CN109734062B - Preparation method of difluorosulfonyl imide acid - Google Patents
Preparation method of difluorosulfonyl imide acid Download PDFInfo
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Abstract
The invention discloses a preparation method of difluorosulfonyl imide acid, which comprises the following steps: adding ammonium bifluoride into a reaction kettle, heating to a molten state under the protection of nitrogen, dropwise adding sulfuric ester, controlling the reaction temperature to be 120-160 ℃, controlling the reaction time to be 8-12 hours, and continuously distilling out byproduct alcohol in the reaction process until no alcohol is produced; and filtering the obtained reaction liquid, transferring the reaction liquid to a rectifying still, carrying out reduced pressure rectification, collecting fractions at the temperature of 90-120 ℃ and the vacuum degree of 14-20 mmHg, and thus obtaining the electronic grade difluorosulfonimide acid. The method has the advantages that the sulfuric acid ester and the ammonium bifluoride are adopted to react to prepare the difluorosulfonyl imide acid, the raw material cost is reduced, the material consumption and the waste generation are reduced, the raw material utilization rate, the product yield and the purity are improved, the product purification is easier, the preparation process flow is simpler and more efficient, and a good technical basis is laid for the large-scale industrialized preparation of the difluorosulfonyl imide acid.
Description
Technical Field
The invention belongs to the field of manufacturing of fluorine-containing lithium ion battery electrolyte additives, and particularly relates to a preparation method of difluorosulfonyl imide (HFSI).
Background
Difluorosulfonimide acid is a very widely used anion donor and has the following structural formula:
its boiling point is 170 deg.C, melting point is 17 deg.C, and density is 1.89g/cm3. Difluorosulfonimide acid can react with organic amine to generate various high-performance ionic liquid solvents, such as diethyl (methyl) propyl ammonium bis (fluorosulfonyl) imide, triethyl ammonium bis (fluorosulfonyl) imide and the like, which are widely applied to various fields of chemical research. The difluorosulfonyl imide acid reacts with alkali metal ions to obtain various alkali metal salts, particularly lithium salts, which are important fluorine-containing lithium ion electrolytes. They are used as super capacitor and lithium ionA key high-performance electrolyte material in new energy devices such as pools and the like. For example: potassium difluorosulfonimide (also known as KFSI) can be used as an additive for supercapacitors. And difluorosulfonimide acid is a core intermediate of lithium difluorosulfonimide (also known as LiFSI). Lithium difluorosulfonimide is a new electrolyte widely believed to be the most likely substitute for lithium hexafluorophosphate, a traditional lithium ion battery electrolyte. The lithium ion battery has excellent application prospect and industrial value in lithium ion batteries and super capacitors.
The current methods for synthesizing difluorosulfimide acid are mainly as follows:
(1) using SOCl2、ClSO3H and HSO2NH2Synthesis of HClSI followed by KF, CsF, SbF3The raw materials used by the method are all acidic and easily-corroded raw materials, and a large amount of acidic gases such as hydrogen chloride, sulfur dioxide and the like produced in the reaction process have high requirements on equipment. The fluorination process uses a fluorinating reagent which is highly toxic and leaves a large amount of byproduct salt after the reaction is completed and requires disposal.
(2) The method for preparing HFSI by heating reaction after mixing urea and fluorosulfonic acid, wherein generated HFSI and excessive fluorosulfonic acid are removed by vacuum rectification, the raw materials used in the method are expensive, a large amount of hydrogen fluoride is generated in the reaction process, the requirement on equipment is extremely high, and the excessive fluorosulfonic acid is easy to cause azeotropic effect in the rectification process to influence the purity and yield of the final product.
(3) HCLSI is unconventional raw material, the acquisition cost is high, the reaction is gas-liquid high-pressure high-risk reaction, the requirement on safety facilities is extremely high, and a large amount of corrosive hydrofluoric acid solution can be generated by tail gas absorption.
