DESIGN AND SYNTHESIS OF NOVEL CHIRAL IONIC LIQUIDS AND THEIR APPLICATION IN FREE RADICAL POLYMERIZATION OF METHYL METHACRYLATE

Two new chiral ionic liquids, 1 -((-)-menthoxycarbonylmethylene)-3-methylimidazolium hexafluorophosphateand 1-((-)-menthoxycarbonylmethylene)-3-hexadecylimidazolium hexafluorophosphate, were designed an d prepared. Theirchemical structures were characterized by ~1H-NMR. Reverse atom transfer radical polymerization of methyl methacrylate(MMA) in these two ionic liquids was carried out using AIBN/CuCl_2/bipy as the initiating system. The resultant well-definedpolymethyl methacrylate (PMMA) was employed as a macroinitiator to induce the atom transfer radical polymerization ofmenthyl methacrylate (MnMA) in chlorobenzene, which yielded a PMMA-b-PMnMA diblock copolymer with narrow polydispersity.

Synthesis and Physicochemical Properties of L-(+)-a-(Positive Butyl)-Leucine Ethyl Ester Chiral Ionic Liquids

L-（＋）-α-（positive butyl）-leucine ethyl ester bromide chiral ionic liquid was synthesized by using microwave-assisted synthesis method and L-（＋）-α-（positive butyl）-leucine ethyl ester terafluoroborate and hexafluorophosphate chiral ionic liquids were synthesized by the anion exchange reaction. The structures were characterized by IR, ~1HNMR and structure optimization calculation. The results of studies on physicochemical properties show that they possess better thermal stability, solubility, bio-solubility and high conductivity. They can serve as effective reaction media as well as chiral catalysts. They are presently being investigated as dispersion agents in molecular imprinting ployer.

Novel N-methylimidazolium Chiral Ionic Liquids with Esterfunction Functionality in Cation

Using （S）-（-）-2-chloropropionie acid ethyl ester and N-methylimidazole as raw materials, we designed and synthesized three N-methylimidazolium chiral ionic liquids by the nucleophilic substitution reaction or anion exchange reaction. These chiral ionic liquids structures were analyzed with structure optimization calculation, IR, and HNMR. Their reaction mechanism and physical chemistry properties were explored. As a result, these chiral ionic liquids possess optical activity, low melting point, high conductivity, and weak acidity, etc. They can serve as effective reaction media as well as chiral catalysts. They are presently being investigated as dispersion agent in molecular imDrinting, nlover in our laboratory.

Stereoselective Photochemical Reaction of Cyclohexyl Phenyl Ketone within Lytropic Liquid Crystals Formed by Chiral Ionic Liquids

Irradiation of cyclohexyl phenyl ketone （1） results in either intra- or intermolecular hydrogen abstraction to af- ford compounds 1-phenylhept-6-en-l-one （2） and a-cyclohexyl benzyl alcohol （3） as photoproducts, in which 3 has a pair of enantiomers. Herein, two types of chiral hexagonal liquid crystals were prepared to direct the enantioselec- tive photochemical reaction of 1. One of the hexagonal liquid crystals is composed of 1-tetradecyl-3-methyl- imidazolium bromide/p-xylene/H2O with the modification by a chiral inductor. The other one is formed by chiral （S）-3-hexadecyl-1-（1-hydroxy-propan-2-yl）-imidazolium bromide/p-xylene/H2O. The product analysis shows that the latter one can be used as a microreactor to achieve stereoselective photochemical reaction, while the former one produced compound 3 with no enantioselectivity at all.

Measurement and correlation of supercritical CO_(2) and ionic liquid systems for design of advanced unit operations

Ionic liquids combined with supercriticalfluid technology hold great promise as working solvents for developing compact processes.Ionic liquids,which are organic molten salts,typically have extremely low volatility and high functionality,but possess high viscos-ities,surface tensions and low diffusion coefficients,which can limit their applicability.CO_(2),on the other hand,especially in its supercritical state,is a green solvent that can be used advantageously when combined with the ionic liquid to provide viscosity and surface tension reduction and to promote mass transfer.The solubility of CO_(2) in the ionic liquid is key to estimating the important physical properties that include partition coefficients,viscosities,densities,interfacial tensions,thermal conductivities and heat capacities needed in contactor design.In this work,we examine a subset of available high pressure pure component ionic liquid PVT data and high pressure CO_(2)-ionic liquid solubility data and report new correlations for CO_(2)-ionic liquid systems with equations of state that have some industrial applications including:(1)general,(2)fuel desulfurization,(3)CO_(2) capture,and(4)chiral separation.New measurements of solubility data for the CO_(2) and 1-butyl-3-methylimidazolium octyl sulfate,[bmim][OcSO4]system are reported and correlated.In the correlation of the CO_(2) ionic liquid phase behavior,the Peng-Robinson and the Sanchez-Lacombe equations of state were considered and are compared.It is shown that excellent correlation of CO_(2) solubility can be obtained with either equation and they share some common characteristics regarding inter-action parameters.In the Sanchez-Lacombe equation,parameters that are derived from the supercritical region were found to be important for obtaining good correlation of the CO_(2)-ionic liquid solubility data.