Molecular weight development in emulsion copolymerization of n‐butyl acrylate and styrene

The seeded emulsion copolymerization of n ‐butyl acrylate and styrene in a weight ratio of 50/50 was investigated. The effect of the type of process (batch vs. semicontinuous) and the amounts of initiator and emulsifier charged into the reactor on the time evolution of the fractional conversion, number of polymer particles, and weight‐average molecular weight ( M w ) was analyzed. It was found that the M w depends to a slight extent on the type of process and the emulsifier concentration and to a larger extent on the initiator concentration. The molecular weight distributions (MWDs) and the gel content of the final latexes were also analyzed. In the absence of chain transfer agents (CTAs), the fraction of gel was higher in the semicontinuous processes. It was also found that the gel content increased with increasing initiator concentration in the recipe. The addition of 1 wt % CTA avoided gel formation and led to an important reduction of the M w . Nevertheless, the MWDs presented a shoulder or even a second peak at high molecular weights that was due to reactions of chain transfer to the polymer.