Poly(lactic acid)

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2 Series Page Wiley Series on Polymer Engineering and TechnologyRichard F. Grossman and Domasius Nwabunma, Series Editors Polyolefin Blends Edited by Domasius Nwabunma and Thein Kyu Polyolefin Composites Edited by Domasius Nwabunma and Thein Kyu Handbook of Vinyl Formulating, Second Edition Edited by Richard F. Grossman Total Quality Process Control for Injection Molding, Second Edition M. Joseph Gordon, Jr. Microcellular Injection Molding Jingyi Xu Poly(Lactic Acid): Synthesis, Structures, Properties, Processing, and Applications Edited by Rafael Auras, Loong‐Tak Lim, Susan E.M. Selke, and Hideto Tsuji Hyperbranched Polymers: Synthesis, Properties, and Applications Edited by Deyue Yan, Chao Gao, and Holger Frey Advanced Thermoforming: Methods, Machines and Materials, Applications, and Automation Sven Engelmann Biopolymer Nanocomposites: Processing, Properties, and Applications Alain Dufresne, Sabu Thomas, Laly A. Pothan Polymers for PEM Fuel Cells Hongting Pu Polyurethanes: Science, Technology, Markets, and Trends Mark F. Sonnenschein Functional Polymer Coatings: Principles, Methods, and Applications Edited by Limin Wu and Jamil Baghdachi Polyurethanes: Science, Technology, Markets, and Trends, Second Edition Mark F. Sonnenschein Poly(lactic acid): Synthesis, Structures, Properties, Processing, Applications, and End of Life, Second Edition Edited by Rafael A. Auras, Loong‐Tak Lim, Susan E.M. Selke, and Hideto Tsuji

3 Title Page POLY(LACTIC ACID) Synthesis, Structures, Properties, Processing, Applications, and End of Life SECOND EDITION Edited by RAFAEL A. AURASLOONG‐TAK LIMSUSAN E. M. SELKEHIDETO TSUJI

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5 Dedication

6 LIST OF CONTRIBUTORS

7 PREFACE REFERENCE

8 AUTHOR BIOGRAPHIES

9 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 1.3 LACTIDE REFERENCES 2 AQUEOUS SOLUTIONS OF LACTIC ACID 2.1 INTRODUCTION 2.2 STRUCTURE OF LACTIC ACID 2.3 VAPOR PRESSURE OF ANHYDROUS LACTIC ACID AND LACTIDE 2.4 OLIGOMERIZATION IN AQUEOUS SOLUTIONS 2.5 EQUILIBRIUM DISTRIBUTION OF OLIGOMERS 2.6 VAPOR–LIQUID EQUILIBRIUM 2.7 DENSITY OF AQUEOUS SOLUTIONS 2.8 VISCOSITY OF AQUEOUS SOLUTIONS 2.9 SUMMARY REFERENCES 3 INDUSTRIAL PRODUCTION OF HIGH‐MOLECULAR‐WEIGHT POLY(LACTIC ACID) 3.1 INTRODUCTION 3.2 LACTIC‐ACID‐BASED POLYMERS BY POLYCONDENSATION 3.3 LACTIC ACID‐BASED POLYMERS BY CHAIN EXTENSION 3.4 LACTIC‐ACID‐BASED POLYMERS BY RING‐OPENING POLYMERIZATION REFERENCES 4 DESIGN AND SYNTHESIS OF DIFFERENT TYPES OF POLY(LACTIC ACID)/POLYLACTIDE COPOLYMERS 4.1 INTRODUCTION 4.2 COMONOMERS WITH LACTIC ACID/LACTIDE 4.3 FUNCTIONALIZED PLA 4.4 MACROMOLECULAR DESIGN OF LACTIDE‐BASED COPOLYMERS 4.5 PROPERTIES OF LACTIDE‐BASED COPOLYMERS 4.6 DEGRADATION OF LACTIDE HOMO‐ AND COPOLYMERS REFERENCES 5 PREPARATION, STRUCTURE, AND PROPERTIES OF STEREOCOMPLEX‐TYPE POLY(LACTIC ACID) 5.1 INTRODUCTION 5.2 STEREOCOMPLEXATION IN POLY(LACTIC ACID) 5.3 CRYSTAL STRUCTURE OF sc‐PLA 5.4 FORMATION OF STEREOBLOCK PLA 5.5 STEREOCOMPLEXATION IN COPOLYMERS 5.6 STEREOCOMPLEX PLA‐BASED COMPOSITES 5.7 Advances in Stereocomplex‐PLA 5.8 CONCLUSIONS REFERENCES

