CN111217755B - Preparation method and application of dialkyl imidazole dicyanoammonium salt - Google Patents
Preparation method and application of dialkyl imidazole dicyanoammonium salt Download PDFInfo
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- CN111217755B CN111217755B CN201811423348.6A CN201811423348A CN111217755B CN 111217755 B CN111217755 B CN 111217755B CN 201811423348 A CN201811423348 A CN 201811423348A CN 111217755 B CN111217755 B CN 111217755B
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- imidazole
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention provides a preparation method of dialkyl imidazole dicyanoammonium salt, which comprises the steps of reacting alkyl imidazole, methanol and dimethyl carbonate for 20-24 hours at the temperature of 110-140 ℃ and the pressure of 0.7-1.5 MPa to obtain dialkyl imidazole bicarbonate reaction liquid; reacting dialkyl imidazole bicarbonate reaction liquid with dicyandiamide metal salt at the temperature of 30-100 ℃ to obtain dialkyl imidazole dicyandiamide salt reaction liquid; and filtering the dialkyl imidazole dicyanamide salt reaction solution, dehydrating under negative pressure, and filtering again to obtain the dialkyl imidazole dicyanamide salt. The invention takes alkyl imidazole, methanol, dimethyl carbonate and dicyandiamide metal salt as raw materials to synthesize a target product through two-step reaction. The method has the advantages of short reaction period, mild reaction conditions in each step, simple post-treatment process, good repeatability and stability, low halogen content, no corrosion to metal electrode materials, suitability for electronic devices and popularization and application.
Description
Technical Field
The invention belongs to the technical field of chemical materials, and relates to a preparation method and application of dialkyl imidazole dicyanoammonium salt.
Background
The ionic liquid is composed of anions and cations, and is in a liquid state at or near room temperature, and is also called as low-temperature molten salt. The ionic liquid has higher melting point, viscosity and strong corrosivity, and the main difference between the ionic liquid and the traditional molten salt is that the melting point of the ionic liquid is lower, so that the ionic liquid can be used for replacing the traditional organic solvent and electrolyte and serving as a novel green medium for a chemical reaction and electrochemical system. And with the deeper exploration and development of the ionic liquid field, the ionic liquid has huge application in solar cells, fuel cells, catalysts and even medical fields.
The dialkylimidazolium dicyanamide salts are low melting compounds, liquid at room temperature, miscible with water and have a low viscosity (for ionic liquids), which effectively avoids the reduction of reaction rate and competitive unimolecular side reactions due to handling difficulties during filtration, decantation and dissolution due to excessive viscosity. The potential market for relatively low viscosity ionic liquids is enormous.
The dialkyl imidazole dicyanamide salt on the market is synthesized by reacting halogenated dialkyl imidazole salt with dicyanamide metal salt, a large amount of halogen ions in raw materials are remained in ionic liquid, and a metal electrode material is corroded under the condition of electrifying, so that the dialkyl imidazole dicyanamide salt is not suitable for electronic devices. The problem to be solved at present is to find a preparation method of dialkyl imidazole dicyanamide salt, wherein the obtained product has extremely low content of halogen ions.
Disclosure of Invention
The invention aims to provide a preparation method and application of dialkyl imidazole dicyan ammonium salt with low content of halogen ions in an obtained product.
In order to solve the technical problems, the invention adopts the following technical scheme:
an object of the present invention is to provide a method for preparing dialkyl imidazole dicyanoammonium salt, comprising the steps of:
(1) Reacting alkyl imidazole, methanol and dimethyl carbonate at the temperature of between 110 and 140 ℃ and under the pressure of between 0.7 and 1.5MPa for 20 to 24 hours to obtain dialkyl imidazole bicarbonate reaction liquid;
(2) Reacting the dialkyl imidazole bicarbonate reaction solution obtained in the step (1) with dicyandiamide metal salt at the temperature of between 30 and 100 ℃ to obtain dialkyl imidazole dicyandiamide salt reaction solution;
(3) And (3) filtering the dialkyl imidazole dicyanamide salt reaction solution obtained in the step (2), dehydrating under negative pressure, and filtering again to obtain the dialkyl imidazole dicyanamide salt.
