Microemulsion Polymerization of Alkyl (Meth)acrylates Initiated by UV Light

Radical polymerizations of polar unsaturated monomers ethyl acrylate, methyl methacrylate and nonyl methacrylate in an o/w microemulsion photoinitiated by a UV light were investigated. Polymerizations were conducted at low temperature to follow the effects of a varied solubility of monomer (coemulsifier) and/or diffusional degradation of monomer droplets on the kinetic and colloidal parameters. The rate versus conversion curve showed four regions with two rate maxima ca. at 5% to 20% and 50 to 70% conversion. The first rate maximum results from abrupt decrease of the monomer concentration at microemulsion loci and the second one from the increased accumulation of radicals in the latex particles. The higher polymerization rate of ethyl acrylate compared to that for methyl methacrylate or nonyl methacrylate was attributed to higher monomer concentration at reaction loci and propagation rate constant and lower quenching rate. The rate of polymerization was found to increase with incident light intensity and was most pronounced with nonyl methacrylate. The reaction order (the dependence of the rate of polymerization or the number of particles on the incident light intensity) was taken as a measure of particle nucleation efficiency. Particle size distribution was observed to be very narrow at low conversion and increased with increasing conversion.