Bio-Based Plastics

EditorStephan KabasciFraunhofer-Institute for Environmental, Safety, and Energy Technology UMSICHT, GermanySeries EditorChristian StevensFaculty of Bioscience Engineering, Ghent University, Ghent, Belgium

“Most chapters are brief, but generally well supported by citations to the original literature. Useful figures and photographs supplement the text. A detailed table of contents and a useful index allow easy access to information. The book is hardbound and produced to a good quality.  An e-book version is available.”  (Biotechnology Advances, 1 August 2014)

• Series Preface xiii Preface xvList of Contributors xvii1 Bio-Based Plastics – Introduction 1Stephan Kabasci1.1 Definition of Bio-Based Plastics 21.2 A Brief History of Bio-Based Plastics 31.3 Market for Bio-Based Plastics 51.4 Scope of the Book 62 Starch 9Catia Bastioli, Paolo Magistrali, and Sebastia Gestý Garcia2.1 Introduction 92.2 Starch 102.3 Starch-Filled Plastics 132.4 Structural Starch Modifications 142.4.1 Starch Gelatinization and Retrogradation 142.4.2 Starch Jet-Cooking 162.4.3 Starch Extrusion Cooking 162.4.4 Starch Destructurization in Absence of Synthetic Polymers 172.4.5 Starch Destructurization in Presence of Synthetic Polymers 192.4.6 Additional Information on Starch Complexation 232.5 Starch-Based Materials on the Market 272.6 Conclusions 28References 283 Cellulose and Cellulose Acetate 35Johannes Ganster and Hans-Peter Fink3.1 Introduction 353.2 Raw Materials 363.3 Structure 373.3.1 Cellulose 373.3.2 Cellulose Derivatives 403.4 Principles of Cellulose Technology 423.4.1 Regenerated Cellulose 433.4.2 Organic Cellulose Esters – Cellulose Acetate 463.5 Properties and Applications of Cellulose-Based Plastics 523.5.1 Fibres 533.5.2 Films 543.5.3 Moulded Articles 563.6 Some Recent Developments 573.6.1 Cellulose 573.6.2 Cellulose Acetate and Mixed Esters 583.7 Conclusion 59References 594 Materials Based on Chitin and Chitosan 63Marguerite Rinaudo4.1 Introduction 634.2 Preparation and Characterization of Chitin and Chitosan 644.2.1 Chitin: Characteristics and Characterization 644.2.2 Chitosan: Preparation and Characterization 664.3 Processing of Chitin to Materials and Applications 694.3.1 Processing of Chitin and Physical Properties of Materials 694.3.2 Applications of Chitin-Based Materials 704.4 Chitosan Processing to Materials and Applications 714.4.1 Processing of Chitosan 714.4.2 Application of Chitosan-Based Materials 744.5 Conclusion 77References 775 Lignin Matrix Composites from Natural Resources – ARBOFORMR  89Helmut N¨agele, J¨urgen Pfitzer, Lars Ziegler, Emilia Regina Inone-Kauffmann, Wilhelm Eckl, and Norbert Eisenreich5.1 Introduction 895.2 Approaches for Plastics Completely Made from Natural Resources 905.3 Formulation of Lignin Matrix Composites (ARBOFORM) 925.3.1 Lignin 925.3.2 Basic Formulations and Processing of ARBOFORM 955.3.3 The Influence of the Fibre Content 975.4 Chemical Free Lignin from High Pressure Thermo-Hydrolysis (Aquasolv) 1005.4.1 Near Infrared Spectroscopy of Lignin Types 1005.4.2 Lignin Extraction by High-Pressure Hydrothermolysis (HPH) 1015.4.3 Thermoplastic Processing of Aquasolv Lignin 1045.5 Functionalizing Lignin Matrix Composites 1055.5.1 Impact Strength 1065.5.2 Flame Retardancy 1065.5.3 Electrical Conductivity with Nanoparticles 1065.5.4 Pyrolysis to Porous Carbonaceous Structures 1085.6 Injection Moulding of Parts – Case Studies 1095.6.1 Loudspeaker Boxes 1105.6.2 Precision Parts 1105.6.3 Thin Walled and Decorative Gift Boxes and Toys 1115.6 Acknowledgements 112References 1126 Bioplastics from Lipids 117Stuart Coles6.1 Introduction 1176.2 Definition and Structure of Lipids 1176.2.1 Fatty Acids 1176.2.2 Mono-, Di- and Tri-Substituted Glycerols 1186.2.3 Phospholipids 1186.2.4 Other Compounds 1196.3 Sources and Biosynthesis of Lipids 1196.3.1 Sources