Poly Ionic Liquid Research Articles

From a single helix to a helical porous metalloenzyme catalyst based on temperature sensitive polyionic liquids

It is a challenging task to construct helical structures through the assembly of achiral polymers.

Ionic Liquid–Poly(lactic acid) Blends as Green Polymer Electrolyte Membranes

Ionic Liquid–Poly(lactic acid) Blends as Green Polymer Electrolyte Membranes

Physical and mechanical investigation for polyionic liquid/poly(vinyl alcohol) blends

PurposeThis study aims to polymerize of 1-butyl-3-vinylimidazolium bromide (PIL). PIL was embedded into PVA with a different content ratio by casting method. This research also deals with the effect of adding PIL in different proportions to PVA on the electrical and mechanical properties properties in addition to the morphology of the prepared samples.Design/methodology/approach1-Butyl-3-vinylimidazolium bromide was synthesized through quaternization and free radical polymerization. The resulting polymer was characterized by Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis and differential scanning calorimetry. In addition to the morphology of PVA, PVA/PIL was investigated by polarizing microscope. Also, the effect of PIL content on the electrical and mechanical properties was evaluated.FindingsThe findings of this study might lead to new applications for PVA and PILs in electrical and dielectrics. The mechanical results revealed that the tensile strength increased slightly with increasing polyionic liquid (PIL) content and decreased above 10% PIL. While the elongation at break increased significantly with increasing PIL content and begin to decrease above 10% PIL. Also, the electrical property of the poly(vinyl alcohol) (PVA)/PIL blends was improved because of the strong plasticizing effect of PIL. Also, the electrical conductivity of these polymer electrolytes is greatly increased. This indicates that the imidazolium-based PIL has an effective approach that leads to an increase in the conductivity of the polymer. The PILs/PVA design will not only enrich the chemical structure but also will contribute to green manufacturing techniques and a processing methodology that enables green membrane manufacture.Originality/valueThis study contributes to green manufacturing techniques and a processing methodology that enables “green” membrane manufacture.

Constructing hollow carbon sphere liquid with permanent porosity via electrostatic modification of polyionic liquids for CO2 gas adsorption

• HCS and polyionic liquid through cation-π electrostatic interaction to construct HCS-based PLs. • The permanent porosity of HCS in PLs was confirmed by the higher CO 2 adsorption capacity of PLs than PILs-PEGS. • Changes in particle size and the outer layer can achieve CO 2 adsorption and viscosity control. • Electrostatic surface modification strategy can be used to prepare rich PLs based on other porous materials. Porous liquids (PLs) are a type of porous materials that combine the porosity of solids and fluidity of liquids, which has attracted widespread attention. In this paper, we report a new TypeⅠhollow carbon sphere-based porous liquids, which are constituted of hollow carbon sphere (HCS) as the porous host, polymeric ionic liquid (PILs) as the corona and poly(ethylene glycol) 4-nonylphenyl 3-sulfopropyl ether potassium salt (PEGS) as the canopy. The viscosity of PLs is 8900 mPa·s at 50 ℃ (like syrup), which has good fluidity. Under 3 MPa pressure conditions, the best CO 2 adsorption capacity of 450-P[VHIm]Br-PEGS and 450-P[VBBI]Cl-PEGS are 2.06 and 1.90 mmol/g at 25 °C, respectively, higher than PILs-PEGS. Under the same conditions, the CO 2 adsorption capacity of PLs is 10.5 times higher than that of N 2 . Therefore, HCS-based PLs have the potential for CO 2 /N 2 selective gas separation. Not only PILs and the anionic alkyl chain of the outer layer widen the liquid range of PLs, but also is suitable for preparing PLs with other cavity units.

