二苯醚烷基化反应中酸性离子液体的循环使用

使用酸性离子液体催化二苯醚与十二烯烷基化反应,考察了离子液体的失活原因,提出了循环使用离子液体的解决办法.在二苯醚与十二烯烷基化反应中, Lewis酸性离子液体不能多次循环使用的原因是离子液体与二苯醚相互作用导致具有催化活性的Al2Cl72－分解、流失.改变离子液体的阳离子不能从本质上解决其与二苯醚间的相互作用.适时补加损失量的AlCl3使离子液体的Lewis酸性得以恢复,可以解决体系中酸性离子液体循环使用问题,循环使用8次后产物产率仍保持90％左右.     

Superbase-derived protic ionic liquids with chelating fluorinated anions

Eighteen new protic ionic liquids were synthesized in one step from five organic superbases and five commercially available fluorinated β-diketones. Physical properties of the ionic liquids, including thermal decomposition temperature were determined. Nine of the ionic liquids were examined as extraction media for La³⁺, with some very large distribution coefficients obtained.     

Tuning the physicochemical properties of diverse phenolic ionic liquids for equimolar CO2 capture by the substituent on the anion

Phenolic ionic liquids for the efficient and reversible capture of CO(2) were designed and prepared from phosphonium hydroxide and substituted phenols. The electron-withdrawing or electron-donating ability, position, and number of the substituents on the anion of these ionic liquids were correlated with the physicochemical properties of the ionic liquids. The results show that the stability, viscosity, and CO(2)-capturing ability of these ionic liquids were significantly affected by the substituents. Furthermore, the relationship between the decomposition temperature, the CO(2)-absorption capacity, and the basicity of these ionic liquids was quantitatively correlated and further rationalized by theoretical calculation. Indeed, these ionic liquids showed good stability, high absorption capacity, and low absorption enthalpy for CO(2) capture. This method, which tunes the physicochemical properties by making use of substituent effects in the anion of the ionic liquid, is important for the design of highly efficient and reversible methods for CO(2)-capture. This CO(2) capture process using diverse phenolic ionic liquids is a promising potential method for CO(2) absorption with both high absorption capacity and good reversibility.     

Synthesis and electric field actuation of an ionic liquid polymer

Polymerizable ionic liquids and their actuation in an electric field are a combination of material and properties with unique potential to display structural and fluid dynamics above that found in small molecule ionic liquids. In an effort to blend ionic liquid nature with actuation response, we have synthesized a new ionic liquid ammonium sulfonate monomer and polymer. The liquid temperature ranges of both the monomer and polymer ionic liquid systems are quite large extending from their respective glass transitions (Tg) of -57 and -49 degrees C to decomposition at approximately 200 degrees C. Particularly remarkable is the small Tg increment that accompanies the transformation from monomer to polymer. The electrowetting behavior of the polymer and of the monomer presents an interesting contrast. This communication will encompass the polymerization, characterization, and actuation of these new ionic liquids.     

Effect of tetrabutylphosphonium cation on the physico-chemical properties of amino-acid ionic liquids

Tetraalkylphosphonium-based amino-acid ionic liquids show lower viscosities and higher decomposition temperatures (>300 degrees C) than previously reported ammonium-based amino-acid ionic liquids.     

Fluorous imidazolium room-temperature ionic liquids based on HFPO trimer

Imidazole substituted with a polyfluoropolyether chain based on HFPO trimer combined with various polyfluoroalkyl triflates produced novel highly fluorous ionic liquids. Their metathesis with four different anions generated a final set of 20 fluorous ionic liquids of waxy or viscous liquid character, which are all soluble in perfluorinated solvents. Two model reactions using selected ionic liquid, the opening of a THF ring with benzoyl chloride under Friedel-Crafts conditions and substitution of benzyl chloride with sodium azide, led to decomposition of the ionic liquid. However, Diels-Alder reaction of 2,3-dimethylbuta-1,3-diene with dimethyl acetylenedicarboxylate in a fluorous ionic liquid resulted in a reasonable enhancing of the reaction rate with smooth recycle of the fluorous solvent. The fluorophilicity of these fluorous ionic liquids ranges from more than 10 for water, toluene or dichloromethane to less than 0.2 for acetonitrile or methanol.     

