Jie Ren Biodegradable Poly(Lactic Acid): Synthesis, Modification, Processing and Applications Jie Ren Biodegradable Poly(Lactic Acid): Synthesis, Modification, Processing and Applications With 150 figures I'M TSINGHI1A ~ Springer ~ UNIVERSITY PRESS AAuutthhoorr PPrrooff.. 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CCoovveerr ddeessiiggnn:: FFrriiddoo SStteeiinneenn--BBrroooo,, EESSttuuddiioo CCaallaammaarr,, SSppaaiinn PPrriinntteedd oonn aacciidd--ffrreeee ppaappeerr SSpprriinnggeerr iiss ppaarrtt ooff SSpprriinnggeerr SScciieennccee++BBuussiinneessss MMeeddiiaa ((wwwwww..sspprriinnggeerr..ccoomm)) About Author Jie Ren Born in 1965, PhD, a professor at the Institute of Nano and Bio Polymeric Materials, Tongji University in Shanghai. He holds the position of the director of the institute and serves as a council member of Chinese Materials Research Society, a vice chairman of Council of Degradable Plastic, China Plastics Processing Industry Association, an expert of new materials forecast designated by Shanghai municipal government, a member of Biological Material Committee in Shanghai Society of Biology and Medical Science, the director of Degradable Materials Com mittee in Shanghai Society of Advanced Materials, an editor of "Plastics" and "Journal of Building Materials". He has concentrated on the research of biodegradable material, controllable drug delivery system and tissue engineering scaffold. In the field of biodegradable material, the main projects he has undertaken include special project for technological innovation of the 2010 Shanghai World Exposition, special project for biomass engineering high-tech industrialization of National Development and Reform Commission, project of the National High Technology Research and Development Program of China (863 Program), Shanghai Key Scientific and Technological Project, Shanghai Key Nano Science and Technology Project, and some international cooperation projects( cooperated with Boeing.etc). His research was supported by Program for New Century Excellent Talents in MOE of China in 2005. In 2007 he was chosen to be one of the "Shanghai Subject Chief Scientist" . He has published a few monographs and more than 160 papers, including over 50 SCI papers which are cited over 300 times. He has achieved 42 China patents and 1 US patents. ii Preface Polymers with biodegradability and renewability have attracted much attention due to the environmental concerns and sustainability issues associated with petroleum-based polymers. At present the depletion of oil resources has been a large concern all over the world and "white pollution" is becoming a serious problem threatened the human health and the environment. Therefore, the low carbon economy has been put on the agenda. Poly(lactic acid) (PLA) is one of the most important environment-friendly biodegradable thermoplastic polyester with extensive application. Because of its renewable resources, low toxicity and its environment-friendly characteristics along with performance comparable with many petroleum-based plastics, much attention has been paid for its use in service ware, grocery, waste-compo sting bags, mulch films, ideal material for food packaging, engineering platics and other consumer products. This book is written for indicating the importance of PLA in material field. The production and properties of lactic acid and the monomeric building block of PLA are described in detail in this book; the synthesis and manufacture of PLA are described, too. In addition, the book aims at introducing the recent developments in preparation of the linear, graft or branch, star-shaped, and dendritic PLA copolymers and the catalysts used in copolymerization. The processing of PLA, such as injection, spinning, blowing, foaming, is also discussed. A variety of products including bottles, fibers, film, and foam can be manufactured from PLA. Furthermore, PLA can be applied in the field of medical industry used as tissue engineering scaffold, controllable drug delivery system, and so on. The standard and test methods of PLA are discussed in the end of the book. Some my colleagues and doctoral candidates have taken part in the writing of this book. These colleagues are professor Shuying Gu, associate professor Hua Yuan, associate professor Tianbin Ren, Dr. Qingang Tan. And the doctoral candidates iii Dakai Chen, Jianbo Li, Yang Cao, Qinfeng Wang, Naiwen Zhang, Tao Yu, Minghao Gu have also joined the above writing. I also express my thanksgiving to the professor Guofang Gu, associate professor Weizhong Yuan, and the doctoral candidates Yan Liu, Yang Qu, Zhonghai Zhang for their help during the completion of this book. Without their help this book wouldn't be published so easily. iv Contents 1 Introduction .................................................................................................... 1 2 Lactic Acid ...................................................................................................... 4 2.1 Introduction ............................................................................................ 4 2.2 Properties ................................................................................................ 4 2.3 Preparation .............................................................................................. 7 2.3.1 Chemical Synthesis ..................................................................... 7 2.3.2 Ferrnentation ............................................................................... 7 2.4 Separation and Purification of LA .......................................................... 9 2.4.1 Esterification and Hydrolysis .................................................... 10 2.4.2 Crystallization ........................................................................... 10 2.4.3 Molecular Distillation ............................................................... 11 2.5 Application ........................................................................................... 12 2.5.1 Raw Materials of PLA .............................................................. 12 2.5.2 Additives in Foods .................................................................... 12 2.5.3 Applications in Cosmetics ........................................................ 13 2.5.4 Applications in Detergents ........................................................ 13 References ..................................................................................................... 14 3 Synthesis and Manufacture ofPLA. ........................................................... 15 3.1 Direct Polycondensation of Lactic acid ................................................ 15 3.2 Azeotropic Dehydrative Polycondensation of LA ................................ 21 3.3 Polycondensation Kinetics of LA ......................................................... 23 3.4 Ring-Opening Polymerization of Lactide ............................................. 23 3.4.1 Cationic Ring-Opening Polymerization of Lactide ................... 24 3.4.2 Anionic Ring-Opening Polymerization of Lactide ................... 26 3.4.3 Coordination-Insertion Polymerization of Lactide ................... 28 3.4.4 Enzymatic Ring-Opening Polymerization of Lactide ............... 33 References ..................................................................................................... 35 4 Modification of PLA .................................................................................... 38 4.1 Copolymerization ofPLA .................................................................... 38 4.1.1 Random and alternating copolymers ofPLA. ........................... 39 4.1.2 Block Copolymers of PLA ........................................................ 45 v
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