CO2 sorption capacity of porous poly(ionic liquid)s

Porous poly(ionic liquid)s based on copolymer of 1-allyl-3-methyimidazolium tetrafluoroborate and acrylonitrile with 70:30 monomer ratio were prepared and characterized for CO₂ sorption. The well-developed pore structure are formed in all the poly(ionic liquid)s and the pore size distribution(PSD) mainly concentrates in 0.4 ~ 0.8 nm. The effects of different pore-forming agents and their amount on the porous structure and CO₂ sorption were also discussed. For example, porous poly(ionic liquid) treated with n-heptane as the pore-forming agent and the amount of n-heptane 16 mL has the highest CO₂ sorption capacity of 1.43 wt % at 273 K and 0.101 MPa.     

Synthesis and characterization of new functional poly(urethane‐imide) crosslinked networks

To synthesize new functional poly(urethane‐imide) crosslinked networks, soluble polyimide from 2,2′‐bis(3,4‐dicarboxyphenyl) hexafluoropropane dianhydride, 4,4′‐oxydianiline, and maleic anhydride and polyurethane prepolymer from polycaprolactone diol, tolylene 2,4‐diisocyanate and hydroxyl ethyl acrylate were prepared. Poly(urethane‐imide) thin films were finally prepared by the reaction between maleimide end‐capped soluble polyimide (PI) and acrylate end‐capped polyurethane (PU). The effect of polyurethane content on dielectric constant, residual stress, morphology, thermal property, and mechanical property was studied by FTIR, prism coupler, Thin Film Stress Analyzer (TFSA), XRD, TGA, DMTA, and Nano‐indentation. Dielectric constant of poly(urethane‐imide) thin films (2.39–2.45) was lower than that of pure polyimide (2.46). Especially, poly(urethane‐imide) thin films with 50% of PU showed lower dielectric constant than other poly(urethane‐imide) thin films did. Lower residual stress and slope in cooling curve were achieved in higher PU content. Compared to typical polyurethane, poly(urethane‐imide) thin films exhibited better thermal stability due to the presence of the imide groups. The glass transition temperature, modulus, and hardness decreased with increase in the flexible PU content even though elongation and thermal expansion coefficient increased. Finally, poly(urethane‐imide) thin films with low residual stress and dielectric constant, which are strongly affected by the morphological structure, chain mobility, and modulus, can be suggested to apply for electronic devices by variation of PU. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 113–123, 2006     

Synthesis and CO2 adsorption behavior of amine‐functionalized porous polystyrene adsorbent

A solid amine adsorbent was prepared by modifying a porous polystyrene resin (XAD‐4) with chloroacetyl chloride through a Friedel–Crafts acylation reaction, followed by aminating with tetraethylenepentamine (TEPA). The adsorption behavior of CO₂ from a simulated flue gas on the solid amine adsorbent was evaluated. Factors that could determine the CO₂ adsorption performance of the adsorbents such as amine species, adsorption temperature, and moisture were investigated. The experimental results showed that the solid amine adsorbent modified with TEPA (XAD‐4‐TEPA), which had a longer chain, showed an amine efficiency superior to the other two amine species with shorter chains. The CO₂ adsorption capacity decreased obviously as the temperature increased because the reaction between CO₂ and amine groups was an exothermic reaction, and its adsorption amount reached 1.7 mmol/g at 10 °C in dry conditions. The existence of water could significantly increase the CO₂ adsorption amount of the adsorbent by promoting the chemical adsorption of CO₂ on XAD‐4‐TEPA. The adsorbent kept almost the same adsorption amount after 10 cycles of adsorption–desorption. All of these results indicated that amine‐functionalized XAD‐4 resin was a promising CO₂ adsorbent. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45046.     

