以离子液体为溶剂的原子转移自由基聚合

离子液体是一种有机盐,在接近室温下呈液状.离子液体是难挥发、极性高的溶剂,它能溶解很多种有机、无机和金属有机化合物.虽然有越来越多的人报道了有关离子液体在有机合成中的应用,但是在聚合过程中的应用却很少.然而在近几年,科学家证明了离子液体在聚合物的合成中的作用很大.在以离子液体为介质的自由基聚合反应中,kp/kt 会增大.尤其是在原子转移自由基聚合中,以离子液体作为溶剂有助于聚合物与残余催化剂的分离.本文主要阐述了原子转移自由基聚合反应的基本原理、特点以及离子液体在原子转移自由基聚合中的应用,并且还介绍了其他研究者的工作和原子转移自由基聚合的发展前景.     

离子液体在自由基聚合反应中的应用研究进展

室温离子液体是完全由离子构成的液体,具有几乎没有蒸汽压、溶解度大、溶解范围广、易于回收利用、稳定性好等特点,广泛应用于电化学、有机反应、分离萃取、复合材料等各个领域。近年来已成为各种聚合反应研究的重要课题,且主要集中于自由基聚合反应。作为聚合反应的溶剂,离子液体对聚合反应速率、分子量、聚合物的结构性能都有一定影响。本文根据近几年的文献,归纳分析了离子液体中的常规自由基聚合和活性自由基聚合的反应动力学、反应机理、聚合产物的结构和性能以及离子液体的回收利用等问题。     

微波促进离子液体相反应在有机合成中的应用

微波促进离子液体相有机合成技术作为一种新型的绿色化学合成法,引起了人们极大的兴趣。在离子液体中,微波辅助下反应快速、收率高、选择性好、后处理简单,离子液体经简单再生后可多次套用。本文综述了以离子液体为反应介质或催化剂的微波辅助技术在多种类型有机反应中的研究成果,主要包括了环合反应、亲核取代反应、金属复分解反应、酰化反应、重排反应、聚合反应、偶联反应、氧化还原反应和选择性脱溴反应等。     

自由基聚合反应的新介质——离子液体的新应用

离子液体具有独特的理化性能,作为一种环境友好、"可设计性"的溶剂,近年来成为化学领域的热点和前沿。离子液体作为自由基聚合反应的溶剂,对聚合速率、聚合产物结构及性能都有一定的影响。离子液体已经被较为广泛地应用于不同介质、不同物相中的自由基聚合反应,但是并不完全。近两年来已有研究工作者将离子液体应用于微乳液和气相中的自由基聚合反应,并和其他有机溶剂及水溶液共同调控自由基聚合反应。离子液体也首次应用于有机碲调控的自由基聚合反应和氮氧稳定的自由基聚合反应。同时离子液体也可以调控自由基聚合反应后聚合物的结构和形貌,是一种很好的进行聚合物自组装的溶剂。本文主要综述了近年来离子液体对自由基聚合反应的影响,特别是对聚合产物结构及性能的影响,最后展望了离子液体在聚合反应中的应用前景。     

波聚合体系、引发、过程及应用

波聚合是一种通过局部反应区域向未反应区域连续移动将单体转化为聚合物的反应模式,具有简便快速、节能降耗和产物性能优异等优势,是化学合成、功能材料与结构材料制备的新方法。本文对波聚合反应体系、引发、过程、应用及存在问题等方面进行综述。重点评述了新型波聚合体系如二元或多元体系、离子液体体系、深共晶溶剂体系等;新型引发剂如光引发剂和离子液体引发剂等特殊引发剂;波聚合反应体系中的助剂如填料、交联剂、链转移剂、活化剂、增稠剂、表面活性剂和催化剂等对聚合过程和产物结构性能的影响;新发展的引发方式如紫外线、水、等离子体和耦合引发等;以及特殊波聚合过程。最后,展望了波聚合存在问题和商业化应用的研究方向。     

含咪唑离子盐的环辛烯在离子液体中开环易位聚合微观研究

用核磁共振方法研究了带电荷的环辛烯单体在离子液体和CDCl3中开环易位聚合反应的微观特征,根据单体在化学位移δ=5.66~5.58处双键氢积分峰面积的减少和聚合物主链上不饱和双键氢移至高场δ=5.38~5.39处峰面积积分的增加来表征聚合反应的情况.检测和记录了单体在有离子液体参与的条件下均相聚合反应和在CDCl3中的异相聚合反应过程,根据在不同反应体系中Grubbs第二代崔化剂中与Ru相连的苯亚甲基上氢在核磁图谱上δ=19.2处的峰型变化,探讨在两种介质中的不同聚合行为.研究表明,该单体在离子液体介质中的均相聚合有可控聚合的微观特点,并通过ln[M]0/[M]与反应时间的关系曲线,证实了反应的活性特征.     

