Blends and Graft Copolymers of Cellulosics (eBook)

Prof. Yoshiyuki Nishio is a Professor of Kyoto University (Division of Forest and Biomaterials Science, Graduate School of Agriculture).Since 1982, his career has covered all academic occupations: 1982-90, Assistant Professor,Fukui University (1985-86, Res. fellow in McGill University); 1990-95, Associate Professor,Nagaoka University of Technology; 1995-99, Associate Professor, Tokyo University of Agriculture & Technology; 1999-2000, Professor, Tokyo University of Agriculture & Technology, and, concurrently, Director of the Museum of Fiber Science and Technology; 2001-Present, Professor, Kyoto University. For these fifteen years, he has also taught as an invited part-time lecturer in many universities/institutes such as The University of Tokyo, Tokyo Institute of Technology, Nagoya University, etc. Honors The Society of Polymer Science, Japan, Progress Award for 1988; The Society of Fiber Science and Technology, Japan, Sakurada Takeshi Memorial Award for 1990; The Cellulose Society of Japan Award for 1997; Fellow of IAWS (International Academy of Wood Science), 2007-present.Prof. Nishio has published 120 original papers, 28 review papers, 17 book chapters; 12 patents (as inventor); ~30 research reports/commentaries and given more than 50 presentations at international conferences (including ~20 invited ones).Dr. Yoshikuni Teramoto is an Associate Professor of Gifu University (Department of Applied Life Science, Faculty of Applied Biological Sciences) in Japan.In 2005, he joined Biomass Technology Research Center of National Institute of Advanced Science and Technology (AIST) Chugoku (Hiroshima, Japan) as a Research Scientist and mainly worked on the conversion of woody lignocellulosic biomass into liquid fuel. In 2008, he moved to Kyoto University (Division of Forest and Biomaterials Science) as an Assistant Professor and spent five years. His work has included material functionalization of cellulosic polysaccharides via molecular multicomposition and supermolecular structure control. Since 2013, he has been an Associate Professor in Department of Applied Life Science within Faculty of Applied Biological Sciences at Gifu University.Dr. Teramoto received the Young Scientist Award of the Cellulose Society of Japan in 2012 and is currently involved in material functionalization of cellulosic polysaccharides via molecular multicomposition and process development. He has published 50 original papers, 11 review papers, 9 book chapters, 3 patents and given more than 20 presentations at international conferences (including 5 invited ones).Dr. Ryosuke Kusumi is an Assistant Professor of Kyoto University (Division of Forest and Biomaterials Science, Graduate School of Agriculture in Japan.Since 2009, he has been an Assistant Professor in Division of Forest and Biomaterials Science within Graduate School of Agriculture at Kyoto University.He has received the following honors: Green & Sustainable Chemistry Network, Japan, 5th GSC Poster Award on GSC-AON 2009; The Magneto-Science Society of Japan, Research Award for Young Scientists 2009; The Japan Society of Applied Physics, and the Young Scientist Presentation Award 2013.Dr. Kusumi is currently involved in Single crystal NMR analysis from a powder sample via magnetically oriented microcrystal array. Crystal orientation of chiral polymers induced by magnetic orientation of a nucleating agent.He has published 7 original papers, 2 review papers, and given 15 presentations at international conferences.From 2013-15, he has been an Associate Editor of the Journal of Wood Science, the Japan Wood Research Society.Dr. Kazuki Sugimura is an assistant research staff member at Kyoto University (Division of Forest and Biomaterials Science, Graduate School of Agriculture) in Japan.From 2013-2015 Dr. Sugimur was an Assistant Technical Staff member of Kyoto University (Division of Forest and Biomaterials Science, Graduate School of Agriculture) and has been an Assistant Research Staff Member since 2015.She won the Best Poster Awards at the 18th and 20th Annual Meeting of the Cellulose Society of Japan in 2011 and 2013 and is currently engaged in designing high-functional multicomponent materials based on cellulosics using the miscible blending technique.Dr. Sugimur has published 4 original papers; 2 review papers; 2 book chapters; and given 3 presentations at international conferences.Dr. Yoshitaka Aranishi joined the Fibers & Textiles Research Laboratories of Toray Industries, Inc. in 1994 as a Research Scientist and mainly worked on poly (ethylene terephthalate) fiber and its textiles. Since 2006, he has worked in the same laboratories as a Research Associate. His work has included the thermo-plasticization of the cellulose, and the melt spinning process for the thermo-plasticized cellulosic composition. He moved to the Research & Development Planning Dept. of Toray Industries, Inc. in 2013, now works as a Deputy General Manager of the department.He received the Sentan Gijyutsu Taisho Award for Excellence in 2008 and is currently engaged in planning the next generation of fiber materials.To date, Dr. Aranishi has published 4 original papers, 6 review papers, 3 book chapters, 52 Patents, and given 3 presentations at international conferences.

