Application of Et3NHCl-AlCl3 ionic liquid as an initiator in cationic copolymerization of 1,3-pentadiene with styrene

Cationic copolymerization of 1,3-pentadiene (PD) with styrene (St) using the triethylamine hydrochloride-aluminium chloride (Et₃NHCl-AlCl₃) room temperature ionic liquid as an initiator in toluene has been investigated. The polymerization proceeds to high conversions, indicating high initiating reactivity of Et₃NHCl-AlCl₃ in these copolymerization systems, although molecular weights of the polymers are limited which are similar to polymerization initiated by Lewis acids such as TiCl₄, BF₃, BF₃·OEt₂. The polymers were analyzed using IR spectra in conjunction with gel permeation chromatography (GPC).     

室温离子液体中的聚合反应

综述了近年来在室温离子液体中聚合反应的研究进展,特别是在配位聚合、自由基聚合、离子聚合及共聚反应,活性自由基聚合,电化学聚合等方面的进展情况;还介绍了离子液体在高分子材料方面的应用情况,展望了离子液体在该领域的应用前景.     

Synthesis and Esterification of 3‐Ferrocenyl Acrylic Acid in Ionic Liquid

3‐Ferrocenyl acrylic acid, synthesized from ferrocenecarboxaldehyde and propandioic acid in water‐insoluble ionic liquid (1‐butyl‐3‐methylimidazolium hexafluorophosphate, [BMIM]PF₆) at 85 °C in high yield, was transformed to a series of 3‐ferrocenyl acrylate of alcohols and phenols in water‐soluble ionic liquid (1,3‐dimethylimidazolium dimethylphosphate, [DMIM]Me₂PO₄) at room temperature in the presence of dicyclohexylcarbodiimide (DCC) and 4‐dimethylaminopyridine (DMAP).     

过渡金属离子液体EMIFeCl3的性质研究

在干燥高纯氩气氛的手套箱内, 直接将摩尔比为1∶1的高纯无水FeCl3与氯化1-甲基-3-乙基咪唑(EMIC)混合, 得到棕色透明的离子液体EMIFeCl4. 在293.15~343.15 K温度范围内测定了该离子液体的密度和表面张力. 利用Glasser经验方程和空隙模型研究了EMIFeCl4的性质, 并与离子液体EMIAlCl4进行比较, 指出空隙模型具有一定的合理性.     

3-甲基噻吩在离子液体 BMIMPF6中的电化学聚合、表征及应用

Poly-3-methylthiophene （P3MT） was synthesized in the room temperature ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate （[BMIM]PF6） by constant potential and constant current respectively. The structure and morphology of P3MT films were characterized by FTIR spectrum and SEM. The undoped （reduction） and doped （oxidation） forms of P3MT film prepared in ionic liquid were reversible and stable. The P3MT film has strong characteristics of electrocatalytic oxidation of ascorbic acid and can separate the oxidation peaks of ascorbic acid and dopamine. Two methods of potential steps were used to observe the response time of the film and the film was found to have perfect electrochromic response.     

稀散金属室温离子液体BMIInCl4的性质研究

在干燥高纯氩气氛的手套箱内,直接将摩尔比为1∶1的高纯无水InCl₃与氯化1-甲基-3-丁基咪唑(BM IC l)混合,得到无色透明的离子液体BM IInCl₄.在278.15-343.15 K温度范围内测定了该离子液体的密度和表面张力.利用G lasser经验方程和空隙模型讨论了BM IInCl₄的性质,并与离子液体BMIAlCl₄作了比较,证明了空隙模型具有一定的合理性.     

