Self-assembly of miktoarm palm tree-like star copolymers in a selective solvent

Abstract

Amphiphilic miktoarm star copolymers with one long solvophobic arm (a “stem”) and several short solvophilic arms (the “leaves”) were studied in a selective solvent using mesoscopic computer simulations. The conventional morphologies (spherical, cylindrical and vesicular) as well as the mixed ones were obtained. However, the resulting diagram of states appeared to be different from the diagram of the linear diblock copolymer with the analogous composition. Namely, the increase of the number of leaves at fixed solvophobic-solvophilic ratio leads to the transition from the vesicles to the cylinders, while the latter ones eventually transform into spherical micelles in the case of highly branched copolymers. The observed effect appears due to the increase of the interfacial area between the collapsed and swollen blocks per single macromolecule. In turn, the increase of the solvent selectivity shifts the stability region of the cylindrical micelles to the region of more symmetric copolymer composition. Meanwhile, the compatibility between the blocks has a weak effect on the resulting morphology. Finally, it was found that the increase in the number of leaves and the simultaneous decrease in their length results in the localization of higher amount of solvophilic segments near the core-solvent interface, which in the case of cylindrical micelles significantly affects the shape of the aggregates making them thinner and longer.