Polycarbonate/1‐(2‐hydroxyethyl)‐2,3‐dimethylimidazolium chloride composite membranes and short‐range chain mobility analysis

In this investigation, the incorporation of imidazolium salt, 1‐(2‐hydroxehtyl)‐2,3‐dimethylimidazolium chloride [hydemmim][Cl] within bisphenol A polycarbonate (PC) matrix and the subsequent formation of membranes via casting were studied. Characterizations that aimed to establish structure‐property correlations by Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, dynamic mechanical thermal analysis, and water vapor transport (WVT) were performed. The results indicated that the presence of ionic liquid (IL) within the PC matrix significantly alter the local and macromolecular structure. The thermal stability is increased for all levels of incorporation. The plasticizing and antiplasticizing effects were observed due to the influence of the proportions of IL incorporated and of the cation's substituent chain of this IL. Distinct mechanisms of WVT were also observed in the presence of IL. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45117.     

Effect of ionic salts on the processing of poly(2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid) nanofibers

We studied the effect of nanofiber uniformity on electrospinning due to the charging of added ionic salts, as compared to the droplet current nonadded ionic salts and the charge‐to‐mass ratio of a highly conducting liquid. Various ionic salt concentrations were investigated. For an ionic salt concentration of 0.01 mol %, an applied electric field of 15 kV, and a spinning distance of 15 cm, the experimental results show that uniform nanofibers that did not contain any beads were synthesized with an optimal ionic salt concentration, when the convective current was two orders of magnitude higher than the nonadded ionic salt droplet current. The obtained fibers were uniform, with diameters of around 70 nm. We were able to produce these uniform nanofibers by controlling the balance between two opposing factors during electrospinning, by increasing the number of charge carriers and decreasing the viscosity of the solution. The effect of the ionic salts on the morphology of the electrospun nanofibers was investigated with field‐emission scanning electron microscopy. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1388–1393, 2005     

Preparation and dielectric properties of poly(ε‐caprolactone) compounded with “bucky gels”‐like mixture

Poly(ε‐caprolactone) (PCL) was melt compounded with “Bucky gels”‐like mixture that prepared by grinding multiwalled carbon nanotubes (MWNTs) and ionic liquids (ILs). Raman spectrum showed the significant interaction between ILs and MWNTs. The dielectric behavior of PCL nanocomposites based on unmodified and IL‐modified MWNTs was studied from 40 Hz to 30 MHz. The addition of ILs significantly enhanced the dielectric property of PCL/IL/MWNT ternary nanocomposites, which was much higher than that of the sum of PCL/IL with PCL/MWNT binary nanocomposites. The dielectric properties of PCL/IL/MWNT nanocomposites were mainly influenced by ILs in low frequency and were dominated by MWNTs in high frequency. SEM results revealed that a more uniform and fine dispersion of MWNTs were achieved throughout the PCL matrix because of ILs. The addition of ILs in nanocomposites changed the crystallinity of PCL. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40231.     

Thermal regimes of Li‐ion conductivity in β‐eucryptite

While it is well‐established that ionic conduction in lithium aluminosilicates proceeds via hopping of Li ions, the nature of the various hoping‐based mechanisms in different temperature regimes has not been fully elucidated. The difficulties associated with investigating the conduction have to do with the presence of grains and grain boundaries of different orientations in these usually polycrystalline materials. Herein, we use electrochemical impedance spectroscopy (EIS) to investigate the ion conduction mechanisms in β‐eucryptite, which is a prototypical lithium aluminosilicate. In the absence of significant structural transitions in grain boundaries, we find that there are three conduction regimes for the one‐dimensional ionic motion along the c axis channels in the grains, and determine the activation energies for each of these temperature regimes. Activation energies computed from molecular statics calculations of the potential energy landscape encountered by Li ions suggest that at temperatures below 440°C conduction proceeds via cooperative or correlated motion, in agreement with established literature. Between 440°C and 500°C, the activation barriers extracted from EIS measurements are large and consistent with those from atomistic calculations for uncorrelated Li ion hopping. Above 500°C the activation barriers decrease significantly, which indicates that after the transition to the Li‐disordered phase of β‐eucryptite, the Li ion motion largely regains the correlated character.     