Application of Imidazolium-based polyionic liquids to separate the 1,3,5-Trioxane-Water/Ethanol-Water system based on experimental verification and molecular mechanism analysis

Polyionic liquids(PILs) have the characteristics of non-volatile, high thermal stability and excellent performance. Because of its strong solubility and molecular recognition ability, it has broad application prospects in the field of azeotropic separation.. In this manuscript, based on COSMO calculation, methylimidazole ionic liquid(ILs) with strong hydrophilic anions was selected as extractant to separate trioxane water and ethanol water azeotropic systems. The screening results were verified by vapor–liquid equilibrium experiments. It was found that [VMIm][DMP] could separate trioxane water and ethanol water azeotropic systems effectively at the same time. In the separation of azeotropes, because the ILs extractant has too strong interaction with H2O and the thermal stability is not satisfactory, the recovery energy consumption is high and the heat loss is serious. In this work, [VMIm][DMP] and [VEIm][DEP] were selected as ionic liquid monomers (ILM), and PILs were prepared by the reversible addition-fragmentation chain transfer (RAFT) method. The molecular dynamics (MD) simulation is performed to study the interactions between the solvent molecules and ILs/PILs, in order to investigate the separation mechanism at the molecular level. The study found that increasing the degree of polymerization is beneficial to improve the thermal stability of PILs and relative volatility of trioxane and ethanol, and the influence of degree of polymerization and alkyl side chain length on the hydrogen bond strength of PILs-H2O, PILs-trioxane and PILs-ethanol were studied by MD simulation.

Flexible, transparent, strong and high dielectric constant composite film based on polyionic liquid coated silver nanowire hybrid

High dielectric constant films with excellent flexibility, transparency and high strength are key materials for flexible electronic devices. Herein, a novel kind of functional hybrid (AgNW@PIL) was synthesized by forming a layer of polyionic liquid (PIL) on surfaces of silver nanowires (AgNWs), which was then added into poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) to develop a series of unique high dielectric constant films (AgNW@PIL/PVDF-HFP). Comprehensive performances of AgNW@PIL/PVDF-HFP films were studied and compared with those of AgNW/PVDF-HFP films and related composite films in literature. With the increase of AgNW@PIL content, the dielectric constant and mechanical strength significantly improve, while the light transmittance gradually decreases. At the same filler content and frequency, AgNW@PIL/PVDF-HFP has higher dielectric constant, lower dielectric loss, higher light transmittance and better mechanical properties than AgNW/PVDF-HFP. The mechanism behind these attractive results is contributed to different microstructures between AgNW/PVDF-HFP and AgNW@PIL/PVDF-HFP. Specifically, different from AgNW, AgNW@PIL has good dispersibility in PVDF-HFP, and form more micro-capacitor structure and good interface polarization effect; besides, PIL coating plays a significant role in suppressing the dielectric loss of composite films. AgNW@PIL/PVDF-HFP with only 0.4 wt% AgNW@PIL simultaneously has high tensile modulus (1152.2 MPa), high tensile strength (30.9 MPa) and large elongation at break (181.0%).

Design and fabrication of novel polymerized dual nature ionic liquid as highly effective catalyst for regioselective synthesis of monospiro derivatives

Poly (ionic liquid)s (PILs) are promising candidates in catalytic transformations; however, hyper cross-linked poly ionic liquids have been rarely reported in catalysis field. In this study, we developed a novel hyper cross-linked PIL (HCPIL) as an effective heterogeneous catalyst for regioselective synthesis of monospiro compounds. For this purpose, a new polymerizable ionic liquid (1-(2-methacryloyloxy)ethyl)-3-vinylimidazolium bromide ([MEVIm]Br)) was designed and synthesized with two different natures; that is, ionic monomer and cross-linker agent. The successful construction of dual nature ionic liquid (IL) was confirmed by analytical techniques such as 1H NMR, 13C NMR, elemental, and FTIR. Next, magnetic HCPIL was fabricated using copolymerization of the prepared IL with N,N-methylenebisacrylamide (MBAA) in the presence of a water soluble initiator (4,4‘-azobis(4-cyanopentanoic acid)) supported on vinyl functionalized Co3O4 nanoparticles (NPs). The results illustrated that the polymerization of ILs and covalent binding onto the magnetic support improved the thermal stability (from 75 to 33% weight loss around 450 °C), reusability, catalytic activity, and generated porous structure. Accordingly, the proposed magnetic Co3O4@p[MEVIm]Br composite was investigated as a heterogeneous catalyst for the ultrasound-assisted synthesis of new and known spirooxindole-2-azapyrrolizidines and spiro-2-amino-4H-pyran-oxindoles; and it showed accelerated mass transfer owing to its great porosity, high surface area (170.0 m2/g), and abundant accessible active sites. The applied scalable catalytic protocol has integrated the rules of an ideal biology-oriented synthesis and organic synthesis to access a spiro heterocyclic skeleton. Easy work-up, high regioselectivity, excellent yields (>90%), short reaction time (6–12 min), and green reaction media are the other advantages of the proposed synthetic method.

