CN104844482A - Method for preparing bis (trifluoromethanesulfonyl) imide lithium - Google Patents
Method for preparing bis (trifluoromethanesulfonyl) imide lithium Download PDFInfo
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- CN104844482A CN104844482A CN201510164337.0A CN201510164337A CN104844482A CN 104844482 A CN104844482 A CN 104844482A CN 201510164337 A CN201510164337 A CN 201510164337A CN 104844482 A CN104844482 A CN 104844482A
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- lithium
- fluoride sulfonyl
- trimethyl fluoride
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Abstract
The invention discloses a method for preparing bis (trifluoromethanesulfonyl) imide lithium. The method is by conducting double decomposition exchange on metal salt of bis (trifluoromethanesulfonyl) imide and a lithium salt in an anhydrous solvent to obtain the bis (trifluoromethylsulfonyl) imide lithium. The method avoids the generation of bound water, can prepare the product with low moisture content, and has the advanategs of simple process route, simple reaction conditions, simple device and easiness to achieve industrialized production.
Description
Technical field
The invention belongs to chemical field, be specifically related to the method that one prepares two (trimethyl fluoride sulfonyl) imine lithium.
Background technology
Two (trimethyl fluoride sulfonyl) imine lithium, its chemical structural formula: LiN (CF
3sO
2)
2, can be used as the electrolyte lithium salt of lithium ion battery, specific conductivity is higher, chemical stability and electrochemical stability high, water stability, is high.When it is not containing Bound moisture, its crystalline structure is tetrahedral coordination structure, because CF
3group can hinder lithium ion and negatively charged ion to form chelate ring, makes them form bridgingligand; When its crystalline structure contains a Bound moisture, water molecules can chelating bridging mutual to negatively charged ion, thus forms more stable octahedral structure.Therefore, this lithium salts is very stable to water, can not be hydrolyzed, but in preparation process, the water of introducing will be difficult to removing, and Bound moisture all cannot remove by physico-chemical process completely.
US Patent No. 5874616 discloses and utilizes trimethyl fluoride sulfonyl amine and its fluoride compounds trimethyl fluoride sulfonyl fluorine reacting by heating under the existence of non-nucleophilic alkali such as triethylamine, and reactant reacts the method for preparation two (trimethyl fluoride sulfonyl) imine lithium with chemical pure Quilonum Retard or lithium hydroxide further.
Japanese Patent JP 2000-086617 discloses a kind of synthetic method of two (trimethyl fluoride sulfonyl) inferior amine salt.The method is at subzero 60 DEG C, the mixture reaction of trimethyl fluoride sulfonyl chlorine and anhydrous liquid ammonia and organic amine, and reactant reaction product further with alkali-metal oxyhydroxide or carbonate reaction to prepare two (trimethyl fluoride sulfonyl) imine lithium, output is 60%.
Chinese patent CN 101983960 A discloses a kind of synthetic method of two (trimethyl fluoride sulfonyl) inferior amine salt.Trimethyl fluoride sulfonyl bromine is joined in ammoniacal liquor and is obtained by reacting trimethyl fluoride sulfonyl amine, by trimethyl fluoride sulfonyl amine solvent in alkylamine solution, continue to add trimethyl fluoride sulfonyl bromine, react rear decompression desolventizing, residuum is dissolved in methylene dichloride, collect organic phase after washing and obtain two (trimethyl fluoride sulfonyl) imines, by two (trimethyl fluoride sulfonyl) imines and alkali-metal oxyhydroxide or carbonate reaction to prepare two (trimethyl fluoride sulfonyl) inferior amine salt.
Several technology is above all first prepare two (trimethyl fluoride sulfonyl) imines, then with alkali-metal carbonate compound or oxyhydroxide in and generate two (trimethyl fluoride sulfonyl) inferior amine salt.Neutralization reaction can generate water, and product two (trimethyl fluoride sulfonyl) imine lithium very easily absorbs water, therefore the product that obtains of this several method is inevitably with Bound moisture, and this Bound moisture uses the method for physics or chemistry all cannot remove completely.
Summary of the invention
The object of the present invention is to provide one to prepare the method for two (trimethyl fluoride sulfonyl) imine lithium, the method can avoid the generation of Bound moisture, the product that preparation moisture content is very low.
Method provided by the invention comprises:
The metal-salt of two (trimethyl fluoride sulfonyl) imines and lithium salts metathesis in anhydrous solvent exchange and obtain two (trimethyl fluoride sulfonyl) imine lithium.Because the crystalline structure of two (trimethyl fluoride sulfonyl) imines potassium is not containing Bound moisture, so take first to prepare anhydrous two (trimethyl fluoride sulfonyl) imines potassium, then metathesis exchange can obtain anhydrous two (trimethyl fluoride sulfonyl) imine lithium.
