CN111116429B - Method for synthesizing alkali metal trifluoromethanesulfonate or alkali metal methanesulfonate - Google Patents
Method for synthesizing alkali metal trifluoromethanesulfonate or alkali metal methanesulfonate Download PDFInfo
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- CN111116429B CN111116429B CN201911386729.6A CN201911386729A CN111116429B CN 111116429 B CN111116429 B CN 111116429B CN 201911386729 A CN201911386729 A CN 201911386729A CN 111116429 B CN111116429 B CN 111116429B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
- C07C303/28—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids by reaction of hydroxy compounds with sulfonic acids or derivatives thereof
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Abstract
The invention relates to a method for synthesizing alkali metal trifluoromethanesulfonate or alkali metal methanesulfonate, and belongs to the technical field of fine chemical engineering. Firstly, adding anhydrous calcium chloride and alcohols into a reactor, vacuumizing, controlling the temperature in the reactor to be-40-25 ℃, introducing excessive sulfonyl fluoride compounds, stirring, controlling the temperature to be-40-70 ℃, controlling the pressure to be 0.05-0.15 MPa, and reacting for 2-3 hours; after the reaction is finished, discharging unreacted sulfonyl fluoride compounds, and distilling to obtain ester compounds; adding alkali metal hydroxide into the ester compound, stirring, reacting for 2-5 h at 20-70 ℃ under 0.05-0.15 MPa, filtering after the reaction is finished, and drying to obtain the alkali metal trifluoromethanesulfonate or the alkali metal methanesulfonate. The yield of the reaction is effectively improved, and the introduction of impurities in the conventional method is avoided; the post-reaction treatment is simple, and the pollution in the synthesis process is reduced.
Description
Technical Field
The invention relates to a method for synthesizing alkali metal trifluoromethanesulfonate or alkali metal methanesulfonate, and belongs to the technical field of fine chemical engineering.
Background
The alkali metal salt of trifluoromethanesulfonic acid includes lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, and trisPotassium fluoromethanesulfonate and rubidium trifluoromethanesulfonate, lithium trifluoromethanesulfonate (CF) among them3SO3Li) is used as a solid electrolyte, its stable anion can improve the structure and composition of a passivation layer between the electrolyte and the cathode material interface, which is beneficial to the stability of the electrolyte, passivation film and motor, so its production and application become a research focus.
At present, the production technology of lithium trifluoromethanesulfonate is mainly controlled by japan and the united states, and foreign manufacturers include japan niter, 3M company, and the like, but the disclosed technology is relatively small. The production method proposed in Japanese laid-open patent JP2005-232040 is as follows: firstly, methyl sulfonyl fluoride is generated by the reaction of methyl sulfonic acid chloride and potassium fluoride, then methyl sulfonyl fluoride and liquid hydrogen fluoride are added into an electrolytic cell for electrolysis, and the generated trifluoro methylsulfonyl fluoride reacts with a lithium carbonate aqueous solution or a lithium carbonate suspension to generate a crude trifluoro methylsulfonyl lithium solution. The method cannot ensure that lithium carbonate can be completely removed, and the product purity is low.
In some studies, lithium trifluoromethanesulfonate was prepared by reacting lithium hydroxide (LiOH) with trifluoromethanesulfonyl fluoride. However, this production method has the following problems: when lithium hydroxide is insufficient, trifluoromethanesulfonic acid is produced. Even if a trace amount of trifluoromethanesulfonic acid is contained in lithium trifluoromethanesulfonate, the battery characteristics are affected and the stability is lowered. Secondly, if LiOH is excessive, lithium hydroxide can form hydrate, so that water cannot be completely removed; on the other hand, the purity of the lithium hydroxide is low, and the purity of the generated lithium trifluoromethanesulfonate cannot reach the standard, so that the performance of the battery is influenced. In addition, lithium trifluoromethanesulfonate can also be prepared by reacting trifluoromethanesulfonic acid with lithium carbonate, but this reaction easily causes lithium carbonate to remain, which seriously affects the conductivity of the battery.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for synthesizing alkali metal trifluoromethanesulfonate or alkali metal methanesulfonate, which has the advantages of simple operation, high yield, mild conditions and low cost.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method of synthesizing an alkali metal triflate or an alkali metal mesylate salt, the method steps comprising:
(1) adding anhydrous calcium chloride and alcohols into a reactor, vacuumizing, controlling the temperature in the reactor to be-40-25 ℃, introducing excessive sulfonyl fluoride compounds, stirring, controlling the temperature to be-40-70 ℃, and the pressure to be 0.05-0.15 MPa, and reacting for 2-3 h; after the reaction is finished, discharging the unreacted sulfonyl fluoride compound, and distilling to obtain an ester compound;
wherein the sulfonyl fluoride compound is trifluoromethyl sulfonyl fluoride or methyl sulfonyl fluoride.
