离子液体溴代1-丁基-3-甲基咪唑盐合成的红外光谱分析

本实验建立以红外光谱法,利用特征吸收频率处的红外吸收率测得合成离子液体1-丁基-3-甲基咪唑六氟磷酸盐的中间产物溴代1-丁基-3-甲基咪唑盐的含量,应用于探索1-丁基-3-甲基溴代咪唑盐合成的最佳反应条件,结果表明反应温度为65℃,时间50分钟时产物得率高。     

离子液体溴代1-丁基-3-甲基咪唑盐合成的红外光谱分析

本实验建立以红外光谱法,利用特征吸收频率处的红外吸收率测得合成离子液体1-丁基-3-甲基咪唑六氟磷酸盐的中间产物溴代1-丁基-3-甲基咪唑盐的含量,应用于探索1-丁基-3-甲基溴代咪唑盐合成的最佳反应条件,结果表明反应温度为65℃,时间50分钟时产物得率高.     

微波法合成离子液体1-羟乙基-3-甲基咪唑四氟硼酸盐的研究

由1-甲基咪唑和2-氯乙醇通过微波法合成中间体氯化1-羟乙基-3-甲基咪唑,考察了原料配比、微波功率、加热方式和加热时间对中间体产率的影响。中间体经阴离子交换得到1-羟乙基-3-甲基咪唑四氟硼酸盐离子液体。通过测定中间体的相对分子量分析其纯度,目标产物的结构通过IR1、H-NMR表征。     

1-己基-3-甲基咪唑六氟磷酸盐离子液体的微波辅助合成与结构表征

采用1-溴代己烷和N-甲基咪唑为原料,微波辅助快速合成了溴化1-己基-3-甲基咪唑([HMIM]Br)中间体,此步反应产率可达到95%。通过将中间体和六氟磷酸钾进行离子交换,制备了离子液体1-己基-3-甲基咪唑六氟磷酸盐([HMIM]PF6),产率约为48%。与传统方法相比,反应时间极大地缩短。产物的结构经傅立叶变换红外光谱(FT-IR)、超导脉冲傅立叶变换核磁共振氢谱(1HNMR)和超导脉冲傅立叶变换核磁共振碳谱(13CNMR)确认,纯度经高效液相色谱法(HPLC)分析达到99.0%以上。     

1-丁基-3-甲基咪唑碘对液体、凝胶电解质及染料敏化太阳电池性能的影响

采用季铵化反应成功合成了[Bmim]I，并制备了含有[Bmim]I、KI和I2的离子液体液体电解质和凝胶电解质。通过对比[Bmim]I浓度对液体和凝胶电解质电导率的影响及液体、凝胶电解质DSC的各项光电性能，发现液体电解质有更高的电导率，其组装的DSC的光电性能均高于凝胶电解质体系，通过对DSC稳定性的对比，发现离子液体凝胶电解质显示了更好的长期稳定性。     

烯丙基咪唑离子液体的合成与溶液性能

室温离子液体氯化1-烯丙基-3-甲基咪唑被合成,利用质谱和NMR对其结构进行了表征。该离子液体与水或乙醇的二相混合液在293.2K的粘度被测定并计算了该混合体系的过量粘度,建立了过量粘度与水或乙醇的摩尔分数的关系。另外,电导率随组分及温度的变化以及电导活化能也被测定,溶液的电导率随温度的升高及溶剂量的增加而增大。     

具有离子响应性的聚(1-乙烯基-3-乙基咪唑四氟硼酸盐)@CaO微胶囊的表征及触发释放

采用相分离法合成了具有离子响应性的聚（1-乙烯基-3-乙基咪唑四氟硼酸盐）（PVEIm+BF₄-）@CaO微胶囊。聚离子液体（PILs）的BF₄-与水溶液中的Cl-发生离子交换使疏水性的交联PILs壳转变为亲水性,在水中形成亲水通道。PVEIm+BF₄-@CaO微胶囊内部的CaO从通道被释放到水中形成Ca（OH）₂。PVEIm+BF₄-@CaO微胶囊加入后,NaCl水溶液中Cl-的浓度由8.3 mmolL-1降低至5.8 mmolL-1,pH值由7.00增加至11.83。提高反应物中的离子液体（ILs）的加入量、苯乙烯（St）∶二乙烯基苯（DVB）的质量比或水溶液中Cl-的浓度均可提高PVEIm+BF₄-@CaO微胶囊中CaO的释放速率。不同含量单体组成的微胶囊或被不同浓度Cl-触发的微胶囊内的CaO均可被全部释放至NaCl溶液中。溶液中的最大Ca2+浓度基本一致,约为3.4 mmolL-1。SO₄2-也可触发微胶囊的释放。结果表明,PVEIm+BF₄-@CaO微胶囊对Cl-和SO₄2-具有良好的响应性。加入PVEIm+BF₄-@CaO微胶囊后,NaCl水溶液中Cl-/OH-的浓度比显著降低,有利于提高钢筋的抗Cl-腐蚀能力。      

