Table Of Content..-
lrl
e
New Concepts in Polymer Science
Thermal Stability of Engineering
Heterochain Thermoresistant Polymers
New Concepts in Polymer Science
Previous titles in this book series:
The Concept of Micellar-Sponge Radiation Chemistry of Polymers
Nanophases in Chemical Physics of Polymers V.S. Ivanov
Yu.A. Mikheev, G.E. Zaikov
Polymeric Composites
Structure of the Polymer Amorphous State R.B. Seymour
G. V. Kozlov and G. E. Zaikov
Reactive Oligomers
The Statistical Nature of Strength and Lifetime S.G. Entelis, V.V. EvreinovandA.I Kuzaev
in Polymer Films and Fibers
Diffusion of Electrolytes in Polymers
B. Tsoi, E.M Kartashov and V.V. Shevelev
G.E. Zaikov, A.L. Iordanskii and V.S. Markin
Cyclolinear Organosilicon Copolymers:
Chemical Physics ofPolymer
Synthesis, Properties, Application
Degradation and Stabilization
0. V. Mukbaniani and G.E. Zaikov
N.M Emanuel and A.L. Buchachenko
Modem Polymer Flame Retardancy
S.M. Lomakin and G.E. Zaikov
Polymeric Biomaterials.
Part I. Polymer Implants
MI. Shtilman
Biodegradation and Durability of
Materials under the Effect of Microorganisms
S.A. Semenov, K.Z Gumargalieva
and G. E. Zaikov
Fire Resistant and Thermally Stable Materials
Derived from Chlorinated Polyethylene
A.A. Donskoi, M.A. Shashkina and G.E. Zaikov
Polymers and Polymeric Materials
for Fiber and Gradient Optics
N. Lekishvili, L. Nadareishvili,
G. Zaikov and L. Khananashvili
Polymers Derived from Isobutylene.
Synthesis, Properties, Application
Yu.A. Sangalov, K.S. Minsker and G. E. Zaikov
Ecological Aspects of Polymer
Flame Retardancy
S.M Lomakin and G.E. Zaikov
Molecular Dynamics of Additives in Polymers
A.L. Kovarski
Structure and Properties of
Conducting Polymer Composites
V.E. Gut'
Interaction of Polymers with
Bioactive and Corrosive Media
A.L. Iordanskii, T.E. Rudakova and G.E. Zaikov
Immobilization on Polymers
M.I. Shtilman
New Concepts in Polymer Science
Thermal Stability of
Engineering Heterochain
Thermoresistant Polymers
E. V. Kalugina, K.Z. Gumargalieva
and G.E. Zaikov
//IVSP/11
2004
UTRECHT • BosTON -
CRC Press
Taylor & Francis Group
6000 Broken Sound Parkway NW, Suite 300
Boca Raton, FL 33487-2742
© 2004 by Taylor & Francis Group, LLC
CRC Press is an imprint of Taylor & Francis Group, an Informa business
No claim to original U.S. Government works
Version Date: 20120727
International Standard Book Number-13: 978-9-04-741422-3 (eBook - PDF)
This book contains information obtained from authentic and highly regarded sources. Reasonable
efforts have been made to publish reliable data and information, but the author and publisher cannot
assume responsibility for the validity of all materials or the consequences of their use. The authors and
publishers have attempted to trace the copyright holders of all material reproduced in this publication
and apologize to copyright holders if permission to publish in this form has not been obtained. If any
copyright material has not been acknowledged please write and let us know so we may rectify in any
future reprint.
Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced,
transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or
hereafter invented, including photocopying, microfilming, and recording, or in any information stor-
age or retrieval system, without written permission from the publishers.
For permission to photocopy or use material electronically from this work, please access www.copy-
right.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 pro-
vides licenses and registration for a variety of users. For organizations that have been granted a pho-
tocopy license by the CCC, a separate system of payment has been arranged.
Trademark Notice: 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 & Francis Web site at
http://www.taylorandfrancis.com
and the CRC Press Web site at
http://www.crcpress.com
Thermal Stability ofE ngineering ...
