The influence of RAFT on the rates and molecular weight distributions of styrene in seeded emulsion polymerizations

Seeded emulsion polymerizations of styrene in the presence of two reversible addition–fragmentation chain-transfer (RAFT) agents were studied. We designed the seed to be small to observe the effects of exit and, we made the seed of poly(methyl methacrylate) so that the molecular weight distributions of poly(styrene) by gel permeation chromatography could be obtained independently by UV detection. The rates were significantly retarded by the presence of a RAFT agent, with the retardation being greater with an EMA RAFT agent [2-(ethoxycarbonyl)propyl-2-yl dithiobenzoate] than with a cumyl RAFT agent (2-phenylprop-2-yl dithiobenzoate). We propose that exit from the particles after fragmentation was the main cause of retardation. In addition, the number-average molecular weight and polydispersities (broad) did not resemble the characteristic living behavior found in bulk or solution. This was a result of the continuous transportation of RAFT agent into the particles during interval II and the transportation of a small amount during interval III. A conspicuous red layer was also observed at the beginning of the polymerization. The red layer consisted of low molecular weight dormant species swollen with monomer. Once the switch from interval II to interval III occurred, the low molecular weight species coalesced to form a red coagulant. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3864–3874, 2000