CN106276829A - A kind of synthetic method of pair of fluorine sulfimide lithium - Google Patents
A kind of synthetic method of pair of fluorine sulfimide lithium Download PDFInfo
- Publication number
- CN106276829A CN106276829A CN201610703561.7A CN201610703561A CN106276829A CN 106276829 A CN106276829 A CN 106276829A CN 201610703561 A CN201610703561 A CN 201610703561A CN 106276829 A CN106276829 A CN 106276829A
- Authority
- CN
- China
- Prior art keywords
- lithium
- pair
- synthetic method
- fluorine sulfimide
- double
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/32—Thermal properties
- C01P2006/33—Phase transition temperatures
- C01P2006/34—Melting temperatures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
- C01P2006/82—Compositional purity water content
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides the method for a kind of pair of fluorine sulfimide lithium of synthesis, step is as follows: the synthetic method of a kind of pair of fluorine sulfimide lithium, it is characterized in that, synthetic method comprises the following steps: 1) in nitrogen atmosphere, inserting in the reactor of band condenser after double chlorine sulfimides and organic solvent being sufficiently mixed, with being sequentially added into lithium fluoride in backward reactor, liquid hydrogen fluoride heats up and reacts；2) reduce the decompression displacement of temperature of reaction system nitrogen and completely remove the hydrogen fluoride gas of remnants, and filtering reacting liquid removing insoluble matter obtains filtrate under nitrogen atmosphere；3) use fine vacuum decompression precipitation method that filtrate is concentrated 4) after concentrated solution cooling, add weak polar solvent low temperature recrystallization, filter and drying under reduced pressure obtains pure double fluorine sulfimide lithium after processing at 40 DEG C, the present invention uses reagent cheap and easy to get, preparation technology is simple, it is swift in response and thoroughly, by-product is few and easy removing, post processing mode are easy, and product purity is high, is especially suitable for industrialized production.
Description
Technical field
The invention belongs to the field of chemical synthesis, be specifically related to the synthetic method of a kind of pair of fluorine sulfimide lithium.
Background technology
It is good and more environment-friendly etc. excellent that double fluorine sulfimide lithium have stability high and low temperature excellent performance, hydrolytic stability
Point simultaneously because it has the electric conductivity of excellence, can be used for ultracapacitor as excellent serondary lithium battery electrolyte
And aluminium electrolutic capacitor etc.；Also act as lewis acid catalyst to use, there is important industrial production value.
In prior art, mainly there is a following report for the preparation of double (fluorine sulphonyl) imine lithium:
China CN101747242 reports the preparation method of double (fluorine sulphonyl) imine lithium, under the protection of nitrogen by sulfamic acid,
Thionyl chloride, chlorosulfonic acid carry out reaction and generate double (chlorine sulphonyl) imines, and yield is 82%；Again by double (chlorine sulphonyl) imines at nitrogen
Protection is lower generates double (fluorine sulphonyl) imines potassium with anhydrous Antimony fluoride, acetonitrile reaction, and yield is 78%；Subsequently by 91.5 grams (-
Double (fluorine sulphonyl) imines potassium 0.42mol) react, warp with the second eyeball solution 150ml (containing 36.2 grams of lithium perchlorates) of lithium perchlorate
Crossing recrystallization, obtain 62 grams (0.33mol) double (fluorine sulphonyl) imine lithium after drying, yield is 79%, final products total recovery
50.5%.The method must operate in vacuum tank, and cost is high, and the yield only (50.5%) of double (fluorine sulphonyl) imine lithium, raw material is easy
It is dissolved in organic solvent, it is impossible to obtain highly purified double (fluorine sulphonyl) imine lithium.
Chinese Patent Application No. be 201280010507.4 patent application disclose the system of a kind of fluorine-containing sulfimide salt
Make method, described manufacture method by making N, fluorine-containing sulfimide ammonium salt and the hydroxide such as N-bis-(fluorosulfonyl) imines ammonium salt
Under reduced pressure, the low temperature of about 40 DEG C reacts the alkali metal hydroxides such as lithium, potassium hydroxide, sodium hydroxide, obtains N, N-
Two (fluorosulfonyl) imines lithium salts, N, N-bis-(fluorine sulphur lithio) imide, N, N-bis-(fluorine sulfonephthalein base) imines sodium salt etc. are fluorine-containing
Sulfonephthalein imine alkali metal salt.But, there is the defect that raw material is difficult to obtain in described manufacture method, course of reaction produces substantial amounts of
Heat, product has the probability of decomposes, is not suitable for industrialized production.
The preparation method of double (fluorine sulphonyl) imine lithiums of Chinese patent CN103524387A report, first use thionyl chloride,
Sulfamic acid, chlorosulfonic acid react in a reaction vessel, do not carry out double chlorine sulfimine compound (HN [SOzCl]
Z) separation of product, is directly added into thionyl chloride and anhydrous lithium salts carries out reaction and prepares double chlorine sulfimide lithium salts, removes chlorination
After sulfoxide solvent, add people's organic solvent, a small amount of triethylamine, utilize anhydrous zinc fluoride to carry out fluorination reaction, filter, filtrate be evaporated or
Imidodisulfuryl fluoride lithium salt is obtained after recrystallization drying under reduced pressure.Reactions steps is the most loaded down with trivial details, and reagent type is more, has bigger
Probability introduces other impurity, and the zinc chloride that the fluorization agent zinc fluoride reaction of this reaction is formed easily remains in solvent, makes final obtaining
The product arrived is impure.
