CN115611244A - Preparation method of bis-chlorosulfonyl imide alkali metal salt and bis-fluorosulfonyl imide alkali metal salt - Google Patents
Preparation method of bis-chlorosulfonyl imide alkali metal salt and bis-fluorosulfonyl imide alkali metal salt Download PDFInfo
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- alkali metal
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- -1 bis-chlorosulfonyl imide alkali metal salt Chemical class 0.000 title claims abstract description 118
- 229910052783 alkali metal Inorganic materials 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims abstract description 40
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims abstract description 27
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 21
- PVMUVDSEICYOMA-UHFFFAOYSA-N n-chlorosulfonylsulfamoyl chloride Chemical compound ClS(=O)(=O)NS(Cl)(=O)=O PVMUVDSEICYOMA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000000376 reactant Substances 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 4
- 239000003880 polar aprotic solvent Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 3
- 159000000002 lithium salts Chemical class 0.000 claims description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 abstract description 11
- 229910010941 LiFSI Inorganic materials 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000006227 byproduct Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001035 drying Methods 0.000 description 6
- 238000003682 fluorination reaction Methods 0.000 description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 description 5
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- SAPIQCCFEBULSH-UHFFFAOYSA-M lithium;sulfamate Chemical compound [Li+].NS([O-])(=O)=O SAPIQCCFEBULSH-UHFFFAOYSA-M 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 235000003270 potassium fluoride Nutrition 0.000 description 2
- 239000011698 potassium fluoride Substances 0.000 description 2
- BTAAXEFROUUDIL-UHFFFAOYSA-M potassium;sulfamate Chemical compound [K+].NS([O-])(=O)=O BTAAXEFROUUDIL-UHFFFAOYSA-M 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ATMIHASMQFJNLZ-UHFFFAOYSA-N dichloro(imino)-$l^{4}-sulfane Chemical compound ClS(Cl)=N ATMIHASMQFJNLZ-UHFFFAOYSA-N 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-UHFFFAOYSA-N 0.000 description 1
- QDWYPRSFEZRKDK-UHFFFAOYSA-M sodium;sulfamate Chemical compound [Na+].NS([O-])(=O)=O QDWYPRSFEZRKDK-UHFFFAOYSA-M 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/086—Compounds containing nitrogen and non-metals and optionally metals containing one or more sulfur atoms
-
- 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
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
In order to overcome the problems of more byproducts and low reaction yield of the existing method for preparing LiFSI, the invention provides a method for preparing the alkali metal salt of the bis (chlorosulfonyl) imide, which comprises the following operation steps: alkali metal salt of sulfamic acid, thionyl chloride and chlorosulfonic acid are used as reactants to react to obtain a mixture containing alkali metal salt of dichlorosulfonimide, and the mixture is purified to obtain alkali metal salt of dichlorosulfonimide. Meanwhile, the invention also discloses a preparation method of the bis-fluorosulfonyl imide alkali metal salt. In the preparation method of the alkali metal salt of the bis-chlorosulfonyl imide, the alkali metal salt of sulfamic acid is used as a reactant to react with thionyl chloride and chlorosulfonic acid to prepare the precursor alkali metal salt of the bis-chlorosulfonyl imide of LiFSI, so that the requirement on reaction temperature is reduced, the synthesis process is simplified, the reaction efficiency is improved, and meanwhile, the utilization rate of raw materials and the yield of reaction products of the preparation method are greatly improved.
Description
Technical Field
The invention belongs to the technical field of halogen-containing compound preparation, and particularly relates to a method for preparing a bis-chlorosulfonyl imide alkali metal salt and a bis-fluorosulfonyl imide alkali metal salt.
Background
The LiFSI is a key high-performance electrolyte material in new energy devices such as lithium ion batteries, super capacitors and the like, and has high industrial application value.
