CN1978434A - Method for preparing ionic liquid - Google Patents
Method for preparing ionic liquid Download PDFInfo
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- CN1978434A CN1978434A CN 200510126589 CN200510126589A CN1978434A CN 1978434 A CN1978434 A CN 1978434A CN 200510126589 CN200510126589 CN 200510126589 CN 200510126589 A CN200510126589 A CN 200510126589A CN 1978434 A CN1978434 A CN 1978434A
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- ionic liquid
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Abstract
This invention relates to a preparation of ionic liquid that is using fatty acid radical as negative ion and does not contain halogen. This preparation uses dialkyl imidazole salt, alkyl pyridine salt or caprolactam and fatty acid as reactant. Ionic liquid can be used as reaction mediator and catalyst. The main characteristics of this method are that reaction is quick, purity is high, operation is simple, clean fatty acid ion replaces halogen ion that is noxious, and it is greener.
Description
Technical field
The present invention relates to a kind of with fatty acid radical as the anionic preparation method of ionic liquid that does not contain halogen.
Background technology
In recent years, the ionic liquid system has been brought into play unique effect as " liquid vehicle " that the reaction solution/liquid spe medium etc. that cleans serves as a kind of " green " solvent or catalyzer and some catalyzer in catalysis and organic reaction, be subjected to the extensive concern of countries in the world catalysis circle and petroleum chemical enterprise circle.Steam forces down, and can work under comparatively high temps, and multiple organic-inorganic material is all had good dissolving ability, does not have characteristics such as coordination ability substantially and form ion liquid ion.Ionic liquid is as the proton inertia medium, and is not moisture, do not have problems such as aquation, hydrolysis, liberation of hydrogen, avoided the drawback of high-temperature molten salt.The eighties, early stage Britain BP company and French research institutions such as IFP began to explore the possibility of ionic liquid at room temperature as solvent and catalyzer.Simultaneously, because ionic liquid itself has very strong designability, this just makes that we can be according to the different different ionic liquid catalyst system of reaction design.
Although ionic liquid is used widely in the Green Chemistry process as novel dissolvent and catalyzer, a lot of ionic liquids contain halide anion (as BF
4 -, CF
3SO
3 -, (CF
3SO
3)
2N
-, AlCl particularly
4 -And PF
6 -) can when taking place, hydrolysis or discarded ionic liquid heat treated emit the compound (as poisonous mordant HCl or HF etc.) that contains halogen in a large number, to these not exclusively is the ion liquid application and the research of " green ", caused problem such as equipment corrosion, environmental pollution be serious, thereby cause the social environment problem that everybody pays close attention to of knowing clearly, impel people to remove development environment close friend's the ionic liquid that does not contain these halogenss.Therefore the research environment close friend can just become the emphasis that people study by reusable ionic liquid.Recently, the research of various novel ion liquids has obtained good result.
Summary of the invention
The purpose of this invention is to provide a kind of with fatty acid radical as the anionic preparation method of ionic liquid that does not contain halogen.
A kind of preparation method of ionic liquid, it is characterized in that using dialkylimidazolium, alkyl pyridine or protonated hexanolactam to be positively charged ion, is reactant with fatty acid radical as negatively charged ion, is 25-150 ℃ in temperature of reaction, reacts to prepare corresponding ionic liquid in 1-48 hour.
The method of the invention, what it is characterized in that used cation source is dialkylimidazolium salt, Fixanol or hexanolactam, wherein the structure of dialkylimidazolium salt is
The structure of alkyl pyridine is
The structure of hexanolactam is
Wherein a is the integer between the 0-15, and b is the integer between the 0-15, and X is Cl or Br.
The method of the invention is characterized in that deriving from structural formula as anionic fatty acid radical is
Lipid acid and oleic acid in a kind of, wherein c is the integer between the 11-19.