氨基酸离子液体清洁催化合成阿司匹林

以氨基酸为原料采用一步法合成了3种氨基酸离子液体,将其代替浓H2SO4用于催化乙酸酐和水杨酸的乙酰化反应,清洁合成阿司匹林。考察了离子液体种类及用量、原料配比、反应温度、时间等因素对合成阿司匹林的影响。结果表明,该离子液体对于合成阿司匹林具有良好的催化效果,在水杨酸20mmol、乙酸酐40mmol、谷氨酸硫酸盐离子液体([Glu]HSO4)2mmol、反应温度70℃、反应时间30min的条件下,阿司匹林分离产率可达84.8%。增大投料量,产率还会进一步升高,并且离子液体可重复使用。     

聚酰亚胺在离子液体中的合成与表征

离子液体由于其溶解能力强、不挥发等特点,使其成为良好的绿色溶剂,由于良好的高温稳定性,适用于缩聚反应体系。以常规的芳香族二酐和芳香族二胺为单体,并分别使用不同结构的离子液体为溶剂,进行缩聚反应得到聚酰亚胺。用红外光谱(FT-IR)和核磁共振(13C-NMR)方法证实了在离子液体中所合成的聚酰亚胺与传统合成路线合成的具有相似的化学结构;采用X射线衍射(WAXD)分析了聚合物的聚集态结构,并探讨了不同的离子液体对聚酰亚胺聚集态结构的影响;经热重法(TGA)测试分析,在以离子液体[BMIM]BF4为反应溶剂时,所得聚酰亚胺具有较好的热稳定性能。     

咪唑基离子液体IL-MPEG1000的合成及其对PLA性能的影响

本研究合成了一种含聚乙二醇单甲醚(MPEG1000)结构的咪唑基离子液体(IL-MPEG1000),并采用核磁共振(1 H NMR)对其进行了结构确认。通过熔融共混法制备系列含IL-MPEG1000的聚乳酸(PLA)试样,应用差示扫描量热法(DSC)、热失重测试(TG)、扫描电子显微镜(SEM)研究了IL-MPEG1000对PLA性能的影响。DSC结果表明,IL-MPEG1000促使PLA玻璃化转变温度的降低,并导致PLA试样在升温过程中出现了明显的结晶峰与熔融双峰,说明IL-MPEG1000提高了PLA链段的运动能力。SEM观察到含IL-MPEG1000的PLA试样出现韧断现象,表明IL-MPEG1000起着增韧作用。然而,TG分析表明IL-MPEG1000的加入降低了PLA的热稳定性。     

Direct-on-barrier copper electroplating on ruthenium from the ionic liquid 1-ethyl-3-methylimidazolium dicyanamide

The "direct-on-barrier" electroplating of copper on ruthenium from a 1 mol dm⁻³ solution of CuCl in the ionic liquid 1-ethyl-3-methylimidazolium dicyanamide, [C₂mim][N(CN)₂], is reported. Continuous layers of copper with a preferential Cu(111) orientation were obtained from this electrolyte. The copper coatings were investigated by top view scanning electron microscopy (SEM), X-ray diffraction (XRD), and focused ion beam transmission electron microscopy (FIB-TEM). The nucleation density was both theoretically and experimentally evaluated by the Scharifker-Hills model and transmission electron microscopy, respectively. The direct plating of copper on resistive substrates for advanced interconnects and package is a promising new application of ionic liquids.     

Studies on electrical double layer capacitor with a low-viscosity ionic liquid 1-ethyl-3-methylimidazolium tetracyanoborate as electrolyte

The performance of an electrical double layer capacitor (EDLC) composed of high surface area activated carbon electrodes and a new ionic liquid, 1-ethyl-3-methylimidazolium tetracyanoborate, [EMIm]TCB, as the electrolyte has been investigated by impedance spectroscopy, cyclic voltammetry and galvanostatic charge–discharge studies. The high ionic conductivity (~1·3 × 10^???2 S cm^???1 at 20 °C) and low viscosity (~22 cP) of the ionic liquid, [EMIm]TCB, make it attractive as electrolyte for its use in EDLCs. The optimum capacitance value of 195·5 F g^???1 of activated carbon has been achieved with stable cyclic performance.     

Experimental vibrational study of imidazolium-based ionic liquids: Raman and infrared spectra of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide and 1-ethyl-3-methylimidazolium ethylsulfate

The vibrational structure of two room-temperature ionic liquids with the cation 1-ethyl-3-methylimidazolium [EMIM] and the respective anions bis(trifluoromethylsulfonyl)imide [TFSI] and ethylsulfate [EtOSO(3)] is investigated. In particular, attenuated total reflection (ATR) infrared (IR) as well as Raman spectra in the spectral range from 500 to 3500 cm(-1) have been recorded and analyzed. Moreover, the depolarization ratios of the Raman lines are determined. The individual peaks are assigned to the corresponding vibrational modes of the molecules. While the CH stretching region around 3000 cm(-1) is dominating in Raman spectra, it is remarkably weak in IR spectra. Finally, the results for 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide are compared to previous studies of single ions available in the literature. This comparison shows good agreement.     

