A Handbook of Applied Biopolymer Technology: Synthesis, Degradation and Applications

A Handbook of Applied Biopolymer Technology

Synthesis, Degradation and Applications

Downloaded on 30 March 2012 Published on 20 June 2011 on http://pubs.rsc.org | doi:10.1039/9781849733458-FP001

RSC Green Chemistry

Series Editors:

James H Clark, Department of Chemistry, University of York, York, UK

George A Kraus, Department of Chemistry, Iowa State University, Iowa, USA

Titles in the Series:

1: The Future of Glycerol: New Uses of a Versatile Raw Material

2: Alternative Solvents for Green Chemistry

3: Eco-Friendly Synthesis of Fine Chemicals

4: Sustainable Solutions for Modern Economies

5: Chemical Reactions and Processes under Flow Conditions

6: Radical Reactions in Aqueous Media

7: Aqueous Microwave Chemistry

8: The Future of Glycerol: 2nd Edition

9: Transportation Biofuels: Novel Pathways for the Production of Ethanol,

Biogas and Biodiesel

10: Alternatives to Conventional Food Processing

11: Green Trends in Insect Control

12: A Handbook of Applied Biopolymer Technology: Synthesis, Degradation

and Applications

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 http://www.rsc.org/Shop/Books/

Downloaded on 30 March 2012 Published on 20 June 2011 on http://pubs.rsc.org | doi:10.1039/9781849733458-FP001 View Online

A Handbook of Applied

Biopolymer Technology

Synthesis, Degradation and Applications

Edited by

Sanjay K. Sharma

Jaipur Engineering College & Research Centre, Jaipur, Rajasthan, India

Ackmez Mudhoo

Department of Chemical and Environmental Engineering,

University of Mauritius, Reduit, Mauritius

Downloaded on 30 March 2012 Published on 20 June 2011 on http://pubs.rsc.org | doi:10.1039/9781849733458-FP001 View Online

RSC Green Chemistry No. 12

ISBN: 978-1-84973-151-5

ISSN: 1757-7039

A catalogue record for this book is available from the British Library

r Royal Society of Chemistry 2011

All rights reserved

Apart from fair dealing for the purposes of research for non-commercial purposes

or for private study, criticism or review, as permitted under the Copyright,

Designs and Patents Act 1988 and the Copyright and Related Rights Regulations

2003, this publication may not be reproduced, stored or transmitted, in any form

or by any means, without the prior permission in writing of The Royal Society of

Chemistry or the copyright owner, or in the case of reproduction in accordance

with the terms of licences issued by the Copyright Licensing Agency in the UK,

or in accordance with the terms of the licences issued by the appropriate

Reproduction 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.

The RSC is not responsible for individual opinions expressed in this work.

Published by The Royal Society of Chemistry,

Thomas Graham House, Science Park, Milton Road,

Cambridge CB4 0WF, UK

Registered Charity Number 207890

For further information see our web site at www.rsc.org

Downloaded on 30 March 2012 Published on 20 June 2011 on http://pubs.rsc.org | doi:10.1039/9781849733458-FP001 View Online

Preface

Researchers are conducting active research in different fields of engineering,

science and technology by adopting the 12 Principles of Green Chemistry and

the inherent green methodologies to devise new processes with a view to help

protect and ultimately save the environment from further anthropogenic

interruptions and damage. With this in focus, this book provides an up-to￾date, coherently written and objectively presented set of book chapters from

eminent international researchers who are actively involved in academic and

technological research in the synthesis, degradation, testing and applications of

biodegradable polymers and biopolymers. Hence, the overall pool of latest

ideas and recent research and technological progress achieved in the synthesis,

degradation, testing and applications of biodegradable polymers/biopolymers

together with a high level of thinking have been presented in a comprehensive

perspective to make progress in the emerging field of biodegradable polymer

science and engineering (or bio-based polymers). The element of environ￾mental sustainability as linked to biopolymer technology also constitutes the

essence and novelty of this very relevant book in today’s era of environmental

depredation.