Gas bubbles in viscous liquids and melts

The basic set of equations and boundary conditions for viscous liquids and melts with gas has been derived. The flux of bubbles in the space of sizes, distribution of bubbles with respect to size, number of bubbles in the unit volume, and swelling of the system of viscous gas with liquid have been found. The initial and intermediate stages of the diffusion decomposition of the metastable system of viscous liquid with gas are considered.     

A "by-productless" cellulose foaming agent for use in imidazolium ionic liquids

Cellulose foams, or sponges, are produced from solutions in ionic liquids by the aqueous acid mediated decomposition of 1-alkyl-3-methylimidazolium-2-carboxylates, where the alkyl group and acid may be selected such that the by-product is the ionic liquid solvent: a by-productless foaming.     

Thermal properties of sulfonic acid group functionalized Brönsted acidic ionic liquids

Thermal decomposition onset temperatures have been measured for a total of 24 methylimidazolium, triethanolammonium, and pyridinium type sulfonic acid groups functionalized Brönsted acidic ionic liquids with Cl^?, Br^?, SO₄ ^2?, PO₄ ^3?, BF₄ ^? _, CH₃CO₂ ^?, and CH₃SO₃ ^? anions, using thermogravimetric analysis. Thermal stabilities of these sulfonic acid group functionalized ionic liquids decreases in the order, methylimidazolium > triethanolammonium > pyridinium. The methylimidazolium, pyridinium, and triethanolammonium ionic liquids investigated showed decomposition onset temperatures (air) in the 213–353, 167–240, and 230–307 °C ranges, respectively. Additionally, the decomposition temperatures of these ionic liquids are highly dependent on the nature of the anion.     

Thermochemical study on the dissolution and regeneration of fibroin from solutions in imidazole-based ionic liquids

The enthalpies of dissolution of fibroin in imidazole-based ionic liquids were determined, and the contribution of polymer crystal structure decomposition to the enthalpy of dissolution was estimated. The heat of mixing of imidazole ionic liquid with water was described.     

以N为中心的阴离子离子液体的合成、表征及应用

首次通过不同阴离子的钾盐和不同的季铵化的咪唑,吡咯溴盐/氯盐进行离子交换,合成了一系列含氰基官能团的阴离子功能化离子液体。通过红外、核磁共振、质谱对离子液体的结构进行表征;通过TGA对离子液体的热稳定性进行测定,结果发现功能化离子液体具有良好的热稳定性,其分解温度在224-289℃范围内。将功能化离子液体[EMIm][N(CN)COC2H5]作为配体应用于无膦配体的Suzuki偶联反应,发现在反应中加入功能化离子液体[EMIm][N(CN)COC2H5]可以使反应收率提高10-20%。     

烷基咪唑离子液体CnmimCl(n=4, 6, 8)对CL-20重结晶的影响

六硝基六氮杂异戊兹烷(CL-20)是高能量密度材料的典型代表之一。重结晶制备高品质CL-20的一个重要难题是晶体微观结构的调控。本文通过在CL-20重结晶过程中加入微量离子液体作为晶形控制剂,探究离子液体浓度、种类和添加方式(加入溶剂或者反溶剂)对CL-20晶体微观结构的影响规律。结果表明：通过改变离子液体的添加方式、种类和浓度,能够实现CL-20晶体尺寸和晶体形貌的调控。热分析结果表明：离子液体的加入可以使ε到γ晶型转变温度提前多达12.6℃;重结晶CL-20的分解峰温和热稳定性提高,放热量增加,最高可达1344 J·g^-1。溶剂中1-己基-3-甲基咪唑氯盐(DmimCl)的加入,能够结晶出没有尖锐棱边和角的类八面体形CL-20晶体,晶粒细小,分解峰温均提高了6℃以上,放热量均在1100 J·g^-1以上,是较理想的晶形控制剂。     

Ionic liquids by proton transfer: vapor pressure, conductivity, and the relevance of DeltapKa from aqueous solutions

