CN106397324A - Purification method of imidazole ionic liquid - Google Patents

Purification method of imidazole ionic liquid Download PDF

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Publication number
CN106397324A
CN106397324A CN201610774246.3A CN201610774246A CN106397324A CN 106397324 A CN106397324 A CN 106397324A CN 201610774246 A CN201610774246 A CN 201610774246A CN 106397324 A CN106397324 A CN 106397324A
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salt
mixed solution
lower floor
ionic liquid
organic
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CN106397324B (en
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方金法
李凯明
王存江
李义伟
付涛
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LINZHOU KENENG MATERIAL TECHNOLOGY Co Ltd
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LINZHOU KENENG MATERIAL TECHNOLOGY Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—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
    • 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

Abstract

The invention relates to a purification method of an imidazole ionic liquid. The purification method comprises the following steps: adding a coarse product of [R1R2IM]X and MY into a water medium to carry out anion exchange reactions; then adding an organic extracting agent into the mixed solution, evenly mixing, allowing the system to stand still to carry out automatic layering; then adding salt D into the mixed solution, evenly mixing, allowing the system to stand still to carry out automatic layering, wherein the upper layer is an organic phase, and the lower layer is an water phase containing MX; discharging the water phase containing MX; then adding purified water and salt D into the organic phase, vibrating the system to carry out layering, discharging the lower layer (water phase); and repeating the steps of adding purified water and salt D for 2 to 3 times until no MX impurity is detected in the organic phase. By selecting a proper solvent and adding proper salt, the water phase density is increased, thus the extraction frequency is reduced, and the product quality is improved.

