CN110436424A - A kind of preparation method of double fluorine sulfimides and double fluorine sulfimide lithiums - Google Patents
A kind of preparation method of double fluorine sulfimides and double fluorine sulfimide lithiums Download PDFInfo
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Abstract
To overcome by-product existing for the preparation method of existing double fluorine sulfimides more, the problem that yield is low and reaction condition is uncontrollable, the present invention provides a kind of preparation methods of double fluorine sulfimides, including following operating procedure: preparation S.nHF complex compound, wherein compound S is selected from liquefied ammonia, N, N '-dimethyl formamide, N, N '-dimethyl acetamide, hexamethyl phosphoramide, 1-Methyl-2-Pyrrolidone, tetramethylurea, N, the third urea of N '-dimethyl, 1, 3- dimethyl-2-imidazolinone, 1, 3- di-n-butyl -2- imidazolone, melamine, one of poly- (vinylpyridine) and ester type compound are a variety of；S.nHF complex compound is mixed with double chlorine sulfimides, collects the fraction of double fluorine sulfimides.Meanwhile the invention also discloses a kind of preparation methods of double fluorine sulfimide lithiums.The preparation method of double fluorine sulfimides provided by the invention can be effectively reduced the generation of by-product, improve the yield of double fluorine sulfimides.
Description
Technical field
The invention belongs to fluorochemical preparation technical fields, and in particular to a kind of double fluorine sulfimides and double fluorine sulphonyl are sub-
The preparation method of amine lithium.
Background technique
Double fluorine sulfimide lithium LiFSI are high-performance crucial in the new energy devices such as lithium ion battery, supercapacitor
Electrolyte has very high industrial application value.
The synthetic method of existing one kind LiFSI is directly to react preparation LiFSI, such as patent with lithium fluoride LiF using HClSI
Documented by US2004097757, this kind of preparation method can generate a large amount of corrosive gas hydrogen fluoride, while excessive LiF
It is difficult to be completely separated with LiFSI, to influence the quality of product.
The synthetic method of existing major part LiFSI is first to synthesize double chlorine sulfimide HClSI, then by itself and fluoro metal
Salt MFxReaction, prepares corresponding double fluorine sulfimide salt intermediates, the intermediate again with lithium hydroxide LiOH or lithium carbonate
Li2CO3Carry out cationic exchange system and obtain LiFSI, as patent US2013331609, US2012041233, EP2415757,
Documented by US2011034716, CN101747242A, the defect of such methods is to be difficult after cation exchange reaches balance
Continue completely, the complete intermediate of unreacted is difficult to be kept completely separate with LiFSI, to be unable to get the product of high-quality.
Existing method the most cost-effective be directly adopt double fluorine sulfimide HFSI directly with LiOH or Li2CO3Instead
It answers, generates LiFSI.Therefore it synthesizes and purification intermediate HFSI has become the key for preparing LiFSI.
In the patent US8377406B1 of U.S. Boulder Ionics Corporation, by by HClSI with it is borontrifluoride
Bismuth BiF3Reaction synthesis HFSI, there are BiF for this method3The higher problem of cost of material, while generating a large amount of by-product tri-chlorination
Bismuth BiCl3, which is processed into BiF3Process is cumbersome and long flow path, is not suitable for industrialized production.
It is to use in patent CN 104925765A and the CN 106044728A of Chemspec International Ltd
HClSI reacts to obtain HFSI under the action of catalyst under 100 DEG C or so with hydrogen fluoride HF, since the boiling point of hydrogen fluoride only has 19
DEG C and there is strong corrosive, therefore the reaction is related to high temperature and pressure, and has very high requirement to equipment material, in industrialized production
There is security risk in the process.
In the patent CN 106829892A of Wuhan Haisipulin Technology Development Co., Ltd., by by chlorosulfonic acid isocyanic acid
Ester ClSO2NCO and fluosulfonic acid FSO3H reacts to obtain HFSI, and there are problems for this method are as follows: FSO3H is super acid, and corrosivity is strong, generally
Equipment can not be resistant to, and unreacted FSO3Close to (171 DEG C), common distillation can not be completely separated by 166 DEG C of H boiling point and HFSI,
It is inadequate so as to cause the purity of HFSI.
In the patent CN 106219503A of Wuhan turquoise Science and Technology Co., Ltd., by the way that HClSI and ether-nHF is cooperated
Object is mixed reaction and obtains HFSI, and there are problems for this method are as follows: the investment of HClSI can not be fully converted in actual production
HFSI, generates a large amount of by-products, and the yield of HFSI product is low.
Suzhou China one New Energy Technology Co., Ltd. patent CN 107215853A in, by by HClSI under solvent with
Hydrogen fluoride complexing agent, initiator generation fluorination reaction generate HFSI, and this method presence can generate a large amount of organic solvent slop and give up
The reluctant problem of ammonium salt, is unfavorable for industrialized production.
