CN102675131A - Preparation method of halide aluminate ionic liquid - Google Patents
Preparation method of halide aluminate ionic liquid Download PDFInfo
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- CN102675131A CN102675131A CN2012101530769A CN201210153076A CN102675131A CN 102675131 A CN102675131 A CN 102675131A CN 2012101530769 A CN2012101530769 A CN 2012101530769A CN 201210153076 A CN201210153076 A CN 201210153076A CN 102675131 A CN102675131 A CN 102675131A
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- salt
- ionic liquid
- methyl alcohol
- alx
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Abstract
The invention relates to a preparation method of halide aluminate ionic liquid. The preparation method is mainly characterized in that A<+>Y<-> salts and AlX3 are dissolved in absolute methanol, solvents are steamed out after the mixed reaction, and ionic liquid with the structure general formula being A<+>B<-> can be obtained, wherein A<+> comprises imidazole ions, pyridine ions, phosphonium ions and quaternary amine ions, and B<-> is AlX3Y<->, X is Cl or Br, and Y is Cl or Br. The preparation method has the advantages that the operation is simple, the reaction time is short, the ionic liquid and the solvents are easy to separate, the preparation method can be used for large-scale industrial production, and higher economic values are realized.
Description
Technical field
The present invention relates to a kind of preparation method of halogen aluminate ion liquid, this method is applicable to that ion liquid general structure is: A
+B
-, A wherein
+Comprise imidazol ion, pyridinium ion, season phosphine ion, quaternary amine ion, B
-Be AlX
3Y
-, X is Cl or Br, Y is Cl or Br.
Background technology
Ionic liquid is meant in room temperature or near presenting salt liquid, that be made up of zwitterion fully under the room temperature, is also referred to as watery fusion salt.Ionic liquid is as ionic compound, and the major cause that its fusing point is lower is that some substituent asymmetry can not be piled into due to the crystal ion regularly in its structure.Ionic liquid has a lot of good physicochemical property and is easy to recycle, and ionic liquid has character such as green solvent and catalyzer concurrently, and ionic liquid is easy to separate with the system that volatile material constitutes, and conveniently reclaims and recycles.Synthesize different ionic liquids through changing the various combination of zwitterion, can designing.Usually, ion liquid positively charged ion mainly comprises: imidazol ion, pyridinium ion, season phosphine ion, quaternary amine ion; Negatively charged ion can be divided into two big types: one type is to contain AlCl
3Halide salt; Another kind of negative ion is used BF more
4 -, PF
6 -, TA is also arranged
-(CF
3COO
-), HB
-(C
3F
7COO
-) etc.The ion liquid synthetic two kinds of basic skills that have substantially: direct synthesis technique and two step synthesis methods.At present; Halogen aluminate ion liquid commonly used adopts directly aluminum chloride is combined preparation or is dissolved in the method for preparing in the acetonitrile with halogen; When reaction raw materials directly is mixed with halogen aluminate ion liquid; Whole process of preparation needs comparatively high temps, and needs comparatively exacting terms of UW or other, is inappropriate for suitability for industrialized production; Adopt acetonitrile to make solvent when synthetic, solvent toxicity is bigger, and the solubleness of raw material in acetonitrile is very big, and the acetonitrile boiling point is higher, causes being difficult to thorough solvent evaporated after the reaction, brings certain degree of difficulty to aftertreatment.
Summary of the invention
In order to overcome above technological deficiency, the invention provides a kind of preparation method of halogen aluminate ion liquid, this method is simple to operate, and the reaction times is short, and ionic liquid is easy to separate with solvent, can be used for suitability for industrialized production in a large number, and bigger economic worth is arranged.
The present invention mainly is with A
+Y
-Salt and AlX
3Be dissolved in the methyl alcohol, steam solvent after the hybrid reaction, can obtain general structure is A
+B
-Ionic liquid;
A wherein
+For imidazol ion or pyridinium ion or season phosphine ion or quaternary amine ion; B
-Be AlX
3Y
-X is Cl or Br; Y is Cl or Br.