Description

A kind of purification process of glyoxaline ion liquid
Technical field
The invention belongs to ionic liquid production technical field is and in particular to a kind of purification process of glyoxaline ion liquid.
Background technology
Ionic liquid has the physical and chemical performance of uniqueness, and ionic liquid at room temperature becomes the one of current scientific worker's concern Individual key discipline.Study increasing of species with ionic liquid, glyoxaline ion liquid synthetic method also obtains with rapid changepl. never-ending changes and improvements Achievement.At present, ionic liquid synthesis adopts two-step method, and the wherein first step is organic addition reaction, synthesis containing halogen cloudy from The intermediate of son, such as 1- butyl -3- methylimidazole villaumite, 1- ethyl-3-methylimidazole bromide.Second step is metathesis reaction, Purpose is to be exchanged by ionic liquid, obtains the particular design product containing desired anion.
Wherein second step reaction can be divided into following several method：
Method one, it is reaction medium by using organic solvent, adds material, ion exchange is carried out by stirring, then through taking out Filter, revolving mode obtain product.But in the product that this kind of method yield height obtains, impurity content is higher, but will in reaction Strict control reaction process, prevents the volatilization of organic solvent, and product is technical grade, be suitably applied and product purity is required Not high field, and use faciostenosis.Typical course of reaction is as follows：
Organic solvent therein is that one or more of dichloromethane, ethyl acetate, methyl alcohol, acetonitrile mix.
Method two, in aqueous phase, by adding a step product and MY salt, according to target product in different solvents distribution ratio Difference, selects suitable solvent, obtains product by way of multiple addition protective agent, extraction cleaning, separating for several times, revolving.
This kind of method is applied to the product high to solvent selectivity, and this reaction condition is gentle, and reaction is simple, product purity Height, is suitable for the synthesis of majority ionic liquid product, using wide general.Typical course of reaction is as follows：
From immiscible dichloromethane, chloroform, carbon tetrachloride, ether etc. with water more than organic solvent, universal density 1.32 ~ 1.6g/cm3Between；One distinct issues is ionic liquid density generally in 1.0 ~ 1.4 g/cm3, and ionic liquid is molten with organic The usual density of mixed liquor of agent is more than 1.2 g/cm3, when cleaning using water, layering will be produced.
Raw materials used inevitably will to introduce micro naked eyes visible or sightless for most of MY salt and a step product Flocculent undissolved substance impurity, salinity density therein is larger, is deposited on the bottom of layering interfaces and point liquid kettle, in this case point Liquid will lead to impurity repeated dispensing below product and organic phase, or layering interfaces, lead to product needed be cleaned multiple times just up to To necessary requirement, and multiple cleaning leads to the reduction of product yield the most at last.
Content of the invention
The purpose of the present invention is to provide a kind of purification process of glyoxaline ion liquid for the deficiencies in the prior art, The method is passed through from suitable solvent, adds suitable salt, aqueous phase densities are increased, be finally reached extraction times reduce, The result that product quality raises, reaches more optimal purpose according to common-ion effect simultaneously.
For achieving the above object, the technical solution used in the present invention is as follows：
The invention provides a kind of purification process of glyoxaline ion liquid, comprise the following steps：
（1）Under stirring, by crude product [R1R2IM] X and the salt MY containing desired anion carry out anion friendship in aqueous medium Change reaction, obtain [R1R2IM] Y and MX mixed solution A；R1For C2~C8Alkyl, one of pi-allyl and ethyl acetate base； R2For C1~C4Alkyl；X is halogen or esters；M is H or alkali metal；Y is BF4 -、PF6 -、 SbF6 -、N(CF3SO2)-、N (C2F5SO2)-、N(FSO2)2 -Or CF3SO3 -；
（2）To step（1）Add organic extractant in mixed solution A, stand after mixing, mixed solution AUTOMATIC ZONING, contain There is ionic liquid [R1R2IM] Y organic phase in lower floor, the aqueous phase containing MX is on upper strata；Described organic extractant be dichloromethane, At least one in chloroform, carbon tetrachloride and ether；
（3）To step（2）Add salt D in mixed solution, stand after mixing, mixed solution AUTOMATIC ZONING, containing ionic liquid Body [R1R2IM] Y organic phase on upper strata, the aqueous phase containing MX, in lower floor, now discharges the aqueous phase that MX is contained in lower floor；
（4）Under stirring, to step（3）Obtain containing ionic liquid [R1R2IM] Y organic phase in add pure water and salt D, stir Mix and uniformly obtain mixed liquor C, stand after mixed liquor C is shaken, mixed liquor C AUTOMATIC ZONING, containing ionic liquid [R1R2IM] Y Organic phase now discharges the aqueous phase of lower floor in upper strata, aqueous phase in lower floor；
（5）Repeat step（4）Operating procedure 2 ~ 3 times, in the detection organic phase no till MX impurities left, then will be organic Through filtering, revolving obtains [R1R2IM] Y product.
According to the purification process of above-mentioned glyoxaline ion liquid, described salt D is niter cake, sodium acid carbonate, sodium carbonate, At least one in potassium acid sulfate, saleratus, potassium carbonate, sodium nitrate, potassium nitrate, calcium nitrate, magnesium nitrate and ammonium carbonate.
The salt D that the present invention adds can not affect properties of product, and does not react with solvent, water, product.
According to the purification process of above-mentioned glyoxaline ion liquid, described MY is sodium tetrafluoroborate, ammonium tetrafluoroborate, hexafluoro At least one in potassium phosphate, niter cake, sodium hexafluoroantimonate, lithium perchlorate and bis-trifluoromethylsulfoandimide lithium.