The preparation method of double (fluorine sulphonyl) imine lithiums of China's CN103664712A report, concentrated sulphuric acid, KN (SO2F) 2, two
Silicon oxide mix and blend, is passed through nitrogen, and air-distillation obtains crude product HFSI, and then distillation column rectification obtains sterling HFSI, carbonic acid
Lithium and deionized water are made into suspension, are then slowly added dropwise HFSI aqueous solution, and about 50 DEG C, PH=6-6.3, stopped reaction, by anti-
Answer liquid to be spray-dried, obtain pressed powder, then about 200 DEG C high, 1-6Pa vacuum drying, finally obtain sterling LiFSI.
HFSI and lithium carbonate react in water environment, and exothermic heat of reaction, product is easy to reaction of decomposing, and the band of water in aqueous
Enter to make precipitation to be dried and become highly difficult.
JP2013091524 has carried out relatively systematic research to the stability of LiFSI, find LiFSI in temperature more than 40 DEG C
Environment in, decomposition rate is accelerated, and moisture is the biggest, decomposes the fastest.
Summary of the invention
In order to overcome above-mentioned technical problem, the invention provides the preparation method of a kind of pair of fluorine sulfimide lithium, the present invention
Use reagent is cheap and easy to get, and preparation technology is simple, is swift in response and thoroughly, and by-product is few and easy removing, post processing mode are easy,
Product purity is high, is especially suitable for industrialized production.
A kind of synthetic method of pair of fluorine sulfimide lithium, synthetic method comprises the following steps:
1) in nitrogen atmosphere, insert in the reactor of band condenser after double chlorine sulfimides and organic solvent are sufficiently mixed,
The addition of described organic solvent is 2 ~ 4 times of the weight of double chlorine sulfimide, with backward reactor is sequentially added into lithium fluoride,
Liquid hydrogen fluoride, then heats to 40 ~ 60 DEG C, reacts 8 ~ 12 hours, and reaction equation is as follows: HN (SO2Cl) 2+LiF+HF → LiN
(SO2F)2+2HCl；
2) reduction temperature of reaction system is to 20 ~ 25 DEG C, replaces with nitrogen decompression and completely removes remaining hydrogen fluoride gas, and
The reactant liquor retained in filtration reactor under nitrogen atmosphere, removes insoluble matter and obtains filtrate；
3) use fine vacuum decompression precipitation method at 40 ~ 60 DEG C by step 2) in filtrate be concentrated in step (1) the double chlorine of raw material
1 ~ 2 times of sulfimide quality obtains concentrated solution；
4) concentrated solution of step 3) is cooled to 20 ~ 25 DEG C, in aforesaid concentrated solution, adds weak polar solvent low temperature heavily tie
Crystalline substance, mixing speed is 500 ~ 1000r/min, and described weak polar solvent is the organic solvent of polarity≤3.4, weak polar solvent
Temperature is 10 ~ 25 DEG C, and described concentrated solution is 1:3 ~ 10, preferably 1:4 ~ 7, most preferably 1:5 with the volume ratio of weak polar solvent, filters
And drying under reduced pressure obtains pure double fluorine sulfimide lithium after processing at 40 DEG C.
Further, the purity of of the present invention pair of chlorine sulfimide is more than 99%, and the purity of lithium fluoride is more than 99%, fluohydric acid gas
Purity more than 99%.
Further, by step 2 in step 3) of the present invention) in filtrate use thin film evaporation to be concentrated into the double chlorine sulphur of raw material
1.2 times of acid imide quality.
Further, the organic solvent described in step of the present invention (1) is the one in esters, ethers, nitrile or several
The mixture planted.
Further, the organic solvent purity described in step 1) of the present invention is more than 99%, and water content is less than 50ppm.
Further, the reaction temperature described in step 1) of the present invention is 40 DEG C, and the described response time is 10 hours.
Further, described in step 1) of the present invention, double chlorine sulfimides, lithium fluoride, the mol ratio of fluohydric acid gas are 1:(1
~ 1.2): (1 ~ 1.4).
Further, described in step 1) of the present invention, double chlorine sulfimides, lithium fluoride, the mol ratio of fluohydric acid gas are 1:
1.1:1.2.
Further, the weak polar solvent described in step 4) of the present invention, dichloromethane, carbon tetrachloride, toluene, just oneself
The mixed solvent of one or more in alkane.
Further, of the present invention pair of chlorine sulfimide is mixed to prepare reaction by sulfamic acid, thionyl chloride, chlorosulfonic acid
Temperature is 120～140 DEG C, and the response time is 20～30 hours.