Preferably, the alkyl imidazole in step (1) is any one or more selected from methyl imidazole, ethyl imidazole, propyl imidazole and butyl imidazole.
Preferably, the molar ratio of the alkyl imidazole, the methanol and the dimethyl carbonate in the step (1) is 1:5 to 6:1 to 1.5, more preferably 1.5 to 6.
Preferably, the reaction in the step (1) is carried out in the presence of water, and the feeding mass of the water is 30-60% of the feeding mass of the dimethyl carbonate.
More preferably, the feeding mass of the water is 40-50% of the feeding mass of the dimethyl carbonate.
Preferably, the reaction temperature in the step (1) is 120-130 ℃, and the reaction pressure is 0.8-1.0 MPa.
Preferably, the dicyanamide metal salt in the step (2) is any one or more selected from lithium dicyanamide, sodium dicyanamide and potassium dicyanamide.
Preferably, the feeding molar ratio of the dicyandiamide metal salt to the dialkyl imidazole bicarbonate is 1-2:1, and more preferably 1.4-1.7.
Preferably, the reaction temperature in step (2) is 80 to 100 ℃.
Preferably, the specific implementation manner of step (2) is: adding the dicyandiamide metal salt into water, heating to 50-70 ℃ to dissolve the dicyandiamide metal salt, then adding the dialkyl imidazole bicarbonate reaction solution, and reacting for 2-4 h at 30-100 ℃ to obtain the dialkyl imidazole dicyandiamide salt reaction solution.
The invention also aims to provide the dialkyl imidazole dicyanamide salt prepared by the preparation method, and the structural general formula of the dialkyl imidazole dicyanamide salt is shown in the specification
Wherein R is 1 Represents an alkyl group having 1 to 4 carbon atoms.
The third purpose of the invention is to provide the application of the dialkyl imidazole dicyan ammonium salt in the electrolyte.
Preferably, the electrolyte comprises an electrolyte salt and a solvent, wherein the electrolyte salt is the dialkyl imidazole dicyan ammonium salt, and the solvent is any one or combination of ethylene glycol, sulfolane, gamma-butyrolactone and propylene carbonate.
Due to the implementation of the technical scheme, compared with the prior art, the invention has the following advantages:
the invention takes alkyl imidazole, methanol, dimethyl carbonate and dicyandiamide metal salt as raw materials to synthesize a target product through two-step reaction. The method has the advantages of short reaction period, mild reaction conditions in each step, simple post-treatment process, good repeatability and stability, low halogen content, no corrosion to metal electrode materials, suitability for electronic devices and popularization and application.
Detailed Description
The following examples are intended to illustrate several embodiments of the present invention, but are not intended to limit the invention to these embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
The first embodiment is as follows: 1-ethyl-3-methylimidazolium dicyanamide salt
(1) 800g of ethylimidazole, 1125g of dimethyl carbonate, 1600g of methanol and 500g of water were put into a pressure vessel. The heating temperature is set to be 130 ℃, the reaction pressure is between 0.8 and 0.9MPA, and the reaction time is 24 hours, so that the 1-ethyl-3-methylimidazole bicarbonate aqueous solution is obtained (the cation content of the 1-ethyl-3-methylimidazole is measured to be 44%).
(2) And adding 250g of deionized water into 100g of dicyanoammonium sodium, heating to 60 ℃, slowly dripping 283.4g of 1-ethyl-3-methylimidazole bicarbonate aqueous solution into the mixture until the dicyanoammonium sodium is completely dissolved, heating to 90 ℃ after dripping, and keeping the temperature for 3 hours.
(3) Cooling the reaction solution to room temperature, performing suction filtration to obtain 144g of wet filter residue (sodium carbonate and sodium bicarbonate), and performing negative pressure dehydration on the filtrate. And (3) performing secondary filtration after dehydration to obtain 40g of wet filter residue (sodium carbonate and sodium bicarbonate), wherein the filtrate is 177.3g of 1-ethyl-3-methylimidazolium dicyanamide salt.
