CN104496928A - Method for preparing quaternary ammonium salt ionic liquid without halogen ions and sodium ions - Google Patents
Method for preparing quaternary ammonium salt ionic liquid without halogen ions and sodium ions Download PDFInfo
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- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
- C07C303/40—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reactions not involving the formation of sulfonamide groups
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- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
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- C07D295/037—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements with quaternary ring nitrogen atoms
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Abstract
The invention provides a method for preparing a quaternary ammonium salt ionic liquid without halogen ions and sodium ions. The method comprises the following steps: 1) dissolving tertiary amine in a non-polar organic solvent for reaction with dialkyl sulfate to obtain monoalkyl sulfate quaternary ammonium salt ionic liquids, standing for layering, washing a lower layer liquid with a non-polar organic solvent for 3-5 times, conducting thin film evaporation under vacuum condition, and removing the residual organic solvent to obtain a semi-finished product; and 2) dissolving semi-finished product obtained in the step 1) and salt in deionized water for a salt exchange reaction to obtain a quaternary ammonium ionic liquid, standing for layering, washing the lower layer oil liquid with deionized water for 3-5 times, conducting thin film evaporation and purification, removing the residual moisture, so as to obtain the quaternary ammonium ionic liquid product free of halogen ions and sodium ions. The quaternary ammonium ionic liquid prepared by the invention has purity reaching up to 99.9%, does not contain halogen ions or sodium ions, and can meet the requirements of lithium battery electrolyte and super capacitor electrolyte.
Description
Technical field
The present invention relates to the preparation method of the quaternary ammonium salt ionic liquid of a kind of not halogen-containing ion and sodium ion, particularly relate to a kind of preparation method that can be used for the high-purity quaternary ammonium salt ionic liquid of lithium battery electrolytes and the electrolytical not halogen-containing ion of super capacitor and sodium ion.
Background technology
Ionic liquid (Ionic liquids), namely the liquid be composed entirely of ions, be the salt be in a liquid state under low temperature (<100 DEG C), also referred to as low temperature molten salt, it is generally made up of organic cation and inorganic anion.First ionic liquid has just been found as far back as 1914---nitro ethamine, but the progress in this field is slow thereafter, until 1992, after the research group of Wikes leader has synthesized low melting point, resistant to hydrolysis, 1-ethyl-3-methylimidazole tetrafluoroborate ion liquid ([EMIM] BF4) that stability is strong, the research of ionic liquid is just developed rapidly, have developed a series of ion liquid system subsequently.Initial ionic liquid is mainly used in electrochemical research, and ionic liquid comes into one's own for organic and Polymer Synthesizing as green solvent in recent years.Compared with conventional solvent, ionic liquid has following characteristic:
(1) liquid state temperature range is wide, and its fusing point at-96 ~ 300 DEG C, and has good physics and chemistry stability; (2) usual no color or smell, steam forces down, not volatile, eliminates organic substance volatilization and the problem of environmental pollution that causes; (3) to a large amount of inorganic and organic substances, there is good dissolving power, and there is the dual-use function of solvent and catalyzer, can be used as solvent or the catalytic activity carrier of many chemical reactions; (4) there is larger polarity Modulatory character, two-phase or multiphase system can be formed, be suitable as and be separated solvent or form coupling reaction and separation new system; (5) electrochemical stability is high, has higher specific conductivity and wider electrochemical window, can be used as electrochemical reaction medium and cell solution; (6) have designability, ionic liquid character can combine by regulating the kind of zwitterion, is referred to as " green can design solvent ", can designs the ionic liquid of satisfied different system demand type in theory as required.Owing to having these special propertys, ionic liquid is acknowledged as the third green solvent after supercutical fluid and double water-phase.
In recent years, ionic liquid (ionic liquid is called for short IL) becomes the emerging research field of Green Chemistry gradually.Ionic liquid has some special physicochemical property due to the structure of its uniqueness, especially its non-volatility and be easy to advantages such as being separated from reaction system, is considered to a kind of green solvent and the green catalyst with wide application prospect.According to the designability of ionic liquid, the zwitterion that the difference that induces one in ionic liquid synthesis has a characteristic functional group then can make ionic liquid have certain characteristic functions maybe to meet specificity requirement, be called " functionalized ion liquid ".Ionic liquid is often combined by large volume, the organic cation of low symmetry and the inorganic anion of small volume.Because positively charged ion volume is large and symmetry is low, the negatively charged ion of small volume with it close to forming strong ionic linkage, can only form liquid, and zwitterion cannot closely combine unlike salt---and be at room temperature solid.Under the tide of chemical greenization, ionic liquid is again concerned, to the demand of novel material and medium, make ionic liquid exceed chemical field, show up prominently in the field such as the energy, material, be widely used in catalysis at present, organic synthesis, compartment analysis, electrochemistry, clean energy, functional fluid, nanotechnology, functional materials, the aspects such as functional additive also present fast-developing situation.In addition, ionic liquid the dissolving of the extraction of the recovery of the abstraction and purification of solvent extraction, material, spent high molecular compound, fuel cell and carbonic acid gas in solar cell, industrial gaseous waste, geological sample, nuclear fuel and nuke rubbish be separated with process etc. in also demonstrate potential application prospect.
