CN106397324B - A kind of purification process of glyoxaline ion liquid - Google Patents
A kind of purification process of glyoxaline ion liquid Download PDFInfo
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- CN106397324B CN106397324B CN201610774246.3A CN201610774246A CN106397324B CN 106397324 B CN106397324 B CN 106397324B CN 201610774246 A CN201610774246 A CN 201610774246A CN 106397324 B CN106397324 B CN 106397324B
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- 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
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Abstract
The present invention relates to a kind of purification process of glyoxaline ion liquid, comprising the following steps: first by crude product [R1R2IM] X and MY carry out anion exchange reaction in an aqueous medium；Then organic extractant is added into mixed solution, stands AUTOMATIC ZONING after mixing；Then salt D is added into mixed solution, stands AUTOMATIC ZONING after mixing, the water phase that MX is contained in lower layer is discharged in lower layer in upper layer, the water phase containing MX in organic phase；Then pure water and salt D are added into organic phase, the water phase of lower layer is discharged in concussion layering；It repeats operating procedure 2 ~ 3 times that pure water and salt D is added, until in detection organic phase without MX impurity residual, obtains product.This method adds suitable salt, aqueous phase densities is increased, be finally reached extraction times reduction, the raised result of product quality by selecting suitable solvent.
Description
Technical field
The invention belongs to ionic liquid production technical fields, and in particular to a kind of purification process of glyoxaline ion liquid.
Background technique
Ionic liquid has unique physical and chemical performance, and ionic liquid at room temperature becomes the one of current scientific worker concern
A key discipline.With increasing for ionic liquid research type, glyoxaline ion liquid synthetic method also obtains with rapid changepl. never-ending changes and improvements
Achievement.Currently, ionic liquid synthesis mostly use two-step method, wherein the first step be organic addition reaction, synthesis containing halogen yin 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 is reaction medium by using organic solvent, and addition material carries out ion exchange by stirring, then
It is filtered, revolving mode obtains product.Impurity content is higher in such method yield height, the product still obtained, but reacts
In want strict control reaction process, prevent the volatilization of organic solvent, and product is technical grade, is suitably applied to product purity
Field of less demanding, and use faciostenosis.Typical reaction process is as follows:
Organic solvent therein is the mixing of one or more of methylene chloride, ethyl acetate, methanol, acetonitrile.
Method two, in water phase, by the way that a step product and MY salt is added, according to target product in different solvents distribution ratio
Difference selects suitable solvent, obtains product by way of protective agent, extraction cleaning, separating for several times, revolving is repeatedly added.
Such method is suitable for the product high to solvent selectivity, this reaction condition is mild, and reaction is simple, product purity
Height, is suitble to the synthesis of majority ionic liquid product, and using face is extensive.Typical reaction process is as follows:
With with the immiscible methylene chloride of water, chloroform, carbon tetrachloride, ether etc., universal density exists organic solvent multiselect
1.32~1.6g/cm3Between；One distinct issues is ionic liquid density generally in 1.0 ~ 1.4 g/cm3, and ionic liquid with have
The usual density of the mixed liquor of solvent is greater than 1.2 g/cm3, when making to wash with water, layering will be generated.
Raw materials used inevitably 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 liquid separation kettle, point in this case
Liquid will lead to impurity repeated dispensing below product and organic phase or layering interfaces, cause product needs to be cleaned multiple times just reachable
To necessary requirement, and multiple cleaning finally will lead to the reduction of product yield.
Summary of the invention
The purpose of the present invention is providing a kind of purification process of glyoxaline ion liquid in view of the deficiencies of the prior art,
This method adds suitable salt, aqueous phase densities is increased by selecting suitable solvent, be finally reached extraction times reduce,
Product quality is raised as a result, reaching more optimal purpose according to common-ion effect simultaneously.
To achieve the above object, The technical solution adopted by the invention is as follows:
The present invention provides a kind of purification process of glyoxaline ion liquid, comprising the following steps:
(1) under stirring, by crude product [R1R2IM] X and the salt MY containing desired anion carry out anion in an aqueous medium
Exchange reaction obtains [R1R2IM] Y and MX mixed solution A；R1For C2~C8One of alkyl, allyl and ethyl acetate base；
R2For C1~C4Alkyl；X is halogen or esters；M is H or alkali metal element；Y is BF4 -、PF6 -、 SbF6 -、N(CF3SO2) -、N
(C2F5SO2) -、N(FSO2)2 -Or CF3SO3 -；
(2) organic extractant is added into step (1) mixed solution A, stands after mixing, mixed solution divides automatically
Layer, contains ionic liquid [R1R2IM] Y organic phase in lower layer, the water phase containing MX is on upper layer；The organic extractant is dichloro
At least one of methane, chloroform, carbon tetrachloride and ether；
(3) into step (2) mixed solution be added salt D, stand after mixing, mixed solution AUTOMATIC ZONING, containing from
Sub- liquid [R1R2IM] Y organic phase on upper layer, the water phase that MX is contained in lower layer is discharged in lower layer in the water phase containing MX at this time；
(4) under stirring, what is obtained to step (3) contains ionic liquid [R1R2IM] Y organic phase in pure water and salt D is added,
It is uniformly mixing to obtain mixed liquor C, will be stood after mixed liquor C concussion, mixed liquor C AUTOMATIC ZONING contains ionic liquid [R1R2IM]Y
Organic phase on upper layer, the water phase of lower layer is discharged in lower layer in water phase at this time；
(5) operating procedure 2 ~ 3 times of step (4) are repeated, until in detection organic phase without MX impurity residual, then will
Organic phase is filtered, rotates to obtain [R1R2IM] Y product.
