Abstract
A volumetric oxygen-absorption test for aging of rubber has been investigated from the point of view of the effect of cure and the effect of mercapto-benzimidazole on the aging behavior. The test has also been evaluated by comparison with conventional air oven and oxygen bomb aging. A compounded but uncured Hevea black stock is more resistant to oxidation than the vulcanized material, but after a reasonable cure is obtained, further heating produces only a small change in the rate of oxygen absorption. The change in physical properties corresponding to a given amount of oxygen absorbed varies somewhat with time of cure in the initial stages, but after the absorption of 4 or 5 cc. of oxygen per gram of rubber, the changes in most physical properties are a direct function of the amount of oxygen absorbed. Neither time of cure nor the presence or absence of inhibitor has any significant effect on the subsequent rate of change in such properties as tensile strength and ultimate elongation for a given amount of oxygen absorbed. Oven aging data on identical time cures confirm the reported superiority of a combination of mercaptobenzimidazole with a conventional type of anti-oxidant. Oxygen absorption data reveal, however, that mercaptobenzimidazole causes a significant decrease in the rate of oxidation of a Hevea black stock, and thus it clearly functions at least in part as an antioxidant in the usually accepted sense. The deterioration of properties is, in general, proportional to the oxygen absorbed, except in the early stages of oxidation where the mercaptobenzimidazole stocks change somewhat less than the controls for a given amount of oxygen absorbed. When the cures are selected to give comparable initial properties, however, the change in tensile strength of the mercaptobenzimidazole stocks with amount of oxygen absorbed is essentially the same as for the controls, even in the initial stages. These data suggest that the observed protection imparted by mercaptobenzimidazole results from a combination of two factors: (1) the normal antioxidant activity of mercaptobenzimidazole, which reduces the amount of oxygen absorbed; and (2) an effect on the nature of the cure attained when mercaptobenzimidazole is present, such that the absorption of a given amount of oxygen in the early stages is not accompanied by as great a change in properties. Thus, it appears that the deactivating effect may be the result of the effect of this material on the vulcanization process rather than a direct effect on the oxidation process. A comparison of the effect of oxygen absorption, air oven, and oxygen bomb aging methods on changes in physical properties of Hevea black stocks shows that the results obtained by oxygen absorption and air oven methods (both at 100° C) are similar, but that the higher oxygen concentration of the oxygen bomb test (70° C and 300 pounds per square inch) apparently results in a higher proportion of chain scission when compared to cross-linking of the polymer chains.
Free Radical Mediated Oxidative Degradation of Carotenes and Xanthophylls