Fabrication of Multilayered Two-Dimensional Micelles and Fibers by Controlled Self-Assembly of Rod-Coil Block Copolymers.

Fabricating hierarchical nanomaterials by self-assembly of rod-coil block copolymers attracts great interest. However, the key factors that affect the formation of the hierarchical nanomaterials have not been thoroughly researched. Herein, we have synthesized two diblock copolymers composed of poly(3-hexylthiophene) (P3HT) and polyethylene glycol (PEG). Through a heating, cooling, and aging process, a series of multilayered hierarchical micelles and fibers were prepared in alcoholic solutions. The transition from fibers to hierarchical micelles are strictly influenced by the strength of the π-π stacking interaction, the PEG chain length, and solvent. In isopropanol, the P3HT--PEG could self-assemble into hierarchical micelles composed of several two-dimensional (2D) laminar layers, driven by the π-π stacking interaction and van der Waals force. The P3HT--PEG could not self-assemble into well-defined nanostructures in methanol and ethanol, but could self-assemble into fibers in isobutanol. However, the P3HT--PEG with a longer corona block only self-assembled into fibers in four alcoholic solutions, due to the increase in dissolving capacity and steric hindrance. The sizes and the size distributions of the nanostructures both increased with the increase in polymer concentration and the decrease in solvent polarity. This study shows a method to fabricate the hierarchical micelles.