WO2012026360A1 - Méthode de fabrication de bis(fluorosulfonyl)imide - Google Patents

Méthode de fabrication de bis(fluorosulfonyl)imide Download PDF

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Publication number
WO2012026360A1
WO2012026360A1 PCT/JP2011/068553 JP2011068553W WO2012026360A1 WO 2012026360 A1 WO2012026360 A1 WO 2012026360A1 JP 2011068553 W JP2011068553 W JP 2011068553W WO 2012026360 A1 WO2012026360 A1 WO 2012026360A1
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WIPO (PCT)
Prior art keywords
fluorosulfonyl
bis
imide
producing
isocyanate
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Application number
PCT/JP2011/068553
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English (en)
Japanese (ja)
Inventor
常俊 本田
武志 神谷
典明 松村
Original Assignee
三菱マテリアル株式会社
三菱マテリアル電子化成株式会社
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Application filed by 三菱マテリアル株式会社, 三菱マテリアル電子化成株式会社 filed Critical 三菱マテリアル株式会社
Publication of WO2012026360A1 publication Critical patent/WO2012026360A1/fr

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    • 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
    • C01B21/087—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms
    • C01B21/093—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms containing also one or more sulfur atoms
    • C01B21/0935—Imidodisulfonic acid; Nitrilotrisulfonic acid; Salts thereof

