CN102020610A - Low-viscosity ionic liquid - Google Patents
Low-viscosity ionic liquid Download PDFInfo
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- CN102020610A CN102020610A CN2009100924850A CN200910092485A CN102020610A CN 102020610 A CN102020610 A CN 102020610A CN 2009100924850 A CN2009100924850 A CN 2009100924850A CN 200910092485 A CN200910092485 A CN 200910092485A CN 102020610 A CN102020610 A CN 102020610A
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Abstract
The invention relates to a method for preparing low-viscosity ionic liquid. The ionic liquid is an oil phase product which is prepared by directly mixing and reacting a chlorinated alkyl imidazole compound and ferric chloride in a molar ratio of more than 1:1 in an open environment. The ionic liquid has low viscosity, high hydrophobicity, high thermostability and high oxidation capacity. The ionic liquid serving as a solvent, a catalyst or an absorbent can be widely applied to scientific researches and industrial production.
Description
Technical field
The present invention relates to the low-viscosity preparation method of ionic liquid, be particularly related to the low and strong ion liquid preparation of iron-based of hydrophobicity of a kind of viscosity, high thermal stability that this ionic liquid showed and strong oxidizing property can be used as solvent, catalyzer, absorption agent and are widely used in scientific research and the industrial production.
Technical background
Ionic liquid is the material that is in a liquid state under room temperature and adjacent temperature, form by asymmetric organic cation and organic or inorganic negatively charged ion, ionic liquid can be divided into two big classes thus, the pure organic ion liquid that one class is made up of organic cation and organic anion, the another kind of metal matrix ionic liquid of forming by organic cation and inorganic complex anion.Ion liquid synthesizing all realizes by ion-exchange.Ion liquid this structure and synthetic characteristics make ionic liquid be called the compound of " structure can design ", and ion liquid kind is difficult to counting.
Moreover, it is strong to studies show that ionic liquid has dissolving power, and volatility is low, the advantage that thermostability is high, so ionic liquid be otherwise known as " green solvent ".Ionic liquid not only is applied to the ionogen in the electrochemistry, and in organic synthesis as aspect fixing the equating in environmentally friendly solvent and the heterogeneous catalyst, a large amount of research reports is all arranged, ion liquid potential prospects for commercial application also receives much concern.
But so far, the application of ionic liquid in industry do not seen large-scale report, wherein main because: (1) existing ionic liquid costs an arm and a leg; (2) ion liquid viscosity is big, is unfavorable for industrial operation; (3) ionic liquid is water-soluble bigger, and it is comparatively serious to run off, and is unfavorable for cycling and reutilization.Therefore, the method for synthesizing ionic liquid that development is green, it is ion liquid synthetic to develop cheap ionic liquid, especially low-viscosity, could satisfy the requirement of ionic liquid in industrial production, finally realizes large-scale application.
The iron-based ionic liquid is to study one of ionic liquid the most widely in the metal matrix ionic liquid, mainly uses the catalyst system of organic synthesis.Originally, most iron-based ionic liquid is that chlorination alkyl imidazolium compounds and FERRIC CHLORIDE ANHYDROUS are reacted in the inert ambient environment of hermetically drying, to avoid airborne moisture interference.From 2004 Japanese scientist's reported first in open environment, adopt the Ferric Chloride Hydrated hybrid reaction directly synthetic can with the iron-based ionic liquid of the automatic phase-splitting of water.This is a kind ofly can adopt cheap raw material and in the simple and easy synthetic ion liquid method of open environment.Thus can be by the proportioning of optimizing materials, acquisition component difference, the ionic liquid that physicochemical characteristic is different, especially reduce ion liquid viscosity, make the ionic liquid of oxidation susceptibility of this super dissolution characteristics that integrates organic ion liquid, strong-hydrophobicity and high thermostability ionic liquid and transition metal ion can satisfy industrial requirement, develop its widespread use aspect the purification of the Separation and Recovery of industrial organic solvent and reductibility waste gas.
