Synthesis and Characterization of Dual Acidic Ionic Liquids

Novel ionic liquids with dual acidity, of which the cation contains Brφnsted acidity and anions contain Lewis acidity were synthesized. These ionic liquids obtained were identified by NMR, FF-IR, SDT and FAB-MS. Their acidities were determined by pyridine probe on IR spectrography.     

Sorption/diffusion behaviour of anionic surfactants in polyacrylamide hydrogels: from experiment to modelling

The sorption and diffusion processes of anionic surfactants with different chain length through polyacrylamide hydrogels with low swelling degree have been studied by electrical conductivity measurements. The multicomponent equilibrium equation has been used to model the sorption isotherms of different anionic surfactant in the hydrogels. Such isotherms show that initial rapid sorption of unimer surfactant into the membranes occurs, suggesting that non-freezing water can be involved in these interactions. In aqueous solution, at concentrations near and above the critical micelle concentration an anti-co-operative region is found. The diffusion coefficients of the anionic surfactants inside the hydrogel matrix show that the mobility of diffusing surfactant entities is dependent on cross-linker concentration and chain length. The Cukier hydrodynamic model and the free volume theory as modified by Peppas and Reinhart were applied to explain the dependence of the diffusion coefficients of surfactant on surfactant concentration inside the hydrogel. The hydrodynamic model was applied with success to the more hydrophilic surfactant, sodium 1-octanesulfonate, showing that the diffusion coefficients, D, increase when the resistance to hydrodynamic medium decreases; when the surfactant chain length increases (sodium dodecyl sulfate and sodium 1-hexadecane sulphonate) the variation of D with the free volume can only be understood considering the sieving effect produced by the surfactant inside gel.     

<Emphasis Type="Italic">Brønsted</Emphasis> Acids in Ionic Liquids: Fundamentals,Organic Reactions,and Comparisons

Summary. A background for studying acids in various solvents is developed, emphasizing the importance of knowing to what extent a solvent conducts electricity and is therefore ionized, the dissociation equilibria of common molecular solvents and the acidic and basic species generated by solvent leveling. Acidity measurements in the atypical solvent water are discussed and the common method of expressing acidity in other systems – by Hammett values – is introduced. Representative examples of reactions involving Br?nsted acids in ionic liquids are presented and attention paid to the questions of speciation and acidity values. It is found that the gas phase proton affinity of a base is often a better guide to the acidity of its conjugate acid in an ionic liquid than is the dissociation constant of the said acid in water.     

羧基丙烯酸酯涂料合成及其防雾性能研究

采用种子乳液聚合法合成了一种互穿网络型羧基丙烯酸酯类聚物乳液，研究了加料方式对羧基分布的影响，结果表明丙烯酸加入到核单体中有利于羧基分布在乳胶粒表面。在体系中引入离子键交联结构提高了乳液涂料的硬度和耐水性能，离子键交联ＰＩＬＮ型涂料具有优良的防雾性能。     

用于锂离子电池的凝胶聚合物电解质的制备与性能

以丙烯腈(AN)、丙烯酸甲酯(MA)和衣康酸锂(IALi)为自由基共聚反应的主要单体, 采用溶液聚合方法, 合成轻度交联的P(AN-MA-IALi)聚合物电解质膜.通过FTIR, DSC和SEM等测试方法对共聚物的结构进行了表征, 利用交流阻抗等电化学方法对该膜的导电性能进行了研究.实验结果表明, 所制备的交联聚合物的室温电导率达到10-5~10-4 S/cm, 当IALi的质量分数为3%时, 所制备的聚合物电解质膜的电导率最大可达到1.89×10-4 S/cm.     

Electrical conductivities of halide salts in aqueous formamide solutions

The electrical conductivities of sodium chloride and sodium iodide solutions in formamide-water mixtures of different composition have been measured at 25°C. From these data, the limiting equivalent conductances for these salts have been determined. The correspondingWalden products are compared together with the one reported for sodium bromide in the same solvent mixtures, and they are analysed as functions of the anion size. Further, the limiting ionic equivalent conductances are estimated for the different ions. The variation of the ionicWalden products with solvent composition is discussed in terms of ionic solvation and solvent structure.

