POLY(LACTIC ACID): Synthesis, Structures, Properties, Processing, and Applications -- CONTENTS -- PREFACE -- CONTRIBUTORS -- PART I: CHEMISTRY AND PRODUCTION OF LACTIC ACID, LACTIDE, AND POLY(LACTIC ACID) -- 1 PRODUCTION AND PURIFICATION OF LACTIC ACID AND LACTIDE -- 1.1 INTRODUCTION -- 1.2 LACTIC ACID -- 1.2.1 History of Lactic Acid -- 1.2.2 Physical Properties of Lactic Acid -- 1.2.3 Chemistry of Lactic Acid -- 1.2.4 Production of Lactic Acid by Fermentation -- 1.2.5 Downstream Processing/Purification of Lactic Acid -- 1.2.6 Quality/Specifications of Lactic Acid -- 1.3 LACTIDE -- 1.3.1 Physical Properties of Lactide -- 1.3.2 Production of Lactide -- 1.3.3 Purification of Lactide -- 1.3.4 Quality and Specifications of Polymer-Grade Lactide -- 1.3.5 Concluding Remarks on Polymer-Grade Lactide -- REFERENCES -- 2 CHEMISTRY AND THERMODYNAMIC PROPERTIES OF LACTIC ACID AND LACTIDE AND SOLVENT MISCIBILITY -- 2.1 GENERAL PROPERTIES -- 2.1.1 Physical and Chemical Properties of Lactic Acid -- 2.1.2 Physical and Chemical Properties of Lactide -- 2.2 THERMODYNAMIC PROPERTIES -- 2.2.1 Vapor Pressures of Lactic Acids at Different Temperatures -- 2.2.2 Temperature Dependence of Densities of Lactic Acid -- 2.2.3 Temperature Dependence of Viscosity of Lactic Acid -- 2.2.4 Thermodynamic Properties -- 2.3 MISCIBILITY PROPERTIES OF LACTIC ACID AND LACTIDE -- 2.3.1 Miscibility of Lactic Acid with Different Solvents -- 2.3.2 Miscibility of Lactic Acid with Modifiers in Diluents -- 2.3.3 Physical andChemical Equilibrium of Lactic Acid -- 2.3.4 Miscibility of Lactide with Solvents -- REFERENCES -- 3 INDUSTRIAL PRODUCTION OF HIGH MOLECULAR WEIGHT POLY(LACTIC ACID) -- 3.1 INTRODUCTION -- 3.2 LACTIC ACID BASED POLYMERS BY POLYCONDENSATION -- 3.2.1 Direct Condensation -- 3.2.2 Solid-State Polycondensation -- 3.2.3 Azeotropic Dehydration.

3.3 LACTIC ACID BASED POLYMERS BY CHAIN EXTENSION -- 3.3.1 Chain Extension with Diisocyanates -- 3.3.2 Chain Extension with Bis-2-oxazoline -- 3.3.3 Dual Linking Processes -- 3.3.4 Chain Extension with Bis-epoxies -- 3.4 LACTIC ACID BASED POLYMERS BY RINGOPENING POLYMERIZATION -- 3.4.1 Polycondensation Processes -- 3.4.2 Lactide Manufacturing -- 3.4.3 Ring-Opening Polymerization -- REFERENCES -- 4 DESIGN AND SYNTHESIS OF DIFFERENT TYPES OF POLY(LACTIC ACID) -- 4.1 INTRODUCTION -- 4.2 COPOLYMERIZATION -- 4.2.1 Synthesis of Copolymers of Lactic Acid: Glycolic Acid -- 4.2.2 Synthesis of Copolymers of Lactic Acid:Poly (ethylene glycol) -- 4.2.3 Synthesis of Copolymers of Lactic Acid:δ- Valerolactone and Lactic Acid:β-Butyrolactone -- 4.2.4 Synthesis of Copolymers of Lactic Acid: ε-Caprolactone -- 4.2.5 Synthesis of Copolymers of Lactic Acid:1,5- Dioxepan-2-one -- 4.2.6 Synthesis of Copolymers of Lactic Acid: Trimethylene Carbonate -- 4.2.7 Synthesis of Copolymers of Lactic Acid:Poly(Nisopropylacrylamide) -- 4.2.8 Synthesis of LA:Alkylthiophene (P3AT) Copolymers -- 4.2.9 Functional Poly(lactic acid) -- 4.2.10 Branched Copolymers -- 4.3 PROPERTIES OF COPOLYMERS -- 4.3.1 Degradation of Homo- and Copolymers -- 4.3.2 Drug Delivery from PLLA Copolymers -- 4.3.3 Radiation Effects -- REFERENCES -- 5 STRUCTURE AND PROPERTIES OF STEREOCOMPLEX-TYPE POLY(LACTIC ACID) -- 5.1 INTRODUCTION -- 5.2 FORMATION OF STEREOCOMPLEX CRYSTALS -- 5.3 THERMAL PROPERTIES OF sc-PLA -- 5.4 CRYSTAL STRUCTURE OF sc-PLA -- 5.4.1 Unit Cell Parameters and Molecular Conformation of sc-PLA -- 5.4.2 Density and Heat of Fusion of sc Crystals -- 5.5 FORMATION OF sb-PLA -- 5.5.1 ROP Routes to Diblock and Mutiblock sb-PLA -- 5.5.2 SSP Routes to Multiblock sb-PLA -- 5.6 APPLICATIONS OF sc-PLA -- REFERENCES -- PART II: PROPERTIES OF POLY(LACTIC ACID) -- 6 CHEMICAL STRUCTURE OF POLY(LACTIC ACID).