Synthesis and Properties of Alkoxyethyl β‐d‐Xylopyranoside

In order to improve the water solubility of sugar‐based surfactants, alkyl β‐d‐ xylopyranosides, novel sugar‐based surfactants, 1,2‐trans alkoxyethyl β‐d‐ xylopyranosides, with alkyl chain length n = 6–12 were stereoselectively prepared by the trichloroacetimidate method. Their properties including hydrophilic–lipophilic balance (HLB) number, water solubility, surface tension, emulsification, foamability, thermotropic liquid crystal, and hygroscopicity were investigated. The results indicated that their HLB number decreased with increase of alkyl chain, the water solubility improved since the hydrophilic oxyethene (─OCH₂CH₂─) fragment was introduced. The dissolution process was entropy driven at 25–45 °C for alkyl chain length n = 6–10. Octyloxyethyl β‐d‐ xylopyranoside had the best foaming ability. Nonyloxyethyl β‐d‐ xylopyranoside had the best foam stability and the emulsifying ability was better in toluene/water system than in rapeseed oil/water system. The surface tension of in aqueous solution dropped to 27.8 mN m^?1 at the critical micelle concentration, and it also showed the most distinct thermotropic liquid phases with cross pattern texture upon heating and the fan schlieren texture on cooling. Hexyloxyethyl β‐d‐ xylopyranoside possessed the strongest hygroscopicity. Based on the effective improvement of water solubility, the prepared alkoxyethyl β‐d‐ xylopyranosides showed excellent surface activity and are expected to develop their practical application as a class of novel sugar‐based surfactants.     

All‐wood biocomposites by partial dissolution of wood flour in 1‐butyl‐3‐methylimidazolium chloride

After cedar‐derived wood flour (WF) and bark flour (BF) were mixed with 1‐butyl‐3‐methylimidazolium chloride (BMIC) at 100°C, the obtained compounds with BMIC content 40 wt % were compression‐molded at 210°C to give WF/BMIC and BF/BMIC composites, respectively. The BMIC contained in the composites was twice extracted with ethanol at 60°C to afford WF/BMIC‐E and BF/BMIC‐E biocomposites, which were subsequently annealed at 200°C for 24 h to produce WF/BMIC‐A and BF/BMIC‐A biocomposites. The Fourier transform infrared spectroscopic analysis revealed that WF has a higher content of cellulose and a lower content of lignin than BF does, and that the BMIC content diminished by the extraction process. The scanning electron microscopy analysis showed that woody particles joined together by the compression molding of WF/BMIC and BF/BMIC compounds, and that the extraction of BMIC roughened the surface and the annealing again smoothed the surface due to the fusion of the residual BMIC and woody particles. The XRD measurements indicated that the annealing enhanced the crystallinity of cellulose component. The tensile properties and 5% weight loss temperature of the biocomposites were considerably improved by the extraction of BMIC and further by the annealing. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

High‐strength regenerated cellulose fibers spun from 1‐butyl‐3‐methylimidazolium chloride solutions

High‐performance regenerated cellulose fibers were prepared from cellulose/1‐butyl‐3‐methylimidazolium chloride (BMIMCl) solutions via dry‐jet wet spinning. The spinnability of the solution was initially evaluated using the maximum winding speed of the solution spinning line under various ambient temperatures and relative humidities in the air gap. The subsequent spinning trials were conducted under various air gap conditions in a water coagulation bath. It was found that low temperature and low relative humidity in the air gap were important to obtain fibers with high tensile strength at a high draw ratio. From a 10 wt % cellulose/BMIMCl solution, regenerated fibers with tensile strength up to 886 MPa were prepared below 22 °C and relative humidity of 50%. High strengthening was also strongly linked with the fixation effect on fibers during washing and drying processes. Furthermore, an effective attempt to prepare higher performance fibers was conducted from a higher polymer concentration solution using a high molecular weight dissolving pulp. Eventually, fibers with a tensile strength of ～1 GPa and Young's modulus over 35 GPa were prepared. These tensile properties were ranked at the highest level for regenerated cellulose fibers prepared by an ionic liquid–based process. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45551.     

