CN102304054A - Chelate type ionic liquid and preparation and purification method thereof - Google Patents
Chelate type ionic liquid and preparation and purification method thereof Download PDFInfo
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Abstract
The invention relates to chelate type ionic liquid prepared by using coordinating capacity of beta-diketone anions. The chelate type ionic liquid is prepared by combining different cations and different anions. The cations may be quaternary amine, quaternary phosphorus, alkyl pyridine, alkyl iminazole or the like, the anions may be different alkyls, fluorinated alkyl, phenyl or furyl substituted beta-diketone complex ions and the metal may be Cu, Ni, Co, Mn, Cr, Zn or Fe. The preparation process of the chelate type ionic liquid is simple, quick, and low in energy consumption, does not require any strict conditions and makes product purification easy; and the chelate type ionic liquid has high chemical stability and high thermodynamic stability, and the melting point is easy to regulate. The ionic liquid enriches the ionic liquid range greatly and has high potential use value.
Description
Technical field
The present invention relates to a kind of coordination ability of beta-diketon anionoid that utilizes and prepare the ion liquid novel method of chelating type, through different positively charged ions and different anions and different metal combination, one type of metallic ionic liquid of novel chelating type preparing.
Background technology
Ionic liquid is made up of organic cation and inorganic or organic anion, at room temperature or the salt that is in a liquid state below 100 ℃.Since the nineties in last century, ionic liquid more and more causes scientist's research interest, because it has the character of a series of uniquenesses: low-steam pressure, liquid range is wide, good electric conductivity, and designability etc.Along with the proposition of " Green Chemistry " notion and the growth of global environment pressure, ionic liquid is applied in growing field as a kind of new reaction medium.
Begin from first-generation ionic liquid-chloroaluminate ionic liquid, metal ion liquid is the focus in ionic liquid field always.Metal ion liquid not only comprises the characteristics of all conventional ion liquid and since the adding of metal they also show a lot of interesting property (electrochemical window is wide for magnetic, optical property, catalytic activity etc.).The investigator to chlorine aluminic acid type ionic liquid the application in electrochemistry and chemical reaction carried out broad research; Especially not only make catalyzer but also done reaction medium; But it is very responsive to moisture and moisture, and institute responds and operates all and will in vacuum and inert atmosphere, carry out.What Weltondx seminar utilized imidazoles villaumite and muriate under nitrogen protection, to react to obtain two structural similitudies contains cobalt, nickel ion liquid [Emim]
2[CoCl
4] and [Emim]
2[NiCl
4] (Emim=1-ethyl-3-Methylimidazole), fusing point still is not an ionic liquid at room temperature at 90-100 ℃.(Dalton.Trans.1993.2639) Kolleh and Dronskowski have prepared the iron content ionic liquid, have studied the effect of hydrogen bond for lattice energy, have reported reaction [Bdmim] Cl and FeCl
3, FeCl
2Ratio is that 4:2:1 grinds in the time of 50 ℃, is cooled to room temperature and obtains yellow-green colour solid [Bdmim]
4[Fe
IICl
4] [Fe
IIICl
4]
2(Bdmim=butyl diformazan imidazoles), fusing point is about 38 ℃.(Inorg. Chem. 43 (2004) 2803) Bolkan and Yoke observe and find that [Emim] Cl-CuCl (ratio is between 1:3-2:3) has formed the room-temperature ion liquid system, have discovered that through the spectrum means multiple compound negatively charged ion exists, for example: CuCl
3 2-, Cu
2Cl
3 -, CuCl
4 -, this type ion liquid system is very sensitive to oxygen.(J.Chem.Eng.Data 31 (1986) 194; Inorg.Chem. 25 (1986) 3586) investigator is to [Rmim] Cl (R=methyl, ethyl, normal-butyl) and different metal chlorate (ZnCl
2, SnCl
2, PdCl
2, AuCl
3, NiCl
2, CoCl
2, InCl
3, UCl
4Deng) the metal ion liquid and the application that form carried out broad research, but be solid under the most of room temperature of such ionic liquid, and the chance water decomposition, this impels the investigator to explore the stable metal ion liquid of searching.