CONTENTS
FOREWORD ................................................................................................. .
INTRODUCTION ........................................................................................... 1
Chapter 1. Degradation of aliphatic-aromatic polyimides - polyalkanimides
······························································································································ 6
POLYALKANIMIDE DEGRADATION IN MELT ...................................... 9
Thermal degradation ................................................................................... 9
Thermal oxidative degradation .................................................................. 21
Solid-phase oxidation ................................................................................. 39
Chapter 2. Degradation of aliphatic-aromatic polyamides .......................... 60
HIGH-TEMPERATURE DEGRADATION ................................................. 61
THERMAL OXIDATION IN THE SOLID PHASE-AGING ................... 80
Chapter 3. Degradation of poly(phenylquinoxaline) (PPQ) and co-
poly(imidophenylquinoxalines) ....................................................................... 88
Chapter 4. Degradation of polysulfones and polyesterimides ..................... 98
DEGRADATION IN MELT ......................................................................... 98
Polysulfones ............................................................................................... 98
Polyesterimides ........................................................................................ 126
On the mechanism ofP SF and P EI thermal oxidation ............................ 140
SOLID-PHASE OXIDATION .................................................................... 146
Polysulfone ............................................................................................... 146
Polyesterimide .......................................................................................... 15 0
Chapter 5. Degradation of aromatic co-polyesters derived from n-
oxybenzoic, tere- and isophthalic acids, and dioxydiphenyl ...................... 151
Heavy products ofL CP degradation ....................................................... 158
Chapter 6. Fundamental regularities of thermal oxidation of heat-resistant
heterochain polymers ..................................................................................... 163
Chapter 7. Practical stabilization of heat resistant polymers .................... 178
LABILE STRUCTURES AND ADDITIVES ............................................. 178
Polysulfones ............................................................................................. 178
Polyesterimide .......................................................................................... 186
Polyphthalamides ..................................................................................... 188
Poly(a lkane imide) ................................................................................... 192
STABILIZATION ....................................................................................... 196
Polysulfones ............................................................................................. 196
Polyesterimides ........................................................................................ 205
E. V. Kalugina, K.Z. Gumargalieva, and G.E. Zaikov
Aliphatic-aromatic polyamides and glass-filled composite materials
derived from them .................................................................................... 205
Stabilization ofg lass-filled composite materials derived from P PA ....... 207
Glass-filled composite materials derived from poly(a lkane imide) ......... 218
On the mechanism oft ransition metal compounds .................................. 221
On the mechanism ofd egradation transformations in heat-resistant
heterochain polymers in the presence ofs tabilizers-phosphorus-
. containing compounds ............................................................................. 23 5
Chapter 8. Conclusion ................................................................................... 250
REFERENCES ............................................................................................ 254
ABBREVIATIONS ..................................................................................... 277
Thermal Stability ofE ngineering ...
FOREWORD
In 1960, the laboratory on degradation and stabilization of polymers was
established in G.S. Petrov Scientific Research Institute of Polymeric Materials
on the initiative of Professor M.B. Neiman from Institute of Chemical Physics,
Academy of Sciences of the former USSR. At that time, development of
technologies for production of engineering polymers and composite materials
derived from them was the main objective of the Institute of Polymeric
Materials. High quality of the final product cannot be achieved without
understanding the features of thermal transformations in polymers, specifically
at the stage of material production (during polymer synthesis), then at
manufacture of articles, and so on. Therefore, very timely was establishment of
such division, directly related to process engineers who developed new
polymeric materials. Actually, in the early 1960's the problem of polymeric
material stabilization was of special interest both in Russia and abroad. Since
works by Soviet scientists had been published in different scientific magazines
during many years, in 1962 this brought up the question about publishing a
monograph about aging and stabilization of polymers. To speed up the process
of the book issue, a large group of specialists - the experts in stabilization of
polymers- was recruited for writing it. Fortunately, in 1964, the first Russian
monograph on this theme (Aging and Stabilization of Polymers, Ed. M.B.
Neiman) was published. Chapter 6 "Aging of polyamides" and Chapter 7
"Aging of some condensed polymers" were written by Doctor 1.1.
