178631-04-4Relevant articles and documents
Solvation structure and dynamics of Li+ in Lewis-basic ionic liquid of 1-octyl-4-aza-1-azoniabicyclo[2.2.2]octane bis(trifluoromethanesulfonyl)amide
Umecky, Tatsuya,Suga, Kenta,Masaki, Eiji,Takamuku, Toshiyuki,Makino, Takashi,Kanakubo, Mitsuhiro
, p. 557 - 562 (2015)
1H, 7Li, 13C, 15N, and 19F NMR spectra of 1-octyl-4-aza-1-azoniabicyclo[2.2.2]octane bis(trifluoromethanesulfonyl)amide ([C8dabco][TFSA]) solutions with and without LiTFSA (lithium mole fractions of xLi = 0 and 0.1) were measured at 313.2 K. The chemical shift measured for each nucleus was corrected for volume magnetic susceptibility of the solution. For comparison, those NMR spectra of 1-methyl-3-octylimidazolium bis(trifluoromethanesulfonyl)amide ([C8mim][TFSA]) solutions were recorded under the same condition. The peak shifts for the nuclei induced by the dissolution of Li+ showed that Li+ interacts with not only TFSA- but also C8dabco+ in [C8dabco][TFSA] solution. Self-diffusion coefficients of the cation, anion, and Li+ in the ionic liquid solutions were determined by a pulsed field gradient NMR technique. Correlation times for jump motion of Li+ were estimated from 7Li longitudinal relaxation times with two different magnetic fields. The diffusion and jump motions of Li+ in [C8dabco][TFSA] and [C8mim][TFSA] solutions are discussed in terms of interionic interactions.
Cross-linked polymer-ionic liquid composite materials
Snedden, Peter,Cooper, Andrew I.,Scott, Keith,Winterton, Neil
, p. 4549 - 4556 (2003)
A series of composites, some with permanent porosity, comprising polymers and ionic liquids have been prepared by in-situ polymerization. The characteristics of both composites and isolated polymers have been investigated. Slow mass and phase transfer characterize the interaction with a range of polymers (1-17) in the N,N′-dialkylimidazolium liquids, [emin]BF4, [bmim]PF6, or [omim]N(SO2CF3)2. Free-radical homopolymerization of 1-vinyl-2-pyrrolidinone in [bmim]PF6 or of 4-vinylpyridine in [omim]N-(SO2CF3)2 gave viscous solutions from which polymer (Mw = 162 500 and 71 500 g mol-1, respectively) could be isolated. Detectable ionic liquid residues were retained in the isolated polymers despite five reprecipitations from methanol. Copolymerization of 4-vinylpyridine (VP) with 5% divinylbenzene (DVB) or trimethylolpropane trimethacrylate (TRIM) in [omim]N(SO2CF3)2, and homopolymerizations of the cross-linking monomes on their own, led with 90-100% monomer conversion to a series of gel-like composite materials, B-H, from which gross-linked polymers, B′-H′, could be isolated by Soxhlet extraction of the ionic liquid. Copolymers of VP with 5-30% DVB (E′, F′) showed a low degree of permanent porosity in the dry state. However, poly(DVB) (G′) and poly(TRIM) (H′) have bulk densities (-3), intrusion volumes (>0.9 cm3 g-1), BET surface area (70-320 m2 g-1), and morphology (from SEM studies) which demonstrate the porogenic character of the ionic liquids used. Comparisons with the related products I and J obtained in toluene reveal the sensitivity of these systems both to the properties of the porogen solvent and to the monomer used.
Physical properties of binary and ternary mixtures of ethyl acetate, ethanol, and 1-octyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide at 298.15 K
Andreatta, Alfonsina E.,Arce, Alberto,Rodil, Eva,Soto, Ana
, p. 1022 - 1028 (2009)
Densities, viscosities, and refractive indices for binary and ternary mixtures of ethanol, ethyl acetate, and l-octyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide have been determined at 298.15 K and atmospheric pressure. Excess molar volumes, and viscosity and molar refraction changes of mixing have been calculated from the measured physical properties. These changes of mixing have been adequately fitted to the Redlieh - Kister polynomial equation. The adjustable parameters and the standard deviations between experimental and calculated values are reported.