Summary of the invention
The objective of the invention is provides a kind of ion liquid simple synthetic method of low-viscosity at the technical barrier that must select to have the raw material of ad hoc structure in the functionalized ion liquid building-up process in order to realize ion liquid specific function and set complicated synthesis technique.This ionic liquid is to be formed by organic cation and the combination of complexing iron negatively charged ion, can obtain the very low ionic liquid of viscosity by regulation and control complexing iron anion-content, for realizing that ionic liquid lays the foundation in industrial application.This ionic liquid is strong and thermostability is high with super dissolving power, the hydrophobicity of organic ion liquid simultaneously, and the ion liquid oxidation susceptibility of transition metal base is integrated in one, at Separation and Recovery industry organic solvent and purify and having wide practical use aspect the reductibility waste gas.
The objective of the invention is to realize by the following technical solutions:
The ion liquid preparation of low-viscosity may further comprise the steps:
1) with the glyoxaline compound is raw material, directly mix (need not solubility promoter) in the reaction unit that has reflux condensing tube with the enpara material. heating in water bath to 60～90 ℃, isothermal reaction 30～90 hours is repeatedly washed with ethyl acetate, and underpressure distillation gets chlorination alkyl imidazo ion liquid product again.
2) aforesaid method synthetic chlorination alkyl imidazo ion liquid is mixed with certain mol proportion with iron(ic) chloride, stir for a long time in the open environment at room temperature, centrifugal layering gets the low-viscosity ionic liquid.
The aforesaid method reaction formula is as follows:
The structural formula of described imidazoles raw material is:
Wherein to represent carbonatoms be 1～4 alkyl substituent to R, and it is 3～16 alkyl substituent (comprising benzyl substituting group and naphthyl substituted base etc.) that R1 represents carbonatoms
Described glyoxaline compound is can be the N-Methylimidazole, also can be N-butyl imidazole, N-propyl imidazole, N-benzyl imidazole etc.
Described chloroparaffin can be a n-propylcarbinyl chloride, also can be the chloroparaffin etc. of 3～16 carbon of chloro octane etc.
Described iron(ic) chloride can be the Ferric Chloride Hydrated that contains six crystal water, also can be Anhydrous Ferric Chloride.
Described open environment is meant the physical environment under the condition of normal pressure of the protector of the hermetically drying that do not dewater and inert atmosphere protection.
Ionic liquid viscosity of the present invention is used rotary viscosity design determining at ambient temperature.
Ion liquid redox potential of the present invention adopts redox electrode directly to measure.
Ion liquid thermostability measuring process of the present invention is as follows: will hold sample crucible and be placed in the retort furnace, 100 ℃ is that initial point is provided with sample heating 1 hour for per 10 ℃ in air atmosphere, sample begins to be cured as stagnation point, is ion liquid thermostability.
Ionic liquid hydrophobic performance of the present invention is in the liquid liquid two-phase system of ionic liquid and water composition, adopts the water content in the karl Fischer method mensuration ionic liquid.
Below by specific embodiment technical scheme of the present invention is further introduced, but the invention is not restricted to this example.
Embodiment 1
In having the 250ml there-necked flask of condensation reflux unit, put into N-butyl imidazole (65g, 0.52mol) and chlorobutane (58.14g, 0.62mol), reaction mixture was 78 ℃ of mechanical stirring reactions 72 hours, unreacted raw material is completely removed with ethyl acetate washing 3～5 times in reaction mixture cooling back, and underpressure distillation gets light yellow viscous liquid again, 1-butyl-3-butyl imidazolitm chloride 110g, productive rate 90%.
Product 1-butyl-3-butyl imidazolitm chloride is divided into four parts, adds FeCl than (1: 1,1: 2,1: 3,1: 4) with amount
36H
2O, normal temperature stir down 24h, centrifugal static layering, 1: 1 take off a layer liquid, 1: 2,1: 3,1: 4 get supernatant liquid respectively.
