Poly(Lactic Acid) Science and Technology : Processing, Properties, Additives and Applications

[BOOK DESCRIPTION]
Biodegradable polymers from renewable resources are sought after for many purposes, from packaging materials in food to biomedical applications. Poly (lactic acid) (PLA) is a well-known biopolymer derived from corn starch or sugar cane used in different food packaging and artificial bones and scaffolds. Poly(lactic acid) Science and Technology first introduces the basic concepts of PLA and then covers PLA synthesis and polymerization, processing, characterization and physical properties of PLA, PLA-based nano-biocomposites, the main applications in active packaging and as biomaterials for tissue engineering, degradation and biodegradation of PLA and finally industrial and legislative issues. This interdisciplinary approach provides readers with a general overview of all relevant aspects related to PLA including fundamental issues, innovative applications, new types of processing and emerging applications, modification of PLA, life cycle assessment, bio-additives, bio/degradation and sustainability and international regulations. Experts provide a complete resource and whole perspective on PLA covering scientific, ecological, social and economic issues.The book will appeal to chemists, food technologists and materials engineers as well as researchers interested in bio-based and biodegradable polymers and composites.

[TABLE OF CONTENTS]

PLA Synthesis and Polymerization
  Chapter 1 PLA Synthesis. From the Monomer to     3  (34)
  the Polymer
          Kazunari Masutani
          Yoshiharu Kimura
      1.1 Introduction                             3  (1)
      1.2 Synthesis of Lactic Acids                4  (3)
        1.2.1 Stereoisomers of Lactic Acid         4  (1)
        1.2.2 Fermentation with Lactic Acid        5  (1)
        Bacteria
        1.2.3 Isolation and Purification of        5  (2)
        Lactic Acids
        1.2.4 Chemical Synthesis of Lactic Acids   7  (1)
      1.3 Synthesis of Lactide Monomers            7  (1)
        1.3.1 Stereoisomers of Lactides            7  (1)
        1.3.2 Synthesis and Purification of        7  (1)
        Lactides
      1.4 Polymerization of Lactide Monomers       8  (17)
        1.4.1 Structural Diversities of the        8  (1)
        Polylactides
        1.4.2 Thermodynamics for the               9  (2)
        Polymerization of n- and L-Lactides
        1.4.3 Metal Catalysts                      11 (4)
        1.4.4 Cationic Catalysts                   15 (1)
        1.4.5 Organic Catalysts                    15 (3)
        1.4.6 Stereo-controlled Polymerization     18 (3)
        1.4.7 Stereo-block Copolymerization        21 (1)
        1.4.8 Copolymerization                     22 (3)
      1.5 Polycondensation of Lactic Acids         25 (6)
        1.5.1 Solution Polycondensation            27 (1)
        1.5.2 Melt/Solid Polycondensation          27 (2)
        1.5.3 Stereo-block Polycondensation        29 (2)
      References                                   31 (6)
  Chapter 2 Polylactide Stereo-complex: From       37 (29)
  Principles to Applications
          Suming Li
          Yanfei Hu
      2.1 Introduction                             37 (1)
      2.2 Synthesis and Structure-Properties of    38 (9)
      PLA Stereo-complex
        2.2.1 Synthesis of PLA Homopolymers and    38 (1)
        Stereo-copolymers
        2.2.2 PLA Stereo-complex by                39 (1)
        Co-crystallization
        2.2.3 Properties of PLA Stereo-complex     40 (4)
        2.2.4 Degradation of PLA Stereo-complex    44 (3)
      2.3 Biomedical Applications of PLA           47 (14)
      Stereo-complex
        2.3.1 PLA Stereo-complex Nanofibre         48 (1)
        Scaffolds
        2.3.2 PLA Stereo-complex Microparticles    49 (1)
        2.3.3 PLA Stereo-complex Micelles          50 (6)
        2.3.4 Stereo-complex Hydrogels             56 (5)
        2.3.5 Other Stereo-complex Systems         61 (1)
      References                                   61 (5)
  Chapter 3 Crystallization of PLA-based           66 (35)
  Materials
          A.J. M?ller
          M. ﾁvila
          G. Saenz
          J. Salazar
      3.1 Introduction                             66 (1)
      3.2 Crystal Structure and Single Crystals    67 (1)
      3.3 Melting and Glass Transition             68 (5)
      Temperatures
      3.4 Superstructural Morphology               73 (1)
      3.5 Crystallization Kinetics                 74 (10)
        3.5.1 Spherulite Growth Kinetics           74 (2)
        3.5.2 Application of the Lauritzen and     76 (4)
        Hoffman Theory to PLLA
        3.5.3 Overall Crystallization Kinetics     80 (4)
      3.6 Block Copolymers Based on PLA            84 (8)
        3.6.1 PLLA-PEO Copolymers                  84 (3)
        3.6.2 Copolymers versus Blends of PLLA     87 (2)
        and PCL
        3.6.3 PE-b-PLA Block Copolymers            89 (3)
      3.7 Conclusions and Outlook                  92 (1)
      References                                   93 (8)
Processing, Characterization and Physical
Properties of PLA
  Chapter 4 Reactive Extrusion of PLA-based        101(23)
  Materials: from Synthesis to Reactive
  Melt-blending