The beneficial effects of the present invention is: 1. this method preparing imidodisulfuryl fluoride lithium salt, use reagent inexpensive easily
, technique is simple, is swift in response and thoroughly.2. the present invention to reaction temperature, concentrate, crystallize, baking temperature is rationally controlled
System, overcome technology barriers, avoid product to greatest extent and decompose during post processing, it is ensured that high yield can
Can, obtain highly purified product simultaneously.3. the technical process of the present invention strictly controls the introducing of water, the complete raw material fluorinated lithium of unreacted
Being prone to remove insoluble in organic solvent, by-product is few and easy removing, the lithium salts of synthesis are not easily decomposed, post processing mode is easy, from
And significantly reduce the cost of product, and it is made to be more suitable for industrialized production.
Detailed description of the invention
Embodiment 1
The preparation method of a kind of pair of fluorine sulfimide lithium, comprises the following steps:
1) in nitrogen atmosphere, take 214g(1mol) double chlorine sulfimides, 428g ethyl acetate, insert full after being sufficiently mixed
Nitrogen with condensing tube, stirring, tail gas absorption 1000ml four-hole boiling flask in stir, the wherein purity 99.9% of ethyl acetate,
Water content 30ppm.Be sequentially added into 27.3g(1.05mol with in backward four-hole boiling flask) lithium fluoride, 24g(1.2mol) liquid fluorinated
Hydrogen, is warming up to 40 DEG C and reacts 10 hours, and reaction equation is as follows: HN (SO2Cl) 2+LiF+HF → LiN (SO2F) 2+2HCl, this enforcement
The double chlorine sulfimide of reactant used in example, lithium fluoride, the purity of fluohydric acid gas are all higher than 99%.
2) reduction temperature of reaction system is to 20 DEG C, replaces with nitrogen decompression and completely removes remaining hydrogen fluoride gas, and
The reactant liquor retained in filtration reactor under nitrogen atmosphere, is filtered to remove a small amount of solid impurity being wherein mixed with and obtains filtrate.
3) use fine vacuum decompression precipitation method at 50 DEG C by step 2) in filtrate to be concentrated into the double chlorine sulphonyl of middle raw material sub-
1.2 times of amine quality obtain concentrated solution.
4) concentrated solution of step 3) being cooled to 20 DEG C, the toluene low temperature adding 900ml in aforesaid concentrated solution is heavily tied
Crystalline substance, mixing speed is 600r/min, and the temperature of toluene is 10 DEG C, filters and drying under reduced pressure obtains pure 170g pair at 40 DEG C
Fluorine sulfimide lithium pressed powder, measures fusing point and is 135-137 DEG C, purity 99.92%, water content 42ppm, Na+ 、K+Content is little
In 5ppm.
Embodiment 2
The preparation method of a kind of pair of fluorine sulfimide lithium, comprises the following steps:
1) in nitrogen atmosphere, take 214g(1mol) double chlorine sulfimides, 428g acetonitrile, insert full nitrogen after being sufficiently mixed
With condensing tube, stirring, tail gas absorption 1000ml four-hole boiling flask in stir, the wherein purity 99.9% of acetonitrile, water content
40ppm, is sequentially added into 27.3g(1.05mol with in backward four-hole boiling flask) lithium fluoride, 24g(1.2mol) liquid hydrogen fluoride, heat up
Reacting 10 hours to 40 DEG C, reaction equation is as follows: HN (SO2Cl) 2+LiF+HF → LiN (SO2F) 2+2HCl, is made in the present embodiment
The double chlorine sulfimide of reactant, lithium fluoride, the purity of fluohydric acid gas be all higher than 99%.
2) reduction temperature of reaction system is to 20 DEG C, replaces with nitrogen decompression and completely removes remaining hydrogen fluoride gas, and
The reactant liquor retained in filtration reactor under nitrogen atmosphere, is filtered to remove a small amount of solid impurity being wherein mixed with and obtains filtrate.
3) use fine vacuum decompression precipitation method at 50 DEG C by step 2) in filtrate to be concentrated into the double chlorine sulphonyl of middle raw material sub-
1.2 times of amine quality obtain concentrated solution, use thin film evaporation, and this kind of precipitation mode, residence time of material is short, is particularly suitable for heat
The process of quick property material.
5) concentrated solution of step 3) is cooled to 20 DEG C, in aforesaid concentrated solution, adds the carbon tetrachloride low temperature of 900ml
Recrystallization, mixing speed is 800r/min, and the temperature of carbon tetrachloride is 25 DEG C, filters and drying under reduced pressure obtains pure at 40 DEG C
The double fluorine sulfimide lithium pressed powder of 168g, measure fusing point and be 135-137 DEG C, purity 99.91%, water content 44ppm, Na+ 、K+Content is less than 5ppm.
