters and Polycarbonates Obtained by Enzymatic Polycondensation Telechelic Polyesters and Polycarbonates Obtained by Combination of Enzymatic ROP and epc Possible Applications of Telechelic Polyesters and Polycarbonates Synthesized Using Enzymes Summary and Prospects 57

9 Contents vii 3. Telechelic Polyhydroxyalkanoates/Polyhydroxybutyrates (PHAs/PHBs) 65 Abdulkadir Alli, Baki Hazer, Grażyna Adamus, and Marek Kowalczuk 3.1 Introduction Natural PHAs/PHBs Derived from Various Bacteria Synthetic Telechelic PHAs Anionic ROP toward Synthetic Telechelic PHBs Other ROP Approaches toward Synthetic Telechelic PHB Analogues Chemical Modifications of Telechelic PHAs Block and Graft Copolymers Derived from Telechelic PHAs Summary and Prospects Telechelic Poly(ε-Caprolactone)s: Synthesis and Applications 115 Timm Heek, Marc Behl, and Andreas Lendlein 4.1 Introduction Synthesis of Telechelic PCLs General Polymerization Methods Postpolymerization Chemical Modification Methods Applications of Telechelic PCLs Telechelic PCLs for the Synthesis of Nanosized Drug Delivery Systems Block copolymers Stimuli-responsive block copolymers Multiblock polyester(urea) urethanes Supramolecular block copolymers based on noncovalent interactions Inorganic hybrid polymer systems Linear dendritic hybrid block copolymers 146

10 viii Contents Telechelic PCLs for the Synthesis of Shape-Memory Polymers Covalently crosslinked networks Physically crosslinked networks Reversible crosslinked polymer networks Summary and Prospects Telechelic Poly(Lactic Acid)s and Polylactides 185 Malgorzata Basko and Andrzej Duda 5.1 Introduction Direct Synthesis of Telechelic Polylactides Telechelic Polylactides from Polycondensation Telechelic Polylactides from Ring-Opening Polymerization Telechelic polylactides from metal-catalyzed polymerization Telechelic polylactides from organocatalyzed polymerization Telechelic Polylactides from Postpolymerization Chemical Modification of a Prepolymer Summary and Prospects Telechelic Polycarbonates 233 Sophie M. Guillaume 6.1 Introduction Telechelic Bisphenol-A and Other Polycarbonates from Polycondensation Telechelic Polycarbonates from Epoxides and Carbon Dioxide Copolymerization Telechelic Polycarbonates from Propylene Oxide and Carbon Dioxide Copolymerization 242

11 Contents ix Telechelic Polycarbonates from Cyclohexene Oxide and Carbon Dioxide Copolymerization Telechelic Polycarbonates from Other Epoxides and Carbon Dioxide Copolymerization Concluding Remarks on the Epoxide and Carbon Dioxide Copolymerization Synthesis of Telechelic Polycarbonates Telechelic Polycarbonates from Enzyme-Catalyzed Polymerization Telechelic Polycarbonates from Enzyme-Catalyzed Polycondensation Telechelic Polycarbonates from Enzyme-Catalyzed Ring-Opening Polymerization Telechelic poly(trimethylene carbonate) Other telechelic polycarbonates Telechelic carbonate copolymers Concluding Remarks on the Enzyme-Catalyzed Synthesis of Telechelic Polycarbonates Telechelic Polycarbonates from Metal-Catalyzed and Organocatalyzed Ring-Opening Polymerization Hydroxy Telechelic Polycarbonates Hydroxy telechelic polycarbonates from metal-based catalysts Hydroxy telechelic polycarbonates from organic catalysts Other Nonhydroxy Telechelic Polycarbonates Concluding Remarks on the ROP Synthesis of Telechelic Polycarbonates 289

12 x Contents 6.6 Telechelic Polycarbonates as Precursors to Polyurethanes Summary and Prospects Telechelic Polyethers by Living Polymerizations and Precise Macromolecular Engineering 309 Pierre J. Lutz, Bruno Ameduri, and Frédéric Peruch 7.1 Introduction From Monofunctional to Multifunctional Telechelic PEOs via AROP General Considerations on AROP of Ethylene Oxide Linear Telechelic PEOs via AROP of Ethylene Oxide Multifunctional Telechelic PEOs via AROP of Ethylene Oxide Polyether Telechelics and Macromonomers General Considerations of Macromonomers PEO Macromonomers Prepared by Initiation PEO Macromonomers Prepared by Deactivation Heterobifunctional PEO Macromonomers Graft Copolymers General Considerations on PEO Graft Copolymers The Grafting-onto Process Grafting-onto via AROP Grafting-onto via telechelic PEOs Noncovalent grafting-onto The Grafting-from Process General remarks on grafting-from processes Grafting-from via AROP of EO Grafting-from hydrophilic PEO-based copolymers 337

13 Contents xi Grafting-through Processes: A Macromonomer Approach General considerations on the grafting-through process PEO graft copolymers via the macromonomer-based grafting-through method Amphiphilic Telechelic PEOs General Considerations on the Water Solubilty of (Amphiphilic) Telechelic PEOs Linear Amphiphilic PEOs End-Modified with Short Alkanes Branched Amphiphilic PEOS End-Capped with Short Alkanes Amphiphilic Telechelic PEOs and POSS General remarks on polyoctahedral silsesquioxanes PEO-grafted POSS structures Fluorinated Telechelic Polyethers General Considerations and Interest of Fluorinated Telechelic Polyethers Synthesis of Fluorinated Telechelic Polyethers Telechelic Polytetrahydrofuran General Considerations Telechelic PTHF Synthesis and Their Applications PTHF macromonomers synthesis and their use Other telechelic polymers Macromolecular architectures Telechelic Poly(Oxymethylene) Summary and Prospects 373 Index 401

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15 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

16 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!

17 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

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