Characterization of PVdF(HFP) gel electrolytes based on 1-(2-Hydroxyethyl)-3-methyl imidazolium ionic liquids

Poly(vinylidenefluoride)-hexafluoropropylene (PVdF(HFP))-ionic liquid gel electrolytes were prepared using ionic liquids based on 1-(2-hydroxyethyl)-3-methyl imidazolium tetrafluoroborate and 1-(2-hydroxyethyl)-3-methyl imidazolium hexafluorophosphate. A conventional metathesis reaction was used to prepare these ionic liquids, which have high purity and exhibit a liquid state at room temperature. The prepared polymer-ionic liquid gel proved to be a free-standing and rubbery film in which the degree of transparency differed according to the ratio and type of ionic liquid used. TGA and FTIR analyses confirmed that the solvent, N,N-Dimethylacetamide (DMAC), used for mixing PVdF(HFP) polymer with ionic liquid was almost totally removed during the gelling and drying processes. SEM photographs were taken of the surface structure of the PVdF(HFP)-ionic liquid gel in order to evaluate the morphology of the film's surface according to the mixing ratio and the nature of the ionic liquid. The thermal behaviors of PVdF(HFP)-ionic liquid gels were observed to be similar to those of neat ionic liquids through DSC analysis, and the compatibility between the polymer and ionic liquid was investigated by XRD analysis. The ionic conductivities of all the gels were 10(-3)-10(-5) S cm(-1) in a temperature range of 20-70 degrees C.     

离子液体中聚3-己基噻吩的制备及电致变色性质和器件的研究

以室温离子液体1-丁基-3-甲基咪唑六氟磷酸盐[BMIM]PF₆为溶剂及支持电解质,通过电化学方法制备聚(3-己基噻吩)(PHexT)膜。采用循环伏安法和扫描电子显微镜,对膜的电化学性质及形貌结构进行表征。同时通过紫外可见光谱、计时电流、计时库仑以及计时吸收曲线等方法研究聚合物膜的光谱电化学和电致变色特性,并在此基础上制备PHexT膜的电致变色器件。实验结果表明,在离子液体中制备的PHexT膜光滑致密,掺杂态时为蓝色,脱掺杂时为桔红色,并且具有高的颜色对比度 (40%),较短的响应时间 (2.5 s) 和高的电致变色着色效率 (230cm²/C),该膜制成的固态电致变色器件具有很好的电致变色性能和长的循环寿命。     

Studies on the properties of ionic liquid BMIInCl4

An ionic liquid (IL) was prepared by directly mixing InCl₃ and 1-methyl-3-butylimidazolium chloride(BMIC) with molar ratio 1:1 under dry argon atmosphere. The densities, and surface tension of pure IL were determined at temperature range of (278.15 to 343.15±0.1K). The properties for ionic liquid based on group III were discussed using Glasser’s theory. The standard entropy, the surface energy and the crystal energy of ionic liquid were calculated, respectively. The crystal energy of ionic liquid is much lower than ionic solid and this is the underlying reason for forming ionic liquid at room temperature. In addition, a new theoretical model of IL, that is interstice model, was applied to calculate the thermal expansion coefficient of BMIInCl₄. The order of magnitude for the thermal expansion coefficient, a, calculated by the theoretical model is in good agreement with experimental value. The result shows that there is much reasonableness for the interstice model of ionic liquid. __________ Translated from Chemical Journal of Chinese University, 2005, 26(10)(in Chinese)     

溴代1-己基-3-甲基咪唑离子液体与丙酮的相互作用

1H and 13C NMR chemical shifts were determined to investigate the interactions of acetone with a room temperature ionic liquid 1-hexyl-3- methylimidazolium bromide C6mimBr at various mole fractions. Changes in chemical shifts of hydrogen nuclei and of carbon nuclei with the acetone concentration indicated the formation of hydrogen bond between anion of the ionic liquid and methyl protons of acetone. The NMR results were in good agreement with the ab initio computational results.     