Ionic liquid/poly(ionic liquid)‐based electrolytes for energy devices

Ionic liquids are organic salts with melting points generally below 100 °C. They are attracting wide attention and are used as electrolytes in electrochemical devices, such as fuel cells, lithium‐ion batteries, dye‐sensitized solar cells, supercapacitors and light‐emitting electrochemical cells, due to their negligible vapor pressure, high ionic conductivity and wide electrochemical window. This perspective article highlights the applications of ionic liquid‐ or poly(ionic liquid)‐based electrolytes in fuel cells, dye‐sensitized solar cells and supercapacitors. © 2013 Society of Chemical Industry     

Polyurethane-based poly (ionic liquid)s for CO2 removal from natural gas

Carbon dioxide separation from CH₄ is important to the environment and natural gas processing. Poly (ionic liquid)s (PILs) based on polyurethane structures are considered as potential materials for CO₂ capture. Thus, a series of anionic PILs based on polyurethane were synthesized. The effects of polyol chemical structure and counter-cations (imidazolium, phosphonium, ammonium, and pyridinium) in CO₂ sorption capacity and CO₂/CH₄ separation performance were evaluated. The synthesized PILs were characterized by NMR, DSC, TGA, dinamical mechanical thermo analysis (DMTA), SEM, and AFM. CO₂ sorption, reusability, and CO₂/CH₄ selectivity were assessed by the pressure-decay technique. The counter-cation and polyol chemical structure play an important role in CO₂ sorption and CO₂/CH₄ selectivity. PILs exhibited competitive thermal mechanical properties. Results showed that PILPC-TBP was the best poly (ionic liquid) for CO₂/CH₄ separation. Moreover, poly (liquid ionic) base polyol (polycarbonate) with phosphonium (PILPC-TBP) demonstrated higher CO₂ sorption capacity (21.4 mgCO₂/g at 303.15 K and 0.08 MPa) as compared to other reported poly (ionic liquids). © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47536.     

离子液体表面活性剂的合成与应用(Ⅱ)——离子液体表面活性剂的合成

按照离子液体表面活性剂的种类,分别介绍了不同类型离子液体表面活性剂的合成方法。阳离子型离子液体表面活性剂可以采用直接季铵化法、复分解法和离子交换法合成;阴离子型离子液体表面活性剂是采用传统阴离子表面活性剂与离子液体在有机溶剂或水/有机溶剂中复分解反应完成的;两性离子液体表面活性剂通常采用直接季铵化法合成;双子和Bola型离子液体表面活性剂与传统双子和Bola型表面活性剂的合成方法相似;微波和超声等新的辅助合成方法将明显促进离子液体表面活性剂的合成。     

Synthesis,extraction, and adsorption properties of calix[4]arene‐poly(ethylene‐glycol) crosslinked polymer

Novel calix[4]arene‐poly(ethylene glycol) crosslinked polymer (CCP) has been synthesized by the polycondensation reaction between a p‐tert‐butylcalix[4]arene derivative and dihydroxyl capped poly(ethylene glycol) (DHPEG, M_n = 1000) catalyzed by neodymium tosylate. The hydrogel, consisted of 66.9% water and 33.1% CCP, can selectively extract aromatic organic molecules from aqueous solution according to the diameter of the guest molecules, which infers that the diameter of the calix[4]arene cavity is about 5.4 Å and the conformation of calix[4]arene units altered from cone conformation to 1,3‐alternate conformation during the polycondensation reaction. Furthermore, CCP can also adsorb naphthalene from gas phase, showing much higher capacity than active carbon does, which may have some potential applications in the field of separation and environment protection. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Fine tuning the hydrophobicity of counter‐anions to tailor pore size in porous all‐poly(ionic liquid) membranes

Charged porous polymer membranes (CPMs) emerging as a multifunctional platform for diverse applications in chemistry, materials science and biomedicine have been attracting widespread attention. Fabrication of CPMs in a controllable manner is of particular significance for optimizing their function and maximizing practical values. Herein, we report the fabrication of CPMs exclusively from poly(ionic liquid)s (PILs), and their pore size and wettability were precisely tailored by rational choice of counter‐anions. Specifically, a stepwise subtle increase in hydrophobicity of the counter‐anions by extending the length of fluorinated alkyl substituents, i.e. from bis(trifluoromethane sulfonyl)imide to bis(pentafluoroethane sulfonyl)imide and bis(heptafluoropropane sulfonyl)imide, decreased the average pore size gradually from 1546 to 157 and 77 nm, respectively. Meanwhile, the corresponding water contact angles increased from 90° to 102° and 120°. The sensitive control over the porous architectures and surface wettability of CPMs by systematic variation of anion hydrophobicity provides solid proof of the impact of PIL anions on CPM structure. © 2019 Society of Chemical Industry     

Synthesis of poly(vinyl acetate)‐graft‐polystyrene and application to preparation of porous membranes

