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Shell growth mechanism in emulsifier-free emulsion polymerization : morphological and kinetic studies

For systems of emulsifier-free emulsion polymerization having particle diameter (D p ) greater than 0.15-0.2 μm, a shell-growth mechanism for particle growth was proposed. According to the mechanism, the polymeric radicals can propagate only within the shell region having a thickness about equal to the most probable end-to-end distance of the terminated polymer. This mechanism was considered to result from anchoring of hydrophilic ends of the growing radicals on the particle surface and from a high average number of radicals per particle