磺酸功能化离子液体催化3-羟基丙酸甲酯酯交换聚合反应

以磺酸功能化咪唑离子液体为催化剂,以3-羟基丙酸甲酯为原料,采用自身酯交换法合成了具有生物可降解性能的聚羟基脂肪酸酯.系统考察了离子液体种类、反应温度以及聚合反应时间对反应性能的影响,同时采用红外、核磁、热分析等手段对产物进行表征.研究结果表明:阴离子为CF3SO-3的磺酸功能化离子液体在120℃的低温下催化聚合反应所得聚酯Mw可达10 159,收率82.1%;通过水洗方法可有效去除产物中的离子液体催化剂,从而避免催化剂污染产物.     

酸性离子液体催化脂肪酸甲酯聚合制备二聚酸甲酯

 以 Brönsted-Lewis 酸性离子液体为催化剂, 用于催化生物柴油中不饱和脂肪酸甲酯聚合制备二聚酸甲酯反应, 考察了催化剂种类、催化剂用量、反应温度和时间等因素对聚合反应性能的影响, 得到较佳的反应条件. 结果表明, 当以 1-(3-磺酸)-丙基-3-甲基咪唑氯锌酸盐[HO3S-(CH2)3-mim]Cl-ZnCl2 (ZnCl2 摩尔分数为 0.67) 为催化剂, 生物柴油 15 g, m(生物柴油):m(离子液体) = 15:1, 于 240 oC 下反应 6 h 时, 二聚酸甲酯收率为 63.2%, 其中三聚体含量小于 5%. 另外, 该催化剂重复使用 5 次后, 二聚酸甲酯收率仍超过 63%, 表明其具有较好的重复使用性能. 离子液体的 Brönsted 和 Lewis 酸位的协同效应显著提高了其催化活性.     

离子液体在有机合成中的应用研究进展

离子液体由于具有特殊的性质, 包括低挥发性、大极性、良好的热稳定性、通过调整阴阳离子选择不同的溶解性等特点, 已经作为反应介质或催化剂广泛应用于有机合成领域, 引起了人们足够的兴趣. 与传统有机溶剂反应相比, 离子液体相反应得到的产物收率高, 选择性好, 加快部分类型反应的速率, 后处理简单以及离子液体催化剂体系简单, 回收后, 可多次重复使用. 综述了离子液体作为反应介质或催化剂在有机合成传统反应类型中的最新研究成果, 主要包括: 偶联反应、Michael加成、Baylis-Hillman反应、Diels-Alder反应、Aldol缩合、Knoevenagel缩合、环化反应、烷基化及酰基化反应和氧化还原反应.     

聚乙二醇功能化离子液体的制备及其在有机反应中的应用

聚乙二醇功能化离子液体作为一个新的研究方向受到了化学研究者关注,该类离子液体已经成功地应用于许多有机合成反应中,可以明显改善催化剂性能,并可在一定程度上解决传统催化剂使用中遇到的难分离、难回收再利用的问题。本文介绍了聚乙二醇功能化离子液体的发展历程、制备方法和其作为反应介质、溶剂或催化剂在有机合成反应中应用的最新研究成果,主要包括加成反应、缩合反应、还原反应、酯化反应、硝化反应、氧化反应、水解反应、Heck 反应以及Suzuki-Miyaura反应等。     

Systematic Investigation of the Photopolymerization of Imidazolium-Based Ionic Liquid Styrene and Vinyl Monomers

The use of ionic liquids (ILs) as media in radical polymerizations has demonstrated the ability of these unique solvents to improve both reaction kinetics and polymer product properties. However, the bulk of these studies have examined the polymerization behavior of common organic monomers (e.g., methyl methacrylate, styrene) dissolved in conventional ILs. There is increasing interest in polymerized ILs (poly(ILs)), which are ionomers produced from the direct polymerization of styrene-, vinyl-, and acrylate-functionalized ILs. Here, the photopolymerization kinetics of IL monomers are investigated for systems in which styrene or vinyl functionalities are pendant from the imidazolium cation. Styrene-functionalized IL monomers typically polymerized rapidly (full conversion ≤1 min) in both neat compositions or when diluted with a nonpolymerizable IL, [C₂mim][Tf₂N]. However, monomer conversion in vinyl-functionalized IL monomers is much more dependent on the nature of the nonpolymerizable group. ATR-FTIR analysis and molecular simulations of these monomers and monomer mixtures identified the presence of multiple intermolecular interactions (e.g., π–π stacking, IL aggregation) that contribute to the polymerization behaviors of these systems. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2364–2375     

石英晶体微天平技术研究咪唑类离子液体与气体分子的相互作用

基于石英晶体微天平(Quartz Crystal Microbalance, QCM)技术, 建立了一种测定气体在离子液体(ILs)中基本热力学参数的方法. 测定了5种可挥发有机物(VOCs)在6种咪唑类离子液体中的亨利常数, 并对可能的作用机理进行了探讨. 结果表明, QCM技术可以作为研究离子液体溶解性和作用规律的有效方法.     

