CN110878053A - Preparation method of dialkyl imidazole bis (trifluoromethyl) sulfonyl imide salt - Google Patents
Preparation method of dialkyl imidazole bis (trifluoromethyl) sulfonyl imide salt Download PDFInfo
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- 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
- C07D233/58—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 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
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- H—ELECTRICITY
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Abstract
The invention discloses a preparation method of dialkyl imidazole bis (trifluoromethyl) sulfonyl imide salt, which comprises the following steps: firstly, in an organic solvent, reacting and layering alkyl imidazole and sulfate to obtain a dialkyl imidazole sulfate crude product; washing, distilling under reduced pressure and drying the crude product of the dialkyl imidazole sulfate to obtain the dialkyl imidazole sulfate; thirdly, reacting dialkyl imidazole sulfate with bis (trifluoromethyl) sulfonyl imide metal salt, and layering to obtain a crude dialkyl imidazole bis (trifluoromethyl) sulfonyl imide salt product; fourthly, washing, decompressing and distilling the crude product of the dialkyl imidazole bistrifluoromethylsulfonyl imide salt, and drying to obtain a target product of the dialkyl imidazole bistrifluoromethylsulfonyl imide salt; the invention has the advantages that: the reaction condition is mild, the operation steps are simple, and the prepared product has high yield, high purity and low content of halogen ions, and is suitable for popularization and application.
Description
Technical Field
The invention relates to the technical field of preparation of additives in lithium ion battery electrolyte, in particular to a preparation method of dialkyl imidazole bis (trifluoromethyl) sulfonyl imide.
Background
The ionic liquid is completely composed of anions and cations, is in a liquid state at room temperature or close to room temperature, and is called as low-temperature molten salt. The ionic liquid has the advantages of low vapor pressure, no flammability, large heat capacity and the like, and shows good performance in application research for eliminating the safety defect of the lithium ion battery. The application of the ionic liquid in the lithium ion battery electrolyte hopefully and thoroughly solves the safety problem of the lithium ion battery under high energy density.
The imidazole ionic liquid has low viscosity and high conductivity, and the conductivity of the imidazole ionic liquid can reach 10 at most-2S/cm, and is therefore widely used. The ionic liquid of bis (trifluoromethyl) sulfonyl imide has the advantages of low viscosity, low melting point, high conductivity and the like because the strong delocalization effect of the fluorine substituent on negative charges weakens the hydrogen bond effect of the bis (trifluoromethyl) sulfonyl imide, so the bis (trifluoromethyl) sulfonyl imide becomes an anion which is widely researched. The ionic liquid which is formed by combining imidazole as a cation and bis (trifluoromethyl) sulfimide as an anion integrates the advantages of the imidazole and the bis (trifluoromethyl) sulfimide and has better application prospect in lithium ion batteries.
The traditional dialkyl imidazole bis (trifluoromethyl) sulfonyl imide salt synthesis method mainly comprises the following two methods.
Firstly, preparing dialkyl imidazole halide salt, wherein some dialkyl imidazole halide salt needs to be reacted under high pressure, such as 1-ethyl-3-methyl imidazole chloride salt; then carrying out salt exchange reaction with bis (trifluoromethyl) sulfonyl imide metal salt to obtain the product. The disadvantages of this method are: a large amount of halogen ions in the raw materials are remained in the ionic liquid, and the metal electrode material is corroded under the condition of electrifying, so that the method is not suitable for being used in electronic devices.
Secondly, preparing dialkyl imidazole bicarbonate through carbonate alkylation reaction, and then carrying out salt exchange reaction with bis (trifluoromethyl) sulfonyl imide metal salt to obtain the product. The disadvantages of this method are: although the introduction of halogen ions can be avoided, the preparation of dialkyl imidazole bicarbonates involves high pressures and complicated work-up and has limitations on carbonate alkylation structure.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: the preparation method of the dialkyl imidazole bis (trifluoromethyl) sulfonyl imide salt is mild in reaction conditions, simple in operation steps, high in yield of the prepared product, high in purity and low in content of halogen ions.
