Anisotropic Self-Assembling Micelles Prepared by the Direct Dissolution of PLA/PEG Block Copolymers with a High PEG Fraction

A series of polylactide-poly(ethylene glycol) (PLA-PEG) block copolymers with a high PEG fraction were synthesized by the ring-opening polymerization of L- or D-lactide in the presence of mono- or dihydroxyl PEG using nontoxic zinc lactate as a catalyst. Micelles were then prepared by direct dissolution of the obtained water-soluble copolymers in an aqueous medium without heating or using any organic solvents. Large anisotropic micelles instead of conventional spherical ones were observed from a transmission electron microscopy examination. Various parameters influencing the structure of the novel micelles were considered, such as the copolymer chain structure, molar mass, PEG fraction, copolymer concentration, and stereocomplexation between L- and D-PLA blocks. Anisotropic micelles were obtained for both diblock and triblock copolymers but vanished with increasing molar mass of the copolymers. The morphology of micelles strongly depends on the PEG fraction. Anisotropic micelles were found only in an intermediate EO/LA ratio range in which a higher PEG fraction leads to a higher length/width ratio of micelles. Stereocomplexation between L- and D-PLA or a lower concentration disfavors the formation of anisotropic micelles. Under appropriate concentrations, spherical and anisotropic micelles coexist in the same micellar solution. Moreover, it was found that anisotropic micelles are susceptible to further self-assemble into more organized complex aggregates. Similar results were obtained from light scattering and aqueous gel permeation chromatography measurements. A novel model is proposed to explain the formation of anisotropic micelles and the effects of various parameters on the structure of micelles in an aqueous medium.