Synthesis of PMMA Microparticles with a Narrow Size Distribution by Photoinitiated RAFT Dispersion Polymerization with a Macromonomer as the Stabilizer

Macromonomers can serve as efficient and effective stabilizers for dispersion polymerization of monomers such as styrene and methyl methacrylate, but the size distributions of the polymer microparticles obtained tend to be broad. We are interested in functional microbeads which can be used for immunoassays, where the size distribution has to be very narrow. We report a photoinitiated RAFT dispersion polymerization of methyl methacrylate (MMA) in ethanol–water mixtures, with methoxy-poly­(ethylene glycol) methacrylate (M_n = 2000 g/mol, EO₄₅) as the reactive steric stabilizer. We identify reaction conditions where one can obtain PMMA microspheres with coefficient of variation in the particle diameter (CV_d) less than 3%. Carboxy-functional PMMA microspheres were obtained by a two-stage (seeded) polymerization with methacrylic acid (MAA) added as a comonomer in the second stage. We show that the functional microspheres prepared in this way are effective substrates for the covalent attachment of proteins such as BSA and IgG immunoglobulins. In one set of experiments with a dye-labeled secondary antibody, we found that we could detect 10⁴ IgGs per PMMA microbead.