ZnCl2离子液体中高区域选择性合成对位柑菁醛

 二烷基咪唑或烷基吡啶卤化物与ZnCl2构成一类新型的具有Lewis酸性的离子液体,以其为催化剂和反应介质,通过月桂烯与丙烯醛的Diels-Alder反应高区域选择性地合成了对位柑菁醛. 结果表明,与常规有机溶剂-ZnCl2催化体系相比,该体系不仅显著地加快了反应速率,而且明显提高了对位柑菁醛的区域选择性. 当ZnCl2与二烷基咪唑或烷基吡啶卤化物的摩尔比为2∶1,温度为15 ℃时月桂烯几乎可完全转化为柑菁醛,且对位柑菁醛的区域选择性p/m＞18. 与氯铝酸盐离子液体相比,该离子液体对水和空气不敏感. 反应结束后,产物与离子液体自动分层,解决了传统均相催化体系中催化剂与产物不易分离的问题. 分离后的离子液体用正己烷清洗提纯后,重复使用4次,其催化活性和区域选择性基本保持不变.     

离子液体用作除硫酸钡垢剂的探讨

通过用不同性质的离子液体(1 L)除硫酸钡垢,考察了离子液体的离子类型、温度、垢尺寸对除硫酸钡垢效果的影响. 结果表明,离子液体(CH2CH3)3NHAl2Cl7具有较好溶解硫酸钡的能力,且溶解速率相对较快;随着温度的升高,垢尺寸的减小,除硫酸钡垢效果明显提高(温度由60 ℃升高至70 ℃,垢尺寸由600～1 000 μm减小至100～200 μm,420 min时1 L (CH2CH3)3NHAl2Cl7的除垢率由5.00%增大到31.6%). 离子液体中的阳离子和阴离子类型对除垢效果亦有很大影响,极性大的亲水性离子液体(CH2CH3)3NHAl2Cl7除硫酸钡垢效果远远大于非极性大的疏水性离子液体[BMIM]PF6(同一条件下,(CH2CH3)3NHAl2Cl7的除垢率为22.45%,而[BMIM]PF6仅为0.47%);同时,离子液体(CH2CH3)3NHAl2Cl7除碳酸钙垢效果也比较明显,而除硫酸钙垢效果较差.     

LiCl-Urea两元体系离子液体的研究

自从1914年第一种离子液体[EtNH3]NO3问世以来,室温离子液体的研究与应用取得了飞速的发展,离子液体以其诸多的优良性能,在催化、有机反应、萃取、以及气相色谱、电化学中得到了广泛地应用。近几年来,多元离子液体体系的研究受到关注。本文报导了由LiCl简单盐和Urea形成的二元体系离子液体,最低共熔点为55℃(LiCl的熔点是608℃,尿素本身的熔点是132℃)。     

稀散金属室温离子液体研究Ⅰ.InCl3/BPC体系

利用差示扫描量热曲线(DSC)方法构筑了InCl3/BPC二元体系相图,并指出该体系可形成含稀散金属的室温离子液体,有一定宽度的室温离子液体窗口和较小的室温离子液体深度.从头算和Raman光谱都指出,在InCl3/BPC体系室温离子液体中InCl-4是主要负离子.     

新型BrΦnsted-Lewis酸性离子液体的合成及其在松香二聚反应中的应用(英文)

合成、表征了新型 Brφnsted-Lewis 酸性离子液体 1-（3-磺酸）-丙基-3-甲基咪唑氯锌酸盐 （[HO3S-（CH2）3-mim]Cl-ZnCl2）, 并将其用于催化松香二聚反应. 结果表明, [HO3S-（CH2）3-mim]Cl-ZnCl2 （ZnCl2摩尔分数x 〉 0.5）为 Brφnsted 和 Lewis 双酸性, 且以 [HO3S-（CH2）3-mim]Cl-ZnCl2 （x = 0.64） 的催化性能较佳. 在松香 5.0 g, 甲苯15 g, 离子液体质量分数 5%, 反应温度 110℃ 和反应时间 4 h 的较佳实验条件下, 所得产物聚合松香的软化点为 118 ℃. 此外, 该催化剂的使用有利于产物的分离且分离的离子液体催化剂具有良好的重复使用性能.     

