Series Preface xiii
Preface xv
List of Contributors xvii
1 Bio-Based Plastics - Introduction 1
Stephan Kabasci
1.1 Definition of Bio-Based Plastics 2
1.2 A Brief History of Bio-Based Plastics 3
1.3 Market for Bio-Based Plastics 5
1.4 Scope of the Book 6
2 Starch 9
Catia Bastioli, Paolo Magistrali, and Sebastia Gestý Garcia
2.1 Introduction 9
2.2 Starch 10
2.3 Starch-Filled Plastics 13
2.4 Structural Starch Modifications 14
2.4.1 Starch Gelatinization and Retrogradation 14
2.4.2 Starch Jet-Cooking 16
2.4.3 Starch Extrusion Cooking 16
2.4.4 Starch Destructurization in Absence of Synthetic Polymers 17
2.4.5 Starch Destructurization in Presence of Synthetic Polymers 19
2.4.6 Additional Information on Starch Complexation 23
2.5 Starch-Based Materials on the Market 27
2.6 Conclusions 28
References 28
3 Cellulose and Cellulose Acetate 35
Johannes Ganster and Hans-Peter Fink
3.1 Introduction 35
3.2 Raw Materials 36
3.3 Structure 37
3.3.1 Cellulose 37
3.3.2 Cellulose Derivatives 40
3.4 Principles of Cellulose Technology 42
3.4.1 Regenerated Cellulose 43
3.4.2 Organic Cellulose Esters - Cellulose Acetate 46
3.5 Properties and Applications of Cellulose-Based Plastics 52
3.5.1 Fibres 53
3.5.2 Films 54
3.5.3 Moulded Articles 56
3.6 Some Recent Developments 57
3.6.1 Cellulose 57
3.6.2 Cellulose Acetate and Mixed Esters 58
3.7 Conclusion 59
References 59
4 Materials Based on Chitin and Chitosan 63
Marguerite Rinaudo
4.1 Introduction 63
4.2 Preparation and Characterization of Chitin and Chitosan 64
4.2.1 Chitin: Characteristics and Characterization 64
4.2.2 Chitosan: Preparation and Characterization 66
4.3 Processing of Chitin to Materials and Applications 69
4.3.1 Processing of Chitin and Physical Properties of Materials 69
4.3.2 Applications of Chitin-Based Materials 70
4.4 Chitosan Processing to Materials and Applications 71
4.4.1 Processing of Chitosan 71
4.4.2 Application of Chitosan-Based Materials 74
4.5 Conclusion 77
References 77
5 Lignin Matrix Composites from Natural Resources - ARBOFORMR 89
Helmut N¨agele, J¨urgen Pfitzer, Lars Ziegler, Emilia Regina Inone-Kauffmann, Wilhelm Eckl, and Norbert Eisenreich
5.1 Introduction 89
5.2 Approaches for Plastics Completely Made from Natural Resources 90
5.3 Formulation of Lignin Matrix Composites (ARBOFORM) 92
5.3.1 Lignin 92
5.3.2 Basic Formulations and Processing of ARBOFORM 95
5.3.3 The Influence of the Fibre Content 97
5.4 Chemical Free Lignin from High Pressure Thermo-Hydrolysis (Aquasolv) 100
5.4.1 Near Infrared Spectroscopy of Lignin Types 100
5.4.2 Lignin Extraction by High-Pressure Hydrothermolysis (HPH) 101
5.4.3 Thermoplastic Processing of Aquasolv Lignin 104
5.5 Functionalizing Lignin Matrix Composites 105
5.5.1 Impact Strength 106
5.5.2 Flame Retardancy 106
5.5.3 Electrical Conductivity with Nanoparticles 106
5.5.4 Pyrolysis to Porous Carbonaceous Structures 108
5.6 Injection Moulding of Parts - Case Studies 109
5.6.1 Loudspeaker Boxes 110
5.6.2 Precision Parts 110
5.6.3 Thin Walled and Decorative Gift Boxes and Toys 111
5.6 Acknowledgements 112
References 112
6 Bioplastics from Lipids 117
Stuart Coles
6.1 Introduction 117
6.2 Definition and Structure of Lipids 117
6.2.1 Fatty Acids 117
6.2.2 Mono-, Di- and Tri-Substituted Glycerols 118
6.2.3 Phospholipids 118
6.2.4 Other Compounds 119
6.3 Sources and Biosynthesis of Lipids 119
6.3.1 Sources of Lipids 119
6.3.2 Biosynthesis of Lipids 120
6.3.3 Composition of Triglycerides 120
6.4 Extraction of Plant Oils, Triglycerides and their Associated Compounds 120
6.4.1 Seed Cleaning and Preparation 121
6.4.2 Seed Pressing 121
6.4.3 Liquid Extraction 121
6.4.4 Post Extraction Processing 122
6.5 Biopolymers from Plant Oils, Triglycerides and Their Associated Compounds 122
6.5.1 Generic Triglycerides 122
