Emulsion polymerization of styrene in a single continuous stirred‐tank reactor

The effects of mean residence time, initiation rate, and emulsifier concentration on particle formation, particle growth, and polymerization rate are examined for the emulsion polymerization of styrene in a completely mixed continuous stirred‐tank reactor. Experimental measurements of number of particles, particle size distribution, polymerization rate, and molecular weights are compared with theoretical predictions. A theoretical model which incorporates Stockmayer's modification of the Smith‐Ewart theory into the particle growth equation allows reasonably accurate prediction of polymerization rate, particle formation rate, and particle size distribution. Agreement between experimental measurements of number‐average and weight‐average molecular weights and a theory based on Smith‐Ewart case 2 kinetics is also reasonable.