Superhigh and reversible NH3 uptake of cobaltous thiocyanate functionalized porous poly ionic liquids through competitive and cooperative interactions

In this work, porous PIL-TAs were reported for superhigh capacity and reversible NH3 uptake, where PIL-TAs are cobaltous thiocyanate (Co(II)(SCN)42-, TA) functionalized poly ionic liquids (PILs). Due to the structural support of TA as well as the interactions between TA and imidazolium cation, the PIL-TAs possess porous structure and optimized properties. Superhigh NH3 uptake capacity of 13.2–20.1 mmol g−1 at STP of PIL-TAs was achieved, which is higher than most of the reported sorbents. In detail, the cooperative interactions including the NH3 coordinating with Co(II) instead of SCN- and hydrogen bonding of C2H in imidazolium (C2H…NH3) benefit to high capacity of NH3 uptake. Reversely, the NH3 release would be directed by the competition of the free SCN- with NH3 to reform PIL-TAs. The competitive interaction with SCN- promotes NH3 release by temperature and pressure swinging, which contributes the adsorbents recyclable. The cooperative and competitive interactions make these PIL-TAs possess high gas capacity and feasible desorption, which might be a potential strategy for designing novel gas sorbents.

Novel Poly(ionic liquid) Augmented Membranes for Unconventional Aqueous Phase Applications in Fractionation of Dyes and Sugar.

Poly(ionic) liquid (PIL) augmented membranes were fabricated through self-polymerization of 2-vinyl pyridine and 4-vinyl pyridine followed by dopamine triggered polymerization and bridging with inert polyamide support. The resulting membranes acquired a positive surface charge with a high degree of hydrophilicity. Fourier transformed Infra-red (FTIR) and Energy dispersive X-ray (EDX) spectroscopic investigation revealed the successful augmentation of PIL surface layer, whereas surface morphology was investigated through scanning electron microscopy (SEM) imaging. This manuscript demonstrates pi electron-induced separation of dyes with the trend in permeability: Coomassie Brilliant Blue G (CBBHG) > Remazol Brilliant Blue R (RBBR) > Eichrome Black T (EBT) > Congo Red (CR). CBBG exhibited extended conjugation over large aromatic domain. RBBR and EBT were associated withtheelectron-donating -NH2 group and electron-withdrawing -NO2 group, respectively, hence pi electron density on aromatic ring varied. The steric repulsion between two pairs of ortho hydrogens (Hs) in biphenyl moieties of CR resulted in deviation of planarity and hence aromaticity leading to the lowest permeability. The sugar fractionation followed the trend: Galactose > Mannose > Fructose > Glucose > Xylose. More hydroxyl (-OH) groups in sugars and their conformational alignment in the same direction, exhibited more lone pair of electrons leading to more interaction with PIL and hence better permeability. Pentose showed poorer permeation than hexose, whereas aldose showed better permeation than ketose.

Rapid synthesis of polyimidazole functionalized MXene via microwave-irradiation assisted multi-component reaction and its iodine adsorption performance

The adsorption applications of MXene-based adsorbents have intensively investigated recently. However, the performance of MXene-based adsorbents has been largely limited owing to their lack of functional groups and adsorptive sites. Therefore, surface functionalization of MXene is an important route to achieve better performance for environmental adsorption. Herein, polyionic liquid functionalized MXene (named as MXene-PIL) was prepared through a multi-component reaction and adsorptive removal of iodine by MXene-PIL was also evaluated. The successful generation of PIL on MXene was confirmed by a series of characterization measurements. Furthermore, the effects of contact time, iodine concentration, environmental temperature and other factors on the adsorption performance of MXene-PIL were investigated. Adsorption kinetic analysis including pseudo-first-order dynamic model, pseudo-second-order dynamic model and Weber-Morris model, adsorption thermodynamic analysis such as Langmuir and Freundlich models and Van’t Hoff equation were used for further analysis the adsorption behavior of iodine by MXene-PIL. We demonstrated that the adsorption capacity could be as high as about 170 mg/g, which is obviously larger than the unmodified MXene and most of other reported adsorbents. Taken together, a simple strategy has been developed for in-situ generation of PIL on MXene and the resultant composites show potential application for adsorptive removal of iodine.