Company of many transnational groups as: German BASF, German Merck, U.S. Shell, Belgian Bakert, Mitsubishi etc. be devoted to ionic liquid utilisation technology research and development, BASIL (the biphasic acid scavengingutilising ionic liquids) deacidification technique that wherein German BASF prepares alkoxyl phenyl phosphine drastically increases efficiency, causes international community's extensive concern.China ionic liquid basis and applied research also very active, application foundation and technical research almost synchronous with the world.The fact shows, ionic liquid rose till now from the nineties in 20th century, pass by one and cultivated to other new technologies, grow up and develop extremely similar " S curve ", just stepped into the turnover stage of from " exploration " to " application ", and breeding and welcome new breakthrough.
In recent years along with the fast development of China's industry, problem of environmental pollution is more and more serious, and a large amount of uses of such as traditional fuel cause greenhouse gases to discharge in a large number, and haze increases the weight of, and every winter, each big city was all absorbed among haze.So, find clean energy be used for replace traditional with oil, the traditional energies such as coal become more and more urgent, and electric energy is that a kind of environmental protection is pollution-free, be convenient to the preferred green energy resource carried, ultracapacitor and lithium cell (or fuel cell) coupling have been acknowledged as the power system of environmental-protecting type electric car the optimal path solving electric powered motor problem.
Ultracapacitor (double layer capacitor) is also electrochemical capacitor, it is a kind of high-energy new electric energy storage element that development in recent years is got up, have the characteristic of classic flat-plate electrical condenser and serondary lithium battery concurrently, it not only can provide the specific energy higher than ordinary flat electrical condenser, but also has the specific power higher than secondary cell and longer cycle life.Therefore ultracapacitor is considered to a kind of efficient, practical new cleaning fuel, is widely used backup power source, the starter gear of Motor vehicles, the clean energy such as wind-power electricity generation and solar power system in regulex, sensor, photographic camera, mobile telephone, computer memory.
Quality a big chunk factor of ultracapacitor depends on kind and the purity of electrolytic solution in ultracapacitor.When ultracapacitor is in running order, require that chemistry or electrochemical redox decomposition can not occur electrolytic solution, also must have good ionic conducting property simultaneously, ultracapacitor will realize thousands of discharge and recharges under operating voltage in addition, trace impurity in electrolytic solution also has fatal impact to the life-span of ultracapacitor and performance, as ultracapacitor electrolytic solution, its purity requirement high (> 99.9%), and must control in pole low-level to there being the detrimental impurity content of detrimental effects device lifetime, such as chlorion, bromide anion, iodide ion content < 1ppm, moisture content < 20ppm, sodium, calcium, magnesium, aluminium, iron, the metal content < 1ppm etc. such as chromium.Therefore, adopt the chemical reagent ionogen that conventional two-step approach method (first tertiary amine halo is generated quaternary ammonium salt, then salt exchanging) obtains at present, its purity can not meet the utilization requirement of ultracapacitor electrolyte.
Summary of the invention
The technical problem to be solved in the present invention is to provide the preparation method of the quaternary ammonium salt ionic liquid of a kind of not halogen-containing ion and sodium ion, the quaternary ammonium salt ionic liquid purity prepared can reach more than 99.9%, and wherein not containing halide-ions and sodium Metal 99.5 ion, lithium battery electrolytes and the electrolytical requirement of super capacitor can be met.
For solving the problems of the technologies described above, the preparation method of the quaternary ammonium salt ionic liquid of a kind of not halogen-containing ion provided by the invention and sodium ion, comprises the following steps:
1) tertiary amine with general formula (I) is dissolved in non-polar organic solvent and reacts with the dialkyl sulfate with general formula (II), obtain the sulfuric acid mono alkyl ester quat ionic liquid with general formula (III), by the non-polar organic solvent washing 3 ~ 5 times of lower floor's liquid after stratification, thin film evaporation is carried out under vacuum condition, remove residual organic solvent, obtain work in-process:
2) by step 1) work in-process that obtain and the salt with general formula (IV) is dissolved in deionized water and carries out salt permutoid reaction, obtain the quaternary ammonium salt ionic liquid with logical formula V, by the oily liquids of lower floor deionized water wash 3 ~ 5 times after stratification, thin film evaporation purifying, remove residual moisture, obtain the quaternary ammonium salt ionic liquid finished product of not halogen-containing ion and sodium ion.
