WO2012026360A1 - Bis(fluorosulfonyl)imide manufacturing method - Google Patents
Bis(fluorosulfonyl)imide manufacturing method Download PDFInfo
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- 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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- C—CHEMISTRY; METALLURGY
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- 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
A simple bis(fluorosulfonyl)imide manufacturing method, with a high reaction rate, characterized in that fluorosulfuric acid and fluorosulfonyl isocyanate are reacted in the presence of one or more salt compounds represented by the chemical formula MX, in which M represents an alkali metal cation, an alkali earth metal cation, or an onium cation, and X represents one of the following anions: F−, Cl−, Br−, I−, SO4
2
−, FSO3
−, or (FSO2)2N−.
Description
本発明は、ビス（フルオロスルホニル）イミドの製造方法の改良に関する。
本願は、２０１０年８月２４日に、日本に出願された特願２０１０－１８７３８１号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to an improved method for producing bis (fluorosulfonyl) imide.
This application claims priority based on Japanese Patent Application No. 2010-187381 filed in Japan on August 24, 2010, the contents of which are incorporated herein by reference.
本願は、２０１０年８月２４日に、日本に出願された特願２０１０－１８７３８１号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to an improved method for producing bis (fluorosulfonyl) imide.
This application claims priority based on Japanese Patent Application No. 2010-187381 filed in Japan on August 24, 2010, the contents of which are incorporated herein by reference.
ビス（フルオロスルホニル）イミド（（ＦＳＯ２）２ＮＨ）は、イオン導電材料やイオン液体のアニオン源として有用な物質であることが知られている。そして、ビス（フルオロスルホニル）イミドの製造方法としては、下記の非特許文献１が知られている。
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.
具体的に、非特許文献１には、フルオロ硫酸（ＦＳＯ３Ｈ）とフルオロスルホニルイソシアネート（ＦＳＯ２ＮＣＯ）とを混合した後に加熱して反応させる方法が開示されている。これにより、下記反応式（Ａ）に示すような化学反応が生じ、ビス（フルオロスルホニル）イミド及び炭酸ガス（ＣＯ２）が生成される。生成したビス（フルオロスルホニル）イミド及び過剰に投入したフルオロ硫酸は減圧蒸留で回収することができる。
Specifically, 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.
しかしながら、非特許文献１に開示されているビス（フルオロスルホニル）イミドの製造方法では、１２０℃の反応温度で１５０時間反応を行なって収率が７８％であり、反応が非常に遅いという問題があった。したがって、非特許文献１に記載の方法は、工業的に実施することが困難であった。
However, 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.
本発明は、上記事情に鑑みてなされたものであって、反応速度が速く、簡便な方法で生産が可能なビス（フルオロスルホニル）イミドの製造方法を提供することを目的とする。
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.
本発明者らは、上記課題について鋭意研究した結果、フルオロ硫酸とフルオロスルホニルイソシアネートとを所定の塩の存在下で反応させることにより、反応速度を向上させることができることを見出し、本発明に至った。
As a result of earnest studies on the above problems, 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. .
本発明の一態様のビス（フルオロスルホニル）イミドの製造方法は、フルオロ硫酸とフルオロスルホニルイソシアネートとを、下記化学式（１）で示される塩化合物のいずれか一種又は二種以上の存在下で反応させるビス（フルオロスルホニル）イミド生成工程を備え、下記化学式（１）の記号Ｍは、アルカリ金属、アルカリ土類金属、オニウムカチオンのいずれか一種のカチオンであり、下記化学式（１）の記号Ｘは、Ｆ－、Ｃｌ－、Ｂｒ－、Ｉ－、ＳＯ４
２－、ＦＳＯ３
－、（ＦＳＯ２）２Ｎ－のいずれか一種のアニオンであるビス（フルオロスルホニル）イミドの製造方法である。
ＭＸ （１） In the method for producing bis (fluorosulfonyl) imide of one embodiment of the present invention, 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). It comprises a bis (fluorosulfonyl) imide production step, the symbol M in the following chemical formula (1) is a cation of any one of an alkali metal, an alkaline earth metal, and an onium cation, and the symbol X in the following chemical formula (1) is This is a method for producing bis (fluorosulfonyl) imide, which is an anion of any one of F − , Cl − , Br − , I − , SO 4 2− , FSO 3 − , and (FSO 2 ) 2 N − .
MX (1)
ＭＸ （１） In the method for producing bis (fluorosulfonyl) imide of one embodiment of the present invention, 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). It comprises a bis (fluorosulfonyl) imide production step, the symbol M in the following chemical formula (1) is a cation of any one of an alkali metal, an alkaline earth metal, and an onium cation, and the symbol X in the following chemical formula (1) is This is a method for producing bis (fluorosulfonyl) imide, which is an anion of any one of F − , Cl − , Br − , I − , SO 4 2− , FSO 3 − , and (FSO 2 ) 2 N − .
