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A hydrophilic macromolecular RAFT (reversible addition–fragmentation chain transfer) agent (macroRAFT agent) composed of 50 mol% methacrylic acid and 50 mol% poly(ethylene oxide) monomethyl ether methacrylate end-capped by a reactive trithiocarbonate group (P(MAA-co-PEOMA)) was used in the polymerization of benzyl methacrylate (BzMA) in different media, ethanol–water and 1,4-dioxane–water mixtures. Depending on the solvent composition, the polymerization showed features of either a dispersion polymerization (monomer soluble in the initial medium) or an emulsion polymerization (monomer insoluble in the initial medium). In all cases, the RAFT mechanism led to the in situ formation of well-defined amphiphilic P(MAA-co-PEOMA)-b-PBzMA block copolymers that self-assembled during the growth step into self-stabilized nano-objects, according to a polymerization-induced micellization process. For a given composition of the block copolymer, the final morphology depended strongly on the solvent composition. The presence of the organic co-solvent was favorable to the formation of fibers while an increased amount of water favored the formation of spherical particles. Compared to the ethanol–water system, in which the non-spherical objects existed only above 77–80 vol% of ethanol, in 1,4-dioxane–water mixtures the morphological transition was observed at a lower proportion of organic co-solvent (close to 20 vol%). For a given molar mass of the macroRAFT agent and an increased molar mass of the PBzMA block in a given solvent composition (ethanol–water, 95/5, v/v), the morphology changed from spheres to fibers and then to large spheres or vesicles. The molar mass window in which fibers were obtained was wider than that observed in pure water at pH 5 using the same macroRAFT agent X. Zhang et al., Macromolecules, 2011, 44, 4149.
Zhang et al. (Sun,) studied this question.