According to the purification process of above-mentioned glyoxaline ion liquid, described organic extractant is dichloromethane.
The inventive method is applied to the principle of following synthetic reaction product：
Compared with prior art, beneficial effects of the present invention：
（1）The process aqueous phase of the present invention is that impurities phase is in lower floor all the time, is easy to lock out operation；
（2）Can obviously reduce insoluble cotton-shaped impurity in product, raw material for technical grade or chemistry pure below when, this effect is brighter Aobvious；
（3）Can obviously reduce extraction times, thus reducing the ratio that product is taken away by aqueous phase, improving product yield；
（4）Easy to operation, suitable large-scale production；
（5）Product quality is improved.
Brief description
Fig. 1 be salt adding before stratification structural representation；
Fig. 2 be salt adding after stratification structural representation.
Specific embodiment
Following examples are intended to further illustrate present disclosure, but do not limit the scope of the invention.
Embodiment 1
A kind of purification process of glyoxaline ion liquid, comprises the following steps：
（1）Under stirring, by crude product [R1R2IM] X and the salt MY containing desired anion carry out anion friendship in aqueous medium Change reaction, obtain [R1R2IM] Y and MX mixed solution A；R1For C2~C8Alkyl, one of pi-allyl and ethyl acetate base； R2For C1~C4Alkyl；X is halogen or esters；M is H or alkali metal；Y is BF4 -、PF6 -、 SbF6 -、N(CF3SO2)-、N (C2F5SO2)-、N(FSO2)2 -Or CF3SO3 -；
（2）To step（1）Add organic extractant in mixed solution A, stand after mixing, mixed solution AUTOMATIC ZONING, contain There is ionic liquid [R1R2IM] Y organic phase in lower floor, the aqueous phase containing MX is on upper strata；Described organic extractant be dichloromethane, At least one in chloroform, carbon tetrachloride and ether；
（3）To step（2）Add salt D in mixed solution, stand after mixing, mixed solution AUTOMATIC ZONING, containing ionic liquid Body [R1R2IM] Y organic phase on upper strata, the aqueous phase containing MX, in lower floor, now discharges the aqueous phase that MX is contained in lower floor；
（4）Under stirring, to step（3）Obtain containing ionic liquid [R1R2IM] Y organic phase in add pure water and salt D, stir Mix and uniformly obtain mixed liquor C, stand after mixed liquor C is shaken, mixed liquor C AUTOMATIC ZONING, containing ionic liquid [R1R2IM] Y Organic phase now discharges the aqueous phase of lower floor in upper strata, aqueous phase in lower floor；
（5）Repeat step（4）Operating procedure 2 ~ 3 times, in the detection organic phase no till MX impurities left, then will be organic Through filtering, revolving obtains [R1R2IM] Y product.
Described salt D is niter cake, sodium acid carbonate, sodium carbonate, potassium acid sulfate, saleratus, potassium carbonate, sodium nitrate, nitre At least one in sour potassium, calcium nitrate, magnesium nitrate and ammonium carbonate, the salt D that the present invention adds can not affect properties of product, and not React with solvent, water, product.
Described MY is sodium tetrafluoroborate, ammonium tetrafluoroborate, Potassium Hexafluorophosphate, niter cake, sodium hexafluoroantimonate, lithium perchlorate With at least one in bis-trifluoromethylsulfoandimide lithium.
Embodiment 2
The purifying of 1- butyl -3- methyl imidazolium tetrafluoroborate
By the 1- butyl -3- methylimidazole bromide 500mL water dissolves of 1.0mol, the lower tetrafluoro boric acid adding 1.0mol of stirring Ammonium, stirring reaction 24 hours under room temperature.
Add the dichloromethane of 400mL in gained mixed solution, be transferred to separatory funnel, add 100g sodium nitrate, shake, Standing, is layered as organic phase on upper strata, aqueous phase is in lower floor；Lower floor's aqueous phase is discharged, organic phase adds 500mL water and 150g again Sodium nitrate, concussion, standing, layering, lower floor's aqueous phase is discharged, repeats this cleaning operation 1 time again；Now detect organic phase no bromine Ion and ammonium ion, obtain colourless transparent liquid product, yield 92.0% through vacuum revolving.
Embodiment 3
The purifying of 1- pi-allyl -3- butyl imidazole hexafluorophosphate
By the 1- pi-allyl -3- butyl imidazole villaumite 500mL water dissolves of 1.0mol, the lower hexafluorophosphoric acid adding 1.0mol of stirring Potassium, stirring reaction 12 hours under room temperature.
Add the dichloromethane of 400mL in gained mixed solution, be transferred to separatory funnel, add 110g potassium carbonate, shake, Standing, is layered as organic phase on upper strata, aqueous phase is in lower floor；Lower floor's aqueous phase is discharged, organic phase adds 500mL water and 180g again Potassium carbonate, concussion, standing, layering, lower floor's aqueous phase is discharged, repeats this cleaning operation 2 times again；Now detect organic phase no bromine Ion and ammonium ion, obtain light yellow transparent liquid product, yield 93.0% through vacuum revolving.
Embodiment 4
The purifying of 1- octyl group -3- ethyl imidazol(e) bis-trifluoromethylsulfoandimide salt
By the 1- octyl group -3- ethyl imidazol(e) salt compounded of iodine 500mL water dissolves of 1.0mol, the lower double fluoroform sulphurs adding 1.0mol of stirring Imide li, stirring reaction 8 hours under room temperature.
Add the dichloromethane of 400mL in gained mixed solution, be transferred to separatory funnel, add 150g ammonium sulfate, shake, Standing, is layered as organic phase on upper strata, aqueous phase is in lower floor.Lower floor's aqueous phase is discharged, organic phase adds 500mL water and 300g again Ammonium sulfate, concussion, standing, layering, lower floor's aqueous phase is discharged；Now detect organic phase no bromide ion and ammonium ion, through vacuum rotation Steaming obtains colourless transparent liquid product, yield 91.0%.

