Ionic Liquid Copolymer Research Articles

Synthesis of bifunctional copolymeric nanofibers with selective extracting U(VI) from the solution and antibacterial property

Facing the problem of future nuclear fuel shortage, developing high-performance adsorbent materials is key. In this work, the amidoxime group/imidazole functionalized ionic liquid copolymer fibers containing bromide salts, and fluoroborate salts (namely P(AO/VEIMBr)8 and P(AO/VEIMBF4)6) were prepared by a one-pot method and free radical polymerization, hydroxyl amination reaction and electrostatic spinning, and characterized by SEM, FT-IR, and 1 H NMR. The influence of solid-liquid ratio, ionic strength, and adsorption time on the adsorption performance was investigated by batch adsorption experiments. In the meanwhile, the adsorption kinetics and thermodynamic processes of U(VI) on the copolymer fibers was also studied. Adsorption mechanism of U (VI) on polymer fibers was explored by XPS spectroscopic analysis combined with DFT method. Finally, the antimicrobial properties of the copolymer fibers were tested. The experimental results showed that the polymer nanofibers synthesized for U(VI) has a fast adsorption, high adsorption capacity at ionic strength close to seawater, and excellent reusability. The adsorption process conformed to the pseudo-second-order kinetic model and Langmuir model, which indicated that chemical adsorption and monolayer adsorption are dominant for adsorption U(VI) on the polymer nanofibers, and exhibits the highest Uranium adsorption capacity (76.92 mg/g and 81.96 mg/g at pH=8.1+0.1, respectively). XPS result showed the amine nitrogen and oxime oxygen in the amidoxime functional group were coordinated with uranyl(VI) ions. The antibacterial experiments showed that the copolymer fibers have antimicrobial properties and the antibacterial rate is over 90 %. Therefore, the nanofibers may be a promising material for extracting uranium from the weak alkaline wastewater or seawater.

Preparation and Performance Evaluation of Ionic Liquid Copolymer Shale Inhibitor for Drilling Fluid Gel System.

An inhibitor that can effectively inhibit shale hydration is necessary for the safe and efficient development of shale gas. In this study, a novel ionic liquid copolymer shale inhibitor (PIL) was prepared by polymerizing the ionic liquid monomers 1-vinyl-3-aminopropylimidazolium bromide, acrylamide, and methacryloyloxyethyl trimethyl ammonium chloride. The chemical structure was characterized using fourier transform infrared spectroscopy (FT-IR) and hydrogen-nuclear magnetic resonance (H-NMR), and the inhibition performance was evaluated using the inhibition of slurrying test, bentonite flocculation test, linear expansion test, and rolling recovery test. The experimental results showed that bentonite had a linear expansion of 27.9% in 1 wt% PIL solution, 18% lower than that in the polyether amine inhibitor. The recovery rate of shale in 1 wt% PIL was 87.4%. The ionic liquid copolymer could work synergistically with the filtrate reducer, reducing filtration loss to 7.2 mL with the addition of 1%. Mechanism analysis showed that PIL adsorbed negatively charged clay particles through cationic groups, which reduced the electrostatic repulsion between particles. Thus, the stability of the bentonite gel systems was destroyed, and the hydration dispersion and expansion of bentonite were inhibited. PIL formed a hydrophobic film on the surface of clay and prevented water from entering into the interlayer of clay. In addition, PIL lowered the surface tension of water, which prevented the water from intruding into the rock under the action of capillary force. These are also the reasons for the superior suppression performance of PIL.

