CN102977031A - Method for synthesizing ionic liquid - Google Patents

Method for synthesizing ionic liquid Download PDF

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CN102977031A
CN102977031A CN2012105350375A CN201210535037A CN102977031A CN 102977031 A CN102977031 A CN 102977031A CN 2012105350375 A CN2012105350375 A CN 2012105350375A CN 201210535037 A CN201210535037 A CN 201210535037A CN 102977031 A CN102977031 A CN 102977031A
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ionic liquid
step
acid
imidazole
halogen
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CN2012105350375A
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高建
谭小耀
刘秀军
潘璠
初园园
卢素敏
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天津工业大学
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Abstract

The invention discloses a method for synthesizing halogen-free imidazole ionic liquid, which comprises the following steps of: slowly dropping dialkyl sulfate in equal molar amount of 1-alkyl imidazole; putting a reactor in an ice bath and continuously stirring because the reaction is severe and is intense in heat discharge; after dropping, continuing to stir until the reaction is completed, to obtain dialkyl imidazole sulfate ionic liquid; separately dissolving the obtained dialkyl imidazole sulfate ionic liquid and potassium carboxylate in alcohol; mixing two solutions, and filtering and removing the generated solid to obtain a colorless clear solution; adding acid of target negative ion to neutralize the obtained colorless clear solution, filtering to obtain a solution of the colorless clear target ionic liquid; evaporating alcohol and water to obtain a target ionic liquid product; and drying in a vacuum environment to obtain pure target ionic liquid. The synthesizing method disclosed by the invention has characteristics of moderate and rapid reaction condition, no need of heating, pressurizing and other conditions, and easiness in implementation; and the solvent used in the synthesizing process can be recycled.

Description

一种离子液体合成方法 The method of synthesizing an ionic liquid

1.技术领域 1. FIELD

[0001] 本发明涉及离子液体合成。 [0001] The present invention relates to the synthesis of ionic liquids.

2.背景技术 2. Background of the Invention

[0002] 离子液体是一类正在备受关注的新型溶剂,它是一类熔点接近室温的盐(参见:Fernicola, A. ;Scrosati, B. ;0hno, Η. , Potentialities of ionic liquids asnew electrolyte mediain advanced electrochemical devices. Ionics 2006,12(2),95-102.)。 [0002] Ionic liquids are a novel class of solvents is of concern, it is a kind of salt melting point close to room temperature (see: Fernicola, A.; Scrosati, B.; 0hno, Η, Potentialities of ionic liquids asnew electrolyte mediain. advanced electrochemical devices. Ionics 2006,12 (2), 95-102.). 离子一体通常由体积较大且对称性较差的阳离子和体积相对较小而对称性良好的阴离子构成。 Ions usually consists of one large and poor symmetry cation and a relatively small volume of the volume of anions and good symmetry. 具有电导高、蒸汽压低以及溶解能力强等特点,被认为是一种可替代传统挥发性溶剂的绿色化学反应介质。 Having a high conductivity, low vapor pressure and dissolved ability, etc., it is considered an alternative to traditional volatile solvents green chemistry reaction medium. 随着对离子液体认识的逐渐深入探索,其应用已远超过当初的绿色化学范畴,在电解、太阳电池、燃料电池、催化剂领域甚至医学领域都存在巨大的应用前景。 With the gradual in-depth exploration of the ionic liquids knowledge, its application has far exceeded the scope of the original green chemistry, medicine and even there is a huge potential applications in electrolysis, solar cells, fuel cells, catalysts fields.

[0003]目前,两步法是制备离子液体较为普遍的合成方法。 [0003] Currently, two-step method of making an ionic liquid is more common synthetic methods. 如专利所述(参见:SeddonProcess for prerarting ambient tmprtature ionic liuids. US 6, 774, 240 B2,Aug. 10,2004,2004.),这种方法中第一步为卤代烷烃RX与咪唑类或其他杂环化合物合成含有目标阳离子的前驱体。 The patent (see:... SeddonProcess for prerarting ambient tmprtature ionic liuids US 6, 774, 240 B2, Aug 10,2004,2004), the first step in this process is a halogenated alkane or RX and other miscellaneous imidazole synthesis of cyclic compound containing a precursor of the target cation. 第二步为以第一步合成的产物作为反应物与含有目标阴离子的无机盐MY或酸HY进行离子交换反应,得到含有目标阳离子和阴离子的离子液体粗产物,然后用有机溶剂萃取离子液体(亲水类离子液体)或大量水洗(疏水类离子液体),最后得目标产物。 The second step is the first step in the synthesis of the product as a reactant with the inorganic salt MY or HY acid containing the target anion ion exchange reaction, to give a crude product containing the target ionic liquid cations and anions, is extracted with an organic solvent and an ionic liquid ( The hydrophilic ionic liquid) or heavy water (hydrophobic ionic liquid), and finally obtain the target product.

