Homogeneous Zinc(II) Catalysis in Accelerated Vulcanization I. Reaction-Stage Modeling and Cross-Link Formation

Author:

Nieuwenhuizen Peter J.1,Timal Sandjai1,van Veen Jeroen M.1,Haasnoot Jaap G.1,Reedijk Jan1

Affiliation:

1. 1Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands

Abstract

Abstract This paper reports a novel approach for the study of the mechanism of accelerated vulcanization, namely, Reaction-Stage Modeling (RSM). By carefully studying the reactivity of relevant model compounds under selected conditions, detailed knowledge about a particular reaction stage of vulcanization can be obtained. Background, experimental details and synthesis of model compounds are described. An RSM study after cross-link formation in the thiuram- and dithiocarbamate type vulcanization has been performed, and the role of zinc compounds herein was investigated. In contrast to earlier studies, it has appeared that at 140 °C, cross-links form from cross-link precursors solely via disproportionation. Allylic substitution was not observed. Zinc compounds act as catalysts for disproportionation, but especially ZDMC can be regarded as an efficient, soluble molecular turntable for sulfur atoms.

Publisher

Rubber Division, ACS

Subject

Materials Chemistry,Polymers and Plastics

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