3D topography design of membranes for enhanced mass transport

This work describes the process of fabrication of 3D topography membranes and the fully quantitative characterisation of their topography using atomic force microscopy (AFM), small-angle light scattering (SALS), scanning electron microscopy (SEM) and polarizing optical microscopy (POM). The use of these membranes and the impact of the 3D membrane topography on the enhancement of mass transport during solute recovery (hexyl acetate) from a viscous room temperature ionic liquid 1-n-butyl-3-methyl-imidazolium tetrafluoroborate ([C₄mim] [BF₄]) by organophilic pervaporation is presented and discussed.     

Deep extractive desulfurization of diesel fuels by FeCl3/ionic liquids

The extractive desulfurization of dibenzothiophene（DBT）,benzothiophene（BT）,and 4,6-dimethyldi-benzothiophene （4,6-DMDBT） in model oil was carried out using anhydrous FeCl₃ and 1-methyl-3-octylimidazolium chloride system（[Omim|Cl·2FeCl₃）.This new system exhibited high extractive efficiency and the sulfur removal of DBT in model oil(V_IL/V_oil=1/20) could reach 99.4%at room temperature for 30 min,which was obviously superior to single[Omim]Cl as extractant（22.9%）.When the[Omim|CI·2FeCl₃ was used,the S-removal of 4,6-DMDBT and BT could also be up to 99.3%and 96.2%, respectively.Moreover,the ionic liquid could be recycled five times without a significant decrease in extractive ability.     

离子液体AlCl3/Et3NHCl中电沉积法制备金属铝

在AlCl3/Et3NHCl型离子液体中铝电极上通过恒电位电解沉积制备出金属铝. 测定了不同摩尔比的AlCl3/Et3NHCl离子液体在不同温度下的电导率, 考察了离子液体AlCl3/Et3NHCl摩尔比为2/1中Al电极上铝沉积的晶核成核过程, 以及恒电位电解沉积铝的工艺条件对电流效率和沉积铝表面形貌的影响. 结果表明, 不同比例AlCl3/Et3NHCl离子液体的电导率随温度升高而升高, 符合Arrhenius规律; 在Al电极上铝沉积的成核机理为三维瞬时成核过程; 恒电位电解沉积结果表明, 室温下在电位-2.4 V(vs Pt)和电解时间20 min条件下, 沉积铝的表面形貌比较平整致密,电流效率达73%, 沉积铝的纯度达96%(w).     

Reference Electrode for Ionic Liquids

Reference electrodes for room temperature ionic liquid (RTIL) applications were constructed that have a known and reproducible potential versus the ferrocene/ferrocenium couple. They are based on reference electrodes of the first kind, Ag/Ag⁺ couple type, or of the second kind, based on Ag/AgCl in M⁺Cl^?. The former uses AgNO₃ salt and the latter tetrabutylammonium chloride, Bu₄NCl, dissolved in acetonitrile which are then introduced to the ionic liquid of choice for a final concentration of 0.1 M. The reference electrodes can be easily and reproducibly constructed. An ionic contact of these reference systems with the test electrolyte was made using an asbestos fiber liquid junction. The internal compartment of the reference system was filled with the same ionic liquid as used for the electrochemical experiment. The performance of these reference electrodes was tested in selected ionic liquids using the ferrocene/ferrocenium redox couple. The stability, reproducibility, and temperature behavior of the two reference systems have been characterized in the following ionic liquids: 1‐butyl‐3‐methylimidazolium tetrafluoroborate (BMIBF₄), 1‐butyl‐3‐methylimidazolium bis(trifluoromethanesulfonyl)imide (BMI(CF₃SO₂)₂N), and 1‐butyl‐3‐methylimidazolium hexafluorophosphate (BMIPF₆). It has been found that the formal potentials of the examined reference systems are stable over several days. There is a linear relationship for the temperature studied in the range from 25 to 60 °C.     

不同离子液体中三氯化铁的电化学行为

本文采用循环伏安法研究了FeCl3在五种不同的离子液体(包括疏水性和亲水性的离子液体)中的电化学行为,计算了不同离子液体中FeCl4的扩散系数.实验结果表明:Fe3+在离子液体中的氧化还原过程是一个具有较高可逆性的扩散控制过程.离子液体的阴、阳离子的结构及大小对Fe3+的电化学响应有影响,且离子液体的阴离子的影响较阳离子更大一些.     