As disclosed in patents US2013331609, US2012041233, EP2415757, US2011034716, CN101747242A, most of the existing methods for synthesizing LiFSI are to synthesize HClSI, which is dichlorosulfonimide, and then to synthesize MF with fluoro-metal salt x Reacting to prepare a corresponding intermediate of bis-fluorosulfonyl imide salt, and reacting the intermediate with LiOH or Li lithium carbonate 2 CO 3 The method for preparing LiFSI by cation exchange has the defects that a large amount of byproducts and hydrogen fluoride are generated in the fluorination process, and the processes are difficult to separate and purify, thereby bringing huge environmental protection pressure to production.
However, when HClSI is directly reacted with lithium fluoride LiF to prepare LiFSI, as shown in patent US2004097757, a large amount of corrosive gas hydrogen fluoride is generated, and excessive LiF is difficult to be completely separated from LiFSI, thereby affecting the quality of the product.
Therefore, the direct synthesis of LiFeSI through fluorination of LiClSI is an economic alternative to the existing preparation methods, but the existing LiClSI synthesis methods are few, mainly through the reaction of HClSI and alkali metal halide salt, and have the problem of low reaction yield.
Disclosure of Invention
Aiming at the problems of more byproducts and low reaction yield of the existing method for preparing LiFSI, the invention provides a method for preparing a bischlorosulfonimide alkali metal salt and a method for preparing a bisfluorosulfonimide alkali metal salt.
The technical scheme adopted by the invention for solving the technical problems is as follows:
in one aspect, the invention provides a preparation method of a bis (chlorosulfonyl) imide alkali metal salt, which comprises the following operation steps:
alkali metal salt of sulfamic acid, thionyl chloride and chlorosulfonic acid are used as reactants to react to obtain a mixture containing the alkali metal salt of bis-chlorosulfonyl imide, and the mixture is purified to obtain the alkali metal salt of bis-chlorosulfonyl imide.
Optionally, the molar addition ratio of the alkali metal sulfamate, the thionyl chloride and the chlorosulfonic acid is as follows: 1: 2.2-2.8: 1 to 1.05.
Optionally, the alkali metal salt of sulfamic acid comprises one or more of a lithium salt of sulfamic acid, a sodium salt of sulfamic acid and a potassium salt of sulfamic acid.
Alternatively, when charging materials for reaction, alkali metal salt of sulfamic acid and thionyl chloride are mixed, and chlorosulfonic acid is added dropwise under stirring conditions for reaction.
Optionally, the temperature of the reaction system is controlled to be 0-60 ℃ during the reaction feeding.
Optionally, after the feeding is finished, the temperature of the reactants is kept at 5-80 ℃ for 2-20 h.
Alternatively, the reaction is carried out under a protective atmosphere that does not participate in the reaction.
Alternatively, after the reaction is finished, unreacted materials are distilled off, and the solid remained at the bottom of the kettle is crude bis (chlorosulfonyl) imide alkali metal salt.
Optionally, adding the crude product of the alkali metal salt of the bischlorosulfonimide into a polar aprotic solvent for recrystallization to obtain the alkali metal salt of the bischlorosulfonimide.
In another aspect, the invention provides a method for preparing an alkali metal salt of bis (fluorosulfonyl) imide, comprising the following steps:
the alkali metal salt of bis (chlorosulfonyl) imide is prepared by the preparation method as described above;
fluorinating the alkali metal salt of the bis-chlorosulfonyl imide to obtain the alkali metal salt of the bis-fluorosulfonyl imide.
According to the preparation method of the alkali metal salt of the dichlorosulfimide provided by the invention, the alkali metal salt of sulfamic acid is adopted as a reactant to react with thionyl chloride and chlorosulfonic acid to prepare the precursor alkali metal salt of the LiFSI, wherein the alkali metal salt of sulfamic acid, thionyl chloride and chlorosulfonic acid have higher reaction activity and can fully react at lower temperature. The prepared alkali metal salt of the bis-chlorosulfonyl imide is used as an intermediate of the subsequent fluorination operation, so that the use of at least half of fluorine sources can be reduced, and the cost of raw materials is greatly reduced.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more clear, the present invention is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
It is to be understood that one or more method steps mentioned in the present invention does not exclude that other method steps may also be present before or after the combined steps or that other method steps may be inserted between these explicitly mentioned steps, unless otherwise indicated; it is also to be understood that a combination connection between one or more devices, means in the present invention does not exclude the presence of other devices, means, or intervening devices, means, or steps, between the two expressly mentioned devices, means, or steps, unless expressly stated otherwise.
