John S. DickCharles P. Rader

Raw Materials Supply Chain for Rubber ProductsOverview of the Global Use of Raw Materials, Polymers, Compounding Ingredients, and Chemical Intermediates

Dick, RaderRaw Materials Supply Chain for Rubber Products

Raw Materials Supply Chain for Rubber Products

John S. DickCharles P. Rader

Hanser Publishers, Munich Hanser Publications, Cincinnati

Overview of the Global Use of Raw Materials, Polymers, Compounding Ingredients, and Chemical Intermediates

Raw Materials Supply Chain for Rubber Products

John S. DickCharles P. Rader

Hanser Publishers, Munich Hanser Publications, Cincinnati

Overview of the Global Use of Raw Materials, Polymers, Compounding Ingredients, and Chemical Intermediates

The Authors:John S. Dick, LLCAlpha Technologies, 3030 Gilchrist Road, Akron, OH 44305-4420, USA, www.rubberchemist.com

Charles P. Rader, Ph.D., RetiredAdvanced 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 978-1-56990-537-1E-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, MünchenCoverdesign: Stephan RönigkPrinted and bound by Kösel, KrugzellPrinted in Germany

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.

Preface

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.

Acknowledgments

Contents

Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . V

Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . VI

1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11.1 Rubber Industry’s Place in the World Economy . . . . . . . . . . . . . . . . . . . . . . . . . . 21.2 The Structure of the Tire Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21.3 The Structure of the Nontire Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51.4 Sectors of the Nontire Rubber Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

1.4.1 The Rubber Hose Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71.4.2 The Belt Segment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71.4.3 Seals and Gaskets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71.4.4 Blowout Preventers and Packers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81.4.5 Single-Ply Roofing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81.4.6 Bushings and Motor Mounts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81.4.7 Molded Rubber Goods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81.4.8 Tank Lining . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81.4.9 Wire and Cable Insulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91.4.10 Shoe Heel and Sole Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91.4.11 Sponge Rubber Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91.4.12 Rubber Weatherstripping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91.4.13 Rubber Latex Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91.4.14 Rubber Rollers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91.4.15 Rubber Tiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101.4.16 Rubber Bands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

1.5 Market Forces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

2 Basic Raw Materials from Earth Extractions and Agriculture . . . . . 132.1 Vital Basic Raw Materials for Rubber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

2.1.1 Crude Petroleum Oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142.1.2 Natural Gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202.1.3 Natural Rubber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232.1.4 Sulfur . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252.1.5 Zinc Ore . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262.1.6 Copper Ore . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 272.1.7 Iron Ore . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28

VIII Contents

2.1.8 Silica . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 292.1.9 Brine and Sea Salt . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 302.1.10 Fluorspar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30

2.2 Important Basic Raw Materials for Rubber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 312.2.1 Antimony Ore . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 312.2.2 Aluminum Ore . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 312.2.3 Clay . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 322.2.4 Coal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 332.2.5 Cobalt Ore . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 342.2.6 Limestone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 352.2.7 Phosphate Rock . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 352.2.8 Pine Trees . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 362.2.9 Tallow (from Cattle) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 372.2.10 Titanium Ore . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 382.2.11 Vegetable Oils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38

2.3 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40

3 General-Purpose Elastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 413.1 Natural Rubber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 413.2 Synthetic Natural Rubber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 433.3 Styrene Butadiene Rubber (SBR) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 453.4 Butadiene Rubber (BR) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 533.5 Ethylene Propylene Diene Rubber (EPDM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 583.6 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62

4 Specialty Elastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 654.1 Butyl Rubber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 664.2 Halobutyl Rubber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 694.3 Brominated Copolymer of Isobutylene and para-Methylstyrene (BIMSM) . . . . . . 734.4 Nitrile Rubber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 754.5 Hydrogenated Nitrile Rubber (HNBR) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 794.6 Curable PVC/NBR Polyblends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 824.7 Acrylic Rubber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 864.8 Polychloroprene (CR) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 884.9 Chlorinated Polyethylene Rubber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 924.10 Chlorosulfonated Polyethylene (CSM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 944.11 Epichlorohydrin Rubber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 964.12 Ethylene Acrylic Elastomer (AEM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 994.13 Ethylene Vinyl Acetate (EVA) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1014.14 Fluoroelastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1044.15 Perfluoroelastomers (FFKM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1094.16 Silicone Rubber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1104.17 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113

Contents IX

5 Textile Reinforcing Materials and Their Adhesive Systems Used in Rubber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115

5.1 Textile Reinforcing Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1155.1.1 Aramid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1155.1.2 Carbon Fibers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1185.1.3 Glass Fibers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1205.1.4 Nylon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1225.1.5 Polyester Fiber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1275.1.6 Rayon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1305.1.7 Steel Cord and Cable . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134

5.2 Adhesive Systems Used in Rubber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1365.2.1 Dips for Rubber-to-Cord Adhesion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136

5.2.1.1 Resorcinol Formaldehyde Resin (Liquid) . . . . . . . . . . . . . . . . . . 1375.2.1.2 Styrene Butadiene Vinylpyridine Latex . . . . . . . . . . . . . . . . . . . 1395.2.1.3 Isocyanate and/or Epoxy Treatment . . . . . . . . . . . . . . . . . . . . . . 142