In order to solve the problems, the invention adopts the technical scheme that: a preparation method of dialkyl imidazole bis (trifluoromethyl) sulfonyl imide salt comprises the following steps:
a preparation method of dialkyl imidazole bis (trifluoromethyl) sulfonyl imide salt comprises the following steps:
firstly, in an organic solvent, reacting and layering alkyl imidazole and sulfate to obtain a dialkyl imidazole sulfate crude product; the alkyl imidazole and the sulfate ester are soluble in the organic solvent, and the dialkyl imidazole sulfate ester is not soluble in the organic solvent;
washing, distilling under reduced pressure and drying the crude product of the dialkyl imidazole sulfate to obtain the dialkyl imidazole sulfate;
thirdly, reacting dialkyl imidazole sulfate with bis (trifluoromethyl) sulfonyl imide metal salt in water, and layering to obtain a crude product of the dialkyl imidazole bis (trifluoromethyl) sulfonyl imide salt;
fourthly, washing, decompressing and distilling the crude product of the dialkyl imidazole bistrifluoromethylsulfonyl imide salt, and drying to obtain a target product of the dialkyl imidazole bistrifluoromethylsulfonyl imide salt; the general structural formula of the dialkyl imidazole bis (trifluoromethyl) sulfonyl imide salt is as follows:
wherein R1 represents an alkyl group having 1 to 8 carbon atoms, and R2 represents an alkyl group having 1 to 2 carbon atoms.
Further, in the preparation method of the dialkyl imidazole bis-trifluoromethyl sulfonyl imide salt, in the first step, the alkyl imidazole is selected from any one or more of N-methyl imidazole, N-ethyl imidazole, N-propyl imidazole, N-butyl imidazole, N-pentyl imidazole, N-hexyl imidazole, N-heptyl imidazole and N-octyl imidazole.
Further, in the preparation method of the dialkyl imidazole bis-trifluoromethyl sulfimide salt, in the step one, the sulfuric ester is selected from any one or more of dimethyl sulfate and diethyl sulfate.
Further, in the preparation method of the dialkyl imidazole bis (trifluoromethyl) sulfonyl imide salt, in the first step, the feeding molar ratio of the alkyl imidazole to the sulfuric ester is 1: 1 to 1.5.
Further, in the preparation method of the dialkyl imidazole bis (trifluoromethyl) sulfonyl imide salt, the reaction in the first step is performed in a nitrogen atmosphere.
Further, in the preparation method of the dialkyl imidazole bis (trifluoromethyl) sulfonyl imide salt, in the first step, toluene is used as the organic solvent, and the feeding mass of the toluene is 100-500% of the total feeding mass of the alkyl imidazole and the sulfuric ester.
Further, in the third step, the bis-trifluoromethyl sulfonyl imide metal salt is selected from any one or more of lithium bis-trifluoromethyl sulfonyl imide, sodium bis-trifluoromethyl sulfonyl imide and potassium bis-trifluoromethyl sulfonyl imide; the feeding molar ratio of the bis (trifluoromethyl) sulfonyl imide metal salt to the dialkyl imidazole sulfate is 1: 0.9-1.3.
Further, in the preparation method of the dialkyl imidazole bis (trifluoromethyl) sulfonyl imide salt, in the step three, the dialkyl imidazole sulfate and the bis (trifluoromethyl) sulfonyl imide metal salt react in a water phase at 30-80 ℃, that is, the solvent is water. The feeding amount of water is 200-500% of the mass of dialkyl imidazole sulfate, and the dialkyl imidazole bis-trifluoromethyl sulfimide salt crude product is obtained after the reaction is finished and the standing is carried out for 1-3 h for layering.