Synthesis and properties of a novel ionic liquid copolymer shale inhibitor

AbstractAs oil reserves in shallow wells continue to deplete, the drilling industry must shift its focus toward extracting oil from deeper and more complex formations. Water‐based drilling fluid inhibitors are currently limited in their ability to withstand high temperatures. In the current work, for the first time, the application of 1‐vinyl‐3‐ethylimidazolium bromide salt‐allyl alcohol polyoxyethylene ether‐2‐acrylamide‐2‐methylpropanesulfonic acid (PIAA) as the shale inhibitor is reported. The incorporation of ionic liquids has made PIAA promising to be an effective shale inhibitor for high‐temperature‐tolerant water‐based drilling fluids. The high‐temperature resistance (300°C) of PIAA was verified through thermogravimetric test. Through mud ball, shale rolling recovery, and linear swelling experiments, we found that PIAA yielded the lowest swelling rate (27.3%) in the 24‐h linear swelling rate test, as compared to HMA‐15 (46.1%) and FA‐367 (31.2%). This confirmed the superior corrosion inhibition performance of PIAA. In addition, we investigated the inhibition mechanism using Zeta potential and other tests. Bentonite inhibition can be achieved through the coating of bentonite particles by PIAA, which effectively plugs shale pores, neutralizes negative charges on the surface of bentonite particles, and adsorbs them onto particle surfaces. Overall, PIAA has excellent high‐temperature resistance and inhibition properties.

Synthesis of water soluble ionic liquid copolymers based on acrylamide and investigation of their properties in flocculating of clay suspensions

To overcome water absorption and swelling by clay mineral layers, it is very important to develop stabilizing additives for water-based drilling fluids, where organic polymers are used as raw materials. Acrylamide copolymers, acting as flocculating agents, have the potential to separate minerals such as montmorillonite. In this study, three water-soluble copolymers containing acrylamide-amphoter, acrylamide-amphoter-anion, and acrylamide-amphoter-cation were synthesized and characterized using various analytical techniques, including Fourier-transform infrared spectroscopy, nuclear magnetic resonance, gel permeation chromatography, differential scanning calorimetry, thermogravimetric analysis, and derivative thermal gravimetric techniques. These copolymers were employed as flocculants to treat water suspensions containing montmorillonite particles, and a range of analytical methods, such as sedimentation volume measurement, scanning electron microscopy analysis, X-ray diffraction analysis, and contact angle measurement, were employed to identify the relationship between inhibitive performance. The flocculation of montmorillonite plates was attributed to the electrostatic attractions between montmorillonite and the synthesized copolymers. High molecular weight copolymers offer greater thermal stability and better flocculation characteristics for water-based drilling fluids. Among the tested copolymers, the acrylamide-amphoter-anion sample, with the highest molecular weight, exhibited the best performance as a coagulant when compared to the other copolymers.

Photodimerization induced hierarchical and asymmetric iontronic micropatterns

Micropatterning various ion-based modality materials offers compelling advantages for functionality enhancement in iontronic pressure sensing, piezoionic mechanoreception, and skin-interfaced electrode adhesion. However, most existing patterning techniques for iontronic materials suffer from low flexibility and limited modulation capability. Herein, we propose a facile and robust method to fabricate hierarchical and asymmetrical iontronic micropatterns (denoted as HAIMs) through programmed regulation of the internal stress distribution and the local ionic migration among an iontronic host. The resultant HAIMs with arbitrarily regulated morphologies and region-dependent ionic electrical performance can be readily made via localized photodimerization of an anthracene-functionalized ionic liquid copolymer (denoted as An-PIL) and subsequent vapor oxidative polymerization of 3,4-ethylenedioxythiophene (EDOT). Based on the piezoionic effect within the resultant distinct doped PEDOT, HAIMs can serve as a scalable iontronic potential generator. Successful syntheses of these fascinating micropatterns may accelerate the development of patterned iontronic materials in a flexible, programmable, and functionally adaptive form.

Bifunctional Solid-State Copolymer Electrolyte with Stabilized Interphase for High-Performance Lithium Metal Battery in a Wide Temperature Range.

Solid-state polymer electrolytes (SPEs) are expected to guarantee safe and durable operations of lithium metal batteries (LMBs). Herein, inspired by the salutary poly(vinyl ethylene carbonate) (PVEC) component in the solid electrolyte interphase, cross-linking vinyl ethylene carbonate and ionic liquid copolymers were synthesized by in-situ polymerization to serve as polymer electrolyte for LMBs. On one hand, due to rich ester bonds of PVEC, Li+ could transfer by coupling/decoupling with oxygen atoms. On the other hand, the imidazole ring of ionic liquid could facilitate the dissociation of lithium salt to promote the free movement of Li+ . The bifunctional component synergistically increased the ionic conductivity of the SPE to 1.97×10-4 S cm-1 at 25 °C. Meanwhile, it also showed a wide electrochemical window, superior mechanical properties, outstanding non-combustibility, and excellent interfacial compatibility. The bifunctional copolymer-based LiFePO4 batteries could normally operate at 0 to 60 °C, making them a promising candidate for wide-temperature-rang LMBs.