In conclusion current most of patents using disclosed method synthesis HClSI (R.Appel et al,
Chem.Ber.1962,95,625；M.Goehring et al,Inorg.Synth.1966,8,105；J.Ruff,
Inorg.Chem.1967,6,2108；M.Berran et al, Z.Anorg.Allg.Chem.2005,631,55), then pass through
Different fluorination process first prepares HFSI, again lithiumation preparation LiFSI.But there are by-products for the fluorination process of these patent reports
Object is difficult to handle more；The reaction environment of high temperature and pressure, security risk are high；Or there are complexing solvents easily to react with HFSI,
Can not the problems such as obtaining intermediate HFSI of high yield, the above has seriously affected the industrialized production of LiFSI.
Summary of the invention
By-product existing for preparation method for existing double fluorine sulfimides is more, yield is low and reaction condition is difficult to control
The problem of processed, the present invention provides a kind of double fluorine sulfimides and the preparation methods of double fluorine sulfimide lithiums.
It is as follows that the present invention solves technical solution used by above-mentioned technical problem:
On the one hand, the present invention provides a kind of preparation methods of double fluorine sulfimides, including following operating procedure:
Hydrogen fluoride and the compound S of liquid are mixed, S.nHF complex compound is prepared, wherein compound S is selected from liquefied ammonia, N,
N '-dimethyl formamide, N, N '-dimethyl acetamide, hexamethyl phosphoramide, 1-Methyl-2-Pyrrolidone, tetramethylurea, N,
The third urea of N '-dimethyl, 1,3- dimethyl-2-imidazolinone, 1,3- di-n-butyl -2- imidazolone, melamine, poly- (ethylene
Yl pyridines) and one of ester type compound or a variety of；N is selected from 1~20, it is therefore preferable to 1-10；
S.nHF complex compound is mixed with double chlorine sulfimides, reaction generates the mixed liquor containing double fluorine sulfimides；
Mixed liquor is distilled, the fraction of double fluorine sulfimides is collected.
Optionally, the ester type compound includes one of ethyl acetate, propyl acetate and butyl acetate or a variety of.
Optionally, the operation for " preparing S.nHF complex compound " includes:
Under protective atmosphere, stirs the compound S of liquid while anhydrous hydrogen fluoride is added, system temperature is maintained at 19 DEG C
~-80 DEG C, it is therefore preferable to 10 DEG C~-80 DEG C, be further preferably -20 DEG C~-80 DEG C, be still more preferably -20 DEG C
~-70 DEG C, it is warming up to room temperature after the completion of mixing, obtains S.nHF complex compound.
Optionally, it is described be added anhydrous hydrogen fluoride operation include:
Gaseous state anhydrous hydrogen fluoride is added, liquefies under system temperature, is mixed with compound S；
Or anhydrous liquid hydrogen fluoride is added, it is mixed with compound S；
Optionally, double chlorine sulfimides are obtained by following operation preparation:
Sulfamic acid, thionyl chloride and chlorosulfonic acid are added in the reaction vessel to be reacted, it will be anti-after no gas generates
Object is answered to keep the temperature at 130 DEG C for 24 hours, the fraction of double chlorine sulfimides is collected in vacuum distillation；
Or chlorosulphonyl isocyanate and chlorosulfonic acid are added in the reaction vessel, 110 DEG C, back flow reaction 12h are warming up to, then
It is warming up to 130 DEG C of heat preservations for 24 hours, the fraction of double chlorine sulfimides is collected in vacuum distillation.
Optionally, with double chlorine sulfimides: HF is that the molar ratio of 1:2~40 mixes double chlorine sulfimides and S.nHF
Complex compound, it is therefore preferable to 1:4~1:20.
Optionally, the hybrid reaction of double chlorine sulfimides and S.nHF complex compound includes following operation:
Under protective atmosphere, S.nHF complex compound is added into reaction vessel, after opening stirring, double chlorine sulphonyl are slowly added dropwise
Imines, reaction temperature are 36 DEG C~150 DEG C, and subsequent continuous insulated and stirred 2h~12h is added dropwise, it is therefore preferable to 2h~8h, into one
Step is preferably 4h~6h.
Optionally, the mixed liquor obtained to the hybrid reaction of double chlorine sulfimides and S.nHF complex compound is evaporated under reduced pressure,
The fraction of 48 DEG C~50 DEG C/650Pa is collected, kettle base solution is used to prepare S.nHF complex compound.
On the other hand, the present invention provides a kind of preparation methods of double fluorine sulfimide lithiums, including following operation:
Double fluorine sulfimides are prepared using preparation method as described above；
Lithium source and solvent are mixed, double fluorine sulfimides are added, then filters, is dry, purification obtains double fluorine sulphonyl
Imine lithium crude product.
