Influence of Sulfur on Stability and Physical Properties of Peroxide Vulcanized Ethylene Propylene Copolymers
Abstract In cumyl peroxide sulfur vulcanizates of ethylene propylene copolymers crosslinked with 4 phr of peroxide, polysulfidic crosslinks are present only at sulfur levels in excess of 0.5 phr in gum vulcanizates and 0.3 phr in black filled vulcanizates. Modulus attains a peak in the presence of 0.5 phr of sulfur in gum vulcanizates and 0.3 phr of sulfur in black filled vulcanizates. Modulus decreases when polysulfides are present. Tensile strength in gum vulcanizates increases continually with increasing sulfur content up to 2.5 phr. The increase in tensile strength is related to a rapid increase in ultimate elongation, promoted by mechanically labile polysulfidic crosslinks. Tensile strength in black filled vulcanizates exhibits peaks at 0.3 and 0.75 phr of sulfur. The first peak represents the technological recipe for this type of vulcanizate and arises from a peak in modulus. The second peak arises from increased breaking elongation promoted by polysulfidic crosslinks. Sulfides present in the vulcanizate act as antioxidants at all sulfur levels. When the sulfides contain one or two sulfur atoms, the antioxidant effect is mild but long lived. The polysulfides yield potent long lived antioxidants. The rapid nonoxidative degradation of the polysulfidic crosslinks is not accelerated by dithiocarbamate and proceeds after the reaction products have been removed by extraction. Dithiocarbamates are potent antioxidants in peroxide vulcanized ethylene propylene rubber both in the presence and in the absence of sulfur.