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SYNOPSISIn emulsion polymerizations, desorption (exit) from latex particles of monomeric radical species that arise from transfer can be a n important determinant of the overall kinetics. An examination of various methodologies for the testing of postulated free radical exit mechanisms is made. These utilize the model descriptions for the exit process presented in the accompanying article of Casey et al., employing data consisting of conversion as a function of time for the approach to steady state polymerization conditions. Experimental data are presented on the exit rate coefficients as a function of such experimental parameters as: particle size, monomer concentration, and aqueous-phase free-radical concentration for a series of styrene polymerizations a t 50°C, where the average number of free radicals per particle ( i i ) never exceeds 0.5. It is demonstrated for these systems that while the conversion/ time dependence from a single run, under conditions sensitive to exit, is insensitive to mechanistic assumptions as to the fate of desorbed free radicals, the variation of the exit rate coefficient with particle size so obtained suggests a second order dependence on 6, implying complete re-entry of desorbed free radicals under all conditions studied. Once the monomeric radicals have re-entered, they are more likely to remain inside the particle where they will either propagate or undergo termination rather than re-escape. The article also presents a n estimate for the rate coefficient at 50°C of the first propagation step of the monomeric radical subsequent to transfer. The conclusions drawn here for seeded systems should prove useful for study of particle nucleation mechanisms, when exit is particularly likely in small, newly formed, particles.

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The microemulsion free-radical polymerization of styrene generates particles containing one or at most a few high molecular weight polymer chains. Space-filling considerations preclude such chains from adopting their random-coil conformation; rather, they adopt a highly compact globular conformation and below Te constitute essentially single-chain glasses. This paper reports apparent spectroscopic and thermal differences between single-chain and conventional multichain polystyrene glasses. FTIR measurements suggest that the conformational temperature of the single-chain glasses as prepared is higher than that for multichain glasses. DSC measurements on these same glasses displayed a first-order exotherm near to the conventional Te of polystyrene but thereafter exhibited behavior similar to the multichain samples. The results were explained in terms of the existence of nematic cohesional entanglements in polystyrene glasses.