[0004] 两步合成法虽然具有一定的普适性,但缺点也十分明显。 [0004] While the two-step synthesis process has some universal, but the disadvantage is also very obvious. 主要是第二步交换反应难以进行完全,导致离子液体纯度低,尤其是卤素含量较高(Br 3〜4%,Cl I〜6% )(参见:Ellis Ionic liquids. WO 9618459.)。 The second step is the main reaction is difficult to complete the exchange, resulting in low purity ionic liquids, in particular high halogen content (Br 3~4%, Cl I~6%) (See:. Ellis Ionic liquids WO 9618459.). 而且过程中一般要采用如丙酮,二氯甲烷,乙腈等挥发性溶剂,溶剂难以回收完全,而且此类溶剂对环境污染较大。 And the process are generally used, such as acetone, dichloromethane, acetonitrile and other volatile solvents, a solvent difficult to recover completely, but such solvents larger environmental pollution. 有人提出利用AgBr低溶解度的特点可以使反应进行得较为完全,但银盐价格昂贵,导致离子液体成本大幅提高,且即使采用银盐,离子液体中仍有较高含量的卤素(参见:Nishida,T. ;Tashiro,Y. ;Yamamoto, Μ. , Physical and electrochemical properties of l-alkyl-3-methylimidazoliumtetrafluoroborate for electrolyte. Journal of Fluorine Chemistry2003,120 (2),135-141.)。 AgBr was proposed using the characteristics of low solubility can be in a more complete reaction, but silver is expensive, resulting in a substantial increase in the cost of the ionic liquid, and even if the silver salt, the ionic liquid remains high halogen content (see: Nishida, T.; Tashiro, Y;.. Yamamoto, Μ, Physical and electrochemical properties of l-alkyl-3-methylimidazoliumtetrafluoroborate for electrolyte Journal of Fluorine Chemistry2003,120 (2), 135-141)... 此外,还可以通过后处理的方式去除离子液体中的卤素。 In addition, the ionic liquid may be removed by way of post-treatment of the halogen. 如专利报道了电解法去除卤素的方法(参见:李作鹏,杜正银,顾彦龙,朱来英,邓友全降低离子液体中卤素含量的方法.CN200510129882. 2,2005.),可将卤素含量从3〜4%降低到1%以下。 The patent reports that a method for removing halogen electrolysis (see: Li Zuopeng, Du Zheng silver, Guyan Long, Zhu to England, Deng Youquan method of ionic liquids halogen content reduced .CN200510129882 2,2005), can be halogen content is reduced from 3 to 4% to 1% or less. 但这种方法需要使用电解设备等,工艺有一定复杂性,且离子液体产率太低。 However, this method requires the use of the electrolysis apparatus and the like, a certain process complexity, low yield and the ionic liquid. 而且无法将离子液体中的卤素完全除去。 The ionic liquid and can not be completely removed halogen. 因而合成无卤离子液体是非常必要的。 Synthesis of a halogen-free ionic liquids are therefore necessary. 目前已有人提出一些无卤合成方法。 Has been suggested that some of the halogen-free synthesis method. 如含烷基硫酸根的离子液体的合成(参见:Holbrey,JD ;Reichert, WM ;Swatloski,RP ;Broker, GA ;Pitner, WR ;Seddon,KR;Rogers,RD,Efficient,halide freesynthesis of new, low cost ionic liquids :1,3-dialkyIimidazoIium salts containing methyl—andethyI—sulfate anions.GreenChem. 2002,4(5) ,407-413.),但这种方法所得离子液体的阴离子局限于烷基硫酸根。 Synthetic ionic liquid containing an alkyl sulfate (see: Holbrey, JD; Reichert, WM; Swatloski, RP; Broker, GA; Pitner, WR; Seddon, KR; Rogers, RD, Efficient, halide freesynthesis of new, low cost ionic liquids: 1,3-dialkyIimidazoIium salts containing methyl-andethyI-sulfate anions.GreenChem 2002,4 (5), 407-413), but this method is the anion resulting ionic liquid confined alkyl sulfate... 也有以碳酸酯类离子液体为前驱体的无卤合成方法,如Holbrey等报道的一种方法,前驱体需要在120°C温度下加压反应24h (参见:Holbrey, JD ;Reichert, ff. M. ;Tkatchenko, I.;Bouajila, E. ;ffalter, 0. ;Tommasi, I. ;Rogers, RD , I,3-dimethylimidazolium-2-carboxylate :the unexpected synthesis of an ionic liquid precursorand carbene_C02adduct. Chem. Commun. 2003,(I),28-29.)。 But also to a halogen-free carbonate-based ionic liquid precursor synthesis method, as a method of Holbrey et al reported, the reaction pressure need precursor 24h (see temperature at 120 ° C for:. Holbrey, JD; Reichert, ff M .; Tkatchenko, I.; Bouajila, E.; ffalter, 0.; Tommasi, I.; Rogers, RD, I, 3-dimethylimidazolium-2-carboxylate:.. the unexpected synthesis of an ionic liquid precursorand carbene_C02adduct Chem Commun. 