Preferably, described step 1) in the tertiary amine with general formula (I) for having the one in the tertiary amine of following formula (1) ~ (7):
Wherein, substituent R
2~ R
6be H or containing the alkyl of 1 ~ 12 carbon atom each other identical or differently, or with general formula-(CH
2)
nthe substituting group that Y ' represents, n=1 ~ 8, Y ' is-CN or-CO
2r, R are 1 ~ 4 carbon atom alkyl.
Preferably, the dialkyl sulfate in described step (1) with general formula (II) and the R had in the sulfuric acid mono alkyl ester quat ionic liquid of general formula (III)
1for methyl or ethyl.
Preferably, there is in described step (2) M in the salt of general formula (IV)
+for hydrogen or lithium, Y
-for two fluoroform sulfimide root, perfluoro alkyl sulfonic acid root or hexafluoro-phosphate radical.
Preferably, the non-polar organic solvent in described step (1) is ethyl acetate or ether.
Preferably, in described step (1), temperature of reaction is 10 ~ 80 DEG C, reaction pressure position normal pressure, in 4 ~ 24 hours reaction times, the mol ratio of the tertiary amine with general formula (I) of input, the dialkylsulfates with general formula (II), non-polar organic solvent is 1 ~ 1.5:1:1 ~ 3.
Preferably, in described step (1), the judgement endpoint criterion with the washing purifying of the sulfuric acid mono alkyl ester quat ionic liquid of general formula (III) is that the non-polar organic solvent content detected with chromatographic detection is 0.
Preferably, in described step (2), salt permutoid reaction temperature is 10 ~ 80 DEG C, and the reaction times is 4 ~ 24 hours.
Preferably, in described step (2), the judgement endpoint criterion of deionized water wash is that in the finished product detected by ICP-AES detection method, lithium ion content is less than 10ppm, and other metal ion contents are less than 5ppm.
Compared with prior art, the present invention has following beneficial effect:
(1) when prepared by conventional quaternary ammonium salts class ionic liquid, the first step all adopts halogenated alkane as alkylating reagent, inevitably halide-ions is introduced while the synthesis of ionic liquid intermediate quaternary ammonium salt, and this process need heating, crystallization, the operation such as centrifugal, more loaded down with trivial details, and the first step of the present invention directly takes dialkyl sulfate as alkylating reagent, direct one-step synthesis ionic liquid, the introducing of halide-ions has been stopped from source, and reaction conditions is gentle, the easy purifying of product;
(2) when prepared by conventional quaternary ammonium salts class ionic liquid, second step all adopts quaternary ammonium halide and desired anion sodium salt to carry out salt exchange in aqueous phase, and then purification by liquid extraction, sodium ion has been brought in reaction process, and in second step of the present invention, specially have chosen hydrophobic anion (two fluoroform sulfimide root of stable in properties, perfluoro alkyl sulfonic acid root or hexafluoro-phosphate radical) lithium salts or hydride, second step salt is exchanged can directly carry out in aqueous phase, decrease the use of organic solvent, be convenient to the purification that dewaters of end product, end product is not containing sodium ion, decrease the discharge of environmentally hazardous substance simultaneously, reduce reaction cost, be convenient to industrial operation.Therefore the not halogen-containing ion of quaternary ammonium salt ionic liquid using present invention process to produce and sodium ion, and purity higher (can more than 99.9% be reached), the requirement of high purity electronic-grade ionogen (lithium battery electrolytes and super capacitor ionogen) can be met.
Embodiment
Describe the present invention in detail below in conjunction with specific embodiment, be used for explaining the present invention in this illustrative examples of the present invention and explanation, but not as a limitation of the invention.