Combustible ionic liquids by design: is laboratory safety another ionic liquid myth?

The non-flammability of ionic liquids (ILs) is often highlighted as a safety advantage of ILs over volatile organic compounds (VOCs), but the fact that many ILs are not flammable themselves does not mean that they are safe to use near fire and/or heat sources; a large group of ILs (including commercially available ILs) are combustible due to the nature of their positive heats of formation, oxygen content, and decomposition products.     

Ionic liquids as novel and green media for clean synthesis of soluble aromatic‐aliphatic poly(amide‐ester)s containing hydroxynaphthalene urazole moiety

Ionic liquids (IL)s are very attractive and environmentally acceptable solvents. They can be used as green media for a number of chemical processes. In this investigation, for the advancement of ecological safety and improvement of technological ability of this process, room temperature ionic liquids (RTIL)s and quaternary ammonium salt, tetrabutylammonium bromide (TBAB) have been used both as an environmentally benign solvent and catalyst for the polycondensation 4‐(3‐hydroxynaphthalene)‐1,2,4‐triazolidine‐3,5‐dione ( 3HNTD ) with aliphatic diacid chlorides, eliminating the need for a volatile organic solvent (VOS) and additional catalyst. The reaction of monomer 3HNTD with acetyl chloride was performed in N,N‐dimethylacetamide solution at different molar ratios, and the resulting mono‐, di‐, and trisubstituted derivatives were obtained in high yields and were finally used as models for polymerization reactions. The effects of various reaction parameters, such as the nature of the ILs, the amount of ILs, the reaction temperature, and the reaction time, on the yields and inherent viscosities of the resulting poly(amide‐ester)s (PAE)s were studied. Polycondensation reactions successfully proceeded in IL without any additional extra components, such as triethylamine or pyridine, which are used in similar reactions in organic solvents. Therefore, ILs can act both as solvent and catalyst. In addition to the solubility test, inherent viscosity as a measure of molecular weight was determined. PAEs were obtained in high yields with inherent viscosities ranging from 0.18 to 0.34 dl g^?1. This method was also compared with conventional method for the synthesis of PAEs. Fluorimetric studies of the model compound as well as polymers were performed. Copyright © 2008 John Wiley & Sons, Ltd.     

A Study on VOCs Released by Lung Cancer Cell Line Using GCMS-SPME

The gas chromatography mass spectrometry (GCMS) with combination of Solid Phase Micro-extraction (SPME) was used to study the volatile organic compounds (VOCs) which emitted by the in-vitro cultured human cells and compared with documented volatile biomarker of lung cancer. For this purpose, the lung cancer cell (A549) and non-cancerous lung cell (WI38VA13) were cultured in identical growth medium, concurrently. The VOCs in the headspace of the cell cultures and the blank growth media (reference sample) were collected directly from the culture flask using SPME for 15minutes. The results show that two different volatile metabolites were screened out between A549 cells and Wi38VA13 cells. A549 cell found to emit 2 noticeable VOC which are decane and heneicosane. While for WI38VA13, the VOCs released were 1-Heptanol and heptadecane. The acquired VOCs were compared with the previous studies. The findings in this work conclude that the specific VOC of cells can be act as their odour signature and can be used to provide non-invasively screening of lung cancer using gas array sensor devices.     

水介质中2,6-二甲基苯酚的氧化偶合聚合

聚2,6-二甲基苯醚(PPO)是重要的工程塑料,一般采用在有机溶剂中使2,6-二甲基苯酚(DMP)氧化聚合的方法合成,这就需要溶剂回收装置和防爆反应器,且污染环境.从绿色化学观点出发,以水作为反应介质,不仅对环境友好,而且PPO不溶于水,容易分离.近年来,一些学者研究了在油/水两相或全水介质中使DMP氧化聚合合成PPO的新方法.本文主要综述了该方法的研究进展,包括DMP氧化聚合的机理,油/水两相或水介质中对聚合速率、氧化偶合选择性及PPO分子量等的影响因素.     