Further, in the second step, the crude dialkyl imidazole sulfate is washed 2-5 times with an organic solvent, the organic solvent is the same as the organic solvent in the first step, and then the crude dialkyl imidazole sulfate is subjected to reduced pressure distillation on a rotary evaporator for 0.5-3 h, the temperature is kept at 30-80 ℃, and finally the crude dialkyl imidazole sulfate is dried in a vacuum drying oven for 12-36 h, and the drying temperature is kept at 40-100 ℃ to obtain the dialkyl imidazole sulfate.
Further, in the fourth step, the crude product of the dialkyl imidazole bistrifluoromethylsulfonyl imide salt is washed with pure water for 2-5 times, and is subjected to reduced pressure distillation on a rotary evaporator for 0.5-3 hours, the temperature is kept at 60-120 ℃, and finally the crude product is dried in a vacuum drying oven for 12-36 hours, and the drying temperature is kept at 80-150 ℃, so that the target product of the dialkyl imidazole bistrifluoromethylsulfonyl imide salt is obtained.
The invention has the advantages that: the reaction condition is mild, the operation steps are simple, and the prepared product has high yield, high purity and low content of halogen ions, and is suitable for popularization and application.
Detailed Description
The present invention will be described in further detail with reference to preferred embodiments.
The first embodiment is as follows: preparing the target product 1-ethyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt.
Firstly, 200g of diethyl sulfate is dropwise added into a toluene solution of 1-methylimidazole (118 g of 1-methylimidazole and 400g of toluene), the mixture is cooled in an ice bath and is operated under a nitrogen atmosphere, the reaction temperature is guaranteed to be between 20 and 30 ℃, the solution is changed from clear to turbid by ionic liquid formed by reaction, and after the dropwise addition is finished, the mixture is stirred at room temperature for 2 hours and then stands for layering, so that 309g of crude 1-ethyl-3-methylimidazole ethyl sulfate is obtained.
And secondly, washing the ethyl sulfate with toluene for three times to obtain 289g of relatively pure 1-ethyl-3-methylimidazole ethyl sulfate, distilling the ethyl sulfate on a rotary evaporator under reduced pressure for 1h, keeping the temperature at 60 ℃, removing residual toluene, and finally drying the ethyl sulfate in a vacuum drying oven at 80 ℃ for 24h to obtain 280g of finished 1-ethyl-3-methylimidazole ethyl sulfate with the detection purity of 99.9%.
And thirdly, putting 200g of 1-ethyl-3-methylimidazole ethyl sulfate, 243g of lithium bis (trifluoromethyl) sulfonyl imide and 500g of pure water into a reaction kettle, heating to 60 ℃, stirring for reacting for 2 hours, standing for phase separation to obtain 335g of 1-ethyl-3-methylimidazole bis (trifluoromethyl) sulfonyl imide crude product.
Washing the crude product of the 1-ethyl-3-methylimidazole bistrifluoromethylsulfonyl imide three times by pure water to obtain 312g of relatively pure 1-ethyl-3-methylimidazole bistrifluoromethylsulfonyl imide, distilling the crude product on a rotary evaporator under reduced pressure for 2 hours, keeping the temperature at 80 ℃, removing most of water, and finally drying the crude product in a vacuum drying oven at the temperature of 110 ℃ for 12 hours to obtain 301g of the target product of the 1-ethyl-3-methylimidazole bistrifluoromethylsulfonyl imide.
The purity of the product is 99.6 percent through liquid chromatography detection, and the yield reaches 90.6 percent; ion chromatography detection: the content of halogen ions is less than 1 ppm; detection by ICP: fe ion is less than 1ppm, Pb ion is less than 1 ppm.
Example two: preparing the target product 1, 3-diethyl imidazole bis (trifluoromethyl) sulfonyl imide salt.
Firstly, 200g of diethyl sulfate is dropwise added into a toluene solution of 1-ethylimidazole (138 g of 1-ethylimidazole and 400g of toluene), the mixture is cooled in an ice bath and is operated under a nitrogen atmosphere, the reaction temperature is guaranteed to be between 20 ℃ and 30 ℃, the solution is changed from clear to turbid by ionic liquid formed by reaction, and after the dropwise addition is finished, the mixture is stirred for 2 hours at room temperature and then stands for layering, so that 318g of crude 1, 3-diethylimidazole ethyl sulfate is obtained.