All of the present invention preparation are positively charged ion with dialkylimidazolium, alkyl pyridine and protonated hexanolactam, with the fatty acid radical be anion ion liquid all pass through infrared spectra (IR), proton nmr spectra (
1H-NMR), structural characterization and affirmation are carried out in mass spectrum (MS) and ultimate analysis.The solid fusing point is measured roughly with micro-fusing point instrument, and the fusing point of solid and liquid is accurately measured with the differential scanning calorimeter DSC Q100 of U.S. TA company.Ion liquid density is with adopting the method for changing of observing volume under the weighing differing temps to measure, and electrochemical window is measured with U.S. CHI660A electrochemical workstation, and specific conductivity is measured with Shanghai DDS-11A digital display conductivitimeter, the acid H of the Br nsted of liquid
0With p-dimethylamino-azo-benzene or 2, the 4-dinitraniline is that indicator adopts ultravioletvisible spectroscopy to measure.Ionic liquid at room temperature of the present invention is stable to water and air, does not show acid substantially, and specific conductivity is also very low simultaneously, and electrochemical window is also very narrow, can be used as the dissolving adsorption medium, has actual application prospect widely.
The present invention and conventional ion liquid and reaction process relatively have following characteristics:
1, raw material sources are easy to get, and price is excellent honest and clean;
2, operation is simple;
3, do not contain the halogen family element;
3, density is little, weightless temperature height, Heat stability is good.
Embodiment
Embodiment 1
5.648g chlorination 1-butyl-3 methyl-imidazole ion liquid and 9.192g stearic acid (octadecanoic acid) are joined in the round-bottomed flask of 100ml, in 120 ℃ of vigorous stirring 30 hours.Obtain light yellow product 1-butyl-3 methyl-imidazoles stearic acid radical ion liquid, molecular weight is 422.5, fusing point is 40.76 ℃, zero pour is 33.83 ℃, density was 1.013g/ml when the vitreous state temperature was-40.03,60 ℃, and density is 1.013g/ml in the time of 80 ℃, very stable to empty G﹠W, temperature was 257.6 ℃ in weightless 5% o'clock.
Embodiment 2
7.083g chlorination 1-butyl-3 methyl-imidazole ion liquid and 8.118g dodecylic acid (lauric acid) are joined in the round-bottomed flask of 100ml, in 120 ℃ of vigorous stirring 30 hours.Obtain light yellow product 1-butyl-3 methyl-imidazoles dodecylic acid radical ion liquid, molecular weight is 338, and fusing point is 28.22 ℃, zero pour is-6.05 ℃, and density is 0.933g/ml in the time of 60 ℃, and density is 0.928g/ml in the time of 80 ℃, very stable to empty G﹠W, temperature was 228.7 ℃ in weightless 5% o'clock.
Embodiment 3
6.754g bromination 1-decyl-3 methyl-imidazole ion liquid and 6.338g stearic acid are joined in the round-bottomed flask of 100ml, in 120 ℃ of vigorous stirring 30 hours.Obtain greyish white product 1-decyl-3 methyl-imidazoles stearic acid radical ion liquid, molecular weight is 506.5, and fusing point is 58.84 ℃, zero pour is 40.91 ℃, and density is 0.968g/ml in the time of 60 ℃, and density is 0.966g/ml in the time of 80 ℃, very stable to empty G﹠W, temperature was 256.4 ℃ in weightless 5% o'clock.
Embodiment 4
3.800g bromination 1-decyl-3 methyl-imidazole ion liquid and 2.508g dodecylic acid are joined in the round-bottomed flask of 100ml, in 120 ℃ of vigorous stirring 30 hours.Obtain light yellow product 1-decyl-3 methyl-imidazoles laurostearic acid radical ion liquid, molecular weight is 422, and fusing point is 69.31 ℃, zero pour is 53.31 ℃, and density is 0.995g/ml in the time of 60 ℃, and density is 0.954g/ml in the time of 80 ℃, very stable to empty G﹠W, temperature was 222.5 ℃ in weightless 5% o'clock.
Embodiment 5
8.569g bromination 1-ethyl-3 methyl-imidazole ion liquid and 12.763g stearic acid are joined in the round-bottomed flask of 100ml, in 120 ℃ of vigorous stirring 30 hours.Obtain white product 1-ethyl-3 methyl-imidazoles stearic acid radical ion liquid, molecular weight is 394.5, and fusing point is 52.97 ℃, zero pour is 37.59 ℃, and density is 0.996g/ml in the time of 60 ℃, and density is 0.988g/ml in the time of 80 ℃, very stable to empty G﹠W, temperature was 243.2 ℃ in weightless 5% o'clock.
