新型氮二烷基吗啉盐酸盐离子液体的合成及其性能研究

以N-甲基吗啉和N-乙基吗啉为原料合成了系列新型的氮二烷基吗啉季铵盐类离子液体, 所有新化合物经元素分析、1H NMR确认了其结构, 同时测定了该类化合物的热稳定性、电导率以及对聚丙烯腈的溶解能力. 试验结果表明, 大多数化合物的熔点较低, 为室温离子液体. 该类化合物具有较好的热稳定性, 可应用于电极和表面活性剂领域. 且N-甲基-N-丁基吗啉盐酸盐具备对聚丙烯腈的溶解能力.     

由季铵盐合成有机胂二茂铁衍生物

由季铵盐合成有机胂二茂铁衍生物杜洪光,师树简（北京化工大学应用化学系,北京,１０００２９）关键词有机胂,二茂铁衍生物,铵甲碘化物,亲核取代关于二茂铁季铵盐的亲核取代反应已有较多报道［１～４］,但对于含胂二茂铁季铵盐的这类反应还未见诸文献,由碘化［２－...     

离子液体超酸清洁催化苯的烷基化反应

研究了在具有Lewis酸性的离子液体体系中进行的苯与烯烃及卤代烃的烷基化反应.以氯化1-甲基-3-乙基咪唑(MEIC)、氯化1-丁基吡啶(BPC)、氯化l-甲基-3-丁基咪唑(MBIC)及盐酸三甲胺(TMHC)季铵盐分别与AlCl3原位合成法制备离子液体催化体系.结果表明:以上各种离子液体均有很高的催化活性,反应转化率在较短的时间内达到100%.其中TMHC-A1Cl3离子液体单烷基化选择性达98.6%.与AlCl3相比,催化活性显著提高,生成烷基化产物不溶于离子液体,因而易于分离,催化剂可重复使用.     

二茂铁甲基季铵盐对异烟肼的电催化氧化及其电分析方法研究

研究了铂电极上二茂铁甲基季铵盐电催化氧化异烟肼的电化学行为,并且对异烟肼药物的电分析方法进行了研究。实验结果发现,二茂铁甲基季铵盐对异烟肼的电化学氧化具有很好的催化作用。当二茂铁甲基季铵盐浓度一定时,催化氧化峰电流与异烟肼浓度在5×10-5~6×10-4mol/L的浓度范围有良好的线性关系(r=0.9984),运用方波伏安法测定了异烟肼样品含量,与紫外分光光度法所得结果进行比较,相对标准偏差在0.5%以内,标准加入的回收率在98.0%~101.0%之间。     

离子液体催化CO_2和环氧化合物的研究进展

离子液体是一类新型的催化CO_2环加成反应的催化剂,因其具有结构可设计性、催化活性高、绿色高效等优点而被广泛应用于催化合成环状碳酸酯.本文主要综述了近几年来各种常规型离子液体及功能化离子液体对CO_2和环氧化合物反应的催化性能的研究进展,其中常规型离子液体主要有咪唑类、季铵盐、季鏻盐、吡啶类等离子液体,而功能化离子液体包括氨基功能化、羟基功能化、羧基功能化、氨基酸类等离子液体.同时对各类离子液体催化CO_2与环氧化合物合成环状碳酸酯的研究中存在的问题进行了分析,并对其应用前景进行了展望.     

新型乙醇胺型离子液体的合成与表征

由乙醇胺,二乙醇胺和三乙醇胺提供阳离子,由有机酸(甲酸,乙酸和丙酸)提供阴离子,合成了8种新型乙醇胺型离子液体,其结构经1H NMR,IR和元素分析表征.熔点、电导率等测定结果表明,他们均具有离子液体的特征.     

十聚钨酸季铵盐的合成

利用离子液体首次合成两种十聚钨酸季铵盐{[Bmim]_4W_(10)O_(32)(Bmin=N-甲基-N'-正丁基咪唑)和[Bu~nPy]_4W_(10)O_(32)},其结构经TG,~1H NMR,~(13)C NMR,IR和元素分析表征.     

功能离子液体水相催化芳醛与5,5-二甲基-1,3-环己二酮的反应

以N,N,N′,N′-四甲基乙二胺、1,3-丙磺酸内酯为原料,经酸化合成了功能化离子液体N,N,N′,N′-四甲基-N,N′-二磺丙基二硫酸氢盐(TSIL). TSIL离子液体兼具Brnsted 酸性官能团和季铵盐相转移催化剂的结构,能够实现水相中芳醛与5,5-二甲基-1,3-环己二酮反应,得到氢化氧杂蒽衍生物. 结果表明,合成的TSIL具有较高的催化活性,在水相中于100 ℃下回流2～3 h即可完成反应,产率可达80%～93%. 反应生成的取代氢化氧杂蒽与离子液体的水溶液不相溶,通过简单的过滤可实现产物与催化体系的分离,简化了分离过程,方法操作简便、环境友好、催化剂可回收并重复使用.     