5.2.2 Rubber Compounding Additives for Cord Adhesion . . . . . . . . . . . . . . . . . 1435.2.2.1 Hydrated Precipitated Silica . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1445.2.2.2 Resorcinol Formaldehyde Resin (Solid) . . . . . . . . . . . . . . . . . . . 1465.2.2.3 Hexamethoxymethylmelamine (HMMM) . . . . . . . . . . . . . . . . . . 1485.2.2.4 Hexamethylene Tetramine (HMT) . . . . . . . . . . . . . . . . . . . . . . . . 1515.2.2.5 Cobalt Stearate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152

5.3 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154

6 Thermoplastic Elastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1556.1 Styrenic Block Copolymers (SBC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1566.2 Thermoplastic Olefins (TPO) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1606.3 Thermoplastic Vulcanizate (TPV) Based on PP/EPDM . . . . . . . . . . . . . . . . . . . . . 1636.4 Thermoplastic Vulcanizate (TPV) Based on NBR/PP . . . . . . . . . . . . . . . . . . . . . . 1676.5 Thermoplastic Vulcanizate (TPV) Based on IIR/PP . . . . . . . . . . . . . . . . . . . . . . . . 1696.6 Thermoplastic Vulcanizate (TPV) Based on ACM/Nylon . . . . . . . . . . . . . . . . . . . 1726.7 Thermoplastic Vulcanizate (TPV) Based on BIMS/Nylon . . . . . . . . . . . . . . . . . . . 1746.8 Thermoplastic Polyurethanes (TPUs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1756.9 Copolyester and Polyamide Block Copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . 1776.10 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 178

7 Polyurethane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1797.1 Polyols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1817.2 Adipic Acid-Ethylene Glycol Polyester Polyol . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1817.3 Polypropylene Glycol Polyol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1837.4 Isocyanates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 184

7.4.1 4,4'-Diphenylmethane Diisocyanate (MDI) . . . . . . . . . . . . . . . . . . . . . . . . 1857.4.2 Toluene Diisocyanate (TDI) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 188

7.5 Chain Extenders . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1897.5.1 1,4-Butanediol (1,4-BD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1907.5.2 Bis(beta-hydroxyethyl) Ether of Resorcinol (HER) . . . . . . . . . . . . . . . . . . . 192

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7.5.3 Hydroquinone Di-(2-hydroxyethyl) Ether (HQEE) . . . . . . . . . . . . . . . . . . . 1947.5.4 Trimethylolpropane (TMP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196

7.6 Methylene-Bis-o-chloroaniline (MBCA) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1977.7 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199

8 Carbon Black, Fillers, Reinforcing Agents, and Coupling Agents . . 2018.1 Furnace Carbon Blacks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2018.2 Thermal Carbon Black . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2068.3 Acetylene Carbon Black . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2088.4 Hydrated Precipitated Silica . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2108.5 Fumed Silica . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2138.6 TESPT Organosilane Coupling Agent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2158.7 Kaolin Clay . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2178.8 Calcium Carbonate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2208.9 Talc . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2228.10 Titanium Dioxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2248.11 Ground Coal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2268.12 Iron Oxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2278.13 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229

9 Process Oils, Synthetic Ester Plasticizers, and Processing Aids . . 2319.1 Aromatic Process Oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2319.2 Naphthenic Process Oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2349.3 Paraffinic Oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2369.4 Rosin Oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2399.5 Dioctyl Phthalate (DOP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2409.6 Diisodecyl Phthalate (DIDP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2449.7 Dioctyl Adipate (DOA) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2469.8 Dioctyl Sebacate (DOS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2489.9 Butyl Oleate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2509.10 Dibutoxyethoxyethyl Adipate (DBEEA) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2539.11 Vulcanized Vegetable Oil (VVO) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2559.12 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 256

10 Curatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25710.1 Activators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 258

10.1.1 Zinc Oxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25810.1.2 Stearic Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261

10.2 Vulcanizing Agents (Sulfur Based) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26310.2.1 Rubber Maker’s Sulfur . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26310.2.2 Insoluble Sulfur . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26610.2.3 Dithiodimorpholine (DTDM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26810.2.4 Tetramethylthiuram Disulfide (TMTD) . . . . . . . . . . . . . . . . . . . . . . . . . . . 271

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10.3 Primary Accelerators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27410.3.1 N-t-butyl-2-benzothiazole Sulfenamide (TBBS) . . . . . . . . . . . . . . . . . . . . . 27410.3.2 N-Cyclohexyl-2-benzothiazole Sulfenamide (CBS) . . . . . . . . . . . . . . . . . . 27710.3.3 2-(4-Morpholinothio)-benzothiazole Sulfenamide (MBS) . . . . . . . . . . . . . 28010.3.4 N,N'-Dicyclohexyl-2-benzothiazole Sulfenamide (DCBS) . . . . . . . . . . . . . 28310.3.5 4-Morpholinyl-2-benzothiazole Disulfide (MBSS) . . . . . . . . . . . . . . . . . . . 28510.3.6 Alkyl Phenol Disulfide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28810.3.7 Ethylene Thiourea (ETU) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289