Optionally, the solvent be hydrophobicity polar non-solute or can with water formed azeotropic mixture solvent, it is described
Hydrophobicity polar non-solute include ethyl acetate, propyl acetate, butyl acetate, methyl tertiary butyl ether(MTBE), glycol dimethyl ether,
One of dimethyl carbonate and methyl ethyl carbonate are a variety of；
Described can include normal propyl alcohol, isopropanol, isobutanol, n-butanol, acrylonitrile, two with the solvent of water formation azeotropic mixture
One of toluene, acetonitrile, pyridine, ethyl alcohol, isoamyl alcohol, ethyl acetate, butyl acetate, n-amyl alcohol and chlorethanol are a variety of.
Optionally, the purification step is molten by hydrophobicity aprotic, polar for the fluorine sulfimide lithium crude product that will be obtained
Agent dissolution, filtering, drying, obtain fluorine sulfimide lithium；
The hydrophobicity polar non-solute include ethyl acetate, propyl acetate, butyl acetate, methyl tertiary butyl ether(MTBE),
One of glycol dimethyl ether, dimethyl carbonate and methyl ethyl carbonate are a variety of.
Optionally, the lithium source includes anhydrous LiOH, anhydrous LiHCO3With anhydrous Li2CO3One of or it is a variety of；
Double fluorine sulfimides and the molar ratio of lithium source are 1:0.9~1.2；
The temperature of reaction system control of double fluorine sulfimide adition process is at -40 DEG C~20 DEG C, reaction temperature control after addition
System is at -20 DEG C~50 DEG C.
The preparation method of the double fluorine sulfimides provided according to the present invention, by liquefied ammonia, N, N '-dimethyl formamide, N, N '-
Dimethyl acetamide, hexamethyl phosphoramide, 1-Methyl-2-Pyrrolidone, tetramethylurea, N, the third urea of N '-dimethyl, 1,3- diformazan
In base -2- imidazolone, 1,3- di-n-butyl -2- imidazolone, melamine, poly- (vinylpyridine) and ester type compound
It is one or more that stable liquid S.nHF complex compound is formed in conjunction with hydrogen fluoride, by the S.nHF complex compound directly with double chlorine sulphurs
Imide reaction obtains double fluorine sulfimides, which does not need to provide hyperbaric environment, reduces operation difficulty and safety
Risk, while compound S will not be with pair outside double fluorine sulfimide amounts incurred in the S.nHF complex compound used in above-mentioned reaction process
Reaction, can be effectively reduced the generation of by-product, improve the yield of double fluorine sulfimides.And in preparation process, HF is with liquid
In the presence of the corrosivity and sealing requirements of production equipment are greatly lowered；S.nHF complex compound is reusable, improves HF benefit
With rate, production cost is reduced.
Specific embodiment
In order to which the technical problems, technical solutions and beneficial effects solved by the present invention is more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
The present invention provides a kind of preparation methods of double fluorine sulfimides, including following operating procedure:
Hydrogen fluoride and the compound S of liquid are mixed, S.nHF complex compound is prepared, wherein compound S is selected from liquefied ammonia, N,
N '-dimethyl formamide, N, N '-dimethyl acetamide, hexamethyl phosphoramide, 1-Methyl-2-Pyrrolidone, tetramethylurea, N,
The third urea of N '-dimethyl, 1,3- dimethyl-2-imidazolinone, 1,3- di-n-butyl -2- imidazolone, melamine, poly- (ethylene
Yl pyridines) and one of ester type compound or a variety of；N is selected from 1~20, it is therefore preferable to 1~10；
S.nHF complex compound is mixed with double chlorine sulfimides, reaction generates the mixed liquor containing double fluorine sulfimides；
Mixed liquor is distilled, the fraction of double fluorine sulfimides is collected.
The double fluorine sulfimides of inventor's discovery are easily decomposed with some organic solvents (such as ethers) at high temperature to react, from
And by-product is generated, the yield of double fluorine sulfimides is influenced, liquefied ammonia, N, N '-dimethyl first have been selected based on discovery inventor
Amide, N, N '-dimethyl acetamide, hexamethyl phosphoramide, 1-Methyl-2-Pyrrolidone, tetramethylurea, N, N '-dimethyl third
Urea, 1,3- dimethyl-2-imidazolinone, 1,3- di-n-butyl -2- imidazolone, melamine, poly- (vinylpyridine) and ester
One of class compound is a variety of, is compounded to form S.nHF complex compound, In as compound S and hydrogen fluoride using the above substance
State is opposite stable between above compound S and double fluorine sulfimides in subsequent reaction process, and will not decompose reaction, from
And the yield of double fluorine sulfimides is effectively increased, avoid the generation of side reaction product.
In some embodiments, the S.nHF complex compound does not include other solvents in addition to compound S.
In some embodiments, the ester type compound includes one of ethyl acetate, propyl acetate and butyl acetate
Or it is a variety of.