Preferably, described anhydrous solvent is described anhydrous solvent is carbonate-based solvent, ether solvent, halogenated hydrocarbon solvent, ketones solvent and/or nitrile solvents, such as methylcarbonate, acetonitrile, methylene dichloride, acetonitrile, methylcarbonate, Nitromethane 99Min., diethyl carbonate, Methyl ethyl carbonate, methyl propyl carbonate, Methyl ethyl carbonate, tetrahydrofuran (THF), acetone, vinyl acetic monomer, methyl-formiate, two trifluoroethyl carbonic ether, trifluoroethyl methyl carbonate, trifluoroethyl ethyl-carbonate, 1,2-glycol dimethyl ether and 1,3-dioxolane.
Preferably, the metal-salt of described two (trimethyl fluoride sulfonyl) imines is sodium salt or sylvite.
Preferably, described lithium salts is the inorganic salt for lithium tetraborate or its derivative, lithium oxalate or derivatives thereof and/or lithium, such as LiBF4, lithium perchlorate, di-oxalate lithium borate, hexafluoroarsenate lithium or oxalic acid boron difluoride lithium.
Preferably, described product is through washing or abstraction purification, and the solvent of described washing or extraction comprises the non-polar solvents such as methylene dichloride, toluene, hexanaphthene.
Preferably, described temperature of reaction is room temperature (15-25 degree Celsius) or the boiling point lower than anhydrous solvent.
Preferably, the described reaction times is 1-12h.
Preferably, the described metal-salt of two (trimethyl fluoride sulfonyl) imines and the ratio of lithium salts are 1:1-1.2.Preferred, the metal-salt of two (trimethyl fluoride sulfonyl) imines and the ratio of lithium salts are 1:1-1.05.
Method of the present invention can avoid the generation of Bound moisture, the product that preparation moisture content is very low, and operational path is simple, and reaction conditions is simple, and device simple, easily realizes industrialization.
Accompanying drawing explanation
The infrared spectrum of Fig. 1, product of the present invention;
Fig. 2, product of the present invention
13cNMR schemes (taking DMSO-d6 as deuterated reagent).
Embodiment
The synthesis of two (trimethyl fluoride sulfonyl) the imines potassium that the present invention mentions or corresponding metal-salt can with reference to above-mentioned mentioned three patent systems for the latter by commercial acquisition, all the other reagent are commercial.
Embodiment 1:
In glove box, in Erlenmeyer flask, add 31.9g (0.1mol) two (trimethyl fluoride sulfonyl) imines potassium and 50ml anhydrous acetonitrile, in constant pressure funnel, add 9.37g LiBF4 and 50ml anhydrous acetonitrile.The acetonitrile solution of LiBF4 is slowly added drop-wise in the acetonitrile solution of two (trimethyl fluoride sulfonyl) imines potassium.3h is stirred until generate without new precipitation, hold over night under normal temperature.Elimination insolubles, solution is removed in decompression, is compressed to about 15ml, adds toluene, after filtration, washing, drying, obtain two (trimethyl fluoride sulfonyl) imine lithium 27.5g.
See Fig. 1, product through infrared detection, at 737cm
-1, 788cm
-1, 1062cm
-1, 1193cm
-1, 1357cm
-1place, by the contrast to standard spectrogram, is defined as the characteristic group of two (trimethyl fluoride sulfonyl) imine lithium, see Fig. 2, which show identical conclusion.
Embodiment 2:
In glove box, in Erlenmeyer flask, add 31.9g (0.1mol) two (trimethyl fluoride sulfonyl) imines potassium and 50ml Carbon Dioxide dimethyl ester, in constant pressure funnel, add 19.4g di-oxalate lithium borate and 50ml Carbon Dioxide dimethyl ester.The methylcarbonate solution of two boron lithium oxalic acid is slowly added drop-wise in the methylcarbonate solution of two (trimethyl fluoride sulfonyl) imines potassium.3h is stirred until generate without new precipitation, hold over night under normal temperature.Elimination insolubles, solution is removed in decompression, is compressed to about 15ml, adds methylene dichloride, after filtration, washing, drying, obtain two (trimethyl fluoride sulfonyl) imine lithium 28g.
Product through infrared detection, at 737cm
-1, 788cm
-1, 1062cm
-1, 1193cm
-1, 1357cm
-1place, by the contrast to standard spectrogram, is defined as the characteristic group of two (trimethyl fluoride sulfonyl) imine lithium.
Embodiment 3:
In glove box, in Erlenmeyer flask, add 31.9g (0.1mol) two (trimethyl fluoride sulfonyl) imines potassium and 50ml Carbon Dioxide dimethyl ester, in constant pressure funnel, add 14.4g LiODFB and 50ml Carbon Dioxide dimethyl ester.The methylcarbonate solution of oxalic acid boron difluoride lithium is slowly added drop-wise in the methylcarbonate solution of two (trimethyl fluoride sulfonyl) imines potassium.3h is stirred until generate without new precipitation, hold over night under normal temperature.Elimination insolubles, solution is removed in decompression, is compressed to about 15ml, adds methylene dichloride, after filtration, washing, drying, obtain two (trimethyl fluoride sulfonyl) imine lithium 28g.