And secondly, washing the mixture for three times by using toluene to obtain 303g of pure 1.3-diethyl imidazole ethyl sulfate, distilling the mixture on a rotary evaporator under reduced pressure for 1h, keeping the temperature at 60 ℃, removing residual toluene, and finally drying the mixture in a vacuum drying oven at 80 ℃ for 24h to obtain 291g of finished 1.3-diethyl imidazole ethyl sulfate with the detection purity of 99.9%.
And thirdly, putting 200g of 1.3-diethyl imidazole ethyl sulfate, 230g of lithium bis (trifluoromethyl) sulfonyl imide and 500g of pure water into a reaction kettle, heating to 60 ℃, stirring for reaction for 2 hours, standing for phase separation to obtain 323g of 1.3-diethyl imidazole bis (trifluoromethyl) sulfonyl imide crude product.
And fourthly, washing the mixture for three times by pure water to obtain 307g of relatively pure 1, 3-diethylimidazole bistrifluoromethylsulfonyl imide, distilling the mixture on a rotary evaporator under reduced pressure for 2h, keeping the temperature at 80 ℃, removing most of water, and finally drying the mixture in a vacuum drying oven at 110 ℃ for 12h to obtain 291g of the target product 1, 3-diethylimidazole bistrifluoromethylsulfonyl imide finished product.
The purity of the product is 99.8 percent and the yield reaches 89.5 percent through liquid chromatography detection; ion chromatography detection: the content of halogen ions is less than 1 ppm; detection by ICP: fe ion is less than 1ppm, Pb ion is less than 1 ppm.
Example three: preparing 1-propyl-3-ethylimidazole bistrifluoromethylsulfonyl imide.
Firstly, 200g of diethyl sulfate is dropwise added into a toluene solution of 1-propylimidazole (159 g of 1-propylimidazole and 400g of toluene), the mixture is cooled in an ice bath and is operated under nitrogen atmosphere, the reaction temperature is guaranteed to be between 20 and 30 ℃, the solution is changed from clear to turbid by ionic liquid formed by reaction, and after the dropwise addition is finished, the mixture is stirred at room temperature for 2 hours and then stands for layering, so that 332g of a crude product of 1-propyl-3-ethylimidazole ethyl sulfate is obtained.
Secondly, washing the mixture for three times by using toluene to obtain 317g of relatively pure 1-propyl-3-ethylimidazole ethyl sulfate, distilling the mixture on a rotary evaporator under reduced pressure for 1h, keeping the temperature at 60 ℃, removing residual toluene, and finally drying the mixture in a vacuum drying oven at 80 ℃ for 24h to obtain 303g of 1-propyl-3-ethylimidazole ethyl sulfate finished product (the detected purity is 99.9%).
And thirdly, putting 200g of 1-propyl-3-ethylimidazole ethyl sulfate, 232g of bis (trifluoromethyl) sulfonyl imide sodium and 500g of pure water into a reaction kettle, heating to 60 ℃, stirring for reaction for 2 hours, standing for phase separation to obtain 312g of 1-propyl-3-ethylimidazole bis (trifluoromethyl) sulfonyl imide crude product.
And fourthly, washing the mixture for three times by pure water to obtain 298g of relatively pure 1-propyl-3-ethylimidazole bistrifluoromethylsulfonyl imide, distilling the mixture on a rotary evaporator under reduced pressure for 2h, keeping the temperature at 80 ℃, removing most of water, and finally drying the mixture in a vacuum drying oven at 110 ℃ for 12h to obtain 279g of a target product 1-propyl-3-ethylimidazole bistrifluoromethylsulfonyl imide finished product.
The purity of the product is 99.5 percent through liquid chromatography detection, and the yield reaches 88.3 percent; ion chromatography detection: the content of halogen ions is less than 1 ppm; detection by ICP: fe ion is less than 1ppm, Pb ion is less than 1 ppm.
