Effect of immobilization of titanocene catalyst in aralkyl imidazolium chloroaluminate media on performance of biphasic ethylene polymerization and polyethylene properties

1-(2-Phenylethyl)-3-methylimidazolium and 1-benzyl-3-methylimidazolium chloroaluminates, [Ph-C₂mim][AlCl₄] and [Bzlmim][AlCl₄], were applied as media of the Cp₂TiCl₂ catalyst for biphasic ethylene polymerization. The studied aralkyl ionic liquids ensure greater stability of the catalyst at higher temperatures and more regular morphology of the produced polyethylene than analogous 1-n-alkyl-3-methylimidazolium chloroaluminates. The alkylaluminium compound participates in the termination reaction of the polymer chain. The catalyst is stable and enables recycling of the ionic liquid phase in the consecutive polymerization reactions. The [Ph-C₂mim][AlCl₄] ionic liquid and AlEt₂Cl alkylaluminium compound turned out to be the most suitable for the biphasic process. The influence of the kind of ionic liquid, alkylaluminium compound (AlEt₂Cl and AlEtCl₂), activator/catalyst molar ratio, reaction temperature, reaction time and catalyst recycling on the polymerization performance as well as polyethylene properties such as molecular weight (M _w ), polydispersity, melting temperature, crystallinity degree, bulk density and particle size is presented.     

Purification of ionic liquids by supercritical CO2 monitored by infrared spectroscopy

Transmission infrared and Attenuated Total Reflection (ATR) in situ infrared spectroscopies were combined for the time-resolved monitoring of both liquid and supercritical phases during extraction of water and other impurities from ionic liquids with supercritical carbon dioxide (scCO₂). Cleaning and drying by scCO₂ at 100 bar and 40 °C proved to be efficient for all ionic liquids tested, including 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF₄]), 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF₆]), and 1-butyl-3-methylimidazolium trifluoromethansulfonate ([bmim][TfO] or [bmim] triflate). Despite the moderate solubility of water in scCO₂ compared to other classical solvents, the amount of water decreased continuously during the drying. The extraction could be followed by simple transmission IR spectroscopy of the supercritical phase. During the extraction, organic impurities and water were removed rapidly from the ionic liquid phase as scCO₂ improved the transport properties in the ionic liquids.     

Extraction Behavior of Cu(II) Ion From Chloride Medium to the Hydrophobic Ionic Liquids Using 1,10-Phenanthroline

The study of liquid-liquid extraction of Cu(II) ion was carried out by using a series of hydrophobic ionic liquids; 1-butyl-3-methylimidazolium hexafluorophosphate ([C₄mimPF₆]), 1-hexyl-3-methylimidazolium hexafluorophospahate ([C₆mimPF₆]), 1-butyl-3-methylimidazolium bistrifluoromethylsulfonyl imide ([C₄mimNTf₂]) and 1-hexyl-3-methylimidazolium bistrifluoromethylsulfonyl imide ([C₆mimNTf₂]) as extraction phase. Cu(II) prefer to extract into [C₄mimPF₆] which is the less hydrophobic of ionic liquids. The extraction behavior of Cu(II) ion depends on the type of counterion and the extraction of Cu(II) ion in ionic liquid system proceeds via similar mechanism with a molecular organic solvent. From these results, it was proposed that the extraction of Cu complexes from chloride medium proceeds through ion pair mechanism.     

Acidic ionic liquid [bmim]HSO4: An efficient catalyst for acetalization and thioacetalization of carbonyl compounds and their subsequent deprotection

Acetalization/thioacetalization of carbonyl compounds, under solvent free conditions, has been described using acidic ionic liquid 1-Butyl-3-methylimidazolium hydrogen sulfate ([bmim]HSO₄) at room temperature, in conjunction with microwave energy and ammonium chloride. The catalyst retains its acidity, catalytic activity, and recyclability in ammonoium chloride, whereas its decomposition is observed under microwave irradiation. The same catalyst has also been used for the deprotection of acetals, thioacetals as well as for transthioacetalization under microwave irradiation.     