On positively charged ion, introduce functional group, the group that particularly has strong coordination ability should obtain stable ionic liquid.There are some investigators on the imidazoles side chain, to introduce coordinating group and prepare positively charged ion metal ion liquid, such as: Shreeve etc. have reported with 1-pyrryl methylene radical-glyoxal ethyline as positively charged ion part and PdCl
2Carry out coordination and obtained the yellow compound that positively charged ion contains Pd, stable in the air, but fusing point is 132 ℃, and fusing point is changed little through regulating simple negatively charged ion.In ion liquid research and design; Change cationic size; Rigidity; Especially symmetry is very big to the influence of fusing point; Generally can obtain ionic liquid at room temperature through introducing asymmetric organic cation; If so coordinating group can be introduced at anionicsite, combining suitable positively charged ion again is the strategy of a design containing metal ionic liquid at room temperature.In order to make ionic liquid have good thermostability and chemical stability, should introduce the strong group of coordination ability, should prepare stable metal ion liquid if can design the chelation group negatively charged ion that contains 2 haptos.Yoshida in 2009 etc. have reported with 4; 4 '-dioctyl phthalate-2; 2 '-dipyridyl is that chelating ligand negatively charged ion and the cationic deep green of asymmetric tetradecyl three n-hexyl phosphines contain the Co ionic liquid at room temperature; But it decomposes about 75 ℃; Possibly be because the instability that the carboxylic acid negative ion decomposition causes; (Inorg.Chem.48 (2009) 9989) prepare one type of stable containing metal ionic liquid at room temperature and remain a significant challenge from present research situation.
Summary of the invention
The purpose of this invention is to provide one type based on chelating coordinate metal ion liquid and preparation method thereof.The metal ion liquid of reporting in paper and the patent before comparing; Such ionic liquid is because the introducing of chelating type anion ligand; Show good chemistry and thermodynamic stability, and, obtain a series of metal ion liquid of different nature through mating with different positively charged ions.
Concrete technical scheme of the present invention is following:
The present invention is a kind of chelating type ionic liquid and preparation purification process thereof, and the step of this method is following:
(1), with beta-diketon (R
5-with mineral alkali neutralization reaction takes place in organic solvent acac); Reaction finishes the back and adds a kind of in divalent metal Lvization Wu ﹑ bromide, vitriol or the nitrate and carry out coordination reaction; Add then and contain in following each general formula a kind of in the cationic chlorine salt ﹑ bromination salt ﹑ sulphur acid salt ﹑ nitrate; Through filtering, revolve dried solvent and obtain thick product;
(2), the thick product that will obtain is dissolved in organic solvent; Add isopyknic water then; Vibrated 3-10 minute; Static layering; Separatory removes water layer, repeats above step 3-5 time, collects rich ionic liquid phase; Utilize Rotary Evaporators to remove organic solvent, products obtained therefrom vacuum-drying promptly obtained the chelating type ionic liquid of purifying in 24 hours.
Chelating type ionic liquid general formula of the present invention is:
Formula I: [AR
1R
2R
3R
4] [M (R
5-acac)
3]
A R wherein
1R
2R
3R
4For quaternary amine or season the phosphine positively charged ion, A is N or P, R
1Be C
1-C
8Aliphatic hydrocarbon, R
2, R
3And R
4Independently take from C
4-C
16Aliphatic hydrocarbon, R
5Be C
1-C
6Aliphatic saturated hydrocarbon, C
1-C
6Fluorine-containing aliphatic saturated hydrocarbon, phenyl, a kind of in the 2-furyl. M is Cu
2+, Ni
2+, Co
2+, Mn
2+, Cr
2+, Zn
2+, Fe
2+In a kind of, [M (R
5-acac)
3The complex anion (same formula I) that]-be chelating type negatively charged ion and metal-complexing form;
General formula II: [R
6-Py] [M (R
5-acac)
3]
R wherein
6Be C
1-C
16Aliphatic hydrocarbon, Py is a pyridine, pyrroles, hexahydropyridine, Pyrrolidine, pyrroline, indoles, carbazole, quinoline, a kind of in the acridine, [M (R
5-acac)
3The complex anion (same formula I) that]-be chelating type negatively charged ion and metal-complexing form;
General formula III: [R
7R
8-Im] [M (R
5-acac)
3]
R wherein
7Be C
1-C
16Aliphatic hydrocarbon, R
8Be C
4-C
16Aliphatic hydrocarbon, Im is an imidazoles, [M (R
5-acac)
3The complex anion (same formula I) that]-be chelating type negatively charged ion and metal-complexing form.