This book consists of book chapters written and contributed by international

experts from academia who are world leaders in research and technology

regarding sustainability and biopolymer and biodegradable polymer synthesis,

characterization, testing and use. The book highlights the following areas: Green

polymers; Biopolymers and bionanocomposites; Biodegradable and injectable

polymers; Biodegradable polyesters: Synthesis and physical properties; Discovery

and characterization of biopolymers; Degradable bioelastomers, Lactic acid￾based biodegradable polymers; Biodegradation of biodegradable polymers;

Biodegradation of polymers in the composting environment; and Recent research

and application development in biodegradable polymers. The book is aimed at

technical, research-oriented and marketing people in industry, universities and

RSC Green Chemistry No. 12

A Handbook of Applied Biopolymer Technology: Synthesis, Degradation and Applications

Edited by Sanjay K. Sharma and Ackmez Mudhoo

r Royal Society of Chemistry 2011

Published by the Royal Society of Chemistry, www.rsc.org

v

Downloaded on 30 March 2012 Published on 20 June 2011 on http://pubs.rsc.org | doi:10.1039/9781849733458-FP005

institutions. The book will also be of value to the worldwide public interested in

sustainability issues and biopolymer development and as well as others interested

in the practical means that are being used to reduce the environmental impacts of

chemical processes and products, to further eco-efficiency, and to advance the

utilization of renewable resources in bio-based production and the supplier chain.

The main outcomes of reading this book should be that the reader will have a

comprehensive and consolidated overview of the immense potential and ongoing

research in bio-based and biodegradable polymer science, engineering and

technology, which is earnestly attempting to make the world of tomorrow

greener. Hence, this handbook is a reasonably comprehensive and applied treatise

of the topic and provides up-to-date information to a very wide audience on the

applied research areas of biopolymers.

Sanjay K. Sharma

Ackmez Mudhoo

vi Preface

Downloaded on 30 March 2012 Published on 20 June 2011 on http://pubs.rsc.org | doi:10.1039/9781849733458-FP005 View Online

This book is for Kunal and Kritika, my twin angels.

Sanjay K. Sharma

For you Neelam.

Ackmez Mudhoo

Downloaded on 30 March 2012 Published on 20 June 2011 on http://pubs.rsc.org | doi:10.1039/9781849733458-FP007

Downloaded on 30 March 2012 Published on 20 June 2011 on http://pubs.rsc.org | doi:10.1039/9781849733458-FP007 View Online

Contents

About the Editors xvii

Chapter 1 History of Sustainable Bio-based Polymers 1

Tim A. Osswald and Sylvana Garcı´a-Rodrı´guez

1.1 Background 1

1.2 Silk: From a Royal Stitch to a Wounded Peasant 4

1.3 Cellulose: The Quintessential Bio-based Plastic 7

1.4 Casein Plastics: From Food to Plastic 9

1.5 Soy Protein Plastic: Back to Nature 12

1.6 Building Scaffolds for Our Bodies: Collagen

and Chitosan 15

1.7 Letting Bacteria Make Our Plastics 17

1.8 Conclusions 19

References 19

Chapter 2 Synthetic Green Polymers from Renewable Monomers 22

Naozumi Teramoto

2.1 Introduction 22

2.2 Triglycerides of Fatty Acids and their Derivatives 24

2.2.1 Monomers from Triglycerides 24

2.2.2 Polymers Synthesized from Triglycerides 29

2.3 Essential Oils, Natural Phenolic Compounds and

their Derivatives 34

2.3.1 Terpenoids 35

2.3.2 Phenylpropanoids 40

2.3.3 Lignin Digests or Extracts and

Liquefied Wood 46

2.3.4 Other and Natural Phenolic Compounds 48

RSC Green Chemistry No. 12

A Handbook of Applied Biopolymer Technology: Synthesis, Degradation and Applications

Edited by Sanjay K. Sharma and Ackmez Mudhoo

r Royal Society of Chemistry 2011

Published by the Royal Society of Chemistry, www.rsc.org

ix

Downloaded on 30 March 2012 Published on 20 June 2011 on http://pubs.rsc.org | doi:10.1039/9781849733458-FP009