One embodiment of the invention provides a preparation method of a bis (chlorosulfonyl) imide alkali metal salt, which comprises the following operation steps:
alkali metal salt of sulfamic acid, thionyl chloride and chlorosulfonic acid are used as reactants to react to obtain a mixture containing the alkali metal salt of bis-chlorosulfonyl imide, and the mixture is purified to obtain the alkali metal salt of bis-chlorosulfonyl imide.
The preparation method adopts the alkali metal salt of sulfamic acid as a reactant to react with thionyl chloride and chlorosulfonic acid to prepare the precursor alkali metal salt of the LiFSI, wherein compared with the traditional sulfamic acid, the alkali metal salt of sulfamic acid has higher reaction activity with thionyl chloride and chlorosulfonic acid and can fully react at lower temperature, presumably because of the introduction of the alkali metal salt of sulfamic acid, the activation energy required by the reaction is reduced, and then the reaction is effectively promoted. The prepared alkali metal salt of the bis-chlorosulfonyl imide is used as an intermediate of the subsequent fluorination operation, so that the use of at least half of fluorine sources can be reduced, and the cost of raw materials is greatly reduced.
In some embodiments, the molar addition ratio of the alkali metal salt of sulfamic acid, the thionyl chloride and the chlorosulfonic acid is: sulfamic acid: thionyl chloride: chlorosulfonic acid =1: 2.2-2.8: 1 to 1.05.
In ideal conditions, when the molar addition ratio of the alkali metal salt of sulfamic acid, the thionyl chloride and the chlorosulfonic acid is 1. In practical operation, in order to increase the reaction rate of specific raw materials, the addition amount of other raw materials can be increased in general to promote the sufficient consumption of the specific raw materials, for example, in the preparation method, in order to increase the utilization rate of alkali metal salt of sulfamic acid, the addition amount of sulfamic acid and/or thionyl chloride can be increased appropriately, and thionyl chloride is volatile, so that the addition amount of thionyl chloride needs to be increased to avoid the problem of incomplete reaction caused by volatilization of thionyl chloride, thionyl chloride can be used as a reaction solvent, and by adding excessive thionyl chloride, the alkali metal salt of sulfamic acid is sufficiently reacted to avoid the residue of too much alkali metal salt of sulfamic acid in the mixture after reaction, and thionyl chloride and chlorosulfonic acid can be removed by distillation, thereby ensuring the purity of the alkali metal salt of bischlorosulfonimide after purification.
In some embodiments, the alkali metal salt of sulfamic acid comprises one or more of a lithium salt of sulfamic acid, a sodium salt of sulfamic acid, and a potassium salt of sulfamic acid.
The alkali metal salt of sulfamic acid is selected mainly in relation to the alkali metal salt of bis (fluorosulfonyl) imide to be finally obtained, for example, if lithium bis (fluorosulfonyl) imide is to be prepared, lithium sulfamate is selected as a reactant; if sodium bis (fluorosulfonyl) imide needs to be prepared, sodium sulfamate is selected as a reactant.
In some embodiments, the alkali metal salt of sulfamic acid and thionyl chloride are mixed at the time of reaction feeding, and chlorosulfonic acid is added dropwise to the mixture under stirring to carry out the reaction.
In the invention, the reaction activity of the alkali metal salt of sulfamic acid, thionyl chloride and chlorosulfonic acid is high, and the dropping of the chlorosulfonic acid can effectively control the reaction rate and reduce the generation of reaction byproducts.
In some embodiments, the temperature of the reaction system is controlled to be 0-60 ℃ during the reaction feeding.
In a preferred embodiment, the temperature of the reaction system is controlled to be 5-10 ℃ during the feeding of the reaction.
