Initiation efficiency reduction in semicontinuous styrene and butyl acrylate emulsion copolymerization reactions

The decrease of initiation efficiency (radical entry efficiency) during seeded emulsion copolymerizations of styrene and butyl acrylate with different residual monomer reduction strategies was evaluated. Experiments were carried out using 50 and 99wt.% of styrene in monomer feed stream. Simulations were performed with a detailed mathematical model of the process that takes into account the diffusion control of initiation, propagation and termination. Results showed that the radical entry into polymer particles is strongly influenced by the aqueous phase kinetics and by the monomer solubility in aqueous phase. Simulation results were compared to experimental results of residual monomer and showed that the residual monomer content can be reduced by a temperature increase at the end of the polymerization. However, an additional feeding of more initiator, even when combined with such an increase of temperature, did not lead to a smaller residual monomer content due, mainly, the kinetic of termination in aqueous phase and radical anchoring. A model that accounts for the reduction of initiator efficiency (free radical entry efficiency) was successfully used to explain the behavior of the experimental observations and was able to correctly predict the qualitative trends of the effectiveness of different residual monomer reduction strategies.