Triblock Copolymer Self-Assemblyin Ionic Liquids:Effect of PEO Block Length on the Self-Assembly of PEO–PPO–PEOin Ethylammonium Nitrate.

The microstructure and rheologicalproperties of micellar solutionsof Pluronic block copolymers (PEOx–PPOy–PEOx)in deuterated ethylammonium nitrate (dEAN, a protic ionic liquid)are studied by small- and ultrasmall-angle neutron scattering (SANSand USANS), fluorescence microscopy, and shear rheology. A homologousseries of three Pluronics with similar PPO block length (F127 (PEO106–PPO70–PEO106), P123(PEO20–PPO70–PEO20),and L121 (PEO5–PPO70–PEO5)) are examined to explore the effect of the relative balance ofsolvophilic to solvophobic block size on the self-assembled microstructure.Both F127 and P123 form spherical micelles in dEAN that assemble intoface-centered and body-centered cubic supramolecular crystals, respectively,upon increasing concentration or temperature. The transition fromdisordered to crystalline (ordered) structures manifests as a sol–gelrheological transition. A richer phase diagram is observed in theL121/dEAN system: due to its low solvophilicity in dEAN, L121 self-assemblesinto structures with low curvatures, namely, vesicles in the diluteregime, elongated (wormlike) micelles at intermediate concentrationsand low temperatures, a nematic phase in concentrated solutions, andmultilamellar phases at high temperatures. Highly viscoelastic solutionsare created by the self-assembly of entangled L121 wormlike micelles.Structural length scales of the three Pluronic/dEAN systems in thevarious mesophases are determined from SANS and USANS. [ABSTRACT FROM AUTHOR]