Improvement of biphasic polymerization by application of binary ionic liquid mixture

The mixture of two ionic liquids, 1-n-butyl-3-methylimidazolium and 1-(2-phenylethyl)-3-methylimidazolium chloroaluminates, [C₄-mim][AlCl₄] and [PhC₂-mim][AlCl₄], were applied as a medium to immobilize the Cp₂TiCl₂ titanocene catalyst for biphasic ionic liquid/hexane ethylene polymerization. The system makes possible to perform the reaction at lower temperatures, below the melting temperature of the aralkyl ionic liquid. A better separation of the ionic liquid phase was observed and an easier mass transfer of the polymer product from the ionic liquid to the hexane phase was obtained. The polyethylene reveals bimodal distribution of molecular weight. It is characterized by a high bulk density (500 g/dm³) and crystallinity degree (86%). The recycling of the ionic liquid medium containing the catalyst activated by AlEtCl₂, results in the highest yield obtained in such systems (550 kg PE(mol Ti)⁻¹).     

Solubility of CO2 in three cellulose-dissolving ionic liquids

The solubility of CO₂ in three cellulose-dissolving ionic liquids (1-ethyl-3-methylimidazolium diethylphosphate, [Emim][DEP], 1-allyl-3-methylimidazolium chloride, [Amim][Cl], and 1-butyl-3-methylimidazolium chloride, [Bmim][Cl]) at temperatures within 298 and 356 K and pressures up to 6.5 MPa was determined using a Van Ness-type apparatus (static isochoric). It was demonstrated that this device can work in isothermal and isoplethal modes, being the latter faster and more precise. Moreover, it was possible to determine CO₂ solubilities in metastable liquid [Bmim][Cl]. Experimental data were modeled using the Extended Henry's law correlation and the group contribution equation of state. New parameters for the binary interaction of CO₂ with ionic liquid groups were calculated.     

Extraction of dioxouranium(VI) in small channels using ionic liquids

The extraction behaviour of dioxouranium(VI) from nitric acid solutions with tributylphosphate (TBP) dissolved (30%, v/v) in room temperature ionic liquids (viz. 1-butyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}amide, [C₄mim][NTf₂], 1-decyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}amide, [C₁₀mim][NTf₂], and trihexyltetradecylphosphonium bis{(trifluoromethyl)sulfonyl}amide, [P_6 6 6 14][NTf₂]) was investigated. The experiments were performed in a capillary (0.5 mm internal diameter) made of Teflon, operated in the plug flow regime. The effects of ionic liquid type, initial nitric acid concentration, and residence time on dioxouranium(VI) extraction were studied. UV–vis spectroscopy was used for the determination of the dioxouranium(VI) concentration in the ionic liquid phase. For increasing [HNO₃]_aq,init, the %extraction decreased and then increased for [C₄mim][NTf₂], while for the other two ionic liquids it increased. The %extraction also increased with residence time in the channel. Overall mass transfer coefficients were about 0.2 s^–1 in all TBP/ionic liquid systems at the initial nitric acid concentration of 3 M when a 10 cm capillary was used.     

Efficient epoxidation of alkenes with sodium periodate catalyzed by manganese porphyrins in ionic liquid: Investigation of catalyst reusability

In the present work, efficient epoxidation of alkenes with sodium periodate catalyzed by tetraphenylporphyrinatomanganese(III) chloride, Mn(TPP)Cl, and octabromotetraphenylporphyrinatomanganese(III) chloride, Mn(Br₈TPP)Cl, using (1-n-butyl-3-methylimidazolium tetrafluoroborate), [bmim][BF₄], as ionic liquid is reported. The effect of substituted bromines on the catalytic activity and reusability of manganese porphyrins was also investigated.     

MBr(M=Na,K)在离子液体[Bmim]Br水溶液中的溶解度

为探索溴化1-丁基-3-甲基咪唑([Bmim]Br)离子液体对无机溴化物MBr(M=Na,K)在水中溶解度的影响,采用等温溶解平衡法在常压下测定了298.15~328.15 K范围内MBr在[Bmim]Br(1)+H₂O(2)溶液中的溶解度,考察了离子液体含量对溶解度的影响。实验结果表明,[Bmim]Br的加入会显著降低MBr(M=Na,K)在水中的溶解度,离子液体[Bmim]Br对KBr的盐析作用比对NaBr的盐析作用大。不同温度下的溶解度数据可用Pitzer混合电解质溶液模型进行关联,得到了混合离子相互作用参数以及MBr在混合溶剂中的平均活度因子和溶剂的渗透系数。模型计算的溶解度与实验结果吻合良好,平均活度因子和溶剂的渗透系数均随离子液体含量的增加而增加。     

