离子液体中制备碳纳米管复合材料的研究

与传统的溶剂相比,离子液体作为一种新型的绿色环保溶剂及优良电解质,在碳纳米管复合材料制备中得到了广泛的应用.对近年来利用离子液体合成出的碳纳米管/金属复合材料、碳纳米管/纤维素复合材料、碳纳米管/聚合物复合材料,以及在高分子离子液体、离子液凝胶中制备的碳纳米管复合材料进行了综述,介绍它们的优势及特点.对今后离子液体在碳...     

离子液体在碳纳米管功能化及复合材料中的应用研究进展

离子液体具有低毒性、不易挥发、高的离子传导率、高的化学和热稳定性等特殊的性质,近几年在碳纳米管中的应用研究引起了广泛的关注.本文作者综述了离子液体近年来在碳纳米管的共价功能化、非共价功能化和聚合物复合材料中的应用研究进展,重点论述了其优势及展望.     

Influence of a rigid polystyrene block on the free volume and ionic conductivity of a gel polymer electrolyte based on poly(methyl methacrylate)‐block‐polystyrene

Diblock copolymers poly(methyl methacrylate)‐block‐polystyrene with three different molar ratios [poly(methyl methacrylate)/polystyrene (PS) = 1:1, 1:1.5, and 1:1.8] were synthesized by atom transfer radical polymerization and used as a polymer matrix for gel polymer electrolytes (GPEs). The positron annihilation lifetime spectroscopy was applied to determine the free‐volume behaviors of different GPEs, respectively. We illustrated that a proper PS ratio may led to the formation of a high fraction of free volume, and the influence of the PS ratio on the free‐volume fraction was caused by the different morphologies of the GPEs because of the different packing densities of the PS rigid block. The ionic conductivity was correlated with the free volume in the GPE through the study of the ionic conductivity dependence on the temperature; this followed the Vogel–Tamman–Fulcher equation. Moreover, an ionic conductive model was proposed, in which variations of the free‐volume behavior provide different ionic‐conducting abilities. Thermogravimetric analysis indicated that GPEs based on different block copolymers exhibited high liquid‐electrolyte preservation properties. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43901.     

衣康酸型可聚合乳化剂的合成及在细乳液聚合法制备聚苯乙烯/氯菊酯纳米胶囊中的应用

合成了可聚合乳化剂衣康酸单十二酯丙基磺酸钠,并将其应用于细乳液聚合法制备聚苯乙烯/氯菊酯纳米胶囊。考察了引发剂类型、乳化剂用量、交联剂和助稳定剂对聚苯乙烯/氯菊酯纳米胶囊粒径、包覆率的影响。采用红外光谱、核磁共振、质谱和透射电镜等表征手段对衣康酸单十二酯丙基磺酸钠的结构和聚苯乙烯/氯菊酯纳米胶囊的形貌进行了研究。研究结果表明:当衣康酸单十二酯丙基磺酸钠的用量占油相质量1.33%时,所制得的纳米胶囊粒径分布均匀,大小在500 nm左右;相比水溶性引发剂,油溶性引发剂引发聚合制得的纳米胶囊具有较大的包覆量;交联剂和助稳定剂的加入有助于对氯菊酯的包覆。     

Aramid pulp with physisorbed imidazolium ionic liquids for solvent‐casted enhanced styrene‐butadiene rubber composites

Poly‐p‐phenyleneterephthalamide is a broadly used aramid for the strengthening of materials. Nevertheless, its relatively inert surface is an obstacle for obtaining composites with enhanced properties. In this work, three ionic liquids (IL) were investigated as compatibilizers in the preparation of styrene‐butadiene rubber (SBR)‐aramid pulp composites. The composites were characterized using hardness and tensile tests, swelling, differential scanning calorimetry, and thermal gravimetric analysis, and also scanning electron microscopy. Aramid pulp treated with IL showed more fibrillation than the untreated pulp. The best characteristics were found for the composite with 5 phr of aramid pulp‐1 wt % of physisorbed IL, which showed the lowest swelling degree compared to the IL‐free SBR‐aramid composite (341% and 410%, respectively) and the highest tensile strength (2.48 MPa), 340% superior to that of SBR (0.73 MPa), and 25% superior to the IL‐free SBR‐aramid composite (2.05 MPa). Confirming the potential of imidazolium IL to be used as compatibilizers in SBR‐aramid composites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46693.     