Spectroscopic studies of the ionic liquid during the electrodeposition of Al-Ti alloy in 1-ethyl-3-methylimidazolium chloride melt

A new approach for the formation of Al-Ti alloy in 1-ethyl-3-methylimidazolium chloride (EmimCl) was investigated. The dissolution of titanium electrodes in presence of EmimCl:AlCl₃ was performed at various potentials to understand the effect of voltage on the reaction rate. It was observed that at low potentials, the presence of titanium hinders the reaction and diminishes the formation of aluminum and aluminum-titanium alloy at the cathode. However, at higher potentials there was substantial formation of Al₃Ti alloy. To understand the reaction mechanism during the electrolysis, the electrolyte was characterized using Fourier transform infrared spectroscopy (FTIR), UV-visible spectroscopy (UV-vis) and nuclear magnetic resonance (NMR) techniques. The material on the cathode was characterized using scanning electron microscope (SEM) and Energy dispersive X-ray (EDX) techniques. From the above analysis it was found that titanium forms a complex with aluminum and also assists in formation of AlCl₄⁻ phase in the acidic ionic liquid.     

Degradation of 1-butyl-3-methylimidazolium chloride ionic liquid in a Fenton-like system

The study examined the usefulness of a Fenton-like system for the degradation of ionic liquid residues in water. The ionic liquid was oxidized in a dilute aqueous solution of 1-butyl-3-methylimidazolium chloride (bmimCl). The ionic liquid decomposes readily and rapidly in aqueous solution by chemical degradation in a Fenton-like system. Under chosen conditions the initial bmimCl solution was reduced by a factor of 0.973 within 90 min. Additional results showed that bmimCl degradations in a Fenton-like system in excess H2O2 could be interpreted as a combined oxidation-reduction mechanism. Preliminary investigations of the mechanism of such degradations have indicated that initial OH* radicals can attack any one of the three carbon atoms on the imidazolium ring. The intermediates of this reaction may be mono- di- or amino- carboxylic acids.     

新型电解质材料[BMIM]ClO3离子液体的合成及其物化性能

以N-甲基咪唑为原料合成了室温离子液体1-丁基-3-甲基咪唑氯酸盐([BMIM]ClO3),用IR、NMR、DSC-TGA等手段对产物进行了表征,测定了相关物化性能,如密度、表面张力、黏度、电导率和电化学窗口等,并考察了该离子液体的溶剂性能。结果表明,该离子液体作为新型的电解质材料,具有低黏度、高电导率,密度、表面张力、黏度均随温度升高而减小,电导率随温度升高而增大,与温度符合Arrhenius方程。该离子液体与多数常规溶剂互溶,并对某些金属氧化物具有较高的溶解度,为离子液体在选矿、电解金属氧化物等方面的应用奠定了基础。     

Crystal structure and aggregation behavior in water of ionic liquid 1-hexadecyl-3-methylimidazolium Bromide

A large-transparent single crystal of 1-hexadecyl-3-methylimidazolium bromide monohydrate ([C₁₆mim]Br·H₂O) with 4-mm length was firstly obtained in the water-trichloromethane-toluene growth system (V_water:V_{trichloromethane}:V_toluene = 0.1:1:2). The crystal structure was determined by single crystal X-ray diffraction method. It crystallizes in the triclinic system, space group P-1, with unit cell parameters a = 5.4962(15) Å, b = 7.839(2) Å, c = 27.279(8) Å, α = 94.375°(4), β = 91.500°(5), γ = 101.999°(4), Z = 2, V = 1145.2(5)ų, Dc = 1.176 Mg/m³, μ = 1.804 mm^− 1, F(000) = 436, the final R1 = 0.0497, wR2 = 0.1154. The 3D supramolecular structure is constructed through the weak interactions between imidazolium cations, Br⁻ anions and lattice water molecules. The long alkyl chain to imidazolium ring and lattice water molecules play an important role in the self-assembled process. Moreover, it is proposed that [C₁₆mim]Br has the aggregation behavior in water at the higher concentration and the possible self-assembled structure is the interdigitated pattern.     

All-cellulose composites by partial dissolution in the ionic liquid 1-butyl-3-methylimidazolium chloride

Fully bio-based and biodegradable all-cellulose composites were prepared in the form of films by partial dissolution of two cellulose sources: a commercially available microfibrillated cellulose (MFC) and filter paper (FP). The solvent selected for this work was the ionic liquid 1-butyl-3-methylimidazolium chloride ([C₄mim]Cl). Both cellulose sources were partially dissolved at 80 °C and consolidated by partial dissolution, resulting in excellent mechanical properties. X-ray diffraction and electron microscopy demonstrated that partial dissolution was a viable path to transform FP into a continuous paracrystalline matrix reinforced with cellulose I crystallites. In contrast, partially dissolved MFC was not as thoroughly dissolved and large amounts of undissolved material were still visible along the centre line of the films after the longest dissolution times. Consequently, partially dissolved MFC retained its initially high crystallinity. The degree of polymerization of the materials after dissolution was significantly reduced.