Association of Block Copolymer in Nonselective Solvent

The behavior of poly(ethylene oxide)-block-poly(N,N-dimethylacrylamide) (PEO-b-PDMA) in aqueous solution at dilute concentrations was studied by laser light scattering. Even though water was a nonselective solvent for both PEO and PDMA blocks, PEO-b-PDMA formed a certain loose associate in aqueous solutions. Different from the micellization of block copolymers in selective solvents, the association of PEO-b-PDMA in aqueous solution showed weak concentration and temperature dependence as well as opposite salt effect. At 4.0 M NaCl, the association was completely suppressed and PEO-b-PDMA existed as individual polymer chains. This opposite salting out effect revealed the association mechanism of block copolymers in nonselective solvent: the solubility of PEO block in aqueous solution was unique, and it exhibited a better hydrophilicity and thick hydration shell than other water-soluble polymers. This inequality or weak incompatibility drove the block copolymer to associate into loose structures containing multi-domains rich of either blocks. The dependence of the association on the block ratio also supported our conclusions.