CN102603644A - Production method of alkylimidazole ionic liquid - Google Patents
Production method of alkylimidazole ionic liquid Download PDFInfo
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- CN102603644A CN102603644A CN2012100165607A CN201210016560A CN102603644A CN 102603644 A CN102603644 A CN 102603644A CN 2012100165607 A CN2012100165607 A CN 2012100165607A CN 201210016560 A CN201210016560 A CN 201210016560A CN 102603644 A CN102603644 A CN 102603644A
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Abstract
The invention discloses a production method of an alkylimidazole ionic liquid, which comprises the following steps: a. adding alkylimidazole and alkylogen R2X in a mol ratio of 1:1-1:5 into a reaction kettle, adding deionized water which is 0.025-0.1 time of imidazole by mass, and stirring at 30-80 DEG C for 5-40 hours, wherein R1 is a C1-C2 alkyl group, R2 is a C2-C6 alkyl group, and X- is a halide ion; b. dissolving the anionic salt Q<+>Y<-> of the target product in deionized water to prepare an approximately saturated solution, adding the approximately saturated solution into the reaction kettle, and stirring to react for 20-72 hours, wherein Q<+> is Na<+>, K<+>, Li<+> or Ag<+>, and Y<-> is BF<4-> or PF<6->; and c. after the reaction finishes, adding dichloromethane as an extractant, washing the salt dissolved in the dichloromethane with water under the protection of the dichloromethane, and finally, distilling out the dichloromethane for cyclic use. The invention has the advantages of simple technological operation (the second reaction step is directly carried out after the first reaction step without any treatment), short synthesis time and wide condition applicability, and is suitable for industrial production; and the product has the advantages of low water content, light color, high purity and low halide ion content.
Description
Technical field
The present invention relates to a kind of production technique of alkyl imidazole ionic liquid, its positively charged ion is a di-alkyl-imidazole, and negatively charged ion is Tetrafluoroboric acid ion, phosphofluoric acid ion, trifluoromethanesulfonic acid ion, two fluoroform sulfimide ion.
Background technology
Ionic liquid is made up of organic cation and inorganic or organic anion.Ionic liquid is of a great variety, and is different according to organic cations, mainly is divided into four big types, i.e. imidazoles, pyridines, quaternary ammonium salt and quaternary phosphine salt.Change negatively charged ion and can design different ionic liquids, its compound method is divided into two kinds substantially: single stage method and two-step approach.Single stage method comprises by nucleophilic reagent---nucleophilic addition takes place with halohydrocarbon or Ester (carboxylicesters, sulfuric ester or SULPHOSUCCINIC ACID ESTER) in tertiary amine (comprising pyridine, imidazoles and pyrroles), or utilizes the alkalescence of tertiary amine and acid generation neutralization reaction to generate object ion liquid.Two-step approach is synthesized ionic liquid, and the first step is prepared through quaterisation and contained the cationic halogen of target, and second step displaced halide-ions or added Lewis acid with the target negatively charged ion and obtains object ion liquid; In the reaction of second step, can utilize complex reaction, replacement(metathesis)reaction, IX or electrolytic process to realize.In addition, novel synthetic ionic liquid method has microwave method and ultrasonic method.
Method for synthesizing ionic liquid is more, but generally adopts ion exchange method to prepare.For example, the alkyl imidazole Tetrafluoroboric acid is ion liquid synthetic more, and 1-ethyl-3-methyl imidazolium tetrafluoroborate adopts compound decomposition method; Being about to chlorination 1-ethyl-3-Methylimidazole is that solvent adds ammonium tetrafluoroborate (J. Electrochem. Soc., Vol.144, No.11 with acetone; 1997,3881 ~ 3886), or use silver tetrafluoroborate to generate halogen silver to promote reaction; These methods are with an organic solvent made solvent, and the silver tetrafluoroborate cost is higher; Employing microwave method (the Tetrahedron Letters 43 that has; 2002,5381 ~ 3583), with chlorination 1-butyl-3-Methylimidazole and ammonium tetrafluoroborate under microwave (360W) condition; Productive rate reached 90% in 150 seconds, and this method only is fit to the synthetic ionic liquid that measures less.There is also one-step, by nitrogen alkylation (Journal? Of? Fluorine? Chemistry,? 2006,127,1261 ~ 1264), the N-alkyl imidazole and trimethyl WU tetrafluoroborate (Me3OBF4) reaction This method does not deal with the impact of a halogen ion, and the reaction yield is higher, but the three high price methyl WU tetrafluoroborate.