Preferably, the molar ratio of the sulfonyl fluoride compound to the alcohol to the anhydrous calcium chloride in the step (1) is 1-8: 1: 0.5 to 2.0. If the amount of the sulfonyl fluoride compound is small, calcium chloride is not sufficiently dissolved, and on the contrary, more alcohol is easily mixed in the generated ester compound.
Preferably, the alcohol in step (1) is methanol or ethanol.
(2) Adding alkali metal hydroxide into the ester compound, stirring, reacting for 2-5 h at 20-70 ℃ under 0.05-0.15 MPa, filtering after the reaction is finished, and drying to obtain the alkali metal trifluoromethanesulfonate or the alkali metal methanesulfonate.
Preferably, the molar ratio of the ester compound to the alkali metal hydroxide in the step (2) is 1: 1.0 to 3.0.
Preferably, the alkali metal hydroxide in step (2) is lithium hydroxide, sodium hydroxide or potassium hydroxide.
Preferably, spray drying is used for drying in step (2).
Preferably, the filtrate obtained after filtration in step (2) is concentrated, the concentrated filtrate is filtered again, and the obtained solid is dried together with the solid obtained after the first filtration.
Preferably, distillation is used for concentration.
Advantageous effects
The method has the advantages of full reaction of reactants, simple process method, easy pollution discharge after the reaction is finished, effective improvement of the reaction yield and avoidance of introduction of impurities in the conventional method; the post-reaction treatment is simple, the pollution in the synthesis process is reduced, and the method belongs to a green synthesis process.
In the method, the alcohol and the ester compound are both a reactant and a solvent, so that new impurities introduced by using the solvent are avoided, the elastic space of reaction process conditions is increased, the process flow and equipment are simplified, and the excessive ester compound or alcohol can be separated from a reaction product through distillation, thereby being beneficial to the purification of the product.
The method has the advantages of cyclic utilization of alcohols, mild conditions, no high temperature and high pressure, less three wastes, higher product purity, low cost and simple steps, and can be industrially used for industrial large-scale production.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
111g (1.0mol) of anhydrous calcium chloride and 64g (2mol) of methanol were charged into a mechanically stirred reactor I equipped with a thermometer, a distillation apparatus, and the system was evacuated to-0.095 MPa, cooled to-40 ℃ and charged with 380g (2.5mol) of trifluoromethanesulfonyl fluoride. Mechanically stirring, controlling the temperature of the system to be 0 ℃, controlling the pressure to be 0.1MPa, and reacting for 2.5 h. After the reaction is finished, slowly opening an outlet valve of the system, and discharging the excessive trifluoromethanesulfonyl fluoride, cooling and collecting. And (3) after the pressure in the reaction container I is reduced to the normal pressure, slowly raising the temperature of the system for distillation, and collecting fractions at the temperature of 90-105 ℃ to obtain 304g of methyl trifluoromethanesulfonate with the yield of 92.7%.