Embodiment 1
The synthesis of the two trifluoromethanesulfonimide salt of methyl tributyl amine
250mL three-necked bottle is placed in cooling bath, add tributylamine 41.17g (0.38mol) successively, ethyl acetate 44.1g (0.5mol), stirring state slowly drips methyl-sulfate and amounts to 47.7g (0.38mol) in lower 3 hours, continue stirring 4 hours, stratification, lower floor's colorless oil reactant methyl tributyl amine methyl sulfate salt is separated in separating funnel, with ethyl acetate washing 3 ~ 5 times, each about 44g, then the methyl tributyl amine methyl sulfate salt after washing is poured into Rotary Evaporators,-0.1Mpa, dryly at 85 DEG C within 3 hours, obtain the methyl tributyl amine methyl sulfate salt 87.85g after the purifying of colorless viscous, productive rate 98.6%.87.85g methyl tributyl amine methyl sulfate salt (0.375mol) is all dissolved in 100g deionized water, add two trifluoromethanesulfonimide lithium 105.4g (0.375mol), open and stir, react 6 hours, turn off stirring, pour separating funnel stratification into and separate the two fluoroform alkyl sulfimide salt viscous fluid of lower floor's water white transparency methyl tributyl amine, with deionized water wash 2 ~ 3 times, each about 100g, then two for methyl tributyl amine fluoroform alkyl sulfimide salt is put into Rotary Evaporators,-0.1MPa, 85 DEG C of condition backspins steam 2 hours, obtain the two fluoroform alkyl sulfimide salt 172.3g after purifying, productive rate 96%.Reaction process is as follows:
Embodiment 2
The synthesis of the two trifluoromethanesulfonimide salt of ethyl tributylamine
250mL three-necked bottle is placed in cooling bath, add tributylamine 38.45g (0.38mol) successively, ethyl acetate 44.1g (0.5mol), stirring state slowly drips ethyl sulfate and amounts to 58.52g (0.38mol) in lower 3 hours, continue stirring 6 hours, stratification, lower floor's colorless oil reactant ethyl tributylamine sulfovinic acid salt is separated in separating funnel, with ethyl acetate washing 3 ~ 5 times, each about 44g, then the ethyl tributylamine methyl sulfate salt after washing is poured into Rotary Evaporators,-0.1MPa, dryly at 85 DEG C within 3 hours, obtain the ethyl tributylamine methyl sulfate salt 94.1g after the purifying of colorless viscous, productive rate 97.1%.94.1g ethyl tributylamine methyl sulfate salt (0.369mol) is all dissolved in 100g deionized water, add two trifluoromethanesulfonimide lithium 105.4g (0.375mol), open and stir, react 6 hours, turn off stirring, pour separating funnel stratification into and separate the two trifluoromethanesulfonimide salt viscous fluid of lower floor's water white transparency ethyl tributylamine, with deionized water wash 2 ~ 3 times, each about 100g, then two for ethyl tributylamine trifluoromethanesulfonimide salt viscous fluid is put into Rotary Evaporators,-0.1MPa, 85 DEG C of condition backspins steam 2 hours, obtain the two trifluoromethanesulfonimide salt 178.6g of the ethyl tributylamine after purifying, productive rate 96.3%.Reaction process is as follows:
Embodiment 3
The synthesis of the two trifluoromethanesulfonimide salt of 1-ethyl-3-methylimidazole
250mL three-necked bottle is placed in ice-water bath, add N-Methylimidazole 41.05g (0.5mol) successively, ethyl acetate 44.1g (0.5mol), stirring state slowly drips ethyl sulfate and amounts to 63.07g (0.5mol) in lower 2 hours, continue stirring 6 hours, stratification, lower floor colorless oil reactant 1-ethyl-3 Methylimidazole sulfovinic acid salt is separated in separating funnel, with ethyl acetate washing 3 ~ 5 times, each about 44g, then 1-ethyl-3 Methylimidazole sulfovinic acid salt after washing is poured into Rotary Evaporators,-0.1MPa, dryly at 85 DEG C within 3 hours, obtain 1-ethyl-3 Methylimidazole sulfovinic acid salt 116.02g after the purifying of colorless viscous, productive rate 98.2%.116.02g1-ethyl-3 Methylimidazole sulfovinic acid salt (0.491mol) is all dissolved in 100g deionized water, add two trifluoromethanesulfonimide lithium 140.1g (0.491mol), open and stir, react 6 hours, turn off stirring, pour separating funnel stratification into and separate the two trifluoromethanesulfonimide salt viscous fluid of lower floor water white transparency 1-ethyl-3-methylimidazole, with deionized water wash 2 ~ 3 times, each about 100g, then two for 1-ethyl-3-methylimidazole trifluoromethanesulfonimide salt viscous fluid is put into Rotary Evaporators,-0.1MPa, 85 DEG C of condition backspins steam 2 hours, obtain the two trifluoromethanesulfonimide salt 224.6g of the 1-ethyl-3-methylimidazole after purifying, productive rate 95.2%.Reaction process is as follows:
The detected result of embodiment 1 ~ 3 is as shown in table 1:
Table 1
Embodiment 4
The synthesis of the two trifluoromethanesulfonimide salt of 1,3-methylimidazole
