The development of polymers as an important class of material was inhibited at the first by the premature failure of these versatile compounds in many applications. The deterioration of important properties of both natural and synthetic polymers is the result of irreversible changes in composition and structure of polymers molecules. As a result of these reactions, mechanical, electrical and/or aesthetic properties are degraded beyond acceptable limits. It is now generally recognized that stabilization against degradation is necessary if the useful life of polymers is to be extended sufficiently to meet design requirements for long-term applications. Polymers degrade by a wide variety of mechanisms, several of which affect all polymers through to varying degree. This monograph will concentrate on those degradation mechanisms which result from reactions of polymers with oxygen in its various forms and which are accelerated by heat and/or radiation. Those stabilization mechanisms are discussed which are based on an understanding of degradation reaction mechanisms that are reasonably well established. The stabilization of polymers is still undergoing a transition from an art to a science as mechanisms of degradation become more fully developed. A scientific approach to stabilization can only be approached when there is an understanding of the reactions that lead to degradation. Stabilization against biodegradation and burning will not be discussed since there is not a clear understanding of how polymers degrade under these conditions.

During the past decade, the field of polymer degradation and stabilization has become a subject of central importance in polymer science and technology. This book provides a fundamental source of information designed for those with only a basic understanding of the background of the field.

The study of polymer degradation and stabilisation is of considerable practical importance as the industrial uses of polymeric materials continue to expand. In this book, the authors lucidly relate technological phenomena to the chemistry and physics of degradation and stabilisation processes. Degradation embraces a variety of technologically important phenomena ranging from relatively low temperature processes such as 'weathering' of plastics, 'fatigue' of rubbers through the processing of polymers in shearing mixers to very high temperature processes such as flammability and ablation. All these technological phenomena have in common certain basic chemical reactions. Thus 'weathering' has its roots in photo-oxidation, 'fatigue' and melt-degradation in mechano-oxidation and flammability, and ablation in ablation in pyrolysis and vapour phase oxidation.

The purpose of this publication is two-fold. In the first place it is intended to review progress in the development of practical stabilising systems for a wide range of polymers and applications. A complemen tary and ultimately more important objective is to accommodate these practical developments within the framework of antioxidant theory, since there can be little question that further major advances in the practice of stabilisation technology will only be possible on a firm mechanistic foundation. With the continual increase in the number of commercial anti oxidants and stabilisers, often functioning by mechanisms not even considered ten years ago, there is a need for a general theory which will allow the potential user to predict the performance of a particular antioxidant structure under specific practical conditions. Any such predictive tool must involve a simplified kinetic approach to inhibited oxidation and, in Chapter 1, Denisov outlines a possible mechanistic approach with the potential to predict the most useful antioxidant to use and the limits of its usefulness. In Chapter 2, Schwetlick reviews the current state of knowledge on the antioxidant mechanisms of the phosphite esters with particular emphasis on their catalytic peroxidolytic activity. Dithiophosphate v vi PREFACE derivatives show a similar behaviour but for quite different reasons and, in Chapter 3, AI-Malaika reviews information available from analytical studies, particularly using 31p_NMR spectroscopy, to elucid ate the complex chemistry that leads to the formation of the antioxidant -active agents.

During the last two decades, the production of polymers and plastics has been increasing rapidly. In spite of developing new polymers and polymeric materials, only 40~60 are used commercially on a large scale. It has been estimated that half of the annual production of polymers is employed outdoors. The photochemical instability of most polymers limits their outdoor application as they are photodegraded quickly over periods from months to a few years. To the despair of technologists and consumers alike, photodegradation and environmental ageing of polymers occur much faster than can be expected from knowledge collected in laboratories. In order to improve polymer photostability there has been a very big effort during the last 30 years to understand the mechanisms involved in photodegradation and environmental ageing. This book represents the author's attempt, based on his 25 years' experience in research on photodegradation and photo stabilization, to collect and generalize a number of available data on the photodegradation of polymers. The space limitation and the tremendous number of publications in the past two decades have made a detailed presentation of all important results and data difficult. The author apologizes to those whose work has not been quoted or widely presented in this book. Because many published results are very often contradictory, it has been difficult to present a fully critical review of collected knowledge, without antagonizing authors. For that reason, all available theories, mechanisms and different suggestions have been presented together, and only practice can evaluate which of them are valid.

