Abstract
A new type of hexane-soluble polymeric surfactant based on poly(4-tert-butoxystyrene) (PtBSt) was prepared by the nitroxide-mediated living radical polymerization, and their self-assemblies in hexane were explored. Polystyrene-block-PtBSt diblock copolymers with six different PtBSt block lengths were obtained by the sequential living radical polymerization of styrene followed by 4-tert-butoxystyrene using 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl as the mediator; Mn(PtBSt block) = 13,500, 21,700, 26,600, 47,500, 91,300, and 108,000 at the constant length of the PSt block (Mn = 12,900). Dynamic light-scattering studies demonstrated that the copolymers self-assembled into monodispersed spherical micelles in hexane. The hydrodynamic diameter of the micelles increased with an increase in the PtBSt block length. The micellar size also increased as the copolymer concentration increased. However, the size decreased as a result of the increasing temperature due to a decrease in the aggregation number. The 1H NMR analysis confirmed that the copolymers formed micelles with PSt cores.
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