As described above, the prior art for synthesizing difluorosulfonyl imide acid has the disadvantages of tedious process, long process, low product conversion rate, difficult separation of by-products, high requirement on reaction equipment, and the like, which results in the defects of difficult operation, high energy consumption, environmental pollution, and the like, so that the difluorosulfonyl imide acid cannot be industrially applied. The existing process needs to be further optimized, the raw material consumption is reduced, the separation difficulty of the product and the byproducts in the reaction process is reduced, and the product purity is improved, so that the production cost is further reduced, and the product performance and the cost competitiveness are improved.
Disclosure of Invention
In order to overcome the defects that the existing method for preparing difluorosulfonyl imide generates byproducts, is complex to operate, has large usage amount of organic solvent, large amount of three wastes and the like, and is not beneficial to industrial production, the invention provides a method for preparing difluorosulfonyl imide.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of difluorosulfonyl imide acid comprises the following steps:
adding ammonium bifluoride into a reaction kettle, heating to a molten state under the protection of nitrogen, dropwise adding sulfuric ester, controlling the reaction temperature to be 120-160 ℃, reacting for 8-12 hours, and continuously distilling out byproduct alcohol in the reaction process until no alcohol is produced;
step two, filtering the reaction liquid obtained in the step one, transferring the reaction liquid to a rectifying still, carrying out reduced pressure rectification, collecting fraction at the temperature of 90-120 ℃ and under the vacuum degree of 14-20 mmHg, and thus obtaining the electronic grade difluorosulfonyl imide acid with the content of more than 99.5%; the reaction formula of the preparation method of the difluorosulfonyl imide acid is shown as follows:
further, the sulfuric acid ester used in the reaction is any one of bis (trimethylsilyl) sulfate, bis (2,2, 2-trifluoroethyl) sulfate, n-butyl sulfate, dimethyl sulfate, diethyl sulfate, diisopropyl sulfate, tert-butyl sulfate, and diamyl sulfate.
Further, the molar ratio of the sulfuric ester to the ammonium bifluoride is (2.1-2.9): 1.0.
According to the technical scheme, the preparation method of the difluorosulfonyl imide acid has the following advantages:
1. the ammonium bifluoride is used as a nitrogen supply body and a fluorine supply body, the atom utilization rate is high, so that an acidic by-product is avoided, and the ammonium bifluoride is an easily obtained industrial raw material with weak acid, so that the production cost of the product is greatly reduced;
2. the sulfate is a widely used and cheap chemical raw material, and is used as a raw material and a solvent in the early stage of the reaction, so that a large amount of non-polar solvents which do not participate in the reaction are avoided;
3. reaction products in the reaction process are difluorosulfimide acid and corresponding alcohol, other complex byproducts do not exist, the boiling point of the alcohol in the reaction process is very low, the reaction is easily separated out of a reaction system during the reaction, the forward proceeding of the reaction is further ensured, the material consumption and the waste generation are reduced, and the utilization rate of raw materials, the product yield and the purity are improved. The recovered by-product alcohol can be used for washing the kettle, and the crude product after kettle washing can be directly incinerated without any damage to incineration equipment;
4. the whole reaction process does not generate acid gas, the conventional equipment can meet the production requirement, the boiling point of the byproduct alcohol is far lower than the reaction temperature, the byproduct alcohol is directly gasified once produced, and the byproduct alcohol is synchronously recovered with the reaction process through a condensation facility, so that the preparation process flow of the product is simplified, and a good foundation is laid for large-scale industrial production.
Drawings
FIG. 1 is a gas chromatogram of a colorless liquid of difluorosulfonimide acid obtained in example 1 of the present invention.
FIG. 2 is a gas chromatograph of the mass content of the sample of example 1.
Detailed Description
The following description will be given with reference to the embodiments in order to explain technical contents, structural features, and objects and effects of the present invention in detail.