In some embodiments, the operation for " preparing S.nHF complex compound " includes:
The compound S of liquid is put into tetrafluoroethene or PFA there-necked flask stirs the compound S of liquid under protective atmosphere
Anhydrous hydrogen fluoride is added simultaneously, system temperature is maintained at 19 DEG C~-80 DEG C, preferably 10 DEG C~-80 DEG C, further preferably
It is -20 DEG C~-80 DEG C, is still more preferably -20 DEG C~-70 DEG C, is warming up to room temperature after the completion of mixing, obtains S.nHF network
Object is closed, isolation steam saves.
The protective atmosphere is the gas that nitrogen or inert gas etc. are not involved in reaction.
In some embodiments, gaseous state anhydrous hydrogen fluoride is added, liquefies under system temperature, is mixed with compound S.
In some embodiments, anhydrous liquid hydrogen fluoride is added, is mixed with compound S.In some embodiments, described double
Chlorine sulfimide is obtained by following operation preparation:
Sulfamic acid, thionyl chloride and chlorosulfonic acid are added in the reaction vessel to be reacted, speed is generated by control gas
Degree keeps the temperature reactant for 24 hours after no gas generates to control heating rate at 130 DEG C, vacuum distillation, collects double chlorine sulphonyl
The fraction of imines.
Reaction equation is as follows:
NH2SO3H+2SOCl2+ClSO3H→HN(SO2Cl)2+2SO2↑+3HCl↑。
In further embodiments, double chlorine sulfimides are obtained by following operation preparation:
Chlorosulphonyl isocyanate and chlorosulfonic acid are added in the reaction vessel, is warming up to 110 DEG C, reflux reacts 12h, then
130 DEG C are warming up to, for 24 hours, the fraction of double chlorine sulfimides is collected in vacuum distillation for heat preservation.
Reaction equation is as follows:
ClSO2NCO+ClSO3H→(ClSO2)2NH+CO2↑。
As an example, collecting lower 95 DEG C of the fraction of 650pa when being evaporated under reduced pressure and obtaining double chlorine sulfimides.
In some embodiments, with double chlorine sulfimides: HF is 1:2~40, it is therefore preferable to which 1:4~1:20's feeds intake mole
Than mixing double chlorine sulfimides and S.nHF complex compound.
In some embodiments, the hybrid reaction of double chlorine sulfimides and S.nHF complex compound includes following operation:
Under protective atmosphere, S.nHF complex compound is added into reaction vessel, after opening stirring, double chlorine sulphonyl are slowly added dropwise
Imines, reaction temperature are 36 DEG C~150 DEG C, and preferably 40 DEG C~140 DEG C, subsequent continuous insulated and stirred 2h~12h is added dropwise, excellent
Selection of land is 2h~8h, is further preferably 4h~6h.
In some embodiments, the mixed liquor that the hybrid reaction of double chlorine sulfimides and S.nHF complex compound obtains is carried out
The fraction of 48 DEG C~50 DEG C/650Pa is collected in vacuum distillation, obtains double fluorine sulfimides, and kettle base solution is used to prepare S.nHF complexing
Object.
In this preparation method, the reaction equation of double chlorine sulfimides and S.nHF complex compound is as follows:
HN(SO2Cl)2+S.nHF→HN(SO2F)2+2HCl↑+S.(n-2)HF。
Since double chlorine sulfimides and S.nHF being complexed in the reaction process of double chlorine sulfimides and S.nHF complex compound
HF in object is consumed, while Cl element is removed by generating HCl gas, and double fluorine sulfimides of generation pass through vacuum distillation
It collects, therefore can be to S. (n-2) HF by adding anhydrous hydrogen fluoride again for the unsaturated complex compound of S. (n-2) HF in kettle base solution
HF in unsaturated complex compound is supplemented, and realizes that compound S is recycled, and reduces production cost, and due to compound S with
Double fluorine sulfimides do not react, and the compound S is enabled to realize reuse in a long time.
Another embodiment of the present invention provides a kind of preparation method of double fluorine sulfimide lithiums, including following operation:
Double fluorine sulfimides are prepared using preparation method as described above；
Lithium source is put into solvent, double fluorine sulfimides are added, it is preferred to use double fluorine are added in the mode of dropwise addition
Then sulfimide filters, is dry, purification obtains double fluorine sulfimide lithiums.
The lithium source includes anhydrous LiOH, anhydrous LiHCO3With anhydrous Li2CO3One of or it is a variety of.
With anhydrous Li2CO3For, lithium source and the reaction equation of double fluorine sulfimides are as follows:
2HN(SO2F)2+Li2CO3→2Li[N(SO2F)2]+H2O+CO2↑。
Above-mentioned filter process is one or more levels, and the aperture of filter membrane is 0.1um~5um, preferably 0.1um~2um.
