Thermal Stability of Engineering Heterochain Thermoresistant Polymers

290 Pages·2004·14.613 MB·\290

by  Kalugina (Author), Gumargalieva (Author), Gennady Zaikov (Author)

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New Concepts in Polymer Science
Thermal Stability of Engineering
Heterochain Thermoresistant Polymers
New Concepts in Polymer Science
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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 -
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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