Lactam-based Polyamides, Volume I-Polymerization Structure PDF
Preview Lactam-based Polyamides, Volume I-Polymerization Structure
Lactam-Based Polyamides Volume I Polymerization, Structure, and Properties Editors Dr. Rudolf Puffr Chief Department of Polyamides Institute of Macromolecular Chemistry Czechoslovak Academy of Sciences Prague Prof. Vladimir Kubanek Former Director Institute of Macromolecular Chemistry Czechoslovak Academy of Sciences Prague Boca Raton London New York CRC Press is an imprint of the Taylor & Francis Group, an informa business CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 © 1991 by Taylor & Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group, an lnforma business No claim to original U.S. Government works ISBN 13: 978-0-8493-4965-2 (hbk) (vol I) This book contains information obtained from authentic and highly regarded sources. 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For permission to photocopy or use material electronically from this work, please access www. copyright.com (http://www.copyright.com/) or contact the Copyright Clearance Center, Inc. (CCC), 222 Rosewood Drive, Danvers, MA 01923, 978-750-8400. CCC is a not-for-profit organization that provides licenses and registration for a variety of users. For organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged. TrademarkN otice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation without intent to infringe. Visit the Taylor& FrancisW eb site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com Library of Congress Card Number 90-2587 Library of Congress Cataloging-in-Publication Data Lactam-based polyamides / editors, Rudolf Puffr, Vladimir Kubanek. p. cm. Includes bibliographical references and index. Contents: v. I. Polymerization, structure, and properties --v. 2. Modification, technology, and application. ISBN 0-8493-4965-6 (v. I). --ISBN 0-8493-4966-4 (v. 2) I. Polyamides. 2. Lactams. I. Puffr, Rudolf. II. Kubanek, Vladimir. QD383.A55L33 1991 668. 4' 235--dc20 90-2587 CIP PREFACE Linear aliphatic polyamides, frequently referred to as nylons, rank among the most important polymers produced on an industrial scale, both because of some exceptional properties and due to the volume of their worldwide production, which exceeds 3 x 106 t per year. They were introduced into the market in the 1930s, as the first synthetic fiber, and, in fact, also as the first crystalline engineering thermoplastic. Up to the present time, they have been predominantly used in the fiber industry, but their application as construction materials is rapidly increasing in various fields. Polyamides are obtained by the condensation of dicarboxylic acids with diamines (AABB type) or co-amino acids, but also by the ring-opening polymerization of lactams (AB type). The generally accepted way is to denote them by a number indicating the number of carbon atoms in the monomer unit, e.g., polyamide 6 (nylon 6) based on 6-hexanelactam, or polyamide 610 according to the parental 1,6-diaminohexane and 1,10-decanedioic acid. The contribution of polyamides of the AB type to the worldwide production of polyamides continues to increase and already exceeds 50%, with polyamide 6 holding the predominant position. This book deals with the synthesis of polyamides via polymerization of lactams, and also with the properties and applications of all polyamides of the AB type, irrespective of the route used in obtaining them, viz., by the polymerization of lactams or by the condensation of co-amino acids. The homologous series of lactams, starting from the three-membered ring and up to the twelve-membered and higher-membered ones, is a unique family of monomers, in which the electronic and molecular structure, acidobasic properties, and reactivity of the amide group can be investigated, thus providing data not only important for the development of new polymerization technologies, but also of interest in e.g., biochemistry, biophysics, and molecular biology. A similarly exceptional position among the polymers is held by the homologous series of polyamides of AB type, involving polyamide 2 (polypeptide poly gly- cine) and the subsequent polyamides up to polyamide 12. The members of this series represent a very broad range of properties, depending on the frequency of the amide group in the chain. An investigation of such relations between properties and the chemical composition is of obvious importance in material engineering. The aim pursued by the authors — research polymer chemists, physical chemists, physicists, and technologists — has been to collect and evaluate the greatest possible amount of relevant information scattered throughout many scientific journals, conference proceed- ings, and patent literature, particularly those covering the period of the last two decades; to supplement these data, where possible, with their own results and experience and thus present a survey of the reactivities, structures, chemical and physical properties, and also applications of the series of lactams and corresponding polyamides which would be as complete as possible. All the chapters are arranged in the same order, i.e., lactams, their polymerization, structure of the polymers, their properties, processing, and applications. The chapters in the first volume of the book are rather theoretical in character, while those in the second volume concern technology and application. A complex approach and new information gathered during the latest period of intensive research made possible a comparison between properties of the individual members of the polyamide series, and partly also their correlation with the molecular structure for predictive purposes. In this way, we would like to supplement several older books (cited in the references), devoted both to polyamide fibers and to plastics. The industrially produced lactams are, and probably also will be in the near future, restricted only to 6-hexanelactam, 12-dodecanelactam, and 4-butanelactam. For these rea- sons, particularly recently, great possibilities offered by various modifications are utilized in extending the assortment of polyamides. This problem, so far not examined in full, is also