Biopolymer Technology

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1 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 RSC Publishing

2 About the Editors xvii Chapter 1 History of Sustainable Bio-based Polymers 1 Tim A. Osswald and Syhana Garcia-Rodriguez 1.1 Background Silk: From a Royal Stitch to a Wounded Peasant Cellulose: The Quintessential Bio-based Plastic Casein Plastics: From Food to Plastic Soy Protein Plastic: Back to Nature Building Scaffolds for Our Bodies: Collagen and Chitosan Letting Bacteria Make Our Plastics Conclusions 19 References 19 Chapter 2 Synthetic Green Polymers Naozumi Teramoto from Renewable Monomers Introduction Triglycerides of Fatty Acids and their Derivatives Monomers from Triglycerides Polymers Synthesized from Triglycerides Essential Oils, Natural Phenolic Compounds and their Derivatives Terpenoids Phenylpropanoids Lignin Digests or Extracts and Liquefied Wood 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 C) Royal Society of Chemistry 2011 Published by the Royal Society of Chemistry, ix

3 Introduction X Contents 2.4 Carbohydrates and their Derivatives Polymers from Popular Carbohydrates Furan Derivatives Monomers Obtained by Fermentation Conclusions and Outlook 60 References 61 Chapter 3 Polyhydroxyalkanoates: The Emerging Polymers New Green of Choice 79 Ranjana Rai and Ipsita Roy 3.1 Introduction History of Polyhydroxyalkanoates Chemical Organization of PHAs Occurrence and Biosynthesis of PH As Cheap Substrates for Cost-effective PHA Production Physical Properties of PHAs Biocompatibility of PHAs Biodegradation of Polyhydroxyalkanoates Factors Affecting Biodegradation Biodegradation in the Environment Biodegradation and Biocompatibility Applications of Polyhydroxyalkanoates Industrial Application Medical Applications PHAs as Green Biofuels Market and Economics of PHAs Concluding Remarks 97 Acknowledgement 97 References 97 Chapter 4 Fully Green Bionanocomposites 102 P. M. Visakh, Sabu Thomas and Laiy A. Pothan 4.1 Green Composites Green Materials: Fibres, Whiskers, Crystals and Particles Cellulose Fibres Chitin Whiskers Starch Crystals Soy Protein Particles Polylactic Acid Natural Rubber Uncross-linked Particles Green Nanocomposites Cellulose-based Green Composites Chitin and Chitosan-based Green Composites 116

4 XI Starch-based Green Composites Soy Protein-based Green Composites PLA-based Green Composites Applications Conclusion 122 References 123 Chapter 5 Biopolymer-based Nanocomposites 129 Kikku Fukushima, Daniela Tabuani and Cristina Abbate 5.1 Introduction Experimental Materials and Methods Biodegradation Conditions and Evaluation Methods Results and Discussions Characterization Biodegradation Conclusions 145 Acknowledgements 146 References 146 Chapter 6 Biodegradable Polyesters: Synthesis and Physical Properties 149 Jasna Djonlagic and Marija S. Nikolic 6.1 Introduction Poly(a-hydroxy acid)s Poly(glycolic acid) PolyOactic acid) Poly(e-caprolactone) Synthesis of Poly(E-caprolactone) Properties and Degradation of Poly(c-caprolactone) Poly(hydroxyalkanoate)s Synthesis of Poly(hydroxyalkanoate)s Properties and Degradation of Poly(hydroxyalkanoate)s Poly(alkylene dicarboxylate)s Synthesis of Poly(alkylene dicarboxylate)s Properties and Degradation of Poly(alkylene dicarboxylate)s Application of Biodegradable Polyesters Ecological Applications Medical Applications Future Trends in Biodegradable Polyesters 185 References 185

5 xii Contents Chapter 7 Synthesis and Characterization of Thermoplastic Agro-polymers C. J. R. Verbeek and J. M. Bier 7.1 Introduction Polysaccharides Proteins Synthesis General Considerations The Role of Additives Starch Proteins Characterization Overview of Characterization Mechanical Behaviour Thermal Properties Conclusions 236 References 237 Chapter 8 Degradable Bioelastomers: Synthesis and Biodegradation 243 Q. Y. Liu, I. Q. Zhang and R. Shi 8.1 Character, Definition and Category of Degradable Bioelastomers Requirements of Degradable Bioelastomers Safety Biodegradation Cross-linking Synthesis and Biodegradation of Degradable Bioelastomers Degradable Segmented Polyurethane Bioelastomers Poly(e-caprolactone) Related Bioelastomers Polylactide-related Bioelastomers Polycarbonate-related Bioelastomers Poly(gIycerol sebacate) Bioelastomer and its Derivatives Citric Acid-related Polyester Bioelastomers Poly(ether ester) Bioelastomers Poly(ester amide) Bioelastomers Other Novel Degradable Bioelastomers Conclusions 284 Acknowledgements 284 References 284