Poly(vinyl acetate)–TEMPO (PVAc–TEMPO) macroinitiators were synthesized by bulk polymerization of vinyl acetate in the presence of benzoyl peroxide (BPO) followed by termination with 2,2,6,6‐tetramethyl‐1‐piperidinyloxy (TEMPO). Radicals were mainly transferred to the acetoxy methyl groups in PVAc during the polymerization. The PVAc–TEMPO macroinitiators had several TEMPO‐dormant sites and styrene bulk polymerization with the macroinitiators produced poly(vinyl acetate)‐graft‐polystyrene (PVAc‐g‐PS). All the TEMPO‐dormant sites of PVAc–TEMPO macroinitiators participated in the styrene polymerization with almost equal reactivity. Methanolysis of PVAc‐g‐PS broke the PS branches apart from the PVAc backbone chains. Hydrophobic or hydrophilic porous membranes with controlled pore size could be prepared by removing the PVAc domains or the PS domains from the graft copolymer. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1658–1667, 2001     

Polymeric ionic liquid modified silica for CO2 adsorption and diffusivity

Two types of polymeric ionic liquids (PILs) modified porous silica for CO₂ sorption were synthesized by the polymerization of dialkylphosphate di‐butyl phosphate [VYIM][Bu₂PO₄] and 1‐allyl‐3‐methylimidazolium tetrafluoroborate [AMIM][BF₄] with alkoxyl‐modified silica. The PILs‐modified silica (SiO₂‐P[VYIM][Bu₂PO₄] and SiO₂‐P[AMIM][BF₄]) were evaluated by CO₂ adsorption isotherms at 273 K for investigating the porous structures. The adsorption and desorption behaviors of CO₂ (at 298, 313, and 333 K) and N₂ (at 313 K) up to 0.2 MPa were also investigated using a gravimetric method. In comparison with bare silica, the grafting of PILs on the support surface leads to a loss of microporosity, resulting in a slight decrease in CO₂ sorption capacity. The difference of CO₂ sorption capacity between SiO₂‐P[VYIM][Bu₂PO₄] and SiO₂‐P[AMIM][BF₄] is little, especially under 0.1 MPa. CO₂/N₂ selectivity is however notably improved, and especially [AMIM][BF₄] modified silica shows the best performance. The homogeneous surface diffusion model (HSDM) was used to estimate the diffusivities and good agreement between experimental values and fitting curves was obtained. The diffusion coefficients of CO₂ in the PILs‐modified silica are level with that of bare silica at level of 10⁻⁷−10⁻⁸ m²/s, about two to three orders of magnitude faster than that of reported [BMIM][BF₄]. POLYM. COMPOS., 38:759–766, 2017. © 2015 Society of Plastics Engineers     

离子液体聚合物CO_2吸附性能研究

为提高离子液体吸附CO_2的性能,通过自由基聚合制备了季铵盐类离子液体聚合物,采用两步种子溶胀法使该聚合物形成多孔结构,并通过扫描电子显微镜和差热-热重分析法对其形貌和热稳定性进行表征。研究了4种溶胀剂制备的多孔聚合物吸附CO_2的性能,试验结果表明:制备的多孔聚合物具有发达的微孔结构,孔径在0.4~0.8 nm内连续分布,且较集中于0.5~0.6 nm,达到38%以上;溶胀剂的种类对孔径分布及累计孔容有显著的影响,可归因于溶胀剂与聚合物的溶解度差异,采用混合溶胀剂得到的孔径分布更加均匀,而采用环乙烷溶胀剂得到的累计孔容明显减少;多孔聚合物的CO_2吸附量主要受累计孔容的影响,累计孔容相当的聚合物吸附CO_2的量也近似,在273 K、0.101 MPa条件下,约为1.1%。     

Synthesis and application of long‐chain alkyl quaternary ammonium‐functionalized hyperbranched polyester

