Studies of the Vulcanization of High Elastic Polymers. II. Vulcanization of Natural Rubber with Thiuram Disulfides. Part 2

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Abstract
This paper gives some insight into the kinetics of thiuram vulcanization. The following results were obtained. 1. The decrease of concentration of thiuram disulfides during vulcanization is a first-order reaction in the range of short vulcanization times. At longer reaction times, departures occur. The process then takes place more slowly. 2. The departures from the course of a first-order reaction are displaced with decreasing temperature toward the range of longer vulcanization times. 3. At 87° C, the reaction of tetramethylthiuram disulfide is of the first order over the whole range of vulcanization temperatures chosen, and at this temperature no deviations whatever are observed. 4. The same relationships are found in the kinetic study of dithiocarbamate formation. 5. From the combined results, it is concluded that, besides the two reactions occurring independently of each other during vulcanization, the diffusion of the reaction partners also has some influence on the kinetics. 6. The limiting value of dithiocarbamate formation is correlated with the macromolecular structure of the polyisoprene, and it is shown to be probable that this limit is not determined fundamentally by the chemistry of the vulcanization reaction.

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