Effect of solution components on the termination mechanism in acrylamide microemulsion polymerizations

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Abstract
A study of the effect of the various solution components on the kinetics of the polymerization of acrylamide in water/oil (w/o) microemulsions has been performed. For the polymerizations with toluene as the continuous phase, both the rate of polymerization, Rp, and the molecular weight of the polyacrylamide were found to be first order in monomer concentration. Furthermore, for the low temperatures (10°C) involved in these experiments, nondegradative chain transfer to monomer appears to be insignificant. When the continuous‐phase solvent was changed, an exponential dependence, X, of Rp on the incident light intensity in the order of toluene (X = 1.06) > heptane (X = 0.73) > benzene (X = 0.55) was found. Thus, the monoradical termination found in the toluene microemulsions is likely due to degradative transfer to toluene, forming a stable benzyl radical, while polymerization in benzene (no labile hydrogen atoms) leads to biradical termination

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