生物质炭的制备、改性以及在挥发性有机物吸附方面的应用

挥发性有机物（VOCs）是大气中重要的污染源之一,对环境和人类健康产生严重的危害。吸附法是工业中最常用的去除VOCs的方法,吸附剂是吸附技术的关键,生物质炭是一种由生物质基材料在高温下热解活化等工艺制得的炭材料,具有较高的比表面积、丰富的孔隙结构和化学活性表面,在环境污染控制领域具有广泛应用。基于最近的研究,本文系统地综述了常用于去除VOCs的生物质炭的制备和改性方法,以及生物质炭在吸附VOCs的应用研究。本文首要目标是评估生物质炭去除VOCs的能力,特别是经过各种改性和活化工艺后,评价生物质炭作为吸附剂去除VOCs的适用性;确定改性和活化后对VOCs吸附能力的影响;揭示生物质炭对VOCs可能存在的吸附机理。最后,文章也对生物质炭的再生提出了建议和展望。     

Biocatalysis and Biomass Conversion in Alternative Reaction Media

In this Minireview, the state of the art in the use of ionic liquids (ILs) and deep eutectic solvents (DESs) as alternative reaction media for biocatalytic processes and biomass conversion is presented. Initial, proof‐of‐concept studies, more than a decade ago, involved first‐generation ILs based on dialkylimidazolium cations and non‐coordinating anions, such as tetrafluoroborate and hexafluorophosphate. More recently, emphasis has switched to more environmentally acceptable second‐generation ILs comprising cations, which are designed to be compatible with enzymes and, in many cases are derived from readily available, renewable resources, such as cholinium salts. Protic ionic liquids (PILs), prepared simply by mixing inexpensive amines and acids, are particularly attractive from both an environmental and economic viewpoint. DESs, prepared by mixing inexpensive salts with, preferably renewable, hydrogen‐bond donors such as glycerol and amino acids, have also proved suitable reaction media for biocatalytic conversions. A broad range of enzymes can be used in ILs, PILs and DESs, for example lipases in biodiesel production. These neoteric solvents are of particular interest, however, as reaction media for biocatalytic conversions of substrates that have limited solubility in common organic solvents, such as carbohydrates, nucleosides, steroids and polysaccharides. This has culminated in the recent focus of attention on their use as (co)solvents in the pretreatment and saccharification of lignocellulose as the initial steps in the conversion of second‐generation renewable biomass into biofuels and chemicals. They can similarly be used as reaction media in subsequent conversions of hexoses and pentoses into platform chemicals.     

Novel synthesis of high‐molecular‐weight prepolymer of poly(p‐phenylene benzoxazole) in ionic liquids

Using ionic liquids (ILs) as the reaction solvent for the synthesis of prepolymer polyamide of poly(p‐phenylene benzoxazole) (PBO) was investigated. The optimum condition of prepolymer preparation was determined in ILs. A series of 1,3‐dialkylimidazolium ILs were used to be the reaction media of the polycondensation. The relationship between the molecular weight of prepolymer and the structure of ILs was analysed by changing the structure of the cation and species of anion of ILs. In order to prove the feasibility of the transformation, the prepolymer was used to prepare PBO in polyphosphoric acid media, and the conversion process was analyzed. The spinnability of the PBO solution was explored by the preparation of PBO fibers. The basic mechanical properties of PBO single fiber were tested. In a word, using 1,3‐dialkylimidazolium ILs as the reaction solvents was feasible for the synthesis of high‐molecular‐weight PBO prepolymer, which could be a promising PBO preparation method.     

From colloidal stability in ionic liquids to advanced soft materials using unique media

Owing to their fascinating properties, ionic liquids (ILs) are now receiving a great deal of attention as alternatives to organic solvents and electrolyte solutions and as synthetic and dispersion media for colloidal systems. Colloidal stability is an essential factor in determining the properties and performance of colloidal systems combined with ILs. The remarkable properties of ILs primarily originate from their highly ionic nature. Although such high ionic strength often causes colloidal aggregation in aqueous and organic suspensions, some colloidal particles can be well suspended in ILs without any stabilizers. In the first part of this article, we focus on recent experiments conducted to investigate the colloidal stability of bare and polymer-grafted silica nanoparticles and on the surface force between silica substrates and ILs. Three different repulsions between colloidal particles (i.e., electrostatic, steric, and solvation forces) are also highlighted, after which a possible interpretation of the results in terms of the stabilization mechanism in ILs both in the presence and in the absence of stabilizers is proposed. The latter part of this article provides an overview of our recent studies on colloidal soft materials with ILs. On the basis of the dispersed states of the silica colloids in ILs, two different soft materials, a colloidal gel and a colloidal glass in ILs, were fabricated. The relationship between their functional properties, such as ionic transport, rheological properties, and optical properties, and the microstructure of the colloidal materials is also described.