10 PART II: PROPERTIES 6 STRUCTURES AND PHASE TRANSITIONS OF PLA AND ITS RELATED POLYMERS 6.1 INTRODUCTION 6.2 STRUCTURAL STUDY OF PLA 6.3 THERMALLY INDUCED PHASE TRANSITIONS 6.4 MICROSCOPICALLY‐VIEWED STRUCTURE‐MECHANICAL PROPERTIES OF PLA 6.5 STRUCTURE AND FORMATION OF PLLA/PDLA STEREOCOMPLEX 6.6 PHB AND OTHER BIODEGRADABLE POLYESTERS 6.7 FUTURE PERSPECTIVES ACKNOWLEDGEMENTS REFERENCES 7 OPTICAL AND SPECTROSCOPIC PROPERTIES 7.1 INTRODUCTION 7.2 ABSORPTION AND TRANSMISSION OF UV–VIS RADIATION 7.3 REFRACTIVE INDEX 7.4 SPECIFIC OPTICAL ROTATION 7.5 INFRARED AND RAMAN SPECTROSCOPY 7.6 1H AND 13C NMR SPECTROSCOPY REFERENCES 8 CRYSTALLIZATION AND THERMAL PROPERTIES * 8.1 INTRODUCTION 8.2 CRYSTALLINITY AND CRYSTALLIZATION 8.3 CRYSTALLIZATION REGIME 8.4 FIBERS 8.5 COMMERCIAL POLYMERS AND PRODUCTS 8.6 DEGRADATION AND CRYSTALLINITY ACKNOWLEDGMENTS REFERENCES 9 RHEOLOGY OF POLY(LACTIC ACID) 9.1 INTRODUCTION 9.2 FUNDAMENTAL CHAIN PROPERTIES FROM DILUTE SOLUTION VISCOMETRY 9.3 PROCESSING OF PLA: GENERAL CONSIDERATIONS 9.4 MELT RHEOLOGY: AN OVERVIEW 9.5 PROCESSING OF PLA: RHEOLOGICAL PROPERTIES 9.6 CONCLUSIONS APPENDIX 9.A DESCRIPTION OF THE SOFTWARE REFERENCES 10 MECHANICAL PROPERTIES 10.1 INTRODUCTION 10.2 GENERAL MECHANICAL PROPERTIES AND MOLECULAR WEIGHT EFFECT 10.3 TEMPERATURE EFFECT 10.4 RELAXATION AND AGING 10.5 ANNEALING 10.6 ORIENTATION 10.7 STEREOREGULARITY 10.8 SELF‐REINFORCED PLA COMPOSITES 10.9 PLA NANOCOMPOSITES 10.10 COPOLYMERIZATION 10.11 PLASTICIZATION 10.12 PLA BLENDS 10.13 CONCLUSIONS REFERENCES 11 MASS TRANSFER 11.1 INTRODUCTION 11.2 BACKGROUND ON MASS TRANSFER IN POLYMERS 11.3 MASS TRANSFER PROPERTIES OF NEAT PLA FILMS 11.4 MASS TRANSFER PROPERTIES OF MODIFIED PLA 11.5 FINAL REMARKS ACKNOWLEDGMENTS REFERENCES 12 MIGRATION AND INTERACTION WITH CONTACT MATERIALS 12.1 INTRODUCTION 12.2 MIGRATION PRINCIPLES 12.3 LEGISLATION 12.4 MIGRATION AND TOXICOLOGICAL DATA OF LACTIC ACID, LACTIDE, DIMERS, AND OLIGOMERS 12.5 EDI OF LACTIC ACID 12.6 OTHER POTENTIAL MIGRANTS FROM PLA 12.7 CONCLUSIONS REFERENCES

