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Polymerization of styrene miniemulsions, prepared using a mixed emulsifier system comprising sodium lauryl sulfate and cetyl alcohol, was carried out using both water‐soluble (potassium persulfate) and oil‐soluble [2,2′‐azobis‐(2‐methyl butyronitrile)] initiators. The effects of variation of initiator concentration, polymerization temperature, and added inhibitor on the kinetics and particle‐size distributions were investigated to obtain more quantitative evidence concerning the locus of polymerization in miniemulsion systems. Experimental results for the kinetics and particle‐size distributions clearly showed that monomer droplets became the main source of polymer particle formation. This was attributed to the fact that stable emulsions with droplet diameters in the range of 0.05 to 0.15 μm were produced using this mixed‐emulsifier system. In this size range, droplet initiation could effectively compete with other mechanisms due to their large surface area. Their size was indeed similar to the corresponding latex particle size obtained after polymerization.

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