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Raw Materials Supply Chain for Rubber Products John S. Dick Charles P. Rader Raw Materials Supply Chain for Rubber Products Overview of the Global Use of Raw Materials, Polymers, Compounding Ingredients, and Chemical Intermediates Dick, Rader Raw Materials Supply Chain for Rubber Products John S. Dick Charles P. Rader Raw Materials Supply Chain for Rubber Products Overview of the Global Use of Raw Materials, Polymers, Compounding Ingredients, and Chemical Intermediates Hanser Publishers, Munich Hanser Publications, Cincinnati John S. Dick Charles P. Rader Raw Materials Supply Chain for Rubber Products Overview of the Global Use of Raw Materials, Polymers, Compounding Ingredients, and Chemical Intermediates Hanser Publishers, Munich Hanser Publications, Cincinnati The Authors: John S. Dick, LLC Alpha Technologies, 3030 Gilchrist Road, Akron, OH 44305-4420, USA, www.rubberchemist.com Charles P. Rader, Ph.D., Retired Advanced Elastomer Systems, L.P., 388 South Main Street, Akron, OH 44311-1059, USA Distributed in North and South America by: Hanser Publications 6915 Valley Avenue, Cincinnati, Ohio 45244-3029, USA Fax: (513) 527-8801 Phone: (513) 527-8977 www.hanserpublications.com Distributed in all other countries by Carl Hanser Verlag Postfach 86 04 20, 81631 München, Germany Fax: +49 (89) 98 48 09 www.hanser-fachbuch.de The use of general descriptive names, trademarks, etc., in this publication, even if the former are not especially identified, is not to be taken as a sign that such names, as understood by the Trade Marks and Merchandise Marks Act, may accordingly be used freely by anyone. While the advice and information in this book are believed to be true and accurate at the date of going to press, neither the authors nor the editors nor the publisher can accept any legal responsibility for any errors or omissions that may be made. The publisher makes no warranty, express or implied, with respect to the material contained herein. Authors’ Disclaimer: The data and information presented in this book have been collected by the authors and publisher from many sources that are believed to be reliable. However, the authors and publisher make no warranty, expressed or implied, to this book’s accuracy or completeness. No responsibility or liability is assumed by the authors and publisher for any loss or damage suffered through reliance on any information presented in this book. The authors do not purport to give any toxicity or safety information. The final determination of the suitability of any information for the use contemplated for a given application remains the sole responsibility of the user. Cataloging-in-Publication Data is on file with the Library of Congress Bibliografische Information Der Deutschen Bibliothek Die Deutsche Bibliothek verzeichnet diese Publikation in der Deutschen Nationalbibliografie; detaillierte bibliografische Daten sind im Internet über <http://dnb.d-nb.de> abrufbar. ISBN 978-1-56990-537-1 E-Book ISBN 978-1-56990-538-8 All rights reserved. No part of this book may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying or by any information storage and retrieval system, without permission in writing from the publisher. © Carl Hanser Verlag, Munich 2014 Editor: Cheryl Hamilton Production Management: Steffen Jörg Coverconcept: Marc Müller-Bremer, www.rebranding.de, München Coverdesign: Stephan Rönigk Printed and bound by Kösel, Krugzell Printed in Germany Preface This book provides a current overview of the chemical supply chain for the $220 billion rubber industry. It reviews the present and future international economic connections and their effects on this chemical supply chain to the rubber producers, compounding ingredient manufacturers, custom mixers, rubber fabricators, molders, extruders, and others. This book explains the chemical connectivity of rubber compounding materials and polymers to their chemical feedstocks. It enables the reader to directly link current commercial changes in 178 commonly used chemical feedstocks to hundreds of dif- ferent rubber compounding ingredients, polymers, textiles, and other raw materials. One of the purposes of this book is to explain in simple terms the chemistry involved in the manufacture of these diverse materials. Also, a goal of this book is to explain why these various rubber chemicals and polymers are used, what comparative advantages they provide the rubber industry, and what competing uses they have in other industries. Lastly, this book provides a wide range of technical terms and abbreviations that are currently used in the rubber industry. Acknowledgments The authors are grateful to the following individuals for help received in completing this venture: Keith Thomas, R.D. Abbott Corp.; Julia Zimmerman, Bridgestone Americas Tire Corp.; and Robert Ohm, Lion Copolymer LLC. Contents Preface . V Acknowledgments . VI 1 Introduction . 