According to the purification process of above-mentioned glyoxaline ion liquid, the salt D be sodium bisulfate, sodium bicarbonate, sodium carbonate,
At least one of 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 influence properties of product, and not react with solvent, water, product.
According to the purification process of above-mentioned glyoxaline ion liquid, the MY is sodium tetrafluoroborate, ammonium tetrafluoroborate, hexafluoro
At least one of potassium phosphate, sodium bisulfate, sodium hexafluoroantimonate, lithium perchlorate and bis-trifluoromethylsulfoandimide lithium.
According to the purification process of above-mentioned glyoxaline ion liquid, the organic extractant is methylene chloride.
The method of the present invention is suitable for the principle of following synthetic reaction product:
Compared with prior art, beneficial effects of the present invention:
(1) process of the invention water phase, that is, impurity phase is in lower layer always, is convenient for lock out operation；
(2) it can obviously reduce insoluble cotton-shaped impurity in product, when raw material is technical grade or chemistry is pure following, this effect is more
Add obvious；
(3) extraction times be can obviously reduce, to reduce the ratio that product is taken away by water phase, improve product yield；
(4) easy to operation, it is suitble to large-scale production；
(5) product quality is improved.
Detailed description of the invention
Fig. 1 is the stratification structural schematic diagram added before salt；
Fig. 2 is the stratification structural schematic diagram added after salt.
Specific embodiment
Following embodiment is intended to further illustrate the contents of the present invention, but does not limit the scope of the invention.
Embodiment 1
A kind of purification process of glyoxaline ion liquid, comprising the following steps:
(1) under stirring, by crude product [R1R2IM] X and the salt MY containing desired anion carry out anion in an aqueous medium
Exchange reaction obtains [R1R2IM] Y and MX mixed solution A；R1For C2~C8One of alkyl, allyl and ethyl acetate base；
R2For C1~C4Alkyl；X is halogen or esters；M is H or alkali metal element；Y is BF4 -、PF6 -、 SbF6 -、N(CF3SO2) -、N
(C2F5SO2) -、N(FSO2)2 -Or CF3SO3 -；
(2) organic extractant is added into step (1) mixed solution A, stands after mixing, mixed solution divides automatically
Layer, contains ionic liquid [R1R2IM] Y organic phase in lower layer, the water phase containing MX is on upper layer；The organic extractant is dichloro
At least one of methane, chloroform, carbon tetrachloride and ether；
(3) into step (2) mixed solution be added salt D, stand after mixing, mixed solution AUTOMATIC ZONING, containing from
Sub- liquid [R1R2IM] Y organic phase on upper layer, the water phase that MX is contained in lower layer is discharged in lower layer in the water phase containing MX at this time；
(4) under stirring, what is obtained to step (3) contains ionic liquid [R1R2IM] Y organic phase in pure water and salt D is added,
It is uniformly mixing to obtain mixed liquor C, will be stood after mixed liquor C concussion, mixed liquor C AUTOMATIC ZONING contains ionic liquid [R1R2IM]Y
Organic phase on upper layer, the water phase of lower layer is discharged in lower layer in water phase at this time；
(5) operating procedure 2 ~ 3 times of step (4) are repeated, until in detection organic phase without MX impurity residual, then will
Organic phase is filtered, rotates to obtain [R1R2IM] Y product.
The salt D is sodium bisulfate, sodium bicarbonate, sodium carbonate, potassium acid sulfate, saleratus, potassium carbonate, sodium nitrate, nitre
At least one of sour potassium, calcium nitrate, magnesium nitrate and ammonium carbonate, the salt D that the present invention adds can not influence properties of product, and not
It reacts with solvent, water, product.
The MY is sodium tetrafluoroborate, ammonium tetrafluoroborate, Potassium Hexafluorophosphate, sodium bisulfate, sodium hexafluoroantimonate, lithium perchlorate
At least one of with bis-trifluoromethylsulfoandimide lithium.
Embodiment 2
The purifying of 1- butyl -3- methyl imidazolium tetrafluoroborate
1- butyl -3- methylimidazole the bromide of 1.0mol 500mL water is dissolved, the tetrafluoro boron of 1.0mol is added with stirring
Sour ammonium is stirred to react 24 hours at room temperature.