新型Br(o)nsted-Lewis酸性离子液体的合成及其在松香二聚反应中的应用

合成、表征了新型Bronsted-Lewis酸性离子液体1-(3-磺酸)-丙基-3-甲基咪唑氯锌酸盐([HO3S-(CH2)3-mim]Cl-ZnCl2),并将其用于催化松香二聚反应.结果表明,[HO3S-(CH2)3-mim]Cl-ZnCl2(ZnCl2摩尔分数x＞0.5)为Bronsted和Lewis双酸性,且以[HO3S-(CH2)3-mim]Cl-ZnCl2 (x=0.64)的催化性能较佳.在松香5.0 g,甲苯15 g,离子液体质量分数5%,反应温度110℃和反应时间4 h的较佳实验条件下,所得产物聚合松香的软化点为118 ℃.此外,该催化剂的使用有利于产物的分离且分离的离子液体催化剂具有良好的重复使用性能.     

功能化酸性离子液体脱除模拟油品中的非碱性氮

合成了一系列功能化酸性离子液体并用于模拟油品中非碱性氮-吲哚的脱除。结果表明,离子液体的阴离子对脱氮率有较大影响,离子液体的酸性越强,对吲哚的选择性脱除效果越好,不同阴离子的脱氮率顺序为:HSO4-CF3COO-H2PO4-CH3COO-。以(CH3CH2)3N(CH2)3SO3HHSO4为例,考察了剂油比、剂水比、沉降时间、反应时间和温度对油品脱氮率的影响。结果表明,在优化的工艺路线下,(CH3CH2)3N(CH2)3SO3HHSO4对油品中的吲哚脱除率可达99.12%,重复使用六次后,脱氮活性未见明显降低,具有良好的稳定性,。     

稀散金属室温离子液体研究I.InCl_3/BPC体系

利用差示扫描量热曲线（DSC）方法构筑了InCl_3/BPC二元体系相图，并指出 该体系可形成含稀散金属的室温离子液体，有一定宽度的室温离子液体窗口和较小 的室温离子液体深度。从头算和Raman光谱都指出，在InCl_3/BPC体系室温离子液 体中InCl_4~-是主要负离子。     

稀散金属室温离子液体研究I.InCl_3/BPC体系

利用差示扫描量热曲线（DSC）方法构筑了InCl_3/BPC二元体系相图，并指出 该体系可形成含稀散金属的室温离子液体，有一定宽度的室温离子液体窗口和较小 的室温离子液体深度。从头算和Raman光谱都指出，在InCl_3/BPC体系室温离子液 体中InCl_4~-是主要负离子。     

离子液体[emim]Br熔点的分子动力学模拟

运用分子动力学模拟, 采用直接加热法和微正则(NVE)系综法计算离子液体[emim]Br的熔点, 以期获得较好的熔点预测方法. 直接加热法通过分析体系的非键合能、密度、径向分布函数、扩散系数和平动序参数随温度的变化关系判断熔点; NVE系综法则通过获得固液共存体系判断熔点. 直接加热法中, 体系易出现过热问题; NVE系综法则能有效克服过热问题, 是在模拟研究中应优先选择的离子液体熔点预测方法.     

Solubility of phosphonium ionic liquid in alcohols, benzene, and alkylbenzenes

The (solid + liquid) phase equilibria and (liquid + liquid) phase equilibria of binary mixtures containing quaternary phosphonium salt-tetrabutylphosphonium methanesulfonate and alcohols or alkylbenzenes were investigated. The systems {[(CH(3)CH(2)CH(2)CH(2))4P][CH(3)SO(3)] + 1-butanol, or 1-hexanol, 1-octanol, 1-decanol, or 1-dodecanol} and {[(CH(3)CH(2)CH(2)CH(2))4P][CH(3)SO(3)] + benzene, or toluene, ethylbenzene, or propylbenzene} have been measured by a dynamic method at a wide range of temperatures from 220 to 386 K. Solid-liquid equilibria with immiscibility in the liquid phase were detected with the aromatic hydrocarbons ethylbenzene and propylbenzene. The basic thermodynamic properties of pure ionic liquid--the melting point, enthalpy of fusion, enthalpy of solid-solid-phase transition, and glass transition--have been determined by differential scanning calorimetry. The experimental data of systems with alcohols were correlated by means of the UNIQUAC ASM and NRTL1 equations and of systems with alkylbenzenes with Wilson and NRTL equations utilizing parameters derived from the (solid + liquid) equilibrium. The root-mean-square deviations of the solubility temperatures for all calculated data are dependent upon the particular system and the particular equation used.     

