The chemical structure of the tread vulcanizate of heavy-duty tires has been investigated before and after service on the road, and after testing under conditions designed to induce tread-lift. Significant changes occurred. These included a marked reduction in the concentration of polysulfide crosslinks, and an increase in the amount of monosulfide crosslinks and main chain modification. Experiments with vulcanizates made in the laboratory indicated that the structural alterations in the tires were due to thermal anaerobic reactions caused by heat build-up, and that they resulted in a deterioration in some of the physical properties of the tread vulcanizate. The rate of desulfuration of ‘model’ polysulfides has been found to depend critically upon the nature of the vulcanization recipe. These novel findings point the way to improving the stability of vulcanizates used in the treads of tires and, consequently, tire performance.
In the last few years several reviews and books have been published on the aging of elastomers, but the overall view which they present of the oxidation of natural rubber and its vulcanizates still contains many puzzling features. Two of these are the variation of antioxidant efficiency in different types of vulcanizate, and the extent of the involvement of crosslink scission in the overall degradation process in sulfurated vulcanizates. Sometimes apparent contradictions have arisen from a failure to appreciate that aging of natural rubber vulcanizates depends primarily on four factors; the purity and type of rubber, the presence of additives, the type and extent of vulcanization, and the purification (if any) after cure. In many cases direct comparisons have been attempted without due consideration being given to all these factors, leading inevitably to some confusion. Recent work on the structure of vulcanizates has enabled the NRPRA to embark on a program of aging studies with vulcanizates of carefully controlled structure and complexity, which has already led to a better understanding of the processes involved in vulcanizate degradation. This review will attempt to elucidate the present state of knowledge, and will therefore be largely concerned with recent work at NRPRA, and its relation to previous studies. The review is divided into two main parts, they are: the effect of vulcanizate structure on aging, and the chemistry of oxidative scission reactions. Before attempting to rationalize the effect of vulcanizate structure on aging, structural characteristics of the most important types of vulcanizate are briefly discussed.
A natural rubber vulcanizate containing almost entirely monosulfidic crosslinks was oxidized in oxygen and with tert‐butyl hydroperoxide. The changes in physical properties due to oxidation were followed by stress–strain measurements, and the changes in chemical structure were investigated with chemical probes, and by spectroscopic methods. The results show that when the oxidized vulcanizates are heated at 75°C., the monosulfidic crosslinks are broken, that crosslinks containing two sulfur atoms are formed, and that conjugated diene and triene structures are introduced into the main polyisoprene chains.
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