2003, (I), 28-29.). 所以这种方法条件相对来说有点苛刻,且反应时间较长。 Therefore, this method is relatively little harsh conditions, and the reaction time is longer. 在此基础上,以碳酸酯类离子液体为前驱体,加入含有目标阴离子的酸可以获得一些其他阴离子的离子液体(参见:Marcin Smiglak, NJB,Meghna Dilip, and RobinD. Rogers, Direct, Atom Efficient, and Halide-Free Syntheses ofAzolium AzolateEnergetic Ionic Liquids and Their Eutectic Mixtures, and Method forDeterminingEutectic Composition. Chem. Eur. J 2008,14,111314-111319.),但脱羧基反应需要反应时间较长,40°C需48小时。 On this basis, to the carbonate-based ionic liquid precursor, addition of an acid containing a target anion other anions can be obtained ionic liquid (see:. Marcin Smiglak, NJB, Meghna Dilip, and RobinD Rogers, Direct, Atom Efficient, and Halide-Free Syntheses ofAzolium AzolateEnergetic Ionic Liquids and Their Eutectic Mixtures, and Method forDeterminingEutectic Composition. Chem. Eur. J 2008,14,111314-111319.), but the decarboxylation reaction requires a long time, 40 ° C for an 48 hours . 还有人提出先合成碱性离子液体溶液([Cation]0H),再采用还有目标阴离子的酸中和获得目标离子液体(参见:Gao, J. ;Liu, JG ;Li, B. ;Liu, ff. M.;Xie, Y. ;Xin, YC ;Yin, Y. ;Jie, X. ;Gu, J. ;Zou, ZG , A quick andgreen approach toprepare[Rmim]OH and its application in hydrophilic ionic liquid synthesis. New Journal of Chemistry 2011, 35 (8) , 1661-1666, Gao, J. ;Liu, J. ;Liu, ff. ;Li,B. ;Xin, Y. ;Yin, Y. ;Gu, J. ;Zou, Z. , An efficient and green approach to preparehydrophilic imidazoliumionic liquids free of halide and its effect on oxygenreduction reaction of Pt/C catalyst. International Journal of Hydrogen Energy2012, 37(17),13167-13177, Matthias Maase, KM , Durkheim Method of PreparingIonic Liquids. US20070142646A1,Jun. 21,2007,2007)。 It was also suggested to synthetic basic ionic liquid solution ([Cation] 0H), then using the target as well as the acid anion, and to obtain the target ionic liquid (see: Gao, J.; Liu, JG; Li, B.; Liu, ff M.;. Xie, Y.; Xin, YC; Yin, Y.; Jie, X.; Gu, J.; Zou, ZG, A quick andgreen approach toprepare [Rmim] OH and its application in hydrophilic ionic liquid synthesis . New Journal of Chemistry 2011, 35 (8), 1661-1666, Gao, J.; Liu, J.; Liu, ff;. Li, B;. Xin, Y.; Yin, Y.; Gu, J. ; Zou, Z., An efficient and green approach to preparehydrophilic imidazoliumionic liquids free of halide and its effect on oxygenreduction reaction of Pt / C catalyst International Journal of Hydrogen Energy2012, 37 (17), 13167-13177, Matthias Maase, KM,. Durkheim Method of PreparingIonic Liquids. US20070142646A1, Jun. 21,2007,2007). 上述方法在合成咪唑类或季铵盐类离子液体时,具有高效、快速等特点。 In the above-described method of synthesis imidazole or quaternary ammonium ionic liquid with high efficiency, and so fast. 但我们发现,由于上述方法中采用KOH或CH3CH2OK等强碱,难以合成吡啶类离子液体,这是因为[Pyd]0H即使在溶液中也不能稳定存在,这与报道的结果想吻合(参见:Kagimoto, J. ;Fukumoto, K. ;0hno, H. , Effect oftetrabutylphosphonium cation on the physico—chemicalproperties of amino-acidionic liquids. Chemical Communications 2006, (21), 2254-2256.)。 However, we found that, since the above method using a strong base like KOH or CH3CH2OK, pyridine ionic liquid difficult, because [Pyd] 0H even not stable in solution, which is consistent with the reported results like (see: Kagimoto , J.; Fukumoto, K.; 0hno, H., Effect oftetrabutylphosphonium cation on the physico-chemicalproperties of amino-acidionic liquids Chemical Communications 2006, (21), 2254-2256)... 而批P定类离子液体也是一类重要的离子液体。 P granted given ionic liquids are an important class of ionic liquids. 因此,采用强碱的酸碱中和法合成离子液体在可合成的离子液体种类方面受到严重限制,有必要开发其他便捷高效的合成方法。 Thus, acid and strong base in the ionic liquid synthesis method is severely limited in terms of the type of ionic liquids can be synthesized, it is necessary to develop a convenient and efficient synthesis of other methods.