Definitions

  • the present invention relates to an improved method for producing bis (fluorosulfonyl) imide.
  • Bis (fluorosulfonyl) imide (FSO 2 ) 2 NH) is known to be a substance useful as an anion source of an ion conductive material or an ionic liquid. And the following nonpatent literature 1 is known as a manufacturing method of bis (fluoro sulfonyl) imide.
  • Non-Patent Document 1 discloses a method in which fluorosulfuric acid (FSO 3 H) and fluorosulfonyl isocyanate (FSO 2 NCO) are mixed and then reacted by heating. Thereby, a chemical reaction as shown in the following reaction formula (A) occurs, and bis (fluorosulfonyl) imide and carbon dioxide gas (CO 2 ) are generated. The produced bis (fluorosulfonyl) imide and the excessively added fluorosulfuric acid can be recovered by distillation under reduced pressure.
  • FSO 3 H fluorosulfuric acid
  • FSO 2 NCO fluorosulfonyl isocyanate
  • Non-Patent Document 1 In the method for producing bis (fluorosulfonyl) imide disclosed in Non-Patent Document 1, the reaction is performed at a reaction temperature of 120 ° C. for 150 hours, the yield is 78%, and the reaction is very slow. there were. Therefore, the method described in Non-Patent Document 1 has been difficult to implement industrially.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing bis (fluorosulfonyl) imide, which has a high reaction rate and can be produced by a simple method.
  • the present inventors have found that the reaction rate can be improved by reacting fluorosulfuric acid and fluorosulfonyl isocyanate in the presence of a predetermined salt, and the present invention has been achieved. .
  • fluorosulfuric acid and fluorosulfonyl isocyanate are reacted in the presence of any one or more of the salt compounds represented by the following chemical formula (1).
  • the method for producing the bis (fluorosulfonyl) imide includes a mixed solution preparing step of preparing a mixed solution by adding the salt compound to fluorosulfuric acid, and adding the fluorosulfonyl isocyanate to the mixed solution after the mixed solution preparing step.
  • An addition step may be further provided.
  • generation process may be performed by heating the said liquid mixture with which the fluoro sulfonyl isocyanate was added after the said addition process.
  • the mixed solution is heated between the mixed solution preparing step and the adding step, and the heated mixed solution is added to the fluorosulfonyl in the adding step.
  • the manufacturing method of the said bis (fluoro sulfonyl) imide adds any 1 type, or 2 or more types of the compound chosen from the group which consists of ammonia and an amine to fluorosulfuric acid, and is shown by the said Chemical formula (1).
  • the reaction solution is heated between the reaction solution preparation step and the addition step, and the reaction solution heated in the addition step is heated to fluorosulfonyl.
  • the amount of the salt compound represented by the chemical formula (1) with respect to the fluorosulfuric acid reacting with the fluorosulfonyl isocyanate is 0.1 to 10 times in molar ratio. It may be within the range.
  • the reaction temperature between the fluorosulfuric acid and the fluorosulfonyl isocyanate may be in the range of 50 to 170 ° C.
  • the reaction rate can be improved by reacting fluorosulfuric acid with fluorosulfonyl isocyanate in the presence of a predetermined salt. Therefore, it is possible to provide a method for producing bis (fluorosulfonyl) imide which has a high reaction rate and can be produced by a simple method.
  • M is any one of an alkali metal cation, an alkaline earth metal cation, and an onium cation.
  • the alkali metal element include lithium (Li), sodium (Na), potassium (K), and the like.
  • the alkaline earth metal element include calcium (Ca), strontium (Sr), barium (Ba), and the like.
  • the onium ion for example, at least one formed by coordination of a cation-type atomic group to a compound containing an element having a lone electron pair such as nitrogen, sulfur, oxygen, phosphorus, selenium, tin, iodine, and antimony. There is no particular limitation as long as it is a cation having an organic group.
  • X is a fluorine anion (F ⁇ ), a chlorine anion (Cl ⁇ ), a bromine anion (Br ⁇ ), an iodine anion (I ⁇ ), a sulfate anion (SO 4 2 ⁇ ), fluorosulfuric acid.
  • the salt compound represented by the chemical formula (2) is used in a molar ratio of 0.1 to 10 times with respect to fluorosulfuric acid that reacts with fluorosulfonyl isocyanate. Preferably it is present. A more preferred molar ratio of the salt compound to fluorosulfuric acid is in the range of 0.1 to 1 times.
  • the reaction temperature between fluorosulfuric acid and fluorosulfonyl isocyanate is preferably in the range of 50 to 170 ° C., and preferably in the range of 60 to 150 ° C. More preferred.
  • the reaction temperature is less than 50 degrees, because the reaction becomes slow.
  • the reaction temperature exceeds 170 ° C., one of the raw materials, fluorosulfonyl isocyanate, tends to volatilize, which is not preferable because the yield of bis (fluorosulfonyl) imide is reduced.
  • reaction mechanism of the present invention is explained as follows.
  • fluorosulfuric acid By reacting fluorosulfuric acid with fluorosulfonyl isocyanate in the presence of the salt compound (MX) represented by the above formula (2), a chemical reaction as represented by the following reaction formula (B) proceeds.
  • MX salt compound represented by the above formula (2)
  • reaction formula (B) As a result, bis (fluorosulfonyl) imide and carbon dioxide (CO 2 ) are generated.
  • carbon dioxide produced as a by-product is a gas, it can be easily discharged out of the reaction system and does not remain in the reaction system.
  • the salt compound represented by the chemical formula (2) is directly added to the reaction system of fluorosulfuric acid and fluorosulfonyl isocyanate.
  • the first method includes a first step of preparing a mixed solution in which the salt compound represented by the chemical formula (2) is added to fluorosulfuric acid, and adding or dropping fluorosulfonyl isocyanate to the mixed solution. And a second step.
  • the mixed liquid to which fluorosulfonyl isocyanate is added may be heated to react fluorosulfuric acid with fluorosulfonyl isocyanate.
  • the mixture containing fluorosulfuric acid and the salt compound prepared in the first step is heated in advance, and fluorosulfonylisocyanate is added thereto, whereby fluorosulfuric acid and fluorosulfonylisocyanate are added. You may make it react.
  • the salt compound represented by the chemical formula (2) is 0.1 to 10 times in molar ratio with respect to fluorosulfuric acid reacting with fluorosulfonyl isocyanate. Note that it is prepared to be in range.
  • the reaction temperature of fluorosulfuric acid and fluorosulfonyl isocyanate is in the range of 50 to 170 ° C. as described above. Note that control.
  • the above chemical formula is obtained by adding a predetermined base to one raw material fluorosulfuric acid and reacting with a part of the fluorosulfuric acid.
  • generating the salt compound shown by (2) is mentioned.
  • the reaction solution is generated by adding one or more compounds (bases) selected from the group consisting of ammonia and amine to fluorosulfuric acid. And a second step of adding or dripping fluorosulfonyl isocyanate to the reaction solution.
  • the reaction liquid to which fluorosulfonyl isocyanate is added may be heated to react fluorosulfuric acid with fluorosulfonyl isocyanate.
  • reaction liquid prepared in the first step and containing the fluorosulfuric acid and the salt compound is heated in advance, and fluorosulfonylisocyanate is added thereto, whereby fluorosulfuric acid and fluorosulfonylisocyanate are added. You may make it react.
  • fluorosulfonyl isocyanate is added to the reaction solution containing the mixture of fluorosulfuric acid and fluorosulfate obtained in the first step, followed by heating.
  • the reaction solution is heated, and fluorosulfonyl isocyanate is added dropwise to the reaction solution.
  • fluorosulfuric acid and fluorosulfonyl isocyanate can be reacted in the presence of the salt compound represented by the chemical formula (2).
  • reaction was complete
  • generation of carbon dioxide gas was confirmed.
  • the reaction solution in the reaction was analyzed by 19 F-NMR.
  • a 51.9 ppm peak indicating the presence of bis (fluorosulfonyl) imide was confirmed.
  • the yield of bis (fluorosulfonyl) imide based on fluorosulfonyl isocyanate was 85%.
  • Example 3 A glass reactor having a capacity of 50 mL equipped with a stirrer and a thermometer was charged with 3.2 g of ammonium chloride, and 15.0 g of fluorosulfuric acid was added dropwise at room temperature. Simultaneously with the dropwise addition of fluorosulfuric acid, generation of hydrogen chloride gas was confirmed. Then, while maintaining the temperature at 120 ° C., 18.8 g of fluorosulfonyl isocyanate was dropped into the reactor over 22 hours, and after the completion of dropping, the reaction was further continued for 6 hours, and then the reaction was terminated. During the reaction, generation of carbon dioxide gas was confirmed.
  • FIG. 1 shows changes in the yield of bis (fluorosulfonyl) imide in Examples 1 to 4 and Comparative Example 1.
  • the horizontal axis shows the elapsed time (hour) from the start of the reaction, and the vertical axis shows the yield (%) of bis (fluorosulfonyl) imide based on fluorosulfonyl isocyanate by the internal standard addition method. Yes.
  • the following results were shown from the results shown in FIG. That is, in Examples 1 to 4 of the present invention, bis (fluorosulfonyl) imide was produced at a higher reaction rate and in a higher yield than Comparative Example 1.
  • the reaction rate can be improved by reacting fluorosulfuric acid with fluorosulfonyl isocyanate in the presence of a predetermined salt. Therefore, it is possible to provide a method for producing bis (fluorosulfonyl) imide which has a high reaction rate and can be produced by a simple method.