Embodiment 3
The preparation method of a kind of pair of fluorine sulfimide lithium, comprises the following steps:
1) in nitrogen atmosphere, take 214g(1mol) double chlorine sulfimides, 642g ethyl acetate, insert full after being sufficiently mixed
Nitrogen with condensing tube, stirring, tail gas absorption 1000ml four-hole boiling flask in stir, the wherein purity 99.9% of ethyl acetate,
Water content 30ppm, is sequentially added into 28.6g(1.1mol with in backward four-hole boiling flask) lithium fluoride, 24g(1.2mol) liquid fluorinated
Hydrogen, is warming up to 40 DEG C and reacts 10 hours, and reaction equation is as follows: HN (SO2Cl) 2+LiF+HF → LiN (SO2F) 2+2HCl, this enforcement
The double chlorine sulfimide of reactant used in example, lithium fluoride, the purity of fluohydric acid gas are all higher than 99%.
2) reduction temperature of reaction system is to 20 DEG C, replaces with nitrogen decompression and completely removes remaining hydrogen fluoride gas, and
The reactant liquor retained in filtration reactor under nitrogen atmosphere, is filtered to remove a small amount of solid impurity being wherein mixed with and obtains filtrate.
3) use fine vacuum decompression precipitation method at 50 DEG C by step 2) in filtrate to be concentrated into the double chlorine sulphonyl of middle raw material sub-
1.2 times of amine quality obtain concentrated solution.
4) concentrated solution of step 3) is cooled to 20 DEG C, add in aforesaid concentrated solution by the carbon tetrachloride of 450ml and
The mixed solvent low temperature recrystallization of 450ml toluene composition, mixing speed is 1000r/min, and the temperature of mixed solvent is 20 DEG C, mistake
Filter and drying under reduced pressure obtain the double fluorine sulfimide lithium pressed powder of pure 172g at 40 DEG C, measure fusing point and be 135-137 DEG C,
Purity 99.93%, water content 34ppm, Na+ 、K+Content is less than 5ppm.
Embodiment 4
The preparation method of a kind of pair of fluorine sulfimide lithium, comprises the following steps:
1) in nitrogen atmosphere, take 214g(1mol) double chlorine sulfimides, 642g oxolane, insert full after being sufficiently mixed
Nitrogen with condensing tube, stirring, tail gas absorption 1000ml four-hole boiling flask in stir, the wherein purity 99.9% of oxolane,
Water content 40ppm, is sequentially added into 26g(1mol with in backward four-hole boiling flask) lithium fluoride, 24g(1.2mol) liquid hydrogen fluoride, rise
Temperature is reacted 10 hours to 40 DEG C, and reaction equation is as follows: HN (SO2Cl) 2+LiF+HF → LiN (SO2F) 2+2HCl, institute in the present embodiment
The reactant lithium fluoride, the purity of fluohydric acid gas that use are all higher than 99%, and the most double chlorine sulfimides are by by sulfamic acid, protochloride
It is 120～140 DEG C that sulfone, chlorosulfonic acid are mixed to prepare reaction temperature, and the response time is 20～30 hours, double chlorine sulphonyl that reaction obtains
The imines Methods For Purification by rectification, purity is more than 99%.
2) reduction temperature of reaction system is to 20 DEG C, replaces with nitrogen decompression and completely removes remaining hydrogen fluoride gas, and
The reactant liquor retained in filtration reactor under nitrogen atmosphere, is filtered to remove a small amount of solid impurity being wherein mixed with and obtains filtrate.
3) use fine vacuum decompression precipitation method at 60 DEG C by step 2) in filtrate to be concentrated into the double chlorine sulphonyl of middle raw material sub-
1.2 times of amine quality obtain concentrated solution.
4) concentrated solution of step 3) is cooled to 20 DEG C, in aforesaid concentrated solution, adds the normal hexane low temperature weight of 900ml
Crystallization, mixing speed is 1000r/min, and the temperature of normal hexane is 15 DEG C, filters and drying under reduced pressure obtains pure at 40 DEG C
The double fluorine sulfimide lithium pressed powder of 166g, measures fusing point and is 135-137 DEG C, purity 99.85%, water content 44ppm, Na+ 、K+
Content is less than 5ppm.
Embodiment 5
The preparation method of a kind of pair of fluorine sulfimide lithium, comprises the following steps:
1) in nitrogen atmosphere, take 214g(1mol) double chlorine sulfimides, 642g ethyl acetate, insert full after being sufficiently mixed
Nitrogen with condensing tube, stirring, tail gas absorption 1000ml four-hole boiling flask in stir, the wherein purity 99.9% of ethyl acetate,
Water content 30ppm, is sequentially added into 28.6g(1.1mol with in backward four-hole boiling flask) lithium fluoride, 26g(1.3mol) liquid fluorinated
Hydrogen, is warming up to 40 DEG C and reacts 10 hours, and reaction equation is as follows: HN (SO2Cl) 2+LiF+HF → LiN (SO2F) 2+2HCl, this enforcement
Reactant lithium fluoride, the purity of fluohydric acid gas used in example are all higher than 99%, the most double chlorine sulfimides by by sulfamic acid,
It is 120～140 DEG C that thionyl chloride, chlorosulfonic acid are mixed to prepare reaction temperature, and the response time is 20～30 hours, and it is double that reaction obtains
The chlorine sulfimide Methods For Purification by rectification, purity is more than 99%.