2.4 Carbohydrates and their Derivatives 51

2.4.1 Polymers from Popular Carbohydrates 51

2.4.2 Furan Derivatives 54

2.5 Monomers Obtained by Fermentation 55

2.6 Conclusions and Outlook 60

References 61

Chapter 3 Polyhydroxyalkanoates: The Emerging New Green

Polymers of Choice 79

Ranjana Rai and Ipsita Roy

3.1 Introduction 79

3.2 History of Polyhydroxyalkanoates 80

3.3 Chemical Organization of PHAs 80

3.4 Occurrence and Biosynthesis of PHAs 81

3.5 Cheap Substrates for Cost-effective PHA Production 86

3.6 Physical Properties of PHAs 86

3.7 Biocompatibility of PHAs 88

3.8 Biodegradation of Polyhydroxyalkanoates 89

3.8.1 Factors Affecting Biodegradation 89

3.8.2 Biodegradation in the Environment 89

3.8.3 Biodegradation and Biocompatibility 90

3.9 Applications of Polyhydroxyalkanoates 90

3.9.1 Industrial Application 90

3.9.2 Medical Applications 91

3.10 PHAs as Green Biofuels 94

3.11 Market and Economics of PHAs 95

3.12 Concluding Remarks 97

Acknowledgement 97

References 97

Chapter 4 Fully Green Bionanocomposites 102

P. M. Visakh, Sabu Thomas and Laly A. Pothan

4.1 Green Composites – Introduction 102

4.2 Green Materials: Fibres, Whiskers,

Crystals and Particles 103

4.2.1 Cellulose Fibres 103

4.2.2 Chitin Whiskers 105

4.2.3 Starch Crystals 107

4.2.4 Soy Protein Particles 110

4.2.5 Polylactic Acid 111

4.2.6 Natural Rubber Uncross-linked Particles 114

4.3 Green Nanocomposites 114

4.3.1 Cellulose-based Green Composites 114

4.3.2 Chitin and Chitosan-based Green Composites 116

x Contents

Downloaded on 30 March 2012 Published on 20 June 2011 on http://pubs.rsc.org | doi:10.1039/9781849733458-FP009 View Online

4.3.3 Starch-based Green Composites 117

4.3.4 Soy Protein-based Green Composites 117

4.3.5 PLA-based Green Composites 118

4.4 Applications 121

4.5 Conclusion 122

References 123

Chapter 5 Biopolymer-based Nanocomposites 129

Kikku Fukushima, Daniela Tabuani and Cristina Abbate

5.1 Introduction 129

5.2 Experimental 131

5.2.1 Materials and Methods 131

5.2.2 Biodegradation Conditions and Evaluation

Methods 133

5.3 Results and Discussions 133

5.3.1 Characterization 133

5.3.2 Biodegradation 139

5.4 Conclusions 145

Acknowledgements 146

References 146

Chapter 6 Biodegradable Polyesters: Synthesis and Physical Properties 149

Jasna Djonlagic and Marija S. Nikolic

6.1 Introduction 149

6.2 Poly(a-hydroxy acid)s 153

6.2.1 Poly(glycolic acid) 153

6.2.2 Poly(lactic acid) 154

6.3 Poly(e-caprolactone) 161

6.3.1 Synthesis of Poly(e-caprolactone) 161

6.3.2 Properties and Degradation of

Poly(e-caprolactone) 164

6.4 Poly(hydroxyalkanoate)s 166

6.4.1 Synthesis of Poly(hydroxyalkanoate)s 166

6.4.2 Properties and Degradation of

Poly(hydroxyalkanoate)s 171

6.5 Poly(alkylene dicarboxylate)s 174

6.5.1 Synthesis of Poly(alkylene dicarboxylate)s 174

6.5.2 Properties and Degradation of Poly(alkylene

dicarboxylate)s 177

6.6 Application of Biodegradable Polyesters 181

6.6.1 Ecological Applications 181

6.6.2 Medical Applications 184

6.7 Future Trends in Biodegradable Polyesters 185

References 185

Contents xi

Downloaded on 30 March 2012 Published on 20 June 2011 on http://pubs.rsc.org | doi:10.1039/9781849733458-FP009 View Online

