The Nature of Vulcanization Part IV

Abstract

Abstract (1) At low temperatures by means of accelerators it is possible to produce vulcanites containing “combined sulfur” considerably in excess of that required for the formula C5H8S. Such vulcanites may be obtained by vulcanizing at 100° with a variety of ultra-accelerators with and without zinc oxide as an activator. If zinc oxide or a zinc salt is used the excess coefficient cannot be explained by the presence of the zinc sulfide in the vulcanite. (2) The amount of sulfur combined with the rubber, given sufficient heating and presence of accelerator, is mainly dependent on the excess of sulfur present. (3) Extraction of the vulcanite with hydrochloric acid-ether mixture removes a part of the “combined” sulfur. A considerable amount is removed when the amount of combined sulfur is very large, but even then the amount of sulfur remaining is considerably in excess of that required by the formula C5H8S. (4) Vulcanization at low temperatures in solution in accordance with Whitby's procedure with the aid of accelerators also yields vulcanites with coefficients in excess of that required for the formula C5H8S. (5) The result of vulcanization at low temperatures is approximately the same, whether the rubber contains all the protein and serum ingredients, the usual proportion, or very little. (6) Extraction of sulfur from vulcanite with hot acetone vapor is not complete after 1210 hrs. (7) Having regard to the hydrogen sulfide and other volatile sulfur compounds evolved in appreciable quantities during vulcanization, it is evident that part of the combined sulfur results from substitution of hydrogen by sulfur. This substituted product is decomposed by the hydrochloric acid-ether mixture. It may not be possible to decompose the whole in this manner. Consequently, any “combined” sulfur in excess of that required by the formula C5H8S may result from substitution in the molecule.