10.4 Secondary Accelerators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29110.4.1 2-Mercaptobenzothiazole (MBT) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29110.4.2 Benzothiazole Disulfide (MBTS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29410.4.3 Tetramethyl Thiuram Monosulfide (TMTM) . . . . . . . . . . . . . . . . . . . . . . . 29710.4.4 Zinc Dibutyldithiocarbamate (ZnDBC) . . . . . . . . . . . . . . . . . . . . . . . . . . . 30010.4.5 Zinc Dimethyldithiocarbamate (ZnDMC) . . . . . . . . . . . . . . . . . . . . . . . . . 30210.4.6 Tellurium Diethyldithiocarbamate (TeDEC) . . . . . . . . . . . . . . . . . . . . . . . 30410.4.7 Diphenyl Guanidine (DPG) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30610.4.8 Di-o-Tolylguanidine (DOTG) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309

10.5 Inhibitors and Retarders . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31110.5.1 Cyclohexylthiophthalimide (CTP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31110.5.2 Benzoic Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31410.5.3 Phthalic Anhydride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31610.5.4 Salicylic Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31710.5.5 Magnesium Oxide (MgO) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 319

10.6 Nonsulfur Vulcanizing Agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32010.6.1 Dicumyl Peroxide (DCP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32110.6.2 Di(2-t-butylperoxyisopropyl)benzene (BBPIB) . . . . . . . . . . . . . . . . . . . . . . 32310.6.3 Methylol-Terminated p-Alkyl-Substituted Phenol Formaldehyde

Curing Resin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32410.6.4 Zinc Oxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 326

10.7 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 327

11 Antioxidants, Antiozonants, Tackifiers, Flame Retardants, and Blowing Agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 329

11.1 Antioxidants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32911.1.1 2,2,4-Trimethyl-1,2-dihydroquinoline (TMQ) . . . . . . . . . . . . . . . . . . . . . . . 32911.1.2 Acetone Diphenylamine Condensation Product (ADPA) . . . . . . . . . . . . . . 33211.1.3 Phenyl-alpha-naphthylamine (PAN) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33411.1.4 Octylated Diphenylamine (8DPA) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33711.1.5 Methylene-bis-methylbutyl phenol (o-MBp14) . . . . . . . . . . . . . . . . . . . . . . 33911.1.6 N,N'-Di-beta-naphthyl-p-phenylene Diamine (DNPD) . . . . . . . . . . . . . . . . 341

11.2 Antiozonants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34311.2.1 N-1,3-Dimethylbutyl-N'-phenyl-p-phenylene Diamine (6PPD) . . . . . . . . . . 34311.2.2 N-N'-bis (1-methylheptyl)-p-phenylene Diamine (i88PD) . . . . . . . . . . . . . . 34811.2.3 N,N'-Diphenyl-p-phenylene Diamine (DPPD) . . . . . . . . . . . . . . . . . . . . . . 35011.2.4 Protective Waxes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 352

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11.3 Tackifiers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35411.3.1 Phenol Formaldehyde Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35411.3.2 Phenol Acetylene Tackifying Resin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35611.3.3 Petroleum Aliphatic Hydrocarbon Resins . . . . . . . . . . . . . . . . . . . . . . . . . 35811.3.4 Polyterpene Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 359

11.4 Blowing Agents (for Sponge Rubber) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36111.4.1 Azodicarbonamide (ADC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36111.4.2 p,p'-Oxybis(benzenesulfonyl) Hydrazide (OBSH) . . . . . . . . . . . . . . . . . . . 362

11.5 Flame Retardants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36511.5.1 Antimony Oxide (Antimony Trioxide) . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36511.5.2 Chlorinated Paraffin (CP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36711.5.3 Alumina Trihydrate (ATH) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36911.5.4 Zinc Borate Hydrate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37011.5.5 Triaryl Phosphate (TAP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 372

11.6 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 373

12 Intermediate Feedstocks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37512.1 Acetaldehyde . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37712.2 Acetic Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37812.3 Acetone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37912.4 Acetylene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38012.5 Acrylonitrile (ACN) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38112.6 Acrylonitrile Butadiene Rubber (NBR) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38212.7 Adipic Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38312.8 p-Alkylphenol (para-Alkylphenol) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38412.9 4-Aminodiphenylamine (4-ADPA) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38412.10 Ammonia . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38512.11 Ammonium Thiocyanate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38712.12 t-Amylene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38812.13 Aniline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38812.14 Aniline Hydrochloride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39012.15 Antimony . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39112.16 Antimony Trichloride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39112.17 Benzene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39212.18 Benzothiazyl Disulfide (MBTS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39412.19 Borates (Borax) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39412.20 Boric Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39512.21 Bromine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39612.22 Butadiene (BD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39712.23 Butane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39912.24 1,4-Butanediol (BDO) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40012.25 Butanol (Butyl Alcohol) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40112.26 n-Butyl Acrylate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 402

