Dimethylammonium dimethyldithiocarbamate-accelerated sulfur vulcanization.II. Vulcanization of rubbers and model compound 2,3-dimethyl-2-butene

Rubber and model compound 2,3-dimethyl-2-butene were vulcanized for various times with dimethylammonium. dimethyldithiocarbamate [(dma)dmte]-accelerat ed sulfur formulations in the absence of ZnO. Model compound systems were a nalyzed by HPLC, and no reaction intermediates containing pendent groups we re found. Crosslinked sulfides, characterized by H-1-NMR, were found to be essentially bis(alkenyl). Residual curatives were extracted from rubber com pounds vulcanized for various times and analyzed by HPLC. Compounds, cured to various crosslink densities, were found to crystallize readily in a dens ity column at subambient temperatures. This supports evidence from model co mpound systems that pendent groups are largely absent from vulcanizates. It is suggested that a reaction mechanism, similar to that applicable to zinc dimethyldithiocarbamate-accelerated sulfur vulcanization, may be applicabl e with (dma)dmte accelerated formulations. Very limited crosslinking occurr ed on heating compounds under vacuum, and this can be attributed largely to the rapid loss of (dma)dmtc from rubber at elevated temperatures. However, the slower rate of crystallization on cooling of the gels, compared to the rate in press-cured vulcanizates of similar crosslink density, was interpr eted as evidence that some pendent groups did form during heating with (dma )dmtc/sulfur. Crosslinking of such pendent groups may be inhibited by the l oss of (dma)dmtc, that, like zinc dimethyldithiocarbamate, may catalyze the ir crosslinking, and/or to the loss under vacuum of dimethyldithiocarbamic acid that would form thiol pendent groups that would rapidly crosslink with thiuram pendent groups. (C) 2001 John Wiley & Sons, Inc.