Production of polyalfaolefin-based lubricants using new (poly)ionic liquid /AlCl3 catalysts as environmentally friendly alternatives to commercial AlCl3 route

Aiming to decrease corrosive AlCl3 dosage in polyalphaolefin production, two new (poly)ionic liquid /AlCl3 catalysts were synthesized from the reaction of 1-vinylimidazole with benzyl chloride (to yield IL) and subsequent polymerization of its vinyl bond by radical route, to achieve polyionic liquid (PIL). Cationic oligomerization of three α-olefin monomers, from 1-hexene to 1-decene, was accomplished using IL(or PIL)/AlCl3 catalysts with 50:50 wt.% composition to halve the usage of hazardous AlCl3. Microstructure and flow characteristic of the obtained PAO oligomers were characterized by 1HNMR, 13CNMR, GPC, viscometry, GC-Mass, and SimDis analyses and compared with those of PAOs from neat AlCl3. Results from GPC, viscometry and GC revealed that molecular weight decreases using lighter α-olefin monomers. Notably, while the PAOs from IL/AlCl3 have almost heavier fractions, the ones from PIL/AlCl3 and neat AlCl3 demonstrated similar molecular weight and KV100 amounts. The PAOs from PIL/AlCl3 and IL/AlCl3 represented a more uniform structures, with low short chain branching, beneficial to higher viscosity index (VI). This achievement featured PIL/AlCl3 as a suitable alternative to corrosive AlCl3, which besides its more environmentally friendly character, thanks to PIL presence, is capable of producing PAOs with the same KV100, however, with much higher VI values.

Some polymeric imidazolates from alkylimidazolium as corrosion inhibitors of API 5L X52 steel in production water

In this work, the synthesis route and evaluation of two poly(ionic liquids) (PolyILs) derived from alkylimidazolium imidazolate to be used as corrosion inhibitors (CIs) of API 5L X52 steel exposed to oil reservoir production water (PW) are discussed. The corrosion inhibition performance of the PolyILs was investigated by potentiodynamic polarization (PDP), electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). According to the PDP analysis, it was concluded that the PolyILs could be classified as mixed-type CIs with anodic tendency, featuring maximal inhibition efficiency (η) of 80%. The adsorption mechanism occurred through the blocking of active sites by means of electrostatic attraction forces and formation of chemical bonds. The SEM and AFM surface analyses evidenced that the metal surface in the presence of the PolyILs was less damaged by steel corrosion. Finally, the XPS studies confirmed that the CI interaction with the steel surface reduced the amount of produced corrosion products such as FeOOH and/or FeCO3.

Zinc Oxide-Based Pseudocapacitors with Electrospun Poly(Vinylidene Fluoride)/Poly(Ionic Liquid) Nanofibers as Solid Polymer Electrolyte

Due to the interesting properties of polymerized ionic liquids (PILs), studies are carried out to evaluate its performance when in composite with other synthetic polymers. Research on blend films prepared through solution casting are typically done to investigate their properties, however, electrospun fibers are of particular interest especially on technologies requiring mechanically robust and high surface area functional materials. In this work, poly (vinylidene fluoride)/poly (ionic liquid) (PVdF/PIL) nanofibers were produced through electrospinning. The PIL, poly (1-hexyl-3-vinyl imidazolium bromide), was synthesized through sonochemical solventless reaction followed by free radical polymerization. The structures of the synthesized IL and PIL were confirmed using FT-IR, 1H-NMR and 13C-NMR spectroscopy. Pseudocapacitor prototypes consisting of electrodeposited ZnO-based electrodes and the electrospun PVdF/PIL nanofibers as the polymer electrolyte were then fabricated at varied PIL concentrations. Contact angle measurements using sessile drop method revealed the decreasing wettability of the fibers attributed to the inherent hydrophobic nature of both the PVdF and PIL. Scanning electron micrographs also showed that increasing fiber diameters were obtained as the PIL concentration increases. In addition, cyclic voltammetry results showed that the calculated areal capacitance also increases with increasing PIL concentration. The development of pseudocapacitor assemblies utilizing ZnO-based electrodes and electrospun polymer electrolyte-separator membranes presents a better promise for the next-generation energy storage devices.