Contents XIII

12.27 t-Butylamine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40312.28 n-Butyl Chloride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40412.29 t-Butylphenol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40412.30 n-Butyraldehyde . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40512.31 Calcium Carbide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40612.32 Calcium Hydroxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40712.33 Calcium Oxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40812.34 Caprolactam . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40812.35 Carbon Disulfide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41012.36 Chlorine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41112.37 Chlorobenzene (Monochlorobenzene) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41212.38 Chlorodifluoromethane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41312.39 Chlorohydrin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41312.40 Coal Tar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41412.41 Crotonaldehyde . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41412.42 Cumene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41512.43 Cyclohexane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41612.44 Cyclohexanone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41812.45 Cyclohexylamine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41912.46 Cyclohexyl Mercaptan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41912.47 Cyclopentadiene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42012.48 p,p'-Diaminodiphenylmethane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42112.49 Diaminotoluene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42112.50 Dibutylamine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42212.51 Dichlorodimethylsilane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42312.52 Dicyclohexylamine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42412.53 Dicyclopentadiene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42412.54 Diethylamine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42512.55 Diisobutylene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42612.56 Dimethylamine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42612.57 Dimethyl Terephthalate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42712.58 p-Dinitrobenzene (para-Dinitrobenzene) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42812.59 2,4-Dinitrotoluene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42912.60 Diphenylamine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42912.61 Diphenylmethane-4,4'-Diisocyanate (MDI) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43012.62 Epichlorohydrin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43212.63 Ethane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43312.64 Ethyl Acrylate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43312.65 Ethyl Alcohol (Ethanol) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43412.66 Ethylbenzene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43512.67 Ethylene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43612.68 Ethylene Carbonate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 438

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12.69 Ethylene Chlorohydrin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43812.70 Ethylenediamine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43912.71 Ethylene Dichloride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44012.72 Ethylene Glycol (EG) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44112.73 Ethylene Oxide (EO) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44112.74 2-Ethylhexanol (2EH) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44312.75 5-Ethylidenenorbornene (ENB) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44412.76 Formaldehyde . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44512.77 1,4-Hexadiene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44712.78 Hexamethylenediamine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44712.79 Hexamethylenetetramine (HMT) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44812.80 Hydrazine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44912.81 Hydrochloric Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45012.82 Hypochlorous Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45112.83 Hydrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45112.84 Hydrogen Fluoride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45212.85 Hydrogen Peroxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45312.86 Hydroquinone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45412.87 Iron . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45512.88 Isobutylene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45512.89 Isobutylene-Isoprene Rubber (IIR, Butyl Rubber) . . . . . . . . . . . . . . . . . . . . . . . . . 45712.90 Isocyanate-Terminated Prepolymer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45812.91 Isoprene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45812.92 Isopropyl Alcohol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45912.93 p-Isopropylphenol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46012.94 Melamine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46112.95 Mercaptobenzothiazole (MBT) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46212.96 Mesityl Oxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46212.97 Methane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46312.98 Methanol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46412.99 Methyl Acrylate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46512.100 Methyl Chloride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46612.101 Methylethyl Ketone (MEK) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46712.102 Methyl Isobutyl Ketone (MIBK) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46812.103 p-Methylphenol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46912.104 p-Methylstyrene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46912.105 Morpholine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47012.106 Naphthalene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47112.107 β -Naphthol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47212.108 a-Naphthylamine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47212.109 Nitric Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47312.110 p-Nitroaniline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 474

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12.111 Nitrobenzene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47512.112 α-Nitronaphthalene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47512.113 n-Octanol (octyl alcohol) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47612.114 p-t-Octylphenol (p-tert-Octylphenol) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47712.115 Oleic Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47812.116 Phenol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47912.117 p-Phenylenediamine (PPDA) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48112.118 Phosgene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48212.119 Phosphorus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48312.120 Phosphorus Oxychloride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48312.121 Phosphorus Pentoxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48412.122 Phosphorus Trichloride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48512.123 Phthalic Anhydride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48612.124 Phthalimide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48712.125 α-Picoline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48812.126 Polyacrylonitrile . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48912.127 Polypropylene (PP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48912.128 Polypropylene Glycol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49012.129 Polyvinyl Chloride (PVC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49112.130 Potassium Bromide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49212.131 Propane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49312.132 Propylene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49412.133 Propylene Glycol (PG) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49512.134 Propylene Oxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49612.135 Quinone (1,4-Benzoquinone) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49712.136 Resorcinol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49812.137 Sebacic Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49912.138 Silicon Metal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50012.139 Silicon Tetrachloride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50112.140 Sodium Bromide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50212.141 Sodium Carbonate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50212.142 Sodium Dimethyldithiocarbamate (NaDMC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50312.143 Sodium Hydroxide (Caustic Soda) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50412.144 Sodium Hypochlorite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50512.145 Sodium Mercaptobenzothiazole (NaMBT or Sodium MBT) . . . . . . . . . . . . . . . . . . 50612.146 Sodium Nitrate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50712.147 Sodium Phenate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50712.148 Sodium Silicate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50812.149 Sodium Sulfate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50812.150 Sodium Sulfite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50912.151 Stannous Chloride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51012.152 Stearic Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 511

XVI Contents

12.153 Styrene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51212.154 Sulfur . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51312.155 Sulfur Dioxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51412.156 Sulfuric Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51512.157 Sulfur Monochloride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51612.158 Terephthalic Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51712.159 Tetrafluoroethylene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51812.160 Tin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51912.161 Titanium Tetrachloride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51912.162 Toluene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52012.163 Toluene Diisocyanate (TDI) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52112.164 o-Toluidine (ortho-Toluidine) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52212.165 1,1,1-Trichloroethane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52312.166 Trichlorosilane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52412.167 1,1,1-Trimethylolpropane (TMP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52412.168 Urea . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52512.169 Vinyl Acetate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52612.170 Vinyl Chloride Monomer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52712.171 Vinyl Fluoride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52812.172 Vinyl Pyridine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52912.173 Wax . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53012.174 Xylene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53012.175 Zinc Metal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53112.176 Zinc Carbonate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53212.177 Zinc Stearate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53312.178 Zinc Sulfate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 533

Glossary of Acronyms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 535

Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 543

About the Authors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 583

1The purpose of this book is to improve understanding of the chemical nature of the global rubber industry in a context of commercial and political forces. These forces have often resulted in higher prices and periodic shortages in the supply of raw materials and intermediates necessary for the continued production of rubber products. Both the 20th and 21st centuries have witnessed numerous raw material shortages that have seriously impacted the global rubber industry. In all probability, these shortages and disruptions will continue for the foreseeable future.

