Synthesis and application of ammonium-based poly(ionic liquids) as novel cationic flocculants

The efficient and environmentally friendly method for preparation of novel flocculants using ILs with non-toxic anions are presented. Poly(ionic liquids) (PILs) were prepared by the photopolymerization of polymerizable ILs. All monomers were obtained via anion exchange reaction. Additionally, the polymers were fully characterized by ¹H NMR and FTIR spectroscopy, thermal analysis and gel permeation chromatography. Furthermore, these cationic polymers containing harmless anions were used as flocculants. The efficiency was tested using the yeast suspension as a model system of negatively charged particles. The synthesized water-soluble PILs exhibited high molecular weight and significant flocculation efficiency in the wide range of concentrations. Furthermore, the results of experiments show that flocculation of yeast occurs by charge neutralization and bridging mechanism.     

Synthesis of polymer particles and nanocapsules stabilized with PEO/PPO containing polymerizable surfactants in miniemulsion

We describe the miniemulsion polymerization of vinyl monomers stabilized in the presence of the polymerizable anionic surfactant Tego XP-1008 and the polymerizable nonionic surfactant Tego XP-1007. Different amounts of polymerizable surfactants and various types of initiators were used to investigate the size and the stability of the final latex particles by transmission electron microscopy and dynamic light-scattering measurements. The grafting of the polymerizable surfactants onto the surface of the latex particles was checked by NMR and XPS measurements and was found to be efficient. Finally, polymerizations of appropriate formulations containing divinylbenzene with the polymerizable surfactant Tego XP-1008 in the presence of a larger amount of hydrophobic agent produced nanocapsules.     

离子液体催化CO2与环氧化物合成环状碳酸酯

综述了离子液体催化CO2与环氧化物的环加成反应制备环状碳酸酯的研究进展。目前报道的离子液体主要包括咪唑盐、季铵盐、季鏻盐等。对比了传统离子液体与功能化离子液体对CO2环加成反应的催化活性、选择性以及催化作用机制。与传统的离子液体相比,功能化离子液体的羟基或羧基等官能团与卤素离子等Lewis碱之间存在协同效应,使得其对CO2与环氧化物的环加成反应具有更好的催化活性;将功能化离子液体固载于无机材料(SiO2,SBA-15,MCM-41等)或聚合物所得的多相催化剂不仅保持了官能团与阴离子之间的协同效应,而且载体与离子液体活性组分之间也显示出协同效应,使得该类催化剂具有很好的催化活性,稳定性好,可以多次重复使用,具有较好的工业化前景,是值得深入研发的一类催化材料。此外,离子液体对于手性环状碳酸酯的合成也具有较好的催化活性和立体选择性。     

Geometric Matching Principle for Adsorption Selectivity of Ionic Liquids: A Simple Method into the Fascinating World of Shape‐Controlled Chemistry

Ionic liquids (ILs) possess effective functions in controlling the phase and morphology of nanomaterials. However, it is still unclear how ILs affect the morphology control and what the origin of adsorption selectivity of ILs is on different crystal facets. It is a challenge to develop a simple method to select the suitable kinds of ILs for achieving the controllable synthesis of nanomaterials with designable shape. Herein, density functional theory (DFT) calculations were combined with experiment to study the interaction mechanism between ILs and crystal facets. An important relationship is proposed, named as the geometric matching principle, in which the adsorption site of substrate should not only need to meet the space requirement for interionic stacking of ILs, but also needs to maximize the interaction between adsorbed ILs and substrate. This new finding is meaningful for prediction of the adsorption selectivity of ILs and clarification of their shape‐controlled chemistry.     

Electrodeposition in Ionic Liquids

Due to their attractive physico‐chemical properties, ionic liquids (ILs) are increasingly used as deposition electrolytes. This review summarizes recent advances in electrodeposition in ILs and focuses on its similarities and differences with that in aqueous solutions. The electrodeposition in ILs is divided into direct and template‐assisted deposition. We detail the direct deposition of metals, alloys and semiconductors in five types of ILs, including halometallate ILs, air‐ and water‐stable ILs, deep eutectic solvents (DESs), ILs with metal‐containing cations, and protic ILs. Template‐assisted deposition of nanostructures and macroporous structures in ILs is also presented. The effects of modulating factors such as deposition conditions (current density, current density mode, deposition time, temperature) and electrolyte components (cation, anion, metal salts, additives, water content) on the morphology, compositions, microstructures and properties of the prepared materials are highlighted.     