Compared with the traditional reaction of sulfamic acid, thionyl chloride and chlorosulfonic acid, the preparation method provided by the invention has higher reaction activity, so that the reaction can be carried out at normal temperature without providing an excessively high reaction temperature condition, and meanwhile, as the reaction releases heat, the reaction temperature can be controlled in a lower range through refrigeration, thereby avoiding the problems of potential safety hazard and increase of byproducts caused by excessively fast reaction.
In some embodiments, after the feeding is completed, the reactants are kept at 5-80 ℃ for 2-20 h.
In some embodiments, the reaction is carried out under a protective atmosphere that does not participate in the reaction.
By adopting the protective atmosphere as the reaction environment, the reaction of the reactant and gases such as oxygen in the air can be effectively avoided, and byproducts in the reaction product can be reduced to a certain extent.
In some examples, after the reaction is completed, unreacted materials are distilled off, and the solid remaining at the bottom of the kettle is crude bischlorosulfimide alkali metal salt.
During the distillation, unreacted thionyl chloride and chlorosulfonic acid may be removed from the alkali metal salt of bis-chlorosulfonyl imide, and in some embodiments, a negative pressure may be applied during the distillation to increase the removal efficiency of thionyl chloride and chlorosulfonic acid.
In some embodiments, the crude alkali metal salt of the bischlorosulfonimide is recrystallized by adding it to a polar aprotic solvent to obtain the alkali metal salt of the bischlorosulfonimide.
The purity of the crude alkali metal salt of the bis (chlorosulfonyl) imide can be further improved by recrystallization due to certain impurities inevitably existing in the crude alkali metal salt of the bis (chlorosulfonyl) imide, and specifically, the polar aprotic solvent can be selected from acetonitrile.
Another embodiment of the present invention provides a method for preparing an alkali metal salt of bis (fluorosulfonyl) imide, comprising the following steps:
the alkali metal salt of bis (chlorosulfonyl) imide is prepared by the preparation method;
fluorinating the alkali metal salt of the bis-chlorosulfonyl imide to obtain the alkali metal salt of the bis-fluorosulfonyl imide.
Compared with the existing preparation method of the bis-fluorosulfonyl imide alkali metal salt, the preparation method provided by the invention can effectively simplify the preparation process and improve the product yield, and has the advantages of easily available raw materials, simple process, high raw material utilization rate, simple and easily-controlled reaction process and suitability for industrial production.
In some embodiments, the alkali metal bis-chlorosulfonyl imide salt is fluorinated with an alkali metal fluoride salt.
The present invention is further illustrated by the following examples.
Example 1
This example is intended to illustrate the preparation of alkali metal salts of bis (chlorosulfonyl) imide disclosed in the present invention, which comprises the following steps:
under nitrogen protection and stirring, 500g of thionyl chloride (4.2 mol) and 226.8g of anhydrous potassium sulfamate (1.68 mol) were added into a dry 1L three-necked flask, and an ice bath was started to cool the system to 0 ℃. Adding 195.8g of chlorosulfonic acid (1.68 mol) into a dry constant-pressure dropping funnel under the protection of nitrogen, then dropping into a three-necked bottle, controlling the dropping speed and keeping the internal temperature of the system to be less than or equal to 5 ℃. After the dropwise addition, the mixture is continuously stirred for 2 hours at the temperature of 5 ℃, and then the temperature is slowly increased to 25 ℃ to continuously react for 4 hours. Drying at 50 deg.C under reduced pressure to obtain crude solid. The crude solid product is recrystallized by anhydrous acetonitrile to obtain the potassium bis (chlorosulfonyl) imide.
