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The kinetics of the emulsion polymerization of butadiene at 60 "C in Smith-Ewart interval I11 were investigated using sodium peroxodisulfate (persulfate) as initiator. The aim of this work was to elucidate and model the persulfate initiator efficiency. Monomer conversion was based on gravimetrically calibrated on-line densitometry. Plots of the product of the propagation rate coefficient, k,, and the average number of radicals per particle, a, versus initiator concentration showed minimal dependence on the initiator concentration if tert-dodecyl mercaptan (TDM) was present during polymerization. These results could not be modeled using normal emulsion polymerization theory. The model used in the absence of TDM fits two separate sets of data, a versus particle diameter and a versus initiator concentration. In the absence of TDM, a depends strongly on the initiator concentration. The significant effect of TDM is ascribed to a decrease in the radical desorption. A possible effect on the radical absorption is refuted on the basis of theory and experiment.

Seeded emulsion polymerization of butadiene. 2. Effects of persulfate and tert-dodecyl mercaptan