Basic ionic liquids promoted chemical transformation of CO_2 to organic carbonates

Ionic liquids(ILs), especially basic ILs with unique physicochemical properties, have wide application in catalysis. Using basic ILs as catalysts for the conversion of cheap, abundant, nontoxic, and renewable CO_2 into value-added organic carbonates is highly significant in view of environmental and economic issues. This review aims at giving a detailed overview on the recent advances on basic ILs promoted chemical transformation of CO_2 to cyclic and linear carbonates. The structures of various basic ILs, as well as the basic ILs promoted reactions for the transformation of CO_2 to organic carbonates are discussed in detail,including the reaction conditions, the yields of target products, the catalytic activities of basic ILs and the reaction mechanism.     

马来酸类可聚合乳化剂及其在乳液聚合中应用

使用可聚合乳化剂可以很好地解决传统乳化剂的缺点,提高乳液的应用性能.马来酸类乳化剂其可聚合基团反应活性适中,可以很好地键合在乳胶粒表面上,且更为突出的是这类乳化剂不易发生均聚,而是倾向于与单体发生共聚.研究表明,马来酸类可聚合乳化剂应用到乳液聚合中,可以改善乳胶液的性能,提高乳胶膜的耐水性等.文章介绍了这一类新型的乳化剂,并根据其亲水基团进行了分类,分别介绍其合成路线,总结了马来酸类乳化剂的特点,概述了在常见乳液聚合体系中的应用与研究.     

Basic ionic liquids promoted chemical transformation of CO<Subscript>2</Subscript> to organic carbonates

Ionic liquids (ILs), especially basic ILs with unique physicochemical properties, have wide application in catalysis. Using basic ILs as catalysts for the conversion of cheap, abundant, nontoxic, and renewable CO₂ into value-added organic carbonates is highly significant in view of environmental and economic issues. This review aims at giving a detailed overview on the recent advances on basic ILs promoted chemical transformation of CO₂ to cyclic and linear carbonates. The structures of various basic ILs, as well as the basic ILs promoted reactions for the transformation of CO₂ to organic carbonates are discussed in detail, including the reaction conditions, the yields of target products, the catalytic activities of basic ILs and the reaction mechanism.     

Recent progress in biphasic catalytic systems using ionic liquids

Catalytic reactions in two liquid phases containing ionic liquids (ILs), in which organic reactions proceed in the ILs phase and products are extracted to the other liquid phase, are efficient and environmentally benign. This short review briefly reports the development of catalytic application in biphasic systems containing ILs in the last two years. Recent progress for the functionalization of ILs themselves and combinations of homogeneous and heterogeneous catalysts with ILs are described. Prospects and future challenges are also addressed.     

Formation and tribological properties of two‐component ultrathin ionic liquid films on Si

Several single‐component and two‐component imidazolium ionic liquids (ILs) ultrathin films were formed on Si substrates by a dip‐coating and heat treatment process. The formation and surface properties of the films were analyzed by means of ellipsometric thickness measurement, X‐ray photoelectron spectra and atomic force microscope. The adhesive and nanotribological behaviors of the films were evaluated by a homemade colloidal probe. A ball‐on‐plate tribometer was used to test the microtribological performances of these films. As a result, the two‐component ILs ultrathin film containing 80% solid‐like ILs phase shows more homogenous surface morphologies and optimal micro/nano‐tribological properties as compared to single‐component ILs films, which is ascribed to a synergic effect between the steady solid‐like ILs phase as the backbone and the proper amount of flowable liquid‐like ILs phase. By studying the influence of various solid/liquid ILs ratios on tribological properties of the two‐component ILs films, we might find the way to design ILs films with excellent comprehensive tribological properties. Copyright © 2010 John Wiley & Sons, Ltd.     