6 Chapter 9 Functionalization of PoIy(L-lactide) and Applications of the Functionalized Poly(L-lactide) 291 Xhtli Hit and Xiahin Jing xiii 9.1 Introduction PLA Functionalization Morpholine Diones a-amino acid A'-Carboxyanhydride (NCA) Cyclic Carbonates Lactones Cyclic Diesters Applications of the Functionalized PLAs Drug Delivery Systems Artificial Oxygen Carriers Protein Separation and Purification Conclusions 305 References 305 Chapter 10 Biodegradation of Poly (3-hydroxyalkanoates) 311 Rachana Bhatt, Kamlesh Patel and Ujjval Trivedi 10.1 Introduction Degradation of Plastics Abiotic Degradation Biotic Degradation Standard Methods for Plastic Biodegradation Studies Biodegradation of Polyhydroxyalkanoates Extracellular Degradation of PHA Intracellular Degradation of PHA Conclusions 327 References 327 Chapter 11 Degradation of Biodegradable and Green Polymers in the Composting Environment 332 Ackmez Mttdhoo, Romeela Mohee, Geeta D. Unmar and Sanjay K. Shanna 11.1 Introduction Biodegradable Polymers Degradability through Composting Degradation of Biodegradable Polymers Polymer Biodegradation Mechanisms Assessment of Biodegradable Polymers Degradability Biodegradable Polymers Blends 338

7 11.3 Composting Process Essentials Composting Chemistry Physical Parameters in Composting Composting Systems Vermicomposting Biopolymer Degradation and Composting Polyhydroxyalkanoates Poly(lactic acid)-based Polymers Polyethylenes Poly-s-caprolactones 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 Biodegradable Polymers and the Environment Biodegradable Polymers and Biomedical Uses Natural Biodegradable Polymers and their Derivatives Starch and Derivatives Cellulose and Derivatives Chitin and Chitosan Alginic Acid Collagen Gelatin Other Biodegradable Natural Polymers Synthetic Polymers Polyesters Polyurethanes Polyamides Polyanhydrides Polyphosphoesters Others Conclusions 383 References 383

8 Chapter 13 Impacts of Biodegradable Polymers: Towards Biomedical Applications 388 Y. Omidi and S. Davaran xv 13.1 Introduction Classification of Biodegradable Polymers Biodegradable Polyesters Properties of PLA/PGA Polymers Pharmaceutical Application of Biodegradable Polyesters Impacts of Micro and Nano Fabrication of PLGA-based Copolymers Biocompatible Magnetite-PLGA Composite Nanoparticles PLGA-based Carriers for Macromolecule Delivery Application of Polyester Polymers in Tissue Engineering Functional Polymers: Cellular Toxicity Genocompatibility and Toxicogenomics of Polymers 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 Rationale and Requirements for Injectable Bone Tissue Engineering Injectability and In Situ Cross-linking Mechanical Properties Porosity Biodegradation Cellular Behavior Biocompatibility Network Formation Free Radical Polymerization (FRP) Chemical Cross-linking Systems (CCS) Thermally Induced Gelation Systems (TGS) Self-assembly Systems (SAS) Ion-mediated Gelation Systems (IGS) 429

9 xvj Contents 14.4 Injectable Ceramics Injectable Cell Vehicles Naturally Derived Hydrogels Synthetic-based Hydrogels Injectable Drug Delivery Systems Antibiotic Delivery Growth Factor Delivery for Osteogenesis Citric Acid-based Systems Future Directions Conclusions 441 Acknowledgments 442 References 442 Chapter 15 Production of Polyhydroxybutyrate (PHB) from Activated Sludge 452 M. Suresh Kumar and Tapan Chakrabarti 15.1 Introduction Polymers Storage Polymers in Microorganisms PHB Biosynthesis Enzymes Involved in Biosynthesis and Degradation Properties of PHB Potential Applications Biodegradation of PHB PHB Production PHB Production with Pure Substrates PHB Production with Wastes PHB Production by Mixed Culture Factors Affecting PHB Production Feast/Famine Conditions Microaerophilic Conditions Carbon/Nitrogen Limitation Conditions Phosphate Limitation Conditions PHB Yields and Recovery Processes Techno-economic Feasibility Conclusions 468 References 468 Subject Index 473