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

Abstract

Rubber and model compound 2,3-dimethyl-2-butene were vulcanized for various times with dimethylammonium dimethyldithiocarbamate [(dma)dmtc]-accelerated sulfur formulations in the absence of ZnO. Model compound systems were analyzed by HPLC, and no reaction intermediates containing pendent groups were found. Crosslinked sulfides, characterized by 1 H-NMR, were found to be essentially bis(alkenyl). Residual curatives were extracted from rubber compounds vulcanized for various times and analyzed by HPLC. Compounds, cured to various crosslink densities, were found to crystallize readily in a density column at subambient temperatures. This supports evidence from model compound 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 applicable with (dma)dmtc accelerated formulations. Very limited crosslinking occurred 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 interpreted as evidence that some pendent groups did form during heating with (dma)dmtc/sulfur. Crosslinking of such pendent groups may be inhibited by the loss of (dma)dmtc, that, like zinc dimethyldithiocarbamate, may catalyze their 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.

Zinc Complexes with 1,3-Diketones as Activators for Sulfur Vulcanization of Styrene-Butadiene Elastomer Filled with Carbon Black

“…MCV is a useful technique for studying the mechanism of accelerated sulfur vulcanization. The effectiveness of this approach in studying the influence of activators on the course of the crosslinking reaction and the structure of the elastomer network has been confirmed by many researchers [48][49][50][51]. Moreover, the density functional study proposed by Maity and Pinĉák [52] could be helpful to explore the interfacial properties of the crosslinking system components.…”