2) reduction temperature of reaction system is to 20 DEG C, replaces with nitrogen decompression and completely removes remaining hydrogen fluoride gas, and
The reactant liquor retained in filtration reactor under nitrogen atmosphere, is filtered to remove a small amount of solid impurity being wherein mixed with and obtains filtrate.
3) use fine vacuum decompression precipitation method at 50 DEG C by step 2) in filtrate to be concentrated into the double chlorine sulphonyl of middle raw material sub-
1.2 times of amine quality obtain concentrated solution.
4) concentrated solution of step 3) is cooled to 20 DEG C, add in aforesaid concentrated solution by the carbon tetrachloride of 450ml and
The mixed solvent low temperature recrystallization of 450ml toluene composition, mixing speed is 1000r/min, and the temperature of mixed solvent is 18 DEG C, mistake
Filter and drying under reduced pressure obtain the double fluorine sulfimide lithium pressed powder of pure 173g at 40 DEG C, measure fusing point and be 135-137 DEG C,
Purity 99.93%, water content 34ppm, Na+ 、K+Content is less than 5ppm.
Embodiment 6
The preparation method of a kind of pair of fluorine sulfimide lithium, comprises the following steps:
1) in nitrogen atmosphere, take 214g(1mol) double chlorine sulfimides, 642g ethyl acetate, insert full after being sufficiently mixed
Nitrogen with condensing tube, stirring, tail gas absorption 1000ml four-hole boiling flask in stir, the wherein purity 99.9% of ethyl acetate,
Water content 30ppm, is sequentially added into 28.6g(1.1mol with in backward four-hole boiling flask) lithium fluoride, 26g(1.3mol) liquid fluorinated
Hydrogen, is warming up to 60 DEG C and reacts 10 hours, and reaction equation is as follows: HN (SO2Cl) 2+LiF+HF → LiN (SO2F) 2+2HCl, this enforcement
Reactant lithium fluoride, the purity of fluohydric acid gas used in example are all higher than 99%, the most double chlorine sulfimides by by sulfamic acid,
It is 120～140 DEG C that thionyl chloride, chlorosulfonic acid are mixed to prepare reaction temperature, and the response time is 20～30 hours, and it is double that reaction obtains
The chlorine sulfimide Methods For Purification by rectification, purity is more than 99%.
2) reduction temperature of reaction system is to 20 DEG C, replaces with nitrogen decompression and completely removes remaining hydrogen fluoride gas, and
The reactant liquor retained in filtration reactor under nitrogen atmosphere, is filtered to remove a small amount of solid impurity being wherein mixed with and obtains filtrate.
3) use fine vacuum decompression precipitation method at 40 DEG C by step 2) in filtrate to be concentrated into the double chlorine sulphonyl of middle raw material sub-
1.5 times of amine quality obtain concentrated solution.
4) concentrated solution of step 3) is cooled to 20 DEG C, adds by 1200ml dichloromethane low in aforesaid concentrated solution
Temperature recrystallization, mixing speed is 1000r/min, and the temperature of dichloromethane is 20 DEG C, filters and drying under reduced pressure obtains at 40 DEG C
The double fluorine sulfimide lithium pressed powder of pure 162g, measures fusing point and is 135-137 DEG C, purity 99.93%, water content 40ppm,
Na+ 、K+Content is less than 5ppm.
Embodiment 7
The preparation method of a kind of pair of fluorine sulfimide lithium, comprises the following steps:
1) in nitrogen atmosphere, take 214g(1mol) double chlorine sulfimides, 642g ethyl acetate, insert full after being sufficiently mixed
Nitrogen with condensing tube, stirring, tail gas absorption 1000ml four-hole boiling flask in stir, the wherein purity 99.9% of ethyl acetate,
Water content 30ppm, is sequentially added into 28.6g(1.1mol with in backward four-hole boiling flask) lithium fluoride, 26g(1.3mol) liquid fluorinated
Hydrogen, is warming up to 50 DEG C and reacts 10 hours, and reaction equation is as follows: HN (SO2Cl) 2+LiF+HF → LiN (SO2F) 2+2HCl, this enforcement
Reactant lithium fluoride, the purity of fluohydric acid gas used in example are all higher than 99%, the most double chlorine sulfimides by by sulfamic acid,
It is 120～140 DEG C that thionyl chloride, chlorosulfonic acid are mixed to prepare reaction temperature, and the response time is 20～30 hours, and it is double that reaction obtains
The chlorine sulfimide Methods For Purification by rectification, purity is more than 99%.
2) reduction temperature of reaction system is to 20 DEG C, replaces with nitrogen decompression and completely removes remaining hydrogen fluoride gas, and
The reactant liquor retained in filtration reactor under nitrogen atmosphere, is filtered to remove a small amount of solid impurity being wherein mixed with and obtains filtrate.
3) use fine vacuum decompression precipitation method at 40 DEG C by step 2) in filtrate to be concentrated into the double chlorine sulphonyl of middle raw material sub-
2 times of amine quality obtain concentrated solution.
