Degradation of Rubber by Chemical Agents in Solution

Abstract

Abstract It is clear that the subject of polymer degradation by chemical agents is an active branch of polymer chemistry. This is reflected in the large number of patents applying to polymer degradation and no attempt has been made to include every appropriate patent. Much of the comparative work is based on equal weights, rather than equal numbers of molecules, so that the true comparisons of the efficiency of peptizers are often difficult. It has been shown that polymer degradation can proceed via several mechanisms all of which involve free radicals and the main points can be summarized as follows :— In solutions at low temperatures the initiatory free radicals come from the added peptizer such as benzoyl peroxide or bis-azoisobutyronitrile. Although oxygen accelerates the reaction, it is not essential, and there is appreciable degradation in the absence of oxygen. Thiols are active only when oxygen is present even at high temperature. This is somewhat surprising, since the rubber radicals produced by thermal scission should be just as active as those produced by mastication and be capable of reaction with thiols, and serves to emphasize the importance of the role of oxygen in peptization by thiols and disulfides. Oxygen is also necessary for degradation by redox systems and in its absence structurizing takes place. The lack of work on triphenyl methane derivatives is somewhat surprising in view of the ease with which they undergo homolysis to give free radicals. However, it is not sufficient to introduce any type of free radical and expect degradation: stabilized free radicals are the best peptizers, unstable radicals can add to olefinic bonds and cause crosslinking rather than chain scission. Squalene has been used as a model compound for the study of the reactions of natural rubber with free radicals in a similar manner to the use of methylcyclohexene as a model compound for oxidation studies. This review forms part of a dissertation submitted in partial fulfillment of the requirements for the London University M.Sc. (External) Examination.