Some aspects of the emulsion polymerisation of vinyl acetate

The present status of work on the mechanism of the emulsion polymerisation of vinyl acetate initiated by potassium persulphate is critically reviewed. In addition, some new data illustrating the effect of adding electrolytes is presented. The polymerisation proceeds by a mechanism different from that of most vinyl monomers. In particular, the rates are approximately zero order on monomer from 20 to 85% conversion with only a minor dependence on the soap concentration and the number of particles. The dependence of the rate on the initiator concentration varies with different investigators from 0.5–1.0 order. The results are discussed in terms of various current theories and an attempt is made to rationalise them in a reasonable way.