Preparation of monodisperse PMMA microspheres in nonpolar solvents by dispersion polymerization with a macromonomeric stabilizer

We discuss a dispersion polymerization procedure for preparing monodisperse and micron-sized poly(methyl methacrylate) (PMMA) particles in hexanes with methacryloxypropyl-terminated polydimethylsiloxane stabilizers. We investigate the effects of the stabilizer molecular weight, stabilizer concentration, and monomer concentration on the particle size and polydispersity. We find that a minimum molecular weight of 10 000 g/mol is necessary to synthesize colloidally stable PMMA dispersions. The particle polydispersity is minimal (≤ 5%) for stabilizer to monomer weight ratios of 0.02 to 0.1, while PMMA particles prepared under conditions outside this range are polydisperse. The particle diameter can be varied from 0.4 to 1.5 μm by appropriate choices of stabilizer and monomer concentrations. Stable PMMA suspensions can be prepared at up to 26.3% solids. The dispersions are stable in most liquid aliphatics, and are monodisperse enough to form ordered domains at high concentration. This single-stage synthesis, requiring only commercially available materials, may be of interest to those seeking a simple way to prepare highly monodisperse non-aqueous dispersions in the micron size range.