Polymerization-induced self-assembly enables the reproducible synthesis of a wide range of block copolymer nano-objects at relatively high copolymer concentration in various media. For example, provided that suitable reaction conditions are selected, RAFT aqueous dispersion polymerization of monomers such as 2-hydroxypropyl methacrylate usually provides access to spheres, worms or vesicles. In contrast, RAFT aqueous <i>emulsion</i> polymerization formulations often produce only kinetically-trapped spheres, even when targeting highly asymmetric diblock copolymer compositions. Recently, we postulated that the aqueous solubility of the vinyl monomer was likely to be a key parameter for overcoming this perplexing morphological limitation. In the present study, the RAFT aqueous emulsion polymerization of 2-methoxyethyl methacrylate (MOEMA) has been explored for the first time. This monomer was selected for its relatively high aqueous solubility of 19.6 g dm<sup>-3</sup> at 70 °C. Chain extension of a relatively short non-ionic poly(glycerol monomethacrylate) (PGMA) precursor led to the formation of sterically-stabilized spheres, worms or vesicles, depending on the precise reaction conditions. These PGMA-PMOEMA nano-objects have been characterized by TEM, DLS, and SAXS. Construction of a suitable phase diagram enabled each morphology to be reproducibly targeted at copolymer concentrations ranging from 10 to 30% w/w solids.

RAFT aqueous emulsion polymerization of 2-methoxyethyl methacrylate

2019 Fall National Meeting

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