CN1521163A - Process for preparing room temperature ionic liquid - Google Patents
Process for preparing room temperature ionic liquid Download PDFInfo
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- CN1521163A CN1521163A CNA031152716A CN03115271A CN1521163A CN 1521163 A CN1521163 A CN 1521163A CN A031152716 A CNA031152716 A CN A031152716A CN 03115271 A CN03115271 A CN 03115271A CN 1521163 A CN1521163 A CN 1521163A
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- China
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- ionic liquid
- room temperature
- alkyl
- ammonium halide
- reaction
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Abstract
The present invention relates to the preparation process of room temperature ionic liquid. The present invention features that the room temperature ionic liquid comprising alkyl pyridine cation or alkyl imidazole cation and fluoride anion is prepared with the object product or room temperature ionic liquid as reaction medium and with alkyl pyridine-ammonium halide or alkyl imidazole-ammonium halide and fluoride salt as material. The process is simple in operation, mild in reaction, high in product quality and environment friendly.
Description
Technical field
The present invention relates to a kind of preparation process of room temperature ionic liquid.Present method is applicable to alkyl pyridine ammonium halide or alkyl imidazole ammonium halide and to contain villiaumite be raw material, the occasion of the ionic liquid at room temperature that preparation is made up of alkyl pyridine positively charged ion or alkyl imidazole positively charged ion and fluo anion.
Background technology
Ionic liquid at room temperature is called " planner's solvent " again, is meant the material that is made of ion that is in a liquid state under near temperature room temperature or the room temperature.Ionic liquid at room temperature is the another big class green solvent system behind water and supercritical co, has broad application prospects at aspects such as sepn process, chemical reaction and electrochemistry.
The ionic liquid at room temperature of being made up of with fluo anion respectively alkyl pyridine positively charged ion, alkyl imidazole positively charged ion is the room-temperature ion liquid series of widespread use the most under study for action at present, its traditional preparation method is normally: with organic solvents such as acetone, acetonitrile, trichloroethane is reaction medium, with alkyl pyridine ammonium halide or alkyl imidazole ammonium halide with contain villiaumite or fluoric-containing acid and carry out anion exchange reaction and make ionic liquid at room temperature.The shortcoming of this method maximum is exactly to need to use a large amount of volatile organic solvents, easily causes the pollution to environment.For fear of the pollution of organic solvent to environment, Namboodiri and Varma have studied with the promoted non-solvent method of microwave technology synthetic 1, method (the Tetrahedron Lett.2002 of 3-dialkyl group a tetrafluoro borate ionic liquid at room temperature, 43,5381-5383), yet this method requires specific installation, should not realize that mass-producing synthesizes ionic liquid at room temperature; In addition, the reaction conditions of microwave method is wayward, and the thermal effect of microwave and electric field action easily cause reaction mass overheated and influence quality product.
Summary of the invention
The objective of the invention is to overcome the shortcoming of existing synthetic method, providing does not need to use volatile organic solvent, preparation process of room temperature ionic liquid easy and simple to handle, eco-friendly in a kind of reaction process.
The preparation process of room temperature ionic liquid that we are bright, it is characterized in that adopting target product is that ionic liquid at room temperature is a reaction medium, is raw material with alkyl pyridine ammonium halide or alkyl imidazole ammonium halide with containing villiaumite, the ionic liquid at room temperature that preparation is made up of alkyl pyridine positively charged ion or alkyl imidazole positively charged ion and fluo anion, wherein, the molar mass of used reaction raw materials ratio is: alkyl pyridine ammonium halide or alkyl imidazole ammonium halide: contain villiaumite=1: 0.9～1.1; Temperature of reaction is 20～120 ℃; Reaction principle is shown below.
Described alkyl pyridine ammonium halide or alkyl imidazole ammonium halide are compound 1, compound 2 or the compound 3 in the following formula, wherein: R, R ' or R " to represent carbonatoms respectively be 1～12 alkyl, comprises straight-chain alkyl or branched hydrocarbyl; X
-=Cl
-, Br
-Or I
-
The described villiaumite that contains is M
+Y
-, M
+=Li
+, Na
+, K
+, Ag
+Or NH
4 +Y
-=BF
4 -, PF
6 -, AsF
6 -, SbF
6 -, CF
3COO
-, C
3F
7COO
-, CF
3SO
2 -, C
4F
9SO
3 -, (CF
3SO
2)
2N
-Or (C
2F
5SO
2)
2N
-
Described reaction medium is that target product is an ionic liquid at room temperature itself, and consumption is that 100～500g/mol contains villiaumite.