MX (1)
上記ビス（フルオロスルホニル）イミドの製造方法は、フルオロ硫酸に前記塩化合物を加えることにより混合液を調製する混合液調製工程と、前記混合液調製工程後に、前記混合液にフルオロスルホニルイソシアネートを添加する添加工程をさらに備えても良い。
また、上記ビス（フルオロスルホニル）イミドの製造方法では、前記添加工程後にフルオロスルホニルイソシアネートが添加された前記混合液を加熱することにより、前記ビス（フルオロスルホニル）イミド生成工程を行ってもよい。
また、上記ビス（フルオロスルホニル）イミドの製造方法では、前記混合液調製工程と前記添加工程との間に、前記混合液を加熱し、前記添加工程にて、加熱された前記混合液にフルオロスルホニルイソシアネートを滴下することにより、前記ビス（フルオロスルホニル）イミド生成工程を行ってもよい。
また、上記ビス（フルオロスルホニル）イミドの製造方法は、フルオロ硫酸に、アンモニア、アミンからなる群から選ばれた化合物のいずれか一種又は二種以上を添加して、前記化学式（１）で示される塩化合物を含む反応液を生成する反応液調製工程と、前記反応液調製工程後に、前記反応液にフルオロスルホニルイソシアネートを添加する添加工程をさらに備えてもよい。
また、上記ビス（フルオロスルホニル）イミドの製造方法では、前記添加工程後にフルオロスルホニルイソシアネートが添加された前記反応液を加熱することにより、前記ビス（フルオロスルホニル）イミド生成工程を行ってもよい。
また、上記ビス（フルオロスルホニル）イミドの製造方法では、前記反応液調製工程と前記添加工程との間に、前記反応液を加熱し、前記添加工程にて、加熱された前記反応液にフルオロスルホニルイソシアネートを滴下することにより、前記ビス（フルオロスルホニル）イミド生成工程を行ってもよい。 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.
Moreover, in the manufacturing method of the said bis (fluoro sulfonyl) imide, the said bis (fluoro sulfonyl) imide production | generation process may be performed by heating the said liquid mixture with which the fluoro sulfonyl isocyanate was added after the said addition process.
In the method for producing bis (fluorosulfonyl) imide, 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. You may perform the said bis (fluoro sulfonyl) imide production | generation process by dripping an isocyanate.
Moreover, 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). You may further provide the reaction liquid preparation process which produces | generates the reaction liquid containing a salt compound, and the addition process which adds fluorosulfonyl isocyanate to the said reaction liquid after the said reaction liquid preparation process.
Moreover, in the manufacturing method of the said bis (fluoro sulfonyl) imide, you may perform the said bis (fluoro sulfonyl) imide production | generation process by heating the said reaction liquid to which fluoro sulfonyl isocyanate was added after the said addition process.
In the method for producing bis (fluorosulfonyl) imide, 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. You may perform the said bis (fluoro sulfonyl) imide production | generation process by dripping an isocyanate.
また、上記ビス（フルオロスルホニル）イミドの製造方法では、前記添加工程後にフルオロスルホニルイソシアネートが添加された前記混合液を加熱することにより、前記ビス（フルオロスルホニル）イミド生成工程を行ってもよい。
また、上記ビス（フルオロスルホニル）イミドの製造方法では、前記混合液調製工程と前記添加工程との間に、前記混合液を加熱し、前記添加工程にて、加熱された前記混合液にフルオロスルホニルイソシアネートを滴下することにより、前記ビス（フルオロスルホニル）イミド生成工程を行ってもよい。
また、上記ビス（フルオロスルホニル）イミドの製造方法は、フルオロ硫酸に、アンモニア、アミンからなる群から選ばれた化合物のいずれか一種又は二種以上を添加して、前記化学式（１）で示される塩化合物を含む反応液を生成する反応液調製工程と、前記反応液調製工程後に、前記反応液にフルオロスルホニルイソシアネートを添加する添加工程をさらに備えてもよい。
また、上記ビス（フルオロスルホニル）イミドの製造方法では、前記添加工程後にフルオロスルホニルイソシアネートが添加された前記反応液を加熱することにより、前記ビス（フルオロスルホニル）イミド生成工程を行ってもよい。
また、上記ビス（フルオロスルホニル）イミドの製造方法では、前記反応液調製工程と前記添加工程との間に、前記反応液を加熱し、前記添加工程にて、加熱された前記反応液にフルオロスルホニルイソシアネートを滴下することにより、前記ビス（フルオロスルホニル）イミド生成工程を行ってもよい。 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.
