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A dynamic mathematical model is developed to represent miniemulsion polymerization reactions using oil‐soluble initiator. Both simulation and experimental results show that the evolution of conversion varies with particle diameter and that reactions become slower as the particle size is increased. For each experimental condition, a limiting diameter is obtained, above which the reaction kinetics does not change anymore with the diameter. These results are explained in terms of the compartmentalization of growing radicals during the miniemulsion polymerizations. The evolution of conversion in bulk polymerizations shows that the kinetic behavior above the limiting diameter is similar to the kinetic behavior of bulk reactions. magnified image
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Costa et al. (2013) studied this question.
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