铝基离子液体BMIAlCl4的热力学性质

在高纯氩气氛下, 直接将摩尔比为1:1的高纯无水AlCl₃和BMIC(氯化1-甲基-3-丁基咪唑)搅拌混合, 得到一种无色透明的离子液体BMIAlCl₄. 在278.2～343.2 K范围内, 用最大气泡法测定了BMIAlCl₄的表面张力, 用Westphal天平法测定了该离子液体的密度；利用Glasser经验方程讨论了该离子液体的热力学性质, 并与其它离子液体作了比较. 根据空隙模型计算了BMIAlCl₄离子液体的恒压热膨胀系数, 与本文实验值基本一致, 说明空隙模型具有一定的合理性.     

Statistical radical copolymerization of styrene and methyl methacrylate in a room temperature ionic liquid

Use of a room temperature ionic liquid as the medium for conventional free radical copolymerization of styrene and methyl methacrylate resulted in reactivity ratios that were significantly different from those obtained in conventional organic solvents or in bulk, demonstrating that polymerization in this alternative medium offers potential to create copolymers having new monomer sequences.     

细菌纤维素在室温离子液体中的溶解性能

研究了细菌纤维素(BC)在绿色溶剂1-烯丙基-3-甲基氯代咪唑室温离子液体中的溶解行为,通过偏光显微镜观察了BC在此离子液体中的溶解过程,热失重(TGA)和红外光谱(FT-IR)测试了再生前后BC的性能,探索了BC在离子液体中溶解、再生的可能性和可行性.结果表明:离子液体是BC的优良溶剂,对BC的溶解属于直接溶解,不发生其他的衍生化反应;再生后BC的热稳定性变好,且离子液体可回收利用.     

室温离子液体FeCl3-BPC体系的研究

利用差示扫描量热法(DSC)建立了无水三氯化铁和氯化正丁基吡啶(BPC)二元体系相图. 依据相图, FeCl₃和BPC形成室温离子液体的窗口是x＝0.26～0.58; 室温离子液体的深度是80 ℃. 利用UHF/6-31G^*对FeCl₃, FeCl₄^－, Fe₂Cl₇^－等配合物的几何结构、键长、能量和Raman频率进行优化, 从头算和Raman光谱证实了相图中FeCl₃摩尔分数x＝0.50处有稳定化合物存在, FeCl₄^－是主要阴离子; x＝0.67处, FeCl₄^－, Fe₂Cl₇^－是主要阴离子.     

Living/controlled radical copolymerization of N‐substituted maleimides with styrene in 1‐butyl‐3‐methylimidazolium hexafluorophosphate and anisole

The atom transfer radical copolymerization of N‐substituted maleimides such as N‐phenylmaleimide (PhMI), N‐cyclohexylmaleimide (ChMI), and N‐butylmaleimide (NBMI) with styrene initiated with dendritic polyarylether 2‐bromoisobutyrates in an ionic liquid, 1‐butyl‐3‐methylimidazolium hexafluorophosphate ([bmim][PF₆]), at room temperature and anisole at 110 °C was investigated. The dendritic‐linear block copolymers obtained in ionic liquid possessed well‐defined molecular weight and low polydispersity (1.05 < M_w/M_n < 1.32) and could be used as a macroinitiator for chain‐extension polymerization, suggesting the living nature of the reaction system. The ionic liquids containing catalyst could be recycled in the atom transfer radical polymerization systems without further treatment. Compared with polymerization conducted in anisole, the polymerization in ionic liquid had a stronger tendency for alternation. The tendency for alternation decreased in the order PhMI > NBMI > ChMI in [bmim][PF₆] and PhMI > ChMI > NBMI in anisole. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2156–2165, 2003