Influence of pendent groups on the tensile properties of polyisoprene vulcanizates

Gum compounds of polyisoprene were vulcanized with a number of different curing systems to give networks with crosslink densities in two different ranges. Stress–strain curves were obtained upon rapid (500 mm/min) and slow (0.5 mm/min) extension. In tetramethylthiuram disulfide (TMTD)/sulfur and zinc dimethyldithiocarbamate/sulfur vulcanizates, which crystallize readily, failure occurred at higher tensile values upon rapid than upon slow extension and this is attributed to a greater contribution to tensile strength by a larger amount of stress‐induced crystallites. X‐ray diffraction showed that 2‐benzothiazole‐2,2′‐disulfide (MBTS)/sulfur vulcanizates did not stress‐crystallize and failure occurred at lower tensile values. Furthermore, samples extended rapidly failed at lower tensile values than did slowly extended samples. These differences, compared to TMTD vulcanizates, are attributed to extensive main‐chain modifications (pendent groups), causing delays in the movement of sections of the chain, leading to the load being unequally distributed between chains. The fewer load‐bearing chains ensure earlier failure. The addition of zinc stearate to TMTD/sulfur and MBTS/sulfur formulations increases the ability of vulcanizates of similar crosslink density to crystallize and enhances tensile properties of vulcanizates with similar crosslink densities, outcomes that are attributed to zinc stearate's promoting crosslinking of pendent groups and reducing impediments to crystallization and chain movement. Dicumyl peroxide–cured networks crystallize readily and exhibit a very rapid upturn in the stress–strain curve. However, failure occurs at lower stress values than apply to accelerated sulfur networks and it is suggested that the distribution of subchain lengths between crosslinks may contribute to their inferior properties. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2587–2596, 2001