of Lipids 1196.3.2 Biosynthesis of Lipids 1206.3.3 Composition of Triglycerides 1206.4 Extraction of Plant Oils, Triglycerides and their Associated Compounds 1206.4.1 Seed Cleaning and Preparation 1216.4.2 Seed Pressing 1216.4.3 Liquid Extraction 1216.4.4 Post Extraction Processing 1226.5 Biopolymers from Plant Oils, Triglycerides and Their Associated Compounds 1226.5.1 Generic Triglycerides 1226.5.2 Common Manipulations of Triglycerides 1236.5.3 Soybean Oil-Based Bioplastics 1256.5.4 Castor Oil-Based Bioplastics 1266.5.5 Linseed Oil-Based Bioplastics 1276.5.6 Other Plant Oil-Based Bioplastics 1276.5.7 Biological Synthesis of Polymers 1286.6 Applications 1286.6.1 Mimicking to Reduce R&D Risk 1286.6.2 Composites 1296.6.3 Coatings 1296.6.4 Packaging Materials 1306.6.5 Foams 1306.6.6 Biomedical Applications 1306.6.7 Other Applications 1316.7 Conclusions 131References 1317 Polyhydroxyalkanoates: Basics, Production and Applications of Microbial Biopolyesters 137Martin Koller, Anna Salerno, and Gerhart Braunegg7.1 Microbial PHA Production, Metabolism, and Structure 1377.1.1 Occurrence of PHAs 1377.1.2 In Vivo Characteristics and Biological Role of PHAs 1397.1.3 Structure and Composition of PHAs 1407.1.4 Metabolic Aspects 1417.2 Available Raw Materials for PHA Production 1437.3 Recovery of PHA from Biomass 1447.3.1 General Aspects of PHA Recovery 1447.3.2 Direct Extraction of PHA from Biomass 1467.3.3 Digestion of the non-PHA Cellular Material 1477.3.4 Disruption of Cells of Osmophilic Microbes in Hypotonic Medium 1487.4 Different Types of PHA 1497.4.1 Short Chain Length vs. Medium Chain Length PHAs 1497.4.2 Enzymatic Background: PHA Synthases 1497.5 Global PHA Production 1517.6 Applications of PHAs 1527.6.1 General 1527.6.2 Packaging and Commodity Items 1527.6.3 Medical Applications 1547.6.4 Application of the Monomeric Building Blocks 1557.6.5 Smart Materials 1567.6.6 Controlled Release of Active Agents 1567.7 Economic Challenges in the Production of PHAs and Attempts to Overcome Them 1567.7.1 PHA Production as a Holistic Process 1567.7.2 Substrates as Economic Factor 1567.7.3 Downstream Processing 1577.7.4 Process Design 1577.7.5 Contemporary Attempts to Enhance PHA Production in Terms of Economics and Product Quality 1587.8 Process Design 1607.9 Conclusion 162References 1638 Poly(Lactic Acid) 171Hideto Tsuji8.1 Introduction 1718.2 Historical Outline 1738.3 Synthesis of Monomer 1748.4 Synthesis of Poly(Lactic Acid) 1768.4.1 Homopolymers 1768.4.2 Linear Copolymers 1768.5 Processing 1788.6 Crystallization 1788.6.1 Crystal Structures 1788.6.2 Crystalline Morphology 1818.6.3 Crystallization Behaviour 1828.7 Physical Properties 1828.7.1 Mechanical Properties 1828.7.2 Thermal Properties 1868.7.3 Permeability 1888.7.4 Surface Properties 1888.7.5 Electrical Properties 1898.7.6 Optical Properties (From Biopolymers) 1898.8 Hydrolytic Degradation 1918.8.1 Degradation Mechanism 1928.8.2 Effects of Surrounding Media 1958.8.3 Effects of Material Parameters 1968.9 Thermal Degradation 2008.10 Biodegradation 2038.11 Photodegradation 2048.12 High-Performance Poly(Lactic Acid)-Based Materials 2068.12.1 Nucleating or Crystallization-Accelerating Fillers 2068.12.2 Composites and Nanocomposites 2088.12.3 Fibre-Reinforced Plastics (FRPs) 2118.12.4 Stereocomplexation 2118.13 Applications 2128.13.1 Alternatives to Petro-Based Polymers 2128.13.2 Biomedical 2138.13.3 Environmental Applications 2158.14 Recycling 2178.15 Conclusions 218References 2199 Other Polyesters from Biomass Derived Monomers 241Daan S. van Es, Frits van der Klis, Rutger J. I. Knoop, Karin Molenveld, Lolke Sijtsma, and Jacco van Haveren9.1 Introduction 2419.2 Isohexide Polyesters 2429.2.1 Introduction 2429.2.2 Semi-Aromatic Homo-Polyesters 2449.2.3 Semi-Aromatic Co-Polyesters 2479.2.4 Aliphatic Polyesters 2489.2.5 Modified Isohexides 2509.3 