The rubber industry today is based on the mixing of batches of rubber compounds. This industry is basically a batch industry where raw rubber(s), filler(s), and other compounding ingredient(s) are mixed together using either a two-roll mill or an internal mixer to prepare batches of rubber compounds (Figure 1.1). These uncured batches are further processed “downstream” through capital-intensive processes involving extruders, calenders, injection-molding machines, continuous vulcaniza-tion units, and curing presses. The continuity of these processes relies on a consist-ent, steady supply of rubber compounding ingredients and base polymers (natural and synthetic rubbers); see Figure 1.2 for how these topics are arranged in this book.

Base Polymer(s)

Compounding IngredientsRubber Mixing

Process

Mixed Rubber Compounds for Making Rubber Products

Figure 1.1 Rubber mixing process

There are three types of material shortages that have occurred and can occur in the rubber industry. These three types of shortages or material disruptions are as fol-lows:

1. Shortage or supply disruptions in base materials from earth extraction or agri-culture.

2. Shortage or supply disruptions in chemical intermediates.3. Shortage or supply disruptions in supply of compounding ingredients or base

polymers (rubbers).

Introduction

2 1  Introduction

Base Materials fromEarth Extraction orAgriculture (Chapter 2)

ChemicalIntermediates in Chemical Processing

Final Rubber CompoundingIngredients or Finished Base Polymers (Rubbers)(Chapters 3–11)

(Chapter 12)

Figure 1.2 Organization of this book

Examples of shortages of extracted base materials from the earth were seen with the oil embargo of 1973 and extraction of cobalt ore in the 1980s. Shortages of the monomer styrene or butadiene needed for the polymerization of styrene butadiene rubber (SBR) are examples of chemical intermediate shortages in the 1980s and the last decade as well. Examples of rubber compounding ingredient or finished base polymer shortages are seen when the United States was cut off from its sources of natural rubber supply during World War II, shortages of zinc oxide and titanium dioxide in the 1970s and 1980s, as well as shortages of various raw elastomers in the recent past.

�� 1.1� Rubber Industry’s Place in the World Economy

The worldwide rubber industry totaled about $220 billion in 2010, which is about one-quarter of one percent of the world GDP. About two-thirds of the rubber indus-try is tire related with one-third being non-tire related.

�� 1.2�The Structure of the Tire Industry

There are over 70 active tire manufacturers in the world (Table 1.1). In 2012, the big three tire companies (Bridgestone, Goodyear, and Michelin) represented about 46% of all tire sales. Bridgestone, Michelin, Goodyear, and Continental represented about 50% in 2010 of all tire sales. If Pirelli, Sumitomo, Yokohama, Hankook, Cooper Tire, Cheng Shin, Hangzhou Zhongce, Kumho Tire, Toyo Tire and Triangle are added as well, these top 14 firms represent a total of 75% of world tire manufacturing.

1.2 The Structure of the Tire Industry 3

Table 1.1 Seventy Tire Manufacturers in Approximately Descending Order by Size

Tire Company Headquarters LocationBridgestone Corp. Tokyo, JapanMichelin Clermont-Ferrand, FranceGoodyear Tire and Rubber Co. Akron, OH, USAContinental AG Hanover, GermanyPirelli SpA Milan, ItalySumitomo Rubber Industries Ltd. Kobe, JapanHankook Tire Co. Ltd. Seoul, South KoreaCooper Tire and Rubber Co. Findlay, OH, USAKumho Tire Co. Seoul, South KoreaToyo Tire and Rubber Co. Osaka, JapanCheng Shin Yuanlin, TaiwanGiti Tire Co. Singapore/ChinaTriangle Group Co. Shandong, ChinaMRF Ltd. Chennai, IndiaNoklan Tyres PLC Nokia, FinlandSibur-Russkie Shiny Moscow, RussiaApollo Tyres Ltd. Kerala, IndiaShanghai Tyre and Rubber Co. Ltd. Shanghai, ChinaAmtel-Vredestein N. V. Moscow, RussiaJ. K. Industries Ltd. New Delhi, IndiaHangzhou Zhongce Rubber Co. Hangzhou, ChinaShandong Chengshan Tire Co. Chengshan, ChinaNexen Tire Corp. Seoul, South KoreaCeat Ltd. Mumbai, IndiaNizhnekamskshina Nizhnekamsk, RussiaAeolus Tyre Co. Jiaozuo, ChinaBRISA/Bridgestone Sabanci Tire Izmit, TurkeyP. T. Gajah Tunggal Jakarta, IndonesiaGPX International Tire Corp. Malden, MA, USAQingdao Doublestar Industrial Co. Qingdao, ChinaKenda Rubber Industrial Co. Yuanlin, TaiwanMatador AS Puchov, SlovakiaTrelleborg AB Trelleborg, SwedenCarlisle Companies, Inc. Charlotte, NC, USASouth China Tire and Rubber Co. Cuangzhou City, ChinaNankang Rubber Tire Corp. Taipei, TaiwanJSC Belshina Belarus Tyre Works Bobruisk, BelarusDunlop Tyres International Pty. Ltd. Durban, South Africa

