Table Of ContentPOLYURETHANES
WILEY SERIES ON POLYMER ENGINEERING AND
TECHNOLOGY
Richard F. Grossman and Domasius Nwabunma,
Series Editors
Polyolefin Blends / Edited by Domasius Nwabunma and Thein Kyu
Polyolefin Composites / Edited by Domasius Nwabunma and Thein Kyu
Handbook of Vinyl Formulating, Second Edition / Edited by Richard F. Grossman
Total Quality Process Control for Injection Molding, Second Edition / M. Joseph Gordon, Jr.
Microcellular Injection Molding / Jingyi Xu
Poly(lactic acid): Synthesis, Structures, Properties, Processing, and Applications / Edited
by Rafael Auras, Loong‐Tak Lim, Susan E.M. Selke, and Hideto Tsuji
Hyperbranched Polymers: Synthesis, Properties, and Applications / Edited by Deyue Yan,
Chao Gao, and Holger Frey
Advanced Thermoforming: Methods, Machines and Materials, Applications and
Automation / Sven Engelmann
Biopolymer Nanocomposites: Processing, Properties and Applications / Alain Dufresne,
Sabu Thomas, Laly A. Pothan
Polymers for PEM Fuel Cells / Hongting Pu
Polyurethanes: Science, Technology, Markets, and Trends / Mark F. Sonnenschein
Functional Polymer Coatings: Principles, Methods, and Applications / Edited by Limin Wu
and Jamil Baghdachi
Polyurethanes: Science, Technology, Markets, and Trends, Second Edition /
Mark F. Sonnenschein
ffirs.indd 2 11/25/2020 10:17:35 AM
POLYURETHANES
Science, Technology, Markets, and
Trends
SECOND EDITION
MARK F. SONNENSCHEIN, Ph.D.
The Dow Chemical Company
Midland, MI, USA
This edition first published 2021
© 2021 John Wiley & Sons, Inc.
Edition History
John Wiley & Sons (1e, 2014)
All rights reserved. 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 or otherwise, except as
permitted by law. Advice on how to obtain permission to reuse material from this title is available at
http://www.wiley.com/go/permissions.
The right of Mark F. Sonnenschein to be identified as the author of this work has been asserted in accordance
with law.
Registered Office
John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, USA
Editorial Office
111 River Street, Hoboken, NJ 07030, USA
For details of our global editorial offices, customer services, and more information about Wiley products visit
us at www.wiley.com.
Wiley also publishes its books in a variety of electronic formats and by print‐on‐demand. Some content that
appears in standard print versions of this book may not be available in other formats.
Limit of Liability/Disclaimer of Warranty
In view of ongoing research, equipment modifications, changes in governmental regulations, and the constant flow
of information relating to the use of experimental reagents, equipment, and devices, the reader is urged to review
and evaluate the information provided in the package insert or instructions for each chemical, piece of equipment,
reagent, or device for, among other things, any changes in the instructions or indication of usage and for added
warnings and precautions. While the publisher and authors have used their best efforts in preparing this work, they
make no representations or warranties with respect to the accuracy or completeness of the contents of this work
and specifically disclaim all warranties, including without limitation any implied warranties of merchantability or
fitness for a particular purpose. No warranty may be created or extended by sales representatives, written sales
materials or promotional statements for this work. The fact that an organization, website, or product is referred to
in this work as a citation and/or potential source of further information does not mean that the publisher and
authors endorse the information or services the organization, website, or product may provide or recommendations
it may make. This work is sold with the understanding that the publisher is not engaged in rendering professional
services. The advice and strategies contained herein may not be suitable for your situation. You should consult
with a specialist where appropriate. Further, readers should be aware that websites listed in this work may have
changed or disappeared between when this work was written and when it is read. Neither the publisher nor authors
shall be liable for any loss of profit or any other commercial damages, including but not limited to special,
incidental, consequential, or other damages.
Library of Congress Cataloging‐in‐Publication Data
Names: Sonnenschein, Mark F., author.
Title: Polyurethanes : science, technology, markets, and trends / Mark F.
Sonnenschein, Ph.D., The Dow Chemical Company, Midland, Michigan, US.
Description: Second edition. | Hoboken : Wiley, 2021. | Series:
Wiley series on polymer engineering and technology | Includes bibliographical
references and index.