Summary of the invention
The object of the invention just is to overcome the working method that above-mentioned deficiency provides a kind of alkyl imidazole ionic liquid.
The object of the invention can be realized through following technical scheme:
A kind of working method of alkyl imidazole ionic liquid may further comprise the steps:
A. with alkyl imidazole
With haloalkane R
2X joins in the reaction kettle for 1:1～1:5 in molar ratio, adds imidazoles quality 0.025-0.1 deionized water doubly, and 30 ℃～80 ℃ were stirred 5～40 hours, wherein: R
1Be 1 ~ 2 alkyl, R
2Be the alkyl of carbon number 2～6, X
-Be halide-ions;
B. use deionized water solubilized target product anion salt Q
+Y
-, be mixed with near saturated solution, join in the reaction kettle stirring reaction 20～72 hours, wherein Q
+Be Na
+, K
+, Li
+, Ag
+In any, Y
-Be BF
4 -, PF
6 -In a kind of;
C. reacted back adding methylene dichloride and made extraction agent, under the protection of methylene dichloride, be dissolved in salt wherein again, distilled out methylene dichloride at last, recycled with water washing.
The ion liquid working method of above-mentioned Methylimidazole class, said step a is 40 ℃～70 ℃ and stirred step b stirring reaction 24～70 hours 10～35 hours.
The ion liquid working method of above-mentioned Methylimidazole class, said step a is 50 ℃～60 ℃ and stirred step b stirring reaction 30～60 hours 15～25 hours.
The ion liquid working method of above-mentioned Methylimidazole class, said step a is 55 ℃ and stirred step b stirring reaction 40～50 hours 20 hours.
The working method of abovementioned alkyl glyoxaline ion liquid, said step a is 30 ℃ and stirred step b stirring reaction 24 hours 6 hours.
Adopt technique scheme, the present invention has following advantage: 1, technological operation is simple, need not after the first step reaction directly to carry out the reaction of second step through handling; 2, generated time is short, and condition of compatibility is wide in range, is fit to suitability for industrialized production; 3, the product water cut is low, and is of light color, and purity is high, and content of halide ions is little.
Embodiment
Embodiment 1
Synthetic ionic liquid: 1-ethyl-3-methyl imidazolium tetrafluoroborate
50 gram N-Methylimidazoles are put in the 250mL there-necked flask, add 2.0g water, agitation and dropping 95.1 gram iodoethane (the two mol ratio is 1:1) under 0 ℃ of cooling bath, reaction 6h.The 118.9g silver tetrafluoroborate is dissolved in 74.0 water, slowly adds in the above-mentioned solution, stirring at room 24 hours, suction filtration, vacuum-drying, yield is 76%.The transparent clarification of product, liquid-phase chromatographic analysis product purity are greater than 99%, and the karl Fischer appearance records the product water cut less than 0.2%, and content of halide ions is less than 100ppm.
Embodiment 2
Synthetic ionic liquid: 1-propyl group-3-Methylimidazole hexafluorophosphate
6.0 kilograms of N-Methylimidazoles and 45.0 kilograms of N-PROPYLE BROMIDEs (the two mol ratio is 1:5) are mixed in the reaction kettle, add 0.25 kg water, 20 ℃ of following stirring reaction 12h; 13.5 kilograms of Potassium Hexafluorophosphates are dissolved in 12.00 kg water, slowly add in the above-mentioned solution, stirring at room 24 hours; Add 20 liters of methylene dichloride, leave standstill and tell organic phase, pure water washs to water halogen ion; Vacuum-drying, yield are 75%.The transparent clarification of product, liquid-phase chromatographic analysis product purity are greater than 99%, and the karl Fischer appearance records the product water cut less than 0.2%, and content of halide ions is less than 100ppm.