Abstract

La présente invention concerne une méthode simple de fabrication de bis(fluorosulfonyl)imide, avec un fort taux de réaction, caractérisée en ce que de l'acide fluorosulfurique et de l'isocyanate fluorosulfurique sont mis à réagir en présence d'un ou plusieurs composés salins représentés par la formule chimique MX, dans lesquels M représente un cation métallique alcalin, un cation métallique alcalino-terreux ou un cation onium, et X représente un des anions suivants : F−, Cl−, Br−, I−, SO4 2−, FSO3 −, ou (FSO2)2N−.
PCT/JP2011/068553 2010-08-24 2011-08-16 Méthode de fabrication de bis(fluorosulfonyl)imide WO2012026360A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010187381A JP5653130B2 (ja) 2010-08-24 2010-08-24 ビス（フルオロスルホニル）イミドの製造方法
JP2010-187381 2010-08-24

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WO2012026360A1 true WO2012026360A1 (fr) 2012-03-01

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8377406B1 (en) 2012-08-29 2013-02-19 Boulder Ionics Corporation Synthesis of bis(fluorosulfonyl)imide
US11267707B2 (en) 2019-04-16 2022-03-08 Honeywell International Inc Purification of bis(fluorosulfonyl) imide
CN114604832A (zh) * 2022-03-19 2022-06-10 珠海市赛纬电子材料股份有限公司 双氟磺酰亚胺锂的制备方法及双氟磺酰亚胺锂的应用

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022510124A (ja) * 2019-08-22 2022-01-26 フジアン ヨンジン テクノロジー カンパニー リミテッド リチウムイオン電池用のフッ素化導電性塩の新しい合成プロセス

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3379509A (en) * 1961-12-09 1968-04-23 Olin Mathieson Imino bis (sulfuryl halide) product and process for preparing the same
US3387946A (en) * 1963-10-29 1968-06-11 Olin Mathieson Process for preparing imino-bis
WO2009123328A1 (fr) * 2008-03-31 2009-10-08 Nippon Shokubai Co., Ltd. Sel sulfonylimide et procédé de production de celui-ci
WO2010010613A1 (fr) * 2008-07-23 2010-01-28 第一工業製薬株式会社 Procédé de production d'un composé de type anion du bis(fluorosulfonyl)imide, et d'un composé de type paire d'ions

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4660596B2 (ja) * 2009-01-22 2011-03-30 株式会社日本触媒 フルオロスルホニルイミド類およびその製造方法
JP5208782B2 (ja) * 2009-01-22 2013-06-12 株式会社日本触媒 フルオロスルホニルイミド類およびその製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3379509A (en) * 1961-12-09 1968-04-23 Olin Mathieson Imino bis (sulfuryl halide) product and process for preparing the same
US3387946A (en) * 1963-10-29 1968-06-11 Olin Mathieson Process for preparing imino-bis
WO2009123328A1 (fr) * 2008-03-31 2009-10-08 Nippon Shokubai Co., Ltd. Sel sulfonylimide et procédé de production de celui-ci
WO2010010613A1 (fr) * 2008-07-23 2010-01-28 第一工業製薬株式会社 Procédé de production d'un composé de type anion du bis(fluorosulfonyl)imide, et d'un composé de type paire d'ions

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8377406B1 (en) 2012-08-29 2013-02-19 Boulder Ionics Corporation Synthesis of bis(fluorosulfonyl)imide
US11267707B2 (en) 2019-04-16 2022-03-08 Honeywell International Inc Purification of bis(fluorosulfonyl) imide
CN114604832A (zh) * 2022-03-19 2022-06-10 珠海市赛纬电子材料股份有限公司 双氟磺酰亚胺锂的制备方法及双氟磺酰亚胺锂的应用

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