Table Of ContentLactam-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
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ISBN 13: 978-0-8493-4965-2 (hbk) (vol I)
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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
