Modeling of the bulk free radical polymerization up to high conversion—three stage polymerization model. II. Number-average molecular weight and apparent initiator efficiency

The equations for predicting the number-average molecular weight are derived on the basis of the three stage polymerization model (TSPM) in this paper. By applying the equations, a plotting approach is proposed to determine the apparent initiator efficiency defined as f[(α_td+1)/2] and the constant of chain transfer to monomer, where f is the initiator efficiency and α_td denotes the fraction of the termination rate constants by disproportionation. Using the approach to plot the experimental data in the literature, it is found that the chain transfer to monomer can be neglected for both methylmethacrylate (MMA) and styrene (St) polymerizations, but it can exert a significant effect on ethylmethacrylate (EMA) polymerization. In addition, the apparent initiator efficiency is found to be independent of reaction temperature and initiator concentration at each stage. The values of f[(α_td+1)/2] at gel effect stage are slightly reduced as compared with that at low conversion stage for MMA and EMA polymerizations. However, it decreases significantly at gel effect stage for St polymerization. Using the equations derived and the apparent initiator efficiencies obtained from TSPM plots, the number-average molecular weights at different conversions can be predicted. Comparisons show that the agreement between predictions and experimental data is satisfactory.