Below be four kinds of ion liquid physical datas of iron-based and detection data.
| Material molar ratio | Color | Viscosity (mPa.s) | Water content (%) | Oxidizing potential (mv) | Decomposition temperature (℃) |
| 1∶1 | Sorrel | 55 | 0 | 558 | 330 |
| 1∶2 | Nattierblue | 55 | 0 | 846 | 330 |
| 1∶3 | Nattierblue | 60 | 0 | 945 | 330 |
| 1∶4 | Nattierblue | 60 | 0 | 1007 | 330 |
Embodiment 2
In having the 250ml there-necked flask of condensation reflux unit, put into N-benzyl imidazole (80g, 0.5mol) and chlorinated dodecane (113.7g, 0.556mol), reaction mixture was 85 ℃ of mechanical stirring reactions 72 hours, add ethyl acetate after the reaction mixture cooling, being heated to 85 ℃ refluxes for some time, cool to room temperature is isolated ethyl acetate again, repeat above operation 3～5 times, remove unreacted raw material completely, decompression is heated to 85 ℃ of distillations again, gets tawny solid 1-benzyl-3-dodecyl chlorination imidazoles 182g, productive rate 94%.
1-benzyl-3-dodecyl chlorination imidazoles is divided into four parts, adds FeCl than (1: 1,1: 2,1: 3,1: 4) with amount
36H
2O, heating in water bath to 45 ℃ stirs 24h, centrifugal static layering, 1: 1 take off a layer liquid, 1: 2,1: 3,1: 4 get supernatant liquid respectively.
Below be four kinds of ion liquid physical datas of iron-based and detection data
| Material molar ratio | Color | Viscosity (mPa.s) | Water content (%) | Oxidizing potential (mv) | Decomposition temperature (℃) |
| 1∶1 | Sorrel | 150 | 0 | 703 | 280 |
| 1∶2 | Nattierblue | 150 | 0 | 900 | 280 |
| 1∶3 | Nattierblue | 140 | 0 | 966 | 280 |
| 1∶4 | Nattierblue | 140 | 0 | 1013 | 280 |
Embodiment 3
In having the 250ml there-necked flask of condensation reflux unit, put into 433.3gN-Methylimidazole and chlorobutane 512.9g, reaction mixture was 78 ℃ of mechanical stirring reactions 72 hours, wash 3～5 times with ethyl acetate reaction mixture cooling back, remove unreacted raw material completely, underpressure distillation gets light yellow viscous liquid again, be 1-methyl-3-butyl imidazolitm chloride 852.9g, productive rate 90.13%.
Product 1-methyl-3-butyl imidazolitm chloride is divided into four parts, adds FeCl than (1: 1,1: 1.5,1: 2,1: 2.5) with amount
36H
2O, normal temperature stir down 24h, centrifugal static layering, 1: 1 and 1: 1.5 take off a layer liquid,, 1: 2 and 1: 2.5 get supernatant liquid respectively.
Four kinds of ion liquid physical datas are as follows with the detection data:
| Material molar ratio | Color | Viscosity (mPa.s) | Water content (%) | Oxidizing potential (mv) | Decomposition temperature (℃) |
| 1∶1 | Sorrel | 111 | 0 | 649 | 280 |
| 1∶1.5 | Nattierblue | 89.4 | 0 | 659 | 280 |
| 1∶2 | Nattierblue | 83 | 0 | 740 | 280 |
| 1∶2.5 | Nattierblue | 78.4 | 0 | 774 | 280 |
Four kinds of ion liquid dissolving poweies: volume ratio is that the dissolving situation of 1/20 ionic liquid in coordinative solvent is as follows:
| Material molar ratio | Methyl alcohol | Toluene | Sherwood oil | N-propyl alcohol | Normal hexane | Ethyl acetate | Benzene | Ethanol |
| 1∶1 | Solvable | Slightly soluble | Insoluble | Slightly soluble | Insoluble | Solvable | Slightly soluble | Solvable |
| 1∶1.5 | Solvable | Slightly soluble | Insoluble | Solvable | Insoluble | Solvable | Slightly soluble | Solvable |
| 1∶2 | Solvable | Slightly soluble | Insoluble | Solvable | Insoluble | Solvable | Slightly soluble | Solvable |
| 1∶2.5 | Solvable | Slightly soluble | Insoluble | Solvable | Insoluble | Solvable | Slightly soluble | Solvable |
Claims (8)
1. a low-viscosity preparation method of ionic liquid is characterized in that glyoxaline compound and iron(ic) chloride hybrid reaction in open environment makes, and has very strong hydrophobic property, may further comprise the steps:
(1) adding mol ratio in having the there-necked flask of mechanical stirring device is 1: 1.2 glyoxaline compound and chloroparaffin, is heated to 60～90 ℃ under mechanical stirring, reacts 30～90 hours, obtains chlorination alkyl glyoxaline compound.