          Jean-Marie Raquez
          Rindra Ramy-Ratiarison
          Marius Murariu
          Philippe Dubois
      4.1 Introduction                             101(1)
      4.2 Polylactide (PLA)-based Materials:       102(3)
      General Aspects and Reactive Extrusion
      (REX) Processing
      4.3 REX Synthesis of PLA-based Materials     105(2)
      via Ring-opening Polymerization
      4.4 REX Coupling Reactions from PLA          107(6)
      Precursors
        4.4.1 REX Isocyanate-based Coupling        108(2)
        Reactions
        4.4.2 REX Epoxy-based Coupling Reactions   110(3)
      4.5 REX Free-radical Grafting Reactions      113(4)
      of PLA Chains
      4.6 REX Transesterification (Exchange)       117(1)
      Reactions
      4.7 Conclusions                              118(1)
      Acknowledgements                             119(1)
      References                                   119(5)
  Chapter 5 Plasticization of Poly(lactide)        124(47)
          Alexandre Ruellan
          Violette Ducruet
          Sandra Domenek
      5.1 Introduction                             124(1)
      5.2 Principles of Plasticizing               125(4)
      5.3 Plasticizer Permanence, Migration and    129(5)
      Interaction with Contact Media
      5.4 PLA Plasticizers: Properties, Effects    134(21)
      and Processability
        5.4.1 Plasticizer Impact on Mechanical     134(19)
        Properties
        5.4.2 Plasticizers as Processing Aids      153(2)
      5.5 Long-term Stability of Plasticized PLA   155(5)
        5.5.1 Physicochemical Studies of           155(4)
        Long-term Stability
        5.5.2 Chemical Stability and Degradation   159(1)
      5.6 PLA Plasticizers Derived from Biomass    160(3)
      5.7 Conclusion                               163(1)
      Symbols and Abbreviations                    164(1)
      Monomeric Plasticizers                       164(1)
      Oligomeric Plasticizers                      165(1)
      References                                   165(6)
  Chapter 6 Electrospinning of PLA                 171(24)
          Laura Peponi
          Alicia Mojica-Garcia
          Jos? M. Kenny
      6.1 Production of PLA fibres by              171(8)
      Electrospinning
        6.1.1 PLA Electrospun Nanofibres:          175(2)
        Diameter, Morphology and Orientation
        6.1.2 PLA Electrospun Nanofibres:          177(1)
        Crystallinity
        6.1.3 PLA Electrospun Nanofibres:          177(2)
        Mechanical Properties
      6.2 PLA Matrix Nanocomposite Electrospun     179(4)
      Fibres
        6.2.1 PLA Electrospun Nanocomposite        180(1)
        Fibres with Montmorillonites
        6.2.2 PLA Electrospun Nanocomposite        180(1)
        Fibres with Halloysite Nanotubes
        6.2.3 PLA Electrospun Nanocomposite        181(1)
        Fibres with Hydroxyapatite
        6.2.4 PLA Electrospun Nanocomposite        182(1)
        Fibres with Carbon Nanotubes
        6.2.5 PLA Electrospun Nanocomposite        183(1)
        Fibres with Graphene
      6.3 Applications of Electrospun-PLA Fibres   183(8)
        6.3.1 Tissue Engineering                   184(3)
        6.3.2 Wound Dressing                       187(1)
        6.3.3 Drug Delivery                        188(3)
      6.4 Conclusions                              191(1)
      References                                   191(4)
  Chapter 7 Modification of PLA by Blending        195(20)
  with Elastomers
          N. Bitinis
          R. Verdejo
          M.A. Lopez-Manchado
      7.1 Copolymerization                         195(1)
      7.2 Blending with other Polymers             196(12)
        7.2.1 Blending with Biodegradable          196(1)
        Polymers
        7.2.2 Blending with Non-biodegradable      197(1)
        Petroleum-based Polymers
        7.2.3 Blending with Elastomers             198(5)
        7.2.4 Blending with Natural Rubber         203(5)
      7.3 Conclusions                              208(1)
      References                                   209(6)
PLA-based Nano-biocomposites
  Chapter 8 Polylactide (PLA)/Clay                 215(10)
  Nano-biocomposites
          Jose M. Lagar?n
          Luis Cabedo
      8.1 Introduction                             215(1)
      8.2 Nanoclays for PLA Nanocomposites         216(6)
        8.2.1 PLA/Clay Nanocomposite Processing    219(1)
        8.2.2 PLA/Clay Nanocomposites Properties   220(2)
      References                                   222(3)
  Chapter 9 PLA-nanocellulose Biocomposites        225(20)
          Qi Zhou
          Lars A. Berglund
      9.1 Introduction                             225(1)
      9.2 Types of Nanocellulose                   226(2)
      9.3 Surface Modification of Nanocellulose    228(2)
      9.4 Processing/Mixing Strategies             230(2)
      9.5 Properties                               232(7)
        9.5.1 Crystallization                      232(1)
        9.5.2 Thermal and Mechanical Properties    233(5)
        9.5.3 Barrier Properties                   238(1)
      9.6 Concluding Remarks                       239(1)
      References                                   239(6)
PLA Main Applications
  Chapter 10 PLA and Active Packaging              245(21)
          Ram?n Catal?
