Polyurethane Elastomers
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POLYURETHANES POLYURETHANES Science, Technology, Markets, and Trends MARK F. SONNENSCHEIN, Ph.D. The Dow Chemical Company Midland, MI, USA Copyright © 2015 by John Wiley & Sons, Inc. All rights reserved Published by John Wiley & Sons, Inc., Hoboken, New Jersey Published simultaneously in Canada No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning, or otherwise, except as permitted under Section 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, (978) 750-8400, fax (978) 750-4470, or on the web at www.copyright.com. 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TP1180.P8S56 2015 668.4′239–dc23 2014023089 Cover Images: Copolymer picture courtesy of Robert Vastenhout, WAXS color picture courtesy of Brian Landes, and TEM picture courtesy of Robert Cieslinski Printed in the United States of America 10 9 8 7 6 5 4 3 2 1 Dedicated to my wife Geraldine Franklin Sonnenschein for her beauty, kindness, and endless support, and to my children Matthew, Anne, and Susan for the inspiration and the laughs. CONTENTS Acknowledgments xi 1 Introduction 1 2 Polyurethane Building Blocks 10 2.1 Polyols, 11 2.1.1 Polyether Polyols, 12 2.1.2 Polyester Polyols, 28 2.1.3 Other Polyols, 42 2.1.4 Filled Polyols, 48 2.1.5 Seed Oil-Derived Polyols, 53 2.1.6 Prepolymers, 59 2.2 Isocyanates, 61 2.2.1 TDI, 63 2.2.2 Diphenylmethane Diisocyanates (MDI), 73 2.2.3 Aliphatic Isocyanates, 81 2.3 Chain Extenders, 89 3 Introduction to Polyurethane Chemistry 105 3.1 Introduction, 105 3.2 Mechanism and Catalysis of Urethane Formation, 107 3.3 Reactions of Isocyanates with Active Hydrogen Compounds, 113 vii viii CONTENTS 3.3.1 Urea Formation, 116 3.3.2 Allophanate Formation, 117 3.3.3 Formation of Biurets, 119 3.3.4 Formation of Uretidione (isocyanate dimer), 119 3.3.5 Formation of Carbodiimide, 120 3.3.6 Formation of Uretonimine, 120 3.3.7 Formation of Amides, 123 4 Theoretical Concepts and Techniques in Polyurethane Science 127 4.1 Formation of Polyurethane Structure, 128 4.2 Properties of Polyurethanes, 137 4.2.1 Models and Calculations for Polymer Modulus, 138 4.2.2 Models for Elastomer Stress Strain Properties, 143 4.2.3 The Polyurethane Glass Transition Temperature, 152 5 Analytical Characterization of Polyurethanes 160 5.1 Analysis of Reagents for Making Polyurethanes, 161 5.1.1 Analysis of Polyols, 161 5.1.2 Analysis of Isocyanates, 166 5.2 Instrumental Analysis of Polyurethanes, 168 5.2.1 Microscopy, 169 5.2.2 IR Spectrometry, 176 5.2.3 X-Ray Analyses, 181 5.3 Mechanical Analysis, 188 5.3.1 Tensile, Tear, and Elongation Testing, 189 5.3.2 DMA, 195 5.4 Nuclear Magnetic Spectroscopy, 199 6 Polyurethane Flexible Foams: Chemistry and Fabrication 207 6.1 Making Polyurethane Foams, 208 6.1.1 Slabstock Foams, 208 6.1.2 Molded Foams, 213 6.2 Foam Processes, 217 6.2.1 Surfactancy and Catalysis, 223 6.3 Flexible Foam Formulation and Structure–Property Relationships, 228 6.3.1 Screening Tests, 228 6.3.2 Foam Formulation and Structure–Property Relationships, 230 7 Polyurethane Flexible Foams: Manufacture, Applications, Markets, and Trends 235 7.1 Applications, 237 7.1.1 Furniture, 238 7.1.2 Mattresses and Bedding, 241 CONTENTS ix 7.1.3 Transportation, 245 7.1.4 The Molded Foam Market, 246 7.2 Trends in Molded Foam Technology and Markets, 249 8 Polyurethane Rigid Foams: Manufacture, Applications, Markets, and Trends 255 8.1 Regional Market Dynamics, 255 8.2 Applications, 260 8.2.1 Construction Foams, 260 8.2.2 Rigid Construction Foam Market Segments, 272 8.2.3 Appliance Foams, 276 8.3 Blowing Agents and Insulation Fundamentals, 281 8.3.1 Blowing Agents, 281 8.3.2 Blowing Agent Phase-Out Schedule, 282 8.4 Insulation Fundamentals, 284 8.5 Trends in Rigid Foams Technology, 287 9 Polyurethane Elastomers: Manufacture, Applications, Markets, and Trends 294 9.1 Regional Market Dynamics, 295 9.2 Applications, 298 9.2.1 