Alkylation of isobutane and butene using chloroaluminate imidazolium ionic liquid as catalyst: Effect of organosulfur compound additive

Alkylation of isobutane and butene was carried out in a batch unit using 1-butyl-3-methylimidazolium chloride (BMIC)-aluminium (III) chloride (AlCl₃) ionic liquid as catalyst. The effects of additives of butyl thioalcohol and ethyl thioether on the properties of ionic liquids for alkylation were investigated. Improvement of production distribution with high yields of isooctane and selectivity of TMP under a mild reaction condition was observed after addition of butyl thioalcohol. Moreover, the effects of operating variables were investigated and the mechanism was discussed.     

Aggregation Behavior of Mixed Micellar System of Dodecyl Sulfate-Based Surface-Active Ionic Liquids and Anionic Surfactant in Aqueous Media

Mixed micellization behavior of dodecyl sulfate-based ionic liquids, i.e., 1-propyl-3-methylimidazolium dodecyl sulfate [C₃mim][DS] and 1-hexyl-3-methylimidazolium dodecyl sulfate [C₆mim][DS] with sodium dodecyl sulfate (SDS), is investigated at (298.15, 308.15, and 318.15) K in aqueous medium. For this, the conductometric measurements are carried out to evaluate the critical micelle concentrations (cmc ), ideal critical micelle concentration (cmc* ), degree of counterion dissociation (g ), thermodynamic parameters, micellar mole fraction of ionic liquids, and interaction parameter (β) of the mixed system based on the different proposed models given in the literature. Further surface tension measurements have been carried out to confirm the value of cmc obtained via a conductivity study for all the studied systems at 298.15 K. Other surface parameters, such as surface tension at cmc (γ_cmc ), surface pressure (ᴨ_cmc ), surface excess (Γ_max ), and minimum area per molecule (A_min), have also been evaluated for both the systems.     

Co-deposition of Al-Zn on AZ91D magnesium alloy in AlCl3-1-ethyl-3-methylimidazolium chloride ionic liquid

The co-deposition of Al and Zn on AZ91D magnesium alloy from a Lewis acidic aluminum chloride-1-ethyl-3-methylimidazolium chloride (AlCl₃-EMIC, with a molar ratio of 60:40) ionic liquid containing 1 wt% ZnCl₂ at room temperature was studied. The effect of potential on the deposition rate, the microstructure and the chemical composition of the deposit was explored. The experimental results show that the simultaneous deposition of Al and Zn on Mg alloy can be achieved under properly controlled potential conditions. The deposition rate increased while the amount of Zn existing in the coating decreased with increasing negative deposition potential. In the ionic liquid studied, a uniform chemical composition of the coating was obtained when the deposition was performed at −0.2 V (vs. Al).     

Novel homogeneous gel fibers and capillaries from blend of titanium tetrabutoxide and siloxane functionalized ionic liquid

The preparation of ionogels by sol–gel processing has attracted much attention, because the final ceramic materials combine properties of both inorganic matrix (thermal and mechanical stability) and the ionic liquid (ionic conductivity). The aim of this study was to combine different imidazolium based ionic liquids (1-ethyl-3-methylimidazolium tetrafluoroborate [EMIM][BF₄], 1-butyl-3-methyl imidazolium tetrafluoroborate [BMIM][BF₄], 1-decyl-3-methylimidazolium tetrafluoroborate [DMIM][BF₄] and 1-methyl-3-[3′-(triethoxysilyl)propyl]imidazolium chloride MTICl) with titanium(IV) butoxide to prepare homogenous hybrid fibers through aqueous sol–gel reaction. The study showed that ionic liquid miscibility with metal alkoxide plays an important role in the preparation of homogenous fibers. Unlike simple imidazolium salts functionalized ionic liquid was dispersed homogenously in fibers, but the main advantage is derived from its chemical structure. New stable ionic liquid can be involved in sol–gel processes through ethoxy groups and as a result it associates with titanium alkoxide network by covalent bonding providing non-leaking ceramic hybrid material. Indirect and direct characterization studies of the product were carried out by energy-dispersive X-ray spectroscopy (EDX), silicon-29 nuclear magnetic resonance spectroscopy (²⁹Si NMR), scanning electron microscopy (SEM) and optical microscopies; also infrared spectra (IR) were recorded. Thermal analyses were performed by differential scanning calorimetry (DSC).     