We describe the behavior of the conductivity, viscosity, and vapor pressure of various binary liquid systems in which proton transfer occurs between neat Br?nsted acids and bases to form salts with melting points below ambient. Such liquids form an important subgroup of the ionic liquid (IL) class of reaction media and electrolytes on which so much attention is currently being focused. Such "protic ionic liquids" exhibit a wide range of thermal stabilities. We find a simple relation between the limit set by boiling, when the total vapor pressure reaches one atm, and the difference in pK(a) value for the acid and base determined in dilute aqueous solutions. For DeltapK(a) values above 10, the boiling point elevation becomes so high (>300 degrees C) that preemptive decomposition prevents its measurement. The completeness of proton transfer in such cases is suggested by the molten salt-like values of the Walden product, which is used to distinguish good from poor ionic liquids. For the good ionic liquids, the hydrogen bonding of acid molecules to the proton-transfer anion is strong enough that boiling points, but not melting points, may maximize at the hydrogen-bonded dianion composition. High boiling liquids of this type constitute an interesting class of high-temperature protonic acid that may have high-temperature fuel cell applications.     

The vapour of imidazolium-based ionic liquids: a mass spectrometry study

Eight common dialkylimidazolium-based ionic liquids have been successfully evaporated in ultra-high vacuum and their vapours analysed by line of sight mass spectrometry using electron ionisation. The ionic liquids investigated were 1-alkyl-3-methylimidazolium bis[(trifluoromethane)sulfonyl]imide, [C(n)C(1)Im][Tf(2)N] (where n = 2, 4, 6, 8), 1-alkyl-3-methylimidazolium tetrafluoroborate, [C(n)C(1)Im][BF(4)] (where n = 4, 8), 1-butyl-3-methylimidazolium octylsulfate, [C(4)C(1)Im][C(8)OSO(3)] and 1-butyl-3-methylimidazolium tetrachloroferrate, [C(4)C(1)Im][FeCl(4)]. All ionic liquids studied here evaporated as neutral ion pairs; no evidence of decomposition products in the vapour phase were observed. Key fragment cations of the ionised vapour of the ionic liquids are identified. The appearance energies, E(app), of the parent cation were measured and used to estimate the ionisation energies, E(i), for the vapour phase neutral ion pairs. Measured ionisation energies ranged from 10.5 eV to 13.0 eV. Using both the identity and E(app) values, the fragmentation pathways for a number of fragment cations are postulated. It will be shown that the enthalpy of vaporisation, Δ(vap)H, can successfully be measured using more than one fragment cation, although caution is required as many fragment cations can also be formed by ionisation of decomposition products.     

含氰基基团的以C为中心的不对称阴离子离子液体的合成、表征及应用

首次通过不对称阴离子的钠盐/钾盐和不同的季胺化的咪唑,吡咯溴盐/氯盐进行离子交换,合成了一系列含氰基官能团的不对称阴离子功能化离子液体。通过红外、核磁共振、质谱和元素分析对离子液体的结构进行表征;通过TGA对离子液体的热稳定性进行测定,结果发现不对称功能化离子液体具有良好的热稳定性,其分解温度在219-319℃范围内。将功能化离子液体[Bmim][C(CN)2COCH3]作为弱配体应用于模型的Suzuki偶联反应,发现在反应中加入功能化离子液体[Bmim][C(CN)2COCH3]可以使反应收率提高10-15%。     

New solvent for polyrotaxane. II. Dissolution behavior of polyrotaxane in ionic liquids and preparation of ionic liquid‐containing slide‐ring gels

The dissolution behavior of polyrotaxanes, consisting of α‐cyclodextrin and poly(ethylene glycol), with different molecular weights (2000 and 35,000) was investigated. Halogen‐containing ionic liquids, such as chlorides or bromides, were found to be good solvents for polyrotaxanes, regardless of their cations. Dissolution required a high temperature (above 90 °C), while intensive heating over 105 °C seemed to cause decomposition of the polyrotaxane. The discovery of new solvents for polyrotaxane was applied in the preparation of ionic liquid‐containing slide‐ring gels (SR gels), that is supramolecular networks of polyrotaxane swollen with ionic liquids, using a devised “non‐drying” technique accompanied by solvent exchange. Significant swelling of the SR gels with the ionic liquids was confirmed by dynamic mechanical measurements. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1985–1994, 2006     