Furan-Based Polyesters 2519.3.1 Introduction 2519.3.2 2,5-Dihydroxymethylfuran (DHMF)-Based Polyesters 2539.3.3 5-Hydroxymethylfuroic Acid (HMFA) Based Polyesters 2549.3.4 Furan-2,5-Dicarboxylic Acid (FDCA) Based Polyesters 2549.3.5 Future Outlook 2569.4 Poly(Butylene Succinate) (PBS) and Its Copolymers 2579.4.1 Succinic Acid 2579.4.2 1,4-Butanediol (BDO) 2589.4.3 Poly(Butylene Succinate) (PBS) 2599.4.4 PBS Copolymers 2599.4.5 PBS Biodegradability 2609.4.6 PBS Processability 2609.4.7 PBS Blends 2609.4.8 PBS Markets and Applications 2609.4.9 Future Outlook 2619.5 Bio-Based Terephthalates 2619.5.1 Introduction 2619.5.2 Bio-Based Diols: Ethylene Glycol, 1,3-Propanediol, 1,4-Butanediol 2629.5.3 Bio-Based Xylenes, Isophthalic and Terephthalic Acid 2639.6 Conclusions 267References 26710 Polyamides from Biomass Derived Monomers 275Benjamin Brehmer10.1 Introduction 27510.1.1 What are Polyamides? 27510.1.2 What is the Polymer Pyramid? 27610.1.3 Where Do Polyamides from Biomass Derived Monomers Fit? 27710.2 Technical Performance of Polyamides 27710.2.1 How to Differentiate Performance 27710.2.2 Overview of Current Applications 27910.2.3 Typical Association of Biopolymers 28010.3 Chemical Synthesis 28110.3.1 Castor Bean to Intermediates 28110.3.2 Undecenoic Acid Route 28310.3.3 Sebacic Acid Route 28310.3.4 Decamethylene Diamine Route 28410.4 Monomer Feedstock Supply Chain 28410.4.1 Description of Supply Chain 28410.4.2 Pricing Situation 28510.5 Producers 28710.6 Sustainability Aspects 28710.6.1 Biosourcing 28710.6.2 Lifecycle Assessments 28810.6.3 Labelling and Certification 29110.7 Improvement and Outlook 292References 29311 Polyolefin-Based Plastics from Biomass-Derived Monomers 295R.J. Koopmans11.1 Introduction 29511.2 Polyolefin-Based Plastics 29611.3 Biomass 29911.4 Chemicals from Biomass 30011.5 Chemicals from Biotechnology 30211.6 Plastics from Biomass 30311.7 Polyolefin Plastics from Biomass and Petrochemical Technology 30311.7.1 One-Carbon Building Blocks 30411.7.2 Two-Carbon Building Blocks 30511.7.3 Three-Carbon Building Blocks 30511.8 Polyolefin Plastics from Biomass and Biotechnology 30511.9 Bio-Polyethylene and Bio-Polypropylene 30611.10 Perspective and Outlook 307References 30812 Future Trends for Recombinant Protein-Based Polymers: The Case Study of Development and Application of Silk-Elastin-Like Polymers 311Margarida Casal, Ant´onio M. Cunha, and Raul Machado12.1 Introduction 31112.2 Production of Recombinant Protein-Based Polymers (rPBPs) 31212.3 The Silk-Elastin-Like Polymers (SELPs) 31412.3.1 SELPs for Biomedical Applications: Hydrogels for Localized Delivery 31712.3.2 Mechanical Properties of SELP Hydrogels 31912.3.3 Spun Fibres 32012.3.4 Solvent Cast Films 32312.4 Final Considerations 324References 32513 Renewable Raw Materials and Feedstock for Bioplastics 331Achim Raschka, Michael Carus, and Stephan Piotrowski13.1 Introduction 33113.2 First- and Second-Generation Crops: Advantages and Disadvantages 33113.3 The Amount of Land Needed to Grow Feedstock for Bio-Based Plastics 33313.4 Productivity and Availability of Arable Land 33613.5 Research on Feedstock Optimization 33813.6 Advanced Breeding Technologies and Green Biotechnology 33913.7 Some Facts about Food Prices and Recent Food Price Increases 34113.8 Is there Enough Land for Food, Animal Feed, Bioenergy and Industrial Material Use, Including Bio-Based Plastics? 343References 34514 The Promise of Bioplastics – Biobased and Biodegradable-Compostable Plastics 347Ramani Narayan14.1 Value Proposition for Bio-Based Plastics 34814.2 Exemplars of Zero or Reduced Material Carbon Footprint – Bio-PE, Bio-PET and PLA 34914.3 Process Carbon Footprint and LCA 35114.4 Determination of Bio-Based Carbon Content 35214.5 End-of-Life Options for Bioplastics – Biodegradability-Compostability 35314.6 Summary 356References 356Index