The main difference between the present invention and the prior art is that: the difluorosulfonyl imide acid is prepared by reacting the sulfuric ester with the ammonium bifluoride, so that the raw material cost is reduced, the material consumption and the waste generation are reduced, the raw material utilization rate, the product yield and the purity are improved, the product is easier to purify, the preparation process flow is simpler and more efficient, and a good technical basis is laid for large-scale industrialized preparation of the difluorosulfonyl imide acid.
The raw materials used in the present invention are commercially available chemicals, unless otherwise specified. The detection equipment used was a Wantong type 850 ion chromatography, Shimadzu type G2014 gas chromatography.
The following examples are given in conjunction with the accompanying drawings for further illustration.
Example 1
This example is provided to illustrate a method for preparing difluorosulfonimide acid disclosed in this invention.
Firstly, 330g (5.79mol) of ammonium bifluoride is added into a dry reaction bottle, the temperature is raised to a molten state under the protection of nitrogen, 3223g (13.32mol) of bis (trimethylsilyl) sulfate is dropwise added, the dropwise adding speed is adjusted according to the reaction temperature, the reaction temperature is controlled to be 135 ℃, a byproduct trimethylsilanol is generated in the reaction process, the trimethylsilanol can be decomposed into hexamethyldisiloxane at high temperature, the hexamethyldisiloxane has a low boiling point, so the hexamethyldisiloxane can be directly vaporized and reflowed to a fractionating device through a condensing tube for extraction, when no hexamethyldisiloxane is extracted, the reaction is finished after the heat preservation reaction is continued for 1 hour, the whole reaction time is 9 hours, then the obtained light yellow reaction liquid is subjected to reduced pressure rectification, and fractions with the vacuum degree of 19mmHg of 108-116 ℃ are collected. 954g (5.27mol) of a highly pure colorless liquid of difluorosulfonimide acid was obtained in a yield of 91%, with a content of 99.6%.
Example 2
This example is provided to illustrate a method for preparing difluorosulfonimide acid disclosed in this invention.
Firstly, adding 130g (2.28mol) of ammonium bifluoride into a dry reaction bottle, heating to a molten state under the protection of nitrogen, adjusting the speed of dropwise adding of 1547g (5.93mol) of bis (2,2, 2-trifluoroethyl) sulfate according to the reaction temperature, controlling the reaction temperature to be 135 ℃, generating a byproduct of trifluoroethanol in the reaction process, directly vaporizing the trifluoroethanol due to low boiling point, refluxing the trifluoroethanol to a fractionating device for extraction through a condenser pipe, continuing to carry out heat preservation reaction for 1 hour when the trifluoroethanol is not extracted, ending the reaction, wherein the whole reaction time is 9 hours, then carrying out reduced pressure rectification on the obtained light yellow reaction liquid, and collecting fractions with the temperature of 102-110 ℃ and the vacuum degree of 16 mmHg. 660g (3.6mol) of high-purity difluorosulfonimide acid colorless liquid are obtained, the content is 99.7 percent, and the yield is 91 percent.
Example 3
This example is provided to illustrate a method for preparing difluorosulfonimide acid disclosed in this invention.
Firstly adding 530g (9.3mol) of ammonium bifluoride into a dry reaction bottle, heating to a molten state under the protection of nitrogen, dropwise adding 1067g (24.18mol) of dimethyl sulfate, adjusting the dropwise adding speed according to the reaction temperature, controlling the reaction temperature to be 135 ℃, generating a byproduct methanol in the reaction process, directly vaporizing the methanol due to low boiling point, refluxing the methanol to a fractionating device for extraction through a condensing tube, continuing to perform heat preservation reaction for 1 hour when no methanol is extracted, ending the reaction, wherein the whole reaction time is 9 hours, then performing reduced pressure rectification on the obtained light yellow reaction liquid, and collecting a fraction with the temperature of 93-105 ℃ and the vacuum degree of 14 mmHg. 660g (3.6mol) of high-purity difluorosulfonimide acid colorless liquid are obtained, the content is 99.7 percent, and the yield is 91 percent.