3发明内容 3 SUMMARY OF THE INVENTION

[0005] 本发明目的在于开发一种无卤素、高纯度且避免使用大量有害有机溶剂,降低成本且无需特殊设备的实用的多种离子液体合成方法。 [0005] The object of the present invention is to develop a halogen-free, high purity and avoid the use of large amounts of harmful organic solvents, without the need to reduce costs and practical method of synthesizing ionic liquids special apparatus.

[0006] 本发明通过以下方式实现。 [0006] The present invention is achieved by the following manner.

[0007] —种无卤素咪唑类离子液体的合成方法,它包括以下步骤: [0007] - halogen-free method for synthesizing imidazole kinds of ionic liquids, comprising the steps of:

[0008] 步骤I.将二烷基硫酸酯缓慢滴入等物质量的I-烷基咪唑或吡啶,由于该反应剧烈且强烈放热,反应器应置于冰浴中并不断搅拌。 [0008] Step I. dialkyl sulfates like was slowly added dropwise I- imidazole or pyridine group of substance, since the reaction vigorously and strongly exothermic, the reactor should be placed in an ice bath and continue stirring. 滴加完毕后再继续搅拌,使反应进行到完全。 Stirring was continued after the addition was complete, the reaction to proceed to completion. 如反应(I)所示,得到二烧基咪唑烧基硫酸根离子液体; The reaction (I), to give two burn burn-yl imidazole sulfate ion liquid;

[0009] 步骤2.将步骤I得到的二烷基咪唑烷基硫酸根离子液体与羧酸盐分别溶于醇中,再将两种溶液混合,如反应(2)所示,将产生的固体过滤除去得无色澄清溶液;[0010] 步骤3.在步骤2得到的无色澄清溶液中加入目标阴离子的酸中和,过滤,得无色透明目标离子液体的溶液; [0009] Step 2. Step I obtained imidazolidinyl dialkyl sulfate ion and carboxylate are dissolved in the liquid alcohol, and then mixing of the two solutions, reaction (2), the resulting solid removed by filtration to give a colorless clear solution; [0010] step 3. Add the solution from step 2 to give a clear, colorless target anion in acid and filtered to give a colorless and transparent solution of an objective ionic liquid;

[0011] 步骤4.将步骤3得到的无色透明目标离子液体的溶液中的醇和羧酸蒸发后,得到目标离子液体处产物,经真空干燥后可得纯的目标离子液体。 [0011] Step 4. The solution was colorless and transparent objective ionic liquid obtained in step 3 alcohols and carboxylic acids and evaporated to give the title product at an ionic liquid, and dried in vacuo to give pure target may be an ionic liquid.