Preface 6
Contents 8
Abbreviations 11
1 General Remarks on Cellulosic Blends and Copolymers 14
Abstract 14
1.1 Introduction: In the Stream of Microcomposition Research 14
1.2 Terminology 16
1.2.1 Structural Parameters of Cellulose Derivatives 16
1.2.2 Miscibility of Polymer Blends 19
1.3 Methods for Miscibility Estimation 20
1.3.1 Tg Measurements 20
1.3.2 Spectroscopic Measurements 22
1.4 Supplementary Techniques 23
1.4.1 Dielectric Relaxation Spectroscopy 23
1.4.2 Fluorescence Polarization Measurement 25
1.5 Outline of the Monograph 26
References 28
2 Cellulosic Polymer Blends 1: With Vinyl Polymers 30
Abstract 30
2.1 Introduction 30
2.2 Cellulose Ester Blends with N-Vinyl Pyrrolidone Copolymer 32
2.2.1 Miscibility Maps as a Function of DS and Copolymer Composition 33
2.2.2 Intermolecular Interaction and Homogeneity Scale 40
2.2.3 Application to Functional Films 46
2.3 Other Prominent Systems of Cellulose Ester/Vinyl Polymer Blend 51
2.3.1 Enhancement of Thermomechanical Performance 52
2.3.2 Intimate Mixing of Cellulosic Blend by In Situ Polymerization of Vinyl Monomer 52
2.4 Concluding Remarks 53
References 54
3 Cellulosic Polymer Blends 2: With Aliphatic Polyesters 57
Abstract 57
3.1 Introduction 57
3.2 Cellulose Ester Blends with Poly(?-caprolactone) 59
3.2.1 Dependence of Miscibility on Alkyl Side-Chain Length and DS 59
3.2.2 Miscibility of Cellulose Mixed Ester Series 61
3.2.3 Miscibility Factors in CE/PCL Blends 62
3.2.4 Crystallization Behavior 63
3.2.5 Spherulite Growth Observation 67
3.3 Acylated Chitin Blends with PCL 68
3.3.1 Molecular Characterization of Acyl-Chs 69
3.3.2 Miscibility Maps of Acyl-Ch/PCL Blends and Comparison with CE Systems 71
3.3.3 Availability as Cytocompatible Flexible Films 73
3.4 Concluding Remarks 80
Acknowledgements 81
References 81
4 Cellulosic Graft Copolymers 86
Abstract 86
4.1 Introduction 86
4.2 Graft Copolymers with Aliphatic Polyester Side-Chains 87
4.2.1 Synthesis and Molecular Characterization 88
4.2.2 Thermal Properties: General Transition Scheme 90
4.2.3 Thermal Treatment Effect on Development of Supramolecular Structures 97
4.2.4 Molecular Dynamics Characterized by Various Relaxation Measurements 103
4.2.5 Tensile Properties and Orientation Characteristics of Films 110
4.2.6 Biodegradation Control 112
4.3 Other Prominences Attained by ATRP: Synthesis and Selected Properties 116
4.4 Conclusion and Prospect 117
Acknowledgements 117
References 118
5 Cellulosic Fiber Produced by Melt Spinning 120
Abstract 120
5.1 Introduction 120
5.2 Strategy for Melt Spinning Process 123
5.2.1 Thermoplasticization of Cellulose 123
5.2.2 Rheological Conditioning 126
5.3 Industrial Example of Success 127
5.3.1 Manufacturing Process 127
5.3.2 Flow Properties 128
5.4 Fiber and Textile Properties 130
5.4.1 General Properties for Clothing 130
5.4.2 Shape Variation and Functional Diversity 132
5.5 Concluding Remarks 134
Acknowledgements 135
References 135