Its concrete steps are:
(1) with A
+Y
-Salt is that 0.1-1:1 mixes with methyl alcohol according to mass ratio, and makes A
+Y
-Salt dissolves fully;
(2) with AlX
3Be dissolved in above-mentioned A
+Y
-In the methanol solution of salt, AlX
3With the mass ratio of methyl alcohol be 0.1-1:1;
(3) ℃-80 ℃ of reactions of the above-mentioned solution to 60 of heating steamed solvent after 0.5-1.5 hour, reduced to room temperature, filtered, and promptly obtained thick ionic liquid.
Wherein, the methyl alcohol of choosing in the said step (1) is anhydrous methanol, why selects anhydrous methanol to make solvent; Be that its toxicity is low, polarity is stronger, the most of salt of solubilized; But compare in acetonitrile, a bit weaker again to the solubleness of raw material, and also the methyl alcohol boiling point is lower; Compare with acetonitrile with water and to be easy to separate with ionic liquid, reaction finishes can be with the thorough evaporate to dryness of solvent.
In addition, anhydrous reaction environment can effectively be avoided the decomposition of raw material and product, guarantees ion liquid effectively syntheticly, in order to reach best effect, reacts raw materials used and must be dried to aqueous massfraction and be lower than 0.5%.
A in the said step (1)
+Y
-The mass ratio of salt and methyl alcohol is 0.1-1:1, preferred 0.5:1.Both mass ratioes are too small, then A
+Y
-Salt concn is low, during hybrid reaction and AlX
3React insufficient; Excessive, then methyl alcohol can't dissolve excessive A
+Y
-Salt.
AlX in the said step (2)
3With the mass ratio of methyl alcohol be 0.1-1:1, preferred 0.5:1.Mass ratio is too small, then AlX
3Concentration is low, during hybrid reaction and A
+Y
-Reactant salt is insufficient; Excessive, then methyl alcohol can't dissolve excessive AlX
3
Temperature of reaction is preferred 60 ℃-80 ℃ in the said step (3).Temperature is low excessively, A
+Y
-Salt and AlX
3Can't dissolve fully; Temperature is too high, and the ionic liquid of generation then can be participated in reaction by catalysis methanol.
Above-mentioned reaction steams solvent after accomplishing, and reduces to room temperature, filters, and gained filtrating is ionic liquid.The solvent that steams is capable of circulation to be applied mechanically, and continues on for dissolving A
+Y
-Salt and AlX
3And do not influence final test-results.
In sum, the present invention is simple to operate, and the reaction times is short; Adopt anhydrous methanol to make solvent, suitable to the dissolving power of raw material, boiling point is lower simultaneously; Be easy to separate, from reaction system, thoroughly remove with the ionic liquid that produces, and; The acetonitrile kind solvent toxicity of comparing is less, can be used for suitability for industrialized production in a large number, and bigger economic worth is arranged.
Embodiment
Below, foregoing of the present invention is done further detailed description, but should this be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following instance through the embodiment of embodiment form.All technology that realizes based on foregoing of the present invention all belong to scope of the present invention.
Used anhydrous methanol is commercial among the embodiment, and all the other raw materials all adopt this area conventional drying method to be dried to water cut to be lower than 0.5% (massfraction).
Embodiment 1
(1) takes by weighing the 79g Tetrabutyl amonium bromide and place in the dry 250ml four-hole boiling flask of crossing, stirring and dissolving behind the adding 100ml anhydrous methanol (but if insufficient low-grade fever of dissolving).
(2) load weighted 60g aluminum trichloride (anhydrous) is added in the above-mentioned solution.
(3) the above-mentioned solution to 60 of heating ℃ insulation reaction steamed solvent after 1.5 hours, reduced to room temperature, filtered, and gained filtrating is ion liquid of quaternaries.
Embodiment 2
(1) takes by weighing 40gN-Methylimidazole hydrochloride and place in the dry 250ml four-hole boiling flask of crossing, stirring and dissolving behind the adding 100ml anhydrous methanol (but if insufficient low-grade fever of dissolving).
(2) load weighted 80g aluminum trichloride (anhydrous) is added in the above-mentioned solution.
(3) the above-mentioned solution to 69 of heating ℃ insulation reaction steamed solvent after 1 hour, reduced to room temperature, filtered, and gained filtrating is the imidazole salt ionic liquid.