Example 2
This example is intended to illustrate the preparation of alkali metal salts of bis (chlorosulfonyl) imide disclosed in the present invention, which comprises the following steps:
under the protection of nitrogen and with stirring, 500g of thionyl chloride (4.2 mol) and 173g of anhydrous lithium sulfamate (1.68 mol) were added into a dry 1L three-necked flask, and an ice bath was started to cool the system to 0 ℃. Adding 195.8g of chlorosulfonic acid (1.68 mol) into a dry constant-pressure dropping funnel under the protection of nitrogen, then dropping into a three-necked bottle, controlling the dropping speed and keeping the internal temperature of the system to be less than or equal to 5 ℃. After the dropwise addition, stirring is continued for 2h at 5 ℃, and then the temperature is slowly raised to 25 ℃ for further reaction for 4h. Drying at 50 deg.C under reduced pressure to obtain crude solid. And dissolving the crude solid with anhydrous acetonitrile, and recrystallizing to obtain the lithium bis (chlorosulfonyl) imide.
Example 3
This example is intended to illustrate the preparation of an alkali metal salt of bis (chlorosulfonyl) imide disclosed in the present invention, which comprises the following steps:
under nitrogen protection and stirring, 500g of thionyl chloride (4.2 mol) and 226.8g of anhydrous potassium sulfamate (1.68 mol) were added into a dry 1L three-necked flask, and an ice bath was started to cool the system to 5 ℃. 195.8g chlorosulfonic acid (1.68 mol) is added into a dry constant pressure dropping funnel under the protection of nitrogen, and then is dropped into a three-necked bottle, the dropping speed is controlled, and the internal temperature of a maintaining system is less than or equal to 10 ℃. After the dropwise addition, stirring is continued for 2h at 10 ℃, and then the temperature is slowly raised to 25 ℃ for further reaction for 4h. And (3) drying at 50 ℃ under reduced pressure to obtain a crude solid, and recrystallizing the crude solid by using anhydrous acetonitrile to obtain the potassium bis (chlorosulfonyl) imide.
Example 4
This example is intended to illustrate the preparation of alkali metal salts of bis (fluorosulfonyl) imide disclosed in this invention, comprising the following steps:
under the protection of nitrogen and stirring, 350g of anhydrous acetonitrile and 150g of anhydrous potassium fluoride (2 mol) are added into a dry 1L three-necked bottle, a prepared KClSI/acetonitrile solution (135 g of KClSI is dissolved in 200g of anhydrous acetonitrile at room temperature) is added into a dry constant-pressure dropping funnel under the protection of nitrogen, then the mixture is dropwise added into the three-necked bottle, the dropwise adding speed is controlled, and the internal temperature of a maintaining system is kept to be less than or equal to 60 ℃. After the dropwise addition, the reaction is continued for 12 hours at 80 ℃, and then the temperature is reduced and the reaction is cooled to room temperature. Filtering, and drying the filtrate under reduced pressure to obtain a crude solid.
Comparative example 1
This comparative example is used to illustrate the preparation of alkali metal salts of bis (chlorosulfonyl) imide disclosed in the present invention, comprising the following steps:
500g of thionyl chloride (4.2 mol), 163g of anhydrous sulfamic acid (1.68 mol) and 125.2g of anhydrous potassium chloride (1.68 mol) are added into a dry 1L three-necked bottle under nitrogen protection and stirring, an ice bath is started, and the temperature is reduced to 0 ℃. Adding 195.8g of chlorosulfonic acid (1.68 mol) into a dry constant-pressure dropping funnel under the protection of nitrogen, then dropping into a three-necked bottle, controlling the dropping speed and keeping the internal temperature of the system to be less than or equal to 5 ℃. Stirring for 2h at 5 ℃ after the dropwise addition is finished, slowly heating to 25 ℃ for reacting for 4h, filtering to obtain a mixed solution after the reaction, and drying the filtrate under reduced pressure to obtain a crude solid.
Comparative example 2
This comparative example is for comparative illustration of the process for preparing alkali metal salts of bis (fluorosulfonyl) imide disclosed in the present invention, comprising the following steps:
under the protection of nitrogen, 350g of anhydrous acetonitrile and 150g of anhydrous potassium fluoride (2 mol) are added into a dry 1L three-neck bottle under stirring, 214g of HClSI is added into a dry constant-pressure dropping funnel under the protection of nitrogen, then the mixture is dripped into the three-neck bottle, the dripping speed is controlled, and the temperature in a system is kept to be less than or equal to 60 ℃. After the dropwise addition, the reaction is continued for 12 hours at 80 ℃, and then the temperature is reduced and the reaction is cooled to room temperature. Filtering to obtain a mixed solution after reaction, and drying the filtrate under reduced pressure to obtain a crude solid which has large acid mist at room temperature.