4 1  Introduction

Tire Company Headquarters LocationMarangoni, S. p. A. Verona, ItalyFATE S. A. I. C. I. San Fernando, ArgentinaHwa Fong Rubber Ind. Co. Ltd. Taipei, TaiwanCGS Ceske Gumarenska Spol. Prague, Czech RepublicGTY Tire Co. Mount Vernon, IL, USAFederal Corp. Tao Yuan, TaiwanAlliance Tire Co. Hadera, IsraelCia. Hulera Tornel S. A. de C. V. Mexico City, MexicoInoue Rubber Co. Ikeda, JapanKerman Tire and Rubber Co. Tehran, IranJSC Dneproshina Dnepropetrovsk, UkraineVredestein NV Enschede, NetherlandsBalkrishna Industries Ltd. Maharashtra, IndiaLoadsar Pvt. Ltd./Solideal Co. Colombo, Sri LankaGuangzhou Pearl River Rubber Tyre Guangzhou, ChinaDenman Tire Corp. Leavittsburg, OH, USADena Tire and Rubber Mfg. Co. Ltd. Tehran, IranBeijing Shouchuang Tyres Co. Beijing, ChinaMetro Tyres Ltd. Ludhiana, IndiaQingdao Yellow Sea Rubber Co., Ltd. Qingdao, ChinaShandong Zhongce Tyre Co. Shouguang City, ChinaSilverstone Corp. Kuala Lumpur, MalaysiaDouble Happiness Tyre Industries Taiyuan, ChinaLiaoning Tyres Group Co. Liaoning, ChinaXuzhou Tyre Group Xuzhou, Jiangsu, ChinaCasumina (Southern Rubber Industry) Ho Chi Minh City, VietnamTVS Srchakra Ltd. Chennai, IndiaSpecialty Tires of America Indiana, PA, USASociete Tunisienne des Pneumatiques Sousse, TunisiaJ. V. Matador-Omskshina Omsk, RussiaGeneral Tyre and Rubber Co. of Pakistan, Ltd. Karachi, PakistanFalcon Tyres Ltd. Mysore, India

The tire industry sales consist of about 60% passenger tires and 30% truck and bus tires, with the remaining 10% represented by farm service, aircraft, motorcycle, bicycle, and earth-moving tires (also called off-the-road or OTR tires).

The world tire industry produced over 1 billion tires of all types in 2010. By the numbers of tires (not sales figures), about 80% of all tires are passenger tires. There

Table 1.1 Seventy Tire Manufacturers in Approximately Descending Order by Size (continuation)

1.3 The Structure of the Nontire Industry 5

are about eight passenger tires made for every truck tire produced. According to the Rubber Manufacturers Association (RMA), a typical passenger tire weighs about 25 pounds and contains about 3.5 pounds of natural rubber, about 6.8 pounds of synthetic rubber, 7 pounds of carbon black, and 3.7 pounds of steel tire cord and bead wire. Likewise, the typical truck tire weighs about 120 pounds and contains about 32.4 pounds of natural rubber, 17 pounds of synthetic rubber, 33.5 pounds of carbon black, and 17.4 pounds of steel tire cord and bead wire.

�� 1.3�The Structure of the Nontire Industry

There are numerous nontire rubber fabricators in the world today (Table 1.2). A far larger number of different rubber fabrication plants exist for the nontire than for the tire sector. The economies of scale are different for tire manufacturing compared to fabrication of rubber articles and products for the nontire sector. Achieving effective economies of scale for a tire plant requires a certain minimal size of perhaps 25,000 tires per day. On the other hand, the minimal capital and size requirements for pro-duction plants in the nontire sector are considerably less. Therefore, the nontire sector is populated with a larger number of production plants, representing a broader mix of large, medium, and small plants.

Table 1.2 Some of the Largest Nontire Rubber Companies in the World in Approximate Descending Order of Their Annual Sales of Nontire Rubber Products

Company Country of OriginContinental AG GermanyHutchinson FranceBridgestone Corp. JapanFreudenberg Group GermanyTrelleborg SwedenTokai Rubber Industries JapanTomkins PLC United KingdomCooper Standard Automotive USAParker Hannifin Corp. USANOK Inc. JapanNew Balance Athletic Shoe USAVeyance Technologies USAMark IV Industries USAFederal-Mogul Corp. USAEaton Corp. USA

6 1  Introduction

Company Country of OriginWolverine World Wide USACarlisle Companies USAMetzeler Automotive Profile Systems GermanyYokohama Rubber Co. JapanAnsell Ltd. AustraliaToyo Tire and Rubber Co. JapanSemperit AG AustriaFenner PLC United KingdomDana Corp. USABando Chemicals Industries JapanZF Boge Elastmetall GermanySumitomo Rubber Industries JapanSKF AB SwedenWest Pharmaceutical Services USAWOCO Industrietechnik GermanyElringKlinger AG GermanyKinugawa Rubber Co. JapanCardinal Health USAVeritas AG GermanySaar Gummi Group GermanyZodiac SA FranceFukoku Co. JapanAvon Rubber p.l.c. United KingdomMitsuboshi Belting Ltd. JapanNishikawa Rubber Co. JapanSSL International PLC United KingdomOkamoto Industries JapanLord Corp. USA

The top four nontire companies are Freudenberg, Hutchinson, Bridgestone, and Continental, each with about three billion dollars in annual sales. Therefore, in 2010 these top four firms represented at least one-fifth of the entire nontire rubber industry.

