Solvent effect on the aggregation behavior of rod-coil diblock copolymers

The water-induced aggregation behavior of rod-coil diblock copolymers based on poly(ethylene oxide) (PEO) and poly{(+)-2,5-bis4'-((S)-2-methylbutoxy)phenyl]styrene} (PMBPS), PEO104-b-PMBPS53, was investigated in the common solvent THF and in the selective solvent dioxane. Before adding water, PEO104-b-PMBPS53 stayed as single polymer chains no matter what conformation the PEO block took (i.e., either the random coil conformation in THF or the compact globule conformation in dioxane). The critical water content ( approximately 6 wt %) at which PEO104-b-PMBPS53 began to aggregate was also similar in both solvents, indicating that PMBPS dominated the aggregation process. However, the size, the size distribution, and the morphology of aggregates in THF/water were quite different from those in dioxane/water. Narrowly distributed spheres with Rh approximately 20 nm were observed in dioxane, whereas in THF, a bimodal distribution peaked at 3 and approximately 300 nm, was observed. The results from 2D wide-angle X-ray diffraction and polarized optical microscopy demonstrated that the PMBPS blocks packed in a parallel pattern upon aggregation in dioxane/water. The anisotropic disclike structures observed in THF/water also indicated the orientation of the PMBPS blocks upon forming aggregates in dilute solution.