Antistatic effects and mechanism of ionic liquids for methyl vinyl silicone rubber

The effect of two ionic liquids (ILs), namely, 1‐allyl‐3‐methyl imidazolium chloride ([AMIM]Cl) and 1‐ethyl‐3‐methyl imidazolium tetrafluoroborate ([EMIM]BF₄), on the surface and volume resistivities, mechanical properties, transparency, and water contact angle of methyl vinyl silicone rubber (MVQ) were investigated. The chemical structures of the two ILs before and after heat treatment were characterized by Fourier transform infrared spectroscopy. The morphology and fluorine and chlorine elemental dispersion were characterized by field emission scanning electron microscopy and energy‐dispersive X‐ray spectroscopy mapping, respectively. The antistatic mechanism was revealed. The results show that the MVQ–[EMIM]BF₄ composites had lower surface and volume resistivities than the MVQ–[AMIM]Cl composites. The mechanical properties of the MVQ–[EMIM]BF₄ and MVQ–[AMIM]Cl composites were slightly lower than those of the pristine MVQ. With increasing [EMIM]BF₄ content, the surface and volume resistivities and water contact angle of the MVQ–[EMIM]BF₄ composites decreased. When the content of [EMIM]BF₄ was 2.0 phr, the MVQ–[EMIM]BF₄ composites showed better antistatic performance with lower surface and volume resistivities of 9.6 × 10⁹ Ω and 1.2 × 10¹¹ Ω cm, respectively. The antistatic mechanism of the MVQ–IL composites was ascribed to the synergistic effect of ionic migration and moisture absorption. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45180.     

Preparation of polystyrene/montmorillonite nanocomposites in supercritical carbon dioxide

The preparation of polystyrene (PS)/montmorillonite (MMT) composites in supercritical carbon dioxide (SC? CO₂) was studied. Lipophilic organically modified MMT can be produced through an ion‐exchange reaction between native hydrophilic MMT and an intercalating agent (alkyl ammonium). PS/clay composites were prepared by free‐radical precipitation polymerization of styrene containing dispersed clay. X‐ray diffraction and transmission electron microscopy indicated that intercalation of MMT was achieved. PS/clay composites have a higher thermal decomposition temperature and lower glass‐transition temperature than pure PS. The IR spectrum analysis showed that the solvent of SC? CO₂ did not change the structures of the PS molecules, but there were some chemical interactions between the PS and the clay in the composites. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 22–28, 2005     

Effect of the medium on the stereostructure of poly(methyl methacrylate) synthesized in ionic liquids

Poly(methyl methacrylate) (PMMA) was synthesized in different ionic liquids (IL) by free radical polymerization. The average molecular weight and polydispersity of the PMMA were measured by gel permeation chromatography. It is found that ILs have effect not only on the molecular weights but also on the stereostructure of PMMA. From the FTIR and NMR analysis, it was confirmed that the chemical structure of PMMA synthesized in ILs was similar to the one obtained in conventional solvents while the stereostructure was influenced by the different IL used. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2199–2202, 2006     

Octanol/water partition coefficients of ionic liquids

BACKGROUND: Room temperature ionic liquids (ILs) are attractive alternatives to environmentally unfriendly volatile organic solvents. Partitioning is one of the most important and fundamental properties of a chemical, and the octanol/water partition coefficient is widely used to measure the tendency of a chemical to cross biological membranes. However, there is very limited information on the concentration dependence of the partition coefficients of ILs. This study investigated the octanol/water partitioning of 1‐butyl‐3‐methylimidazolium ([bmim]) ILs containing either hexafluorophosphate ([PF₆]) or bis[(trifluoromethyl)sulfonyl]amide ([Tf₂N]) over a wide range of IL concentrations of three to five orders of magnitude. RESULTS: It was found that the apparent partition coefficients of the ILs increased with increasing IL concentration. A model based on the ionic nature of ILs was proposed to explain this behaviour, and the results showed a good fit with the experimental data. The intrinsic partition coefficients and dissociation constants of the ILs were determined using the equations from the proposed model. The differences in the intrinsic partition parameter values between the two ILs showed a good correlation with other physicochemical properties. CONCLUSIONS: The present study clearly shows that the octanol/water partition coefficients of ILs increase with increasing IL concentration owing to the formation of ion pairs. By using the proposed partition model, it was possible to determine the intrinsic partition coefficients of ILs, and it was found that the apparent partition coefficients of ILs converge to the intrinsic partition coefficients of the ionic species and ion pairs of ILs with decreasing and increasing IL concentration respectively. Copyright © 2008 Society of Chemical Industry     