The bright preparation process of room temperature ionic liquid of we, its key problem in technology be with target product be ionic liquid at room temperature as reaction medium, its advantage is: 1) reaction medium environmental friendliness, cause pollution when having avoided with an organic solvent to environment.2) product separation is simple, because used reaction medium is target product, has removed the separating step of product and reaction medium from.In addition, the reaction conditions gentleness of present method, good product quality is a kind of eco-friendly preparation process of room temperature ionic liquid, both has been suitable for that the laboratory is synthetic also to be suitable for large-scale industry and to be combined to ionic liquid at room temperature.
Embodiment
Embodiment 1
In the there-necked flask of 50mL, add 18.4g Potassium Hexafluorophosphate, 17.5g 1-normal-butyl-3-Methylimidazole ammonium chloride and 20.0g 1-normal-butyl-3-Methylimidazole hexafluorophosphate ionic liquid successively, stirring reaction is 10 hours under 80 ℃ of temperature.Reaction finishes, and reaction solution is used the water washing 3 times of 20mL * 3 respectively, and then, decompression removes residual water, obtains the colourless 1-normal-butyl of 46.0g-3-methyl hexafluorophosphate ionic liquid, the newly-generated 26.0g ionic liquid of real reaction, yield 91.5%.
Embodiment 2
In the there-necked flask of 150mL, add 11.0g ammonium borofluoride, 21.6g N-normal-butyl pyridine brometo de amonio and 30.0g N-normal-butyl pyridinium tetrafluoroborate salt ion liquid successively, 50 ℃ of stirring reactions 12 hours.Reaction finishes, add 30mL water, fully stir, then, the ionic liquid of the dichloromethane extraction aqueous phase of usefulness 40mL * 33 times, combined dichloromethane extraction liquid, distillation removes solvent, obtaining 50.7g almost is colourless N-normal-butyl pyridinium tetrafluoroborate salt ion liquid, the newly-generated 20.7g ionic liquid of real reaction, yield 92.8%.
Embodiment 3
In the there-necked flask of 150mL, add 22.1g trifluoroacetic acid silver, 19.1g 1-ethyl-3-Methylimidazole brometo de amonio and 40.0g 1-ethyl-3-Methylimidazole trifluoroacetate ionic liquid successively, stirring reaction is 1 hour under 25 ℃ of temperature.Reaction finishes, add the 30mL methylene dichloride, fully stir, remove by filter Silver monobromide, filter cake is successively used 10mL * 3 washed with dichloromethane 3 times, then, combined dichloromethane solution, decompression removes solvent, obtains the subdiaphanous 1-ethyl of 62.2g-3-Methylimidazole trifluoroacetate ionic liquid, the newly-generated 22.2g ionic liquid of real reaction, yield 99.1%.
Embodiment 4
In the there-necked flask of 150mL, add 11.0g Sodium tetrafluoroborate, 27.5g 1-n-octyl-3-Methylimidazole brometo de amonio and 25.0g 1-n-octyl-3-methyl imidazolium tetrafluoroborate ionic liquid successively, 50 ℃ of stirring reactions 10 hours.Reaction finishes, add 30mL water, fully stir, then, with 30mL * 3 dichloromethane extractions 3 times, then, combined dichloromethane solution, decompression removes solvent, obtains 50.9g 1-n-octyl-3-methyl imidazolium tetrafluoroborate ionic liquid, the newly-generated 25.9g ionic liquid of real reaction, yield 91.8%.