4) concentrated solution of step 3) is cooled to 20 DEG C, add in aforesaid concentrated solution by 800ml dichloromethane and
The mixed solvent low temperature recrystallization of 800ml toluene composition, mixing speed is 1000r/min, and the temperature of mixed solvent is 20 DEG C, mistake
Filter and drying under reduced pressure obtain the double fluorine sulfimide lithium pressed powder of pure 155g at 40 DEG C, measure fusing point and be 135-137 DEG C,
Purity 99.96%, water content 44ppm, Na+ 、K+Content is less than 5ppm.
Claims (10)
1. the synthetic method of double fluorine sulfimide lithium, it is characterised in that synthetic method comprises the following steps:
In nitrogen atmosphere, insert in the reactor of band condenser after double chlorine sulfimides and organic solvent are sufficiently mixed, institute
State the weight that the addition of organic solvent is double chlorine sulfimide 2 ~ 4 times, with being sequentially added into lithium fluoride, liquid in backward reactor
State fluohydric acid gas, then heats to 40 ~ 60 DEG C, reacts 8 ~ 12 hours；
Reduction temperature of reaction system, to 20 ~ 25 DEG C, completely removes the hydrogen fluoride gas of remnants with nitrogen decompression displacement, and at nitrogen
The reactant liquor retained in filtration reactor under atmosphere, removes insoluble matter and obtains filtrate；
Use fine vacuum decompression precipitation method at 40 ~ 60 DEG C by step 2) in filtrate be concentrated in step (1) the double chlorine sulphur of raw material
1 ~ 2 times of acid imide quality obtains concentrated solution；
The concentrated solution of step 3) is cooled to 20 ~ 25 DEG C, in aforesaid concentrated solution, adds weak polar solvent low temperature recrystallization, stir
Mixing speed is 500 ~ 1000r/min, and described weak polar solvent is the organic solvent of polarity≤3.4, the temperature of weak polar solvent
Being 10 ~ 25 DEG C, described concentrated solution is 1:3 ~ 10 with the volume ratio of weak polar solvent, filters and after drying under reduced pressure process at 40 DEG C
Obtain pure double fluorine sulfimide lithium.
The synthetic method of a kind of pair of fluorine sulfimide lithium the most according to claim 1, it is characterised in that: double chlorine sulfimides
Purity more than 99%, the purity of lithium fluoride is more than 99%, and the purity of fluohydric acid gas is more than 99%.
The synthetic method of a kind of pair of fluorine sulfimide lithium the most according to claim 1, it is characterised in that: institute in step (1)
The organic solvent purity stated is more than 99%, and water content is less than 50ppm.
4. according to the synthetic method of a kind of pair of fluorine sulfimide lithium described in any claim in claim 1 or 2 or 3, its
Be characterised by: by step 2 in step 3)) in filtrate use thin film evaporation to be concentrated into the 1.2 of the double chlorine sulfimide quality of raw material
Times.
5. according to the synthetic method of a kind of pair of fluorine sulfimide lithium described in any claim in claim 1 or 2 or 3, its
It is characterised by: the organic solvent described in step 1) is the mixture of one or more in esters, ethers, nitrile.
6. according to the synthetic method of a kind of pair of fluorine sulfimide lithium described in any claim in claim 1 or 2 or 3, its
Being characterised by: the reaction temperature described in step 1) is 40 DEG C, the described response time is 10 hours.
7. according to the synthetic method of a kind of pair of fluorine sulfimide lithium described in any claim in claim 1 or 2 or 3, its
It is characterised by: described in step 1), double chlorine sulfimides, lithium fluoride, the mol ratio of fluohydric acid gas are 1:(1 ~ 1.2): (1 ~ 1.4).
The synthetic method of a kind of pair of fluorine sulfimide lithium the most according to claim 7, it is characterised in that: described in step 1)
Double chlorine sulfimides, lithium fluoride, the mol ratio of fluohydric acid gas are 1:1.1:1.2.
9. according to the synthetic method of a kind of pair of fluorine sulfimide lithium described in any claim in claim 1 or 2 or 3 or 8,
It is characterized in that: the weak polar solvent described in step 4) be the one in dichloromethane, carbon tetrachloride, toluene, normal hexane or
Several mixed solvents.
