Emulsion polymerization of butyl methacrylate initiated by 2,2′‐azoisobutyronitrile, 1. Kinetics and mechanism

Abstract The effect of 2,2′‐azoisobutyronitrile (AIBN) on the kinetics and mechanism of emulsion polymerization of butyl methacrylate was studied in the presence of anionic emulsifier disodium dodecylphenoxybenzene disulfonate (Dowfax® 2A1) at 60°C. The ratio between the proportion of the polymerization in monomer droplets and that of the polymerization in the aqueous phase was determined for the overall initial rate of butyl methacrylate polymerization in the region of the increasing polymerization rate (interval I). Using the model of polymerization in discrete particles, the portion of the polymerization in monomer droplets with a diameter of 100 nm in the overall polymerization rate is 24,4%; the portion of the polymerization in the water phase is only 0,022% for a concentration of Dowfax® 2A1 of 5 · 10−2 mol · dm−3, and 60,4% and 0,054% for a Dowfax® 2A1 concentration of 1 · 10−2 mol · dm−3. The exponent of the emulsifier concentration in the equation for the polymerization rate is 0,56 for interval I and 0,36 for interval II; the exponent for the concentration of AIBN over the conversion range between 0 and 30% is 0,34. For the proposed reaction mechanism it is assumed that 2‐cyanoisopropyl radicals, generated from AIBN in the water phase, are responsible for the initiation of polymerization in micelles swollen by monomer and in polymer/monomer particles. Polymer/monomer particles are formed also by co‐precipitation of oligomer radicals, which in turn are formed by polymerization of monomer molecules present in the water phase. Polymerization within monomer droplets has no significant influence on the course of emulsion polymerization.