dealt with in the book. The polymerization of lactams may proceed by the hydrolytic, anionic, or cationic mechanism. Up to now, the time- and energy-consuming hydrolytic process has been of the greatest importance in technology, especially in the fiber industry. Extensive research of the anionic mechanism of polymerization of lactams allowed new technologies of fast poly- merization with simultaneous molding to be introduced, such as monomer casting or reactive injection molding, discussed in Chapter 4 of Volume 2. By employing these technologies, variously modified products may be prepared, which opens new fields of application of polyamides. We hope that our book will be useful to specialists from the research field and testing laboratories, but also to students, technologists in the plastics and textile industry, designers, and all those engaged in the application of polyamides. We would be happy if the book will not only help to extend our knowledge of the preparation and properties of these polymers, but also assist in further development of their production and application. Editors THE EDITORS Rudolf Puffr, Ph.D., is Chief, Department of Polyamides, Institute of Macromolecular Chemistry, Czechoslovak Academy of Sciences, Prague. Dr. Puffr graduated in 1959 from the Prague Institute of Chemical Technology with a M.Sc. degree in organic chemistry. He obtained his Ph.D. degree in 1962 from the Institute of Macromolecular Chemistry, Czechoslovak Academy of Sciences, Prague, for research in the thermodynamics of polyamides. Dr. Puffr has presented many invited lectures at international and national meetings and is the author of more than 50 scientific papers. His over 30 years lasting interest in the chemistry and physics of polyamides covers the investigation of mechanism and kinetics of lactam polymerizations, modification of polyamides, coordination chemistry of the amide group, and interaction of polyamides with gases, vapors, and inorganic substances. Vladimir Kubanek, Ph.D., D.Sc., was Director of the Institute of Macromolecular Chemistry, Czechoslovak Academy of Sciences, Prague, from 1983 to 1990. Dr. Kubanek graduated in 1964 from the Prague Institute of Chemical Technology with a M.Sc. degree. Several years before his university studies, and after them, he worked in the Czechoslovak chemical industry, namely in the research and production of synthetic fibers. In 1973 he obtained a Ph.D. degree, again from the Prague Institute of Chemical Technology, where he was appointed an Associate Professor in 1977 and Professor in 1983 at the Department of Polymers. He received his D.Sc. degree in 1989. Among other awards he has received the Czechoslovak State Prize, National Prize of the Czech Republic, and the honorary award of Respected Inventor. Dr. Kubanek is the author and coauthor of more than 100 scientific papers and 150 patents of inventions, many of which have been employed in industry, for example, new catalysts for monomer casting of nylon 6 and polymeric sorbents for medical applications and the food industry. CONTRIBUTORS, Volume I Josef Baldrian, Ph.D. Rudolf Puffr, Ph.D. Institute of Macromolecular Chemistry Institute of Macromolecular Chemistry Czechoslovak Academy of Sciences Czechoslovak Academy of Sciences Prague, Czechoslovakia Prague, Czechoslovakia Bfetislav Dolezel, Ph.D. Miroslav Raab, Ph.D. Materials Protection and Corrosion State Institute of Macromolecular Chemistry Research Institute Czechoslovak Academy of Sciences Prague, Czechoslovakia Prague, Czechoslovakia Bozena Lan ska, Ph.D. Jan Sebenda, Ph.D., D.Sc. Institute of Macromolecular Chemistry Institute of Macromolecular Chemistry Czechoslovak Academy of Sciences Czechoslovak Academy of Sciences Prague, Czechoslovakia Prague, Czechoslovakia Frantiâek Lednickÿ, Ph.D. Jaroslav Stehlicek, Ph.D. Institute of Macromolecular Chemistry Institute of Macromolecular Chemistry Czechoslovak Academy of Sciences Czechoslovak Academy of Sciences Prague, Czechoslovakia Prague, Czechoslovakia Zdenek Tuzar, Ph.D. Institute of Macromolecular Chemistry Czechoslovak Academy of Sciences Prague, Czechoslovakia DEDICATION This book is dedicated to our esteemed teacher and pioneer of Czechoslovak polyamide chemistry, Professor Otto Wichterle. LACTAM-BASED POLYAMIDES Volume I Polymerization, Structure, and Properties Lactams Polymerization Chemical Analysis Molecular Characterization Physical Structure Properties Degradation and Stabilization Volume II Modification, Technology, and Application Modified Polyamides Monomer Technology Fibers Reaction Processing Processing Technology of Plastics Designing and Application Each volume contains a list of symbols and abbreviations and a subject index. TABLE OF CONTENTS, Volume I Chapter 1 Lactams............................................................................................................................ 1 Rudolf Puffr Chapter 2 Polymerization..................................................................................................................29 Jan Sebenda Chapter 3 Chemical Analysis.............................................................................................................73 Bozena Lânskâ and Jaroslav Stehlicek Chapter 4 Molecular Characterization...............................................................................................95 Zdenék Tuzar Chapter 5 Physical Structure...........................................................................................................131 Josef Baldrian and Frantisek Lednickÿ Chapter 6 Properties.........................................................................................................................187 Rudolf Puffr, Miroslav Raab, and Bfetislav Dolezel Chapter 7 Degradation and Stabilization........................................................................................261 Bozena Lânskâ Appendix Nomenclature of Polyamides, Symbols and Abbreviations............................................303 Index..............................................................................................................................3307
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