Network Scission Processes in Peroxide Cured Methylvinyl Silicone Rubber
Abstract In what appeared to be a complex system it transpires that network scission in methylvinyl silicone rubbers at temperatures below 250° C is due largely to hydrolytic reactions in the main chain polymer. At temperatures of 250° C and above there are indications that a significant amount of scission arises from oxidative reactions in the crosslinks, and that this reaction is catalyzed by acidic residues in the rubber. There is no indication that acidic byproducts of the vulcanization reaction catalyze the hydrolysis of siloxane bonds in the polymer. In conventional heat aging tests in which the rubber remains in an unstrained condition the effects of hydrolysis will only be observed if the concentration of water in the system is allowed to rise. Under these circumstances softening will occur because of a shift in the position of equilibrium in the reaction ∼Si—O—Si—O∼ + H2O→∼Si—OH+ HO—Si—O∼ On aging the material in a well ventilated situation the effects of hydrolysis are not seen and the silicone rubber becomes brittle after long exposure at high temperature. This embrittlement must result from additional crosslinking caused by oxidative reactions in the methyl groups of the main chain polymer. When the rubber is used in compression or tension, hydrolytic scission will affect performance, and in applications of this sort it is important to dry the rubber before use and prevent access of moisture to the component during use. With filled rubber the silica filler is a further source of moisture and drying needs to be carried out at elevated temperatures immediately before use. In order to improve the confined heat aging performance of silicone rubber an alternative filler to fine silica is needed which does not have the same affinity for water. It may be, however, that ability to reinforce silicone rubber and affinity for water are inseparable.