1 1.1 Rubber Industry’s Place in the World Economy . 2 1.2 The Structure of the Tire Industry . 2 1.3 The Structure of the Nontire Industry . 5 1.4 Sectors of the Nontire Rubber Industry . 7 1.4.1 The Rubber Hose Industry ...................................... 7 1.4.2 The Belt Segment ............................................. 7 1.4.3 Seals and Gaskets ............................................. 7 1.4.4 Blowout Preventers and Packers ................................. 8 1.4.5 Single-Ply Roofing ............................................. 8 1.4.6 Bushings and Motor Mounts .................................... 8 1.4.7 Molded Rubber Goods ......................................... 8 1.4.8 Tank Lining .................................................. 8 1.4.9 Wire and Cable Insulation ...................................... 9 1.4.10 Shoe Heel and Sole Applications ................................. 9 1.4.11 Sponge Rubber Products ....................................... 9 1.4.12 Rubber Weatherstripping ....................................... 9 1.4.13 Rubber Latex Products ......................................... 9 1.4.14 Rubber Rollers ................................................ 9 1.4.15 Rubber Tiles ................................................. 10 1.4.16 Rubber Bands ................................................ 10 1.5 Market Forces . 10 2 Basic Raw Materials from Earth Extractions and Agriculture . 13 2.1 Vital Basic Raw Materials for Rubber . 14 2.1.1 Crude Petroleum Oil . 14 2.1.2 Natural Gas . 20 2.1.3 Natural Rubber . 23 2.1.4 Sulfur . 25 2.1.5 Zinc Ore . 26 2.1.6 Copper Ore . 27 2.1.7 Iron Ore . 28 VIII Contents 2.1.8 Silica . 29 2.1.9 Brine and Sea Salt . 30 2.1.10 Fluorspar . 30 2.2 Important Basic Raw Materials for Rubber . 31 2.2.1 Antimony Ore . 31 2.2.2 Aluminum Ore . 31 2.2.3 Clay . 32 2.2.4 Coal . 33 2.2.5 Cobalt Ore . 34 2.2.6 Limestone . 35 2.2.7 Phosphate Rock . 35 2.2.8 Pine Trees . 36 2.2.9 Tallow (from Cattle) . 37 2.2.10 Titanium Ore . 38 2.2.11 Vegetable Oils . 38 2.3 Summary . 40 3 General-Purpose Elastomers . 41 3.1 Natural Rubber . 41 3.2 Synthetic Natural Rubber . 43 3.3 Styrene Butadiene Rubber (SBR) . 45 3.4 Butadiene Rubber (BR) . 53 3.5 Ethylene Propylene Diene Rubber (EPDM) . 58 3.6 Summary . 62 4 Specialty Elastomers . 65 4.1 Butyl Rubber . 66 4.2 Halobutyl Rubber . 69 4.3 Brominated Copolymer of Isobutylene and para-Methylstyrene (BIMSM) . 73 4.4 Nitrile Rubber . 75 4.5 Hydrogenated Nitrile Rubber (HNBR) . 79 4.6 Curable PVC/NBR Polyblends . 82 4.7 Acrylic Rubber . 86 4.8 Polychloroprene (CR) . 88 4.9 Chlorinated Polyethylene Rubber . 92 4.10 Chlorosulfonated Polyethylene (CSM) . 94 4.11 Epichlorohydrin Rubber . 96 4.12 Ethylene Acrylic Elastomer (AEM) . 99 4.13 Ethylene Vinyl Acetate (EVA) . 101 4.14 Fluoroelastomers . 104 4.15 Perfluoroelastomers (FFKM) . 109 4.16 Silicone Rubber . 110 4.17 Summary . 113 Contents IX 5 Textile Reinforcing Materials and Their Adhesive Systems Used in Rubber . 115 5.1 Textile Reinforcing Materials . 115 5.1.1 Aramid . 115 5.1.2 Carbon Fibers . 118 5.1.3 Glass Fibers . 120 5.1.4 Nylon . 122 5.1.5 Polyester Fiber . 127 5.1.6 Rayon . 130 5.1.7 Steel Cord and Cable . 134 5.2 Adhesive Systems Used in Rubber . 136 5.2.1 Dips for Rubber-to-Cord Adhesion . 136 5.2.1.1 Resorcinol Formaldehyde Resin (Liquid) . 137 5.2.1.2 Styrene Butadiene Vinylpyridine Latex . 139 5.2.1.3 Isocyanate and/or Epoxy Treatment . 142 5.2.2 Rubber Compounding Additives for Cord Adhesion . 143 5.2.2.1 Hydrated Precipitated Silica . 144 5.2.2.2 Resorcinol Formaldehyde Resin (Solid) . 146 5.2.2.3 Hexamethoxymethylmelamine (HMMM) . 148 5.2.2.4 Hexamethylene Tetramine (HMT) . 151 5.2.2.5 Cobalt Stearate . 152 5.3 Summary . 154 6 Thermoplastic Elastomers . 155 6.1 Styrenic Block Copolymers (SBC) . 156 6.2 Thermoplastic Olefins (TPO) . 160 6.3 Thermoplastic Vulcanizate (TPV) Based on PP/EPDM . 163 6.4 Thermoplastic Vulcanizate (TPV) Based on NBR/PP . 167 6.5 Thermoplastic Vulcanizate (TPV) Based on IIR/PP . 169 6.6 Thermoplastic Vulcanizate (TPV) Based on ACM/Nylon . 172 6.7 Thermoplastic Vulcanizate (TPV) Based on BIMS/Nylon . 174 6.8 Thermoplastic Polyurethanes (TPUs) . 175 6.9 Copolyester and Polyamide Block Copolymers . 177 6.10 Summary . 178 7 Polyurethane . 179 7.1 Polyols . 181 7.2 Adipic Acid-Ethylene Glycol Polyester Polyol . 181 7.3 Polypropylene Glycol Polyol . 183 7.4 Isocyanates . 184 7.4.1 4,4'-Diphenylmethane Diisocyanate (MDI) . 185 7.4.2 Toluene Diisocyanate (TDI) . 188 7.5 Chain Extenders . 189 7.5.1 1,4-Butanediol (1,4-BD) . 190 7.5.2 Bis(beta-hydroxyethyl) Ether of Resorcinol (HER) . 192 X Contents 7.5.3 Hydroquinone Di-(2-hydroxyethyl) Ether (HQEE) . 194 7.5.4 Trimethylolpropane (TMP) . 196 7.6 Methylene-Bis-o-chloroaniline (MBCA) . 197 7.7 Summary . 199 8 Carbon Black, Fillers, Reinforcing Agents, and Coupling Agents . 201 8.1 Furnace Carbon Blacks . 201 8.2 Thermal.
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