Continuously uniform latices were applied in an experimental study of molecular weight development in constant‐rate styrene emulsion polymerization. The formulation around which this study centered exhibited Smith‐Ewart, case II kinetics from zero to about 60% conversion with a constant conversion rate of 13 ± 2%/hr and a final particle diameter of 2300 Å. By utilizing an inhibitor perturbation technique, we directly confirmed that free radicals are generated from K 2 S 2 O 8 by a first‐order process with 100% efficiency. We further confirmed that, in contrast to current theories for constant rate polymerization, both the instantaneous values of M̄ n and M̄ v may increase 6‐ to 9‐fold. Little or no chain branching is evidenced. We interpret these findings to mean that radicals are not utilized with 100% efficiency in emulsion polymerization.
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Grancio et al. (1970) studied this question.
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