A kinetic study on bulk thermal polymerization of styrene

The kinetics of bulk thermal polymerization of styrene over the range of 100–200 °C has been studied based on three stage polymerization model (TSPM) in this paper. TSPM plots showed that the whole polymerization course only exhibits two stages, low conversion stage and gel effect stage, which is consistent with TSPM as the reaction temperature is higher than the glass transition temperature of polystyrene. It was found that the critical conversion, x1, for the transition from low conversion stage to gel effect stage is independent of the reaction temperature and approximately equal to 0.5. In addition, the apparent reaction rate constants obtained from TSPM plots could be correlated to temperature by Arrhenius equation. Expressions predicting number-average molecular weight were also derived according to TSPM. Using the expressions to treat experimental data available in the literature, it was found that number-average molecular weight is independent of the conversion and relative to the reaction temperature at low conversion stage. However, it varies with the conversions at gel effect stage and the variations are more obvious as the reaction temperature rises.