| Abstract: | The kinetics of the surfactant-free emulsion polymerisation of styrene have been studied. Reactions were sampled at several stages throughout their course, and the samples characterized by electron microscopy, gravimetric weights analysis and gel permeation chromatography, After an initial period of particle nucleation and coagulation, the reaction proceeds at a constant number density. The theories developed for emulsion polymerisation in the presence of surfactant above its critical micelle concentration might be expected, in Interval II, to apply to the surfactant-free system if due regard is taken of the lower number densities and larger particle sizes developed. The results are in best accord with theories invoking a surface phase polymerisation mechanism. None of these theories predict a bimodel molecular weight distribution as found here and which is ascribed to polymerisation in two loci. The activation energy was found to be the same as for surfactant containing emulsion polymerisations. |
