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1 AMSTERDAM BOSTON CAMBRIDGE HEIDELBERG LONDON ; Chemistry, Manufacture and Applications of Natural Rubber Edited by Shinzo Kohjiya and Yuko Ikeda WP NEW YORK OXEORD PARIS SAN DIEGO, I i'. SAN FRANCISCO SINGAPORE SYDNEY TOKYO ELSEVIER Viuodhcj.1 l\.l.l»l.mi! is.hi impiim,.l EKcvi. r,

2 Contents Contributor contact details.xiii Introduction S. Kohjiya, Kyoto University, Japan of Technology, Japan and Y. Ikeda, Kyoto Institute xvii Part I Properties and processing of natural rubber 1 1 Biosynthesis of natural rubber (NR) in different rubber-producing species 3 K. Cornish, The Ohio State University, USA 1.1 Introduction Rubber biosynthesis Rubber particles and rubber biosynthesis Kinetic analyses of rubber transferase Regulation of biosynthetic rate Regulation of molecular weight Identification and purification of rubber transferase Conclusions Acknowledgments References 25 2 Natural rubber (NR) biosynthesis: perspectives from polymer chemistry 30 J. E. Puskas and K. Chiang, University of Akron, USA and B. Barkakatv, Oak Ridge National laboratory, USA, formerly of University of Akron, USA 2.1 Introduction Background on natural rubber (NR) Synthetic polyisoprenes (PIPs) Biosynthesis of NR //; vitro biosynthesis of NR 47

3 vi Contents 2.6 NR in health care Future trends Acknowledgments References and further reading 57 3 Chemical modification of natural rubber (NR) for improved performance 68 P. Phinyocheep, Mahidol University, Thailand 3.1 Introduction: The role of chemical modification in creating high-performance natural rubber (NR) The main types of chemical modification of NR Chemical modification by changing the structure or weight of rubber molecules Chemical modification of the carbon-carbon double bond Chemical modification by grafting molecules of a different polymer type Conclusions: Key issues in improving the properties of NR Future trends Sources of further information and advice References Understanding network control by vulcanization for sulfur cross-linked natural rubber (NR) 119 Y. Ikbda, Kyoto Institute of Technology, Japan 4.1 Introduction: The importance of sulfur cross-linking of rubber Using small-angle neutron scattering to analyze the network structure of sulfur cross-linked cis-1,4- polyisoprene Network control in sulfur cross-linked m-1,4- polyisoprene Effect of network structure on strain-induced crystallization of sulfur cross-linked cis-\,4-polyisoprene Future trends: Key issues in improving the properties of natural rubber (NR) Acknowledgments References The effect of strain-induced crystallization (SIC) on the physical properties of natural rubber (NR) 135 S. Toki, National Metal and Materials Technology Center, Thailand 5.1 Introduction 135

4 Contents vii 5.2 Temperature-induced crystallization (TIC) and straininduced crystallization (SIC) Stress relaxation and SIC Stress-strain relation and SIC Tear resistance and SIC Green strength and SIC Conclusions Acknowledgment References Generating particulate silica fillers in situ to improve the mechanical properties of natural rubber (NR) 168 A. Tohsan and Y. Ikeda, Kyoto Institute of Technology, Japan 6.1 Introduction: Silica as a filler for rubber Particulate silica generated //; situ Recent processes for adding filler to rubber Applications of in situ silica Conclusions: Key issues in improving the properties of natural rubber (NR) Future trends Acknowledgments References Hydrophobic and hydrophilic silica-filled cross-linked natural rubber (NR): structure and properties 193 A. Kato, NISSAN ARC Ltd, Japan and Y. Kokubo, R. I si sin and Y. Ikeda, Kyoto Institute of Technology, Japan 7.1 Introduction: Silica reinforcement of natural rubber (NR) Testing hydrophobic and hydrophilic silica fillers: sample preparation Methods for analyzing silica filler behavior in crosslinked NR matrix Understanding the behavior of hydrophobic and hydrophilic silica fillers in cross-linked NR matrix Comparing hydrophobic and hydrophilic silica-filled cross-linked NR Conclusions Future trends Acknowledgments References 212

