Effect of ethylbenzene proportion on thermal behavior in styrene polymerization: kinetics and the glass transition temperature

A rapid increase in viscosity during the polymerization process impacts the polymerization rate. To address this issue, ethylbenzene is often introduced into the polymerization system in order to reduce viscosity. The thermal characteristics of styrene–ethylbenzene polymerization have been identified using differential scanning calorimetry. The rate of heat generation significantly decreases as the proportion of ethylbenzene increases. The polymerization product mixtures were analyzed using gel permeation chromatography. Polymerization at low viscosity yields a higher proportion of low molecular mass polymers and a more uniform distribution of product chain lengths compared to polymerization at high viscosities. The glass transition temperature and the activation energy for viscous flow of the products were also determined. The apparent kinetics of styrene polymerization may be described using the “autocatalytic + Nth-order” model. Two stages of monomer conversion are apparent: polymerization reactions initiated by AIBN and thermally induced polymerization. Valuable insights into the polymerization process which can contribute to the optimization of industrial polymerization reactions have been obtained.