Preface xvii Contributors xxi Part I Chemistry and Production of Lactic Acid, Lactide, and Poly(Lactic Acid) 1 1 Production and Purification of Lactic Acid and Lactide 3 Wim Groot, Jan van Krieken, Olav Sliekersl, and Sicco de Vos 1.1 Introduction 3 1.2 Lactic Acid 4 1.2.1 History of Lactic Acid 4 1.2.2 Physical Properties of Lactic Acid 4 1.2.

3 Chemistry of Lactic Acid 4 1.2.4 Production of Lactic Acid by Fermentation 5 1.2.5 Downstream Processing/Purification of Lactic Acid 8 1.2.6 Quality/Specifications of Lactic Acid 10 1.3 Lactide 10 1.

3.1 Physical Properties of Lactide 10 1.3.2 Production of Lactide 11 1.3.3 Purification of Lactide 13 1.3.4 Quality and Specifications of Polymer-Grade Lactide 14 1.

3.5 Concluding Remarks on Polymer-Grade Lactide 16 References 16 2 Chemistry and Thermodynamic Properties of Lactic Acid and Lactide and Solvent Miscibility 19 Zhengyu Jin, Yaoqi Tian, and Jinpeng Wang 2.1 General Properties 19 2.1.1 Physical and Chemistry Properties of Lactic Acid 19 2.1.2 Physical and Chemical Properties of Lactide 19 2.2 Thermodynamic Properties 19 2.

2.1 Vapor Pressures of Lactic Acids at Different Temperatures 19 2.2.2 Temperature Dependence of Densities of Lactic Acid 20 2.2.3 Temperature Dependence of Viscosity of Lactic Acid 20 2.2.4 Thermodynamic Properties 21 2.

3 Miscibility Properties of Lactic Acid and Lactide 21 2.3.1 Miscibility of Lactic Acid with Different Solvents 21 2.3.2 Miscibility of Lactic Acid with Modifiers in Diluents 21 2.3.3 Physical and Chemical Equilibrium of Lactic Acid 22 2.3.

4 Miscibility of Lactide with Solvents 25 References 25 3 Industrial Production of High Molecular Weight Poly(Lactic Acid) 27 Anders S öderg ård and Mikael Stolt 3.1 Introduction 27 3.2 Lactic Acid Based Polymers by Polycondensation 28 3.2.1 Direct Condensation 29 3.2.2 Solid-State Polycondensation 30 3.2.

3 Azeotropic Dehydration 31 3.3 Lactic Acid Based Polymers by Chain Extension 32 3.3.1 Chain Extension with Diisocyanates 32 3.3.2 Chain Extension with Bis-2-oxazoline 33 3.3.3 Dual Linking Processes 34 3.

3.4 Chain Extension with Bis-epoxies 34 3.4 Lactic Acid Based Polymers by Ring-Opening Polymerization 34 3.4.1 Polycondensation Processes 35 3.4.2 Lactide Manufacturing 35 3.4.

3 Ring-Opening Polymerization 36 References 37 4 Design and Synthesis of Different Types of Poly(Lactic Acid) 43 Ann-Christine Albertsson, Indra Kumari Varma, Bimlesh Lochab, Anna Finne-Wistrand, and Kamlesh Kumar 4.1 Introduction 43 4.2 Copolymerization 43 4.2.1 Synthesis of Copolymers of Lactic Acid: Glycolic Acid 44 4.2.2 Synthesis of Copolymers of Lactic Acid: Poly(ethylene glycol) 44 4.2.

3 Synthesis of Copolymers of Lactic Acid: d-Valerolactone and Lactic Acid: b-Butyrolactone 45 4.2.4 Synthesis of Copolymers of Lactic Acid: e-Caprolactone 46 4.2.5 Synthesis of Copolymers of Lactic Acid: 1,5-Dioxepan-2-one 46 4.2.6 Synthesis of Copolymers of Lactic Acid: Trimethylene Carbonate 46 4.2.

7 Synthesis of Copolymers of Lactic Acid: Poly(N-isopropylacrylamide) 47 4.2.8 Synthesis of LA: Alkylthiophene (P3AT) Copolymers 47 4.2.9 Functional Poly(lactic acid) 47 4.2.10 Branched Copolymers 48 4.3 Properties of Copolymers 53 4.

3.1 Degradation of Homo- and Copolymers 54 4.3.2 Drug Delivery from PLLA Copolymers 54 4.3.3 Radiation Effects 55 References 55 5 Structure and Properties of Stereocomplex-Type Poly(lactic acid) 59 Masayuki Hirata and Yoshiharu Kimura 5.1 Introduction 59 5.2 Formation of Stereocomplex Crystals 59 5.

3 Thermal Properties of sc-PLA 60 5.4 Crystal Structure of sc-PLA 60 5.4.1 Unit Cell Parameters and Molecular Conformation of sc-PLA 60 5.4.2 Density and Heat of Fusion of Sccrystals 60 5.5 Formation of sb-PLA 61 5.5.

1 ROP Routes to Diblock and Multiblock sb-PLA 61 5.5.2 SSP Routes to Multiblock sb-PLA 63 5.6 Applications of sc-PLA 64 References 65 Part II Properties of Poly(Lactic Acid) 67 6 Chemical Structure of Poly(lactic acid) 69 Xue Jiang, Yan Luo, Xiuzhi Tian, Dan Huang, Narendra Reddy, and Yiqi Yang 6.1 Introduction 69 6.2 Chain Structure and Configuration 69 6.2.1 Chain Structure 69 6.

