We describe the LCST-type phase behavior of poly(ethylene oxide) (PEO) dissolved in imidazolium-based tetrafluoroborate ionic liquids (ILs). Phase diagrams were determined by a combination of small-angle neutron scattering (SANS) and cloud point (CP) measurements. Unlike typical LCST phase diagrams of polymer solutions, the PEO/IL phase diagram is either roughly symmetric with a critical composition near 50% polymer or asymmetric with a critical composition shifted to an even higher concentration of PEO. As the molecular weight decreases from 20 500 to 4200 g/mol, the critical temperature (T c) increases slightly (∼10 °C). However, a larger increase in T c (27 °C) was observed as the molecular weight decreases from 4200 to 2100 g/mol, likely due to the increasing importance of hydrogen bonds between the −OH end groups of PEO and the fluorine atoms of the anions. This inference is supported by the strong dependence of the phase diagram on the identity of the PEO end groups (hydroxy vs methoxy). Furthermore, replacing the most acidic proton of the imidazolium ring (in the C2 position) with a methyl group lowers the T c and changes the shape of the phase diagram significantly, suggesting that the hydrogen bonds between the H atoms on the C2 position of the imidazolium ring and the O atoms of PEO play an important role in determining the LCST phase behavior of this system.

Hydrogel modified porous matrix with the super-wetting surface (i.e., superhydrophilic/underwater super-oleophobic) is ideal for oil/water separation. However, the deterioration in mechanical strength and separation efficiency during the swelling process and complicated synthesis procedure limits its industrial application. In this study, a strategy of using ethanol to dynamically regulate the hydrogen bond crosslinking between polyvinyl alcohol (PVA) and tannic acid (TA) is proposed to prepare a "hydrogel paint", which can be simply applied on the porous substrate surface by different one-step operations (dipping, brushing, spraying, etc.) without additional cross-linking. The underline mechanism is attributed to the re-establishment of intermolecular hydrogen bond mediated cross-linking between PVA and TA during ethanol evaporation. Consequently, the resultant hydrogel coating exhibits ultra-high strength (>10 MPa), swelling volume stability, and excellent oil-water separation efficiency (>99%). This study will provide new insights into the scalable fabrication of hydrogel-coated porous materials for oil/water separation in industrial scenarios.

Four poly((1,2-butadiene)- block-ethylene oxide) (PB-PEO) diblock copolymers were shown to self-assemble into micelles with PB cores and PEO coronas (including spheres, cylinders, and vesicles) in the ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][TFSI]). All four systems exhibited the "micelle shuttle" (He, Y.; Lodge, T. P. J. Am. Chem. Soc. 2006, 128, 12666-12667), whereby PB-PEO micelles transferred, reversibly and with preservation of micelle structure, from an aqueous phase at room temperature to a hydrophobic ionic liquid at high temperature. The micelle size (both mean and distribution) depends on whether it was initially dissolved in water or in the ionic liquid, but the initial micelle structures in the ionic liquid were shown by dynamic light scattering to be preserved during the transfer and persist essentially unchanged for months in both the ionic liquid and water. The transfer was shown to be driven by the deteriorating solvent quality of water for PEO at high temperature, while the ionic liquid remains a good solvent. The transfer temperature could be tuned by adding ionic or nonionic additives to the aqueous phase to change the solvent quality of water for PEO, and by using ionic liquids with different polarity.

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The viscosity (η) of [EMIM][BF 4 ] was measured on an ARES rheometer using 50 mm parallel plates. A nominal gap of 1 mm was employed, and the gap was adjusted at each temperature to keep an even sample loading. The samples were enclosed in a nitrogen convection oven, maintaining the temperature within ± 0.5 °C. The viscosity was measured