新型二茂铁甲基季铵盐离子液体的合成与表征

以二茂铁与二甲胺为原料合成了碘化二茂铁甲基季铵盐,再经复分解反应得到乙酸二茂铁甲基季铵盐离子液体;表征了离子液体的结构,测定了其熔点和溶解性.结果表明,合成的乙酸二茂铁甲基季铵盐离子化合物熔点低于100℃,是一种新型的二茂铁甲基季铵盐离子液体.     

Nitroxide/substrate weak hydrogen bonding: attitude and dynamics of collisions in solution

The study of intermolecular collisions and bonding interactions in solutions is of critical importance in understanding and predicting solute/solvent properties. Previous work has established that stable paramagnetic nitroxide molecules are excellent probes of intermolecular interactions for hydrogen bonding in polar solvents. In this study, 1H, 2H, 13C, 15N NMR and liquid/liquid intermolecular transfer dynamic nuclear polarization (L2IT DNP) results are obtained for the paramagnetic probe molecule, TEMPO, interacting with the common aprotic and protic polar solvents, CH3CN and CH3CONH2, yielding a profile of both dipolar and scalar interactions. A significant scalar contact hyperfine is observed for the N-O...H-C interaction (13CH3 hyperfine, a/h=0.66 MHz) in the CH3CN/TEMPO system, whereas the N-O...H-C and N-O...H-N interactions for the TEMPO/CH3CONH2 system yield 13CH3 and 15N hyperfine couplings of a/h=0.16 and -0.50 MHz, respectively. The distance and attitude of the scalar interaction for the nitroxide hydrogen bonding at the methyl group in CH3CN and the amino group in CH3CONH2 are computed using density functional theory (DFT), yielding good agreement with the experimental results. These results show that the hyperfine coupling provides a sensitive probe of weak hydrogen-bonding interactions in solution.     

Physicochemical properties and solubility of alkyl-(2-hydroxyethyl)-dimethylammonium bromide

Quaternary ammonium salts, which are precursors of ionic liquids, have been prepared from N,N-dimethylethanolamine as a substrate. The paper includes specific basic characterization of synthesized compounds via the following procedures: nuclear magnetic resonance (NMR) and Fourier transform infrared (FTIR) spectra, water content, mass spectroscopy (MS) spectra, temperatures of decompositions, basic thermodynamic properties of pure ionic liquids (the melting point, enthalpy of fusion, enthalpy of solid-solid phase transition, glass transition), and the difference in the solute heat capacity between the liquid and solid at the melting temperature determined by differential scanning calorimetry (DSC). The (solid + liquid) phase equilibria of binary mixtures containing (quaternary ammonium salt + water, or + 1-octanol) has been measured by a dynamic method over wide range of temperatures, from 230 K to 560 K. These data were correlated by means of the UNIQUAC ASM and modified nonrandom two-liquid NRTL1 equations utilizing parameters derived from the (solid + liquid) equilibrium. The partition coefficient of ionic liquid in the 1-octanol/water binary system has been calculated from the solubility results. Experimental partition coefficients (log P) were negative at three temperatures.     

Thermodynamic modeling of the phase behavior of binary systems of ionic liquids and carbon dioxide with the group contribution equation of state

The group contribution equation of state (GC-EOS) was applied to predict the phase behavior of binary systems of ionic liquids of the homologous families 1-alkyl-3-methylimidazolium hexafluorophosphate and tetrafluoroborate with CO2. Pure group parameters for the new ionic liquid functional groups [-mim][PF6] and [-mim][BF4] and interaction parameters between these groups and the paraffin (CH3, CH2) and CO2 groups were estimated. The GC-EOS extended with the new parameters was applied to predict high-pressure phase equilibria in binary mixtures of the ionic liquids [emim][PF6], [bmim][PF6], [hmim][PF6], [bmim][BF4], [hmim][BF4], and [omim][BF4] with CO2. The agreement between experimental and predicted bubble point data for the ionic liquids was excellent for pressures up to 20 MPa, and even for pressures up to about 100 MPa, the agreement was good. The results show the capability of the GC-EOS to describe phase equilibria of systems consisting of ionic liquids.     