[0012] 上述的无卤素咪唑类离子液体的合成方法,步骤I中所述的I-烷基咪唑或吡啶的烷基可以是I〜2个碳原子的烷基。 [0012] The method of synthesizing the above-described halogen-imidazolium ionic liquids, I- alkyl imidazole or pyridine group according to step I may be I~2 alkyl carbon atoms.

[0013] 上述的无卤素咪唑类离子液体的合成方法,步骤I中所述的二烷基硫酸酯的烷基可以是I〜2碳原子的烧基。 [0013] The method of synthesizing the above-described halogen-imidazolium ionic liquids, dialkyl esters of sulfuric acid in the step I may be burned group I~2 carbon atoms.

[0014] 上述的无卤素咪唑类离子液体的合成方法,步骤2中所述的羧酸盐可以是羧酸钠或羧酸钾。 [0014] The method of synthesizing the above-described halogen-imidazolium ionic liquids, in Step 2 carboxylic acid salt may be sodium carboxylate or potassium carboxylate.

[0015] 上述的无卤素咪唑类离子液体的合成方法,步骤2中所述的醇可以是I〜4个碳原子的醇。 [0015] The method of synthesizing the above-described halogen-imidazolium ionic liquids, the alcohol in Step 2 may be an alcohol I~4 carbon atoms.

[0016] 上述的无卤素咪唑类离子液体的合成方法,步骤2中所述的二烷基咪唑烷基硫酸根离子液体与羧酸钾的物质的量之比为I : I〜I : 4。 [0016] The method of synthesizing the above-described halogen-imidazolium ionic liquids, the amount of substance dialkylimidazolium ionic liquid alkyl sulfate to potassium in the second step the carboxylic acid ratio of I: I~I: 4.

[0017] 上述的无卤素咪唑类离子液体的合成方法,步骤3中所述的目标阴离子的酸可以是硫酸、磷酸、硼氟酸、六氟磷酸。 [0017] The method of synthesizing the above-described halogen-imidazolium ionic liquids, the step of the target anion of the acid may be a 3 sulfuric acid, phosphoric acid, fluoroboric acid, hexafluorophosphoric acid.

[0018] 利用烷基硫酸盐类离子液体([Rmim]RSO4, [RPydlRSO4)、羧酸盐在醇类中溶解度较高,而反应产物中的烷基硫酸盐在乙醇中溶解度极小的特点加快反应速度。 [0018] The use of alkyl sulfates ionic liquids ([Rmim] RSO4, [RPydlRSO4), carboxylates high solubility in the alcohols, the alkyl sulphates of the reaction product minimal solubility characteristics in ethanol accelerate reaction speed. 将烷基硫酸咪唑类离子液体和羧酸钾的醇溶液混合,烷基硫酸咪唑类离子液体中的烷基硫酸阴离子以钾盐沉淀方式除去,得到含有目标阳离子的羧酸盐离子液体溶液,然后加入含有目标阴离子的酸加入上述溶液,得到产物。 Imidazolidinyl mixed ionic liquid and sulfuric acid alcohol solution of potassium, alkyl imidazolium ionic liquids in the acid alkyl sulfate anion potassium salt precipitate was removed manner, to give the ionic liquid solution containing the desired cations of the carboxylate, and acid solution containing a target anion added to the solution to give the product. 副产物羧酸可以方便地随乙醇一起蒸出(低级羧酸的易挥发),得到目标产物其主要原理如下(以吡啶类离子液体合成为例,也可将吡啶替换为烷基咪唑): Carboxylic acid byproducts may be easily distilled off along with ethanol (volatile lower carboxylic acids), to give the desired product as its main principle (pyridine ionic liquid synthesis, for example, may alternatively be pyridine-alkyl imidazole):

