Journal of Polymer Science Part A: Polymer Chemistry, Vol.35, No.6, 989-1006, 1997
An Experimental Investigation on the Evolution of the Molecular-Weight Distribution in Styrene Emulsion Polymerization
Styrene ab initio emulsion polymerizations were conducted at 70 degrees C in an automated reaction calorimeter. Two polymerizations were performed, one above and the other below the critical micelle concentration (CMC) of the surfactant, thus ensuring differing polymerization kinetics between the two : the system below the CMC gave large particles that were expected to follow pseudobulk kinetics, while that above the CMC gave small particles that were expected to follow zero-one kinetics. The evolutions of the molecular weight distributions (MWDs) were characterized by removing samples periodically during the course of the reactions and analyzing with gel permeation chromatography. Interpretation of the data used average molecular weights, the GPC MWDs, and the number MWDs, as functions of conversion. It was found that all of the number MWDs (plotted as In (number of polymer chains) vs. molecular weight of polymer chains) were concave-up at low molecular weights and become nearly linear at molecular weights (greater than or equal to 3-4 x 10(6)); this linearity is expected from theory. The slope of the high molecular weight region was consistent with theory for the dominant mode for chain stoppage : termination and transfer for the pseudobulk system and (predominantly) chain transfer to monomer for the zero-one system. The most likely explanation for the concavity of the number MWDs is a heterogeneity of radicals : some surface anchored with sulfate end groups and others (with hydrogen end groups arising from transfer to monomer and/or reentry) being more mobile. Thus, two types of termination are proposed : slow reaction-diffusion for the less mobile surface anchored chains, and rapid short-long (center of mass) termination for the more mobile hydrogen-terminated chains.
Keywords:FREE-RADICAL POLYMERIZATIONS;TERMINATION RATE-PROCESSES;LATEX-PARTICLES;RATE COEFFICIENTS;LOW CONVERSION;KINETICS;INHOMOGENEITIES;SCATTERING;SYSTEMS;MONOMER