Preparation of Pyridine Polyionic Liquid Porous Microspheres and Their Application in Organic Dye Adsorption

Preparation of Pyridine Polyionic Liquid Porous Microspheres and Their Application in Organic Dye Adsorption

VERSATILE APPLICATIONS OF THE IONIC LIQUID

The first ionic liquid Ethyl ammonium nitrate was discovered in the year 1914. Ionic liquids are organic salt that is composed of organic cations and organic or inorganic anions. Ionic liquids subsist as liquid below the 100˚C or in the room temperature. A huge number of ionic liquid can be synthesized by the amalgamation of the various anions and cations through numerous kind of bonds. Ionic liquids are considered as green solvents because of non-volatility, lowviscosity, colourless, polar, wide range of solubility of biopolymers, absorption and desorption of gases. The environmental factor (E-factor), atom efficiency also supported the greenness of the ionic liquid. In chemistry, ionic liquid can replace the usual volatile organic solvents, mineral acids, solid acids etc., due to the non-corrosive green nature. For this reason, ionic liquids can be employed to numerous organic syntheses. The synthesis of ionic liquids can be done in single or multiple steps. Microwave irradiations and ultrasound assisted reactions are commonly employed to synthesise the green ionic liquids. Purification of ionic liquids can be done through crystallisation, extraction, distillation, biphasic separation and also through composed method of centrifugation or membrane separation followed by distillation. Broadly, ionic liquids are classified as basic ionic liquids, protic ionic liquids, neutral ionic liquids, chiral ionic liquids, metallic ionic liquids, poly ionic liquids, bio-ionic liquids, task specific ionic liquids etc. The major application of ionic liquids in the field of solvents and catalysts, electrochemistry, physical chemistry, analytical chemistry, pharmaceutical, biological, engineering field is well documented in this paper.

Design of a New Poly Imidazolium-Tagged Cobalt (II) Schiff Base Complex for Selective Oxidation of Alcohols and Sulfides in a Water Solvent

In this study, a new catalyst including polymeric imidazolium ionic liquid functionalized Cobalt (II) Schiff base complex [PIL-SB-Co (II)] was prepared and characterized using various analyses like FT-IR, H-NMR, FE-SEM, Energy-dispersive X-ray, thermogravimetric analysis, and ICP-OES. Then, its catalytic activity was studied in oxidation reaction of sulfides and alcohols. This polymeric heterogeneous catalyst can catalyze the oxidation reactions in water as a green solvent, and mild conditions (room temperature) with good to excellent yields of sulfoxides, aldehydes, and ketones as worthwhile and critical products. Highlights First preparation and characterization of poly ionic liquid functionalized Co (II) Schiff base catalyst. First oxidation reaction of sulfides and alcohols catalyzed by polymeric ionic liquid Schiff base complex. Oxidation reaction of sulfides and alcohols to sulfoxides and aldehydes and ketones in water as a green solvent and room temperature. Reusable catalyst at least for five runs.

Simultaneous extraction of six phthalic acid esters from polyethylene terephthalate (PET) bottled water using poly (ionic liquid) functionalised silica coated-iron oxide nanoparticles: a risk assessment study