Example four: preparation of 1-butyl-3-ethylimidazole bistrifluoromethylsulfonyl imide.
Firstly, 200g of diethyl sulfate is dropwise added into a toluene solution of 1-butylimidazole (180 g of 1-propylimidazole and 400g of toluene), the mixture is cooled in an ice bath and is operated under nitrogen atmosphere, the reaction temperature is guaranteed to be between 20 and 30 ℃, the solution is changed from clear to turbid by ionic liquid formed by reaction, and after the dropwise addition is finished, the mixture is stirred at room temperature for 2 hours and then stands for layering, so 346g of crude 1-butyl-3-ethylimidazole ethyl sulfate is obtained.
And secondly, washing the mixture for three times by using toluene to obtain 321g of relatively pure 1-butyl-3-ethylimidazole ethyl sulfate, distilling the mixture on a rotary evaporator under reduced pressure for 1h, keeping the temperature at 60 ℃, removing residual toluene, and finally drying the mixture in a vacuum drying oven at 80 ℃ for 24h to obtain 306g of finished 1-butyl-3-ethylimidazole ethyl sulfate product with the purity of 99.7 percent.
Thirdly, 200g of 1-butyl-3-ethylimidazole ethyl sulfate, 208g of lithium bis (trifluoromethyl) sulfonyl imide and 500g of pure water are put into a reaction kettle, the temperature is raised to 60 ℃, the mixture is stirred for reaction for 2 hours, the mixture is kept stand and phase separation is carried out, 326g of 1-butyl-3-ethylimidazole bis (trifluoromethyl) sulfonyl imide crude product is obtained,
and fourthly, washing the mixture for three times by pure water to obtain 278g of relatively pure 1-butyl-3-ethylimidazole bistrifluoromethylsulfonyl imide, distilling the mixture on a rotary evaporator under reduced pressure for 2h, keeping the temperature at 80 ℃, removing most of water, and finally drying the mixture in a vacuum drying oven at 110 ℃ for 12h to obtain 279g of a target product 1-butyl-3-ethylimidazole bistrifluoromethylsulfonyl imide finished product.
The purity of the product is 99.5 percent and the yield reaches 89.1 percent through liquid chromatography detection; ion chromatography detection: the content of halogen ions is less than 1 ppm; detection by ICP: fe ion is less than 1ppm, Pb ion is less than 1 ppm.
Example five: preparing the target product 1, 3-dimethyl imidazole bis (trifluoromethyl) sulfonyl imide salt.
Firstly, 200g of dimethyl sulfate is dropwise added into a toluene solution of 1-methylimidazole (130 g of 1-methylimidazole and 400g of toluene), the mixture is cooled in an ice bath, the reaction temperature is guaranteed to be between 20 and 30 ℃ under the condition of nitrogen atmosphere, the solution is changed from clear to turbid by ionic liquid formed by reaction, and after the dropwise addition is finished, the mixture is stirred at room temperature for 2 hours and then stands for layering, so that 334g of a crude product of 1, 3-dimethyl imidazole methyl sulfate is obtained.
And secondly, washing the raw materials with toluene for three times to obtain 312g of relatively pure 1, 3-dimethyl imidazole methyl sulfate, distilling the raw materials on a rotary evaporator under reduced pressure for 1 hour, keeping the temperature at 60 ℃, removing residual toluene, and finally drying the raw materials in a vacuum drying oven at 80 ℃ for 24 hours to obtain 303g of 1-ethyl-3-methyl-imidazole methyl sulfate finished product with the purity of 99.9 percent.
And thirdly, putting 200g of 1, 3-dimethyl imidazole methyl sulfate, 280g of lithium bis (trifluoromethyl) sulfonyl imide and 500g of pure water into a reaction kettle, heating to 60 ℃, stirring for reaction for 2 hours, standing for phase separation to obtain 365g of 1, 3-dimethyl imidazole bis (trifluoromethyl) sulfonyl imide crude product.