Product through infrared detection, at 737cm
-1, 788cm
-1, 1062cm
-1, 1193cm
-1, 1357cm
-1place, by the contrast to standard spectrogram, is defined as the characteristic group of two (trimethyl fluoride sulfonyl) imine lithium.
Embodiment 4:
In glove box, in Erlenmeyer flask, add 31.9g (0.1mol) two (trimethyl fluoride sulfonyl) imines potassium and 60ml Glacial acetic acid ethyl ester, in constant pressure funnel, add 19.4g di-oxalate lithium borate and 60ml Glacial acetic acid ethyl ester.The ethyl acetate solution of two boron lithium oxalic acid is slowly added drop-wise in the ethyl acetate solution of two (trimethyl fluoride sulfonyl) imines potassium.3h is stirred until generate without new precipitation, hold over night under normal temperature.Elimination insolubles, solution is removed in decompression, is compressed to about 20ml, adds methylene dichloride, after filtration, washing, drying, obtain two (trimethyl fluoride sulfonyl) imine lithium 28g.
Product through infrared detection, at 737cm
-1, 788cm
-1, 1062cm
-1, 1193cm
-1, 1357cm
-1place, by the contrast to standard spectrogram, is defined as the characteristic group of two (trimethyl fluoride sulfonyl) imine lithium.
Claims (7)
1. prepare a method for two (trimethyl fluoride sulfonyl) imine lithium, comprising:
The metal-salt of two (trimethyl fluoride sulfonyl) imines and lithium salts react and obtain two (trimethyl fluoride sulfonyl) imine lithium in anhydrous solvent.
2. method according to claim 1, is characterized in that, described anhydrous solvent is carbonate-based solvent, ether solvent, halogenated hydrocarbon solvent, ketones solvent or nitrile solvents.
3. method according to claim 1, is characterized in that, the metal-salt of described two (trimethyl fluoride sulfonyl) imines is sodium salt or sylvite.
4. method according to claim 1, is characterized in that, described lithium salts is the inorganic salt of lithium tetraborate or its derivative, lithium oxalate or derivatives thereof and/or lithium.
5. method according to claim 1, is characterized in that, described product is through washing or abstraction purification, and the solvent of described washing or extraction is non-polar solvent.
6. method according to claim 1, is characterized in that, the described reaction times is 1-12h.
7. method according to claim 1, is characterized in that, the metal-salt of described two (trimethyl fluoride sulfonyl) imines and the ratio of lithium salts are 1:1-1.2.
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| CN201510164337.0A CN104844482A (en) | 2015-04-08 | 2015-04-08 | Method for preparing bis (trifluoromethanesulfonyl) imide lithium |
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| CN201510164337.0A CN104844482A (en) | 2015-04-08 | 2015-04-08 | Method for preparing bis (trifluoromethanesulfonyl) imide lithium |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107055493A (en) * | 2017-05-10 | 2017-08-18 | 浙江永太科技股份有限公司 | A kind of preparation method of imidodisulfuryl fluoride lithium salt |
| CN109369474A (en) * | 2018-12-29 | 2019-02-22 | 江苏长园华盛新能源材料有限公司 | A kind of preparation method of two (trimethyl fluoride sulfonyl) imines lithium salts |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101747244A (en) * | 2008-12-05 | 2010-06-23 | 华中科技大学 | Method for synthesizing perfluoroalkyl sulfimide alkali metal salt and ionic liquid synthesized by same |
| CN101983960A (en) * | 2009-09-10 | 2011-03-09 | 上海恩氟佳科技有限公司 | Method for preparing sulfimide compound |
| CN103377833A (en) * | 2012-04-27 | 2013-10-30 | 张家港市国泰华荣化工新材料有限公司 | Electrolyte, electrolyte solution with electrolyte and electrochemistry element |
| 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 |
-
2015
- 2015-04-08 CN CN201510164337.0A patent/CN104844482A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101747244A (en) * | 2008-12-05 | 2010-06-23 | 华中科技大学 | Method for synthesizing perfluoroalkyl sulfimide alkali metal salt and ionic liquid synthesized by same |
| CN101983960A (en) * | 2009-09-10 | 2011-03-09 | 上海恩氟佳科技有限公司 | Method for preparing sulfimide compound |
| CN103377833A (en) * | 2012-04-27 | 2013-10-30 | 张家港市国泰华荣化工新材料有限公司 | Electrolyte, electrolyte solution with electrolyte and electrochemistry element |
| 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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107055493A (en) * | 2017-05-10 | 2017-08-18 | 浙江永太科技股份有限公司 | A kind of preparation method of imidodisulfuryl fluoride lithium salt |
| CN109369474A (en) * | 2018-12-29 | 2019-02-22 | 江苏长园华盛新能源材料有限公司 | A kind of preparation method of two (trimethyl fluoride sulfonyl) imines lithium salts |
| CN109369474B (en) * | 2018-12-29 | 2021-02-05 | 江苏华盛锂电材料股份有限公司 | Preparation method of lithium bis (trifluoromethylsulfonyl) imide |
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