The mineral alkali that the present invention uses is a kind of in the Qing Yangization Na ﹑ Tan Suan Na ﹑ Qing Yangization Jia ﹑ An Shui ﹑ salt of wormwood; Reaction solvent is one or both in acetone, ethanol, benzyl cyanide, ethyl acetate, acetonitrile, phenyl trichloromethane, dimethyl formamide, trichloromethane, the toluene, and the solvent that dissolves thick product is ether or ethyl acetate.
Temperature of reaction of the present invention is 0 ℃-100 ℃, and the reaction times is 0.5-72 hour.
Embodiment
Technical scheme of the present invention is described in further detail as follows:
The new chelating type metal ion liquid of the present invention is represented with formula:
General formula (1): [AR
1R
2R
3R
4] [M (R
5-acac)
3]
AR wherein
1R
2R
3R
4For quaternary amine or season the phosphine positively charged ion, A is N or P, wherein R
1Be C
1-C
8Aliphatic hydrocarbon, R
2, R
3And R
4Independently take from C
4-C
16Aliphatic hydrocarbon.R
5Be C
1-C
6Aliphatic saturated hydrocarbon, C
1-C
6Fluorine-containing aliphatic saturated hydrocarbon, phenyl, a kind of in the 2-furyl.M is Cu
2+, Ni
2+, Co
2+, Mn
2+, Cr
2+, Zn
2+, Fe
2+In a kind of, M (R
5-acac)
3Complex anion for chelating type negatively charged ion and metal-complexing formation.Preferred general formula (1) compound is: R
1Be C
1-C
4Aliphatic hydrocarbon; R
2, R
3And R
4Independently take from C
10-C
16Aliphatic hydrocarbon; R
5Be C
1-C
3Aliphatic saturated hydrocarbon, C
1-C
3Fluorine-containing aliphatic saturated hydrocarbon or phenyl; M is Cu
2+﹑ Ni
2+﹑ Co
2+﹑ Zn
2+In a kind of.
General formula (2): [R
6-Py] [M (R
5-acac)
3]
R wherein
6Be C
1-C
16Aliphatic hydrocarbon, Py is a pyridine, pyrroles, hexahydropyridine, Pyrrolidine, pyrroline, indoles, carbazole, quinoline, a kind of in the acridine, [M (R
5-acac)
3The complex anion (same formula I) that]-be chelating type negatively charged ion and metal-complexing form.Preferred general formula (2) compound is: R
6Be C
8-C
16Aliphatic hydrocarbon, Py is an indoles, pyridine, pyrroles, hexahydropyridine, a kind of in the Pyrrolidine.
General formula (3): [R
7R
8-Im] [M (R
5-acac)
3]
R wherein
7Be C
1-C
16Aliphatic hydrocarbon, R
8Be C
4-C
16Aliphatic hydrocarbon, Im is an imidazoles, [M (R
5-acac)
3The complex anion (same formula I) that]-be chelating type negatively charged ion and metal-complexing form.Preferred general formula (3) compound is: R
7Be C
1-C
6Aliphatic hydrocarbon, R
8Be C
10-C
16Aliphatic hydrocarbon.