离子液体在纳米ZnO材料制备中的研究进展

离子液体（ILs）具有蒸气压低、液程宽、热稳定性好、结构和性质可调节等特点, 作为反应溶剂、模板剂或结构导向剂等在纳米材料制备领域得到了广泛的应用。纳米ZnO在传感器、太阳能电池、光催化和发光二极管等领域具有广泛的应用。总结了近年来ILs在纳米ZnO材料制备中的研究进展, 重点归纳和比较了常规非质子型ILs、质子型ILs、碱性ILs和聚ILs在制备纳米ZnO中的应用,及其调控纳米ZnO形貌、尺寸和性能的作用特点, 并为今后ILs应用于金属纳米材料的制备提出了建议。     

An easy method for the preparation of anion exchange membranes: Graft‐polymerization of ionic liquids in porous supports

A novel way for anion exchange membrane (AEM) preparation has been investigated, avoiding the use of expensive and toxic chemicals. This new synthetic approach to prepare AEMs was based on the use of a porous polybenzylimidazole membrane as support in which functionalized ILs were introduced and subsequently grafted on the polymer backbone. These new AEMs were prepared and their chemical structures and properties including morphology, thermal stability, and ionic conductivity were characterized. The hydroxyl ionic conductivity of the synthesized membranes can reach values upto 6.62 × 10^?3 S cm^?1 at 20°C. Although the ionic conductivity is not very high yet, the work shows the strength of the concept. Membrane properties can be easily tailored toward specific applications by choosing the proper chemistry, i.e., porous polymer support, ionic liquid, and method of initiation and polymerization. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of ionic liquids on stability of O/W miniemulsion for application of low emission coating products

Room temperature ionic liquids (RTILs) are non-volatile organic salts. They may replace conventional coalescing agents in latex coating thus reducing volatile organic compounds (VOCs) emission as well as improving performance of latex coating products such as better thermal stability, conductivity, and antifouling property. The formation of latex coating containing RTILs can be achieved by encapsulation of RTILs inside particles via miniemulsion polymerization. In this study, the role of RTILs and its concentration on stability of miniemulsion during storage and polymerization were investigated. It has been found that, above a critical concentration (10 wt%), adding more RTILs to oil phase may weaken miniemulsion stability during storage aswell as polymerization. Such observations were consistent with the zeta potential measurement for miniemulsions prepared at the similar conditions. The results obtained here would be a useful guideline for the development of new waterborne coating products with desirable functions and particle sizes.     

Effect of imidazolium ionic liquid type on the properties of nitrile rubber composites

We investigated the influence of hydrophilic and hydrophobic imidazolium ionic liquids on the curing kinetic, mechanical, morphological and ionic conductivity properties of nitrile rubber composites. Two room temperature ionic liquids with a common cation—1‐ethyl‐3‐methylimidazolium thiocyanate (EMIM SCN; hydrophilic) and 1‐ethyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIM TFSI; hydrophobic)—were used. Magnesium–aluminium layered double hydroxide (MgAl‐LDH; also known as hydrotalcite) was added to carboxylated acrylonitrile–butadiene rubber (XNBR) whereas fumed silica Aerosil 380 was used in acrylonitrile–butadiene rubber (NBR) as reinforcing fillers. NBR compounds were vulcanized with a conventional sulfur‐based crosslinking system whereas XNBR compounds were cured with MgAl‐LDH. The optimum cure time reduction and tensile properties improvement were obtained when both ionic liquids were added at 5 parts per hundred rubber (phr). The results revealed that EMIM SCN and EMIM TFSI induced an increase in the AC conductivity of nitrile rubber composites from 10^?10 to 10^?8 and to 10^?7 S cm^?1, respectively (at 15 phr ionic liquid concentration). The presence of ionic liquids in NBR slightly affected the glass transition temperature (T_g) whereas the presence of EMIM TFSI in XNBR contributed to a shift in T_g towards lower temperatures from ?23 to ?31 °C, at 15 phr loading, which can be attributed to the plasticizing behaviour of EMIM TFSI in the XNBR/MgAl‐LDH system. Dynamic mechanical analysis was also carried out and the related parameters, such as the mechanical loss factor and storage modulus, were determined. © 2013 Society of Chemical Industry     

Use of ionic liquids for the efficient utilization of lignocellulosic materials

Lignocellulosic materials are the most abundant renewable resource in the world and their efficient utilization provides a practical route to maintain social sustainable development. Application of ionic liquids has opened new avenues for the efficient utilization of lignocellulosic materials in such areas as fractionation, preparation of cellulose composites and derivatives, analysis, and removal of pollutants. However, there are still many challenges in putting these potential applications into practical use, for example, the high price of ionic liquids and lack of basic physico‐chemical and toxicological data. Further research and financial support are required to address such challenges. Copyright © 2008 Society of Chemical Industry     

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.     