The liquid filtered carries out reduced pressure drying, and dry system temperature is 30 DEG C~80 DEG C, preferably 40 DEG C~
60℃。
In some embodiments, the solvent is hydrophobicity polar non-solute, and the hydrophobicity aprotic, polar is molten
Agent includes ethyl acetate, propyl acetate, butyl acetate, methyl tertiary butyl ether(MTBE), glycol dimethyl ether, dimethyl carbonate and carbonic acid first
One of ethyl ester is a variety of, and lithium source is put into hydrophobicity polar non-solute and double fluorine sulfimides directly carry out instead
It answers, hydrophobicity polar non-solute can guarantee fully dispersed, the moisture and gas of generation of lithium source and double fluorine sulfimides
It is automatically separated with hydrophobicity polar non-solute, to reduce the water content in double fluorine sulfimide lithiums.
In further embodiments, as a further improvement of the present invention, the solvent is that can form azeotropic mixture with water
Solvent, including normal propyl alcohol, isopropanol, isobutanol, n-butanol, acrylonitrile, dimethylbenzene, acetonitrile, pyridine, ethyl alcohol, isoamyl alcohol, second
One of acetoacetic ester, n-amyl alcohol and chlorethanol are a variety of.
When the solvent, which is used, forms the solvent of azeotropic mixture with water, lithium source is generated with double fluorine sulfimide reaction process
Water and solvent carry out dilution dispersion of dissolving each other, and reaction is promoted to carry out towards the direction for generating double fluorine sulfimide lithiums, improve double fluorine sulphurs
The yield of imide li can remove the moisture in double fluorine sulfimide lithium crude products of generation in subsequent drying process.
It is sub- in order to further decrease double fluorine sulphonyl since double fluorine sulfimide lithium crude products after drying still contain a small amount of moisture
Water content in amine lithium, the purification step are that the fluorine sulfimide lithium crude product that will be obtained passes through hydrophobicity polar non-solute
Dissolution, filtering, drying, obtain fluorine sulfimide lithium；Hydrophobicity polar non-solute can be by double fluorine sulfimide lithium crude products
In the dissolution of double fluorine sulfimide lithiums, while avoiding the absorption to moisture, it is sub- to effectively reduce finally obtained double fluorine sulphonyl
The moisture content of amine lithium.
The hydrophobicity polar non-solute include ethyl acetate, propyl acetate, butyl acetate, methyl tertiary butyl ether(MTBE),
One of glycol dimethyl ether, dimethyl carbonate and methyl ethyl carbonate are a variety of.
In some embodiments, double fluorine sulfimides and the molar ratio of lithium source are 1:0.9~1.2, preferably 1:1.01
~1.1.
The temperature of reaction system of double fluorine sulfimide adition process is controlled at -40 DEG C~20 DEG C, preferably -20 DEG C~5 DEG C,
Reaction temperature control is at -20 DEG C~50 DEG C, preferably 20 DEG C~50 DEG C after dropwise addition.
The present invention is further detailed by the following examples.
The HClSI used in following embodiment and comparative example is mixed by commercially available sulfamic acid, thionyl chloride, chlorosulfonic acid
It is made.
Embodiment 1
The present embodiment is used to illustrate the preparation method of double fluorine sulfimides disclosed by the invention, including following operating procedure:
HFSI is prepared by 1-Methyl-2-Pyrrolidone hydrofluoric acid complex
1) under nitrogen protection stirring, the 1-Methyl-2-Pyrrolidone of 85.1g is added into dry 1L three-necked bottle
(1mol) is cooled to -20 DEG C under stirring, is then slowly added into the anhydrous hydrofluoric acid (9.23mol) of 185g, -2 pyrrole of 1- methyl is made
The complex solution of pyrrolidone .HF, is denoted as NMP.nHF, then heats to room temperature isolation air and saves；
2) NMP.nHF (methyl -2- pyrroles of 1- containing 1mol of 270.1g is added under nitrogen protection into dry there-necked flask
Alkanone, 9.23mol HF), stirring is opened, 45 DEG C is warming up to, the HClSI of 112g is then added dropwise to by constant pressure funnel
(0.5mol) controls rate of addition, and temperature is warming up at 105 DEG C after being added dropwise at 45 DEG C ± 5 DEG C and continues to stir in holding system
Mix 4h, after be evaporated under reduced pressure, collect 48 DEG C~50 DEG C/650Pa fraction, collect 82.5g, yield 91.16% altogether.
Embodiment 2
The present embodiment is used to illustrate the preparation method of double fluorine sulfimides disclosed by the invention, including following operating procedure:
By N, N '-dimethyl formamide hydrofluoric acid complex prepares HFSI
1) under nitrogen protection stirring, the N of addition 73.9g into dry 1L three-necked bottle, N ' dimethylformamide (1mol),
- 60 DEG C are cooled under stirring, is then slowly added into the anhydrous hydrofluoric acid (5mol) of 100g, N, N '-dimethyl formamide .HF is made
Complex solution, be denoted as DMF.nHF, then heat to room temperature isolation air save；
2) DMF.nHF (N containing 2mol, the N '-dimethyl first of 347.8g is added under nitrogen protection into dry there-necked flask
Amide, 10mol HF), stirring is opened, 45 DEG C is warming up to, the HClSI of 224g is then added dropwise to by constant pressure funnel
(1mol) controls rate of addition, and temperature is warming up at 95 DEG C that the reaction was continued at 45 DEG C ± 5 DEG C after being added dropwise in holding system
4h, after be evaporated under reduced pressure, collect 48 DEG C~50 DEG C/650Pa fraction, collect 158g, yield 87.29% altogether.