Example 4
This example is provided to illustrate a method for preparing difluorosulfonimide acid disclosed in this invention.
Firstly, 460g (8.07mol) of ammonium bifluoride is added into a dry reaction bottle, the temperature is raised to a molten state under the protection of nitrogen, 2940g (19.09mol) of diethyl sulfate is dropwise added, the dropwise adding speed is adjusted according to the reaction temperature, the reaction temperature is controlled at 141 ℃, a byproduct ethanol is generated in the reaction process, the boiling point of the ethanol is low, so the ethanol is directly vaporized and flows back to a fractionating device for extraction through a condensing tube, when no ethanol is extracted, the heat preservation reaction is continued for 1.5 hours, the reaction is ended, the whole reaction time is 11 hours, then the obtained light yellow reaction liquid is subjected to reduced pressure rectification, and fractions with the temperature of 98-109 ℃ and the vacuum degree of 18mmHg are collected. 1380g (7.62mol) of a high-purity colorless liquid of difluorosulfonimide acid was obtained, the content of which was 99.6%, and the yield was 95%.
Example 5
This example is provided to illustrate a method for preparing difluorosulfonimide acid disclosed in this invention.
Firstly, 690g (12.1mol) of ammonium bifluoride is added into a dry reaction bottle, the temperature is raised to a molten state under the protection of nitrogen, 5700g (31.32mol) of diisopropyl sulfate is dropwise added, the dropwise adding speed is adjusted according to the reaction temperature, the reaction temperature is controlled to be 159 ℃, a byproduct isopropanol is generated in the reaction process, the boiling point of the isopropanol is low, so the isopropanol is directly vaporized and flows back to a fractionating device for extraction through a condenser pipe, when no isopropanol is extracted, the heat preservation reaction is continued for 2 hours, the reaction is ended, the whole reaction time is 12 hours, then the obtained light yellow reaction liquid is subjected to reduced pressure rectification, and fractions with the temperature of 99-115 ℃ and the vacuum degree of 20mmHg are collected. 2026g (11.19mol) of a high-purity colorless liquid of difluorosulfonimide acid was obtained with a content of 99.5% and a yield of 93%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (5)
1. A method for preparing difluorosulfonyl imide acid is characterized in that: the method comprises the following steps:
adding ammonium bifluoride into a reaction kettle, heating to a molten state under the protection of nitrogen, dropwise adding sulfuric ester, controlling the reaction temperature and the reaction time, and continuously distilling out byproduct alcohol in the reaction process until no byproduct alcohol is produced;
step two, filtering the reaction liquid obtained in the step one, transferring the reaction liquid to a rectifying still, carrying out reduced pressure rectification, and collecting fractions to obtain electronic grade difluorosulfonimide acid; the reaction formula for the preparation of difluorosulfonimide acid is shown below:
2. the method according to claim 1, wherein the method comprises the steps of: the sulfuric acid ester used in the reaction is any one of bis (trimethylsilyl) sulfate, bis (2,2, 2-trifluoroethyl) sulfate, n-butyl sulfate, dimethyl sulfate, diethyl sulfate, diisopropyl sulfate, tert-butyl sulfate and diamyl sulfate.
3. The method according to claim 2, wherein the difluorosulfonimide acid is prepared by: the molar ratio of the sulfuric ester to the ammonium bifluoride is (2.1-2.9): 1.0.
4. The method according to claim 1, wherein the difluorosulfonimide acid is prepared by: in the first step, the reaction temperature is 135-160 ℃, and the reaction time is 8-12 hours.
5. The method according to claim 4, wherein the difluorosulfonimide acid is prepared by: and in the second step, the reduced pressure rectification collection temperature is 90-120 ℃, the vacuum degree is 14-20 mmHg, and the electronic grade difluorosulfonimide acid with the content of more than 99.5 percent is obtained.
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