Emulsion polymerization process provides a unique polymerization locus that has a confined tiny space with a higher polymer concentration, compared with the corresponding bulk polymerization, especially for the ab initioemulsion polymerization. Assuming the ideal polymerization kinetics and a constant polymer/monomer ratio, the effect of such a unique reaction environment is explored for both conventional and living free-radical polymerization (FRP), which involves chain transfer to the polymer, forming polymers with long-chain branches. Monte Carlo simulation is applied to investigate detailed branched polymer architecture, including the mean-square radius of gyration of each polymer molecule, <s2>0. The conventional FRP shows a very broad molecular weight distribution (MWD), with the high molecular weight region conforming to the power law distribution. The MWD is much broader than the random branched polymers, having the same primary chain length distribution. The expected <s2>0 for a given MW is much smaller than the random branched polymers. On the other hand, the living FRP shows a much narrower MWD compared with the corresponding random branched polymers. Interestingly, the expected <s2>0 for a given MW is essentially the same as that for the random branched polymers. Emulsion polymerization process affects branched polymer architecture quite differently for the conventional and living FRP.

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Processes 20186(2), 14; doi:10.3390/pr6020014