A) preparation method of chelating type metal ion liquid crude product is following:
At first with beta-diketon (R
5-acac) with Qing Yangization Na ﹑ Tan Suan Na ﹑ Qing Yangization Jia ﹑ An Shui ﹑ salt of wormwood in a kind of mineral alkali generation neutralization reaction; Reaction solvent can be one or both in acetone, benzyl cyanide, ethyl acetate, acetonitrile, phenyl trichloromethane, dimethyl formamide, trichloromethane, the toluene, and ethyl acetate, acetone, acetonitrile.Preferred mineral alkali comprises: Tan Suan Na ﹑ Qing Yangization Jia ﹑ An Shui ﹑ salt of wormwood; Temperature of reaction is 0 ℃-100 ℃, and preferred temperature of reaction is 10 ℃-90 ℃; Reaction times is 2-48 hour, and the preferred time is 10-40 hour.Reaction finishes the back and adds divalent metal (Cu
2+, Ni
2+, Co
2+, Mn
2+, Cr
2+, Zn
2+, Fe
2+) a kind of in the Lvization Yan ﹑ Bromide carry out coordination reaction; Reaction times is 2-72 hour, and the preferred time is 10-60 hour.Add at last and contain cationic salt in above-mentioned each general formula, be preferably the sulfur-bearing acid group, nitrate radical, bromide anion, the salt of chlorion; Reaction times is 2-72 hour, and the preferred time is 10-60 hour.Filter at last, revolve dried solvent and obtain thick product.
B) purification process of chelating type metal ion liquid crude product is following:
With the thick product that obtains be dissolved in ethers (for example: ether) or lipid (for example: ethyl acetate); Add isopyknic water then; Vibrated 3-10 minute, static layering, the upper strata is rich ionic liquid phase; Lower floor is a water; Separatory removes water layer, repeats above step 3-5 time, collects rich ionic liquid phase; Utilize Rotary Evaporators to remove solvent, products obtained therefrom vacuum-drying promptly obtained the chelating type metal ion liquid of purifying in 24 hours.
With existing metal ion liquid phase ratio, it is simple that this method prepares process, and the time is short, and it is low to consume energy, without any need for exacting terms, and easy purification of products.The most important thing is that because the introducing of chelating type anion ligand, the metal ion liquid that obtains shows 3 clear superiorities: 1) good chemical stability (air-stable, meet water stable); 2) thermodynamic stability good (the decomposition temperature overwhelming majority is more than 250 degree); 3) can obtain room temperature metal ion liquid through regulating asymmetric organic cation.And such ionic liquid is water insoluble, almost with all organic solvent (methyl alcohol, ethanol, acetone, ethyl acetate; Tetrahydrofuran (THF), ether, 1,4-dioxane; Methylene dichloride, trichloromethane, methyl-sulphoxide) miscible, have the potential using value of great chemical reaction.
To more comprehensively describe the present invention through following embodiment again.
Embodiment 1
In 50ml round bottom single port flask, add 0.208g, the hexafluoroacetylacetone of 1mmol, the acetonitrile of 15ml is put into 35 ℃ water-bath, adds ammoniacal liquor again.React and add CoCl after 24 hours
2.4H
2O 0.33mmol carried out 8 hours again, added trimethylammonium n-hexadecyl brometo de amonio 0.33mmol, and reaction was carried out 10 hours again, crossed to filter out inorganic salt (NH
4Br, NH
4Cl), Rotary Evaporators boils off acetonitrile and promptly obtains red liquid, becomes solid after the cooling.
The thick product that obtains is dissolved in the 10mL ethyl acetate; Add isopyknic water then; Vibrated 3 minutes, static layering, the upper strata is rich ionic liquid phase; Lower floor is a water; Separatory removes water layer, repeats above step 3 time, collects rich ionic liquid phase; Utilize Rotary Evaporators to remove solvent, products obtained therefrom vacuum-drying promptly obtained the [(CH of purifying in 24 hours
3)
3C
16H
33N] [Co (CF
3-acac)
3] ionic liquid, whole process yield 65%, the ionic liquid behind the purifying are red, and fusing point is 71 degree, and decomposition temperature is 286 degree.
Embodiment 2
In 50ml round bottom single port flask, add 0.208g, the hexafluoroacetylacetone of 1mmol, the acetonitrile of 15ml is put into 35 ℃ water-bath, adds ammoniacal liquor again.React and add CoCl after 24 hours
2.4H
2O 0.33mmol carried out 8 hours again, added tetrabutylammonium chloride 0.33mmol, and reaction was carried out 10 hours again, crossed and filtered out inorganic salt (NH
4Cl), Rotary Evaporators boils off acetonitrile and promptly obtains red liquid, becomes solid after the cooling.