And fourthly, washing the mixture for three times by pure water to obtain 345g of pure 1, 3-dimethyl imidazole bistrifluoromethyl sulfimide, distilling the mixture on a rotary evaporator under reduced pressure for 2h, keeping the temperature at 80 ℃, removing most of water, and finally drying the mixture in a vacuum drying oven at 110 ℃ for 12h to obtain 327g of 1, 3-dimethyl imidazole bistrifluoromethyl sulfimide finished products.
The purity of the product is 99.72 percent by liquid chromatography detection, and the yield reaches 90.2 percent; ion chromatography detection: the content of halogen ions is less than 1 ppm; detection by ICP: fe ion is less than 1ppm, Pb ion is less than 1 ppm.
Two comparative examples are given below.
Comparative example one: preparation of 1-ethyl-3-methylimidazolium bistrifluoromethylsulfonyl imide salt.
Firstly, 800g of ethylimidazole, 1125g of dimethyl carbonate, 1600g of methanol and 500g of water are put into a pressure kettle. Setting the heating temperature at 130 ℃, the reaction pressure at 0.8-0.9 MPA, and the reaction time at 24 hours to obtain 1-ethyl-3-methylimidazole bicarbonate aqueous solution, and measuring the content of 1-ethyl-3-methylimidazole cations to be 44%.
And secondly, dissolving 200g of lithium bis (trifluoromethyl) sulfonyl imide in 200g of pure water, heating to 60 ℃, beginning to dropwise add 235g of 1-ethyl-3-methylimidazole hydrogen carbonate aqueous solution, ending dropwise addition, heating to 80 ℃, and keeping the temperature for 2 hours.
And thirdly, cooling the reaction liquid to room temperature, filtering to obtain 54g of wet filter residue (lithium carbonate and lithium bicarbonate), and standing and layering the filtrate to obtain 286g of crude 1-ethyl-3-methylimidazole bis (trifluoromethyl) sulfonyl imide salt.
And fourthly, washing the mixture for three times by pure water to obtain 243g of relatively pure 1-ethyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt, distilling the mixture on a rotary evaporator under reduced pressure for 2h, keeping the temperature at 80 ℃, removing most of water, cooling and filtering to obtain 6g of wet filter residue, finally drying the wet filter residue in a vacuum drying oven at the temperature of 110 ℃ for 12h, wherein the water content is lower than 500ppm, and cooling and filtering to obtain 203g of finished 1-ethyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt.
The purity of the product is 97.62 percent and the yield is 73.55 percent by liquid chromatography detection; ion chromatography detection: halogen ion < 1 ppm; detection by ICP: fe ion is less than 1ppm, Pb ion is less than 1 ppm.
Comparative example two: preparation of 1-ethyl-3-methylimidazolium bistrifluoromethylsulfonyl imide salt.
Firstly, 200g of methylimidazole and 250g of bromoethane are placed in a three-neck flask and cooled and refluxed for reaction for 2 hours at room temperature. And (3) carrying out vacuum filtration on the product, putting the obtained white crystal into 500ml of acetonitrile and ethyl acetate, heating until the crystal is molten, cooling to room temperature to separate out the crystal, carrying out vacuum filtration to obtain 396g of solid, transferring the solid to a vacuum drying oven, and drying for 12h to obtain 391g of 1-ethyl-3-methylimidazole bromine salt, wherein the purity is detected to be 99.76%.
And secondly, putting 200g of lithium bis (trifluoromethyl) sulfonyl imide, 152g of 1-ethyl-3-methylimidazole bromine salt and 400g of pure water into a reaction kettle, heating to 60 ℃, reacting for 2 hours, standing and phase-splitting to obtain 283g of crude 1-ethyl-3-methylimidazole bis (trifluoromethyl) sulfonyl imide salt.
And thirdly, washing with pure water for three times to obtain 251g of relatively pure 1-ethyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt, distilling the salt on a rotary evaporator under reduced pressure for 2h, keeping the temperature at 80 ℃, removing most of water, and finally drying in a vacuum drying oven at 110 ℃ for 12h to obtain 237g of the finished product of 1-ethyl-3-methylimidazole bistrifluoromethylsulfonyl imide.