Pd on thermo-responsive composite of silica-coated carbon nanotube and 1-vinyl-3-butylimidazolium-based ionic liquid copolymers as an efficient catalyst for hydrogenation of nitro compounds

In this work, an ionic liquid-containing thermo-responsive heterogeneous catalyst with utility for promoting hydrogenation of nitro-compounds in aqueous media is developed. To prepare the catalyst, silica-coated carbon nanotubes were synthesized and vinyl-functionalized. The resulted compound was then polymerized with 1-viny-3-butylimidazolium bromide and N-isopropylacrylamide. The obtained ionic liquid-containing thermo-responsive composite was palladated via wet-impregnation method to give the final catalyst. Study of the performance of the catalyst confirmed high catalytic activity of the catalyst at temperature above the lower critical solution temperature. Furthermore, the catalyst was highly recyclable and showed negligible Pd leaching upon recycling. Broad substrate scope and selectivity of the catalyst towards reduction of nitro functionality were also confirmed. Furthermore, hot filtration test implied the heterogeneous nature of the catalysis. The comparison of the activity of Pd/CNT-P with some control catalysts approved the importance of hybridization of P and CNT and the presence of ionic liquid for the catalytic activity.

Interface Engineered Microcellular Magnetic Conductive Polyurethane Nanocomposite Foams for Electromagnetic Interference Shielding

HighlightsCarbon nanotubes/polymerizable ionic liquid copolymer (CNTs/PIL) provides nucleation sites and inhibits the combination of microcellular structures.The increase in evaporate time improves the conductive network of composite foams.Electromagnetic interference shielding effectiveness (EMI SE) and specific EMI SE of the composite foam displays 69.9 dB and 211.5 dB/(g cm−3).Polarization, conduction and magnetic loss attenuate microwave energy.

Influence of nitrogen configuration on the electrochemical properties of carbonized poly(acrylonitrile)-ionic liquid as anode materials in lithium ion batteries

Abstract A sequence of N-doped carbon materials has been synthesized using poly(acrylonitrile)-ionic liquid copolymers as carbon precursors. The nitrogen content and configuration in carbon materials has been changed regularly within a certain range by adjusting the proportion of ionic liquids. We found that the capacity and rate performance increased dramatically after the introduction of ionic liquids, which was attributed to incorporation of higher amount pyridinic-N, pyrrolic-N into the carbon materials. Besides, with the increase of the graphitic-N, the initial Coulombic efficiency decreased from 58.5 % to 53.47 % and the RSEI raised from 66.34 Ω to 140.96 Ω, which was attributed to the higher cohesive energy of Li dimmer than adsorption energy of graphitic-N with Li, since more lithium clusters during the formation of SEI film were formed. The electrochemical tests also revealed the negative role of graphitic-N in the capacity. Therefore, this work provides a feasible method to design the nitrogen content and configuration of the N-doped carbon materials.

Synthesis of a series of novel imidazolium-containing ionic liquid copolymers for dye-sensitized solar cells

A series of imidazolium-containing ionic liquid copolymers has been synthesized through free radical copolymerizations of an imidazolium-containing ionic liquid monomer (MEBIm-I), poly(ethylene glycol) methyl ether methacrylate (POEM), and acrylonitrile at various molar ratios. A thorough investigation has been conducted to study the effects of the chemical structure on the ionic conductivities, ionic diffusion coefficients, and catalytic activities of the ionic liquid copolymers. The presence of the ethylene oxide segments enhanced the ionic diffusion coefficients and conductivities of the POEM-containing ionic liquid copolymers. The incorporation of suitable contents of acrylonitrile units enhanced the catalytic activities of the ionic liquid copolymers. The photovoltaic and electrochemical impedance properties of dye-sensitized solar cells (DSSCs) assembled from these ionic liquid copolymer–based electrolytes have been evaluated. A maximum power conversion efficiency of 7.57%, with a maximum short-circuit current density of 16.0 mA cm−2, an open-circuit voltage of 0.84 mV, and a fill factor of 57.0%, has been achieved for DSSCs based on the ionic liquid copolymers (architecture: fluorine-doped tin oxide (FTO) glass/TiO2/N719 dye/ionic liquid polymer–based electrolyte/Pt/FTO glass) under AM 1.5 illumination with an intensity of 100 mW cm−2.