Claims (4)

1. a kind of purification process of glyoxaline ion liquid is it is characterised in that comprise the following steps：
（1）Under stirring, by crude product [R1R2IM] X and the salt MY containing desired anion carry out anion exchange in aqueous medium Reaction, obtains [R1R2IM] Y and MX mixed solution A；R1For C2~C8Alkyl, one of pi-allyl and ethyl acetate base；R2 For C1~C4Alkyl；X is halogen or esters；M is H or alkali metal；Y is BF4 -、PF6 -、 SbF6 -、N(CF3SO2)-、N (C2F5SO2)-、N(FSO2)2 -Or CF3SO3 -；
（2）To step（1）Add organic extractant in mixed solution A, stand after mixing, mixed solution AUTOMATIC ZONING, contain There is ionic liquid [R1R2IM] Y organic phase in lower floor, the aqueous phase containing MX is on upper strata；Described organic extractant be dichloromethane, At least one in chloroform, carbon tetrachloride and ether；
（3）To step（2）Add salt D in mixed solution, stand after mixing, mixed solution AUTOMATIC ZONING, containing ionic liquid Body [R1R2IM] Y organic phase on upper strata, the aqueous phase containing MX, in lower floor, now discharges the aqueous phase that MX is contained in lower floor；
（4）Under stirring, to step（3）Obtain containing ionic liquid [R1R2IM] Y organic phase in add pure water and salt D, stirring Uniformly obtain mixed liquor C, stand after mixed liquor C is shaken, mixed liquor C AUTOMATIC ZONING, containing ionic liquid [R1R2IM] the having of Y Machine now discharges the aqueous phase of lower floor in upper strata, aqueous phase in lower floor；
（5）Repeat step（4）Operating procedure 2 ~ 3 times, in the detection organic phase no till MX impurities left, then will be organic Through filtering, revolving obtains [R1R2IM] Y product.
2. glyoxaline ion liquid according to claim 1 purification process it is characterised in that：Described salt D is hydrogen sulfate Sodium, sodium acid carbonate, sodium carbonate, potassium acid sulfate, saleratus, potassium carbonate, sodium nitrate, potassium nitrate, calcium nitrate, magnesium nitrate and carbonic acid At least one in ammonium.
3. glyoxaline ion liquid according to claim 1 purification process it is characterised in that：Described MY is tetrafluoro boric acid In sodium, ammonium tetrafluoroborate, Potassium Hexafluorophosphate, niter cake, sodium hexafluoroantimonate, lithium perchlorate and bis-trifluoromethylsulfoandimide lithium At least one.
4. glyoxaline ion liquid according to claim 1 purification process it is characterised in that：Described organic extractant is Dichloromethane.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1579609A (en) * 2004-05-18 2005-02-16 浙江大学 Water-soluble ion liquid synthesizing method
CN101016176A (en) * 2006-12-13 2007-08-15 辽宁大学 Novel ionic liquid-inorganic salt-water double aqueous phase system
CN101664612A (en) * 2009-09-29 2010-03-10 东华大学 Method for purifying and separating ionic liquid from water
CN103965141A (en) * 2013-02-04 2014-08-06 海洋王照明科技股份有限公司 Pyrrolidine ionic liquid, and preparation method, electrolyte and capacitor thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1579609A (en) * 2004-05-18 2005-02-16 浙江大学 Water-soluble ion liquid synthesizing method
CN101016176A (en) * 2006-12-13 2007-08-15 辽宁大学 Novel ionic liquid-inorganic salt-water double aqueous phase system
CN101664612A (en) * 2009-09-29 2010-03-10 东华大学 Method for purifying and separating ionic liquid from water
CN103965141A (en) * 2013-02-04 2014-08-06 海洋王照明科技股份有限公司 Pyrrolidine ionic liquid, and preparation method, electrolyte and capacitor thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
KEITH E. GUTOWSKI,等: "Controlling the Aqueous Miscibility of Ionic Liquids: Aqueous Biphasic Systems of Water-Miscible Ionic Liquids and Water-Structuring Salts for Recycle, Metathesis, and Separations", 《J. AM. CHEM. SOC.》 *
周雪玲，等: "二烷基咪唑离子液体的合成、纯化及表征", 《应用科技》 *

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