The purity of the product is 99.23 percent and the yield is 87.1 percent through liquid chromatography detection; ion chromatography detection: 450ppm of halogen ions; detection by ICP: fe ion is less than 1ppm, Pb ion is less than 1 ppm.
Example one and comparative example one, in comparative example two, bis-trifluoromethyl sulfonyl imide metal salt was fixed as lithium bis-trifluoromethyl sulfonyl imide, and the other reaction mass was 1-ethyl-3-methylimidazole ethyl sulfate, 1-ethyl-3-methylimidazole bicarbonate, and 1-ethyl-3-methylimidazole bromide, respectively, to prepare the same target product, 1-ethyl-3-methylimidazole bis-trifluoromethyl sulfonyl imide salt. The comparative results are shown in Table 1. Table 1:
from the comparison results, it can be seen that: the dialkyl imidazole bis-trifluoromethyl sulfonyl imide salt is prepared by the reaction of dialkyl imidazole sulfate and bis-trifluoromethyl sulfonyl imide metal salt, and has the advantages of mild reaction conditions, high yield and high purity compared with the traditional reaction of dialkyl imidazole bicarbonate and bis-trifluoromethyl sulfonyl imide metal salt; compared with the traditional reaction adopting dialkyl imidazole halide salt and bis (trifluoromethyl) sulfonyl imide metal salt, the method has the advantage of low halogen ions.
Therefore, the preparation method of the dialkyl imidazole bis (trifluoromethyl) sulfonyl imide salt has the advantages of mild reaction conditions, simple operation steps, high yield and purity of the prepared product, low content of halogen ions and suitability for popularization and application.
Claims (10)
1. A preparation method of dialkyl imidazole bis (trifluoromethyl) sulfonyl imide salt comprises the following steps:
firstly, in an organic solvent, reacting and layering alkyl imidazole and sulfate to obtain a dialkyl imidazole sulfate crude product; the alkyl imidazole and the sulfate ester are soluble in the organic solvent, and the dialkyl imidazole sulfate ester is not soluble in the organic solvent;
washing, distilling under reduced pressure and drying the crude product of the dialkyl imidazole sulfate to obtain the dialkyl imidazole sulfate;
thirdly, reacting dialkyl imidazole sulfate with bis (trifluoromethyl) sulfonyl imide metal salt in a solvent, and layering to obtain a crude product of the dialkyl imidazole bis (trifluoromethyl) sulfonyl imide salt; the dialkyl imidazole sulfate and the bis-trifluoromethyl sulfonyl imide metal salt can be dissolved in the solvent, and the dialkyl imidazole bis-trifluoromethyl sulfonyl imide salt is not dissolved in the solvent;
fourthly, washing, decompressing and distilling the crude product of the dialkyl imidazole bistrifluoromethylsulfonyl imide salt, and drying to obtain a target product of the dialkyl imidazole bistrifluoromethylsulfonyl imide salt; the general structural formula of the dialkyl imidazole bis (trifluoromethyl) sulfonyl imide salt is as follows:
wherein R1 represents an alkyl group having 1 to 8 carbon atoms, and R2 represents an alkyl group having 1 to 2 carbon atoms.
2. The method according to claim 1, wherein the dialkyl imidazole bistrifluoromethylsulfonyl imide salt is prepared by: in the first step, the alkyl imidazole is selected from any one or more of N-methylimidazole, N-ethylimidazole, N-propylimidazole, N-butylimidazole, N-pentylimidazole, N-hexylimidazole, N-heptylimidazole and N-octylimidazole.
3. The method according to claim 1, wherein the dialkyl imidazole bistrifluoromethylsulfonyl imide salt is prepared by: in the first step, the sulfuric ester is selected from any one or more of dimethyl sulfate and diethyl sulfate.