11 PART III: PROCESSING AND CONVERSION 13 PROCESSING OF POLY(LACTIC ACID) 13.1 INTRODUCTION 13.2 PROPERTIES OF PLA RELEVANT TO PROCESSING 13.3 MODIFICATION OF PLA PROPERTIES BY PROCESS AIDS AND OTHER ADDITIVES 13.4 DRYING AND CRYSTALLIZING 13.5 EXTRUSION 13.6 INJECTION MOLDING 13.7 FILM AND SHEET CASTING 13.8 STRETCH BLOW MOLDING 13.9 EXTRUSION BLOWN FILM 13.10 THERMOFORMING 13.11 MELT SPINNING 13.12 SOLUTION SPINNING 13.13 ELECTROSPINNING 13.14 FILAMENT EXTRUSION AND 3D‐PRINTING 13.15 CONCLUSION: PROSPECTS OF PLA POLYMERS REFERENCES 14 BLENDS 14.1 INTRODUCTION 14.2 PLA NONBIODEGRADABLE POLYMER BLENDS 14.3 PLA/BIODEGRADABLE POLYMER BLENDS 14.4 PLASTICIZATION OF PLA 14.5 CONCLUSIONS REFERENCES 15 FOAMING 15.1 INTRODUCTION 15.2 PLASTIC FOAMS 15.3 FOAMING AGENTS 15.4 FORMATION OF CELLULAR PLASTICS 15.5 PLASTIC FOAMS EXPANDED WITH PHYSICAL FOAMING AGENTS 15.6 PLA FOAMED WITH CHEMICAL FOAMING AGENTS 15.7 MECHANICAL PROPERTIES OF PLA FOAMS 15.8 FOAMING OF PLA/STARCH AND OTHER BLENDS REFERENCES 16 COMPOSITES 16.1 INTRODUCTION 16.2 PLA MATRIX 16.3 REINFORCEMENTS 16.4 NANOCOMPOSITES 16.5 SURFACE MODIFICATION 16.6 PROCESSING 16.7 PROPERTIES 16.8 APPLICATIONS 16.9 FUTURE DEVELOPMENTS AND CONCLUDING REMARKS REFERENCES 17 NANOCOMPOSITES 17.1 INTRODUCTION 17.2 NANOCLAY‐CONTAINING PLA NANOCOMPOSITES 17.3 CARBON‐NANOTUBES‐CONTAINING PLA NANOCOMPOSITES 17.4 GRAPHENE‐CONTAINING PLA NANOCOMPOSITES 17.5 NANOCELLULOSE‐CONTAINING PLA NANOCOMPOSITES 17.6 OTHER NANOPARTICLE‐CONTAINING PLA NANOCOMPOSITES 17.7 MECHANICAL PROPERTIES OF PLA‐BASED NANOCOMPOSITES 17.8 POSSIBLE APPLICATIONS AND FUTURE PROSPECTS ACKNOWLEDGMENT REFERENCES 18 MECHANISM OF FIBER STRUCTURE DEVELOPMENT IN MELT SPINNING OF PLA 18.1 INTRODUCTION‐FUNDAMENTALS OF STRUCTURE DEVELOPMENT IN POLYMER PROCESSING 18.2 HIGH‐SPEED MELT SPINNING OF PLLAs WITH DIFFERENT D‐LACTIC ACID CONTENT 18.3 HIGH‐SPEED MELT‐SPINNING OF RACEMIC MIXTURE OF PLLA AND PDLA 18.4 BICOMPONENT MELT SPINNING OF PLLA AND PDLA 18.5 CONCLUDING REMARKS REFERENCES

12 PART IV: DEGRADATION, ENVIRONMENTAL IMPACT, AND END OF LIFE 19 PHOTODEGRADATION AND RADIATION DEGRADATION 19.1 INTRODUCTION 19.2 MECHANISMS OF PHOTODEGRADATION 19.3 MECHANISM OF RADIATION DEGRADATION 19.4 PHOTODEGRADATION OF PLA 19.5 RADIATION DEGRADATION OF PLA 19.6 IRRADIATION EFFECTS ON BIODEGRADABILITY 19.7 MODIFICATION AND COMPOSITES OF PLA REFERENCES 20 THERMAL DEGRADATION 20.1 INTRODUCTION 20.2 THERMAL DEGRADATION BEHAVIOR OF PLLA BASED ON WEIGHT LOSS 20.3 KINETIC ANALYSIS OF THERMAL DEGRADATION 20.4 KINETIC ANALYSIS OF COMPLEX THERMAL DEGRADATION BEHAVIOR 20.