Microwave-assisted synthesis of CdF2 nanoflakes in ionic liquid

Cadmium fluoride (CdF₂) nanoflakes have been successfully synthesized using an ionic liquid (1-n-butyl-3-methylimidazolium tetrafluoroborate, [BMIM]BF₄) under microwave heating for 10 min. Not only did the ionic liquid act as the reaction medium in this route but also as an efficient fluridizer for the formation of CdF₂ species. The crystal phase, size and morphology of as-prepared nanomaterials were characterized by X-ray powder diffraction (XRD) and transmission electron microscopy (TEM).     

The combustion behavior of epoxy-based multifunctional electrolytes

Multifunctional or structural electrolytes are characterized by ionic conductivity high enough to be used in the electrochemical devices and mechanical performance suitable for the structural applications. Preliminary insights are provided into the combustion behavior of structural bi-continuous electrolytes based on bisphenol A diglycidyl ether (DGEBA), synthesized using the techniques of reaction induced phase separation and emulsion templating. The effect of the composition of the structural electrolytes and external heat flux on the behavior of the formulations were studied using a cone calorimeter with gases formed during testing analyzed using FTIR. The composition of the formulations investigated was changed by varying the type and amount of the ion conductive part of the bi-continuous electrolyte. Two ionic liquids, 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide (EMIM-TFSI) and 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM-BF₄), as well as a deep eutectic solvent (DES) based on ethylene glycol and choline chloride, were used. The results obtained confirm that time to ignition, heat release rate (HRR), total mass loss, as well as the composition of the gases released during tests depend on the composition of the formulations. Addition of liquid electrolyte is found to reduce the time to ignition by up to 10% and the burning time by between 28% and 60% with the added benefit of reducing the HRR by at least 34%. Gaseous products such as CO₂, CO, H₂O, CH₄, C₂H₂, N₂O, NO, and HCN were detected for all formulations with the gases SO₂, NH₃, HCl, C₂H₄, and NH₃ found to be for certain formulations only.     

Thermal Performance Analysis of Ionic Liquid-Pretreated Spent Coffee Ground Using Aspen Plus®

Thermal analysis and gasification study of spent coffee ground (SCG) pretreated with ionic liquids (ILs) is presented. Four ILs, namely, 1-butyl-3-methylimidazolium chloride ([Bmim][Cl]), 1-ethyl-3-methylimidazolium chloride ([Emim][Cl]), tributylmethylammonium chloride ([N₁₄₄₄][Cl]), and trihexyltetradecylphosphonium chloride ([P₆₆₆₁₄][Cl]), were investigated. The pretreatment was followed by thermogravimetric analysis. The syngas composition was computed using an equilibrium-based steam-O₂ gasification model developed in Aspen Plus® by varying gasifier temperature and steam/biomass ratio. All ILs reduced the ash content, enhanced the volatility as well as the higher heating value of SCG. IL pretreatment also decreased CO₂ and CH₄ contents showing environmental benefits of using ILs.     

Synthesis of cyanoethyl konjac glucomannan and its liquid crystalline behavior in an ionic liquid

Cyanoethyl konjac glucomannan (CKGM) products with various degree of substitution (DS) were synthesized, and their chemical structure was characterized by infrared spectroscopy and ¹H and ¹³C NMR spectroscopy. Direct evidence of the formation of liquid crystalline phase of cyanoethyl KGM (DS = 2.10) solution in 1-allyl-3-methylimidazolium chloride (AMIMCl), a room temperature ionic liquid, was confirmed by using polarized optical microscopy (POM). The mesophase and anisotropic phase of cyanoethyl KGM solutions and the phase transition boundaries were investigated by steady shear and dynamic sweep measurements. The crystalline state of the cyanoethyl KGM powder and solution were studied by wide X-ray diffraction.     

