Previous kinetic studies in emulsion polymerization have almost always involved an assumption of uniform distribution of free radicals in the latex particle. Such an assumption is not likely to reflect reality in many systems that employ water‐soluble initiators because the hydrophilic end‐group of the oligomeric free radical will preferentially stay in the surface layer of the particle. This constrained end‐group location would result in nonuniform distribution of free radicals in the polymerizing latex particles. A Monte Carlo simulation of the growth of a single polymer chain within the latex particle supports this hypothesis. Such a nonuniform distribution of free radicals in the latex particle is expected to have an influence on reaction kinetics and product properties. The mechanism for transport of free radicals out of polymerizing latex particles is reexamined based on the proposed concept, and a modified expression for the desorption rate constant is presented.
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Chern et al. (1987) studied this question.
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