This nontire rubber industry is about 38% dependent on the automotive industry, 32% industrial, 12% construction, 12% aerospace and other transportation, and 6% other application areas.

Table 1.2 Some of the Largest Nontire Rubber Companies in the World in Approximate Descending Order of Their Annual Sales of Nontire Rubber Products (continuation)

1.4 Sectors of the Nontire Rubber Industry 7

�� 1.4�Sectors of the Nontire Rubber Industry

The major sectors of the nontire industry include the following:

� Hoses � Conveyor belts � Transmission belts � Seals and gaskets � Blowout preventers � Single-ply roofing � Bushings and motor mounts � Molded rubber goods � Tank lining � Wire and cable insulation � Shoe heels and soles � Sponge rubber � Weatherstripping � Latex products � Rubber rollers � Rubber tiles � Rubber bands

1.4.1 The rubber hose industry is one of the two largest segments of nontire rubber fabricators. Worldwide, the hose industry had about $6 billion dollars in total sales in 2010. Automotive and industrial are two very large market areas for hose. Some hose processes, for machine-made and hand-built hose, are very labor intensive. Processes for braided and spiral hose are less labor intensive. Hoses constructed in the factory are commonly cured in autoclaves.

1.4.2 The belt segment is approximately the same size as the hose segment, $6 bil-lion dollars worldwide in 2010. Conveyor belts (or large belts) are used as an effi-cient conveyance system for ores and mineral deposits for both surface and under-ground mining. Power transmission belts are used extensively in the automotive and industrial equipment markets. Light belts are used in such applications as food cafeterias.

1.4.3 Seals and gaskets are another multibillion dollar industry. Modern machinery requires many seals and gaskets, which are used everywhere in industry. There are static seals such as traditional O-rings and gaskets. Also, there are dynamic seals used under reciprocating conditions such as radial lip seals. Dynamic seals are also used under rotary conditions. These rotary seals can be either contacting or noncon-

8 1  Introduction

tacting. Contacting rotary, dynamic seals are represented by radial shaft seals, axial slingers, mechanical face seals, and packings. Noncontacting, rotary, dynamic seals are represented by viscoseals, fluid seals, labyrinths, and bushings. Seals are usu-ally manufactured by either injection or compression molding.

1.4.4 Blowout preventers and packers are adjustable sealing devices made of rubber and metal that are used extensively in oil drilling operations (called “downhole”). These devices are relatively large and critical to successful oil exploration and pro-duction. Because of the increasing need for more oil, this market has been growing significantly. About 5% of the available nitrile rubber goes into BOP (blowout preven-ter) production. Significant quantities of fluoroelastomers, HNBR and XNBR, are also used in this area. Much of the manufacture of these devices is carried out in the states of Texas and California.

1.4.5 Single-ply roofing is one of the largest single uses for EPDM rubber. It is the preferred roofing material for most commercial buildings, especially in the United States. Warranties are very important in this market. These roofing materials must function as an effective barrier for many years.

1.4.6 Bushings and motor mounts are components used in virtually all motorized vehicles. Here dynamic performance is critical. Rubber is compounded to impart specific, targeted dynamic property characteristics to these components. Rubber compounds in these components can be formulated to function as “isolators,” which pass mechanical energy through the component with only a minimal amount of heat generation. Or, rubber compounds can be formulated as “dampers,” which deliber-ately absorb energy being passed through the component and dissipate that energy as heat. Dynamic targets are set up for the quality assurance of these products, so they can function in the field as they were designed. Usually, injection or compres-sion molding is used to manufacture these rubber-metal components.

1.4.7 Besides seals and dynamic rubber components (bushings and motor mounts), other molded rubber goods represent a sizable market. Products are manufactured through compression molding or the more productive injection molding. Also, liquid injection molding (LIM) has been gaining a larger market share. In fact, many molded rubber goods for the medical industry are made from liquid silicone rubber (LSR) through LIM. Some other common examples of molded rubber goods include bumpers, grommets, end stops, buffers, diaphragms, and bellows (cylindrical extendable vessels).

1.4.8 Tank lining is a relatively small market where rubber is specially formulated and cured to make an effective barrier to contain various liquids for transportation and storage. Worldwide, there are just a few rubber fabricators serving this market. Rubber lining is also used as a wear layer, protecting steel pipe from highly abrasive mining slurry.

1.4 Sectors of the Nontire Rubber Industry 9

1.4.9 Wire and cable insulation has a significant volume of rubber consumption. Rub-ber compounds based on such elastomers as CPE, EPDM, silicone, and thermoplas-tic elastomers are used for this purpose. In a continuous extrusion process, these compounds are applied to the wire as insulation.

1.4.10 Shoe heel and sole applications were one of the first commercial applications for rubber in the late 1800s. Today, much natural rubber, SBR, BR, EVA, and other elastomers are used in the production of shoes in Southeast Asia, Latin America, and other areas of the world.