Phase equilibria and modeling of ammonium ionic liquid, C2NTf2, solutions

Novel quaternary ammonium ionic liquid, ethyl(2-hydroxyethyl)dimethylammonium bis(trifluomethylsulfonyl)imide (C2NTf2), has been prepared from N,N-dimethylethanolamine as a substrate. The paper includes a specific basic characterization of the synthesized compound by NMR and the basic thermophysical properties: the melting point, enthalpy of fusion, enthalpy of solid-solid phase transition, glass transition determined by the differential scanning calorimetry (DSC), temperature of decomposition, and water content. The density of the new compound was measured. The solid-liquid or liquid-liquid phase equilibria of binary mixtures containing {C2NTf2+water or an alcohol (propan-1-ol, butan-1-ol, hexan-1-ol, octan-1-ol, decan-1-ol), aromatic hydrocarbons (benzene, toluene), aliphatic hydrocarbons (n-hexane, n-octane), dimethylsulfoxide (DMSO), or tetrahydrofuran (THF)} have been measured by a dynamic method in a wide range of temperatures from 230 to 430 K. These data were correlated by means of the nonrandom two-liquid (NRTL) equation utilizing temperature-dependent parameters derived from the solid-liquid or liquid-liquid equilibrium. From the solubility results, the negative value of the partition coefficient of ionic liquid in binary system octan-1-ol/water (log P) at 298.15 K has been calculated.     

Phase Diagram of RbI-SmI_2 Binary System and Structural Investigation of RbSm_2I_5 and RbSmI_3

The RbI-SmI2 , binary system was studied with DTA and X-ray powder diffraction. Its phase diagram shows that it has a congruently melting compound,RbSm2I5 , with a melting point 524℃; an incongru-ently melting compound, Rb2SmI4 , with an inconsruently point 467℃ and two compounds, RbSmI3, and Rb3SmI5, being decomposed at 433℃ and 460℃, respectively. The measured structure of RbSm2I5 shows that it is isomorphous with NH4 Pb2 Cl5 space group P21/c, a=10 . 063(3)A, b=9.003(3)A. c =14 . 242(5)A°,β=90.23(3)°;z = 4, MVx= 1 94 . 3cm3/mol;D=5.255g/cm3 and Do =5. 334g/cm3 (25. 0℃).The structural, investigation ofRbSmI3 shows that it belongs to the orthorhombic system with a = 15.914(6)A, b=8.898(3)A c =12.193(5)A; Z=8, MVx =130.0cm3/mol, Dx =4 . 743g/cm3,Do = 4.597g/cm3(25.0℃).     

Synthesis and characterization of ionic liquids incorporating the nitrile functionality

A series of imidazolium salts with the nitrile functional group attached to the alkyl side chain, viz. [CnCNmim][X] (where CnCNmim is the 1-alkylnitrile-3-methylimidazolium cation and Cn= (CH2)(n), n = 1-4; X = Cl, PF(6), and BF(4)) and [C3CNdmim][X] (where CnCNdmim is the 1-alkylnitrile-2,3-dimethylimidazolium cation and C(n) = (CH2)(n), n = 3; X = Cl, PF(6), and BF(4)), have been prepared and characterized using spectroscopic methods. The majority of the nitrile-functionalized imidazolium salts can be classed as ionic liquids since they melt below 100 degrees C. Four of the imidazolium salts have been characterized in the solid state using single-crystal X-ray diffraction analysis to reveal an extensive series of hydrogen bonds between H atoms on the cation and the anion. The relationship between the solid-state structure and the melting point is discussed. Key physical properties (density, viscosity, and solubility in common solvents) of the low melting ionic liquid have been determined and are compared with those of the related 1-alkyl-3-methylimidazolium and 1-alkyl-2,3-dimethylimidazolium ionic liquids. It was envisaged that these ionic liquids could act as both solvent and ligand for catalyzed reactions, and this application is demonstrated in hydrogenation reactions, which show that retention of the catalyst in the ionic liquid during product extraction is extremely high.     

吡啶甲磺酸盐离子液体的固载化及其在聚甲醛二甲醚合成中的催化作用

采用键合法将吡啶甲磺酸盐离子液体负载在HZSM-5分子筛上,得到分子筛负载型离子液体催化剂,并将其用于聚甲醛二甲醚(PODEn)的合成。X射线衍射、红外光谱和N2吸附-脱附表征结果显示,吡啶甲磺酸盐离子液体较好地固载于分子筛上。用于催化合成PODEn时较适宜的反应条件为:离子液体负载量0.25 g、甲醇与三聚甲醛的物质的量比(即醇醛比)1.5、110℃、反应时间3 h,催化剂用量为总反应物质量的2.2%。缩合产物中柴油添加组分PODE3~8收率可达67.35%;与单纯离子液体或分子筛催化效果相比,PODE3~8收率得到提高。固载化离子液体易回收,可重复利用;当重复使用3次后,PODE3~8收率仍能达到45.62%。