Journal of Polymer Science Part A: Polymer Chemistry, Vol.37, No.23, 4449-4457, 1999
Miniemulsion polymerization of styrene using the oil-soluble initiator AMBN
The Mettler RC1 calorimeter was used to measure the rate of polymerization of conventional emulsion, homogenized emulsion, and miniemulsion polymerizations of styrene initiated with 2,2'-azobis(2-methylbutyronitrile). It was noted that the rate of polymerization significantly increased as the surface area of the monomer droplets increased. This was taken as strong evidence that in the miniemulsion and homogenized emulsion polymerizations, the fraction of the initiator soluble in the oil phase was responsible for single radical generation. The partitioning of AMBN at 70 degrees C was measured by high-pressure liquid chromatography to be 134 parts in the oil : 1 part in the water. Predissolving polystyrene in the miniemulsion prior to homogenization resulted in an enhancement in the rate of polymerization, although to a lesser extent than what has been previously noted far parallel miniemulsion polymerizations initiated with potassium persulfate. It was also noted that the method of addition of the oil-soluble initiator (either predissolved in the monomer prior to homogenization or dissolved in a small separate phase of monomer and added directly to the reactor) has a measurable effect on the kinetics in the miniemulsion polymerization of styrene.