CN102351796A - Production process of imidazole ionic liquid - Google Patents
Production process of imidazole ionic liquid Download PDFInfo
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- CN102351796A CN102351796A CN2011102422042A CN201110242204A CN102351796A CN 102351796 A CN102351796 A CN 102351796A CN 2011102422042 A CN2011102422042 A CN 2011102422042A CN 201110242204 A CN201110242204 A CN 201110242204A CN 102351796 A CN102351796 A CN 102351796A
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- glyoxaline
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Abstract
The invention discloses a production process of imidazole ionic liquid and aims to provide an industrialized method for preparing imidazole ionic liquid. The technical scheme of the method comprises the following steps: adding an imidazole compound and halogenated hydrocarbon in a reaction kettle, wherein the molar ratio of the imidazole compound to halogenated hydrocarbon is 1:(2-5), refluxing and stirring, heating with a water bath, reacting at 20-60 DEG C for 6-48 hours, standing, recycling the excess raw material to obtaining a solid product, washing the solid product to purify, separating in a centrifugal machine and performing vacuum drying. The reaction process in the invention does not use the solvent; as the reactant halogenated hydrocarbon is excess, the product is dispersed to tiny particles, the subsequent washing purification operation is easy to perform and the product is convenient to extract and use; the excess reactant halogenated hydrocarbon can be recycled and distilled for recycling; the production process has low reaction temperature, short reaction time and less energy consumption; and the solid product of the reaction has small particles and is convenient to wash and separate.
Description
Technical field
The present invention relates to a kind of glyoxaline ion liquid the preparation method.
Background technology
Ionic liquid is called the room temperature melting salt again, be to constitute by organic cation and organic or inorganic negatively charged ion, and room temperature and near the salt that is in a liquid state under the temperature.Just found as far back as 1914 first ionic liquid----nitro ethamine; 1992, Wikes leader's research group synthesized low melting point, anti-hydrolysis, stable strong 1-ethyl-3-methyl imidazolium tetrafluoroborate ionic liquid, and ion liquid afterwards research is able to develop rapidly.Because ionic liquid has many special physico-chemical properties that are different from the molecule-type solvent, make it show many advantages: (1) ionic liquid is tasteless, do not fire, and its vapour pressure is extremely low, has good thermostability and chemical stability; (2) ionic liquid has high conductivity and good electrochemical stability; (3) ionic liquid all has the good solubility ability to organic with inorganics; (4) show the acidity of Lewis, Franklin acid, and strength of acid is adjustable.Ionic liquid at room temperature has obtained in fields such as organic synthesis, catalytic science, compartment analysis, electrochemistry, Materials science using widely as one type of novel green solvent and " soft " functional materials.
Positively charged ion is the ionic liquid of imidazoles, is easy to advantages such as preparation, structure are easy to adjustment, fusing point is lower, is one of the maximum ionic liquid of studying at present.Anion is generally smaller and good symmetry of ions, such as halide ions,?
,
,
,
, of which the maximum production of halide ions, which are widely used in the synthesis of ionic liquids other intermediates.The traditional heating means of the many employings of preparation ionic liquid at present; One Chinese patent application number is 200910218249.9 method and the technologies thereof of having announced a kind of preparing imidazole ionic liquid under microwave condition; Reduced the ratio of the amount of reactant species; Obviously shortened the reaction times, but this preparation method is not suitable for scale production.At present also seldom for the report of ionic liquid scale production technology; Application number is 200910065927.2 to have announced a kind of imidazole ionic liquid production technology; Equipment is simple; Easy handling; But for being solid-state ionic liquid under the room temperature, all need under comparatively high temps, operate from being reacted to the purification drying, energy consumption is high; And the crystalline solid that obtains after the cooling becomes piece, inconvenience transfer and use.
Summary of the invention
The technical problem that the present invention will solve provide a kind of suitability for industrialized production glyoxaline ion liquid method.
Technical scheme of the present invention is: a kind of production technique of glyoxaline ion liquid, glyoxaline compound and halohydrocarbon are added in the reaction kettle, and glyoxaline compound is 1:2 ~ 5 with the ratio of the amount of substance of halohydrocarbon; Refluxing and stirring; Heating in water bath is under 20-60 ℃ the condition, to react 6-48 hour in temperature; After leaving standstill; Reclaim redundance, obtain solid product, solid product is washed purifying; After the whizzer separation, vacuum-drying.