Moreover, in the manufacturing method of the said bis (fluoro sulfonyl) imide, the said bis (fluoro sulfonyl) imide production | generation process may be performed by heating the said liquid mixture with which the fluoro sulfonyl isocyanate was added after the said addition process.
In the method for producing bis (fluorosulfonyl) imide, 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. You may perform the said bis (fluoro sulfonyl) imide production | generation process by dripping an isocyanate.
Moreover, 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). You may further provide the reaction liquid preparation process which produces | generates the reaction liquid containing a salt compound, and the addition process which adds fluorosulfonyl isocyanate to the said reaction liquid after the said reaction liquid preparation process.
Moreover, in the manufacturing method of the said bis (fluoro sulfonyl) imide, you may perform the said bis (fluoro sulfonyl) imide production | generation process by heating the said reaction liquid to which fluoro sulfonyl isocyanate was added after the said addition process.
In the method for producing bis (fluorosulfonyl) imide, 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. You may perform the said bis (fluoro sulfonyl) imide production | generation process by dripping an isocyanate.
また、上記ビス（フルオロスルホニル）イミドの製造方法では、前記フルオロスルホニルイソシアネートと反応する前記フルオロ硫酸に対する、前記化学式（１）で示される塩化合物の量が、モル比で０．１～１０倍の範囲内であってもよい。
また、上記ビス（フルオロスルホニル）イミドの製造方法では、前記フルオロ硫酸と前記フルオロスルホニルイソシアネートとの反応温度が、５０～１７０℃の範囲内であってもよい。 In the method for producing bis (fluorosulfonyl) imide, 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.
In the method for producing bis (fluorosulfonyl) imide, the reaction temperature between the fluorosulfuric acid and the fluorosulfonyl isocyanate may be in the range of 50 to 170 ° C.
また、上記ビス（フルオロスルホニル）イミドの製造方法では、前記フルオロ硫酸と前記フルオロスルホニルイソシアネートとの反応温度が、５０～１７０℃の範囲内であってもよい。 In the method for producing bis (fluorosulfonyl) imide, 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.
In the method for producing bis (fluorosulfonyl) imide, the reaction temperature between the fluorosulfuric acid and the fluorosulfonyl isocyanate may be in the range of 50 to 170 ° C.
本発明のビス（フルオロスルホニル）イミドの製造方法によれば、フルオロ硫酸とフルオロスルホニルイソシアネートとを所定の塩の存在下で反応させることにより、反応速度を向上させることができる。したがって、反応速度が速く、簡便な方法で生産が可能なビス（フルオロスルホニル）イミドの製造方法を提供することができる。
According to the method for producing bis (fluorosulfonyl) imide of the present invention, 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.
以下、本発明のビス（フルオロスルホニル）イミドの製造方法について詳細に説明する。
本発明のビス（フルオロスルホニル）イミドの製造方法は、フルオロ硫酸（ＦＳＯ３Ｈ）とフルオロスルホニルイソシアネート（ＦＳＯ２ＮＣＯ）とを、下記化学式（２）で示される塩化合物の存在下で反応させることを特徴としている。
ＭＸ （２） Hereinafter, the method for producing bis (fluorosulfonyl) imide of the present invention will be described in detail.
In the method for producing bis (fluorosulfonyl) imide of the present invention, fluorosulfuric acid (FSO 3 H) and fluorosulfonyl isocyanate (FSO 2 NCO) are reacted in the presence of a salt compound represented by the following chemical formula (2). It is characterized by.
MX (2)
本発明のビス（フルオロスルホニル）イミドの製造方法は、フルオロ硫酸（ＦＳＯ３Ｈ）とフルオロスルホニルイソシアネート（ＦＳＯ２ＮＣＯ）とを、下記化学式（２）で示される塩化合物の存在下で反応させることを特徴としている。
ＭＸ （２） Hereinafter, the method for producing bis (fluorosulfonyl) imide of the present invention will be described in detail.
In the method for producing bis (fluorosulfonyl) imide of the present invention, fluorosulfuric acid (FSO 3 H) and fluorosulfonyl isocyanate (FSO 2 NCO) are reacted in the presence of a salt compound represented by the following chemical formula (2). It is characterized by.
MX (2)
但し、上記化学式（２）において、上記Ｍは、アルカリ金属カチオン、アルカリ土類金属カチオン、オニウムカチオンのいずれか一種のカチオンである。
具体的には、アルカリ金属元素としては、リチウム（Ｌｉ）、ナトリウム（Ｎａ）、カリウム（Ｋ）等が挙げられる。
アルカリ土類金属元素としては、カルシウム（Ｃａ）、ストロンチウム（Ｓｒ）、バリウム（Ｂａ）等が挙げられる。
オニウムイオンとしては、例えば、窒素、硫黄、酸素、リン、セレン、錫、ヨウ素、アンチモン等の孤立電子対を有する元素を含んだ化合物に陽イオン型の原子団が配位して生ずる少なくとも一つの有機基を有するカチオンであればよく、特に制限されない。 However, in the chemical formula (2), M is any one of an alkali metal cation, an alkaline earth metal cation, and an onium cation.
