A comparison of tetraethylthiuram and tetramethylthiuram disulfide vulcanization. II. Reactions in rubber

The reactions of tetraethylthiuram disulfide (TETD) with polyisoprene were investigated under vulcanization conditions. Samples of polyisoprene compounded with various combinations of TETD, sulfur, and ZnO were heated in a differential scanning calorimeter to various degrees of vulcanization. The cr...

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Bibliographic Details
Published in:Journal of applied polymer science 2002-01, Vol.83 (5), p.1119-1127
Main Authors: Gradwell, M. H. S., Grooff, D.
Format: Article
Language:English
Subjects:
Applied sciences
Chemical reactions and properties
crosslinking
Crosslinking, vulcanization
Exact sciences and technology
Organic polymers
Physicochemistry of polymers
polyisoprene
polysulfides
sulfur
tetramethylthiuram disulfide
vulcanization mechanism
zinc oxide
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Summary:The reactions of tetraethylthiuram disulfide (TETD) with polyisoprene were investigated under vulcanization conditions. Samples of polyisoprene compounded with various combinations of TETD, sulfur, and ZnO were heated in a differential scanning calorimeter to various degrees of vulcanization. The crosslink density of the compounds was determined by swelling, and the extractable residual curatives and reaction products were analyzed with high‐performance liquid chromatography. TETD caused crosslinking to occur in the absence of added sulfur, as did tetramethylthiuram disulfide (TMTD), both sulfur donors. In the presence of sulfur, the formation of TETD polysulfides occurred immediately before the crosslinking reaction started. The TETD polysulfides were the initial crosslinking agents. The ready reaction between TETD and zinc oxide to form zinc diethyldithiocarbamic acid resulted in considerably higher crosslink densities. This greater reactivity between TETD and zinc oxide, compared with that between TMTD and zinc oxide, did not lead to any noticeable differences in the vulcanizate. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1119–1127, 2002
ISSN:0021-8995
1097-4628
DOI:10.1002/app.10138