Stress Relaxation Studies of Scission in Rubber Vulcanizates

Deterioration of many vulcanized hydrocarbon rubbers is known to be due to reaction with molecular oxygen. Such a process is independent of oxygen concentration down to several mm of oxygen pressure and hence proceeds quite readily in an air atmosphere provided that experiments are conducted with thin enough samples to eliminate oxygen diffusion effects. Two chemically distinct loci for attack by oxygen are available. These are the crosslinked sites which are added during the vulcanization process and the network chains which are essentially the same as in the unvulcanized material. The prime objective of this study is to show clearly that vulcanized natural rubber suffers oxidative scission predominantly along the polyisoprene chains and not at the crosslinked sites as proposed by Berry and Watson. Other literature has appeared which indicates that this important point needs further clarification. Stress relaxation experiments, which measure the rate of breaking of the weakest chemical bonds recurring throughout the structure, have been utilized. If the crosslinks are oxidized, then similar rates of scission should be obtained for different chain structures so long as the common crosslink is present in all of them. On the other hand, if chains are oxidized, then rates of scission should be essentially independent of the crosslinking agent used but rather depend markedly on each chain structure. The five chain structures used in this study are depicted in Table I. In each case at least a few per cent of double bond-containing segments are present in the main chain to allow for ordinary chemical vulcanization methods. All of these have been crosslinked by sulfur and by a nonsulfur containing agent.