Embodiment 6
10.793g bromination 1-ethyl-3 methyl-imidazole ion liquid and 11.302g dodecylic acid are joined in the round-bottomed flask of 100ml, in 120 ℃ of vigorous stirring 30 hours.Obtain white product 1-ethyl-3 methyl-imidazoles laurostearic acid radical ion liquid, molecular weight is 310, and fusing point is 38.68 ℃, zero pour is 22.06 ℃, and density is 1.027g/ml in the time of 60 ℃, and density is 1.027g/ml in the time of 80 ℃, very stable to empty G﹠W, temperature was 204.8 ℃ in weightless 5% o'clock.
Embodiment 7
5.702g bromination 1-decyl-3 methyl-imidazole ion liquid and 4.826g hexadecanoic acid (Palmiticacid) are joined in the round-bottomed flask of 100ml, in 120 ℃ of vigorous stirring 30 hours.Obtain canescence product 1-decyl-3 methyl-imidazoles palmitic acid radical ion liquid, molecular weight is 478, and fusing point is 66.48 ℃, zero pour is 46.47 ℃, and density is 0.964g/ml in the time of 60 ℃, and density is 0.956g/ml in the time of 80 ℃, very stable to empty G﹠W, temperature was 249.6 ℃ in weightless 5% o'clock.
Embodiment 8
8.432g chlorination 1-butyl-3 methyl-imidazole ion liquid and 12.391g hexadecanoic acid are joined in the round-bottomed flask of 100ml, in 120 ℃ of vigorous stirring 30 hours.Obtain white product 1-butyl-3 methyl-imidazoles palmitic acid radical ion liquid, molecular weight is 394, fusing point is 49.64 ℃, zero pour is 28.77 ℃, the vitreous state temperature is-45.86 ℃, and density is 0.929g/ml in the time of 60 ℃, and density is 0.929g/ml in the time of 80 ℃, very stable to empty G﹠W, temperature was 249.0 ℃ in weightless 5% o'clock.
Embodiment 9
9.752g bromination 1-ethyl-3 methyl-imidazole ion liquid and 13.093g hexadecanoic acid are joined in the round-bottomed flask of 100ml, in 120 ℃ of vigorous stirring 30 hours.Obtain white product 1-ethyl-3 methyl-imidazoles palmitic acid radical ion liquid, molecular weight is 366, and fusing point is 59.09 ℃, zero pour is 47.46 ℃, and density is 1.006g/ml in the time of 60 ℃, and density is 1.003g/ml in the time of 80 ℃, very stable to empty G﹠W, temperature was 238.1 ℃ in weightless 5% o'clock.
Embodiment 10
5.851g hexanolactam and 10.357g dodecylic acid are joined in the round-bottomed flask of 100ml, in 120 ℃ of vigorous stirring 30 hours.Obtain black product hexanolactam laurostearic acid radical ion liquid, molecular weight is 313, and fusing point is 18.27 ℃, zero pour is 2.41 ℃, and density is 0.909g/ml in the time of 60 ℃, and density is 0.898g/ml in the time of 80 ℃, very stable to empty G﹠W, temperature was 195.7 ℃ in weightless 5% o'clock.
Embodiment 11
5.416g hexanolactam and 12.273g hexadecanoic acid are joined in the round-bottomed flask of 100ml, in 120 ℃ of vigorous stirring 30 hours.Obtain darkorange product hexanolactam palmitic acid radical ion liquid, molecular weight is 369.5, and fusing point is 36.7 ℃, zero pour is 33.38 ℃, and density is 0.901g/ml in the time of 60 ℃, and density is 0.878g/ml in the time of 80 ℃, very stable to empty G﹠W, temperature was 206.2 ℃ in weightless 5% o'clock.
Embodiment 12
5.355g hexanolactam and 13.462g stearic acid are joined in the round-bottomed flask of 100ml, in 120 ℃ of vigorous stirring 30 hours.Obtain yellow product hexanolactam stearic acid radical ion liquid, molecular weight is 397.5, and fusing point is 30.32 ℃, zero pour is 32.82 ℃, and density is 0.902g/ml in the time of 60 ℃, and density is 0.901g/ml in the time of 80 ℃, very stable to empty G﹠W, temperature was 214.5 ℃ in weightless 5% o'clock.