Embodiment 3
(1) takes by weighing the 23.8g pyridine hydrochloride and place in the dry 250ml four-hole boiling flask of crossing, stirring and dissolving behind the adding 100ml anhydrous methanol (but if insufficient low-grade fever of dissolving).
(2) load weighted 24g aluminum trichloride (anhydrous) is added in the above-mentioned solvent.
(3) the above-mentioned solution to 70 of heating ℃ insulation reaction steamed solvent after 1 hour, reduced to room temperature, filtered, and gained filtrating is pyridine salt ionic liquid.
Embodiment 4
(1) takes by weighing 10g 4-carboxylic butyl triphenyl bromo-phosphonium and place in the dry 250ml four-hole boiling flask of crossing, stirring and dissolving behind the adding 100ml anhydrous methanol (but if insufficient low-grade fever of dissolving).
(2) load weighted 10g aluminum trichloride (anhydrous) is added in the above-mentioned solution.
(3) the above-mentioned solution to 80 of heating ℃ insulation reaction steamed solvent after 0.5 hour, reduced to room temperature, filtered, and gained filtrating is quaternary phosphonium salt ionic liquid.
Embodiment 5
(1) takes by weighing 40g tetrabutylammonium chloride and 39gN-Methylimidazole hydrochloride respectively and place in the dry 250ml four-hole boiling flask of crossing, stirring and dissolving behind the adding 100ml anhydrous methanol (but if insufficient low-grade fever of dissolving).
(2) load weighted 60g aluminum trichloride (anhydrous) is added in the above-mentioned solution.
(3) the above-mentioned solution to 65 of heating ℃ insulation reaction steamed solvent after 1.2 hours, reduced to room temperature, filtered, and gained filtrating is promptly mixed a type ionic liquid.
Embodiment 6
(1) takes by weighing 10gN-Methylimidazole hydrochloride and 20g pyridine hydrochloride and place in the dry 250ml four-hole boiling flask of crossing, stirring and dissolving behind the adding 100ml anhydrous methanol (but if insufficient low-grade fever of dissolving).
(2) load weighted 20g aluminum trichloride (anhydrous) is added in the above-mentioned solution.
(3) the above-mentioned solution to 75 of heating ℃ insulation reaction steamed solvent after 1 hour, reduced to room temperature, filtered, and gained filtrating is promptly mixed a type ionic liquid.
Embodiment 7
(1) takes by weighing the 78g Tetrabutyl amonium bromide and place in the dry 250ml four-hole boiling flask of crossing, add 100ml anhydrous methanol (reclaiming gained among the embodiment 1) back stirring and dissolving (but if insufficient low-grade fever of dissolving).
(2) the anhydrous alchlor of load weighted 60g is added in the above-mentioned solution.
(3) the above-mentioned solution to 69 of heating ℃ insulation reaction steamed solvent after 1 hour, reduced to room temperature, filtered, and gained filtrating is ion liquid of quaternaries.
Embodiment 8
(1) takes by weighing 40gN-Methylimidazole hydrochloride and place in the dry 250ml four-hole boiling flask of crossing, stirring and dissolving behind the adding 100ml anhydrous methanol (but if insufficient low-grade fever of dissolving).
(2) the anhydrous alchlor of load weighted 40g is added in the above-mentioned solution.
(3) the above-mentioned solution to 69 of heating ℃ insulation reaction steamed solvent after 1 hour, reduced to room temperature, filtered, and gained filtrating is the imidazole salt ionic liquid.
Embodiment 9
(1) takes by weighing the 55.4g pyridine hydrochloride and place in the dry 250ml four-hole boiling flask of crossing, stirring and dissolving behind the adding 100ml anhydrous methanol (but if insufficient low-grade fever of dissolving).
(2) the anhydrous alchlor of load weighted 60g is added in the above-mentioned solution.
(3) the above-mentioned solution to 63 of heating ℃ insulation reaction steamed solvent after 1.5 hours, reduced to room temperature, filtered, and gained filtrating is pyridine salt ionic liquid.
