Bio-Based Plastics
Materials and Applications
Wiley Series in Renewable Resource Series

The field of bio-based plastics has developed significantly in the last 10 years and there is increasing pressure on industries to shift existing materials production from petrochemicals to renewables.

Bio-based Plastics presents an up-to-date overview of the basic and applied aspects of bioplastics, focusing primarily on thermoplastic polymers for material use. Emphasizing materials currently in use or with significant potential for future applications, this book looks at the most important biopolymer classes such as polysaccharides, lignin, proteins and polyhydroxyalkanoates as raw materials for bio-based plastics, as well as materials derived from bio-based monomers like lipids, poly(lactic acid), polyesters, polyamides and polyolefines. Detailed consideration is also given to the market and availability of renewable raw materials, the importance of bio-based content and the aspect of biodegradability.

Topics covered include:

• Starch
• Cellulose and cellulose acetate
• Materials based on chitin and chitosan
• Lignin matrix composites from natural resources
• Polyhydroxyalkanoates
• Poly(lactic acid)
• Polyesters, Polyamides and Polyolefins from biomass derived monomers
• Protein-based plastics

Bio-based Plastics is a valuable resource for academic and industrial researchers who are interested in new materials, renewable resources, sustainability and polymerization technology. It will also prove useful for advanced students interested in the development of bio-based products and materials, green and sustainable chemistry, polymer chemistry and materials science.

For more information on the Wiley Series in Renewable Resources, visit www.wiley.com/go/rrs

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

Editor

Stephan Kabasci
Fraunhofer-Institute for Environmental, Safety, and Energy Technology UMSICHT, Germany

Series Editor

Christian Stevens
Faculty of Bioscience Engineering, Ghent University, Ghent, Belgium