A novel kind of macromolecule, long‐chain alkyl quaternary ammonium functionalized hyperbranched polyester (QHPE), was synthesized by the reaction of hyperbranched polyester Boltorn H30 (H30) and 2,3‐epoxypropyl alkyl dimethyl ammonium chloride under alkaline conditions in dimethylformamide. After modification, the hydroxyl terminal group of H30 was converted into an ammonium functional group. A series of products was obtained with different lengths of an alkyl chain (C8, C12, C16, and C18) in the ammonium functional group. All of the products were characterized by Fourier transform infrared and NMR spectroscopy. The application of QHPEs as accelerators for the alkaline hydrolysis of poly(ethylene terephthalate) (PET) fabric was studied. The influences of the structure of QHPEs and hydrolysis conditions, such as alkaline concentration, hydrolysis time, and temperature, on the weight loss of PET fabrics were investigated. The results indicated that QHPE was a novel, efficient accelerator for the alkaline hydrolysis of PET fabrics. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

离子液体表面活性剂的合成与应用(XII)——微乳液

离子液体表面活性剂替代传统表面活性剂构建微乳液具有明显的优势,且结构可设计;所制备的微乳液分为单相微乳液和多相微乳液,其相图主要包括拟三元相图和“鱼状”相图;微乳液的微观结构,如液滴尺寸、相互作用或极性等,可通过电化学技术、动态激光散射、小角X射线散射等技术来确定。此类微乳液可广泛应用于纳米粒子制备、聚合反应、金属离子萃取等领域。     

固载离子液体聚合物的二氧化碳吸附行为研究

采用溶液聚合法,将1-烯丙基三丁基膦双三氟甲烷磺酰亚胺盐离子液体聚合物固载在空白硅胶上,并对硅胶固载离子液体聚合物进行了FTIR红外光谱和CO2吸附性能检测。研究了温度、压力和孔径分布等对CO2吸附选择性的影响,并计算了其CO2吸附热力学参数。结果表明:相比于空白硅胶,采用溶液聚合法制备的固载离子液体聚合物具有发达的孔结构,且这种差异在孔径分布为0.5~0.6nm时表现更加明显;制备的吸附剂在常温高压条件下表现出良好的吸附性能,且对CO2/N2具有较高选择性;该固载离子液体聚合物的吸附为放热反应,且为自发的物理吸附过程。     

离子液体的合成与应用

离子液体即在常温及附近温度下为液体的离子物质,已合成的主子液体已达上百种,离子液体的合成方法有复分解法和中和法,其应用研究领域有分离过程,化学反应特别是催化反应以及电化学等方面。     

Synthesis and swelling characteristics of poly(4‐vinylpyridine) gels crosslinked by irradiation

The effect of irradiation under vacuum on thermal properties and swelling behavior on poly(4‐vinylpyridine) (P4VP) was investigated. The gel percentage in the irradiated P4VP films was determined by Soxhlet extraction. UV spectroscopy was also used to determine sol percentage, which decreased as the radiation dose increased. The changes in thermal properties, such as glass‐transition temperature (T_g), were followed by differential scanning calorimetry before and after Soxhlet extraction. The gels prepared after irradiation were characterized with respect to their swelling properties and network structures. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2609–2614, 2001     

Synthesis and characterization of poly(N‐vinyl imidazole) hydrogels crosslinked by gamma irradiation

Crosslinked poly(N‐vinyl imidazole) (PVIm) hydrogels in the form of rods have been prepared by ⁶⁰Co γ‐radiation initiated simultaneous polymerization and crosslinking of N‐vinyl imidazole in bulk and water. In binary aqueous systems, the percentage gelation decreased with increasing water content. The PVIm hydrogels synthesized were further protonated in HCl solutions of different concentration. PVIm and protonated PVIm (H‐PVIm) hydrogels have been characterized using spectroscopic and thermal methods, and the swelling behaviour of these two types of hydrogel has been investigated. PVIm hydrogels originally swelled to 600% (by volume) but in their protonated form at pH 7.0 reached 4000% swelling. © 2002 Society of Chemical Industry     

离子液体表面活性剂的合成与应用(III)——离子液体表面活性剂的物化性能

重点介绍了离子液体表面活性剂的熔点与结构的关系。阳离子母体结构越不对称熔点越低,烷基链长增加熔点稍有提高;对阴离子型离子液体表面活性剂,阳离子的半径越大,其熔点越低;双子和Bola型离子液体表面活性剂比单疏水基离子液体表面活性剂的熔点高。室温呈液态的离子液体表面活性剂一般为黏稠液体,密度比一般有机溶剂大,在1 g/cm3左右,其表面张力为25~35 mN/m。