Aggregation Behavior of Imidazolium-Based Amino Acid Ionic Liquid Surfactants in Aqueous Solution: The Effect of Amino Acid Counterions

Three kinds of imidazolium-based amino acid ionic liquid surfactants (AAILS), 1-tetradecyl-3-methylimidazolium _L-aminopropionic acid salt ([C₁₄mim][Ala]), 1-tetradecyl-3-methylimidazolium _L-2-pyrrolidinecarboxylic acid salt ([C₁₄mim][Pro]), and 1-tetradecyl-3-methylimidazolium _L-aminohydrocinnamic acid salt ([C₁₄mim][Phe]), were synthesized by employing natural amino acids as counterions. Their adsorption and self-aggregation behaviors in aqueous solution were investigated systematically by means of surface tension and electrical conductivity measurements. Surface tension results indicate that surface properties and micellization behavior of AAILS are significantly affected by counterions. The micellization of [C₁₄mim][Pro] and [C₁₄mim][Phe] is entropy-driven at low temperatures but enthalpy-driven at high temperatures, whereas [C₁₄mim][Ala] is enthalpy-driven throughout the whole temperature range, owing to the variation in hydrophobicity and size of amino acid counterions. The surface activity of [C₁₄mim][Phe] is superior to that of conventional imidazolium-based ionic liquid surfactants with the same hydrocarbon chain length, 1-tetradecyl-3-methylimidazolium bromide (C₁₄mimBr), indicating that the aromatic counterion can promote the micellar formation process.     

Biphasic and Flow Systems Involving Water or Supercritical Fluids

Two processes are described for improving reaction rates for relatively hydrophobic substrates in aqueous biphasic systems. In the first, 1-octyl-3-methylimidazolium bromide ([Octmim]Br) increases the rate of hydroformylation of 1-octene from 8% conversion in 24 h to full conversion of 1.5 h. Phase separation is fast and catalyst retention is good. 1-Hexyl-3-methylimidazolium bromide gives little rate enhancement, whilst 1-decyl-3-methylimidazolium bromide gives stable emulsions., The mechanism of action of these additives is discussed. In the second approach, functionalising PPh₃ with amidine groups allows the rhodium catalysed hydroformylation of 1-octene in toluene with a very high reaction rate. The catalyst can be switched between toluene and water by bubbling CO₂ and back into toluene by bubbling N₂ at 60 °C. This switching has been used to separate the catalyst from hydrophobic (from 1-octene) or hydrophilic (from allyl alcohol) aldehydes obtained from hydroformylation reactions. CO₂ expanded liquids have been shown to be effective media for transporting substrates and catalysts over supported ionic liquid phase (SILP) catalysts. The advantages offered over all gas phase and liquid phase catalysts are discussed.     

Green and facile preparation of self-supporting nanoporous gold electrode and effect of ionic liquids on its electrocatalytic oxidation toward glucose

Green and facile fabrication of self-supporting nanoporous gold electrodes (NPGE) was successfully achieved in an air/water-stable Lewis acid ionic liquid [Choline]Cl·2ZnCl₂ via electrochemical method. In this medium, the effects of the scan cycle at different temperatures on the preparation process were investigated firstly. It was found that the Au–Zn alloy and porous structure could be formed at the temperature as low as 50 °C after five cycles and at 90 °C only after one cycle, indicating the easier formation of the porous structure in the present ionic liquid than that in the reported solvents. The porous structure was formed directly on the gold surface and the NPGE could catalyze the oxidation of glucose without any modification or covered film. The electrocatalytic ability of the NPGEs for glucose oxidation was evaluated in the neutral and alkaline solutions. Ionic liquids were correlated closely with the dissolution and conversation of glucose. The effect of three ionic liquids (choline acetate, 1-butyl-3-methylimidazolium tetrafluoroborate and 1-butyl-3-methylimidazolium chloride) on the conversation of glucose on the NPGE was studied. These ionic liquids had great influence on the electrochemical signal of glucose and inhibited the catalytic ability of the NPGE. Glucose was electrochemically detected on the best NPGE in neutral medium finally. This work introduced a green and facile method for the fabrication of the self-supporting NPGE, expanded the application of gold nanomaterials in the electrocatalysis for glucose and provided a scientific support for the effect of ionic liquids on the conversation of glucose.