2.2 Configuration 70 6.2.3 Interlocked Structure, Polymer Blend, and Resistance to Hydrolysis 71 6.3 Syndiotactic Polymerization and Syndiotacticity 72 6.4 Conformation 74 6.5 Amorphous Structure and Thermal Properties 74 6.5.

1 Amorphous and Three-Phase Models 74 6.5.2 Glass Transition 75 6.6 Orientation Structure of PLA 77 6.6.1 Mechanical Orientation by Stretching or Compression 77 6.6.2 Thermal Orientation (Phase Transition) 77 6.

7 Semicrystalline Structure 78 6.7.1 General 78 6.7.2 Three Forms (a, b and c) of the Crystal Structure 78 6.8 Frustrated Structure 79 6.9 Molecular Weight 80 6.10 Summary 80 References 80 7 Chemical Compatibility of Poly(lactic acid): A Practical Framework Using Hansen Solubility Parameters 83 Steven Abbott 7.

1 A Practical Framework 83 7.1.1 Thermodynamics Versus Kinetics 83 7.1.2 Hansen Solubility Parameters 83 7.2 Solvent Compatibility 84 7.3 Plasticizers 86 7.4 Polymer Compatibility 87 7.

5 Environmental Stress Cracking 89 7.6 Rational Composite Design 89 7.7 Diffusion and Barrier Properties 90 7.7.1 Gases 91 7.7.2 Water 91 7.8 Pharmacological Transport 93 7.

9 Summary 93 References 94 8 Optical Properties 97 Carla M. B. Gon çalves, Jo ão A. P. Coutinho, and Isabel M. Marrucho 8.1 Introduction 97 8.2 Absorption and Transmission of UV-Vis Radiation 97 8.

3 Refractive Index 99 8.4 Specific Optical Rotation 100 8.5 Infrared and Raman Spectroscopy 100 8.5.1 Infrared Spectroscopy 101 8.5.2 Raman Spectroscopy 105 8.6 1H and 13C NMR Spectroscopy 108 References 111 9 Crystallization and Thermal Properties 113 Luca Fambri and Claudio Migliaresi 9.

1 Introduction 113 9.2 Crystallinity and Crystallization 114 9.3 Crystallization Regime 118 9.4 Fibers 119 9.5 Hydrolytic Degradation 121 References 123 10 Rheology of Poly(lactic acid) 125 John R. Dorgan 10.1 Introduction 125 10.2 Fundamental Chain Properties from Dilute Solution Viscometry 126 10.

2.1 Unperturbed Chain Dimensions 126 10.2.2 Real Chains 126 10.2.3 Solution Viscometry 127 10.2.4 Viscometry of PLA 128 10.

3 Processing of PLA: General Considerations 130 10.4 Melt Rheology: An Overview 131 10.5 Processing of PLA: Rheological Properties 132 10.6 Conclusions 137 Appendix 10.A Description of the Software 138 References 138 11 Mechanical Properties 141 Gabriele Perego and Gian Domenico Cella 11.1 Introduction 141 11.2 General Mechanical Properties and Molecular Weight Effect 141 11.2.

1 Tensile and Flexural Properties 141 11.2.2 Impact Resistance 143 11.2.3 Hardness 143 11.3 Temperature Effect 143 11.4 Annealing 144 11.5 Orientation 147 11.

6 Stereoregularity 148 11.7 Plasticization 149 11.8 Relaxation and Aging 151 11.9 Conclusions 152 References 152 12 Permeation, Sorption, and Diffusion in Poly(lactic acid) 155 Eva Almenar and Rafael Auras 12.1 Introduction 155 12.2 Factors Affecting Permeability, Sorption, and Diffusion in PLA 157 12.2.1 L-Lactide Unit Content 157 12.

2.2 Plasticizers 158 12.2.3 Crystallization 159 12.2.4 Orientation 160 12.2.5 Free volume 160 12.

2.6 Branching 160 12.2.7 Environmental Factors 161 12.3 Permeability, Sorption, and Diffusion of Pure PLA 163 12.3.1 Gases 163 12.3.

2 Water Vapor 165 12.3.3 Organics 167 12.4 Copolymers 169 12.5 PLA Blends 169 12.5.1 PLA/Starch Blends 169 12.5.

2 PLA/Poly(e-caprolactone) Blends 170 12.5.3 PLA/Chitosan Blends 171 12.5.4 PLA/Poly(( R )-3-hydroxybutyrate) Blends 171 12.6 PLA Laminations 171 12.7 Coated PLA 171 12.8 PLA Composites and Fibers 171 12.

8.1 PLA Composites 172 12.8.2 Fiber-Reinforced PLA 172 12.9 PLA Nanocomposites 172 12.10 Future of PLA Membranes 176 References 176 13 Migration 181 Herlinda Soto-Valdez 13.1 Migration Principles 181 13.2 Legislation 182 13.

3 Migration and Toxicological Data of Lactic Acid, Lactide, Dimers and Oligomers 182 13.3.1 Lactic Acid 182 13.3.2 Lactide 186 13.3.3 Oligomers 186 13.4 EDI of Lactic Acid 187 13.

5 Other Potential Migrants from PLA 187 13.6 Conclusions 187 References 188 Part III Processing and Conversion of Poly(Lactic Acid) 189 14 Processing of Poly(lactic acid) 191 Loong-Tak Lim, Kevin Cink, and Tim Vanyo 14.1 Introduction 191 14.2 Properties of PLA Relevant to Processing 191 14.3 Modification of PLA Properties by Process Aids and O.