The rate of polymerization and the size of the latex particles formed in the thermally initiated emulsion polymerization of 1,4‐divinylbenzene (DVB) was studied as a function of emulsifier concentration, monomer‐to‐water ratio and reaction temperature. Furthermore, kinetic data of the thermal polymerization in solution have been determined. Contrary to normal emulsion polymerization the thermal polymerization of DVB occurs preferentially in the monomer droplets at the rate of a bulk polymerization, whereas latex particles are formed only from the monomer solubilized in micelles at a rate similar to a polymerization in solution. This results in an apparent decrease of the polymerization rate and an increase in size of the latex particles with increasing emulsifier concentration. Crosslinking in polymerization of DVB is discussed as the ultimate reason for the observed features and a mechanism of polymerization based on these conclusions is presented.
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Kast et al. (1981) studied this question.
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