ABSTRACT In this research, a poly (ionic liquid) functionalised silica-coated magnetic nanoparticles were synthesised for the first time and utilised as a novel adsorbent for the simultaneous extraction of six phthalic acid esters from polyethylene terephthalate bottled drinking water samples. The adsorbent was prepared by grafting poly (1-benzyl-3-vinyl-1 H-imidazol-3-ium chloride) onto silica-coated Fe3O4nanoparticles via Cu(0)-mediated reversible-deactivation radical polymerisation method. Various techniques were used to characterise the synthesised nanomaterials. A qualitative analysis was performed using ultra-performance liquid chromatography triple–quadrupole tandem mass spectrometry. Response surface methodology based on central composite design was used to optimise the extraction procedure and the optimised condition for each factor was; pH of3.9, 22 mg of adsorbent, 3.5 min extraction time, 3 min desorption time, 340 µL of elution solvent (methanol).The results of the validation of the method indicated its acceptable accuracy (88.6-100.1%), good linearity (r > 0.995), satisfactory repeatabilities (RSDs ≤ 6% for intra- and inter–day precisions) and high enrichment factors (535–572). The limits of detection and limits of quantification of the proposed method achieved were 1.1-4.6 ngL–1and 3.6-15.3 ngL–1, respectively. In this study, six common PAEs, including dimethyl phthalate, diethyl phthalate, dibutyl phthalate, benzyl butyl phthalate, bis (2-ethylhexyl) phthalate, and di-n–octyl phthalate, were found in PET bottled water within the range of 0.21-0.94 μgL–1, under different storage conditions. Nevertheless, only a negligible risk is caused by the PAEs in PET bottled water for consumers following the recommendations, such as storing at a common place (25°C), in a short period away from the sun.

Novel anion exchange membrane with poly ionic liquid-confined hypercrosslinked polymer for enhanced anion conduction and stability

Hypercrosslinked polymer (HCP) holds great potential for utilization as novel anion exchange membrane (AEM) material due to their rich microporous structure and high thermal/chemical stability while remaining challenges due to lack of hydroxide carriers. Herein we report a novel strategy of fabricating poly ionic liquid (PIL)-confined HCP for ion transfer. PIL precursors are loaded into the pores of HCP and in-situ polymerized to prepare PIL@HCP, which is then incorporated into quaternized poly (2,6-dimethyl-1,4-phenylene oxide) (QAPPO) to fabricate composite membrane. The introduction of PIL provides high concentration of quaternary ammonium (QA) groups in the porous networks of HCP. And the organic components impart outstanding compatibility between PIL@HCP and QAPPO matrix. All these permit the formation of interconnected hydroxide transfer channels through the membranes. Especially, the rigid and hydrophobic HCP functions with steric hindrance effectively impedes the attack of hydroxide ions on QA groups and maintains structure stability. Accordingly, the PIL@HCP/QAPPO composite membrane with high ion exchange capacity (IEC) of 2.33 mmol g−1 achieves a hydroxide conductivity of 98 mS cm−1 (80 °C, 100% RH), 92% higher than that of QAPPO. Meanwhile, the area swelling degree of PIL@HCP/QAPPO reduces to 13.6% in comparison to QAPPO (25.7%) and its conductivity retains 88% after alkaline treatment.

Piperidinium functionalized poly(2,6 dimethyl 1,4 phenylene oxide) based polyionic liquid/ionic liquid (PIL/IL) composites for CO2 separation

In this study, free-standing PIL/IL composite membranes of 1-bromohexyl-1 methylpiperidinium bromide (Br-6-MPRD) grafted poly(2,6 dimethyl 1,4 phenylene oxide) (ILPPO) incorporated with different amounts of free Br-6-MPRD (0, 2, 5 and 10 wt%) were prepared and the effect of free ionic liquid on CO2, N2 and O2 transport properties were reported. The structure of piperidinium based polyionic liquid (PIL) synthesised was confirmed using nuclear magnetic resonance (NMR) and Fourier transform infrared (FTIR) spectral techniques. Gas permeation results at 1 bar pressure and 25 °C revealed the best CO2 permeability and CO2/N2 as well as CO2/O2 permselectivities of the membrane stretch to 907.20 Barrer (higher than Pebax® 1657), 12.94 and 14.90 respectively for ILPPO/Br-6-MPRD-2 which come within reach of the 2008 Robeson limit. Apart from most of the published works, ILPPO/Br-6-MPRD-2 membrane revealed an anti-trade-off permeability-selectivity performances which is most required and a great challenge for CO2 separation and capture applications.

Facile Preparation of Poly(ionic liquid)s-zinc Halide Composite Toward Highly Efficient Conversion of CO<sub>2</sub> into Cyclic Carbonates

Facile Preparation of Poly(ionic liquid)s-zinc Halide Composite Toward Highly Efficient Conversion of CO<sub>2</sub> into Cyclic Carbonates