The measurement of rates of initiation in the thermal polymerization of styrene

The thermal initiation of the polymerization of styrene has been studied at temperatures from 60–140°C using DPPH as a free radical scavenger. Rates of free radical formation, measured by the decrease in absorbance at 525 nm, are about seven times greater than those obtained from inhibition period measurements. The difference is probably due to the much greater reactivity of trinitrobenzene derivatives towards diradicals from styrene than towards styryl monoradicals. This view is supported by the different behaviour of the AIBN initiated polymerization of styrene in the presence of DPPH. The thermal initiation process has a low efficiency of initiation and the activation energy is 121 kJ/mole. The results strongly support the diradical mechanism for the thermal initiation of styrene polymerization.