Kinetics of Emulsion Polymerization

TLDR

The kinetics of free‑radical reactions in isolated loci, supplied externally, provide the foundation for understanding emulsion polymerization. The study examines three regimes of free‑radical concentration per locus, showing that when the average is about one‑half the reaction rate per locus is independent of locus size and can be used, together with monomer concentration and locus number, to compute the monomer propagation constant; a simplified model then predicts how particle number scales with surfactant and radical generation rates. The analysis shows that when the average free‑radical count per locus is about one‑half, the reaction rate per locus is independent of locus size and the resulting particle number scales as the 3/5 power of surfactant concentration, the 2/5 power of radical generation rate, and inversely with the 2/5 power of radical growth rate.

Abstract

As a basis for understanding emulsion polymerization, the kinetics of free radical reactions in isolated loci is discussed subject to the condition that the free radicals are supplied to the loci from an external source. Three cases of interest are considered: that in which the average number of free radicals per locus is small compared with unity, that in which this number approximates one-half, and that in which the number is large. Of these three possibilities, the second, in which the free radicals per locus approximate one-half, is by far the most interesting as it explains in a satisfactory manner the characteristic features of styrene emulsion polymerization. For this case the average rate of reaction per locus is independent of the size of the locus, since this rate is simply one-half the rate of polymerization of a single free radical. Thus the rate of emulsion polymerization, the concentration of monomer in the loci, and the number of loci present provide the information needed for calculating the chain propagation constant for the monomer. A simplified treatment is given for approximating the number of reaction loci (polymer particles) produced in emulsion polymerization when the rate of polymerization per locus is constant (see case 2 above). The law obtained indicates that the number of particles should increase with the soap concentration (3/5ths power) and with the rate of formation of free radicals (2/5ths power), but should decrease with increasing rate of growth of the free radicals (−2/5ths power).