1.4.11 Sponge rubber products are very common in automotive, appliance, windows and doors, and leisure applications. Through correct formulation of rubber com-pounds based on EPDM, EVA, NBR, CR, or SBR, a special “closed cell” sponge is produced with desirable physical properties. This closed cell structure is partially achieved by producing what is called the correct “cure-blow” balance between the cure system and the blowing agents used in the formulation during the curing pro-cess. Many times closed cell products also take the form of gaskets, seals, weather-stripping, and thermal insulation. On the other hand, “open cell” sponge permits the flow of air or liquids through its structure. Open cell sponge is used for rug car-pet underlay and for filtration for example.

1.4.12 Rubber weatherstripping for automotive exteriors is usually produced from compounds based on EPDM. These weatherstrips can be “dense” (no voids), cellular (closed cell structure), or semidense. Weatherstripping is commonly extruded and cured in a continuous vulcanization unit (CVU). Some new production lines are switching over to thermoplastic elastomers (TPEs), which eliminate the curing step, with a reduction in production costs.

1.4.13 Rubber latex products are another rubber market of significance. Typical products in this sector are condoms, surgeon gloves, and medical examination gloves, which have traditionally been made from natural rubber latex. Recently, however, the demand for these traditional natural rubber latex products has been declining because of concerns for anaphylactic shock. Hevea natural rubber latex contains certain proteins and other ingredients to which some people have allergic reactions. Now, some of the producers of these latex products are switching over to the new hypoallergenic guayule latex, which is safer. Guayule NR is derived from a shrub native to the southwest United States and Mexico. Other synthetic rubbers are being evaluated as well.

1.4.14 Rubber rollers are used in all kinds of industrial environments, they are made from virtually every class of rubber commercially available. The rubber roller indus-try is composed of mostly smaller firms rather than larger ones. Also, each firm’s market tends to be regional rather than national or international. This is because much of the rubber roller business is in the replacement of existing rollers (replace-ment business). When the rubber rollers wear out, the rubber roller company

10 1  Introduction

replaces them as a service. This service involves sending a truck out to the customer to collect worn rollers (called cores), bringing them back to the rubber roller plant, prepping and recoating them, and returning them to the customer. Most rubber roller companies are not large enough to have their own internal mixer. Instead, they either buy their rubber compounds from custom mixers or mix small batches on a mill. A typical rubber roller plant might have 500 to 1000 different recipes for rubber com-pounds because of the different service environments of their customers.

1.4.15 Rubber tiles are used for industrial, residential, and athletic floorings. These rubber tiles are available with very high or very low hardness (such as for athletic use). They can be compounded to possess bright colors of the customer’s choice. Commonly, SBR is the rubber of choice for many applications. Some tiles use rubber buffing and ground rubber.

1.4.16 Rubber bands (sometimes also called elastic bands, “lackey” bands, or gum-bands) are manufactured by slicing with heat along the width of an extruded rubber tube on a mandrel. Therefore a rubber band is actually produced from slices of a cured rubber tube. Usually, rubber bands are made from rubber compounds based on natural rubber. Rubber-band tubes are commonly cured in a continuous vulcani-zation unit.

�� 1.5�Market Forces

Of course, market prices of the raw elastomers, reinforcing agents, and other com-pounding ingredients are determined by the economic laws of supply and demand. When the supply is constant, an increase in demand causes a rise in market price. If, for example, the world supply of oil were geologically limited, at least in the short term, to only 85 million barrels of oil per day, while the demand from rising new markets in Asia caused the total world oil demand to rise to 87 million barrels per day, the world price would have to rise to a level that would “kill off” 2 million bar-rels per day of new demand. However, if the price of oil were to stay high for a long period of time, there would be incentive to develop more oil production from tertiary oil recovery, shale oil refining, or even the development of processes to produce oil-like products from coal.

On the other hand, when the demand is constant, the market price increases with a drop in supply. If an extraordinary event, such as a hurricane, were to “knock out” some oil supply in the Gulf of Mexico, then oil prices would increase rapidly. (In fact, even the anticipation of a shortage would cause the price of oil to rise). With a higher price of oil, there is even more motivation for the oil producers to repair and restore lost oil supply.

1.5 Market Forces 11

Market substitutability is another consideration when predicting the price of a com-modity raw material in the rubber industry. If a given commodity is highly substi-tutable with another commodity, a sudden scarcity of supply for that commodity has less effect on its market price. For example, if there were a partial shortage of avail-able natural rubber, some other synthetic elastomers could be substituted for NR to a limited extent for some products. This substitutability could moderate the effect on the natural rubber price to some extent. On the other hand, if there were a sudden shortage of perfluoroelastomer (FFKM), the effects on price could be much greater because there are some uses for FFKM for which no other elastomer can be used. This is why discussions on substitutability are given throughout this book.

2The following basic raw materials extracted from the earth or from agriculture are critical to the success of the rubber industry as we know it today.

� Crude oil, naphthenic, and paraffin base � Natural gas � Natural rubber latex � Sulfur � Zinc ore � Copper ore � Iron ore � Silica � Brine (for chlorine) � Fluorspar

The following additional basic raw materials extracted from the earth or from agri-culture are important but not vital for continued rubber product manufacture.

� Antimony ore � Bauxite � Clay (kaolin) � Coal � Cobalt ore � Limestone � Phosphate rock � Pine trees � Tallow (from cattle) � Titanium ore � Vegetable oils

Basic Raw Materials from Earth Extractions and Agriculture