Polyvinyl chloride has played a key role in the development of the plastics industry over the past 40 years and continues to be a polymer of major importance. The reasons for its enormous versatility and range of application derive from a combination of the basic structure which gives rise to a relatively tough and rigid material and its ability to accept a range of plasticisers and other additives which can modify its physical characteristics to produce a range of flexible products. Two major problems, however, have tested the skill and ingenuity of PVC technologists since earliest times. One is the thermal instability of the material at the temperatures required for melt processing and fabrication, and the second is the photochemical instability which until recently has limited the potentially large range of outdoor applications. Both problems have been handled in a commercially satisfactory way by the gradual development of a range of stabilisers, lubricants and other processing aids and the high quality material which has resulted has led to massive utilisation of PVC by industry. Totally adequate stabilisation requires a detailed understanding of the mechanisms by which degradation processes are initiated and propagated. Although great advances have been made in this respect in recent years the problem remains incompletely understood. This book presents an account of the present position and the problems which remain to be solved.

Plastics are used worldwide in everyday life, e.g. as food packaging, electronics, construction, automotive parts, and household appliances. To produce these products with the desired service lifetimes the use of suitable stabilizers is necessary. This book provides a concise and comprehensive overview of the basic mechanisms of plastic degradation processes caused by heat and light. At its core is a detailed description of the stabilization of different polymers, including an explanation of stabilization mechanisms and the influence of commonly used additives such as fillers, flame retardents and pigments on the stability of plastic. Every polymer scientist, material technologist, or application engineer dealing with the design of the properties of plastics will benefit from this new overview.

Understanding the thermal degradation of polymers is of paramount importance for developing a rational technology of polymer processing and higher-temperature applications. Controlling degradation requires understanding of many different phenomena, including chemical mechanisms, the influence of polymer morphology, the complexities of oxidation chemistry, and the effects of stabilisers, fillers and other additives. This book offers a wealth of information for polymer researchers and processors requiring an understanding of the implications of thermal degradation on material and product performance.

Provides a comprehensive overview of the science of polymer durability. Discusses the molecular mechanisms of polymer aging and deterioration, emphasizing UV and thermal exposure environments. Describes a variety of analytical techniques for studying degradation, with special emphasis on chemiluminescence. Covers advances in the use of additives and other approaches for enhancing polymer stability. Reviews mechanisms and applications of major classes of stabilizers, and discusses the problem of stabilizer migration and loss. Examines new methods for predicting the aging rate and lifetime of a material.

The need for a broad development of the production of polymer ma terials has become evident. All these materials are subject to various types of aging (destruction); hence, stabilizers which permit the stor age, reprocessing, and use of polymer materials without any appreci able change in their properties must be introduced into them. In recent years, this problem of stabilizing polymers has attracted the attention of many scientists and technologists, both in the USSR and abroad. The scientific basis of the foreign studies will be found in a number of theo retical premises, but chiefly the theory of chain reactions with un branched chains. In the Soviet Union, the concepts of Academician N. N. Semenov on chain reactions with degenerate branches have become the starting point of theoretical studies of the stabilization and destruction of polymers. Soviet scientists have developed a theory of critical concentrations of antioxidants and have shown that the processes of stabilization have a very complex chemical character. The nature of the polymers them selves greatly affects these processes and consequently, different stabil izers are required for polymers of different structures. In addition, it has been shown that the antioxidants used thus far can not only cause chain termination, but can also initiate oxidation and give rise to de generate branches.