          Gracia Lopez-Carballo
          Pilar Herndez-Mu?oz
          Rafael Gavara
      10.1 Introduction to Active Packaging        245(4)
      10.2 Antimicrobial Active Packaging          249(8)
        10.2.1 Antimicrobial Agents                250(1)
        10.2.2 Incorporation of the Agent into     251(1)
        the Polymer Matrix
        10.2.3 Antimicrobial PLA-based             251(6)
        Packaging Developments
      10.3 Antioxidant Active Packaging            257(5)
        10.3.1 Antioxidant Agents                  258(1)
        10.3.2 Incorporation of the Agent into     258(4)
        the Polymer Matrix
        10.3.3 Other Packaging Applications        262(1)
      Acknowledgements                             262(1)
      References                                   262(4)
  Chapter 11 Biomaterials for Tissue               266(23)
  Engineering Based on Nano-structured
  Poly(Lactic Acid)
          Ilaria Armentano
          Elena Fortunati
          Samantha Mattioli
          Nicoletta Rescignano
          Jos Maria Kenny
      11.1 Tissue Engineering                      266(1)
      11.2 Stem Cells                              267(2)
        11.2.1 Embryonic Stem Cells                268(1)
        11.2.2 Adult Stem Cell Sources             268(1)
        11.2.3 Induced Pluripotent Stem Cells      268(1)
        11.2.4 Differentiation Induction           269(1)
        Factors in Tissue Engineering
      11.3 Biomaterials and Nanotechnology         269(1)
      11.4 Nanostructured PLA                      270(9)
        11.4.1 Blends                              271(3)
        11.4.2 Nanoparticles and Nanoshells        274(2)
        11.4.3 Nanocomposites                      276(1)
        11.4.4 Surface Modification                277(2)
      11.5 Conclusions                             279(1)
      Acknowledgements                             279(1)
      References                                   279(10)
Degradation and Biodegradation of PLA
  Chapter 12 Abiotic-hydrolytic Degradation of     289(28)
  Poly(lactic acid)
          Kikku Fukushima
          Giovanni Camino
      12.1 Introduction                            289(1)
      12.2 Molecular Hydrolytic Degradation        290(2)
      Mechanisms of PLA
      12.3 Factors Controlling Hydrolytic          292(13)
      Degradation of PLA
        12.3.1 Degradation Medium Conditions       292(3)
        12.3.2 Structure and Properties of         295(10)
        PLA-based Materials
      12.4 Possible Benefits of Hydrolytic         305(3)
      Degradation of PLA
        12.4.1 Modifications in the Surface        306(1)
        Hydrophilicity Level
        12.4.2 Structural Modification             306(2)
      12.5 Conclusions                             308(1)
      References                                   309(8)
Industrial and Legislative Issues
  Chapter 13 Industrial Uses of PLA                317(17)
          Stefano Fiori
      13.1 Introduction                            317(1)
      13.2 PLA Mechanical and Thermal Properties   318(1)
      13.3 Stereochemistry                         319(1)
      13.4 Use of Additives                        320(2)
        13.4.1 Plasticizers                        321(1)
      13.5 PLA Processing                          322(4)
        13.5.1 Extrusion                           322(1)
        13.5.2 Film and Sheet Casting              322(1)
        13.5.3 Stretch Blow Moulding               323(1)
        13.5.4 Blown Film Extrusion                323(1)
        13.5.5 Thermoforming                       324(1)
        13.5.6 Spinning and Electrospinning        325(1)
        13.5.7 Foaming                             325(1)
      13.6 PLA Commercial Applications             326(5)
        13.6.1 Food Contact Materials              326(2)
        13.6.2 Medical and Biomedical              328(1)
        Applications
        13.6.3 Agriculture                         329(1)
        13.6.4 Electrical Appliances               329(1)
        13.6.5 Textiles                            330(1)
        13.6.6 Home Furnishing                     331(1)
      References                                   331(3)
  Chapter 14 Legislation Related to PLA            334(13)
          Mercedes A. Peltzer
          Ana Beltr-Sanahuja
      14.1 Food Packaging and Legislation          334(3)
      14.2 Biodegradation and Compostability       337(2)
      Legislation
      14.3 Nanomaterials in Food Packaging         339(2)
      Legislation
      14.4 Life Cycle Assessment (LCA)             341(2)
      14.5 Conclusions                             343(1)
      References                                   344(3)
Subject Index                                      347