Copper(I) bromide coordinated by the ionic liquid 1‐[(diethyl amine)amine]ethyl‐3‐methyl imidazolium chloride to catalyze the atom transfer radical polymerization of methyl methacrylate in 1‐allyl‐3‐methyl imidazolium chloride

A coordinating ionic liquid (IL), 1‐[(diethyl amine)amine]ethyl‐3‐methyl imidazolium chloride ([N₃MIM]Cl), was prepared as an alternative to a simple organic ligand to coordinate to copper(I) bromide (CuBr). We, thereby, obtained a novel catalyst for atom transfer radical polymerization (ATRP) reactions. This catalyst was applied to the ATRP of methyl methacrylate in the IL 1‐allyl‐3‐methyl imidazolium chloride ([AMIM]Cl). The chemical structures of the ILs obtained were confirmed by Fourier transform infrared spectroscopy, mass spectrometry, and ¹H‐NMR analyses. The coordination ability of [N₃MIM]Cl was assessed by cyclic voltammetry, and the redox potential of [N₃MIM]Cl–CuBr was ?0.507 V. The [N₃MIM]Cl–CuBr complex was expected to be a markedly more active catalyst than the amine DETA–CuBr complex. The coordination mode toward CuBr was also examined. The [N₃MIM]Cl–CuBr catalyst system showed good controllability in the aforementioned ATRP reaction in [AMIM]Cl. The Cu catalyst was easily separated from the obtained polymer with the coordinating IL as a ligand. Consequently, the coordinating IL overcame the shortcomings of traditional organic ligands, such as poor compatibility with IL media and poor separation of the catalyst from the polymer; this makes it highly promising for applications in the ATRP field. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45484.     

1‐Allyl‐3‐methylimidazolium halometallate ionic liquids as efficient catalysts for the glycolysis of poly(ethylene terephthalate)

Series of 1‐allyl‐3‐methylimidazolium halometallate ionic liquids (ILs) were synthesized and used to degrade poly(ethylene terephthalate) (PET) as catalysts in the solvent of ethylene glycol. One important feature of these new IL catalysts is that most of them, especially [amim][CoCl₃] and [amim][ZnCl₃], exhibit higher catalytic activity under mild reaction condition, compared to the traditional catalysts [e.g., Zn(Ac)₂], the conventional IL catalysts (e.g., [bmim]Cl), Fe‐containing magnetic IL catalysts (e.g., [bmim][FeCl₄]), and metallic acetate IL catalysts (e.g., [Deim][Zn(OAc)₃]). For example, using [amim][ZnCl₃] as catalyst, the conversion of PET and the selectivity of bis(hydroxyethyl) terephthalate (BHET) reach up to 100% and 80.1%, respectively, under atmospheric pressure at 175°C for only 1.25 h. Another important feature is that BHET can be easily separated from the catalyst and has a high purity. Finally, based on the experimental phenomena, in ‐situ infrared spectra, and experimental results, the possible mechanism of degradation with synthesized IL is proposed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of 1‐butyl‐3‐methylimidazolium iodide containing electrospun poly(vinylidene fluoride‐co‐hexafluoropropylene) membrane electrolyte on the photovoltaic performance of dye‐sensitized solar cells

Electrospun poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVdF‐HFP) membrane was prepared from a solution of 16 wt % of PVdF‐HFP containing acetone/N,N‐dimethyl acetamide (7:3 wt %). The prepared electrospun PVdF‐HFP membrane (esPM) was then soaked in ionic liquid electrolyte containing 0.5M LiI, 0.05M I₂ , and 0.5M 4‐tert butylpyridine, 0.5M 1‐butyl‐3‐methylimidazolium iodide (BMImI) in acetonitrile to get electrospun PVdF‐HFP membrane electrolyte (esPME). The effect of various concentrations of BMImI containing esPME on ionic conductivity was studied by AC‐impedance measurements and the diffusion co‐efficients was determined by linear sweep voltammetry. The photovoltaic performance of a DSSC fabricated using 0.5M BMImI containing electrospun PVdF‐HFP membrane electrolyte (0.5M BMImI‐esPME) has power conversion efficiency (PCE) of 6.42%. But the stability of the DSSC fabricated using 0.5M BMImI‐esPME was considerably superior to that fabricated using 0.5M BMImI containing liquid electrolyte (0.5M BMImI‐LE). © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42032.     