Embodiment 3
Synthetic ionic liquid: 1-butyl-3-methyl imidazolium tetrafluoroborate
8 kilograms of N-Methylimidazoles and 27.10 kilograms of chlorobutanes (the two mol ratio is 1:3) are mixed in the reaction kettle, add 0.32 kg water, 50 ℃ of stirring reaction 48h; 9.2 kilograms of LiBF4s are dissolved in 12 kg water, slowly add in the above-mentioned solution, stirring at room 24 hours; Add 25 liters of methylene dichloride, leave standstill and tell organic phase, pure water washs to water halogen ion; Vacuum-drying, yield are 81%.The transparent clarification of product, liquid-phase chromatographic analysis product purity are greater than 99%, and the karl Fischer appearance records the product water cut less than 0.2%, and content of halide ions is less than 100ppm.
Embodiment 4
Synthetic ionic liquid: 1-amyl group-3-Methylimidazole hexafluorophosphate
8 kilograms of N-Methylimidazoles and 29.5 kilograms of bromo pentane silanes (the two mol ratio is 1:2) are mixed in the reaction kettle, add 0.32 kg water, 50 ℃ of stirring reaction 12h; 17.9 kilograms of Potassium Hexafluorophosphates are dissolved in 20 kg water, suspension-s are slowly added in the above-mentioned solution stirring at room 36 hours; Add 30 liters of methylene dichloride, leave standstill and tell organic phase, pure water washs to water halogen ion; Vacuum-drying, yield are 88%.The transparent clarification of product, liquid-phase chromatographic analysis product purity are greater than 99%, and the karl Fischer appearance records the product water cut less than 0.2%, and content of halide ions is less than 100ppm.
Embodiment 5
Synthetic ionic liquid: 1-is base-3-ethyl imidazol(e) a tetrafluoro borate
9.4 kilograms of N-ethyl imidazol(e)s and 64.4 kilograms of bromohexanes (the two mol ratio is 1:4) are mixed in the reaction kettle, add 0.32 kg water, 50 ℃ of stirring reaction 48h; 10.73 kilograms of sodium tetrafluoroborates are dissolved in 12 kg water, slowly add in the above-mentioned solution, stirring at room 24 hours; Add 25 liters of methylene dichloride, leave standstill and tell organic phase, pure water washs to water halogen ion; Vacuum-drying, yield are 81%.The transparent clarification of product, liquid-phase chromatographic analysis product purity are greater than 99%, and the karl Fischer appearance records the product water cut less than 0.2%, and content of halide ions is less than 100ppm.
Working method of the present invention, said step a. is with alkyl imidazole
With haloalkane R
2X joins in the reaction kettle for 1:1～1:5 in molar ratio, adds imidazoles quality 0.025-0.1 deionized water doubly, and 30 ℃～80 ℃ were stirred 5～40 hours, and wherein: R1 is 1～2 alkyl, and R2 is the alkyl of carbon number 2～6, and X-is a halide-ions;
Step b. is mixed with saturated or approaching saturated solution with deionized water solubilized target product anion salt Q+Y-, joins in the reaction kettle, and stirring reaction 20～72 hours, wherein Q+ is Na+, K+, Li
+, Ag
+In any, Y
-Be BF
4 -, PF
6 -In a kind of;
Step c has been reacted back adding methylene dichloride and has been made extraction agent, under the protection of methylene dichloride, is dissolved in salt wherein with water washing again, distills out methylene dichloride at last, recycles.
Claims (5)
1. the working method of an alkyl imidazole ionic liquid may further comprise the steps:
A. with alkyl imidazole
With haloalkane R
2X joins in the reaction kettle for 1:1～1:5 in molar ratio, adds imidazoles quality 0.025-0.1 deionized water doubly, and 30 ℃～80 ℃ were stirred 5～40 hours, and wherein: R1 is 1～2 alkyl, and R2 is the alkyl of carbon number 2～6, and X-is a halide-ions;
B. use deionized water solubilized target product anion salt Q+Y-, be mixed with saturated or approaching saturated solution, join in the reaction kettle, stirring reaction 20～72 hours, wherein Q+ is Na+, K+, Li
+, Ag
+In any, Y
-Be BF
4 -, PF
6 -In a kind of;
C. reacted back adding methylene dichloride and made extraction agent, under the protection of methylene dichloride, be dissolved in salt wherein again, distilled out methylene dichloride at last, recycled with water washing.