6.5.2 Common Manipulations of Triglycerides 123
6.5.3 Soybean Oil-Based Bioplastics 125
6.5.4 Castor Oil-Based Bioplastics 126
6.5.5 Linseed Oil-Based Bioplastics 127
6.5.6 Other Plant Oil-Based Bioplastics 127
6.5.7 Biological Synthesis of Polymers 128
6.6 Applications 128
6.6.1 Mimicking to Reduce R&D Risk 128
6.6.2 Composites 129
6.6.3 Coatings 129
6.6.4 Packaging Materials 130
6.6.5 Foams 130
6.6.6 Biomedical Applications 130
6.6.7 Other Applications 131
6.7 Conclusions 131
References 131
7 Polyhydroxyalkanoates: Basics, Production and Applications of Microbial Biopolyesters 137
Martin Koller, Anna Salerno, and Gerhart Braunegg
7.1 Microbial PHA Production, Metabolism, and Structure 137
7.1.1 Occurrence of PHAs 137
7.1.2 In Vivo Characteristics and Biological Role of PHAs 139
7.1.3 Structure and Composition of PHAs 140
7.1.4 Metabolic Aspects 141
7.2 Available Raw Materials for PHA Production 143
7.3 Recovery of PHA from Biomass 144
7.3.1 General Aspects of PHA Recovery 144
7.3.2 Direct Extraction of PHA from Biomass 146
7.3.3 Digestion of the non-PHA Cellular Material 147
7.3.4 Disruption of Cells of Osmophilic Microbes in Hypotonic Medium 148
7.4 Different Types of PHA 149
7.4.1 Short Chain Length vs. Medium Chain Length PHAs 149
7.4.2 Enzymatic Background: PHA Synthases 149
7.5 Global PHA Production 151
7.6 Applications of PHAs 152
7.6.1 General 152
7.6.2 Packaging and Commodity Items 152
7.6.3 Medical Applications 154
7.6.4 Application of the Monomeric Building Blocks 155
7.6.5 Smart Materials 156
7.6.6 Controlled Release of Active Agents 156
7.7 Economic Challenges in the Production of PHAs and Attempts to Overcome Them 156
7.7.1 PHA Production as a Holistic Process 156
7.7.2 Substrates as Economic Factor 156
7.7.3 Downstream Processing 157
7.7.4 Process Design 157
7.7.5 Contemporary Attempts to Enhance PHA Production in Terms of Economics and Product Quality 158
7.8 Process Design 160
7.9 Conclusion 162
References 163
8 Poly(Lactic Acid) 171
Hideto Tsuji
8.1 Introduction 171
8.2 Historical Outline 173
8.3 Synthesis of Monomer 174
8.4 Synthesis of Poly(Lactic Acid) 176
8.4.1 Homopolymers 176
8.4.2 Linear Copolymers 176
8.5 Processing 178
8.6 Crystallization 178
8.6.1 Crystal Structures 178
8.6.2 Crystalline Morphology 181
8.6.3 Crystallization Behaviour 182
8.7 Physical Properties 182
8.7.1 Mechanical Properties 182
8.7.2 Thermal Properties 186
8.7.3 Permeability 188
8.7.4 Surface Properties 188
8.7.5 Electrical Properties 189
8.7.6 Optical Properties (From Biopolymers) 189
8.8 Hydrolytic Degradation 191
8.8.1 Degradation Mechanism 192
8.8.2 Effects of Surrounding Media 195
8.8.3 Effects of Material Parameters 196
8.9 Thermal Degradation 200
8.10 Biodegradation 203
8.11 Photodegradation 204
8.12 High-Performance Poly(Lactic Acid)-Based Materials 206
8.12.1 Nucleating or Crystallization-Accelerating Fillers 206
8.12.2 Composites and Nanocomposites 208
8.12.3 Fibre-Reinforced Plastics (FRPs) 211
8.12.4 Stereocomplexation 211
8.13 Applications 212
8.13.1 Alternatives to Petro-Based Polymers 212
8.13.2 Biomedical 213
8.13.3 Environmental Applications 215
8.14 Recycling 217
8.15 Conclusions 218
References 219
9 Other Polyesters from Biomass Derived Monomers 241
Daan S. van Es, Frits van der Klis, Rutger J. I. Knoop, Karin Molenveld, Lolke Sijtsma, and Jacco van Haveren
9.1 Introduction 241
9.2 Isohexide Polyesters 242
9.2.1 Introduction 242
9.2.2 Semi-Aromatic Homo-Polyesters 244
9.2.3 Semi-Aromatic Co-Polyesters 247
9.2.4 Aliphatic Polyesters 248
9.2.5 Modified Isohexides 250
9.3 Furan-Based Polyesters 251
9.3.1 Introduction 251
9.3.2 2,5-Dihydroxymethylfuran (DHMF)-Based Polyesters 253
9.3.3 5-Hydroxymethylfuroic Acid (HMFA) Based Polyesters 254