Embodiment 10
(1) takes by weighing 10g 4-carboxylic butyl triphenyl bromo-phosphonium and place in the dry 250ml four-hole boiling flask of crossing, stirring and dissolving behind the adding 100ml anhydrous methanol (but if insufficient low-grade fever of dissolving).
(2) the anhydrous alchlor of load weighted 12g is added in the above-mentioned solution.
(3) the above-mentioned solution to 73 of heating ℃ insulation reaction steamed solvent after 1 hour, reduced to room temperature, filtered, and gained filtrating is quaternary phosphonium salt ionic liquid.
Claims (6)
1. the preparation method of a halogen aluminate ion liquid is characterized in that: with A
+Y
-Salt and AlX
3Be dissolved in the methyl alcohol, steam methyl alcohol after the hybrid reaction, can obtain general structure is A
+B
-Ionic liquid;
A wherein
+For imidazol ion or pyridinium ion or season phosphine ion or quaternary amine ion; B
-Be AlX
3Y
-X is Cl or Br; Y is Cl or Br.
2. the preparation method of halogen aluminate ion liquid according to claim 1 is characterized in that: its concrete steps are:
(1) with A
+Y
-Salt is that 0.1-1:1 mixes with methyl alcohol according to mass ratio, and makes A
+Y
-Salt dissolves fully;
(2) with AlX
3Be dissolved in above-mentioned A
+Y
-In the methanol solution of salt, AlX
3With the mass ratio of methyl alcohol be 0.1-1:1;
(3) ℃-80 ℃ of reactions of the above-mentioned solution to 60 of heating steamed solvent after 0.5-1.5 hour, reduced to room temperature, filtered, and promptly got ionic liquid.
3. the preparation method of halogen aluminate ion liquid according to claim 2 is characterized in that: the methyl alcohol of choosing in the step (1) is anhydrous methanol.
4. the preparation method of halogen aluminate ion liquid according to claim 2 is characterized in that: A in the step (1)
+Y
-The mass ratio of salt and methyl alcohol is 0.5:1.
5. the preparation method of halogen aluminate ion liquid according to claim 2 is characterized in that: AlX in the step (2)
3Mass ratio 0.5:1 with methyl alcohol.
6. the preparation method of halogen aluminate ion liquid according to claim 2 is characterized in that: A
+Y
-Salt and AlX
3In aqueous massfraction be lower than 0.5%.
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|---|---|---|---|
| CN2012101530769A CN102675131A (en) | 2012-05-17 | 2012-05-17 | Preparation method of halide aluminate ionic liquid |
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|---|---|---|---|
| CN2012101530769A CN102675131A (en) | 2012-05-17 | 2012-05-17 | Preparation method of halide aluminate ionic liquid |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109562365A (en) * | 2016-06-07 | 2019-04-02 | 塞特工业公司 | San Wan Ji phosphonium ion liquid, manufacturing method and the alkylation using San Wan Ji phosphonium ion liquid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101764255A (en) * | 2009-11-20 | 2010-06-30 | 无锡欧力达新能源电力科技有限公司 | Rechargeable aluminum-sulfur battery and preparation method thereof |
| US20110040784A1 (en) * | 2008-04-25 | 2011-02-17 | Guillaume Rousseau | Computer device for the time-based management of digital documents |
-
2012
- 2012-05-17 CN CN2012101530769A patent/CN102675131A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110040784A1 (en) * | 2008-04-25 | 2011-02-17 | Guillaume Rousseau | Computer device for the time-based management of digital documents |
| CN101764255A (en) * | 2009-11-20 | 2010-06-30 | 无锡欧力达新能源电力科技有限公司 | Rechargeable aluminum-sulfur battery and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| THOMAS WELTON: "Room-Temperature Ionic Liquids. Solvents for Synthesis and Catalysis", 《CHEM. REV.》 * |
| 张鹏等: "室温离子液体的研究进展", 《辽宁化工》 * |
| 朱佳媚等: "离子液体的制备及其酸性研究", 《化学工业与工程技术》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109562365A (en) * | 2016-06-07 | 2019-04-02 | 塞特工业公司 | San Wan Ji phosphonium ion liquid, manufacturing method and the alkylation using San Wan Ji phosphonium ion liquid |
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Application publication date: 20120919 |