Embodiment 3
The present embodiment is used to illustrate the preparation method of double fluorine sulfimides disclosed by the invention, including following operating procedure:
HFSI is prepared by butyl acetate hydrofluoric acid complex
1) under nitrogen protection stirring, 111.2g butyl acetate (1mol) is added into dry 1L three-necked bottle, stirring decline
Temperature is then slowly added into the anhydrous hydrofluoric acid (5mol) of 100g, the complex solution of butyl acetate .HF is made, is denoted as to -60 DEG C
BAC.nHF then heats to room temperature isolation air and saves；
2) BAC.nHF (butyl acetate containing 2mol, the 10mol of 422.4g is added under nitrogen protection into dry there-necked flask
HF), stirring is opened, is warming up to 45 DEG C, the HClSI (1mol) of 224g is then added dropwise to by constant pressure funnel, control is added dropwise
Speed, temperature is at 45 DEG C ± 5 DEG C in holding system, the 4h that is warming up at 110 DEG C that the reaction was continued after being added dropwise, after depressurize and steam
It evaporates, collects the fraction of 48 DEG C~50 DEG C/650Pa, collect 167g, yield 92.26% altogether.
Embodiment 4
The present embodiment is used to illustrate the preparation method of double fluorine sulfimides disclosed by the invention, including following operating procedure:
HFSI is prepared by tetramethylurea hydrofluoric acid complex
1) under nitrogen protection stirring, the tetramethylurea (1mol) of 116.16g is added into dry 1L three-necked bottle, under stirring
It is cooled to 0 DEG C, the anhydrous hydrofluoric acid (9.19mol) of 183.84g is then slowly added into, the complex solution of tetramethylurea .HF is made,
It is denoted as TMU.nHF, room temperature isolation air is then heated to and saves；
2) TMU.nHF (tetramethylurea containing 1mol, the 9.19mol of 400g is added under nitrogen protection into dry there-necked flask
HF), stirring is opened, is warming up to 45 DEG C, the HClSI (1mol) of 224g is then added dropwise to by constant pressure funnel, control is added dropwise
Speed, temperature is warming up at 110 DEG C after being added dropwise at 45 DEG C ± 5 DEG C and continues to stir 4h in holding system, after depressurize and steam
It evaporates, collects the fraction of 48 DEG C~50 DEG C/650Pa, collect 162g, yield 89.5% altogether.
Embodiment 5
The present embodiment is used to illustrate the preparation method of double fluorine sulfimides disclosed by the invention, including following operating procedure:
HFSI is prepared by 1,3- dimethyl-2-imidazolinone hydrofluoric acid complex
1) under nitrogen protection stirring, the 1,3-Dimethyl-2-imidazolidinone of 114.15g is added into dry 1L three-necked bottle
(1mol) is cooled to 10 DEG C under stirring, be then slowly added into the anhydrous hydrofluoric acid (9.29mol) of 185.85g, 1,3- diformazan is made
The complex solution of base -2- imidazolone .HF, is denoted as DMEU.nHF, then heats to room temperature isolation air and saves；
2) DMEU.nHF (dimethyl -2- miaow of 1,3- containing 1mol of 400g is added under nitrogen protection into dry there-necked flask
Oxazoline ketone, 9.29mol HF), stirring is opened, 45 DEG C is warming up to, the HClSI of 224g is then added dropwise to by constant pressure funnel
(1mol) controls rate of addition, and temperature is warming up at 110 DEG C after being added dropwise at 45 DEG C ± 5 DEG C and continues to stir in holding system
4h, after be evaporated under reduced pressure, collect 48 DEG C~50 DEG C/650Pa fraction, collect 164g, yield 90.61% altogether.
Embodiment 6
The present embodiment is used to illustrate the preparation method of double fluorine sulfimide lithiums disclosed by the invention, including following operation step
It is rapid:
LiFSI is prepared using the HFSI of 1 method of above-described embodiment synthesis
Under nitrogen protection stirring, the butyl acetate of 600g and the Carbon Dioxide of 40.7g are added into dry 1L three-necked bottle
Lithium (0.55mol) opens ice bath, and being cooled to system temperature is -10 DEG C.Add under nitrogen protection into dry constant pressure funnel
The HFSI (1mol) for entering 181g, is then added dropwise into three-necked bottle, controls rate of addition, and temperature is -10 DEG C ± 5 in holding system
℃.Continue after being added dropwise to stir 2h at 0 DEG C, be then to slowly warm up to 25 DEG C the reaction was continued 4h, detection solution is in neutrality.It crosses
It filters, is dried under reduced pressure at 50 DEG C, when product is in starchiness, be changed to high vacuum dry, vacuum degree≤10-2Pa obtains 181g solid,
Yield 96.79%, measuring moisture content is 12ppm, and it is 99.96% that IC, which detects main content,.
