Structural Evolution of a Polystyrene-Block-Poly(Ethylene Oxide) Block Copolymer in Tetrahydrofuran/Water Cosolvents

This study aims to quantitatively investigate the effect of water content on the self-assembly behavior of polystyrene-block-poly(ethylene oxide) (PS-b-PEO) in tetrahydrofuran/water cosolvents by small-angle X-ray scattering. PS-b-PEO chains preferentially form fractal aggregates at a dilute concentration in neat tetrahydrofuran (THF). By adding a small amount of water into THF, PS-b-PEO forms gelled networks. The gelled networks have correlated inhomogeneities, which were generated through mesophase separation. These gelled networks are not present when PS-b-PEO is dissolved in THF/methanol and THF/ethanol cosolvents. The substitution of water with 12 M HCl reduces the viscosity of the gelled networks. Those results indicate that the gelled networks of PS-b-PEO need hydrogen bonds formed from surrounding water molecules to be bridging agents, which connect different PEO block chains together. Upon increasing the water content in THF/water cosolvents, dispersed micelles with a core-shell conformation or aggregated micelles preferentially coexist with fractal aggregates.