[0019] [0019]

Figure CN102977031AD00051

[0020] 上述离子液体的合成方法的特点是反应条件温和而且快速,无需加热、加压等条件,易于实施。 [0020] features a method of synthesizing an ionic liquid is rapid and mild reaction conditions, without heating, pressure and other conditions, is easy to implement. 合成过程中的溶剂可以回收。 The solvent can be recovered during synthesis. 与传统的离子液体两步合成法相比本发明具有以下明显优点: Conventional ion liquid with a two-step synthesis has the following significant advantages over the present invention:

[0021] (I)该合成过程只用到了廉价且低毒甚至无毒的醇和水作为溶剂,不仅保护环境,而且溶剂易于回收利用。 [0021] (I) The synthesis uses only cheap and of low toxicity or even non-toxic alcohol and water as a solvent, not only to protect the environment, but also easy to recycle the solvent. 并保留了传统两步法普适性强的优点,可以根据需要采用不同的酸合成目标离子液体,另外阳离子也可方便地更换。 And retains the advantages of conventional two-step process universal strong, acid synthesis can target different ionic liquids as necessary, additional cations can also be easily replaced. (2)副产物为金属盐,易于净化提纯,可作为产品回收利用。 (2) a metal salt byproduct, easy to purify purification, can be recycled as a product. 此外还有反应迅速的特点,该方法中的控制步骤为两步,一是复分解反应,另一个是中和反应,这两步反应几乎都可以瞬间完成,因而反应时间大大缩短。 There is also responsive to the characteristics, the controlling step process steps, first the metathesis reaction, and the other is in the reaction, this two-step reaction can be almost instantaneous, and thus the reaction time was shortened. (3)该过程只涉及到溶解、过滤、及蒸发等常规单元操作,一般实验室均可操作,也易于实现工业化生产。 (3) The process involves only routine unit operations to dissolve, filtered, evaporated and the like, general laboratory can be operated, but also easy to realize industrial production. 虽然存在专门合成羧酸盐离子液体的方法(烷基咪唑前驱体乙醇溶液与醋酸钾溶液反应),但仅限于合成醋酸盐类离子液体。 Although the method specifically carboxylic acid salt of the ionic liquid (ethanol solution of potassium acetate solution and the reaction precursor imidazole group) is present, but only to the acetic acid synthesis Ionic Liquids.

4附图说明 BRIEF DESCRIPTION OF 4

[0022] 图.I是本专利的合成流程图。 [0022] FIG. .I is a synthesis scheme of this patent.

5具体实施方式 5 DETAILED DESCRIPTION

[0023] 以下给出本发明的4个最佳实施例。 Gives [0023] of the present invention the following four preferred embodiments.

[0024] 实施例一:乙基甲基咪唑硫酸氢盐(I-甲基-3-乙基咪唑硫酸氢盐)合成 Ethyl methylimidazolium hydrogensulfate (the I-methyl-3-ethylimidazolium hydrogensulfate) Synthesis: a [0024] Example

[0025] (I)在单口烧瓶中加入O. Imol I-甲基咪唑,并将O. Imol硫酸二乙酯逐滴加入,力口完后继续搅拌3小时左右,得无色透明离子液体I-甲基-3-乙基咪唑乙基硫酸盐([Emim]EtSO4),是为前驱体。 [0025] (I) in a single neck flask was added O. Imol I- methylimidazole, and O. Imol diethyl sulfate was added dropwise, stirring was continued for 3 hours after the opening force, to give a transparent ionic liquid I - 3-ethyl ethylsulfate ([Emim] EtSO4), is the precursor.

[0026] (2)将前躯体溶于丙醇,另外取等摩尔CH3COOK溶于丙醇。 [0026] (2) A precursor is dissolved in alcohol, to take additional equimolar CH3COOK is dissolved in alcohol. 将两种溶液混合,立即产生白色沉淀,该沉淀经过滤除去后得无色透明液体。 The two solutions were mixed, a white precipitate was immediately produced to give a colorless transparent liquid The precipitates were removed by filtration.