Embodiment 7
The present embodiment is used to illustrate the preparation method of double fluorine sulfimide lithiums disclosed by the invention, including following operation step
It is rapid:
LiFSI is prepared using the HFSI of 1 method of above-described embodiment synthesis and is purified
Under nitrogen protection stirring, the dehydrated alcohol of 374g and the Carbon Dioxide of 40.7g are added into dry 1L three-necked bottle
Lithium (0.55mol) opens ice bath, and being cooled to system temperature is -10 DEG C.Add under nitrogen protection into dry constant pressure funnel
Enter 181gHFSI (1mol), be then added dropwise into three-necked bottle, control rate of addition, temperature is -10 DEG C ± 5 DEG C in holding system.
Continue after being added dropwise to stir 2h at 0 DEG C, be then to slowly warm up to 25 DEG C the reaction was continued 4h, detection solution is in neutrality.Filtering, 50
It is dried under reduced pressure at DEG C, when product is in starchiness, is changed to high vacuum dry, vacuum degree≤10-2Pa obtains 185g crude solid,
Measuring moisture content is 93ppm, yield 98.93%.It is 99.85% that IC, which detects main content,.
Above-mentioned crude solid 185 is dissolved with methyl tertiary butyl ether(MTBE) according to mass ratio 1:4, is then filtered, it is dry, it obtains
183g solid, yield 98.91%, measuring moisture content is 15ppm, and it is 99.98% that IC, which detects main content,.
Embodiment 8
The present embodiment is used to illustrate the preparation method of double fluorine sulfimide lithiums disclosed by the invention, including following operation step
It is rapid:
LiFSI is prepared using the HFSI of 1 method of above-described embodiment synthesis and is purified
Under nitrogen protection stirring, the dehydrated alcohol of 374g and the Carbon Dioxide of 40.7g are added into dry 1L three-necked bottle
Lithium (0.55mol) opens ice bath, and being cooled to system temperature is -10 DEG C.Add under nitrogen protection into dry constant pressure funnel
The HFSI (1mol) for entering 181g, is then added dropwise into three-necked bottle, controls rate of addition, and temperature is -10 DEG C ± 5 in holding system
℃.Continue after being added dropwise to stir 2h at 0 DEG C, be then to slowly warm up to 25 DEG C the reaction was continued 4h, detection solution is in neutrality.It crosses
It filters, is dried under reduced pressure at 50 DEG C, when product is in starchiness, be changed to high vacuum dry, vacuum degree≤10-2Pa obtains 185g crude product
Solid, measuring moisture content is 93ppm, yield 98.93%.It is 99.85% that IC, which detects main content,.
Above-mentioned crude solid 185 is dissolved with dimethyl carbonate (DMC) according to mass ratio 1:3, then filters, is contained
The DMC solution of LiFSI, it is dry, 182g solid is obtained, yield 98.37%, measuring moisture content is 5ppm, and IC detection master contains
Amount is 99.97%.
Comparative example 1
This comparative example is used for the preparation method of comparative illustration double fluorine sulfimides disclosed by the invention, including following operation step
It is rapid:
HFSI is prepared by ether hydrofluoric acid complex
2) under nitrogen protection stirring, the ether (1mol) of 74.12g is added into dry 1L three-necked bottle, stirs lower cooling
Extremely -- 60 DEG C, it is then slowly added into the anhydrous hydrofluoric acid (6.29mol) of 125.88g, the complex solution of ether .HF is made, is denoted as
DEE.nHF then heats to room temperature isolation air and saves；
2) the ether .nHF (ether containing 1mol, 6.29molHF) of 200g is added under nitrogen protection into dry there-necked flask,
Stirring is opened, is warming up to 45 DEG C, the HClSI (0.5mol) of 112g is then added dropwise to by constant pressure funnel, speed is added dropwise in control
Degree, temperature is at 45 DEG C ± 5 DEG C in holding system, solution changes color during dropwise addition, after be warming up at 65 DEG C and continue to stir 4h,
After be evaporated under reduced pressure, collect 48 DEG C~50 DEG C/650Pa fraction, be collected into 0g, yield 0%, that is, the HFSI generated and second altogether
Ether reacts, and cannot obtain HFSI product.
In conclusion the test result of comparative example 1~8 and comparative example 1 is adopted it is found that relative to conventional ether solvent
With solvent provided by the invention be complexed with hydrofluoric acid the complex liquid to be formed can be effectively prevented from double fluorine sulfimides decomposition it is anti-
It answers, to effectively increase the yield and purity of double fluorine sulfimides.