The thick product that obtains is dissolved in the 10mL ethyl acetate; Add isopyknic water then; Vibrated 3 minutes, static layering, the upper strata is rich ionic liquid phase; Lower floor is a water; Separatory removes water layer, repeats above step 3 time, collects rich ionic liquid phase; Utilize Rotary Evaporators to remove solvent, products obtained therefrom vacuum-drying promptly obtained the [(C of purifying in 24 hours
4H
9)
4N] [Co (CF
3-acac)
3], whole process yield 54%.Ionic liquid behind the purifying is red, and fusing point is 73 degree, and decomposition temperature is 279 degree.
Embodiment 3
In 50ml round bottom single port flask, add 0.208g, the hexafluoroacetylacetone of 1mmol, the acetonitrile of 15ml is put into 35 ℃ water-bath, adds ammoniacal liquor again.React and add CoCl after 24 hours
2.4H
2O 0.33mmol carried out 8 hours again, added triphenyl normal-butyl chlorination phosphine 0.33mmol, and reaction was carried out 10 hours again, crossed to filter out inorganic salt (NH
4Cl), Rotary Evaporators boils off acetonitrile and promptly obtains red liquid, becomes solid after the cooling.
The thick product that obtains is dissolved in the 10mL ethyl acetate; Add isopyknic water then; Vibrated 3 minutes, static layering, the upper strata is rich ionic liquid phase; Lower floor is a water; Separatory removes water layer, repeats above step 3 time, collects rich ionic liquid phase; Utilize Rotary Evaporators to remove solvent, products obtained therefrom vacuum-drying promptly obtained [the Ph of purifying in 24 hours
3C
4H
9P] [Co (CF
3-acac)
3].Whole process yield 81%.Ionic liquid behind the purifying is red, and fusing point is 94 degree, and decomposition temperature is 320 degree.
Embodiment 4
In 50ml round bottom single port flask, add 0.208g, the hexafluoroacetylacetone of 1mmol, the acetonitrile of 15ml is put into 35 ℃ water-bath, adds ammoniacal liquor again, reacts to add CoCl after 24 hours
2.4H
2O 0.33mmol carried out 8 hours again, added the positive decyl imidazoles reaction of 0.33mmol chlorination 1-methyl-3-and carried out 10 hours again, crossed and filtered out inorganic salt (NH
4Cl), Rotary Evaporators boils off acetonitrile and promptly obtains red liquid, is cooled to room temperature and still is liquid.
The thick product that obtains is dissolved in the 10mL ethyl acetate; Add isopyknic water then; Vibrated 3 minutes, static layering, the upper strata is rich ionic liquid phase; Lower floor is a water; Separatory removes water layer, repeats above step 3 time, collects rich ionic liquid phase; Utilize Rotary Evaporators to remove solvent, products obtained therefrom vacuum-drying promptly obtained the [(C of purifying in 24 hours
10Min] [Co (CF
3-acac)
3].Whole process yield 70%, the ionic liquid behind the purifying are red, and fusing point is lower than 25 degree, and decomposition temperature is 279 degree, density 1.39g.cm
-3(273.15K).
Embodiment 5-7
Be similar to embodiment 4, changing hexafluoroacetylacetone is 1-phenyl-4,4,4-three fluoro-1, and the 3-dimethyl diketone can obtain different room temperature metal ion liquid through adding different metallic salt.Reaction result such as following table:
Embodiment 8-10
Be similar to embodiment 4, changing the positive decyl imidazoles of chlorination 1-methyl-3-is chlorination n-tetradecane yl pyridines, can obtain different metal ion liquid through adding different metallic salt.Reaction result such as following table:
Claims (7)
1. chelating type ionic liquid and preparation purification process thereof is characterized in that the step of this method is following:
(1), with beta-diketon (R
5-with mineral alkali neutralization reaction takes place in organic solvent acac); Reaction finishes the back and adds a kind of in divalent metal Lvization Wu ﹑ bromide, vitriol or the nitrate and carry out coordination reaction; Add then and contain in following each general formula a kind of in the cationic chlorine salt ﹑ bromination salt ﹑ sulphur acid salt ﹑ nitrate; Through filtering, revolve dried solvent and obtain thick product;
(2), the thick product that will obtain is dissolved in organic solvent; Add isopyknic water then; Vibrated 3-10 minute; Static layering; Separatory removes water layer, repeats above step 3-5 time, collects rich ionic liquid phase; Utilize Rotary Evaporators to remove organic solvent, products obtained therefrom vacuum-drying promptly obtained the chelating type ionic liquid of purifying in 24 hours.