Chapter 7 Synthesis and Characterization of Thermoplastic

Agro-polymers 197

C. J. R. Verbeek and J. M. Bier

7.1 Introduction 197

7.1.1 Polysaccharides 198

7.1.2 Proteins 200

7.2 Synthesis 200

7.2.1 General Considerations 201

7.2.2 The Role of Additives 201

7.2.3 Starch 202

7.2.4 Proteins 204

7.3 Characterization 206

7.3.1 Overview of Characterization 206

7.3.2 Mechanical Behaviour 210

7.3.3 Thermal Properties 218

7.4 Conclusions 236

References 237

Chapter 8 Degradable Bioelastomers: Synthesis and

Biodegradation 243

Q. Y. Liu, L. Q. Zhang and R. Shi

8.1 Character, Definition and Category of

Degradable Bioelastomers 243

8.2 Requirements of Degradable Bioelastomers 245

8.2.1 Safety 245

8.2.2 Biodegradation 246

8.2.3 Cross-linking 247

8.3 Synthesis and Biodegradation of Degradable

Bioelastomers 247

8.3.1 Degradable Segmented Polyurethane

Bioelastomers 248

8.3.2 Poly(e-caprolactone) Related Bioelastomers 254

8.3.3 Polylactide-related Bioelastomers 259

8.3.4 Polycarbonate-related Bioelastomers 264

8.3.5 Poly(glycerol sebacate) Bioelastomer and

its Derivatives 267

8.3.6 Citric Acid-related Polyester Bioelastomers 271

8.3.7 Poly(ether ester) Bioelastomers 276

8.3.8 Poly(ester amide) Bioelastomers 278

8.3.9 Other Novel Degradable Bioelastomers 280

8.4 Conclusions 284

Acknowledgements 284

References 284

xii Contents

Downloaded on 30 March 2012 Published on 20 June 2011 on http://pubs.rsc.org | doi:10.1039/9781849733458-FP009 View Online

Chapter 9 Functionalization of Poly(L-lactide) and Applications

of the Functionalized Poly(L-lactide) 291

Xiuli Hu and Xiabin Jing

9.1 Introduction 291

9.2 PLA Functionalization 293

9.2.1 Morpholine Diones 293

9.2.2 a-Amino acid N-Carboxyanhydride (NCA) 295

9.2.3 Cyclic Carbonates 297

9.2.4 Lactones 299

9.2.5 Cyclic Diesters 299

9.3 Applications of the Functionalized PLAs 299

9.3.1 Drug Delivery Systems 300

9.3.2 Artificial Oxygen Carriers 302

9.3.3 Protein Separation and Purification 304

9.4 Conclusions 305

References 305

Chapter 10 Biodegradation of Poly (3-hydroxyalkanoates) 311

Rachana Bhatt, Kamlesh Patel and Ujjval Trivedi

10.1 Introduction 311

10.2 Degradation of Plastics 314

10.2.1 Abiotic Degradation 314

10.2.2 Biotic Degradation 314

10.2.3 Standard Methods for Plastic Biodegradation

Studies 315

10.3 Biodegradation of Polyhydroxyalkanoates 316

10.3.1 Extracellular Degradation of PHA 316

10.3.2 Intracellular Degradation of PHA 325

10.4 Conclusions 327

References 327

Chapter 11 Degradation of Biodegradable and Green Polymers in the

Composting Environment 332

Ackmez Mudhoo, Romeela Mohee, Geeta D. Unmar and

Sanjay K. Sharma

11.1 Introduction 332

11.1.1 Biodegradable Polymers 333

11.1.2 Degradability through Composting 333

11.2 Degradation of Biodegradable Polymers 334

11.2.1 Polymer Biodegradation Mechanisms 334

11.2.2 Assessment of Biodegradable

Polymers Degradability 336

11.2.3 Biodegradable Polymers Blends 338

Contents xiii

Downloaded on 30 March 2012 Published on 20 June 2011 on http://pubs.rsc.org | doi:10.1039/9781849733458-FP009 View Online