10. according to the synthesis side of a kind of pair of fluorine sulfimide lithium described in any claim in claim 1 or 2 or 3 or 8
Method, it is characterised in that: described double chlorine sulfimides are mixed to prepare reaction temperature by sulfamic acid, thionyl chloride, chlorosulfonic acid are
120～140 DEG C, the response time is 20～30 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610703561.7A CN106276829B (en) | 2016-08-23 | 2016-08-23 | A kind of synthetic method of double fluorine sulfimide lithiums |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610703561.7A CN106276829B (en) | 2016-08-23 | 2016-08-23 | A kind of synthetic method of double fluorine sulfimide lithiums |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106276829A true CN106276829A (en) | 2017-01-04 |
| CN106276829B CN106276829B (en) | 2018-08-07 |
Family
ID=57662251
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610703561.7A Active CN106276829B (en) | 2016-08-23 | 2016-08-23 | A kind of synthetic method of double fluorine sulfimide lithiums |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106276829B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111527045A (en) * | 2018-04-10 | 2020-08-11 | 株式会社Lg化学 | Method for preparing lithium bis (fluorosulfonyl) imide |
| CN111547689A (en) * | 2020-04-26 | 2020-08-18 | 广州理文科技有限公司 | Chemical drying and purifying method of diimine lithium |
| CN112174101A (en) * | 2020-09-23 | 2021-01-05 | 湖南博信新能源科技有限公司 | Preparation method of high-purity lithium bis (fluorosulfonyl) imide |
| CN112320772A (en) * | 2020-11-24 | 2021-02-05 | 泰兴华盛精细化工有限公司 | Preparation method of lithium bis (fluorosulfonyl) imide |
| CN112479165A (en) * | 2020-11-27 | 2021-03-12 | 湖北迈可凯科技有限公司 | Method for synthesizing lithium bis (fluorosulfonyl) imide by one-step method |
| CN112850667A (en) * | 2021-02-05 | 2021-05-28 | 广东巨氟节能技术有限公司 | Synthetic method of liquid-cooled fluorinated liquid of data center |
| CN113247871A (en) * | 2021-06-04 | 2021-08-13 | 江苏华盛锂电材料股份有限公司 | Preparation method of lithium bis (fluorosulfonyl) imide |
| US11267707B2 (en) | 2019-04-16 | 2022-03-08 | Honeywell International Inc | Purification of bis(fluorosulfonyl) imide |
| WO2022199643A1 (en) * | 2021-03-26 | 2022-09-29 | 广州理文科技有限公司 | Synthesis method for bis(fluorosulfonyl)imide |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040097757A1 (en) * | 2000-12-29 | 2004-05-20 | Milos Cernik | Method for fluorinating a compound comprising a halosulphonyl or dihalophosphonyl group |
| JP2013091524A (en) * | 2011-08-12 | 2013-05-16 | Nippon Shokubai Co Ltd | Package obtained by packaging ionic compound containing fluorine atom or ionic compound-containing composition containing fluorine atom |
| CN101747242B (en) * | 2008-11-28 | 2013-06-19 | 华中科技大学 | Method for preparing bi-(sulfonyl fluoride) imine and (fluorinated alkyl sulfonyl fluorine sulfonyl) imine alkali metal salt |
| CN103524387A (en) * | 2013-10-25 | 2014-01-22 | 中国海洋石油总公司 | Preparation method of imidodisulfuryl fluoride lithium salt |
| CN103664712A (en) * | 2013-11-27 | 2014-03-26 | 中国船舶重工集团公司第七一八研究所 | Method for preparing fluorine sulfimide lithium |
| CN104495767A (en) * | 2014-11-21 | 2015-04-08 | 湖南有色郴州氟化学有限公司 | Preparation method of lithium bis(fluorosulfonyl)amide |
| CN105731399A (en) * | 2016-04-29 | 2016-07-06 | 多氟多化工股份有限公司 | Preparation method of difluoro-sulfonyl imide lithium |
-
2016
- 2016-08-23 CN CN201610703561.7A patent/CN106276829B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040097757A1 (en) * | 2000-12-29 | 2004-05-20 | Milos Cernik | Method for fluorinating a compound comprising a halosulphonyl or dihalophosphonyl group |
| CN101747242B (en) * | 2008-11-28 | 2013-06-19 | 华中科技大学 | Method for preparing bi-(sulfonyl fluoride) imine and (fluorinated alkyl sulfonyl fluorine sulfonyl) imine alkali metal salt |
| JP2013091524A (en) * | 2011-08-12 | 2013-05-16 | Nippon Shokubai Co Ltd | Package obtained by packaging ionic compound containing fluorine atom or ionic compound-containing composition containing fluorine atom |
| CN103524387A (en) * | 2013-10-25 | 2014-01-22 | 中国海洋石油总公司 | Preparation method of imidodisulfuryl fluoride lithium salt |
| CN103664712A (en) * | 2013-11-27 | 2014-03-26 | 中国船舶重工集团公司第七一八研究所 | Method for preparing fluorine sulfimide lithium |
| CN104495767A (en) * | 2014-11-21 | 2015-04-08 | 湖南有色郴州氟化学有限公司 | Preparation method of lithium bis(fluorosulfonyl)amide |
| CN105731399A (en) * | 2016-04-29 | 2016-07-06 | 多氟多化工股份有限公司 | Preparation method of difluoro-sulfonyl imide lithium |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021505510A (en) * | 2018-04-10 | 2021-02-18 | エルジー・ケム・リミテッド | Method for producing lithium bis (fluorosulfonyl) imide salt |
