Abstract: | Micron‐sized monodisperse crosslinked polystyrene (PS) beads have been prepared by a multistage emulsion polymerization using styrene monomer, divinylbenzene crosslinking agent, and potassium persulfate initiator in the absence of emulsifier. In the first stage of the reaction, the lower the reaction temperature, the larger the bead size obtained. In the later stages of the reaction, the particle size is increased with the initiator concentration and monomer content. Particle nucleation of the preexisting polymer seed of 0.7–0.8 μm in diameter is prepared at 60°C, then the monodisperse crosslinked PS beads > 2 μm are synthesized up to the third stage of the reaction. As the particle size grows, the number of free radicals in the growing particles increases, and the conversion of the next stage is continuously increased. The reaction mechanism is suggested that the continuous polymerization be conducted due to the diffusion of monomer into the preexisting particles to induce spherical beads in the later stages of the reaction. Otherwise, phase separation or the formation of protrusion by the capture of free radicals will be taking place. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2259–2269, 1999 |