164g (1.0mol) of methyl trifluoromethanesulfonate were placed in a mechanically stirred reactor II equipped with a thermometer, and 44g (1.0mol) of lithium hydroxide monohydrate were added. Mechanically stirring, controlling the temperature of the system at 25 ℃ and the pressure at 0.1MPa, and reacting for 3 h. And (3) filtering after the reaction is completed, distilling the filtrate, collecting fractions at 65-70 ℃, distilling to one third of the original solution, filtering, distilling and filtering the filtrate again, and performing spray drying on the solid obtained after twice filtration to obtain a final product, wherein the final product is 143g of lithium trifluoromethanesulfonate, the yield is 90.5%, and the purity is 99.7% through detection.
Example 2
111g (1.0mol) of calcium chloride and 96.6g (2.1mol) of ethanol were charged into a mechanically-stirred reactor I equipped with a thermometer, a distillation apparatus, and the system was evacuated to-0.095 MPa, the system was cooled to-40 ℃ and 380g (2.5mol) of trifluoromethanesulfonyl fluoride was introduced thereinto. Mechanically stirring, controlling the temperature of the system to be 0 ℃, controlling the pressure to be 0.05MPa, and reacting for 3 hours. After the reaction is finished, slowly opening an outlet valve of the system, and discharging the excessive trifluoromethanesulfonyl fluoride, cooling and collecting. And (3) after the pressure in the reaction container I is reduced to the normal pressure, slowly raising the temperature of the system for distillation, and collecting fractions at the temperature of 90-105 ℃ to obtain 316.8g of ethyl trifluoromethanesulfonate with the yield of 88.9%.
178g (1.0mol) of ethyl trifluoromethanesulfonate was placed in a mechanically stirred reactor II equipped with a thermometer, 40g (1.0mol) of sodium hydroxide was added, and the mixture was mechanically stirred while controlling the system temperature at 30 ℃ and the pressure at 0.1MPa, and reacted for 3.5 hours. And (3) filtering after complete reaction, distilling the filtrate, collecting fractions at 75-85 ℃, distilling to one third of the original solution, filtering, distilling and filtering the filtrate again, and performing spray drying on the solid obtained after twice filtration to obtain a final product, wherein the final product is 148g of sodium trifluoromethanesulfonate, the yield is 86.0%, and the purity is 99.8% through detection.
Example 3
111g (1.0mol) of calcium chloride and 64g (2.0mol) of methanol were charged into a mechanically stirred reactor I equipped with a thermometer, a distillation apparatus, and the system was evacuated to-0.095 MPa, the reactor temperature was 25 ℃ and 245g (2.5mol) of methanesulfonyl fluoride was introduced. Mechanically stirring, controlling the temperature of the system at 68 ℃ and the pressure at 0.1MPa, and reacting for 2 h. After the reaction is finished, slowly opening an outlet valve of the system, and discharging, cooling and collecting the excessive methanesulfonyl fluoride. Slowly raising the temperature of the system, carrying out reduced pressure distillation at the pressure of-0.095 MPa, and collecting fractions at the temperature of 90-95 ℃ to obtain 204g of methyl methanesulfonate with the yield of 92.7%.
110g (1.0mol) of methyl methanesulfonate were introduced into a mechanically stirred reactor II equipped with a thermometer, and 44g (1.0mol) of lithium hydroxide monohydrate were added. Mechanically stirring, controlling the temperature of the system at 50 ℃ and the pressure at 0.1MPa, and reacting for 5 hours. And (3) filtering after complete reaction, distilling the filtrate, collecting fractions at 65-70 ℃, distilling to one third of the original solution, filtering, distilling and filtering the filtrate again, and performing spray drying on the solid obtained after twice filtration to obtain a final product, wherein the final product is 143g of lithium methanesulfonate, the yield is 90.5%, and the purity is 99.5%.
In summary, the invention includes but is not limited to the above embodiments, and any equivalent replacement or local modification made under the spirit and principle of the invention should be considered as being within the protection scope of the invention.
