Partitioned polymerization, 4. Seeded emulsion polymerization of methyl methacrylate

The shape of the conversion curves and the rates of the emulsion polymerization in batch of methyl methacrylate (MMA) in the presence of seed particles of poly(butyl acrylate) (PBA) depend on the mass ratio of methyl methacrylate/poly(butyl acrylate) MMA/PBA and on the presence or absence of 2,2,6,6‐tetramethyl‐4‐octadecanoyloxypiperidinyl‐1‐oxyl (STMPO). Irrespective of the presence and/or absence of STMPO in the reaction system, the diameter of a polumer particle experimentally found and calculated on the assumption that no new crop of polymer particles is formed, agrees well for systems with “low” (0,632) mass ratio of MMA/PBA. For systems with “high” (3,160) mass ratio of MMA/PBA, the calculated diameter is higher than that experimentally measured. This indicates that for “low” values of MMA/PBA, all poly(methyl methacrylate) formed was only used for building up shells of poly(butyl acrylate) particles. For “high” values of MMA/PBA, about 37 mass‐% (in the absence of STMPO) or 57 mass‐% (in the presence of STMPO) of poly(methyl methacrylate) formed was used for generating a crop of poly(methyl methacrylate) particles. Retardation of the polymerization rate in the presence of STMPO is more pronounced for systems characterized by a “low” value of the mass ratio MMA/PBA. Only short inhibition periods (up to five minutes) were observed for both “low” and “high” MMA/PBA ratios. It is shown that for the “low” mass ratio of MMA/PBA the “inner” monomer transport (from PBA particles swollen with MMA) to the locus of propagation is decisive. For systems with a “hugh” mass ratio MMA/PBA, the “outer” monomer transport from monomer droplets and micelles swollen by monomer to the locus of propagation is of primary importance. To explain the experimental results a reaction mechanism for the seeded emulsion polymerization is proposed.