250mL three-necked bottle is placed in ice-water bath, add N-Methylimidazole 41.05g (0.5mol) successively, ethyl acetate 44.1g (0.5mol), stirring state slowly drips methyl-sulfate and amounts to 63.07g (0.5mol) in lower 2 hours, continue stirring 6 hours, stratification, lower floor's colorless oil reactant 1 is separated in separating funnel, 3-methylimidazole sulfovinic acid salt, with ethyl acetate washing 3 ~ 5 times, each about 44g, then by 1 after washing, Rotary Evaporators poured into by 3-methylimidazole sulfovinic acid salt,-0.1MPa, dryly at 85 DEG C within 3 hours, obtain 1 after the purifying of colorless viscous, 3-methylimidazole sulfovinic acid salt 105.3g, productive rate 94.7%.By 105.3g 1, 3-methylimidazole sulfovinic acid salt (0.74mol) is all dissolved in 100g deionized water, add two trifluoromethanesulfonimide lithium 136.1g (0.474mol), open and stir, react 6 hours, turn off stirring, pour separating funnel stratification into and separate lower floor's water white transparency 1, the two trifluoromethanesulfonimide salt viscous fluid of 3-methylimidazole, with deionized water wash 2 ~ 3 times, each about 100g, then by 1, Rotary Evaporators put into by the two trifluoromethanesulfonimide salt viscous fluid of 3-methylimidazole,-0.1MPa, 85 DEG C of condition backspins steam 2 hours, obtain 1 after purifying, the two trifluoromethanesulfonimide salt 218.4g of 3-methylimidazole, productive rate 98.6%.Reaction process is as follows:
Embodiment 5
The synthesis of the two trifluoromethanesulfonimide salt of 1,2,3-tri-methylimidazolium
250mL three-necked bottle is placed in ice-water bath, add 1 successively, 2-methylimidazole 43.23g (0.45mol), ethyl acetate 44.1g (0.5mol), stirring state slowly drips methyl-sulfate and amounts to 56.76g (0.5mol) in lower 2 hours, continue stirring 6 hours, stratification, with separate lower floor's colorless oil reactant 1 in separating funnel, 2, 3-tri-methylimidazolium sulfovinic acid salt, with ethyl acetate washing 3 ~ 5 times, each about 44g, then by 1 after washing, 2, Rotary Evaporators poured into by 3-tri-methylimidazolium sulfovinic acid salt,-0.1MPa, 85 times DEG C of dryings obtain 1 after the purifying of colorless viscous for 3 hours, 2, 3-tri-methylimidazolium sulfovinic acid salt 97.3g, productive rate 97.3%.By 97.3g 1, 2, 3-tri-methylimidazolium sulfovinic acid salt (0.44mol) is all dissolved in 100g deionized water, add two trifluoromethanesulfonimide lithium 136.1g (0.474mol), open and stir, react 6 hours, turn off stirring, pour separating funnel stratification into and separate lower floor's water white transparency 1, 2, the two trifluoromethanesulfonimide salt viscous fluid of 3-tri-methylimidazolium, with deionized water wash 2 ~ 3 times, each about 100g, then by 1, 2, Rotary Evaporators put into by the two trifluoromethanesulfonimide salt viscous fluid of 3-tri-methylimidazolium,-0.1MPa, 85 DEG C of condition backspins steam 2 hours, obtain 1 after purifying, 2, the two trifluoromethanesulfonimide salt 206.4g of 3-tri-methylimidazolium, productive rate 97.56%.Reaction process is as follows:
Embodiment 6
The synthesis of the two trifluoromethanesulfonimide salt of 1-ethyl-2,3-methylimidazole
250mL three-necked bottle is placed in ice-water bath, add 1 successively, 2-methylimidazole 43.23g (0.45mol), ethyl acetate 44.1g (0.5mol), stirring state slowly drips ethyl sulfate and amounts to 63.65g (0.5mol) in lower 2 hours, continue stirring 6 hours, stratification, lower floor colorless oil reactant 1-ethyl-2 is separated in separating funnel, 3-methylimidazole sulfovinic acid salt, with ethyl acetate washing 3 ~ 5 times, each about 44g, then by the 1-ethyl-2 after washing, Rotary Evaporators poured into by 3-methylimidazole sulfovinic acid salt,-0.1MPa, dryly at 85 DEG C within 3 hours, obtain the 1-ethyl-2 after the purifying of colorless viscous, 3-methylimidazole sulfovinic acid salt 122.3g, productive rate 97.7%.By 122.3g 1-ethyl-2, 3-methylimidazole sulfovinic acid salt (0.49mol) is all dissolved in 100g deionized water, add two trifluoromethanesulfonimide lithium 140.67g (0.49mol), open and stir, react 6 hours, turn off stirring, pour separating funnel stratification into and separate lower floor water white transparency 1-ethyl-2, the two trifluoromethanesulfonimide salt viscous fluid of 3-methylimidazole, with deionized water wash 2 ~ 3 times, each about 100g, then by 1-ethyl-2, Rotary Evaporators put into by the two trifluoromethanesulfonimide salt viscous fluid of 3-methylimidazole,-0.1MPa, 85 DEG C of condition backspins steam 2 hours, obtain the 1-ethyl-2 after purifying, the two trifluoromethanesulfonimide salt 188.7g of 3-methylimidazole, productive rate 96.9%.Reaction process is as follows:
Embodiment 4 ~ 6 detected result is as shown in table 2:
Table 2
Embodiment 7
The synthesis of 1-ethyl-2,3-methylimidazole hexafluorophosphate