(2) hybrid reaction in open environment with chlorination alkyl imdazole derivatives in the step (1) and iron(ic) chloride by a certain percentage obtains the ionic liquid product by being separated.
2. be imdazole derivatives and the synthetic product that obtains of chloroparaffin reaction as the glyoxaline compound in the claim 1, imdazole derivatives can be the N-Methylimidazole, also can be N-butyl imidazole, N-propyl imidazole, N-benzyl imidazole etc., chloroparaffin can be a n-propylcarbinyl chloride, also can be the chloroparaffin etc. of 3～16 carbon of chloro octane etc.
3. " by a certain percentage " as the preparation process (2) of claim 1 intermediate ion liquid is meant that the mol ratio of raw material iron(ic) chloride and chlorination alkyl imidazole surpasses 1: 1 (containing 1: 1), but is not more than 4: 1.
4. being the Ferric Chloride Hydrated that contains six crystal water as the iron(ic) chloride in the claim 1, also can be Anhydrous Ferric Chloride.
5. be meant as " being separated " in the claim 1 to form liquid-liquid-solid heterogeneous system in reaction process, the phase-splitting of product ion liquid independence can directly separate, and need not pass through distillation, crystallization, drying treatment.
As the viscosity of claim 1 intermediate ion liquid less than 200mPa.S.
7. be meant liquid liquid two phase systems that synthetic ionic liquid and water form as " hydrophobic property " in the claim 1, and to measure ion liquid water content through the karl Fischer method be zero.
8. be meant physical environment under the condition of normal pressure of the protector of the hermetically drying that do not dewater and inert atmosphere protection as the open environment in the claim 1.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911120A (en) * | 2012-10-22 | 2013-02-06 | 北京化工大学 | Method for synthesizing iron-base ionic liquid through water-phase cyclic utilization |
| CN102993101A (en) * | 2012-11-29 | 2013-03-27 | 南京工业大学 | Imidazolium-based ionic liquids and application thereof |
| CN103254031A (en) * | 2012-02-17 | 2013-08-21 | 北京化工大学 | Method for separating alcohol-water system by extracting through using hydrophobic Fe-based ionic liquid |
| CN105198815A (en) * | 2015-08-24 | 2015-12-30 | 四川大学 | Iron-based imidazole ion liquid for removing SO2 from smoke and preparation method of iron-based imidazole ion liquid |
| CN106064053A (en) * | 2016-06-03 | 2016-11-02 | 华中科技大学 | A kind of flue gas demercuration adsorbent and preparation method thereof |
-
2009
- 2009-09-16 CN CN2009100924850A patent/CN102020610A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103254031A (en) * | 2012-02-17 | 2013-08-21 | 北京化工大学 | Method for separating alcohol-water system by extracting through using hydrophobic Fe-based ionic liquid |
| CN103254031B (en) * | 2012-02-17 | 2014-12-10 | 北京化工大学 | Method for separating alcohol-water system by extracting through using hydrophobic Fe-based ionic liquid |
| CN102911120A (en) * | 2012-10-22 | 2013-02-06 | 北京化工大学 | Method for synthesizing iron-base ionic liquid through water-phase cyclic utilization |
| CN102993101A (en) * | 2012-11-29 | 2013-03-27 | 南京工业大学 | Imidazolium-based ionic liquids and application thereof |
| CN102993101B (en) * | 2012-11-29 | 2015-02-18 | 南京工业大学 | Imidazolium-based ionic liquids and application thereof |
| CN105198815A (en) * | 2015-08-24 | 2015-12-30 | 四川大学 | Iron-based imidazole ion liquid for removing SO2 from smoke and preparation method of iron-based imidazole ion liquid |
| CN106064053A (en) * | 2016-06-03 | 2016-11-02 | 华中科技大学 | A kind of flue gas demercuration adsorbent and preparation method thereof |
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Application publication date: 20110420 |