2. chelating type ionic liquid according to claim 1 and preparation purification process thereof is characterized in that described chelating type ionic liquid general formula is:
Formula I: [AR
1R
2R
3R
4] [M (R
5-acac)
3]
A R wherein
1R
2R
3R
4For quaternary amine or season the phosphine positively charged ion, A is N or P, R
1Be C
1-C
8Aliphatic hydrocarbon, R
2, R
3And R
4Independently take from C
4-C
16Aliphatic hydrocarbon, R
5Be C
1-C
6Aliphatic saturated hydrocarbon, C
1-C
6Fluorine-containing aliphatic saturated hydrocarbon, phenyl, a kind of in the 2-furyl. M is Cu
2+, Ni
2+, Co
2+, Mn
2+, Cr
2+, Zn
2+, Fe
2+In a kind of, [M (R
5-acac)
3The complex anion (same formula I) that]-be chelating type negatively charged ion and metal-complexing form;
General formula II: [R
6-Py] [M (R
5-acac)
3]
R wherein
6Be C
1-C
16Aliphatic hydrocarbon, Py is a pyridine, pyrroles, hexahydropyridine, Pyrrolidine, pyrroline, indoles, carbazole, quinoline, a kind of in the acridine, [M (R
5-acac)
3The complex anion (same formula I) that]-be chelating type negatively charged ion and metal-complexing form;
General formula III: [R
7R
8-Im] [M (R
5-acac)
3]
R wherein
7Be C
1-C
16Aliphatic hydrocarbon, R
8Be C
4-C
16Aliphatic hydrocarbon, Im is an imidazoles, [M (R
5-acac)
3The complex anion (same formula I) that]-be chelating type negatively charged ion and metal-complexing form.
3. chelating type ionic liquid according to claim 1 and preparation purification process thereof is characterized in that the mineral alkali that uses is a kind of in the Qing Yangization Na ﹑ Tan Suan Na ﹑ Qing Yangization Jia ﹑ An Shui ﹑ salt of wormwood.
4. chelating type ionic liquid according to claim 1 and preparation purification process thereof is characterized in that reaction solvent is one or both in acetone, ethanol, benzyl cyanide, ethyl acetate, acetonitrile, phenyl trichloromethane, dimethyl formamide, trichloromethane, the toluene.
5. chelating type ionic liquid according to claim 1 and preparation purification process thereof, the solvent that it is characterized in that dissolving thick product is ether or ethyl acetate.
6. chelating type ionic liquid according to claim 1 and preparation purification process thereof is characterized in that temperature of reaction is 0 ℃-100 ℃.
7. chelating type ionic liquid according to claim 1 and preparation purification process thereof is characterized in that the reaction times is 0.5-72 hour.
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| CN107794536A (en) * | 2017-10-25 | 2018-03-13 | 浙江星丰科技有限公司 | A kind of metal surface treating method of high-efficiency environment friendly |
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| CN103880868B (en) * | 2014-03-31 | 2016-04-27 | 许东东 | A kind of organic copper antibacterial nylon silk, organic copper complex preparation method |
| CN107603588A (en) * | 2017-10-25 | 2018-01-19 | 浙江星丰科技有限公司 | One metal ion species liquid corrosion inhibitor and preparation method thereof |
| CN107794536A (en) * | 2017-10-25 | 2018-03-13 | 浙江星丰科技有限公司 | A kind of metal surface treating method of high-efficiency environment friendly |
| CN107794535A (en) * | 2017-10-25 | 2018-03-13 | 浙江星丰科技有限公司 | One metal ion species liquid rust remover |
| CN109752356A (en) * | 2018-11-27 | 2019-05-14 | 河南师范大学 | A kind of method of quick visualization screening ionic-liquid catalyst |
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| CN110283063B (en) * | 2019-06-11 | 2020-06-16 | 中山华明泰科技股份有限公司 | Preparation method and application of lanthanum acetylacetonate |
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