Stable poly(methyl methacrylate-co-divinylbenzene) (poly(MMA-co-DVB)) microspheres were prepared by precipitation polymerization using acetonitrile as the main medium under various polymerization conditions, including modifications of the agitation speed, monomer and initiator concentrations, DVB content in the monomer mixture, and the use of various cosolvents. Gentle agitation was required to obtain smooth spherical particles. The individually stable microspheres were obtained at monomer concentrations of up to 15 vol% in an acetonitrile medium. The number-average diameter increased linearly with respect to increases in the monomer and initiator concentrations. We found, however, that the uniformity of the microspheres was independent of the variation of the polymerization ingredients because nuclei formation was solely influenced by the crosslinking reaction of the monomers. We obtained higher yields for the polymerization at higher concentrations of monomer and initiator. The concentration of DVB in the monomer mixture composition played an important role in determining not only the size of the microspheres but also the yield of the polymerization. In addition, although we employed various cosolvents as the polymerization medium, we found that acetonitrile/2-methoxyethanol was the only system that provided spherical particles without coagulation. This finding indicates that the precipitation polymerization is strongly dependent on the solvent used as the medium.

We have synthesized a novel macromonomer of vinyl-terminated bifunctional polyurethane having a molecular weight of 37,000 g/mol and successfully applied it to the dispersion polymerization of methylmethacrylate (MMA). We verified the presence of the vinyl terminal group and the macromonomer grafted onto the poly(ethylene glycol)(PEG) block in the PMMA particles by using 1 H and 13 C NMR spectroscopies. Monodisperse PMMA microspheres that have good uniformity of 1.01 were prepared at 20 wt% macromonomer content; we investigated the characteristics of the PMMA particles in terms of their molecular weight, molecular weight distribution, size of the particles, thermal properties, and glass transition temperature. We have found that the synthesized polyurethane macromonomer is an effective stabilizer.