11.3 Composting Process Essentials 339

11.3.1 Composting Chemistry 339

11.3.2 Physical Parameters in Composting 344

11.3.3 Composting Systems 345

11.3.4 Vermicomposting 345

11.4 Biopolymer Degradation and Composting 345

11.4.1 Polyhydroxyalkanoates 346

11.4.2 Poly(lactic acid)-based Polymers 348

11.4.3 Polyethylenes 350

11.4.4 Poly-e-caprolactones 355

11.5 Concluding Remarks 357

Acknowledgements 358

References 358

Chapter 12 Biodegradable Polymers: Research and

Applications 365

X. W. Wei, G. Guo, C. Y. Gong, M. L. Gou and

Zhi Yong Qian

12.1 Introduction 365

12.1.1 Biodegradable Polymers and

the Environment 366

12.1.2 Biodegradable Polymers and

Biomedical Uses 367

12.2 Natural Biodegradable Polymers and

their Derivatives 368

12.2.1 Starch and Derivatives 368

12.2.2 Cellulose and Derivatives 369

12.2.3 Chitin and Chitosan 370

12.2.4 Alginic Acid 371

12.2.5 Collagen 372

12.2.6 Gelatin 373

12.2.7 Other Biodegradable Natural

Polymers 373

12.3 Synthetic Polymers 374

12.3.1 Polyesters 374

12.3.2 Polyurethanes 379

12.3.3 Polyamides 380

12.3.4 Polyanhydrides 380

12.3.5 Polyphosphoesters 381

12.3.6 Others 382

12.4 Conclusions 383

References 383

xiv Contents

Downloaded on 30 March 2012 Published on 20 June 2011 on http://pubs.rsc.org | doi:10.1039/9781849733458-FP009 View Online

Chapter 13 Impacts of Biodegradable Polymers: Towards Biomedical

Applications 388

Y. Omidi and S. Davaran

13.1 Introduction 388

13.2 Classification of Biodegradable Polymers 390

13.3 Biodegradable Polyesters 391

13.3.1 Properties of PLA/PGA Polymers 392

13.3.2 Pharmaceutical Application of Biodegradable

Polyesters 393

13.3.3 Impacts of Micro and Nano Fabrication of

PLGA-based Copolymers 394

13.3.4 Biocompatible Magnetite-PLGA Composite

Nanoparticles 399

13.3.5 PLGA-based Carriers for Macromolecule

Delivery 400

13.3.6 Application of Polyester Polymers in Tissue

Engineering 405

13.4 Functional Polymers: Cellular Toxicity 408

13.5 Genocompatibility and Toxicogenomics of Polymers 409

13.6 Final Remarks 413

Acknowledgements 414

References 414

Chapter 14 Biodegradable Injectable Systems for Bone Tissue

Engineering 419

Richard T. Tran, Dipendra Gyawali, Parvathi Nair and

Jian Yang

14.1 Introduction 419

14.2 Rationale and Requirements for Injectable

Bone Tissue Engineering 421

14.2.1 Injectability and In Situ Cross-linking 422

14.2.2 Mechanical Properties 422

14.2.3 Porosity 423

14.2.4 Biodegradation 423

14.2.5 Cellular Behavior 424

14.2.6 Biocompatibility 425

14.3 Network Formation 425

14.3.1 Free Radical Polymerization (FRP) 426

14.3.2 Chemical Cross-linking Systems (CCS) 427

14.3.3 Thermally Induced Gelation Systems (TGS) 428

14.3.4 Self-assembly Systems (SAS) 428

14.3.5 Ion-mediated Gelation Systems (IGS) 429

Contents xv

Downloaded on 30 March 2012 Published on 20 June 2011 on http://pubs.rsc.org | doi:10.1039/9781849733458-FP009 View Online