The purity of the product is 99.5 percent and the yield reaches 86 percent by liquid chromatography detection.
Ion chromatography detection: the chloride ion content is less than 10ppm.
Detection by ICP: fe ion: 0.8ppm, pb ion: 0.4ppm.
Preparing electrolyte, namely preparing the 1-ethyl-3-methylimidazole dicyanamide salt into 25 mass percent of butyrolactone/ethylene glycol (mass ratio of butyrolactone to ethylene glycol is 9:1) system electrolyte, and testing that the conductivity of the electrolyte at 30 ℃ is 27mS/cm.
Example two: 1, 3-dimethyl imidazole dicyanamide salt
(1) 684g of 1-methylimidazole, 1125g of dimethyl carbonate, 1600g of methanol and 500g of water were put into the autoclave. The heating temperature is set at 130 ℃, the reaction pressure is between 0.8 and 0.9MPA, and the reaction time is 24 hours, so that 1.3-dimethyl imidazole bicarbonate aqueous solution is obtained (the content of 1.3-dimethyl imidazole cation is measured to be 41.15 percent).
(2) And adding 250g of deionized water into 100g of dicyanoammonium sodium, heating to 60 ℃, slowly dripping 264.8g of 1.3-dimethyl imidazole bicarbonate aqueous solution into the mixture until the dicyanoammonium sodium is completely dissolved, heating to 90 ℃ after dripping, and keeping the temperature for 3 hours.
(3) Cooling the reaction solution to room temperature, carrying out suction filtration to obtain 152g of wet filter residue (sodium carbonate and sodium bicarbonate), and carrying out negative pressure dehydration on the filtrate. And after dehydration, carrying out secondary filtration to obtain 38.6g of wet filter residue (sodium carbonate and sodium bicarbonate), wherein the filtrate is 143.8g of 1.3-dimethyl imidazole dicyanamide salt.
The purity of the product is 99.6 percent and the yield reaches 88.2 percent by liquid chromatography detection.
Ion chromatography detection: the chloride ion content is less than 10ppm.
Detection by ICP: fe ion: 0.5ppm, pb ion: 0.6ppm.
Preparing electrolyte, namely preparing the 1, 3-dimethyl imidazole dicyanamide salt into a butyrolactone/ethylene glycol (mass ratio of butyrolactone to ethylene glycol is 9:1) system electrolyte with the content of 25% by mass, and testing that the conductivity of the electrolyte at 30 ℃ is 25.4mS/cm.
Example three: 1-n-butyl-3-methylimidazolium dicyanoammonium salt
(1) The autoclave was charged with 1032.8g of 1-n-butylimidazole, 1125g of dimethyl carbonate, 1600g of methanol and 500g of water. Setting the heating temperature at 130 ℃, the reaction pressure between 0.8 and 0.9MPA and the reaction time at 24 hours to obtain 1-n-butyl-3-methylimidazole bicarbonate aqueous solution (the measured cation content of 1-n-butyl-3-methylimidazole is 40.82%)
(2) Adding 250g of deionized water into 100g of potassium dicyanamide, heating to 60 ℃, slowly dripping 314.7g of 1-n-butyl-3-methylimidazole bicarbonate aqueous solution into the mixture after sodium dicyanamide is completely dissolved, heating to 90 ℃ after dripping is finished, and keeping the temperature for 3 hours.
(3) Cooling the reaction solution to room temperature, performing suction filtration to obtain 143.5g of wet filter residue (potassium carbonate and potassium bicarbonate), and performing negative pressure dehydration on the filtrate. After the dehydration, the mixture was filtered twice to obtain 56.8g of wet residue (potassium carbonate and potassium bicarbonate), and the filtrate was 158.7g of 1-n-butyl-3-methylimidazolium dicyanamide salt
The purity of the product is 99.2 percent and the yield reaches 83.1 percent by liquid chromatography detection.