Supported absorption of CO2 by tetrabutylphosphonium amino acid ionic liquids

A new type of "task specific ionic liquid", tetrabutylphosphonium amino acid [P(C4)4][AA], was synthesized by the reaction of tetrabutylphosphonium hydroxide [P(C4)4][OH] with amino acids, including glycine, L-alanine, L-beta-alanine, L-serine, and L-lysine. The liquids produced were characterized by NMR, IR spectroscopies, and elemental analysis, and their thermal decomposition temperature, glass transition temperature, electrical conductivity, density, and viscosity were recorded in detail. The [P(C4)4][AA] supported on porous silica gel effected fast and reversible CO2 absorption when compared with bubbling CO2 into the bulk of the ionic liquid. No changes in absorption capacity and kinetics were found after four cycles of absorption/desorption. The CO2 absorption capacity at equilibrium was 50 mol % of the ionic liquids. In the presence of water (1 wt %), the ionic liquids could absorb equimolar amounts of CO2. The CO2 absorption mechanisms of the ionic liquids with and without water were different.     

Naked metal nanoparticles from metal carbonyls in ionic liquids: Easy synthesis and stabilization

An overview with more than 160 references on the synthesis and stabilization of metal nanoparticles (M-NPs) from metal carbonyls, metal salts in ionic liquids (ILs) and in particular from metal carbonyls in ionic liquids is given. The synthesis of M-NPs can proceed by chemical reduction, thermolysis, photochemical decomposition, electroreduction, microwave and sonochemical irradiation. Commercially available metal carbonyls M_x(CO)_y are elegant precursors as they contain the metal atoms already in the zero-valent oxidation state needed for M-NPs. No extra reducing agent is necessary. The side product CO is largely given off to the gas phase and removed from the dispersion. The microwave induced thermal decomposition of metal carbonyls M_x(CO)_y in ILs provides an especially rapid and energy-saving access to M-NPs because of the ILs significant absorption efficiency for microwave energy due to their high ionic charge, high polarity and high dielectric constant. The electrostatic and steric properties of ionic liquids allow for the stabilization of M-NPs without the need of additional stabilizers, surfactants or capping ligands and are highlighted by pointing to the DLVO (Derjaugin–Landau–Verwey–Overbeek) and extra-DLVO theory. Examples for the direct use of M-NP/IL dispersions in hydrogenation catalysis of cyclohexene and benzene are given.     

Characterizing the structural properties of N,N-dimethylformamide-based ionic liquid: density-functional study

Amide-based ionic liquids are receiving great enthusiasm recently. In this work, the structures of a kind of N,N-dimethylformamide-based (DMF-based) ionic liquid are investigated theoretically by means of density-functional theory methods. Enol and keto forms of the cation with anions are optimized. The enol form of the DMFH+ cation can form three stable configurations of ion pairs with the anion, while the cation of the keto form is unstable and the proton transfer occurs to form three kinds of neutral molecule pairs. Moreover, the neutral pairs are more stable than the ion pairs, and the ion pairs tend to tautomerize to neutral pairs without barriers. It is suggested that the transformation from the ion pairs to neutral pairs may be the first step for decomposition of DMF-based ionic liquids.     

复合离子液体中纤维素的催化分解

通过将酸性功能化离子液体与对纤维素具有溶解作用的离子液体进行复合, 构建了一类新型的高效催化纤维素分解的体系, 并采用热重(TG)分析方法, 研究了复合离子液体中纤维素的分解行为. 结果表明: 复合离子液体中纤维素的分解温度明显降低, 溶于离子液体中的纤维素可被酸性离子液体原位催化分解. 纤维素的分解温度受离子液体催化剂的酸性及纤维素在复合离子液体中的溶解度影响明显: 酸性越强, 溶解度越大, 纤维素的分解温度越低.