Identifiers: LCCN 2020024254 (print) | LCCN 2020024255 (ebook) | ISBN
9781119669418 (hardback) | ISBN 9781119669463 (adobe pdf) | ISBN
9781119669470 (epub)
Subjects: LCSH: Polyurethanes.
Classification: LCC TP1180.P8 S56 2021 (print) | LCC TP1180.P8 (ebook) |
DDC 668.4/239–dc23
LC record available at https://lccn.loc.gov/2020024254
LC ebook record available at https://lccn.loc.gov/2020024255
Cover Design: Wiley
Cover Image: Courtesy of The Dow Chemical Company
Set in 10/12pt Times by SPi Global, Pondicherry, India
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. My canines, Arlo, Lark, Bugle, and Sprite, are
acknowledged for patiently and cheerfully keeping me company throughout the
writing process.
CONTENTS
Preface xi
Acknowledgments xiii
1 Introduction 1
2 Polyurethane Building Blocks 13
2.1 Polyols, 14
2.1.1 Polyethers, 15
2.1.2 Polyester Polyols, 32
2.1.3 Other Polyols, 47
2.1.4 Filled Polyols, 53
2.1.5 Seed Oil‐Derived Polyols, 57
2.1.6 Prepolymers, 64
2.2 Isocyanates, 66
2.2.1 TDI, 69
2.2.2 Diphenylmethane Diisocyanates (MDI), 77
2.2.3 Aliphatic Isocyanates, 87
2.3 Chain Extenders, 94
vii
viii CONTENTS
3 Introduction to Polyurethane Chemistry 111
3.1 Introduction, 111
3.2 Mechanism and Catalysis of Urethane Formation, 113
3.3 Reactions of Isocyanates with Active Hydrogen Compounds, 119
3.3.1 Urea Formation, 123
3.3.2 Allophanate Formation, 124
3.3.3 Formation of Biurets, 124
3.3.4 Formation of Uretdione (Isocyanate Dimer), 125
3.3.5 Formation of Carbodiimide, 126
3.3.6 Formation of Uretonimine, 128
3.3.7 Formation of Amides, 128
4 Theoretical Concepts and Techniques in Polyurethane Science 133
4.1 Formation of Polyurethane Structure, 134
4.2 Properties of Polyurethanes, 144
4.2.1 Models and Calculations for Polymer Modulus, 145
4.2.2 Models for Elastomer Stress–Strain Properties, 149
4.2.3 The Polyurethane Glass Transition Temperature, 159
5 Analytical Characterization of Polyurethanes 167
5.1 Analysis of Reagents for Making Polyurethanes, 168
5.1.1 Analysis of Polyols, 168
5.1.2 Analysis of Isocyanates, 173
5.2 Instrumental Analysis of Polyurethanes, 176
5.2.1 Microscopy, 176
5.2.2 IR Spectrometry, 183
5.2.3 X‐Ray Analyses, 189
5.3 Mechanical Analysis, 197
5.3.1 Tensile, Tear, and Elongation Testing, 198
5.3.2 DMA, 205
5.4 Nuclear Magnetic Resonance Spectroscopy, 208
5.5 Foam Screening: FOAMAT®, 211
6 Polyurethane Flexible Foams: Chemistry and Fabrication 219
6.1 Making Polyurethane Foams, 220
6.1.1 Slabstock Foams, 220
6.1.2 Molded Foams, 224
6.2 Foam Processes, 230
6.2.1 Surfactancy and Catalysis, 234
6.3 Flexible Foam Formulation and Structure–Property Relationships, 241
6.3.1 Screening Tests, 241
6.3.2 Foam Formulation and Structure–Property Relationships, 243
CONTENTS ix
7 Polyurethane Flexible Foams: Manufacture, Applications,
Markets, and Trends 249
7.1 Applications, 252
7.1.1 Furniture, 252
7.1.2 Mattresses and Bedding, 257
7.1.3 Transportation, 262
7.1.4 The Molded Foam Market, 265
7.2 Trends in Molded Foam Technology and Markets, 266
8 Polyurethane Rigid Foams: Manufacture, Applications,
Markets, and Trends 273
8.1 Regional Market Dynamics, 273
8.2 Applications, 279
8.2.1 Construction Foams, 279
8.2.2 Rigid Construction Foam Market Segments, 293
8.2.3 Appliance Foams, 294
8.3 Blowing Agents and Insulation Fundamentals, 300
8.3.1 Blowing Agents, 300
8.3.2 Blowing Agent Phase‐Out Schedule, 301
8.4 Insulation Fundamentals, 304
8.5 Trends in Rigid Foams Technology, 308
9 Polyurethane Elastomers: Manufacture, Applications,
Markets, and Trends 315
9.1 Regional Market Dynamics, 316
9.2 Applications, 320
9.2.1 Footwear, 320
9.2.2 Nonfootwear Elastomer Applications and Methods
of Manufacture, 329
9.3 Trends in Polyurethane Elastomers, 349
