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.

The purpose of this volume, like that of its predecessors in the series, is to present a selection of topics which are representative of the continually expanding area of polymer degradation. It will be obvious that some of these topics emanate from academic studies, others from more applied backgrounds, but it is anticipated that all will be seen to be of vital relevance to one or other of the currently advancing fields of polymer technology. The first two chapters deal with specific classes of polymers, and particularly with their mechanisms and products of thermal degrada tion. Thus in Chapter 1 Dr McNeill discusses the reactions of the ammonium, alkali and alkaline earth metal salts of poly(methacrylic acid) and their copolymers with methyl methacrylate. These water soluble 'ionomers' have valuable technological applications. In Chap ter 2 Professor Montaudo and Dr Puglisi perform a valuable service by drawing together and critically reviewing, for the first time to my knowledge, the mechanisms of thermal degradation of the various classes of condensation polymers which are of industrial significance. This includes, for example, the polyurethanes, polyureas, polyesters, polycarbonates, polyamides, polyimides, polyethers, polysulphides, polysulphones, polyschiff bases, polysiloxanes and polyphosphazenes.

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.

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.

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.

Few scientific developments in recent years have captured the popular imagination like the subject of'biodegradable' plastics. The reasons for this are complex and lie deep in the human subconscious. Discarded plastics are an intrusion on the sea shore and in the countryside. The fact that nature's litter abounds in the sea and on land is acceptable because it is biodegradable - even though it may take many years to be bioassimilated into the ecosystem. Plastics litter is not seen to be biodegradable and is aesthetically unacceptable because it does not blend into the natural environment. To the environmentally aware but often scientifically naive, biodegradation is seen to be the ecologically acceptable solution to the problem of plastic packaging waste and litter and some packaging manufacturers have exploited the 'green' consumer with exaggerated claims to 'environmentally friendly' biodegradable packaging materials. The principles underlying environmental degradation are not understood even by some manufacturers of 'biodegradable' materials and the claims made for them have been categorized as 'deceptive' by USA legislative authorities. This has set back the acceptance of plastics with controlled biodegradability as part of the overall waste and litter control strategy. At the opposite end of the commercial spectrum, the polymer manufactur ing industries, through their trade associations, have been at pains to discount the role of degradable materials in waste and litter management. This negative campaign has concentrated on the supposed incompatibility of degradable plastics with aspects of waste management strategy, notably materials recycling.

The book is in five parts: Part I introduces the physical and chemical structure of polymers and their breakdown; Part II reviews electrical degradation in polymers, and Part III reviews conduction and deterministic breakdown in solids. Part IV discusses the stochastic nature of break-down from empirical and modelling viewpoints, and Part V indicates practical implications and strategies for engineers. Much of the discussion applies to non-crystalline materials generally.