Decomposition of polymerization initiators under high pressures

A number of diacylperoxides, peroxydicarbonates, peresters and dialkylperoxides with various substituents were chosen to investigate their homolytic decomposition under pressures of up to 3000 bar and high temperatures of up to 200°C, discontinuously in steel autoclaves, in an optical high pressure cell and in flow processes. The measurements, carried out in isododecane as solvent with a peroxide concentration of 1% by weight show that pressure has a strong influence on the decomposition: the half‐life time at 3000 bar is twice that at normal pressure. The pressure dependence, which varies according to the structure of the peroxide and the decomposition mechanism, is interpreted by means of the activation volumes. On the basis of the results, recommendations are made on the choice of peroxides suitable as polymerization initiators for application at high pressures and temperatures.