10 Polyurethane Adhesives and Coatings: Manufacture, Applications,
Markets, and Trends 359
10.1 Adhesives and Coatings Industries: Similarities
and Differences, 359
10.2 Adhesives, 362
10.2.1 Adhesive Formulations, 367
10.3 Trends in Polyurethane Adhesives, 374
10.4 Coatings, 379
10.4.1 Polyurethane Coating Formulations, 386
10.4.2 Trends in Polyurethane Coatings, 394
x CONTENTS
11 Special Topic: Medical Uses of Polyurethane 401
11.1 Markets and Participants, 402
11.2 Technology, 406
11.2.1 Catheters, 406
11.2.2 Wound Dressings, 406
11.2.3 Bioabsorbable Polyurethanes, 409
11.2.4 Hydrogels, 412
11.2.5 Gloves and Condoms, 414
11.3 Future Trends, 415
12 Special Topic: Nonisocyanate Routes to Polyurethanes 421
12.1 Governmental Regulation of Isocyanates, 421
12.2 Nonisocyanate Routes to Polyurethanes, 425
12.2.1 Reactions of Polycyclic Carbonates with Polyamines, 426
12.2.2 Direct Transformations of Amines to Urethanes, 432
12.2.3 Reactions of Polycarbamates, 433
12.2.4 Conversion of Hydroxamic Acids to Polyurethane, 436
12.2.5 Conversion of Hydroxylamines to Polyurethanes, 436
13 Polyurethane Hybrid Polymers 441
13.1 Introduction, 441
13.2 Polyurethane–Acrylate Hybrids, 445
13.3 Urethane–Epoxy Hybrids, 449
13.4 Urethane–Silicone Hybrids, 452
13.4.1 Silicone‐Modified Prepolymers, 452
13.4.2 Urethane–Silicone Hybrids Produced Using Diblock
Compatibilizers, 454
13.4.3 Hybrids Employing Covalent and Hydrogen‐Bonded
Cross‐Links, 456
13.4.4 Polyurethane Hybridization with Polyhedral Oligomeric
Silsesquixanes, 456
13.5 Polyurethane–Polyolefin Hybrids, 458
13.6 Hybridization Via Transurethanification, 460
14 Recycling of Polyurethanes 465
14.1 Introduction, 465
14.2 Glycolysis, Hydrolysis, Aminolysis, and Acidolysis, 469
14.3 Pyrolysis, 474
14.4 Recycle for Fuel Value, 475
14.5 Regrinding and Incorporation, 477
Index 481
PREFACE
I want to begin by thanking the people and organizations that bought the first edition
of Polyurethanes: Science, Technology, Markets, and Trends. I have received many
encouraging and constructive comments since it appeared at the end of 2014. At the
same time I have also had a certain amount of angst about the number of errors in the
book, most of them typographical, but not all of them! In addition, I have been
acutely aware as time has passed, even over just 6 years, that the polyurethane indus-
try is continuously changing and evolving. The “Science” and “Technology” parts of
the first edition title have changed somewhat, but the “Markets” and “Trends” com-
ponents of the first edition were badly in need of updating. What was also striking
was how third‐party industry forecasts made in 2014 about subsequent years were in
most cases wrong, demonstrating how poorly crystal ball analyses of economic
activity perform. In this second edition there is much less attention paid to these
prognostications.
An interesting macrotrend at the time of this writing is the rapid expansion of
global capacity with only moderate growth occurring now and in the future. This
assures that producer prices will remain under pressure and help maintain low price
inflation for the foreseeable future. This may also result in additional consolidation
in the polyurethanes industry, or the spinning out of polyurethane businesses from
chemical conglomerates as was see when Bayer AG spun off its polyurethane assets
into a separate company called Covestro AG. An additional market complication is
the introduction of large chemical concerns that represent and depend on national
subsidies, such as those appearing in China and Saudi Arabia. As a statement of a
societal commitment apart from market forces, they are capable of distorting market
xi