The general structure of said glyoxaline compound is:
In the formula: R
1, R
2, R
3Be respectively the alkyl that H or carbon number are 1-4.
The preferred N-Methylimidazole of said glyoxaline compound, glyoxal ethyline, 4-methylimidazole, N-butyl imidazole.
Said halohydrocarbon is monochloroethane, monobromethane, iodoethane, chlorobutane, n-butyl bromide, butyl iodide.
Said glyoxaline compound is preferably 1:3 ~ 5 with the ratio of the amount of substance of halohydrocarbon.
Said glyoxaline compound is 1:4 with the ratio optimum of the amount of substance of halohydrocarbon.
The invention has the beneficial effects as follows: do not use solvent in the reaction process of the present invention, because the reactant halohydrocarbon is excessive, make product be dispersed into molecule, the washing purification process after being convenient to also is convenient to extract and is used; The excessive reactant halohydrocarbon can reclaim, the distillation recycling; Temperature of reaction of the present invention is low, and the reaction times is short, and power consumption is few; The solid product particle that reaction obtains is little, is convenient to wash lock out operation; The ionic liquid purity that the present invention makes is high, and water content is low.
Embodiment
Embodiment 1
Synthetic ionic liquid: bromination 1-ethyl-3-Methylimidazole
7 kilograms of N-Methylimidazoles and 37.22 kilograms of monobromethanes (ratio of the two amount of substance is 1:4) are mixed in the reaction kettle; 30 ℃ of following stirring reaction 6h; Standing separation goes out the upper strata excessive reactant; Solid product is washed three times with ethyl acetate; Put into whizzer centrifugation washing composition at every turn; Last vacuum-drying, yield is 91%.The fusing point that the fusing point appearance records solid product is 72-76 ℃, and the liquid-phase chromatographic analysis product purity is greater than 99%, and the Ka Erfeixiu appearance records the product water content less than 0.2%.
The nuclear magnetic spectrogram of bromination 1-ethyl-3-Methylimidazole is:
1H NMR (DMSO-D
6): 9.41 (s, 1H, CH), 7.78 (t, 1H, CH), 7.69 (t, 1H, CH), 4.18-4.15 (q, 2H, CH
2), 3.28 (s, 3H, CH
3), 1.37-1.35 (t, 3H, CH
3).The proof products therefrom is bromination 1-ethyl-3-Methylimidazole.
Embodiment 2
Synthetic ionic liquid: bromination 1-ethyl-3-Methylimidazole
6 kilograms of N-Methylimidazoles and 39.88 kilograms of monobromethanes (ratio of the two amount of substance is 1:5) are mixed in the reaction kettle; 20 ℃ of following stirring reaction 12h; Standing separation goes out the upper strata excessive reactant; Solid product is washed three times with ethyl acetate; Put into whizzer centrifugation washing composition at every turn; Last vacuum-drying, yield is 89%.The fusing point that the fusing point appearance records solid product is 72-76 ℃, and the liquid-phase chromatographic analysis product purity is greater than 99%, and the Ka Erfeixiu appearance records the product water content less than 0.2%.
Nuclear magnetic spectrogram such as embodiment 1.
Embodiment 3
Synthetic ionic liquid: bromination 1-butyl-3-Methylimidazole
8 kilograms of N-Methylimidazoles and 40.10 kilograms of n-butyl bromide (ratio of the two amount of substance is 1:3) are mixed in the reaction kettle; 50 ℃ of stirring reaction 36h; Standing separation goes out the upper strata excessive reactant; Solid product is washed three times with ethyl acetate; Put into whizzer centrifugation washing composition at every turn, last vacuum-drying, yield is that the fusing point that 89%. fusing point appearance record solid product is 70-75 ℃; The liquid-phase chromatographic analysis product purity is greater than 98.5%, and the Ka Erfeixiu appearance records the product water content less than 0.2%.
The nuclear magnetic spectrogram of bromination 1-butyl-3-Methylimidazole is:
1H NMR (DMSO-D
6): 9.44 (s, 1H, CH), 7.89 (t, 1H, CH), 7.80 (t, 1H, CH), 4.19-4.15 (t, 2H, CH
2), 3.86 (s, 3H, CH
3), 1.72-1.69 (m, 2H, CH
2), 1.18-1.69 (m, 2H, CH
2), 0.81-0.79 (t, 3H, CH
3).The proof products therefrom is bromination 1-butyl-3-Methylimidazole.