[0027] (3)向该溶液中加入等摩尔硫酸溶液,可见有少量固体产生,该同体为金属硫酸氢盐,由于NaHSO4或KHSO4在醇中溶解度极低(难溶),所以析出。 [0027] (3) To the solution was added an equimolar solution of sulfuric acid, a small amount of solid was visible, with the body of the metal salt is a hydrogen sulphate, KHSO4 or NaHSO4 since very low solubility in an alcohol (insoluble), so that the precipitation. 将固体在此过滤除去并计量。 The solid was removed by filtration, and this measurement.

[0028] (4)将溶液蒸发除去乙酸及醇,得离子液体乙基甲基咪唑硫酸盐^!11加]肥04粗产物,该产物经真空干燥后得到纯产物,收率97%以上。 [0028] (4) The solution was evaporated to remove acetic acid and an alcohol, to give the ionic liquid ethylmethylimidazolium sulfate ^! 11 The crude product was added 04] fat, the product was dried in vacuo to give pure product, a yield of more than 97%. 产物做核磁检测,结果为:[Emim]HSO4 =1H NMR (D20,500MHz) : δ = 8· 64 (s,1H),7· 42 (s,1H),7· 36 (s,1H),4· 12-4. 15 (m,2H), NMR detection products do, the result is: [Emim] HSO4 = 1H NMR (D20,500MHz): δ = 8 · 64 (s, 1H), 7 · 42 (s, 1H), 7 · 36 (s, 1H), 4 · 12-4. 15 (m, 2H),

3. 83(s,3H),I. 44 (t, J = 7. 25Hz,3H)。 3. 83 (s, 3H), I. 44 (t, J = 7. 25Hz, 3H).

[0029] 实施例二乙基甲基咪唑磷酸二氢盐合成 Synthesis Example dihydrogen phosphate, diethyl-methylimidazo [0029] Embodiment

[0030] 步骤基本与实例一相似,只是将CH3COOK与[Emim] EtSO4摩尔比改为I. 5 : I,将硫酸改为磷酸,丙醇改为乙醇。 [0030] Example Step a substantially similar, except that the CH3COOK [Emim] EtSO4 molar ratio to I. 5: I, the sulfuric acid to phosphoric acid, propanol instead of ethanol. 收率98. 7%。 98.7% yield. 核磁数据为:[Emim] H2PO4 : 1H NMR (D2O, 500MHz):δ = 8· 66 (s,1Η),7. 44 (s, 1Η),7. 37 (s, 1Η),4. 19-4. 09 (m, 2Η),3. 78 (s, 3Η), I. 45 (t, J =7. 5Ηζ,3Η)。 NMR data: [Emim] H2PO4: 1H NMR (D2O, 500MHz): δ = 8 · 66 (s, 1Η), 7 44 (s, 1Η), 7 37 (s, 1Η), 4 19-... 4. 09 (m, 2Η), 3. 78 (s, 3Η), I. 45 (t, J = 7. 5Ηζ, 3Η).

[0031] 实施例三乙基甲基咪唑硼氟酸盐合成 Example methylimidazole fluoroboric Synthesis of triethylammonium salt [0031] Embodiment

[0032] 步骤基本与实例一相似,将KOH与[EminJEtSO4摩尔比改为1.5 : 1,采用甲醇做溶剂,将硫酸改为硼氟酸。 [0032] Step a substantially similar instance, the mole ratio of KOH to EminJEtSO4 [to 1.5: 1, using methanol as the solvent, sulfuric acid is replaced by borofluoride. 收率92%。 Yield 92%. 核磁数据为:[Emim] BF4 :¾ NMR (D2O, 500MHz):δ = 8· 65 (s,1Η),7. 45 (s, 1Η),7. 38 (s, 1Η),4. 22-4. 18 (m, 2Η),3. 86 (s, 3Η), I. 47 (t, J =7. 25Ηζ,3Η)。 NMR data: [Emim] BF4: ¾ NMR (D2O, 500MHz): δ = 8 · 65 (s, 1Η), 7 45 (s, 1Η), 7 38 (s, 1Η), 4 22-... 4. 18 (m, 2Η), 3. 86 (s, 3Η), I. 47 (t, J = 7. 25Ηζ, 3Η). [0033] 实施例四乙基吡啶硫酸氢盐合成 Hydrogen sulfate salt of tetraethyl pyridine Example [0033] Embodiment

