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.

No abstract

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

The micelle shuttle utilizing block copolymer micelles as nanocarriers for transportation between water and a hydrophobic ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][TFSI]), is examined in detail. Rhodamine B, a dye with a high molar absorptivity and fluorescence quantum yield, is conjugated to a short poly(1,2-butadiene) homopolymer and then loaded in amphiphilic poly((1,2-butadiene)-block-ethylene oxide) (PB-PEO) block copolymer micelles. The round-trip transportation of the micelles between water and the ionic liquid is simply triggered by temperature; it is fully reversible, quantitative, and without leakage. Quantitative fluorescence analysis reveals that the micelle distribution in the biphasic system has a very strong temperature dependence, which is favorable for control of the transportation. The standard Gibbs free energy change (DeltaG(o)), standard enthalpy change (DeltaH(o)), and standard entropy change (DeltaS(o)) of the micelle shuttle are extracted from the temperature dependence of the micelle distribution. Both DeltaH(o) and DeltaS(o) are positive, indicating an entropy-driven process. The slow yet spontaneous micelle shuttle is explored under quiescent conditions to understand the transfer kinetics. Both of the two-way transfers involve three steps, formation of micelle-concentrated [EMIM][TFSI]/water droplets in the initial phase, sedimentation/creaming of the droplets to the interface, and diffusion of the micelles to the destination phase. A detailed mechanism for the transfer is therefore proposed.

The glass transition behavior and viscoelastic properties of poly(methyl methacrylate) in mixtures with the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide are examined at compositions from 10 wt % polymer to pure polymer, over the temperature range from −180 to 230 °C. Polymers of two different molecular weights (125 and 335 kg/mol) are studied. Glass transitions are analyzed by differential scanning calorimetry, and derivative heat flow curves are used to extract glass transition temperatures and breadths. Distinct composition dependences are observed for the polymer and ionic liquid components, with two apparent glass transitions at intermediate compositions. The glass transition breadths of the mixtures (∼30−70 °C) are much broader than those of the pure components (<25 °C). These results reflect distinct effective local compositions arising from the chain connectivity of the polymer component. The frequency-dependent dynamic moduli G′ and G′′ show a shift from unentangled to entangled behavior as concentration is increased from 10 to 20 wt % polymer. The application of time−temperature superposition is successful over the full range of compositions, leading to master curves extending up to 11 orders of magnitude in reduced frequency. The plateau modulus (G N) exhibits a concentration dependence of G N ∼ c 2.2, and analyses of the longest relaxation times and viscosity show the general trends expected for entangled solutions of increasing polymer concentration. Overall, ionic liquids are demonstrated to be effective model solvents for studying viscoelastic properties over wide temperature and composition ranges due to their nonvolatility and stability.

This article describes the temperature-induced phase transfer behavior of a series of thermosensitive polymer brush-grafted particles between water and a hydrophobic ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][TFSI]). Six samples were made by surface-initiated atom transfer radical polymerization: silica particles grafted with poly(methoxypoly(ethylene glycol) methacrylate) (PPEGMMA) with two different molecular weights, poly(methoxytri(ethylene glycol) methacrylate) (PTEGMMA), poly(methoxydi(ethylene glycol) methacrylate) (PDEGMMA), and two copolymers of PEGMMA and TEGMMA with different compositions (P(PEGMMA-co-TEGMMA)-82 and P(PEGMMA-co-TEGMMA)-74). The cloud points of free PPEGMMA with M(n,SEC) of 23 and 40 kDa, P(PEGMMA-co-TEGMMA)-82, P(PEGMMA-co-TEGMMA)-74, and PTEGMMA in [EMIM][TFSI]-saturated water were 95, 94, 80, 72, and 43 °C, respectively. PDEGMMA was not soluble in the ionic liquid-saturated water. PPEGMMA brush-grafted particles moved spontaneously and completely from water to the [EMIM][TFSI] phase upon heating at 80 °C. When cooled to 22 °C, all particles returned to the water layer. From UV-vis absorbance measurements, the transfer temperature (T(tr)) of PPEGMMA-grafted particles from water to the ionic liquid was 42 °C. Thermodynamic analysis showed that the particle transfer was an entropically driven process. P(PEGMMA-co-TEGMMA)-82, P(PEGMMA-co-TEGMMA)-74, and PTEGMMA brush-grafted particles also underwent reversible and quantitative transfer between the two phases upon heating at 70 °C and cooling at 0 °C; their transfer temperatures from water to [EMIM][TFSI] were 36, 30, and 16 °C, respectively. T(tr) was a linear function of the cloud point of the corresponding free polymer in ionic liquid-saturated water. In contrast, PDEGMMA-grafted particles moved spontaneously to the ionic liquid layer upon heating but did not return to water even after prolonged stirring at 0 °C.