Preparation, characterization and evaluation of an imidazolium ionic liquid copolymer stationary phase for mixed-mode chromatography

A novel imidazolium ionic liquid mixed-mode stationary phase (named IBON) was successfully prepared by a controlled thiol-initiated radical polymerization method.

Unipolar Polymerized Ionic Liquid Copolymers as High-Capacitance Electrolyte Gates for n-Type Transistors

A series of well-defined polymerized ionic liquid (PIL) statistical and block copolymers consisting of ionic liquid monomer, 1-(4-vinylbenzyl)-3-butylimidazolium bis(trifluoromethylsulfonyl)imide, ...

What is the effect of lipophilic polymeric ionic liquids on friction and wear?

In this work, methacrylate-type ionic liquid (IL) monomers containing a quaternary ammonium cation and two different counter-anions were synthesized and used as co-monomers to obtain functional poly(alkyl methacrylates) (PAMAs). They were then evaluated as friction and wear reducing additives for lubricants. The effect of molecular weight, polymer topology (random or diblock), and IL counter anion on friction and wear behavior of polymer PAO (poly-alpha olefin) solutions have been investigated. The results were compared to those of PAO solutions additized with a small molecule, non-polymeric ionic liquid, or non-ionic copolymers containing 2-(dimethylamino)ethyl methacrylate (DMAEMA) as the polar comonomer. No clear correlation between polymer molecular weight and friction or wear behavior was observed. Random ionic liquid copolymers led to lower wear volumes than their block counterparts. Polymers containing dicyanamide (DCA) counter anion showed lower wear volume compared to those containing bis((trifluoromethyl)sulfonyl)imide (TFSI) anion. Surprisingly, none of the IL copolymers studied outperformed the DMAEMA containing block copolymer in terms of wear volume reduction, suggesting the IL moiety had no beneficial effect on wear.

Fabrication of N-doped Carbon Derived from poly(acrylonitrile)-ionic Liquid Copolymer and Application in Lithium Ion Batteries

Fabrication of N-doped Carbon Derived from poly(acrylonitrile)-ionic Liquid Copolymer and Application in Lithium Ion Batteries

Improving the charged and antifouling properties of PVDF ultrafiltration membranes by blending with polymerized ionic liquid copolymer P(MMA‐b‐MEBIm‐Br)

ABSTRACTThis study describes the fabrication and properties of poly(vinylidene fluoride) (PVDF) filtration membranes modified by blending with ionic liquid block copolymer P(MMA‐b‐MEBIm‐Br), which is synthesized via reversible addition‐fragmentation chain transfer polymerization method. The attenuated total reflectance‐Fourier transform infrared spectroscopy and X‐ray photoelectron analyses reveal that the ionic liquid block copolymers are immobilized on PVDF membrane surface. The modified PVDF membrane exhibits excellent charged and antifouling properties because of the charged and hydrophilic properties of the copolymer. Scanning electron microscopy and atomic force microscopy also indicate the morphological characteristics of the membrane and demonstrate that the surface porous structure becomes denser after adding the copolymer. The data of filtration and the zeta potential of the membranes suggest that the charged properties of the ionic liquid block copolymers are mainly responsible for the improvement of the reversible fouling ratio and the decrease in the total fouling ratio of the membranes. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44751.

Polymerizable ionic liquid copolymer P(MMA-co-BVIm-Br) and its effect on the surface wettability of PVDF blend membranes

