Abstract
AbstractThis manuscript reports on an experimental investigation of the chemical‐initiated (AIBN) bulk polymerization of methyl methacrylate to limiting conversion at temperatures of 50°C, 70°, and 90°C. The change in the cumulative differential molecular weight distribution (CDMWD) with respect to conversion was measured by gel permeation chromatography (GPC). These CDMWD's were differentiated to determine the instantaneous differential molecular weight distribution (instantaneous DMWD) over the range of conversions investigated. These experimental instantaneous DMWD's were found to agree with theoretical distributions predicted by classical free‐radical kinetics over the entire conversion range and where diffusion control of the termination reactions is dramatic. A correlation of the dimensionless group α (where α = ktdRp/kp2M2) with free volume is proposed. This correlation appears to adequately account for diffusion control of the termination reaction. A kinetic model for the bulk polymerization of methyl methacrylate has been developed. This model should find use in the design, simulation, and optimization of PMMA reactors.
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