250mL three-necked bottle is placed in ice-water bath, add 1 successively, 2-methylimidazole 43.23g (0.45mol), ethyl acetate 44.1g (0.5mol), stirring state slowly drips ethyl sulfate and amounts to 63.65g (0.5mol) in lower 2 hours, continue stirring 6 hours, stratification, lower floor colorless oil reactant 1-ethyl-2 is separated in separating funnel, 3-methylimidazole sulfovinic acid salt, with ethyl acetate washing 3 ~ 5 times, each about 44g, then by the 1-ethyl-2 after washing, Rotary Evaporators poured into by 3-methylimidazole sulfovinic acid salt,-0.1MPa, dryly at 85 DEG C within 3 hours, obtain the 1-ethyl-2 after the purifying of colorless viscous, 3-methylimidazole sulfovinic acid salt 122.3g, productive rate 97.7%.By 122.3g 1-ethyl-2, 3-methylimidazole sulfovinic acid salt (0.49mol) is all dissolved in 100g deionized water, add lithium hexafluoro phosphate 74.44g (0.49mol), open and stir, react 24 hours, turn off stirring, pour separating funnel stratification into and separate lower floor water white transparency 1-ethyl-2, 3-methylimidazole hexafluorophosphate viscous fluid, with deionized water wash 2 ~ 3 times, each about 100g, then by 1-ethyl-2, Rotary Evaporators put into by 3-methylimidazole hexafluorophosphate viscous fluid,-0.1MPa, 85 DEG C of condition backspins steam 2 hours, obtain the 1-ethyl-2 after purifying, 3-methylimidazole hexafluorophosphate 106.8g, productive rate 87.8%.Reaction process is as follows:
Embodiment 8
The synthesis of two (fluoroform alkyl) sulfimide salt of N, N-diethyl tetramethyleneimine
250mL three-necked bottle is added N-ethyl pyrrolidine 49.6g (0.5mol) successively under room temperature, ethyl acetate 44.1g (0.5mol), stirring state slowly drips ethyl sulfate and amounts to 63.65g (0.5mol) in lower 2 hours, continue stirring 6 hours, stratification, with separate lower floor colorless oil reactant N in separating funnel, N-diethyl tetramethyleneimine sulfovinic acid salt, with ethyl acetate washing 3 ~ 5 times, each about 44g, then by the N after washing, Rotary Evaporators poured into by N-diethyl tetramethyleneimine sulfovinic acid salt,-0.1MPa, dryly at 85 DEG C within 3 hours, obtain the N after the purifying of colorless viscous, N-diethyl tetramethyleneimine sulfovinic acid salt 162.4g, productive rate 96.8%.By the N after 162.4g purifying, N-diethyl tetramethyleneimine sulfovinic acid salt (0.484mol) is all dissolved in 100g deionized water, add two (fluoroform alkyl) sulfimide lithium 74.44g (0.49mol), open and stir, react 24 hours, turn off stirring, pour separating funnel stratification into and separate lower floor water white transparency N, two (fluoroform alkyl) the sulfimide viscous fluid of N-diethyl tetramethyleneimine, with deionized water wash 2 ~ 3 times, each about 100g, then by N, Rotary Evaporators put into by two (fluoroform alkyl) the sulfimide viscous fluid of N-diethyl tetramethyleneimine,-0.1MPa, 85 DEG C of condition backspins steam 2 hours, obtain the N after purifying, two (fluoroform alkyl) the sulfimide salt 196.4g of N-diethyl tetramethyleneimine, productive rate 94.3%.Reaction process is as follows:
Embodiment 9
The synthesis of two (fluoroform alkyl) sulfimide salt of N, N-diethyl-3-nitrogen band tetrahydrofuran (THF)
250mL three-necked bottle is added N-ethyl-3-nitrogen band tetrahydrofuran (THF) 38.4g (0.38mol) successively under room temperature, ethyl acetate 44.1g (0.5mol), stirring state slowly drips ethyl sulfate and amounts to 63.65g (0.5mol) in lower 2 hours, continue stirring 6 hours, stratification, lower floor colorless oil reactant N is separated in separating funnel, N-diethyl-3-nitrogen band tetrahydrofuran (THF) sulfovinic acid salt, with washed with diethylether 3 ~ 5 times, each about 44g, then by the N after washing, Rotary Evaporators poured into by N-diethyl-3-nitrogen band tetrahydrofuran (THF) sulfovinic acid salt,-0.1MPa, dryly at 85 DEG C within 3 hours, obtain the N after the purifying of colorless viscous, N-diethyl-3-nitrogen band tetrahydrofuran (THF) sulfovinic acid salt 94.13g, productive rate 97.1%.By the N after 94.13g purifying, N-diethyl-3-nitrogen band tetrahydrofuran (THF) sulfovinic acid salt (0.37mol) is all dissolved in 100g deionized water, add two (fluoroform alkyl) sulfimide lithium 106.2g (0.37mol), open and stir, react 48 hours, turn off stirring, pour separating funnel stratification into and separate lower floor water white transparency N, two (fluoroform alkyl) the sulfimide viscous fluid of N-diethyl-3-nitrogen band tetrahydrofuran (THF), with deionized water wash 2 ~ 3 times, each about 100g, then by N, Rotary Evaporators put into by two (fluoroform alkyl) the sulfimide viscous fluid of N-diethyl-3-nitrogen band tetrahydrofuran (THF),-0.1MPa, 85 DEG C of condition backspins steam 2 hours, obtain the N after purifying, two (fluoroform alkyl) the sulfimide salt 119.23g of N-diethyl-3-nitrogen band tetrahydrofuran (THF), productive rate 92.1%.Reaction process is as follows:
Embodiment 7 ~ 9 detected result is as shown in table 3:
Table 3
From table 1 ~ table 3, the purity of the product that the present invention obtains is all higher (> 99.9%), and not halogen-containing ion and sodium Metal 99.5 ion, lithium battery electrolytes and the electrolytical requirement of super capacitor can be met.