The test result of comparative example 6~8 passes through elder generation it is found that during subsequent preparation double fluorine sulfimide lithiums
It is reacted in the solvent for forming azeotropic mixture with water, the rear method by the dissolution purification of hydrophobicity polar non-solute, energy
The yield of double fluorine sulfimide lithiums is enough effectively improved, while reducing its water content.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of preparation method of double fluorine sulfimides, which is characterized in that including following operating procedure:
Hydrogen fluoride and the compound S of liquid are mixed, S.nHF complex compound is prepared, wherein compound S is selected from liquefied ammonia, N, N '-two
Methylformamide, N, N '-dimethyl acetamide, hexamethyl phosphoramide, 1-Methyl-2-Pyrrolidone, tetramethylurea, N, N '-two
Methyl-prop urea, 1,3- dimethyl-2-imidazolinone, 1,3- di-n-butyl -2- imidazolone, melamine, poly- (vinylpyridine
Pyridine) and one of ester type compound or a variety of；N is selected from 1~20；
S.nHF complex compound is mixed with double chlorine sulfimides, reaction generates the mixed liquor containing double fluorine sulfimides；
Mixed liquor is distilled, the fraction of double fluorine sulfimides is collected.
2. the preparation method of double fluorine sulfimides according to claim 1, which is characterized in that the ester type compound includes
One of ethyl acetate, propyl acetate and butyl acetate are a variety of.
3. the preparation method of double fluorine sulfimides according to claim 1, which is characterized in that " preparation S.nHF complex compound "
Operation include:
System temperature is maintained at 19 DEG C~-80 DEG C, and under protective atmosphere, the compound S and anhydrous hydrogen fluoride of liquid are mixed, mixed
It is warming up to room temperature after the completion of closing, obtains S.nHF complex compound.
4. the preparation method of double fluorine sulfimides according to claim 1, which is characterized in that with double chlorine sulfimides: HF
Double chlorine sulfimides and S.nHF complex compound are mixed for the molar ratio of 1:2~40.
5. the preparation method of double fluorine sulfimides according to claim 1, which is characterized in that double chlorine sulfimides with
The hybrid reaction of S.nHF complex compound includes following operation:
Under protective atmosphere, S.nHF complex compound is added into reaction vessel, double chlorine sulfimides are added dropwise and is stirred, reacts
Temperature is 36 DEG C~150 DEG C, and subsequent continuous insulated and stirred 2h~12h is added dropwise.
6. the preparation method of double fluorine sulfimides according to claim 1, which is characterized in that double chlorine sulfimides with
The mixed liquor that the hybrid reaction of S.nHF complex compound obtains is evaporated under reduced pressure, and the fraction of 48 DEG C~50 DEG C/650Pa, bottom are collected
Liquid is used to prepare S.nHF complex compound.
7. a kind of preparation method of double fluorine sulfimide lithiums, which is characterized in that including following operation:
Double fluorine sulfimides are prepared using preparation method described in claim 1~6 any one；
Lithium source is mixed with solvent, double fluorine sulfimides are added, then filters, is dry, purification obtains double fluorine sulfimides
Lithium.
8. the preparation method of double fluorine sulfimide lithiums according to claim 7, which is characterized in that the solvent is hydrophobicity
Polar non-solute or the solvent that azeotropic mixture can be formed with water；
The hydrophobicity polar non-solute includes ethyl acetate, propyl acetate, butyl acetate, methyl tertiary butyl ether(MTBE), second two
One of diethylene glycol dimethyl ether, dimethyl carbonate and methyl ethyl carbonate are a variety of；
Described can include normal propyl alcohol, isopropanol, isobutanol, n-butanol, acrylonitrile, diformazan with the solvent of water formation azeotropic mixture
One of benzene, acetonitrile, pyridine, ethyl alcohol, isoamyl alcohol, ethyl acetate, butyl acetate, n-amyl alcohol and chlorethanol are a variety of.
9. the preparation method of double fluorine sulfimide lithiums according to claim 7, which is characterized in that the purification step is
By obtained fluorine sulfimide lithium crude product by the dissolution of hydrophobicity polar non-solute, filtering, drying, fluorine sulfimide is obtained
Lithium；
The hydrophobicity polar non-solute includes ethyl acetate, propyl acetate, butyl acetate, methyl tertiary butyl ether(MTBE), second two
One of diethylene glycol dimethyl ether, dimethyl carbonate and methyl ethyl carbonate are a variety of.
10. the preparation method of double fluorine sulfimide lithiums according to claim 7, which is characterized in that
The lithium source includes anhydrous LiOH, anhydrous LiHCO3With anhydrous Li2CO3One of or it is a variety of；
Double fluorine sulfimides and the molar ratio of lithium source are 1:0.9~1.2；
The temperature of reaction system of double fluorine sulfimide adition process is controlled at -40 DEG C~20 DEG C, after addition reaction temperature control -
20 DEG C~50 DEG C.
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