| CN111527045A (en) * | 2018-04-10 | 2020-08-11 | 株式会社Lg化学 | Method for preparing lithium bis (fluorosulfonyl) imide |
| EP3750848A4 (en) * | 2018-04-10 | 2021-06-09 | Lg Chem, Ltd. | Method for preparing lithium bis(fluorosulfonyl)imide salt |
| US11618687B2 (en) * | 2018-04-10 | 2023-04-04 | Lg Energy Solution, Ltd. | Method for preparing lithium bis(fluorosulfonyl)imide salt |
| US11267707B2 (en) | 2019-04-16 | 2022-03-08 | Honeywell International Inc | Purification of bis(fluorosulfonyl) imide |
| CN111547689A (en) * | 2020-04-26 | 2020-08-18 | 广州理文科技有限公司 | Chemical drying and purifying method of diimine lithium |
| CN112174101A (en) * | 2020-09-23 | 2021-01-05 | 湖南博信新能源科技有限公司 | Preparation method of high-purity lithium bis (fluorosulfonyl) imide |
| CN112320772A (en) * | 2020-11-24 | 2021-02-05 | 泰兴华盛精细化工有限公司 | Preparation method of lithium bis (fluorosulfonyl) imide |
| CN112479165A (en) * | 2020-11-27 | 2021-03-12 | 湖北迈可凯科技有限公司 | Method for synthesizing lithium bis (fluorosulfonyl) imide by one-step method |
| CN112479165B (en) * | 2020-11-27 | 2023-08-08 | 湖北迈可凯科技有限公司 | Method for synthesizing lithium difluorosulfimide by one-step method |
| CN112850667A (en) * | 2021-02-05 | 2021-05-28 | 广东巨氟节能技术有限公司 | Synthetic method of liquid-cooled fluorinated liquid of data center |
| WO2022199643A1 (en) * | 2021-03-26 | 2022-09-29 | 广州理文科技有限公司 | Synthesis method for bis(fluorosulfonyl)imide |
| CN113247871B (en) * | 2021-06-04 | 2021-09-24 | 江苏华盛锂电材料股份有限公司 | Preparation method of lithium bis (fluorosulfonyl) imide |
| CN113247871A (en) * | 2021-06-04 | 2021-08-13 | 江苏华盛锂电材料股份有限公司 | Preparation method of lithium bis (fluorosulfonyl) imide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106276829B (en) | 2018-08-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106276829B (en) | A kind of synthetic method of double fluorine sulfimide lithiums | |
| CN107074543B (en) | Preparation of imides containing fluorosulfonyl groups | |
| CN108002355B (en) | A kind of preparation method of imidodisulfuryl fluoride lithium salt | |
| EP2660196B1 (en) | Manufacturing method for fluorosulfonylimide ammonium salt | |
| CN106044728B (en) | A kind of preparation method of imidodisulfuryl fluoride lithium salt | |
| KR101890787B1 (en) | Process for producing lithium bisfluorosulfonylimide | |
| CN106006586B (en) | A kind of preparation method of double fluorine sulfimide potassium | |
| WO2015143866A1 (en) | Preparation method for bis-fluorosulfonyl imide and alkali metal salts thereof | |
| KR102294348B1 (en) | Method for producing high purity fluoroethylene carbonate | |
| CN113135554A (en) | Preparation method of lithium bis (fluorosulfonyl) imide | |
| CN104477861B (en) | Preparation method of difluoro-sulfonyl imine salt | |
| CN107986248B (en) | Preparation method of bis (fluorosulfonyl) imide | |
| CN106241757A (en) | A kind of preparation method of imidodisulfuryl fluoride lithium salt | |
| CN104495767A (en) | Preparation method of lithium bis(fluorosulfonyl)amide | |
| CN111517293B (en) | Preparation method of bis-fluorosulfonyl imide compound and metal salt thereof | |
| CN113511639A (en) | Lithium bis (fluorosulfonyl) imide and preparation method and application thereof | |
| CN101747242A (en) | Method for preparing bi-(sulfonyl fluoride) imine and (fluorinated alkyl sulfonyl fluorine sulfonyl) imine alkali metal salt | |
| CN102153493A (en) | Novel method for preparing di(trimethyl fluoride sulfonyl)imine lithium | |
| CN113979454B (en) | Preparation method of alkali metal fluorosulfonate | |
| CN113929711A (en) | Preparation method of lithium difluoroborate | |
| CN113912028A (en) | Method for purifying bis (fluorosulfonyl) imide | |
| CN106829891A (en) | A kind of pair of preparation method of fluorine sulfimide lithium | |
| CN102786452B (en) | Preparation method of bis(sulfonyl fluoride) imine and (perfluoroalkyl sulfonyl fluorine sulfonyl) imine alkali metal salt | |
| CN116143088A (en) | Preparation method of difluoro-sulfonyl imide and difluoro-sulfonyl imide lithium | |
| CA3200173A1 (en) | Method for producing onium sulfonyl imide salts and alkali metal sulfonyl imide salts |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: No.8 Xingyu Road, Rongcheng City, Weihai City, Shandong Province, 264300 Patentee after: QING MU HIGH-TECH MATERIALS Co.,Ltd. Address before: 264300 south of Rongchang Road, Rongcheng City, Weihai City, Shandong Province Patentee before: RONGCHENG QING MU HIGH-TECH MATERIALS Co.,Ltd. |
|
| CP03 | Change of name, title or address |