[0034] 与实例一步骤相似,甲基咪唑换为吡啶,收率可到90%以上。 [0034] Example Step a similar change methylimidazole pyridine, the yield can be 90% or more. 核磁数据为:[EPy]HSO4 =1H NMR(D2O, 500ΜΗζ) : δ = 8· 59 (s, 2H) , 7· 38 (s, 2H) , 7· 75 (s, 1H) , 3· 77 (m, 2H),I. 51(t,3H)。 NMR data: [EPy] HSO4 = 1H NMR (D2O, 500ΜΗζ): δ = 8 · 59 (s, 2H), 7 · 38 (s, 2H), 7 · 75 (s, 1H), 3 · 77 ( m, 2H), I. 51 (t, 3H).

Claims (4)

1. 一种无卤素二烷基咪唑类及烷基吡啶类离子液体的合成方法,其特征在于: 综合利用硫酸单烷基酯类离子液体、烷基硫酸钾、醋酸钾、醋酸的性质。 A dialkyl imidazoles and pyridines synthesis of alkyl halogen free ionic liquid, wherein: sulfuric acid monoalkyl esters utilization ionic liquids, alkyl potassium, potassium acetate nature, acetate. 以醋酸盐类离子液体为中间体合成阴离子多样化的无卤素二烷基咪唑及烷基吡啶类离子液体。 Acetic acid salt Synthesis of intermediate ionic liquid anion diverse halogen-dialkylimidazolium and alkylpyridinium ionic liquid.
2.如权利要求I所述,合成的步骤如下: 步骤I. 二烷基硫酸酯与I-烷基咪唑或吡啶反应,得硫酸单乙酯为阴离子的离子液体; 步骤2.将步骤I得到的二烷基咪唑烷基硫酸根离子液体与羧酸盐分别溶于醇中,再将两种溶液混合,得到以羧酸根为阴离子的离子液体中间体; 步骤3.在步骤2得到的无色澄清溶液中加入含有目标阴离子的酸进行酸化。 I as recited in claim 2, the step synthesis as follows: Step I. dialkyl sulfate with an alkyl imidazole or pyridine I-, mono ethyl sulfate to give an ionic liquid anion; obtained in step 2. Step I imidazolidinyl dialkyl sulfate ion liquid and carboxylates are soluble in the alcohol, and then the two solutions are mixed to obtain a carboxylate anion of the ionic liquid as an intermediate; step 3. step 2 obtained as a colorless clear solution containing a target anion of the acid to acidify. 步骤4.将步骤3得到的无色透明目标离子液体的溶液中的醇和羧酸蒸发后,得到目标离子液体处产物,经真空干燥后可得纯的目标离子液体。 Step 4. After the solution was colorless transparent objective ionic liquid obtained in step 3 alcohols and carboxylic acids and evaporated to give a liquid product at a target ion, and dried in vacuo to give pure target may be an ionic liquid.
3.上述的无卤素咪唑类离子液体的合成方法,步骤I中所述的I-烷基咪唑或吡啶的烷基可以是I〜2个碳原子的烷基; 上述的无卤素咪唑类离子液体的合成方法,步骤I中所述的二烷基硫酸酯的烷基是I〜4碳原子的烧基; 上述的离子液体的合成方法,步骤2中所述的羧酸盐可以是羧酸钠或羧酸钾。 3. The above-described method for synthesizing a halogen-free ionic liquid imidazole, I- alkyl imidazole or pyridine group according to step I may be I~2 alkyl carbon atoms; and the halogen-free ionic liquids imidazole synthesis method, the alkyl step I are dialkyl sulfates group I~4 burn carbon atoms; the above-described method for synthesizing an ionic liquid, the step 2 in the carboxylate may be sodium carboxylate or potassium carboxylate.
4.上述无卤素咪唑类离子液体的合成方法,步骤3中所述的目标阴离子的酸可以是硫酸、磷酸、硼氟酸、六氟磷酸、硝酸等强于醋酸的酸。 4. The method of synthesizing the above-described halogen-imidazolium ionic liquids, the step of the target anion of the acid may be a 3 sulfuric acid, phosphoric acid, fluoroboric acid, hexafluorophosphoric acid, nitric acid and other acids stronger than acetic acid.
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