The methylene chloride of 400mL is added in gained mixed solution, is transferred to separatory funnel, 100g sodium nitrate is added, shakes,
It stands, is layered as organic phase on upper layer, water phase is in lower layer；Lower layer's water phase is discharged, 500mL water and 150g is added in organic phase again
Sodium nitrate shakes, and stands, and lower layer's water phase is discharged, repeats this cleaning operation again 1 time by layering；Detection organic phase is without bromine at this time
Ion and ammonium ion rotate to obtain colourless transparent liquid product, yield 92.0% through vacuum.
Embodiment 3
The purifying of 1- allyl -3- butyl imidazole hexafluorophosphate
1- allyl -3- butyl imidazole the villaumite of 1.0mol 500mL water is dissolved, the hexafluoro of 1.0mol is added with stirring
Potassium phosphate is stirred to react 12 hours at room temperature.
The methylene chloride of 400mL is added in gained mixed solution, is transferred to separatory funnel, 110g potassium carbonate is added, shakes,
It stands, is layered as organic phase on upper layer, water phase is in lower layer；Lower layer's water phase is discharged, 500mL water and 180g is added in organic phase again
Potassium carbonate shakes, and stands, and lower layer's water phase is discharged, repeats this cleaning operation again 2 times by layering；Detection organic phase is without bromine at this time
Ion and ammonium ion rotate to obtain light yellow transparent liquid product, yield 93.0% through vacuum.
Embodiment 4
The purifying of 1- octyl -3- ethyl imidazol(e) bis-trifluoromethylsulfoandimide salt
1- octyl -3- ethyl imidazol(e) the salt compounded of iodine of 1.0mol 500mL water is dissolved, double trifluoros of 1.0mol are added with stirring
Methylsulfonimide lithium is stirred to react 8 hours at room temperature.
The methylene chloride of 400mL is added in gained mixed solution, is transferred to separatory funnel, 150g ammonium sulfate is added, shakes,
It stands, is layered as organic phase on upper layer, water phase is in lower layer.Lower layer's water phase is discharged, 500mL water and 300g is added in organic phase again
Ammonium sulfate shakes, and stands, and lower layer's water phase is discharged for layering；Detection organic phase is revolved without bromide ion and ammonium ion through vacuum at this time
Steaming obtains colourless transparent liquid product, yield 91.0%.
Claims (1)
1. a kind of purification process of glyoxaline ion liquid, it is characterised in that the following steps are included:
(1) under stirring, by crude product [R1R2IM] X and the salt MY containing desired anion carry out anion exchange in an aqueous medium
Reaction, obtains [R1R2IM] Y and MX mixed solution A；R1For C2~C8Alkyl, one of allyl；R2For C1~C4Alkane
Base；X is halogen or ester group；
(2) organic extractant is added into step (1) mixed solution A, stands after mixing, mixed solution AUTOMATIC ZONING contains
There is ionic liquid [R1R2IM] Y organic phase in lower layer, the water phase containing MX is on upper layer；
(3) salt D is added into step (2) mixed solution, stands after mixing, mixed solution AUTOMATIC ZONING contains ionic liquid
Body [R1R2IM] Y organic phase on upper layer, the water phase that MX is contained in lower layer is discharged in lower layer in the water phase containing MX at this time；
(4) under stirring, what is obtained to step (3) contains ionic liquid [R1R2IM] Y organic phase in pure water and salt D, stirring is added
Mixed liquor C uniformly is obtained, will be stood after mixed liquor C concussion, mixed liquor C AUTOMATIC ZONING contains ionic liquid [R1R2IM] Y has
For machine mutually on upper layer, the water phase of lower layer is discharged in lower layer in water phase at this time；
(5) operating procedure 2 ~ 3 times of step (4) are repeated, it, then will be organic until in detection organic phase without MX impurity residual
Mutually is filtered, rotates to obtain [R1R2IM] Y product；
The salt D be sodium bisulfate, sodium bicarbonate, sodium carbonate, potassium acid sulfate, saleratus, potassium carbonate, sodium nitrate, potassium nitrate,
At least one of calcium nitrate, magnesium nitrate and ammonium carbonate；
The MY is sodium tetrafluoroborate, ammonium tetrafluoroborate, Potassium Hexafluorophosphate, sodium bisulfate, sodium hexafluoroantimonate, lithium perchlorate and double
At least one of fluoroform sulfimide lithium；
The organic extractant is methylene chloride.
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Citations (4)
| 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 |
-
2016
- 2016-08-31 CN CN201610774246.3A patent/CN106397324B/en active Active
Patent Citations (4)
| 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)
| Title |
|---|
| Controlling the Aqueous Miscibility of Ionic Liquids: Aqueous Biphasic Systems of Water-Miscible Ionic Liquids and Water-Structuring Salts for Recycle, Metathesis, and Separations;Keith E. Gutowski,等;《J. AM. CHEM. SOC.》;20030510;第125卷;6632-6633，全文 |
| 二烷基咪唑离子液体的合成、纯化及表征;周雪玲，等;《应用科技》;20151231;第42卷(第6期);72-76 |
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