Solubility of CO2, H2S, and their mixture in the ionic liquid 1-octyl-3-methylimidazolium bis(trifluoromethyl)sulfonylimide
Jalili, Amir Hossein,Safavi, Mohammadali,Ghotbi, Cyrus,Mehdizadeh, Ali,Hosseini-Jenab, Masih,Taghikhani, Vahid
, p. 2758 - 2774 (2012)
Gaseous solubilities of carbon dioxide (1), hydrogen sulfide (2), and their binary mixture (x2 ≈ 0.2, 0.5, 0.8) have been measured in the ionic liquid 1-octyl-3-methylimidazolium bis(trifluoromethyl)sulfonylimide ([C8mim][Tf2N]) at temperatures ranging from (303.15 to 353.15) K and at pressures under 2 MPa. The observed PTx solubility data were used to obtain Henry's law constants and correlated by three models: (1) the simple Krichevsky-Kasarnovsky (KK) equation, (2) a model comprised of the extended Henry's law and the Pitzer's virial expansion for the excess Gibbs free energy, and (3) the generic Redlich-Kwong (RK) cubic equation of state proposed for gas-ionic liquid systems. The correlations from the three models show quite good consistency with the experimental data for IL/CO2 and IL/H 2S binary mixtures within experimental uncertainties. For IL/CO 2/H2S ternary mixtures, the RK model shows the best correlation with the experimental data. The comparison showed that the solubility of H2S is about two times as great as that of CO 2 in the ionic liquid studied in this work. It was further found, by comparison of the experimental data of this study with those of previous reports, that the solubility of H2S in [Cnmim][Tf 2N] ILs increases as the number of carbon atoms in the alkyl substituent of methylimidazolium cation, n, increases. In addition, quantum chemical calculations at DFT/B3LYP level of theory using 6-311+G(d) and 6-311++G(2d,2p) basis sets were performed on the isolated systems studied in this work to provide explanations from a molecular point of view for the observed experimental trends.
Anion Analysis of Ionic Liquids and Ionic Liquid Purity Assessment by Ion Chromatography
Rutz, Christina,Schmolke, Laura,Gvilava, Vasily,Janiak, Christoph
supporting information, p. 130 - 135 (2017/02/05)
The simultaneous determination of halide impurities (fluoride, chloride, bromide, and iodide) and ionic liquid (IL) anions (tetrafluoroborate, hexafluorophosphate, and triflimide) using ion chromatography was developed with a basic, non-gradient ion chromatography system. The non-gradient method uses the eluent Na2CO3/NaHCO3in water/acetonitrile (70:30 v:v) on the AS 22 column to enable a rapid and simultaneous analysis of different IL and halide anions within an acceptable run-time (22 min) and with good resolution R of larger than 2.4, a capacity k′ between 0.4 and 5.1, selectivities α between 1.3 and 2.1, and peak asymmetries Asof less than 1.5. Halide impurities below 1 ppm (1 mg·L–1of prepared sample solution) could be quantified. A range of ionic liquids with tetrafluoroborate [BF4]–, hexafluorophosphate [PF6]–, and bis(trifluoromethylsulfonyl)imide (triflimide) [NTf2]–anions combined with cations based on imidazole, pyridine, and tetrahydrothiophene could be analyzed for their anion purity. The IL-cations do not influence the chromatographic results. With the analysis of 18 ILs differing in their cation-anion combination we could prove the general applicability of the described method for the anion purity analysis of ionic liquids with respect to halide ions. The IL-anion purity of most ILs was above 98 wt %. The highest IL-anion purity was 99.8 wt %, implying anion impurities of only 0.2 wt %. The used halide anion from the synthesis route was the major anion impurity, yet with chloride also bromide and fluoride (potentially from hydrolysis of [BF4]–) were often detected. When iodide was used, at least chloride but sometimes also bromide and fluoride was present. However, even if the IL-anion content is above 99 wt %, it does not necessarily indicate an ionic liquid devoid of other impurities. From the IC analysis, one can also deduce a possible cation impurity if one takes into account the expected (calculated) IL-anion content. A matching experimental and theoretical IL-anion content excludes, a higher experimental content indicates the presence of residual KBF4, NH4PF6, or LiNTf2salt from the halide to IL-anion exchange.
Liquid-Crystalline Ionic Liquids as Ordered Reaction Media for the Diels–Alder Reaction
Bruce, Duncan W.,Gao, Yanan,Canongia Lopes, José Nuno,Shimizu, Karina,Slattery, John M.
supporting information, p. 16113 - 16123 (2016/10/26)
Liquid-crystalline ionic liquids (LCILs) are ordered materials that have untapped potential to be used as reaction media for synthetic chemistry. This paper investigates the potential for the ordered structures of LCILs to influence the stereochemical outcome of the Diels–Alder reaction between cyclopentadiene and methyl acrylate. The ratio of endo- to exo-product from this reaction was monitored for a range of ionic liquids (ILs) and LCILs. Comparison of the endo:exo ratios in these reactions as a function of cation, anion and liquid crystallinity of the reaction media, allowed for the effects of liquid crystallinity to be distinguished from anion effects or cation alkyl chain length effects. These data strongly suggest that the proportion of exo-product increases as the reaction media is changed from an isotropic IL to a LCIL. A detailed molecular dynamics (MD) study suggests that this effect is related to different hydrogen bonding interactions between the reaction media and the exo- and endo-transition states in solvents with layered, smectic ordering compared to those that are isotropic.