9.3.4 Furan-2,5-Dicarboxylic Acid (FDCA) Based Polyesters 254
9.3.5 Future Outlook 256
9.4 Poly(Butylene Succinate) (PBS) and Its Copolymers 257
9.4.1 Succinic Acid 257
9.4.2 1,4-Butanediol (BDO) 258
9.4.3 Poly(Butylene Succinate) (PBS) 259
9.4.4 PBS Copolymers 259
9.4.5 PBS Biodegradability 260
9.4.6 PBS Processability 260
9.4.7 PBS Blends 260
9.4.8 PBS Markets and Applications 260
9.4.9 Future Outlook 261
9.5 Bio-Based Terephthalates 261
9.5.1 Introduction 261
9.5.2 Bio-Based Diols: Ethylene Glycol, 1,3-Propanediol, 1,4-Butanediol 262
9.5.3 Bio-Based Xylenes, Isophthalic and Terephthalic Acid 263
9.6 Conclusions 267
References 267
10 Polyamides from Biomass Derived Monomers 275
Benjamin Brehmer
10.1 Introduction 275
10.1.1 What are Polyamides? 275
10.1.2 What is the Polymer Pyramid? 276
10.1.3 Where Do Polyamides from Biomass Derived Monomers Fit? 277
10.2 Technical Performance of Polyamides 277
10.2.1 How to Differentiate Performance 277
10.2.2 Overview of Current Applications 279
10.2.3 Typical Association of Biopolymers 280
10.3 Chemical Synthesis 281
10.3.1 Castor Bean to Intermediates 281
10.3.2 Undecenoic Acid Route 283
10.3.3 Sebacic Acid Route 283
10.3.4 Decamethylene Diamine Route 284
10.4 Monomer Feedstock Supply Chain 284
10.4.1 Description of Supply Chain 284
10.4.2 Pricing Situation 285
10.5 Producers 287
10.6 Sustainability Aspects 287
10.6.1 Biosourcing 287
10.6.2 Lifecycle Assessments 288
10.6.3 Labelling and Certification 291
10.7 Improvement and Outlook 292
References 293
11 Polyolefin-Based Plastics from Biomass-Derived Monomers 295
R.J. Koopmans
11.1 Introduction 295
11.2 Polyolefin-Based Plastics 296
11.3 Biomass 299
11.4 Chemicals from Biomass 300
11.5 Chemicals from Biotechnology 302
11.6 Plastics from Biomass 303
11.7 Polyolefin Plastics from Biomass and Petrochemical Technology 303
11.7.1 One-Carbon Building Blocks 304
11.7.2 Two-Carbon Building Blocks 305
11.7.3 Three-Carbon Building Blocks 305
11.8 Polyolefin Plastics from Biomass and Biotechnology 305
11.9 Bio-Polyethylene and Bio-Polypropylene 306
11.10 Perspective and Outlook 307
References 308
12 Future Trends for Recombinant Protein-Based Polymers: The Case Study of Development and Application of Silk-Elastin-Like Polymers 311
Margarida Casal, Ant´onio M. Cunha, and Raul Machado
12.1 Introduction 311
12.2 Production of Recombinant Protein-Based Polymers (rPBPs) 312
12.3 The Silk-Elastin-Like Polymers (SELPs) 314
12.3.1 SELPs for Biomedical Applications: Hydrogels for Localized Delivery 317
12.3.2 Mechanical Properties of SELP Hydrogels 319
12.3.3 Spun Fibres 320
12.3.4 Solvent Cast Films 323
12.4 Final Considerations 324
References 325
13 Renewable Raw Materials and Feedstock for Bioplastics 331
Achim Raschka, Michael Carus, and Stephan Piotrowski
13.1 Introduction 331
13.2 First- and Second-Generation Crops: Advantages and Disadvantages 331
13.3 The Amount of Land Needed to Grow Feedstock for Bio-Based Plastics 333
13.4 Productivity and Availability of Arable Land 336
13.5 Research on Feedstock Optimization 338
13.6 Advanced Breeding Technologies and Green Biotechnology 339
13.7 Some Facts about Food Prices and Recent Food Price Increases 341
13.8 Is there Enough Land for Food, Animal Feed, Bioenergy and Industrial Material Use, Including Bio-Based Plastics? 343
References 345
14 The Promise of Bioplastics - Biobased and Biodegradable-Compostable Plastics 347
Ramani Narayan
14.1 Value Proposition for Bio-Based Plastics 348
14.2 Exemplars of Zero or Reduced Material Carbon Footprint - Bio-PE, Bio-PET and PLA 349
14.3 Process Carbon Footprint and LCA 351
14.4 Determination of Bio-Based Carbon Content 352
14.5 End-of-Life Options for Bioplastics - Biodegradability-Compostability 353
14.6 Summary 356
References 356
Index
