Telechelic polymers have garnered a great deal of scientific interest due to their reactive chain-end functions. This comprehensive book compiles and details the basic principles of and cutting-edge research in telechelic polyesters, polycarbonates, and polyethers, ranging from synthesis to applications. It discusses general strategies toward telechelic polymers, centered on the fundamental aspects of polycondensation reactions, of cationic, anionic, coordination-insertion, 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. All main classes of polymers are covered separately, comprising polyhydroxyalkanoates, poly(ε-caprolactone)s, poly(lactic acid)s, polylactides, polycarobnates, and polyethers, including synthetic approaches as well as some illustrative, up-to-date examples and uses. The book also addresses 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 polymers and micelles to precursors for ATRP macroinitiators, polyurethane copolymers, shape-memory polymers, or nanosized drug delivery systems. The book will appeal to advanced undergraduate- and graduate-level students of polymer science; researchers in macromolecular science, especially those with an interest in functional and reactive polymers; and polymer chemists in academia and industry.

Sophie M. Guillaume received her PhD from the University of Syracuse, New York, USA, and did her postdoctoral research at the Alternative Energies and Atomic Energy Commission (CEA), France. She then joined the National Center for Scientific Research (CNRS), France, and moved to the Laboratoire de Chimie des Polymères Organiques (LCPO), Bordeaux, France. She now holds a CNRS

Research Director position at the Institut des Sciences Chimiques de Rennes (ISCR) in Rennes, France. Her research mainly focuses on the development of green pathways for the synthesis and structure–property relationships of synthetic polymers (especially polyesters, polycarbonates, polyolefins, and polyurethanes). Areas of emphasis include biobased degradable polymers and functionalized and reactive (co)polymers for advanced industrial and biomedical applications. Guillaum

eSophie M. Guillaumeedited by

Handbook of Telechelic Polyesters, Polycarbonates, and Polyethers

Telechelic Polyesters, Polycarbonates, and Polyethers

Handbook of

ISBN 978-981-4745-62-8V556

Telechelic Polyesters, Polycarbonates, and Polyethers

Handbook of

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! Handbook of Telechelic PolyestersPolycarbonates! and Polyethers edited by

Sophie M. Guillaume

PAN STANFORD 1rrr PUBLISHING

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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 DataA catalogue record for this book is available from the British Library.

Handbook of Telechelic Polyesters, Polycarbonates, and PolyethersCopyright © 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.

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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 end-functionalized 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

viiContents

3. Telechelic Polyhydroxyalkanoates/Polyhydroxybutyrates (PHAs/PHBs) 65

AbdulkadirAlli,BakiHazer,GrażynaAdamus, 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

ixContents

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

xiContents

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

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. End-functional polymers can react selectively with other chemically different monomers, thus acting as macroinitiators, to afford AB- or 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 tailor-made 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 mil-lion 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

Preface

xiv Preface

can be read on its own. The general strategies toward telechelic polymers are first discussed in Chapter 1, centered on fundamen-tal aspects of polycondensation reactions, of cationic, anionic, co-ordination-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 polycar-bonate, poly(propylene carbonate), poly(trimethylene carbonate), and poly(cyclohexene carbonate), and also including synthetic ap-proaches 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 poly-mer architectures, ranging from block, graft, and star-shaped co-polymers and micelles to precursors for ATRP macroinitiators, pol-yurethane 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!

xvPreface

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