5 viii Contents 8 Computer simulation of network formation in natural rubber (NR) 216 T. Nakao, The University of Tokyo, Japan, formerly of Sumitomo Bakelite Co. Ltd, Japan and S. Kohjiya, Kyoto University, Japan 8.1 Introduction Simulation methods for cold mastication of natural rubber (NR) Simulation methods for vulcanization of NR Summary Future trends Sources of further information and advice Acknowledgement References Appendix: Basic concept of cascade theory 236 Part II Applications of natural rubber Eco-friendly bio-composites using natural rubber (NR) matrices and natural fiber reinforcements 249 A. B. Nair and R. Joseph, Cochin University of Science and Technology, India 9.1 Introduction The importance of eco-friendly bio-composites from natural rubber (NR) Natural fiber reinforcement materials for NR biocomposites Factors influencing the effectiveness of fiber reinforcement Methods to improve the properties of NR bio-composites Physical properties of NR bio-composites Processing of NR bio-composites Applications of NR-based bio-composites with NR reinforcements Future trends Sources of further information and advice References Natural rubber (NR) composites using cellulosic fiber reinforcements 284 R. C. R. Nunes, Universidade Federal do Rio de Janeiro, Brazil 10.1 Introduction: The importance of natural rubber (NR)/cellulose composites 284

6 Contents ix 10.2 NR/cellulose composites NR/natural cellulose nanocomposites NR/regenerated cellulose nanocomposites Applications Future trends References Soft bio-composites from natural rubber (NR) and marine products 303 S. Poompradub, Chulalongkorn University, Thailand 11.1 Introduction Processes and materials for developing natural rubber (NR) composites Effects of marine product fillers on rubber composites Conclusion Future trends Sources of further information and advice References Natural rubber (NR) for the tyre industry 325 Y. Hirata, H. Kondo and Y. Ozawa, Bridgestone Corporation, Japan 12.1 Introduction Tyre types, manufacture and requirements Natural rubber (NR) properties required in tyre manufacture NR properties required in tyre products Examples of NR use in demanding tyre applications Quality standards for NR as a raw material Future trends References Application of epoxidized natural rubber (NR) in pressure sensitive adhesives (PSAs) 353 A. S. Hashim and S. K. Ong, Universiti Kuala Lumpur, Malaysia 13.1 Introduction to pressure sensitive adhesives (PSAs) Processing of natural rubber (NR) and NR4jased PSAs Assessing the performance of a PSA The use of epoxidi/.ed NR as an adhesive Effect of coating thickness Effect of tackifier and filler Effect of molecular weight Effect of testing rate Other factors affecting performance 368

7 X Contents Future trends Sources of further information and advice References Use of natural rubber (NR) for vibration isolation and earthquake protection of structures 371 Y. FuKAHORi, Queen Mary University of London, UK 14.1 Introduction The concept of vibration isolation and earthquake protection Vibration isolation and earthquake protection systems Characteristics of natural rubber (NR) for vibration isolation and earthquake protection Conclusion References 381 Part III Environmental and safety issues Improving the sustainable development of natural rubber (NR) 385 S. Kohjiya, Kyoto University, Japan 15.1 Introduction Supply and demand of natural rubber (NR) in the twentyfirst century Biodiversity Applications of state-of-the-art biotechnology Biosafety Conclusion and future trends References Recycling of natural and synthetic isoprene rubbers 395 A. I. Isavev, University of Akron, USA 16.1 Introduction Approaches to the reuse and recycling of natural rubber (NR) Reuse of NR Recycling of NR Recycling of synthetic isoprene rubber Future trends Conclusions Acknowledgements References 429

8 Contents xi 17 Recycling of sulfur cross-linked natural rubber (NR) using supercritical carbon dioxide 436 Y. Ikeda, Kyoto Institute of Technology, Japan 17.1 Introduction: Key problems in recycling sulfur crosslinked natural rubber (NR) Advantages of supercritical C02 (scc()2) for the devulcanization of sulfur cross-linked rubber Devulcanization of sulfur cross-linked NR in scc Devulcanization of carbon black-filled sulfur cross-linked NR Devulcanization of an NR-based truck tire vulcanizate The role of scc02 in the devulcanization of sulfur crosslinked rubber Conclusion: Key issues in ensuring effective recycling of sulfur cross-linked NR Future trends Acknowledgements References" Recent research on natural rubber latex (NRL) allergy 452 T. Palosuo, National Institute for Health and Welfare, Finland 18.1 Introduction: The problem of natural rubber latex (NRL) allergy Medical background to NRL allergy Mechanisms of development and clinical presentation of NRL allergy Recent trends in the prevalence of NRL allergy Key issues in reducing NRL allergy Future trends Conclusion Sources of further information and advice References Appendix: Abbreviations 481 Index 483

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