Performance test
(1) The crude solids prepared in examples 1 to 3 and comparative example 1 were weighed and the yield thereof was calculated, and the alkali metal salt of bischlorosulfonimide recrystallized in examples 1 to 3 and comparative example 1 was weighed and the crystallization yield thereof was calculated.
The test results obtained are filled in table 1.
TABLE 1
From the test results in table 1, it can be seen that the use of alkali metal salt of sulfamic acid as a reactant of the present invention can effectively lower the temperature required for the reaction to proceed, and the yield of the product is higher, compared to the use of sulfamic acid as a reactant.
(2) The crude solids prepared in example 4 and comparative example 2 above were weighed and the yield calculated and the purity checked by IC.
The test results obtained are filled in table 2.
TABLE 2
From the test results in table 2, compared with the fluorination operation using HClSI, the preparation method provided by the invention uses the alkali metal bis (chlorosulfonyl) imide salt to perform the fluorination operation to prepare the alkali metal bis (fluorosulfonyl) imide salt, so that the preparation process can be effectively simplified, and the product yield can be improved.
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 (10)
1. The preparation method of the alkali metal salt of the bis-chlorosulfonyl imide is characterized by comprising the following operation steps of:
alkali metal salt of sulfamic acid, thionyl chloride and chlorosulfonic acid are used as reactants to react to obtain a mixture containing alkali metal salt of dichlorosulfonimide, and the mixture is purified to obtain alkali metal salt of dichlorosulfonimide.
2. The method for producing an alkali metal salt of bis (chlorosulfonyl) imide according to claim 1, wherein the molar addition amounts of the alkali metal salt of sulfamic acid, thionyl chloride and chlorosulfonic acid are in the following ratios: 1: 2.2-2.8: 1 to 1.05.
3. The method for preparing an alkali metal salt of bis-chlorosulfonyl imide according to claim 1, wherein said alkali metal salt of sulfamic acid comprises one or more of a lithium salt of sulfamic acid, a sodium salt of sulfamic acid and a potassium salt of sulfamic acid.
4. The method for producing an alkali metal salt of bischlorosulfonimide according to claim 1, wherein said alkali metal salt of sulfamic acid and thionyl chloride are mixed together and said mixture is added dropwise to said chlorosulfonic acid under stirring to react therewith.
5. The method for producing an alkali metal salt of bischlorosulfonimide according to claim 4, wherein the temperature of the reaction system is controlled to 0 to 60 ℃ during the reaction charging.
6. The method for preparing alkali metal salt of bis (chlorosulfonyl) imide according to claim 4, wherein the temperature of the reaction mixture is maintained at 5 to 80 ℃ for 2 to 20 hours after the completion of the charging.
7. The method for producing an alkali metal salt of bis (chlorosulfonyl) imide according to claim 1, wherein the reaction is carried out in a protective atmosphere which does not participate in the reaction.
8. The method for preparing alkali metal salt of bis (chlorosulfonyl) imide according to claim 1, wherein after completion of the reaction, unreacted materials are distilled off, and the solid remaining at the bottom of the reaction vessel is crude alkali metal salt of bis (chlorosulfonyl) imide.
9. The method for preparing an alkali metal salt of bischlorosulfonimide according to claim 8, wherein said crude alkali metal salt of bischlorosulfonimide is recrystallized by adding a polar aprotic solvent to obtain an alkali metal salt of bischlorosulfonimide.
10. The preparation method of the bis-fluorosulfonyl imide alkali metal salt is characterized by comprising the following operation steps:
an alkali metal salt of bis (chlorosulfonyl) imide produced by the production method according to any one of claims 1 to 9;
fluorinating the alkali metal salt of the bis-chlorosulfonyl imide to obtain the alkali metal salt of the bis-fluorosulfonyl imide.
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