Embodiment 13
8.052g chlorination 1-butyl-pyridinium ionic liquid and 9.399g dodecylic acid are joined in the round-bottomed flask of 100ml, in 120 ℃ of vigorous stirring 30 hours.Obtain white product 1-butyl-pyridinium laurostearic acid radical ion liquid, molecular weight is 335, and fusing point is 32.25 ℃, zero pour is 14.01 ℃, and density is 0.932g/ml in the time of 60 ℃, and density is 0.932g/ml in the time of 80 ℃, very stable to empty G﹠W, temperature was 223.2 ℃ in weightless 5% o'clock.
Embodiment 14
8.573g chlorination 1-butyl-pyridinium ionic liquid and 12.811g hexadecanoic acid are joined in the round-bottomed flask of 100ml, in 120 ℃ of vigorous stirring 30 hours.Obtain white product 1-butyl-pyridinium palmitic acid radical ion liquid, molecular weight is 391.5, and fusing point is 62.49 ℃, zero pour is 39.46 ℃, and density is 0.862g/ml in the time of 60 ℃, and density is 0.862g/ml in the time of 80 ℃, very stable to empty G﹠W, temperature was 241.0 ℃ in weightless 5% o'clock.
Embodiment 15
7.565g chlorination 1-butyl-pyridinium ionic liquid and 12.541g stearic acid are joined in the round-bottomed flask of 100ml, in 120 ℃ of vigorous stirring 30 hours.Obtain canescence product 1-butyl-pyridinium stearic acid radical ion liquid, molecular weight is 419.5, and fusing point is 59.61 ℃, zero pour is 30.43 ℃, and density is 0.92g/ml in the time of 60 ℃, and density is 0.92g/ml in the time of 80 ℃, very stable to empty G﹠W, temperature was 247.2 ℃ in weightless 5% o'clock.
Claims (3)
1, a kind of preparation method of ionic liquid, it is characterized in that using dialkylimidazolium, alkyl pyridine or protonated hexanolactam to be positively charged ion, is reactant with fatty acid radical as negatively charged ion, is 25-150 ℃ in temperature of reaction, reacts to prepare corresponding ionic liquid in 1-48 hour.
2, as the said method of claim 1, what it is characterized in that used cation source is dialkylimidazolium salt, Fixanol or hexanolactam, and wherein the structure of dialkylimidazolium salt is
, the structure of alkyl pyridine is
, the structure of hexanolactam is
, wherein a is the integer between the 0-15, and b is the integer between the 0-15, and X is Cl or Br.
3,, it is characterized in that deriving from structural formula as anionic fatty acid radical is as the said method of claim 1
Lipid acid and oleic acid in a kind of, wherein c is the integer between the 11-19.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510126589 CN1978434A (en) | 2005-11-30 | 2005-11-30 | Method for preparing ionic liquid |
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|---|---|---|---|
| CN 200510126589 CN1978434A (en) | 2005-11-30 | 2005-11-30 | Method for preparing ionic liquid |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9233928B2 (en) | 2014-05-06 | 2016-01-12 | Uop Llc | Synthesis of lactam based ionic liquid |
| US9416071B2 (en) | 2014-05-06 | 2016-08-16 | Uop Llc | Hydrocarbon conversion processes using lactamium-based ionic liquids |
| US9518023B2 (en) | 2014-05-06 | 2016-12-13 | Uop Llc | Synthesis of N-derivatized lactam based ionic liquid |
-
2005
- 2005-11-30 CN CN 200510126589 patent/CN1978434A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9233928B2 (en) | 2014-05-06 | 2016-01-12 | Uop Llc | Synthesis of lactam based ionic liquid |
| US9416071B2 (en) | 2014-05-06 | 2016-08-16 | Uop Llc | Hydrocarbon conversion processes using lactamium-based ionic liquids |
| US9518023B2 (en) | 2014-05-06 | 2016-12-13 | Uop Llc | Synthesis of N-derivatized lactam based ionic liquid |
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