Embodiment 4
Synthetic ionic liquid: chlorination 1-butyl-3-Methylimidazole
10 kilograms of N-Methylimidazoles and 28.20 kilograms of chlorobutanes (ratio of the two amount of substance is 1:2.5) are mixed in the reaction kettle; 50 ℃ of stirring reaction 36h; Standing separation goes out the upper strata excessive reactant; Solid product is washed three times with ethyl acetate; Put into whizzer centrifugation washing composition at every turn, last vacuum-drying, yield is that the fusing point that 89%. fusing point appearance record solid product is 65-70 ℃; The liquid-phase chromatographic analysis product purity is greater than 99%, and the Ka Erfeixiu appearance records the product water content less than 0.2%.
The nuclear magnetic spectrogram of chlorination 1-butyl-3-Methylimidazole is:
1H NMR (DMSO-D
6): 9.52 (s, 1H, CH), 7.85 (t, 1H, CH), 7.76 (t, 1H, CH), 4.17-4.15 (t, 2H, CH
2), 3.85 (s, 3H, CH
3), 1.73-1.71 (m, 2H, CH
2), 1.21-1.19 (m, 2H, CH
2), 0.86-0.84 (t, 3H, CH
3).The proof products therefrom is chlorination 1-butyl-3-Methylimidazole.
Embodiment 5
To synthesize ionic liquid: chlorination 1-butyl-3-Methylimidazole
10 kilograms of N-Methylimidazoles and 28.20 kilograms of chlorobutanes (ratio of the two amount of substance is 1:2.5) are mixed in the reaction kettle; 60 ℃ of stirring reaction 48h; Standing separation goes out the upper strata excessive reactant; Solid product is washed three times with ethyl acetate; Put into whizzer centrifugation washing composition at every turn, last vacuum-drying, yield is that the fusing point that 91%. fusing point appearance record solid product is 65-70 ℃; The liquid-phase chromatographic analysis product purity is greater than 99%, and the Ka Erfeixiu appearance records the product water content less than 0.2%.
Nuclear magnetic spectrogram such as embodiment 4.
Embodiment 6
Synthetic ionic liquid: iodate 1-ethyl-3-Methylimidazole
8.2 kilograms of N-Methylimidazoles and 31.2 kilograms of iodoethane (ratio of the two amount of substance is 1:2) are mixed in the reaction kettle; 25 ℃ of stirring reaction 12h; Standing separation goes out the upper strata excessive reactant; Solid product is washed three times with ethyl acetate; Put into whizzer centrifugation washing composition at every turn, last vacuum-drying, yield is that the fusing point that 95%. fusing point appearance record solid product is 76-80 ℃; The liquid-phase chromatographic analysis product purity is greater than 99%, and the Ka Erfeixiu appearance records the product water content less than 0.2%.
The nuclear magnetic spectrogram of iodate 1-ethyl-3-Methylimidazole is:
1H NMR (DMSO-D
6): 9.17 (s, 1H, CH), 7.78 (t, 1H, CH), 7.69 (t, 1H, CH), 4.18-4.15 (q, 2H, CH
2), 3.83 (s, 3H, CH
3), 1.37-1.35 (t, 3H, CH
3).The proof products therefrom is iodate 1-ethyl-3-Methylimidazole.
Claims (6)
1. the production technique of a glyoxaline ion liquid, it is characterized in that: glyoxaline compound and halohydrocarbon are added in the reaction kettle, and glyoxaline compound is 1:2 ~ 5 with the ratio of the amount of substance of halohydrocarbon; Refluxing and stirring; Heating in water bath is under 20-60 ℃ the condition, to react 6-48 hour in temperature; After leaving standstill; Reclaim redundance, obtain solid product, solid product is washed purifying; After the whizzer separation, vacuum-drying.
2. the preparation method of glyoxaline ion liquid according to claim 1, it is characterized in that: the general structure of said glyoxaline compound is:
In the formula: R
1, R
2, R
3Be respectively the alkyl that H or carbon number are 1-4.