2. the ion liquid working method of Methylimidazole class according to claim 1 is characterized in that: said step a is 40 ℃～70 ℃ and stirred step b stirring reaction 24～70 hours 10～35 hours.
3. the ion liquid working method of Methylimidazole class according to claim 1 is characterized in that: said step a is 50 ℃～60 ℃ and stirred step b stirring reaction 30～60 hours 15～25 hours.
4. the ion liquid working method of Methylimidazole class according to claim 1 is characterized in that: said step a is 55 ℃ and stirred step b stirring reaction 40～50 hours 20 hours.
5. the working method of alkyl imidazole ionic liquid according to claim 1 is characterized in that: said step a is 30 ℃ and stirred step b stirring reaction 24 hours 6 hours.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105130902A (en) * | 2015-09-05 | 2015-12-09 | 侯颖 | Preparation method of ionic liquid |
| CN105315215A (en) * | 2015-11-13 | 2016-02-10 | 江南大学 | Efficient ionic liquid synthesis method |
| CN106380450A (en) * | 2016-08-31 | 2017-02-08 | 林州市科能材料科技有限公司 | Method for preparing low-energy consumption imidazoles ionic liquid |
| CN110294712A (en) * | 2019-08-06 | 2019-10-01 | 山东科技大学 | A kind of preparation method of high-purity imidazole acetate ionic liquid |
| CN110967425A (en) * | 2019-12-10 | 2020-04-07 | 江苏国泰超威新材料有限公司 | Determination of N-alkyl imidazole impurity in imidazole type ionic liquid |
| CN113528041A (en) * | 2021-07-29 | 2021-10-22 | 江苏斯迪克新材料科技股份有限公司 | Flame-retardant antistatic protective film and preparation method thereof |
| CN114602420A (en) * | 2022-01-24 | 2022-06-10 | 中国神华煤制油化工有限公司 | Demercuration adsorbent and preparation method and application thereof |
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| CN101058559A (en) * | 2006-04-21 | 2007-10-24 | 南京理工大学 | Method of continuously synthesizing ionic liquid at room temperature |
| CN101492423A (en) * | 2009-03-12 | 2009-07-29 | 中国科学院长春应用化学研究所 | Method for preparing achromatic imidazole ionic liquids |
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2012
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Patent Citations (2)
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| CN101058559A (en) * | 2006-04-21 | 2007-10-24 | 南京理工大学 | Method of continuously synthesizing ionic liquid at room temperature |
| CN101492423A (en) * | 2009-03-12 | 2009-07-29 | 中国科学院长春应用化学研究所 | Method for preparing achromatic imidazole ionic liquids |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105130902A (en) * | 2015-09-05 | 2015-12-09 | 侯颖 | Preparation method of ionic liquid |
| CN105315215A (en) * | 2015-11-13 | 2016-02-10 | 江南大学 | Efficient ionic liquid synthesis method |
| CN106380450A (en) * | 2016-08-31 | 2017-02-08 | 林州市科能材料科技有限公司 | Method for preparing low-energy consumption imidazoles ionic liquid |
| CN106380450B (en) * | 2016-08-31 | 2018-11-06 | 林州市科能材料科技有限公司 | A kind of preparation method of low energy consumption glyoxaline ion liquid |
| CN110294712A (en) * | 2019-08-06 | 2019-10-01 | 山东科技大学 | A kind of preparation method of high-purity imidazole acetate ionic liquid |
| CN110294712B (en) * | 2019-08-06 | 2022-05-24 | 山东科技大学 | Preparation method of high-purity imidazole acetate ionic liquid |
| CN110967425A (en) * | 2019-12-10 | 2020-04-07 | 江苏国泰超威新材料有限公司 | Determination of N-alkyl imidazole impurity in imidazole type ionic liquid |
| CN113528041A (en) * | 2021-07-29 | 2021-10-22 | 江苏斯迪克新材料科技股份有限公司 | Flame-retardant antistatic protective film and preparation method thereof |
| CN114602420A (en) * | 2022-01-24 | 2022-06-10 | 中国神华煤制油化工有限公司 | Demercuration adsorbent and preparation method and application thereof |
| CN114602420B (en) * | 2022-01-24 | 2024-03-26 | 中国神华煤制油化工有限公司 | Mercury-removing adsorbent and preparation method and application thereof |
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Application publication date: 20120725 |