Polymerizable ionic liquid copolymer P(MMA-co-BVIm-Br) was synthesized by radical polymerization technique, and characterized by Fourier transform infrared spectrometry (FTIR), 1H Nuclear magnetic resonance (1H-NMR) and gel permeation chromatography (GPC). The resulting copolymer was used to prepare poly(vinylidene fluoride) (PVDF) blend membranes via a phase inversion method. The effects of the copolymer on the polymorphism, surface wettability and zeta potential (ζ) of the blend membranes were investigated by ATR-FTIR, contact angle instrument and zeta potential analyzer. Scanning electron microscopy (SEM and SEM-EDS) was also applied to investigate the morphology and the surface element changes of the fabricated membranes. The results indicated that P(MMA-co-BVIm-Br) copolymer existed on the surface of the membrane which made the blend membrane have a positive surface during the experimental pH range. The copolymer was also in favor of the formation of β crystal phase in PVDF membranes. The contact angle experiment indicated that P(MMA-co-BVIm-Br) copolymer could switch the wettability of the blend membranes from hydrophilic to hydrophobic by exchanging Br− anion with PF6 −. Compared with pure PVDF membranes, the water flux and water recovery flux of the blend membranes were enhanced obviously. The results from the flux recovery ratio (FR) and total fouling ratio (R t) all suggested that the blend membranes had good anti-fouling properties.

Nanoporous array anodic titanium-supported co-polymeric ionic liquids as high performance solid-phase microextraction sorbents for hydrogen bonding compounds

A nanoporous array anodic titanium-supported co-polymeric ionic liquids (NAAT/PILs) solid-phase microextraction (SPME) fiber was prepared in situ on the titanium wire. NAAT was selected as the substrate, in view of its high surface-to-volume ratio, easy preparation, mechanical stability, and rich titanol groups on its surface which can anchor silica coupling agent containing vinyl and then introduce ionic liquid copolymers as sorbents. In this work, 1-vinyl-3-nonanol imidazolium bromide ([C9OHVIm]Br) and 1,4-di(3-vinylimidazolium) butane dibromide ([(VIM)2C4]2[Br]) were synthesized and used as monomer and crosslinker, respectively. Extraction properties of the NAAT/PILs fiber for polar alcohols and volatile fatty acids (VFAs) in aqueous matrix were examined using gaseous sampling–SPME (GS–SPME) and headspace SPME (HS–SPME) mode, respectively. Combining the superior properties of NAAT substrate and the strong hydrogen bond interaction of PILs to polar compounds, the NAAT/PILs SPME fiber showed much higher adsorption affinity to aliphatic alcohols than bare NAAT and pure PILs fibers. The detection limits (LOD) of established GS–SPME–GC–FID method are in the range of 0.35–17.30ngL−1 with a linear range from 0.01 to 500ngmL−1. Also, it showed high extraction performance toward volatile fatty acids (VFAs) compounds from aqueous matrix. Under the optimized SPME conditions, wide linear ranges were obtained with correlation coefficients (R2) greater than 0.99 and limits of detection were in the range of 0.85–8.74ngL−1. Moreover, real-world samples were analyzed and good results were obtained.

Synthesis and foaming of styrene–ionic liquid copolymer

Poly(ionic liquid), which had a strong carbon dioxide (CO 2) absorption ability, was introduced into polystyrene (PS) by the radical copolymerization between styrene and an ionic liquid monomer, i.e. [2-(methacryloyloxy)ethyl]-trimethylammonium tetrafluoroborate ([MATMA][BF 4]). The [MATMA][BF 4] segments in the copolymer greatly increased the solubility of CO 2, which was demonstrated by the significant glass transition temperature ( T g ) reduction of the copolymer under high pressured CO 2. The copolymer microcellular foams were then prepared by a batch foaming process using supercritical CO 2 as the blowing agent. The morphology characterization indicated that the copolymer microcellular foams had the much higher cell density and the much smaller cell size compared with the pure PS foams.

Solvent‐Reversible Poration in Ionic Liquid Copolymers

Mal offen, mal geschlossen: Bei der Polymerisation von Mikroemulsionen, die durch Tenside auf der Basis von ionischen Flüssigkeiten stabilisiert sind, entstehen vernetzte Polymergele, die durch Anionenaustausch bei der ionischen Flüssigkeit in poröse Polymere überführt werden können. Deren Eintauchen in organische Lösungsmittel ergibt wieder Polymergele, und das Eintauchen dieser Gele in Wasser liefert dann wieder die porösen Polymere (siehe Schema). Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2001/2007/z604127_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

Preparation and Characterization of Ionic Liquid Copolymers for Lithium Ion Conduction

Preparation and Characterization of Ionic Liquid Copolymers for Lithium Ion Conduction