6.1 INTRODUCTION -- 6.2 CHAIN STRUCTURE AND CONFIGURATION -- 6.2.1 Chain Structure -- 6.2.2 Configuration -- 6.2.3 Interlocked Structure, Polymer Blend, and Resistance to Hydrolysis -- 6.3 SYNDIOTACTIC POLYMERIZATION AND SYNDIOTACTICITY -- 6.4 CONFORMATION -- 6.5 AMORPHOUS STRUCTURE AND THERMAL PROPERTIES -- 6.5.1 Amorphous and Three-Phase Models -- 6.5.2 Glass Transition -- 6.6 ORIENTATION STRUCTURE OF PLA -- 6.6.1 Mechanical Orientation by Stretching or Compression -- 6.6.2 Thermal Orientation (Phase Transition) -- 6.7 SEMICRYSTALLINE STRUCTURE -- 6.7.1 General -- 6.7.2 Three Forms (α, β, and γ) of the Crystal Structure -- 6.8 FRUSTRATED STRUCTURE -- 6.9 MOLECULAR WEIGHT -- 6.10 SUMMARY -- REFERENCES -- 7 CHEMICAL COMPATIBILITY OF POLY(LACTIC ACID): A PRACTICAL FRAMEWORK USING HANSEN SOLUBILITY PARAMETERS -- 7.1 A PRACTICAL FRAMEWORK -- 7.1.1 Thermodynamics Versus Kinetics -- 7.1.2 Hansen Solubility Parameters -- 7.2 SOLVENT COMPATIBILITY -- 7.3 PLASTICIZERS -- 7.4 POLYMER COMPATIBILITY -- 7.5 ENVIRONMENTAL STRESS CRACKING -- 7.6 RATIONAL COMPOSITE DESIGN -- 7.7 DIFFUSION AND BARRIER PROPERTIES -- 7.7.1 Gases -- 7.7.2 Water -- 7.8 PHARMACOLOGICAL TRANSPORT -- 7.9 SUMMARY -- REFERENCES -- 8 OPTICAL PROPERTIES -- 8.1 INTRODUCTION -- 8.2 ABSORPTION AND TRANSMISSION OF UV-Vis RADIATION -- 8.3 REFRACTIVE INDEX -- 8.4 SPECIFIC OPTICAL ROTATION -- 8.5 INFRARED AND RAMAN SPECTROSCOPY -- 8.5.1 Infrared Spectroscopy -- 8.5.2 Raman Spectroscopy -- 8.6 1H AND 13C NMR SPECTROSCOPY -- REFERENCES -- 9 CRYSTALLIZATION AND THERMAL PROPERTIES -- 9.1 INTRODUCTION -- 9.2 CRYSTALLINITY AND CRYSTALLIZATION -- 9.3 CRYSTALLIZATION REGIME -- 9.4 FIBERS -- 9.5 HYDROLYTIC DEGRADATION -- REFERENCES -- 10 RHEOLOGY OF POLY(LACTIC ACID) -- 10.1 INTRODUCTION -- 10.2 FUNDAMENTAL CHAIN PROPERTIES FROM DILUTE SOLUTION VISCOMETRY -- 10.2.1 Unperturbed Chain Dimensions.

