Self-Assembly Behavior of Amphiphilic Diblock Copolymer PS-b-P4VP in CO2-Expanded Liquids

The self-assembly behavior of block copolymers and their assembled micellar morphologies have attracted considerable attention because of their potential applications in biomedicine, drug delivery, and catalysis. Herein we report that CO2-expanded liquids (CXLs) facilitate the morphology control of the self-assembled aggregates (SAAs) of polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) formed CO2-expanded toluene. It is found that the anti-solvent effect of CXLs can successfully regulate the self-assembly behavior of the copolymer PS-b-P4VP. The difference in amphiphilicity between PS and P4VP block is reduced with increasing pressure of CO2-expanded toluene owing to the anti-solvent effect of CO2. In addition, this diminished difference may influence the interfacial tension at the P4VP core-PS corona interface, which triggers a morphological change of the aggregate. The SAA structures are dependent on both CXL pressure and copolymer composition under the experimental conditions implemented in this work. The morphological evolution of the SAAs in CXLs exhibits remarkable pressure dependence. As the pressure increases, the SAA structure of PS168-b-P4VP(420) transits from primarily spheres (0.1 MPa) to mostly interconnected rods (6.35 MPa), the SAA of PS790-b-P4VP(263) evolves from small vesicles (0.1 MPa) to large compound vesicles (LCVs, 6.35 MPa), whereas the PS153-b-P4VP(1530) counterpart switches from large compound micelles (LCMs, 0.1 MPa ) to mainly large compound vesicles (LCVs, 6.35 MPa). Moreover, transmission electron microscopy (TEM) data on constant copolymer composition implies that the packing parameter p of the SAAs increases with the CXLs pressure. Especially, under the experimental conditions employed in this work, we find that the major factor controlling the SAA shape in conventional toluene is the copolymer composition, while in CO2-expanded toluene, the dominant factor controlling the SAA morphology might be the varying contact area between shell-forming segment PS and the CXLs with increasing pressure. This work proves that the CXL method facilitates the modulation of morphology of the SAAs, and opens a green route for the development of new nano-functional materials.