可聚合型离子液体乳化剂的性能及在SAN合成中的应用

甲基丙烯酸二甲氨基乙酯与溴代烷烃反应合成可聚合离子液体——甲基丙烯酸二甲氨基乙酯丁基溴盐([DMC4]Br)、甲基丙烯酸二甲氨基乙酯癸基溴盐([DMC10]Br)、双甲基丙烯酸二甲氨基乙酯丁基溴盐([DM-C4-DM]Br2)和双甲基丙烯酸二甲氨基乙酯癸基溴盐([DM-C10-DM]Br2)。采用1HNMR和FTIR对其结构进行了表征。用电导率法测得其临界胶束浓度分别为16.20、11.20、25.61和16.13 mmol/L。分别以[DMC10]Br、[DM-C10-DM]Br2和十二烷基磺酸钠(SDS)为乳化剂制备了苯乙烯-丙烯腈共聚物(SAN);当[DM-C10-DM]Br2添加量(以单体总质量计,下同)为4%时,所制备的SAN单体转化率为90.2%;粒径为320.3 nm;SAN主链热分解起始温度为353℃;制备后废水的化学需氧量(COD)为937mg/L。该乳化剂制备的SAN的主链热分解温度比SDS制备的SAN提高了22℃,废水COD降低了1512 mg/L。     

Single component, reversible ionic liquids for energy applications

Single component, reversible ionic liquids have excellent potential as novel solvents for a variety of energy applications. Our energy industry is faced with many new challenges including increased energy consumption, depleting oil reserves, and increased environmental awareness. We report the use of reversible ionic liquids to solve two energy challenges: extraction of hydrocarbons from contaminated crude oil and carbon capture from power plant flue gas streams. Our reversible solvents are derived from silylated amine molecular liquids which react with carbon dioxide reversibly to form ionic liquids. Here we compare the properties of various silylated amine precursors and their corresponding ionic liquids. We show how the property changes are advantageous in the two aforementioned energy applications. In the case of hydrocarbon purification, we take advantage of the polarity switch between precursor and ionic liquid to enable separations. In carbon capture, our solvents act as dual physical and chemical capture agents for carbon dioxide. Finally, we show the potential economics of scale-up for both processes.     

Preparation and properties of polystyrene/SiCw/SiCp thermal conductivity composites

The silicon carbide whisker (SiCw) and silicon carbide particle (SiCp) were employed to prepare polystyrene/silicon carbide whisker/silicon carbide particle (PS/SiCw/SiCp) thermal conductivity composites, and the titanate coupling reagent of NDZ‐105 was introduced to functionalize the surface of fillers. The thermal conductive coefficient λ improved from 0.18 W/mK for native PS to 1.29 W/mK for the composites with 40% volume fraction of SiCw/SiCp (volume fraction, 3 : 1) hybrid fillers. Both the thermal decomposition temperature and dielectric constant of the composites increased with the addition of SiCw/SiCp hybrid fillers. At the same addition of SiCw/SiCp hybrid fillers, the surface modification of hybrid fillers by NDZ‐105 could improve the thermal conductivity and the mechanical properties of the composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Morphology and properties of polystyrene/agave fiber composites and foams

In this work, agave fibers were blended with polystyrene to produce foamed and unfoamed composites. The effect of fiber size and density reduction on the morphological, thermal, mechanical, and rheological properties, as well as crystallinity and water absorption kinetics of the composites was assessed. The results show that Young's modulus and tensile strength increased with increasing fiber content, but decreased with density reduction. Increasing fiber content and decreasing the size of the fibers both increased crystallinity of the composites. Finally, water uptake and diffusion coefficient were found to increase with increasing fiber content for all sizes. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

离子液体汽化焓的测量方法

离子液体具有蒸气压低、不易挥发、导电能力强、化学性质稳定、可循环利用等特点,具有以下作用：能够替代有机溶剂作为绿色环保的新型溶剂;可以作为催化剂催化化学反应;可以作为电解质溶液参与电化学反应,制作新型电池;可以作为吸附气体的吸附剂等。过去人们认为离子液体不挥发,也不能测量它们的汽化焓,回顾了近年来离子液体的相关研究成果,发现陆续有研究者提出测量离子液体汽化焓的方法,鉴于目前缺少相关总结工作,将系统性地介绍这些方法并阐述其原理,为今后的离子液体研究提供指导。