Antimicrobial properties and thermal stability of polycarbonate modified with 1‐alkyl‐3‐methylimidazolium tetrafluoroborate ionic liquids

Four water immiscible ionic liquids (ILs): 1‐hexyl‐3‐methylimidazolium tetrafluoroborate, 1‐heptyl‐3‐methylimidazolium tetrafluoroborate, 1‐octyl‐3‐methylimidazolium tetrafluoroborate and 1‐dodecyl‐3‐methylimidazolium tetrafluoroborate have been synthesized. Polycarbonate (PC) films containing ILs were prepared by solvent casting from methylene chloride solutions. Scanning electron microscopy measurements showed the high homogeneity of PC/IL films with the IL content up to 4 wt %. The tendency to IL aggregation was observed for polymeric films with higher IL content (5%). PC/IL composites were found to have the reduced thermal decomposition temperature under both an air and a nitrogen atmosphere in comparison with the neat PC. The effect of IL content on the antimicrobial activity of PC films against Escherichia coli bacteria was studied. Pronounced antimicrobial efficacy was revealed for PC/IL films for all studied ILs starting from 3 wt % of IL. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40050.     

Dissolution and utilization of chitosan in a 1‐carboxymethyl‐3‐methylimidazolium hydrochloride ionic salt aqueous solution

1‐Carboxymethyl‐3‐methylimidazolium hydrochloride ([IMIM–COOH]Cl), a new ionic salt, is proposed as a green, promising solvent for dissolving chitosan. However, because of the optimal dosage of chitosan dissolved in [IMIM–COOH]Cl, a 12 wt % [IMIM–COOH]Cl aqueous solution was selected as an optimum solvent system for dissolving chitosan. The structures of the original and regenerated chitosan were characterized by Fourier transform infrared spectroscopy and X‐ray diffraction analysis. Scanning electron microscopy was used to visualize the morphological features of the reconstituted chitosan membranes. Meanwhile, the absorbance, tensile strength, and breaking elongation of the chitosan membranes were measured. The results reveal that 10–11 wt % was an optimal chitosan concentration for preparing membranes. Furthermore, the adsorption capacity for Cu(II) ion of the chitosan membranes was increased with the chitosan concentration decreased from 12 to 8 wt %. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41965.     

Rheology of 1‐butyl‐3‐methylimidazolium chloride cellulose solutions. II. Solution character and preparation

The focus of this article of a three part series is the effects of preparation and composition on the shear rheology of cellulose in the ionic liquid 1‐butyl‐3‐methylimidazolium chloride ([Bmim]Cl). Included are the effects of three different degrees of polymerization, (i.e., average molecular weight), manual versus high shear mixing, a range of cellulose concentrations, and the effects of controlled amounts of lignin and a hemicellulose. The rheology implies that a gel phase develops at higher degrees of polymerization, higher concentration, and at lower temperatures. The first article focused primarily on shear rheology of cellulose in [Bmim]Cl with a high shear preparation technique, one degree of polymerization, a narrow range of cellulose concentrations, and temperature. The third article focuses on elongational rheology of cellulose in [Bmim]Cl. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Evaluation of 1‐ethyl‐3‐methylimidazolium acetate based ionic liquid systems as a suitable solvent for collagen

Collagen, a prominent biopolymer, which is famous for its excellent biological activity, has been used extensively for tissue engineering applications. In this study, a novel solvent system for collagen was developed with an ionic liquid, 1‐ethyl‐3‐methylimidazolium acetate ([EMIM][Ac]), solvent system. A series of sodium salts were introduced into this solvent system to enhance collagen's dissolution procedure. The results show that the solubility of collagen was significantly influenced by the temperature and sodium salts. The solubility reached up to approximately 11% in the [EMIM][Ac]/Na₂HPO₄ system at 45°C. However, the structure of the regenerated collagen (Col‐regenerated) may have been damaged. Hence, we focused on the structural integrity of the collagen regenerated from the [EMIM][Ac] solvent system by the methods of sodium dodecyl sulfate–polyacrylamide gel electrophoresis, Fourier transform infrared spectroscopy, ultrasensitive differential scanning calorimetry, atomic force microscopy, X‐ray diffraction, and circular dichroism because its signature biological and physicochemical properties were based on its structural integrity. Meanwhile, a possible dissolution mechanism was proposed. The results show that the triple‐helical structure of collagen regenerated from the [EMIM][Ac] solvent system below 35°C was retained to a large extent. The biocompatibility of Col‐regenerated was first characterized with a fibroblast adhesion and proliferation model. It showed that the Col‐regenerated had almost the same good biological activity as nature collagen, and this indicated the potential application of [EMIM][Ac] in tissue engineering. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2245–2256, 2013     

Investigations on esterification reactions of starches in 1‐N‐butyl‐3‐methylimidazolium chloride and resulting substituent distribution