Claims (4)
1. preparation process of room temperature ionic liquid, it is characterized in that adopting target product is that ionic liquid at room temperature is a reaction medium, is raw material with alkyl pyridine ammonium halide or alkyl imidazole ammonium halide with containing villiaumite, the ionic liquid at room temperature that preparation is made up of alkyl pyridine positively charged ion or alkyl imidazole positively charged ion and fluo anion, wherein, the molar mass of used reaction raw materials ratio is: alkyl pyridine ammonium halide or alkyl imidazole ammonium halide: contain villiaumite=1: 0.9～1.1; Temperature of reaction is 20～120 ℃; The chemical structural formula of ionic liquid at room temperature is:
2. synthetic method according to claim 1 is characterized in that the chemical structural formula of alkyl pyridine ammonium halide and alkyl imidazole ammonium halide is respectively:
Wherein, R, R ' or R " to represent carbonatoms respectively be 1～12 alkyl, comprises straight-chain alkyl or branched hydrocarbyl; X
-=Cl
-, Br
-Or I
-
3. synthetic method according to claim 1, it is characterized in that containing villiaumite is M
+Y
-, M
+=Li
+, Na
+, K
+, Ag
+Or NH
4 +Y
-=BF
4 -, PF
6 -, AsF
6 -, SbF
6 -, CF
3COO
-, C
3F
7COO
-, CF
3SO
2 -, C
4F
9SO
3 -, (CF
3SO
2)
2N
-Or (C
2F
5SO
2)
2N
-
4. synthetic method according to claim 1, it is characterized in that adopting target product is that ionic liquid at room temperature is made reaction medium, consumption is that 100～500g/mol contains villiaumite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03115271 CN1235879C (en) | 2003-01-27 | 2003-01-27 | Process for preparing room temperature ionic liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03115271 CN1235879C (en) | 2003-01-27 | 2003-01-27 | Process for preparing room temperature ionic liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1521163A true CN1521163A (en) | 2004-08-18 |
| CN1235879C CN1235879C (en) | 2006-01-11 |
Family
ID=34284210
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03115271 Expired - Fee Related CN1235879C (en) | 2003-01-27 | 2003-01-27 | Process for preparing room temperature ionic liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1235879C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304376C (en) * | 2005-03-04 | 2007-03-14 | 清华大学 | Method for preparing ion liquid in halogenated alkyl imidazole type |
| CN1332957C (en) * | 2005-02-06 | 2007-08-22 | 浙江工业大学 | Process for preparing ketal or acetal compounds with normal temperature ion liquid as catalyst |
| CN100344380C (en) * | 2004-12-08 | 2007-10-24 | 北京化工大学 | Room temperature ionic liquid and its preparation method |
| CN100369900C (en) * | 2006-01-24 | 2008-02-20 | 广东工业大学 | Process for preparing ionic liquid |
| CN101813685A (en) * | 2010-04-20 | 2010-08-25 | 长安大学 | Method for determining residual erythrocin in environment by hydrophobic ionic liquid |
| WO2011000490A3 (en) * | 2009-06-30 | 2011-02-24 | Merck Patent Gmbh | Synthesis of ionic liquids |
| CN109867622A (en) * | 2017-12-01 | 2019-06-11 | 武汉软件工程职业学院 | It prepares the method for ionic liquid and prepares the device of ionic liquid |
-
2003
- 2003-01-27 CN CN 03115271 patent/CN1235879C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100344380C (en) * | 2004-12-08 | 2007-10-24 | 北京化工大学 | Room temperature ionic liquid and its preparation method |
| CN1332957C (en) * | 2005-02-06 | 2007-08-22 | 浙江工业大学 | Process for preparing ketal or acetal compounds with normal temperature ion liquid as catalyst |
| CN1304376C (en) * | 2005-03-04 | 2007-03-14 | 清华大学 | Method for preparing ion liquid in halogenated alkyl imidazole type |
| CN100369900C (en) * | 2006-01-24 | 2008-02-20 | 广东工业大学 | Process for preparing ionic liquid |
| WO2011000490A3 (en) * | 2009-06-30 | 2011-02-24 | Merck Patent Gmbh | Synthesis of ionic liquids |
| CN101813685A (en) * | 2010-04-20 | 2010-08-25 | 长安大学 | Method for determining residual erythrocin in environment by hydrophobic ionic liquid |
| CN109867622A (en) * | 2017-12-01 | 2019-06-11 | 武汉软件工程职业学院 | It prepares the method for ionic liquid and prepares the device of ionic liquid |
| CN109867622B (en) * | 2017-12-01 | 2023-05-05 | 武汉软件工程职业学院 | Method for preparing ionic liquid and device for preparing ionic liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1235879C (en) | 2006-01-11 |
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Granted publication date: 20060111 Termination date: 20200127 |