Footwear, 300 9.2.2 Nonfootwear Elastomer Applications and Methods of Manufacture, 307 9.3 Trends in PU Elastomers, 328 10 Polyurethane Adhesives and Coatings: Manufacture, Applications, Markets, and Trends 336 10.1 Adhesive and Coating Industries: Similarities and Differences, 336 10.2 Adhesives, 339 10.2.1 Adhesive Formulations, 342 10.2.2 Trends in PU Adhesives, 350 10.3 Coatings, 353 10.3.1 PU Coating Formulations, 359 10.3.2 Trends in PU Coatings, 368 11 Special Topics: Medical Uses of Polyurethane 375 11.1 Markets and Participants, 375 11.2 Technology, 377 11.2.1 Catheters, 377 11.2.2 Wound Dressings, 380 11.2.3 Bioabsorbable Polyurethanes, 382 x CONTENTS 11.2.4 Hydrogels, 386 11.2.5 Gloves and Condoms, 387 12 Special Topic: Nonisocyanate Routes to Polyurethanes 392 12.1 Governmental Regulation of Isocyanates, 392 12.2 Nonisocyanate Routes to Polyurethanes, 395 12.2.1 Reactions of Polycyclic Carbonates with Polyamines, 395 12.2.2 Direct Transformations of Amines to Urethanes, 400 12.2.3 Reactions of Polycarbamates, 403 12.2.4 Conversion of Hydroxamic Acids to Polyurethane, 404 12.2.5 Conversion of Hydroxylamines to Polyurethanes, 406 Index 409 ACKNOWLEDGMENTS I would like to express my deep gratitude to the people who have helped me through the years and provided fertile ground for growth. Particularly I would like to mention my Dow colleagues whom I have worked with in the field of polyurethanes over the past 20 years. First I would like to mention my constant collaborator Benjamin Wendt who has worked with me closely in the lab for many years, and excelled at making hard things work easily. Many people have provided guidance, encouragement, and excellent collaboration over the years. Especially I would like to mention Prof. Alan Schrock, Dr. Justin Virgili, Dr. Mark Cox, Dr. Jack Kruper, Dr. Chris Christenson, Dr. Valeriy Ginzburg, Dr. Jozef Bicerano, Mr. Will Koonce, Prof. Tony Ryan, Dr. David Babb, Dr. Robbyn Prange, Dr. Nelson Rondan, Dr. Maria Pollard, Dr. Jorge Jimenez, Dr. Kshitish Patankar, Dr. Steve Guillaudeu, Dr. Cecile Boyer, Dr. Steve Montgomery, Dr. Brian Landes, Dr. Steve Webb, and Dr. John Kramer. I would also like to recognize the great support I received from the Dow Chemical Company in writing this book. Particularly I would like to mention Dr. Jai Venkatesan, Dr. David Bem, and Dr. Florian Schattenmann for giving me the encouragement, time, resources, and freedom to realize this vision. Lastly I would like to acknowledge the people who gave me my scientific foundations and inspired in me a love of experiment and a respect for theory. Particularly I would like to mention Prof. Richard G. Weiss (Georgetown University), Dr. C. Michael Roland (The United States Naval Research Lab), and Prof. Gordon Johnson (Kenyon College) for putting up with me in my early years. xi 1 INTRODUCTION In the early 1900s, there were very few of the synthetic polymers we have grown accustomed to now. During succeeding years, polymer science experienced explosive growth with the invention of polyvinyl chloride (PVC, 1913), polyethylene (1933), polyvinylidene chloride (Saran, 1933), polyamides (nylon, 1934), and polytetrafluo- roethylene (Teflon, 1938). In addition, during the 1930s, the polymer family known as polyurethanes was invented. Now, of course, polyurethanes, and all the polymers developed during this period, have become an integral part of modern life. As you read this, you may not be aware of how many ways polyurethanes surround you. They are present in the shoes you stand in, the seat cushion you sit upon, the carpet backing and foam pad underlay you walk upon, the fibers of your clothing, insulation of your walls and roof, your refrigerator, dishwasher, water heater, automotive seat- ing, automotive structural foam, automotive paints and coatings, furniture coatings, your bed mattress, and the adhesive holding this book together—the list just goes on.