Kinetics of thiuram–accelerated sulfur vulcanization

Abstract

On the basis of continuous measurements in a Vuremo curemeter at 145°C, kinetics of tetramethylthiuram disulfide (TMTD)-accelerated sulfur vulcanization of natural rubber has been investigated. It was found that the cure rates increase with increasing TMTD concentration, the sulfur content being kept constant, up to a TMTD:S weight ratio of 2:1. Beyond this value, the cure rates again decrease. This TMTD:S ratio corresponds to 3.8 gram atoms of sulfur per mole TMTD, and it is in good agreement with findings that in TMTD-accelerated sulfur vulcanization systems the peak value of zinc dimethyldithiocarbamate (ZnDMDC) formation reaches an endvalue when the stocks contain 4 gram atoms of sulfur per mole TMTD. These facts lead us to suppose that ZnDMDC is the actual accelerator in TMTD-accelerated sulfur systems. Support for this view derives from our experiments with model curing systems as well as from the generally known practical experience that dithiocarbamates are faster accelerators than thiuram disulfides. For the reasons described above and for the finding that the dependences of the ultimate extent of vulcanization (network chain density) on the concentration of TMTD in the absence and in the presence of elemental sulfur are analogous, the mechanism of thiuram-accelerated sulfur vulcanization is very probably similar to that of sulfur-free thiuram vulcanization.