新型室温离子液体六烷基胍盐的制备及性质

近年来 ,离子液体 (IL)作为“绿色”溶剂受到学术和工业界的关注 .英国 BP公司和法国的 IFP等研究机构从 2 0世纪 80年代起就开始探索离子液体作为溶剂与催化剂的可能性 ,至今在离子液体体系中已实现了许多催化反应 [1～ 5] .室温离子液体 (RTIL S)是指在常温下呈液态的熔盐体系 .通常由烷基吡啶或双烷基咪唑季铵阳离子与氯铝酸根、氟硼酸根及氟磷酸根等阴离子组成 .在季铵盐类离子液体中 ,咪唑盐的合成和应用研究尤为突出 .目前 ,对于既可作为溶剂又可作为催化剂的室温离子液体的合成和应用已成为研究热点 [6 ] ,如室温离子液体 [EMI…     

一类新型酯类离子液体的合成

以氯乙酸乙酯和氮杂环化合物(1-甲基咪唑、吡啶、N-乙基哌啶、N-甲基吗啉)为原料, 采用两步法合成了一类新型的酯类离子液体, 对合成的12个化合物进行了元素分析, ¹H NMR谱和一些物理性质的测定. 大多数化合物的熔点低于100 ℃, 为室温离子液体. 所合成离子液体的热稳定范围都比较宽, 性质稳定.     

二茂铁甲基季铵盐的电化学行为

二茂铁是具有夹心型结构和芳香性的高度富电子体系,热稳定性好,有良好的电化学反应活性,具有易受环境影响的可逆氧化还原电对的特点。通过分子设计将二茂铁衍生物引入自组装单分子膜体系,考察其电子转移过程以及与膜结构的对应关系,可以为更深层次的分子设计和功能组装反馈信息;以二茂铁衍生物结构单元设计合成的氧化还原型大环化合物对离子的选择性迁移、氧化还原催化及发展为新一代的传感器有着诱人的应用前景。     

有机改性膨润土对己唑醇水悬浮体系物理稳定性的影响

利用4种季铵盐阳离子表面活性剂（十二烷基二甲基苄基氯化铵(1227)、十四烷基二甲基苄基氯化铵(1427)、十六烷基三甲基氯化铵(1631)和十八烷基三甲基氯化铵(1831)）分别对钠基膨润土（Na-Ben）进行有机改性,制得4种有机膨润土（1227-Ben、1427-Ben、1631-Ben和1831-Ben）并进行了红外光谱及X射线分析,考察了4种有机膨润土在水中的悬浮性能及对5%己唑醇水悬体系物理稳定性能的影响。 FT-IR及XRD分析结果表明,供试季铵盐阳离子的有机碳链均进入到膨润土的片层间。 水中悬浮性能测定实验表明,1831-Ben在水中悬浮性能相对较好,而其它3种均不理想,特别是1227-Ben和1427-Ben表现出强烈的斥水现象。 沉降试验表明,有机膨润土的使用有助于5%己唑醇水悬浮剂物理稳定性的提高,其中用1831-Ben制备出的水悬浮体系的物理稳定性明显优于其它3种,制剂析水率最低,屈服值与粘度最大,体系悬浮率最高,可见1831-Ben可以用作5%己唑醇水悬浮剂的抗沉降剂。     

Charged ultrafiltration membranes of polyacrylonitrile covalently binding amphiphilic quaternary ammonium group: effect of aliphatic hydrophobic groups on the filtration properties

Amphiphilic monomers of chloromethylstyrene derivative were synthesized and then copolymerized with acrylonitrile for the preparation of positively charged ultrafiltration membranes. Four types of the polyacrylonitrile charged membranes having quaternary ammonium group with trimethyl, dimethylbutyl, dimethyloctyl and dimethylstearyl groups were prepared by the phase-inversion method. The ultrafiltration properties of the charged membranes were measured by using dextran molecular probes at various NaCl concentrations. Then, the filtration behavior was compared in these charged membranes. For membranes with trimethyl and dimethylbutyl groups on the quaternary ammonium salt, the values of the molecular weight cutoff and the permeation rate of the solute solution increased when the salt concentration increased. However, for membranes having amphiphilic quaternary ammonium groups with octyl and stearyl aliphatic chains, the filtration properties did not change with the salt concentration. We concluded that a compact conformation of the amphiphilic polyionic segments in the membrane causes stable filtration properties.     

A liquid derivative of 12-tungstophosphoric acid with unusually high conductivity

Surface functionalization of the solid heteropolyacid H3PW12O40 with a bulky PEG-containing quaternary ammonium cation through partial proton exchange leads to a polyoxometalate-based liquid salt with high-temperature proton conductivity ( approximately 10-3 S cm-1 at 140 degrees C) under dry conditions. The proton conductivity of the liquid salt is 4 orders of magnitude higher than that of the solid analogue under identical conditions and shows super ionic behavior as defined by Walden plot.     