The ionic liquid (IL) 1‐N‐butyl‐3‐methylimidazolium chloride ([C₄mim]⁺Cl^?) was used as solvent for different esterification reactions of the biopolymer starch. Therefore, maize starches with varying content of amylose were used. Different carboxylic acid anhydrides were applied to esterify starch with a degree of substitution (DS) in the range of 0.7–3.0. For example, starch acetates with the mentioned DS are accessible within 30 min at a 105°C‐reaction temperature. The DS distribution of starch acetates synthesized in IL was compared with the common starch acetate synthesis of Mark and Mehltretter. Also, a consideration of starch acetates and cellulose acetates synthesized in [C₄mim]⁺Cl^? is given. The starch esters were characterized by means of Raman spectroscopy for qualitative‐ and nuclear magnetic resonance spectroscopy for quantitative determination of the functionalization pattern. Moreover, the molecular mass distribution was determined after saponification by means of GPC‐MALLS. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Molecularly imprinted polymers for the selective recognition of l‐phenylalanine based on 1‐buty‐3‐methylimidazolium ionic liquid

To enhance the affinity of 4‐vinyl pyridine to l ‐phenylalanine (l ‐Phe) and convert the imprinting process from the aqueous phase to the organic phase, an oil‐soluble amino acid ionic liquid was introduced as a template. In this study, 1‐butyl‐3‐methylimidazolium α‐aminohydrocinnamic acid salt was first applied to prepared surface molecularly imprinted polymers (MIPs) in acetonitrile for the selective recognition of l ‐Phe. Fluorescence quenching analysis of the functional monomer on the template was investigated under different conditions to study the imprinting mechanism. Several binding studies, such as the sorption kinetics, sorption thermodynamics, and solid‐phase extraction application, and the chiral resolution of racemic phenylalanine were investigated. The binding isotherms were fitted by nonlinear regression to the Freundlich model to investigate the recognition mechanism. The affinity distribution analysis revealed that polymers imprinted by ionic liquid showed higher homogeneous binding sites than those imprinted by l ‐Phe. The competition tests were conducted by a molecularly imprinting solid‐phase extraction procedure to estimate the selective separation properties of the MIPs for l ‐Phe. The target MIP was shown to be successfully for the separation of l ‐Phe from an amino acid mixture. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42485.     

Three‐Component One‐Pot Synthesis of α‐Hydroxylamino Phosphonates using Ionic Liquids

α‐Hydroxylamino phosphonates are synthesised in a one‐pot operation by three‐component coupling reactions of aldehydes, hydroxylamines and diethyl phosphite using 1‐butyl‐3‐methylimidazolium tetrafluoroborate ([bmim]BF₄) or 1‐butyl‐3‐methylimidazolium hexafluorophosphate ([bmim]PF₆) ionic liquids under mild and neutral conditions. The recovered ionic liquids can be recycled for four to five runs without loss of activity.     

Electrospun poly(lithium 2‐acrylamido‐2‐methylpropanesulfonic acid) fiber‐based polymer electrolytes for lithium‐ion batteries

Novel single‐ion conducting polymer electrolytes based on electrospun poly(lithium 2‐acrylamido‐2‐methylpropanesulfonic acid) (PAMPSLi) membranes were prepared for lithium‐ion batteries. The preparation started with the synthesis of polymeric lithium salt PAMPSLi by free‐radical polymerization of 2‐acrylamido‐2‐methylpropanesulfonic acid, followed by ion‐exchange of H⁺ with Li⁺. Then, the electrospun PAMPSLi membranes were prepared by electrospinning technology, and the resultant PAMPSLi fiber‐based polymer electrolytes were fabricated by immersing the electrospun membranes into a plasticizer composed of ethylene carbonate and dimethyl carbonate. PAMPSLi exhibited high thermal stability and its decomposition did not occur until 304°C. The specific surface area of the electrospun PAMPSLi membranes was raised from 9.9 m²/g to 19.5 m²/g by varying the solvent composition of polymer solutions. The ionic conductivity of the resultant PAMPSLi fiber‐based polymer electrolytes at 20°C increased from 0.815 × 10^?5 S/cm to 2.12 × 10^?5 S/cm with the increase of the specific surface area. The polymer electrolytes exhibited good dimensional stability and electrochemical stability up to 4.4 V vs. Li⁺/Li. These results show that the PAMPSLi fiber‐based polymer electrolytes are promising materials for lithium‐ion batteries. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012