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Elektrische Leitfähigkeit von Halogensalzen in wäßrigen Formamid-Lösungen

Zusammenfassung Es wurden die elektrischen Leitfähigkeiten von Natriumchlorid- und Natriumjodidlösungen in Formamid-Wasser-Mischungen verschiedener Zusammensetzung bei 25°C gemessen. Aus diesen Daten wurden die Grenzäquivalenzleitfähigkeiten für diese Salze bestimmt. Die entsprechendenWalden-Produkte wurden mit den für Natriumbromid in den gleichen Lösungsmittelgemischen berichteten verglichen und hinsichtlich der Anionengrößen analysiert. Außerdem wurden die ionischen Grenzäquivalenzleitfähigkeiten für die einzelnen Ionen abgeschätzt. Die Variation der ionischenWalden-Produkte mit der Lösungsmittelzusammensetzung wurde bezüglich Ionensolvatation und Lösungsmittelstruktur diskutiert.

     

A Bloembergen–Purcell–Pound <Superscript>13</Superscript>C NMR relaxation study of the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate

The molecular structure and rotational motion of the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]) were studied over a wide temperature range using the Bloembergen–Purcell–Pound ¹³C NMR spin–lattice relaxation method and NOE factors. Examination of the spin–lattice relaxation times (T ₁) and the rates (R ₁=1/T ₁) of the 1-butyl-3-methylimidazolium cation reveals the relative motions of each carbon in the imidazolium cation. The rotational characteristics of the [BMIM] cation are supported by ab-initio molecular structures of [BMIM][PF6] using density functional theory (DFT) and Hartree–Fock (HF) methods. The ab-initio gas phase structures of [BMIM][PF6] indicate that the 1-butyl-3-methylimidazolium C2 hydrogen, the ring methyl group, and the butyl side-chain hydrogen atoms form hydrogen bonds with the hexafluorophosphate anion.     

Olefin metathesis in room temperature ionic liquids using imidazolium-tagged ruthenium complexes

New recyclable imidazolium-tagged ruthenium catalysts have been developed to perform olefin metathesis in room temperature ionic liquids (RTILs). High level of recyclability combined with a high reactivity were obtained in the ring-closing metathesis (RCM) of a variety of di- or tri-substituted and/or oxygen-containing dienes. Extremely low residual ruthenium levels were detected in the RCM products (average of 7.3 ppm per run). Several examples of olefin cross-metathesis (CM) have been also studied.     

POE incorporation into ionic clusters of ionomer and ion-conduction behaviors

Poly(oxyethylene) (POE) was incorporated into the ionic clusters of ionomers, ethylene and methacrylic acid (7.2% neutralized with KOH) copolymer membrane. The changes of properties were studied from SAXS, DSC, IR and ionic conductivity. The IR study suggested that the coordinated structures in ionic clusters of the membrane were destroyed by POE incorporation, and also SAXS suggested that ionic clusters were swollen by POE incorporation. The ionic conductivity, a carrier being K⁺ in this system, increases from 10^?16 S/cm to 10^?9 S/cm at 30°C by the incorporation of POE (20.5 wt%). On the other hand, a large amount of POE (63 wt%) could be incorporated into ionomer membrane by the esterification of methacrylic acid groups (93%) with POE. When LiClO₄ was added, ionic conduction occurred in the phase-separated POE domain, which had a low glass transition temperature (?55.2°C), showing an ionic conductivity 2.6 × 10^?6 S/cm at 25°C.     

Electrochemical Study of Indium in a Water‐Stable 1‐Ethyl‐3‐Methylimidazolium Chloride/Tetrafluoroborate Room Temperature Ionic Liquid

The electrochemistry of indium species was investigated at glassy carbon, tungsten and nickel electrodes in a basic 1‐ethyl‐3‐methylimidazolium chloride/tetrafluoroborate ionic liquid. Amperometric titration experiments suggest that In(III) chloride is complexed as [InCl₅]^2? in this ionic liquid. The electrochemical reduction of [InCl₅]^2? to indium metal is preceded by overpotential driven nucleations. The effective anodic dissolution of indium to indium(III) requires, however, the presence of sufficient chloride ions at the electrode surface. The electrodeposition of indium at glassy carbon and tungsten electrodes proceeds via three‐dimensional instantaneous nucleation with diffusion‐controlled growth of the nuclei. At the nickel electrode, the deposition proceeds via three‐dimensional progressive nucleation with diffusion‐controlled growth of the nuclei. Raising the deposition temperature decreases the average radius of the individual nuclei, r. Scanning electron microscopic and x‐ray diffraction data indicated that bulk crystalline indium electrodeposits could be prepared on nickel substrates within a temperature range between 30 and 120 °C.