Ion chromatography detection: chloride ion content < 10ppm
Detection by ICP: fe ion: 0.7ppm, pb ion: 0.1ppm of
Preparing electrolyte, namely preparing the 1-n-butyl-3-methylimidazole dicyanoammonium salt into a butyrolactone/ethylene glycol (mass ratio of butyrolactone to ethylene glycol is 9:1) system electrolyte with the content of 25% by mass, and testing that the conductivity of the electrolyte is 23.8mS/cm at the temperature of 30 ℃.
The present invention includes but is not limited to the above embodiments, and those skilled in the art can convert more embodiments within the claims of the present invention.
Claims (2)
1. A preparation method of dialkyl imidazole dicyan ammonium salt is characterized in that: the method comprises the following steps:
(1) Reacting alkyl imidazole, methanol and dimethyl carbonate for 20 to 24 hours at the temperature of between 110 and 140 ℃ and under the pressure of between 0.7 and 1.5MPa to obtain dialkyl imidazole bicarbonate reaction liquid;
(2) Reacting the dialkyl imidazole bicarbonate reaction solution obtained in the step (1) with dicyandiamide metal salt at the temperature of between 30 and 100 ℃ to obtain dialkyl imidazole dicyandiamide salt reaction solution;
(3) Filtering the dialkyl imidazole dicyanamide salt reaction solution obtained in the step (2), dehydrating under negative pressure, and filtering again to obtain the dialkyl imidazole dicyanamide salt;
the molar ratio of the alkyl imidazole, the methanol and the dimethyl carbonate in the step (1) is 1:5 to 6:1 to 1.5;
the alkyl imidazole in the step (1) is any one or more selected from methyl imidazole, ethyl imidazole, propyl imidazole and butyl imidazole;
the reaction in the step (1) is carried out in the presence of water, and the feeding mass of the water is 30-60 percent of that of the dimethyl carbonate
The dicyandiamide metal salt in the step (2) is any one or more selected from lithium dicyandiamide, sodium dicyandiamide and potassium dicyandiamide;
the specific implementation mode of the step (2) is as follows: adding the dicyandiamide metal salt into water, heating to 50-70 ℃ to dissolve the dicyandiamide metal salt, then adding the dialkyl imidazole bicarbonate reaction liquid, and reacting for 2-4 h at 30-100 ℃ to obtain the dialkyl imidazole dicyandiamide salt reaction liquid
The general structural formula of the dialkyl imidazole dicyanamide salt is
Wherein R1 represents an alkyl group having 1 to 4 carbon atoms.
2. The method for preparing a dialkyl imidazole dicyanoammonium salt according to claim 1, wherein: the feeding molar ratio of the dicyandiamide metal salt to the dialkyl imidazole bicarbonate is 1-2:1.
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| CN114591245B (en) * | 2022-03-17 | 2024-04-05 | 浙江肯特催化材料科技有限公司 | Method for preparing 1, 3-dialkyl imidazole ionic liquid |
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Non-Patent Citations (4)
| Title |
|---|
| Evaluating Ionic Liquids as Hypergolic Fuels: Exploring Reactivity from Molecular Structure;Parker D. McCrary等;《Energy Fuels》;20140321;第28卷;3460-3473 * |
| Ionic Liquids Based on Dicyanamide Anion: Influence of Structural Variations in Cationic Structures on Ionic Conductivity;Yukihiro Yoshida等;《J. Phys. Chem. B》;20070118;第111卷;4742-4749 * |
| Peralkylated imidazolium carbonate ionic liquids: synthesis using dimethyl carbonate, reactivity and structure;C. Maton等;《New J. Chem.》;20141016;第39卷;461-468 * |
| Yukihiro Yoshida等.Ionic Liquids Based on Dicyanamide Anion: Influence of Structural Variations in Cationic Structures on Ionic Conductivity.《J. Phys. Chem. B》.2007,第111卷8-10. * |
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