Advanced Materials Based on Polymers and Ionic Liquids

Ionic liquids (ILs) are ambient temperature molten salts, which have attracted considerable attention owing to their unique properties. In this contribution, we review advanced materials composed of ILs and polymers for the basis of a new design protocol to fabricate novel materials. As electrolytes for electrochemical devices, cross‐linked polymers containing ILs (ion gels) are endowed with functional properties inherited from ILs and mechanical consistency derived from polymers. To create such materials, micro‐phase separation of block copolymers and colloidal arrays in the ILs are utilized. Based on the molecular design of task‐specific ILs, the resultant ion gels are applicable as electrolytes for actuator, fuel cell, and secondary battery applications. Thermo‐ and photo‐responsive polymers in ILs are also highlighted, whereby such stimuli elicit changes in the solubility of the self‐assembly of block copolymers and colloidal arrays in the ILs. Further, thermo‐ and photo‐reversible changes in the self‐assembled structure can be exploited to demonstrate sol‐gel transitions and fabricate photo‐healable materials.     

Combustible ionic liquids by design: is laboratory safety another ionic liquid myth?

The non-flammability of ionic liquids (ILs) is often highlighted as a safety advantage of ILs over volatile organic compounds (VOCs), but the fact that many ILs are not flammable themselves does not mean that they are safe to use near fire and/or heat sources; a large group of ILs (including commercially available ILs) are combustible due to the nature of their positive heats of formation, oxygen content, and decomposition products.     

离子液体的前沿、进展及应用

离子液体作为一类新型绿色介质,近年来获得了突飞猛进的发展.离子液体的多项应用研究正在进行中试或工业性试验,甚至已经进入产业化阶段.推动离子液体研究迅速发展的直接动力来源于国际社会对清洁生产、环境保护、循环经济的强烈愿望,以及离子液体本身的科学探索价值和巨大的应用潜力.离子液体不仅可替代传统有机溶剂或酸碱成功用作化工反应和分离的新介质,而且展示了作为新型磁性材料、纳微结构功能材料、润滑材料、航空航天推进剂等潜力,甚至有望成为食品和医药.     

Electrochemical Quantification of Hygroscopicity of Ionic Liquids with Solution‐Dissolved Potassium Ferricyanide as the Redox Probe

Quantification of hygroscopicity of ionic liquids (ILs) is of great importance in both fundamental studies and practical applications of ILs. This study demonstrates an electrochemical method for effectively quantifying the hygroscopicity of ILs through electrochemically monitoring water contents absorbed into ILs. The measurements of water content absorbed into the ILs are performed with square wave voltammetry (SWV) based on the water‐induced enhancement of diffusion of solution‐dissolved potassium ferricyanide (K₃Fe(CN)₆) redox probe. For demonstration, two kinds of ILs with different hygroscopicity (i.e., hydrophilic Bmim⁺Gly^? and hydrophobic Bmim⁺PF₆^?) are employed in this study. The dissolution of K₃Fe(CN)₆ redox probe into ILs is found to have little effect on the hygroscopicity of ILs. The hygroscopicity of ILs is thus able to be quantified by monitoring water content absorbed into ILs as a function of time when ILs are stored at room temperature and standard atmospheric pressure under 55 % relative humidity (RH). Under the conditions employed in this study, the hygroscopicity of Bmim⁺Gly^? and Bmim⁺PF₆^? is determined to be 1.33 M per hour and 0.05 M per hour, respectively, which are almost consistent with those measured with Karl Fischer titration under the same conditions. The electrochemical method demonstrated in this study is experimentally simply and environmentally benign and may be potentially extended for general quantification of hygroscopicity of ILs.     