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not for limiting the present invention.Any person skilled in the art scholar all without prejudice under spirit of the present invention and category, can modify above-described embodiment or changes.Therefore, such as have in art usually know the knowledgeable do not depart from complete under disclosed spirit and technological thought all equivalence modify or change, must be contained by claim of the present invention.
Claims (9)
1. a preparation method for the quaternary ammonium salt ionic liquid of not halogen-containing ion and sodium ion, is characterized in that: comprise the following steps:
1) tertiary amine with general formula (I) is dissolved in non-polar organic solvent and reacts with the dialkyl sulfate with general formula (II), obtain the sulfuric acid mono alkyl ester quat ionic liquid with general formula (III), by the non-polar organic solvent washing 3 ~ 5 times of lower floor's liquid after stratification, thin film evaporation is carried out under vacuum condition, remove residual organic solvent, obtain work in-process:
2) by step 1) work in-process that obtain and the salt with general formula (IV) is dissolved in deionized water and carries out salt permutoid reaction, obtain the quaternary ammonium salt ionic liquid with logical formula V, by the oily liquids of lower floor deionized water wash 3 ~ 5 times after stratification, thin film evaporation purifying, remove residual moisture, obtain the quaternary ammonium salt ionic liquid finished product of not halogen-containing ion and sodium ion.
2. the preparation method of the quaternary ammonium salt ionic liquid of a kind of not halogen-containing ion according to claim 1 and sodium ion, is characterized in that: described step 1) in the tertiary amine with general formula (I) for having the one in the tertiary amine of following formula (1) ~ (7):
Wherein, substituent R
2~ R
6be H or containing the alkyl of 1 ~ 12 carbon atom each other identical or differently, or with general formula-(CH
2)
nthe substituting group that Y ' represents, n=1 ~ 8, Y ' is-CN or-CO
2r, R are 1 ~ 4 carbon atom alkyl.
3. the preparation method of the quaternary ammonium salt ionic liquid of a kind of not halogen-containing ion according to claim 1 and sodium ion, is characterized in that: the dialkyl sulfate in described step (1) with general formula (II) and the R had in the sulfuric acid mono alkyl ester quat ionic liquid of general formula (III)
1for methyl or ethyl.
4. the preparation method of the quaternary ammonium salt ionic liquid of a kind of not halogen-containing ion according to claim 1 and sodium ion, is characterized in that: have the M in the salt of general formula (IV) in described step (2)
+for hydrogen or lithium, Y
-for two fluoroform sulfimide root, perfluoro alkyl sulfonic acid root or hexafluoro-phosphate radical.
5. the preparation method of the quaternary ammonium salt ionic liquid of a kind of not halogen-containing ion according to claim 1 and sodium ion, is characterized in that: the non-polar organic solvent in described step (1) is ethyl acetate or ether.
6. the preparation method of the quaternary ammonium salt ionic liquid of a kind of not halogen-containing ion according to claim 1 and sodium ion, it is characterized in that: in described step (1), temperature of reaction is 10 ~ 80 DEG C, reaction pressure position normal pressure, in 4 ~ 24 hours reaction times, the mol ratio of the tertiary amine with general formula (I) of input, the dialkylsulfates with general formula (II), non-polar organic solvent is 1 ~ 1.5:1:1 ~ 3.
7. the preparation method of the quaternary ammonium salt ionic liquid of a kind of not halogen-containing ion according to claim 1 and sodium ion, it is characterized in that: in described step (1), the judgement endpoint criterion with the washing purifying of the sulfuric acid mono alkyl ester quat ionic liquid of general formula (III) is that the non-polar organic solvent content detected with chromatographic detection is 0.