Levantovskaya, the senior scientific worker, and B.M. Kovarskaya, the Head of
Laboratory of degradation and stabilization of polymers, Institute of Polymeric
Materials.
That primary monograph initiated a series of publications on the above
mentioned problems. One of the following monographs was "Thermal Stability
of Heterochain Polymers" which united results of investigations, carried out in
the laboratory of degradation and stabilization of polymers during next 15 years.
It was published in 1977, written by Doctors B.M. Kovarskaya, A.B.
Blumenfeld and 1.1. Levantovskaya.
In 1970's- the early 1990's a definite intensification was observed in
researches and development of new thermally stable polymers (polysulfones,
polyester sulfones, polyester ketones, polyester imides, aliphatic-aromatic
polyamides and polyimides, etc.). This outburst was induced by development of
E. V. Kalugina, K.Z. Gumargalieva, and G.E. Zaikov
high technologies in the branch of aerospace industry, electronics and other
types of special engineering. Therefore, this naturally initiated development of
new directions in studies of heat-resistant polymer degradation in the mentioned
laboratory. The features of mechanisms of degradation transformations in these
polymers happened at high temperatures (during processing, for example)
required new, untraditional approaches to their stabilization. However, despite
the urgency of this problem, up to now it was shortly illustrated in generalizing
publications, which were mostly reviews and articles, published from time to
time in international and Russian scientific magazines and collections.
The present monograph is intended to pool the data, recently
accumulated in Russia and other countries in the branch of heat-resistant
heterochain polymers. The book shows investigation results of degradation
transformations in aliphatic-aromatic polyimides and polyamides, polysulfones
and polyester imides, liquid-crystal copolyesters and polyphenyl quinoxalines in
a wide temperature range, which includes temperature ranges of polymer
processing to articles and operation of the latter. High-temperature stabilization
of polymers is also discussed as an important applied task.
The authors of the book high appreciate the scientists of G.S. Petrov
Research Institute of Polymeric Materials from the laboratory of degradation
and stabilization of polymers, recently headed by Dr. A.B. Blumenfeld, the
leading specialists Drs. L.M. Bolotina, A.G. Chernov, M.E. Savina,
physicochemical and physicomechanical test departments, etc. for presented
materials and fruitful discussion of the monograph.
E.V. Kalugina, K.Z. Gumargalieva, and G.E. Zaikov
INTRODUCTION
The development of special machinery, aircraft and missile engineering,
and automotive industry brought up the task of creating heat-resistant polymeric
materials before chemistry of high-molecular compounds. By now
manufacturing of articles by press molding or extrusion is one of the most
effective and progressive methods. Therefore, polymeric materials must possess
thermoplastic property.
In recent decades, the achievements in chemistry of high-molecular
compounds are associated with creation of several polycondensation polymers,
which combine aromatic, carbo- and heterochain groups with aliphatic branches
in their structure. On the one hand, high softening temperatures which usually
fall above 250 - 350°C represent an important positive feature of these
compounds. It indicates the shape stability of even unfilled polymers in articles
up to 200 - 300°C or even higher. On the other hand, closeness of the melting
point and the start of degradation hamper processing of these materials.
Therefore, of importance becomes stabilization of heat-resistant polymers at
increased processing temperatures, usually falling in the range of 300 - 400°C.
Hence, the traditional task of polymer stabilization during long-term operation
(currently, also at increased temperatures) is actual still. Development of these
tasks requires implementation of a set of studies which include:
- Detection of thermally labile or defect structures in macromolecules;
Determination of acceptable content of primary and process additives in the
polymer;
- Setting the upper temperature border of processing, above which
degradation makes problems with the final product quality or abruptly
decreases sanitary-hygienic conditions of processing;
- A set of data for making sanitary-chemical passports for processing of
polymeric materials: identification and quantitative analysis of volatile
products extracted in the processing cycle;
- Estimation of operation property changes of polymeric materials at aging
and forecasting of temperature-time criteria of operation (durability).
Such applied setting of the problem allows posing of definite
requirements to raw materials and production process, which provide the