3. the preparation method of glyoxaline ion liquid according to claim 1 and 2, it is characterized in that: said glyoxaline compound is N-Methylimidazole, glyoxal ethyline, 4-methylimidazole, N-butyl imidazole.
4. the preparation method of glyoxaline ion liquid according to claim 1, it is characterized in that: said halohydrocarbon is monochloroethane, monobromethane, iodoethane, chlorobutane, n-butyl bromide, butyl iodide.
5. the preparation method of glyoxaline ion liquid according to claim 1, it is characterized in that: said glyoxaline compound is 1:3 ~ 5 with the ratio of the amount of substance of halohydrocarbon.
6. the preparation method of glyoxaline ion liquid according to claim 5, it is characterized in that: said glyoxaline compound is 1:4 with the ratio of the amount of substance of halohydrocarbon.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107641104A (en) * | 2017-11-24 | 2018-01-30 | 林州市科能材料科技有限公司 | The preparation method of the methylimidazole villaumite ionic liquid of 1 ethyl 3 |
| CN107698514A (en) * | 2017-11-24 | 2018-02-16 | 林州市科能材料科技有限公司 | A kind of preparation method of the methylimidazole bromide of 1 butyl 3 |
| CN108822757A (en) * | 2018-05-30 | 2018-11-16 | 宁波科莱恩新材料科技有限公司 | A kind of low viscous PET protection film of foam material |
| CN114315730A (en) * | 2022-01-14 | 2022-04-12 | 上海健倬生物科技有限公司 | Synthesis method of 1-ethyl-3-methylimidazolium dicyanamide salt ionic liquid |
| CN115010668A (en) * | 2022-06-07 | 2022-09-06 | 林州市科能材料科技有限公司 | Preparation method of 1-ethyl-3-methylimidazole chloride salt |
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| CN101054362A (en) * | 2006-04-14 | 2007-10-17 | 南京理工大学 | Method of synthesizing ion liquid at room temperature |
| CN101058559A (en) * | 2006-04-21 | 2007-10-24 | 南京理工大学 | Method of continuously synthesizing ionic liquid at room temperature |
| CN101215262A (en) * | 2007-01-05 | 2008-07-09 | 中国纺织科学研究院 | ionic liquid and its preparing process and use |
| CN101225073A (en) * | 2008-02-15 | 2008-07-23 | 江南大学 | Ionic liquid as well as preparation method and its use in biological transesterification synthesis |
| CN101654438A (en) * | 2009-08-14 | 2010-02-24 | 河南利华制药有限公司 | Imidazole ionic liquid production technology |
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2011
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| CN101054362A (en) * | 2006-04-14 | 2007-10-17 | 南京理工大学 | Method of synthesizing ion liquid at room temperature |
| CN101058559A (en) * | 2006-04-21 | 2007-10-24 | 南京理工大学 | Method of continuously synthesizing ionic liquid at room temperature |
| CN101215262A (en) * | 2007-01-05 | 2008-07-09 | 中国纺织科学研究院 | ionic liquid and its preparing process and use |
| CN101225073A (en) * | 2008-02-15 | 2008-07-23 | 江南大学 | Ionic liquid as well as preparation method and its use in biological transesterification synthesis |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107641104A (en) * | 2017-11-24 | 2018-01-30 | 林州市科能材料科技有限公司 | The preparation method of the methylimidazole villaumite ionic liquid of 1 ethyl 3 |
| CN107698514A (en) * | 2017-11-24 | 2018-02-16 | 林州市科能材料科技有限公司 | A kind of preparation method of the methylimidazole bromide of 1 butyl 3 |
| CN108822757A (en) * | 2018-05-30 | 2018-11-16 | 宁波科莱恩新材料科技有限公司 | A kind of low viscous PET protection film of foam material |
| CN108822757B (en) * | 2018-05-30 | 2021-05-07 | 宁波科莱恩新材料科技有限公司 | Low-viscosity PET (polyethylene terephthalate) protective film for foam material |
| CN114315730A (en) * | 2022-01-14 | 2022-04-12 | 上海健倬生物科技有限公司 | Synthesis method of 1-ethyl-3-methylimidazolium dicyanamide salt ionic liquid |
| CN115010668A (en) * | 2022-06-07 | 2022-09-06 | 林州市科能材料科技有限公司 | Preparation method of 1-ethyl-3-methylimidazole chloride salt |
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Application publication date: 20120215 |