4. The method for preparing a dialkyl imidazole bistrifluoromethylsulfonyl imide salt according to claim 1 wherein: in the first step, the feeding molar ratio of the alkyl imidazole to the sulfuric ester is 1: 1 to 1.5.
5. The method for preparing a dialkyl imidazole bistrifluoromethylsulfonyl imide salt according to claim 1 wherein: the reaction in step one is carried out under nitrogen atmosphere.
6. The process for the preparation of a dialkyl imidazole bistrifluoromethylsulfonyl imide salt according to claim 1 or 2 or 3 or 4 or 5 wherein: in the first step, the organic solvent is toluene, and the feeding mass of the toluene is 100-500% of the total feeding mass of the alkyl imidazole and the sulfuric ester.
7. The process for the preparation of a dialkyl imidazole bistrifluoromethylsulfonyl imide salt according to claim 1 or 2 or 3 or 4 or 5 wherein: in the third step, the bis (trifluoromethyl) sulfonyl imide metal salt is selected from any one or more of bis (trifluoromethyl) sulfonyl imide lithium, bis (trifluoromethyl) sulfonyl imide sodium and bis (trifluoromethyl) sulfonyl imide potassium; the feeding molar ratio of the bis (trifluoromethyl) sulfonyl imide metal salt to the dialkyl imidazole sulfate is 1: 0.9-1.3.
8. The process for the preparation of a dialkyl imidazole bistrifluoromethylsulfonyl imide salt according to claim 1 or 2 or 3 or 4 or 5 wherein: in the third step, dialkyl imidazole sulfate and bis (trifluoromethyl) sulfonyl imide metal salt react in a water phase at 30-80 ℃, the feeding amount of water is 200-500% of the mass of the dialkyl imidazole sulfate, and the mixture is kept stand for 1-3 h for layering after the reaction is finished, so that a crude product of the dialkyl imidazole bis (trifluoromethyl) sulfonyl imide salt is obtained.
9. The process for the preparation of a dialkyl imidazole bistrifluoromethylsulfonyl imide salt according to claim 1 or 2 or 3 or 4 or 5 wherein: and in the second step, washing the crude dialkyl imidazole sulfate product for 2-5 times by using an organic solvent, wherein the organic solvent is the same as the organic solvent in the first step, then carrying out reduced pressure distillation on a rotary evaporator for 0.5-3 h, keeping the temperature at 30-80 ℃, and finally drying in a vacuum drying oven for 12-36 h, wherein the drying temperature is kept at 40-100 ℃ to obtain the dialkyl imidazole sulfate.
10. The process for the preparation of a dialkyl imidazole bistrifluoromethylsulfonyl imide salt according to claim 1 or 2 or 3 or 4 or 5 wherein: in the fourth step, the crude dialkyl imidazole bistrifluoromethylsulfonyl imide salt product is washed by pure water for 2-5 times, and is subjected to reduced pressure distillation on a rotary evaporator for 0.5-3 h, the temperature is kept at 60-120 ℃, and finally the crude dialkyl imidazole bistrifluoromethylsulfonyl imide salt product is dried in a vacuum drying oven for 12-36 h, and the drying temperature is kept at 80-150 ℃, so that the target dialkyl imidazole bistrifluoromethylsulfonyl imide salt product is obtained.
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| CN1854129A (en) * | 2005-03-29 | 2006-11-01 | 第一工业制药株式会社 | Superhigh purity ionic liquid |
| CN104496928A (en) * | 2014-11-21 | 2015-04-08 | 绍兴佳华高分子材料股份有限公司 | Method for preparing quaternary ammonium salt ionic liquid without halogen ions and sodium ions |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1854129A (en) * | 2005-03-29 | 2006-11-01 | 第一工业制药株式会社 | Superhigh purity ionic liquid |
| CN104496928A (en) * | 2014-11-21 | 2015-04-08 | 绍兴佳华高分子材料股份有限公司 | Method for preparing quaternary ammonium salt ionic liquid without halogen ions and sodium ions |
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