Macromolecules, Vol.44, No.22, 8744-8754, 2011
Effect of Stabilizer Functionality on the Kinetics of Emulsion Polymerization in Hairy Particles
Two model polystyrene seed-latexes were studied by gamma-irradiation dilatometry, with one latex stabilized by short chain poly(acrylic acid) the other stabilized by short chain poly(methacrylic acid), anchored to the surface. The distinction between the two latexes studied is that the poly(acrylic acid) stabilized latex has abstractable hydrogens in the backbone which could form midchain radicals while the poly(methacrylic acid) stabilized latex does not have abstractable hydrogens, Despite this difference in functionality of the hairs, these two latexes displayed essentially the same kinetics. The overall polymerization rates, average number of radicals per particle and the rate coefficient:3 for radical entry and exit were comparable for the two different latexes, and both latexes showed significantly better agreement with first order than second order radical loss. These data are consistent with the idea that exit of a radical from a latex particle leads to complete loss of that radical, rather than re-entry and reinitiation. In the past, the apparent first order radical loss observed in small particle size poly(acrylic acid) stabilized latexes was attributed to termination of the exiting radical with mid chain radicals on the poly(acrylic acid) hairs. However, the poly(methacrylic acid) stabilized latex cannot form these mid chain radicals and the similarity between the polymerization kinetics of both the poly(acrylic acid) and poly(methacrylic acid) stabilized latexes suggests that the apparent first order loss cannot be due to termination with mid chain radicals. We demonstrate that the lower than expected exit rate coefficients observed in these small particle size systems can be explained by a competition between particle growth and radical exit.