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Journal of Polymer Science Part A: Polymer Chemistry, Vol.39, No.14, 2547-2556, 2001
Methyl methacrylate emulsion polymerization at low monomer concentration: Kinetic modeling of nucleation, particle size distribution, and rate of polymerization
The results of a mathematical model developed in the authors' previous work are discussed and compared against final number (N) and size distribution of particles (PSD) and the rate of polymerization (RP) experimental data of methyl methacrylate (MMA) emulsion polymerization above the critical micelle concentration (cmc) of the surfactant. On the basis of the model results, the hypothesis that the observed bimodal PSD can be ascribed to secondary nucleation as proposed in the literature is questionable. It is discussed that this PSD can also be caused by differences in the growing rate of different-size particles as predicted for styrene emulsion polymerization, Because of the small particle size obtained at low initial monomer concentration, the high rate of free-radical desorption reduces the accumulation of these species; therefore, the autoacceleration effect is less pronounced for the conditions under study compared with the usual behavior of the RP during MMA emulsion polymerization above cmc. Similarities and differences between model predictions and experimental data are discussed.
Keywords:emulsion polymerization;methyl methacrylate;kinetics;nucleation;particle size distribution;rate of polymerization;free-radical entry and exit