A thermodynamic study of the crosslinking of methyl silicone rubber

The crosslinking reaction in a two component methyl silicone rubber has been studied by thermomechanical analysis (TMA) and differential scanning calorimetry (DSC). The rubber was formed from two methyl silicone prepolymers; one containing reactive hydrogens every 50 to 100 groups and the other polymer containing pendant vinyl groups at the same frequency. In the presence of a platinum catalyst above 60°C crosslinking proceeds without a loss or gain in weight. The heat of reaction, energy of activation (calculated by two methods) crosslink density and elastic modulus (Young's) were studied as a function of prepolymer concentration, dilution and swelling. A preliminary value for the heat of reaction per mole of SiH and SiCHCH2 has been calculated. From crosslink density measurements both by hexane swelling and TMA and DSC heats of reaction a qualitative picture has been obtained of the role of entangled chains in producing effective crosslinks.