Static dielectric constant of room temperature ionic liquids: internal pressure and cohesive energy density approach

Measurements of the static dielectric constant (epsilon) of ionic liquids (ILs) are very difficult because of the decay of field by the ionic conductivity of ILs. Herein, we describe an easy method for the prediction of epsilon of various imidazolium-based ILs [C_n mim] from n, i.e. the ratio of internal pressure (P_i) and cohesive energy density (ced). A calibration curve of n vs epsilon for conventional organic solvents (mainly the linear alcohols) has been used to estimate the epsilon of the ILs. Estimated epsilon values for ILs having the anions [Cl]-, [BF 4]-, [PF 6]-, [TfO]-, and [Tf 2N]- showed a very good comparison with the literature results, whereas ILs having the anions [C_n OSO3]- tend to deviate from such correlation. Also, for a series of ILs having a common anion, the epsilon is shown to follow a very good correlation with the molecular volumes. Predicted values show that both the nature of the anion and alkyl chain length of the cation contribute significantly to the epsilon of the ILs. The method developed makes use of properties which can be either experimentally determined or estimated with good accuracy and can be extended to the other categories of ILs with ease and reasonable accuracy.     

Influence of Substituents and Functional Groups on the Surface Composition of Ionic Liquids

We have performed a systematic study addressing the surface behavior of a variety of functionalized and non‐functionalized ionic liquids (ILs). From angle‐resolved X‐ray photoelectron spectroscopy, detailed conclusions on the surface enrichment of the functional groups and the molecular orientation of the cations and anions is derived. The systems include imidazolium‐based ILs methylated at the C2 position, a phenyl‐functionalized IL, an alkoxysilane‐functionalized IL, halo‐functionalized ILs, thioether‐functionalized ILs, and amine‐functionalized ILs. The results are compared with the results for corresponding non‐functionalized ILs where available. Generally, enrichment of the functional group at the surface is only observed for systems that have very weak interaction between the functional group and the ionic head groups.     

Preparation of Covalently‐colored Polymer Latex via Batch Emulsion Polymerization

Covalently‐colored polymer latex was synthesized via batch emulsion copolymerization of styrene, butyl acrylate and methacrylic acid in the presence of red polymerizable dye monomer consisting of anthraquinone chromophore, alkyl spacer and acryloyl group, and the influences of the initiator, surfactant and polymerizable dye on the polymerization and the latex properties were investigated. Results showed that the initiator amount was a determinative factor for the monomer conversion, and a high conversion of the polymerizable dye could be achieved when the ammonium persulfate amount was equal to or more than 1 wt% to the total monomers. Most of the chromophores were covalently bonded to the polymer chains if the polymerizable dye was used in the range of 0–1.5 wt%. The light fastness of the resulting latex film was much better than that of the noncovalently‐colored polymer film.     

离子液体在乙烯/乙烷和乙烯/乙炔分离中的应用

乙烯,作为石油化工行业的龙头原料,其高效回收分离具有重要的战略意义。离子液体作为一种结构可调控的新型绿色溶剂,在乙烯的回收分离中展现出巨大的应用前景。本文总结了近年来离子液体在乙烯/乙烷和乙烯/乙炔分离方面的研究进展,从溶剂吸收、膜吸收和与多孔材料相结合的吸附分离法等角度展开,系统地阐述了常规离子液体、功能化离子液体、聚离子液体等纯组分体系及多组分体系在不同分离方法中的研究现状,展望了离子液体在乙烯回收分离方面的应用前景和发展趋势。     

离子液体谱学性质和热力学数据关联的新进展

离子液体的性质是其微观结构和相互作用的外在表现,与其应用密切相关.谱学手段能从分子水平上探测离子液体的微观环境和相互作用,近年来在定量关联或预测离子液体宏观性质方面发挥着越来越重要的作用.本文着重概述了红外光谱(IR)、拉曼光谱(Raman)、核磁共振波谱(NMR)和电子顺磁波谱(ESR)等常见谱学手段在定量关联离子液体及其溶液体系宏观性质方面的研究进展以及发展方向.     

石英晶体微天平技术研究咪唑类离子液体与气体分子的相互作用

基于石英晶体微天平(Quartz Crystal Microbalance, QCM)技术, 建立了一种测定气体在离子液体(ILs)中基本热力学参数的方法. 测定了5种可挥发有机物(VOCs)在6种咪唑类离子液体中的亨利常数, 并对可能的作用机理进行了探讨. 结果表明, QCM技术可以作为研究离子液体溶解性和作用规律的有效方法.