8. the preparation method of the quaternary ammonium salt ionic liquid of a kind of not halogen-containing ion according to claim 1 and sodium ion, it is characterized in that: in described step (2), salt permutoid reaction temperature is 10 ~ 80 DEG C, and the reaction times is 4 ~ 24 hours.
9. the preparation method of the quaternary ammonium salt ionic liquid of a kind of not halogen-containing ion according to claim 1 and sodium ion, it is characterized in that: in described step (2), the judgement endpoint criterion of deionized water wash is that in the finished product detected by ICP-AES detection method, lithium ion content is less than 10ppm, and other metal ion contents are less than 5ppm.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107602396A (en) * | 2017-10-10 | 2018-01-19 | 常州大学 | A kind of preparation method of the low quaternary ammonium salt of content of halide ions |
| US10270114B2 (en) | 2015-09-25 | 2019-04-23 | Samsung Electronics Co., Ltd. | Electrolyte for lithium air battery and lithium air battery including the same |
| CN110878053A (en) * | 2019-12-05 | 2020-03-13 | 江苏国泰超威新材料有限公司 | Preparation method of dialkyl imidazole bis (trifluoromethyl) sulfonyl imide salt |
| CN111138368A (en) * | 2020-01-10 | 2020-05-12 | 浙江蓝德能源科技发展有限公司 | Synthesis method of 1-butyl-3-methylimidazole tetrafluoroborate ionic liquid |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1182196A1 (en) * | 2000-08-24 | 2002-02-27 | Solvent Innovation GmbH | Halogenide-free preparation of ionic fluids |
| EP1201657A1 (en) * | 2000-10-27 | 2002-05-02 | Centre National De La Recherche Scientifique (Cnrs) | Imidazolium salts and the use of these ionic liquids as a solvent and as a catalyst |
| CN1672094A (en) * | 2002-06-21 | 2005-09-21 | 加利福尼亚大学董事会 | Electrolytes for electrooptic devices comprising ionic liquids |
| CN101006062A (en) * | 2004-08-24 | 2007-07-25 | 巴斯福股份公司 | Imidazolium-methyl sulfites for use as starting compounds for producing ionic liquids |
| CN103833677A (en) * | 2012-11-26 | 2014-06-04 | 海洋王照明科技股份有限公司 | Pyrrole ionic liquid, and preparation method and application thereof |
-
2014
- 2014-11-21 CN CN201410673288.9A patent/CN104496928A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1182196A1 (en) * | 2000-08-24 | 2002-02-27 | Solvent Innovation GmbH | Halogenide-free preparation of ionic fluids |
| EP1201657A1 (en) * | 2000-10-27 | 2002-05-02 | Centre National De La Recherche Scientifique (Cnrs) | Imidazolium salts and the use of these ionic liquids as a solvent and as a catalyst |
| CN1672094A (en) * | 2002-06-21 | 2005-09-21 | 加利福尼亚大学董事会 | Electrolytes for electrooptic devices comprising ionic liquids |
| CN101006062A (en) * | 2004-08-24 | 2007-07-25 | 巴斯福股份公司 | Imidazolium-methyl sulfites for use as starting compounds for producing ionic liquids |
| CN103833677A (en) * | 2012-11-26 | 2014-06-04 | 海洋王照明科技股份有限公司 | Pyrrole ionic liquid, and preparation method and application thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10270114B2 (en) | 2015-09-25 | 2019-04-23 | Samsung Electronics Co., Ltd. | Electrolyte for lithium air battery and lithium air battery including the same |
| CN107602396A (en) * | 2017-10-10 | 2018-01-19 | 常州大学 | A kind of preparation method of the low quaternary ammonium salt of content of halide ions |
| CN110878053A (en) * | 2019-12-05 | 2020-03-13 | 江苏国泰超威新材料有限公司 | Preparation method of dialkyl imidazole bis (trifluoromethyl) sulfonyl imide salt |
| CN111138368A (en) * | 2020-01-10 | 2020-05-12 | 浙江蓝德能源科技发展有限公司 | Synthesis method of 1-butyl-3-methylimidazole tetrafluoroborate ionic liquid |
| CN113964376A (en) * | 2021-10-18 | 2022-01-21 | 南京大学 | Preparation and application of novel low eutectic agent |
| CN114105907A (en) * | 2021-12-14 | 2022-03-01 | 河北工业大学 | Pyrrolidine ionic liquid and preparation method and application thereof |
| CN115058239A (en) * | 2022-06-22 | 2022-09-16 | 中国石油大学(华东) | Ionic liquid microemulsion thickened oil modifying viscosity reducer and preparation method thereof |
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