Claims (8)
1. A method for synthesizing alkali metal trifluoromethanesulfonate or alkali metal methanesulfonate is characterized in that: the method comprises the following steps:
(1) adding anhydrous calcium chloride and alcohols into a reactor, vacuumizing, controlling the temperature in the reactor to be-40-25 ℃, introducing excessive sulfonyl fluoride compounds, stirring, controlling the temperature to be-40-20 ℃, controlling the pressure to be 0.05-0.15 MPa, and reacting for 2-3 h; after the reaction is finished, discharging the unreacted sulfonyl fluoride compound, and distilling to obtain an ester compound;
wherein the sulfonyl fluoride compound is trifluoromethyl sulfonyl fluoride or methyl sulfonyl fluoride;
(2) adding alkali metal hydroxide into the ester compound, stirring, reacting for 2-5 h at 20-70 ℃ under 0.05-0.15 MPa, filtering after the reaction is finished, and drying to obtain the alkali metal trifluoromethanesulfonate or the alkali metal methanesulfonate.
2. The method for synthesizing an alkali metal trifluoromethanesulfonate or an alkali metal methanesulfonate according to claim 1, wherein: in the step (1), the molar ratio of the sulfonyl fluoride compound to the alcohols to the anhydrous calcium chloride is 1-8: 1: 0.5 to 2.0.
3. The method for synthesizing an alkali metal trifluoromethanesulfonate or an alkali metal methanesulfonate according to claim 1, wherein: the alcohol in the step (1) is methanol or ethanol.
4. The method for synthesizing an alkali metal trifluoromethanesulfonate or an alkali metal methanesulfonate according to claim 1, wherein: in the step (2), the molar ratio of the ester compound to the alkali metal hydroxide is 1: 1.0 to 3.0.
5. The method for synthesizing an alkali metal trifluoromethanesulfonate or an alkali metal methanesulfonate according to claim 1, wherein: in the step (2), the alkali metal hydroxide is lithium hydroxide, sodium hydroxide or potassium hydroxide.
6. The method for synthesizing an alkali metal trifluoromethanesulfonate or an alkali metal methanesulfonate according to claim 1, wherein: spray drying is adopted during drying in the step (2).
7. The method for synthesizing an alkali metal trifluoromethanesulfonate or an alkali metal methanesulfonate according to claim 1, wherein: and (3) concentrating the filtered solution obtained in the step (2), filtering the concentrated filtrate again, and drying the obtained solid together with the solid obtained after the first filtration.
8. The method for synthesizing an alkali metal trifluoromethanesulfonate or an alkali metal methanesulfonate according to claim 7, wherein: the concentration is carried out by distillation.
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| CN112778170B (en) * | 2020-12-30 | 2022-12-27 | 中船(邯郸)派瑞特种气体股份有限公司 | Method and device for preparing lithium trifluoromethanesulfonate |
| CN113845446B (en) * | 2021-10-26 | 2023-03-14 | 中船(邯郸)派瑞特种气体股份有限公司 | Preparation method of trifluoromethanesulfonic acid |
| CN114380721B (en) * | 2022-01-20 | 2023-04-14 | 中船(邯郸)派瑞特种气体股份有限公司 | Method for preparing zinc trifluoromethanesulfonate from trifluoromethanesulfonic acid |
| CN115894308B (en) * | 2022-11-04 | 2024-04-05 | 中船(邯郸)派瑞特种气体股份有限公司 | Technological method for preparing trifluoromethanesulfonic acid |
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| CN102272096A (en) * | 2009-01-05 | 2011-12-07 | 三菱综合材料株式会社 | Process for producing perfluoroalkylsulfonic acid salt |
| CN108129531A (en) * | 2018-01-24 | 2018-06-08 | 邯郸市赵都精细化工有限公司 | A kind of preparation method of hesperidin methyl |
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| CN102272096A (en) * | 2009-01-05 | 2011-12-07 | 三菱综合材料株式会社 | Process for producing perfluoroalkylsulfonic acid salt |
| CN108129531A (en) * | 2018-01-24 | 2018-06-08 | 邯郸市赵都精细化工有限公司 | A kind of preparation method of hesperidin methyl |
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