10.2.2 Real Chains -- 10.2.3 Solution Viscometry -- 10.2.4 Viscometry of PLA -- 10.3 PROCESSING OF PLA: GENERAL CONSIDERATIONS -- 10.4 MELT RHEOLOGY: AN OVERVIEW -- 10.5 PROCESSING OF PLA: RHEOLOGICAL PROPERTIES -- 10.6 CONCLUSIONS -- APPENDIX 10.A DESCRIPTION OF THE SOFTWARE -- REFERENCES -- 11 MECHANICAL PROPERTIES -- 11.1 INTRODUCTION -- 11.2 GENERAL MECHANICAL PROPERTIES AND MOLECULAR WEIGHT EFFECT -- 11.2.1 Tensile and Flexural Properties -- 11.2.2 Impact Resistance -- 11.2.3 Hardness -- 11.3 TEMPERATURE EFFECT -- 11.4 ANNEALING -- 11.5 ORIENTATION -- 11.6 STEREOREGULARITY -- 11.7 PLASTICIZATION -- 11.8 RELAXATION AND AGING -- 11.9 CONCLUSIONS -- REFERENCES -- 12 PERMEATION, SORPTION, AND DIFFUSION IN POLY(LACTIC ACID) -- 12.1 INTRODUCTION -- 12.2 FACTORS AFFECTING PERMEABILITY, SORPTION, AND DIFFUSION IN PLA -- 12.2.1 L-Lactide Unit Content -- 12.2.2 Plasticizers -- 12.2.3 Crystallization -- 12.2.4 Orientation -- 12.2.5 Free Volume -- 12.2.6 Branching -- 12.2.7 Environmental Factors -- 12.3 PERMEABILITY, SORPTION, AND DIFFUSION OF PURE PLA -- 12.3.1 Gases -- 12.3.2 Water Vapor -- 12.3.3 Organics -- 12.4 COPOLYMERS -- 12.5 PLA BLENDS -- 12.5.1 PLA/Starch Blends -- 12.5.2 PLA/Poly(ε-caprolactone) Blends -- 12.5.3 PLA Chitosan Blends -- 12.5.4 PLA/Poly((R)-3-hydroxybutyrate) Blends -- 12.6 PLA LAMINATIONS -- 12.7 COATED PLA -- 12.8 PLA COMPOSITES AND FIBERS -- 12.8.1 PLA Composites -- 12.8.2 Fiber-Reinforced PLA -- 12.9 PLA NANOCOMPOSITES -- 12.10 FUTURE OF PLA MEMBRANES -- REFERENCES -- 13 MIGRATION -- 13.1 MIGRATION PRINCIPLES -- 13.2 LEGISLATION -- 13.3 MIGRATION AND TOXICOLOGICAL DATA OF LACTIC ACID, LACTIDE, DIMERS, AND OLIGOMERS -- 13.3.1 Lactic Acid -- 13.3.2 Lactide -- 13.3.3 Oligomers -- 13.4 EDI OF LACTIC ACID -- 13.5 OTHER POTENTIAL MIGRANTS FROM PLA -- 13.6 CONCLUSIONS -- REFERENCES.

PART III: PROCESSING AND CONVERSION OF POLY(LACTIC ACID) -- 14 PROCESSING OF POLY(LACTIC ACID) -- 14.1 INTRODUCTION -- 14.2 PROPERTIES OF PLA RELEVANT TO PROCESSING -- 14.3 MODIFICATION OF PLA PROPERTIES BY PROCESS AIDS AND OTHER ADDITIVES -- 14.4 DRYING -- 14.5 EXTRUSION -- 14.6 INJECTION MOLDING -- 14.7 FILM AND SHEET CASTING -- 14.8 STRETCH BLOW MOLDING -- 14.9 EXTRUSION BLOWN FILM -- 14.10 THERMOFORMING -- 14.11 ELECTROSPINNING -- 14.12 CONCLUSION: PROSPECTS OF PLA POLYMERS -- REFERENCES -- 15 POLY(LACTIC ACID)/STARCH BLENDS -- 15.1 INTRODUCTION -- 15.2 BLENDING HYDROPHOBIC PLA WITH HYDROPHILIC STARCH -- 15.3 COMPATIBILIZERS USED FOR STARCH/PLA BLENDS -- 15.4 ENHANCING FUNCTION OF COMPATIBILIZER BY CONTROLLING COMPATIBILIZER DISTRIBUTION -- 15.5 REACTIVE BLENDING -- 15.6 SUMMARY -- REFERENCES -- 16 POLY(LACTIC ACID) BLENDS -- 16.1 INTRODUCTION -- 16.2 PLA/NONBIODEGRADABLE POLYMER BLENDS -- 16.2.1 Polyolefins -- 16.2.2 Vinyl and Vinylidene Polymers and Copolymers -- 16.2.3 Elastomers and Rubbers -- 16.2.4 PMMA/PLA Blends -- 16.3 PLA/BIODEGRADABLE POLYMER BLENDS -- 16.3.1 Polyanhydrides -- 16.3.2 Vinyl and Vinylidene Polymers and Copolymers -- 16.3.3 Aliphatic Polyesters and Copolyesters -- 16.3.4 Aliphatic-Aromatic Copolyesters -- 16.3.5 Elastomers and Rubbers -- 16.3.6 Poly(ester amide) -- 16.3.7 Polyethers and Copolymer -- 16.3.8 Annually Renewable Biodegradable Materials -- 16.4 PLASTICIZATION OF PLA -- 16.5 CONCLUSION -- REFERENCES -- 17 FOAMING -- 17.1 INTRODUCTION -- 17.2 PLASTIC FOAMS -- 17.3 FOAMING AGENTS -- 17.3.1 Physical Foaming Agents -- 17.3.2 Chemical Foaming Agents -- 17.4 FORMATION OF CELLULAR PLASTICS -- 17.4.1 Dissolution of Blowing Agent in Polymer -- 17.4.2 Bubble Formation -- 17.4.3 Bubble Growth and Stabilization -- 17.5 PLASTIC FOAMS EXPANDED WITH PHYSICAL FOAMING AGENTS -- 17.5.1 Microcellular Foamed Polymers.

17.5.2 Solid-State Batch Microcellular Foaming Process.