Mineral Sulfide as Index of Disulfide Cross-Bonding

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Abstract
1. The mechanism proposed by Armstrong, Little, and Doak to explain sulfur vulcanization in the presence of metal soap was investigated in polyprene and simpler systems from the viewpoint of the inorganic sulfide produced and, in the case of polyprenes, of the accompanying modulus. 2. Dodecanethiol was found to react with sulfur and zinc soap to produce inorganic sulfide equivalent to the oxidation of 80 to 100 per cent of the thiol to disulfide ; with excess thiol substantially quantitative conversion of sulfur or of zinc soap to inorganic sulfide can be obtained. 3. Several simple olefins were found to react readily with sulfur and zinc soap under vulcanizing conditions. The reaction is promoted by M.B.T. On the basis of the mechanism assumed, the inorganic sulfide formed is sufficient to indicate extensive conversion of the olefin to a substituted diallyl disulfide. 4. Assuming the validity of the proposed mechanism, inorganic sulfide production indicates substantial disulfide cross-linking between α-carbon atoms in conventional cures with natural rubber, and appreciable, though relatively less, cross-bonding of this type in the case of GR-S. The smaller extent of this type of cross-linking with GR-S is believed to result from greater tendency on the part of this elastomer to add the intermediate mercapto compound to double bonds, as proposed in the first paper of this series.

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