基于辛可宁的几种手性季铵盐的合成及对查尔酮的催化不对称环氧化

手性相转移催化剂;合成;醚化;不对称环氧化;查尔酮     

Task-specific ionic liquid as base, ligand and reaction medium for the palladium-catalyzed Heck reaction

A novel ionic liquid, which was based on ethanolamine-functionalized quaternary ammonium salt was designed and synthesized. 4-Di(hydroxyethyl)aminobutyl tributylammonium bromide (DHEABTBAB) 1, a task-specific ionic liquid, which acts as a base, ligand and reaction medium, exhibits a very high activity and recyclability to palladium-catalyzed Heck reaction. The olefinations of iodoarenes, bromoarenes and chloroarenes with olefins generated the corresponding cross-coupling products in good to excellent yields only in the presence of DHEABTBAB and palladium acetate under phosphine-free reaction conditions. It is noteworthy that palladium and DHEABTBAB could be repeatedly recycled and reused for six consecutive trials without significant loss of their activities.     

Properties of the Nanoscale Hydrophilic Cationic Pigment Based on Quaternary Surfactant

Dispersions of four nanoscale hydrophilic cationic pigments were prepared by micro jet milling process, in which the dodecyl trimethyl ammonium chloride (DTAC), tetradecyl trimethyl ammonium chloride (TDAC), hexadecyl trimethyl ammonium chloride (CTAC), and octadecyl trimethyl ammonium chloride (STAC) were used as the dispersers respectively. Zeta potential, particle size, viscosity and dispersion stability were tested. The effect of the hydrophobic chain of cationic quaternary surfactant on pigment dispersion's properties was discussed. The results showed that good dispersion effects were obtained when the hydrophobic chain were 14 or 16.     

The role of cationic monomers in emulsion polymerization

[2-(methacryloyloxy)ethyl] trimethylammonium chloride (MATMAC), and vinylbenzyl trimethyl ammonium chloride (VBTMAC) were chosen to be used as ionic comonomers in the emulsion polymerization of styrene. The cationic nature of the two comonomers is the same (quaternary ammonium salts), however the styrene derivate (VBTMAC) is more hydrophobic than the methacrylic one (MATMAC). With the more hydrophobic cationic comonomer (VBTMAC) higher conversions were obtained due to the in situ creation of an amphiphilic copolymer with styrene and faster rates of polymerization were observed by increasing the cationic comonomer concentration. The same behavior was observed with the more hydrophilic cationic comonomer (MATMAC) at concentrations up to 0.012 M. At higher concentrations the ionic strength controls the colloidal stability of the system and coagulation occurs.     

Molecular dynamics simulation of the ionic liquid N-ethyl-N,N-dimethyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide

Thermodynamics, structure, and dynamics of an ionic liquid based on a quaternary ammonium salt with ether side chain, namely, N-ethyl-N,N-dimethyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide, MOENM2E TFSI, are investigated by molecular dynamics (MD) simulations. Average density and configurational energy of simulated MOENM2E TFSI are interpreted with models that take into account empirical ionic volumes. A throughout comparison of the equilibrium structure of MOENM2E TFSI with previous results for the more common ionic liquids based on imidazolium cations is provided. Several time correlation functions are used to reveal the microscopic dynamics of MOENM2E TFSI. Structural relaxation is discussed by the calculation of simultaneous space-time correlation functions. Temperature effects on transport coefficients (diffusion, conductivity, and viscosity) are investigated. The ratio between the actual conductivity and the estimate from ionic diffusion by the Nernst-Einstein equation indicates that correlated motion of neighboring ions in MOENM2E TFSI is similar to imidazolium ionic liquids. In line with experiment, Walden plot of conductivity and viscosity indicates that simulated MOENM2E TFSI should be classified as a poor ionic liquid.     

Polymerization of methylmethacrylate with cetyl benzyl dimethyl ammonium chloride and benzoyl peroxide as redox initiator system

Polymerization of methylmethacrylate was studied using benzoyl peroxide and cetyl benzyl dimethyl ammonium chloride (CBDAC) combination as the redox initiator at 40°. Equilibrium complexation between the redox components precedes the radical generation process, and the complex acts as the actual initiating species. Initiator exponent was 0.5 under various conditions of homogeneous polymerization. Kinetics of polymerization in diluted systems were variable in respect of order with respect to monomer depending on the nature of the solvent or additive. DMF, acetonitrile and pyridine produced rate enhancing effects through actively influencing the initiation step; cyclohexanone, acetone, chloroform, methanol and benzene behaved as (normal) inert diluents, while formamide and acetamide produced retardation. Termination of polymerization occurred exclusively bimolecularly. As a redox component, the quaternary chloride salt, CBDAC behaved somewhat differently from quaternary bromide salts cetyl trimethyl ammonium bromide and cetyl pyridinium bromide.