Specifically, examples of the alkali metal element include lithium (Li), sodium (Na), potassium (K), and the like.
Examples of the alkaline earth metal element include calcium (Ca), strontium (Sr), barium (Ba), and the like.
As 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.
具体的には、アルカリ金属元素としては、リチウム（Ｌｉ）、ナトリウム（Ｎａ）、カリウム（Ｋ）等が挙げられる。
アルカリ土類金属元素としては、カルシウム（Ｃａ）、ストロンチウム（Ｓｒ）、バリウム（Ｂａ）等が挙げられる。
オニウムイオンとしては、例えば、窒素、硫黄、酸素、リン、セレン、錫、ヨウ素、アンチモン等の孤立電子対を有する元素を含んだ化合物に陽イオン型の原子団が配位して生ずる少なくとも一つの有機基を有するカチオンであればよく、特に制限されない。 However, in the chemical formula (2), M is any one of an alkali metal cation, an alkaline earth metal cation, and an onium cation.
Specifically, examples of the alkali metal element include lithium (Li), sodium (Na), potassium (K), and the like.
Examples of the alkaline earth metal element include calcium (Ca), strontium (Sr), barium (Ba), and the like.
As 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.
上記化学式（２）において、上記Ｘは、フッ素アニオン（Ｆ－）、塩素アニオン（Ｃｌ－）、臭素アニオン（Ｂｒ－）、ヨウ素アニオン（Ｉ－）、硫酸アニオン（ＳＯ４
２－）、フルオロ硫酸アニオン（ＦＳＯ３
－）、ビス（フルオロスルホニル）イミドアニオン（（ＦＳＯ２）２Ｎ－）のいずれか一種のアニオンである。
In the chemical formula (2), 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. An anion (FSO 3 − ) or a bis (fluorosulfonyl) imide anion ((FSO 2 ) 2 N − ).
本発明のビス（フルオロスルホニル）イミドの製造方法では、上記化学式（２）で示される塩化合物の少なくともいずれか一種の存在下で、フルオロ硫酸およびフルオロスルホニルイソシアネートを反応させることが必要とされる。また、上記化学式（２）で示される塩化合物を二種以上存在させても良い。
In the method for producing bis (fluorosulfonyl) imide of the present invention, it is necessary to react fluorosulfuric acid and fluorosulfonyl isocyanate in the presence of at least one of the salt compounds represented by the chemical formula (2). Two or more salt compounds represented by the chemical formula (2) may be present.
本発明のビス（フルオロスルホニル）イミドの製造方法では、上記化学式（２）で示される塩化合物を、フルオロスルホニルイソシアネートと反応するフルオロ硫酸に対して、モル比で０．１～１０倍の範囲で存在させることが好ましい。さらに好ましい塩化合物のフルオロ硫酸に対するモル比としては、０．１～１倍の範囲が挙げられる。ここで、フルオロスルホニルイソシアネートと反応するフルオロ硫酸に対して、モル比で０．１倍未満の上記塩化合物の存在下では、フルオロ硫酸とフルオロスルホニルイソシアネートとの反応速度を向上させる効果が十分に得られないために好ましくない。一方、フルオロスルホニルイソシアネートと反応するフルオロ硫酸に対して、モル比で１０倍を超えると経済的に無駄である。
In the method for producing bis (fluorosulfonyl) imide of the present invention, 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. Here, in the presence of the above salt compound having a molar ratio of less than 0.1 times with respect to fluorosulfuric acid that reacts with fluorosulfonyl isocyanate, the effect of improving the reaction rate between fluorosulfuric acid and fluorosulfonyl isocyanate is sufficiently obtained. This is not preferable because On the other hand, when it exceeds 10 times in molar ratio with respect to the fluorosulfuric acid which reacts with fluorosulfonyl isocyanate, it is economically useless.
さらに、本発明のビス（フルオロスルホニル）イミドの製造方法では、フルオロ硫酸とフルオロスルホニルイソシアネートとの反応温度を、５０～１７０℃の範囲とすることが好ましく、６０～１５０℃の範囲とすることがより好ましい。ここで、上記反応温度が５０度未満であると、反応が遅くなるため好ましくない。一方、上記反応温度が１７０℃を超えると、一方の原料であるフルオロスルホニルイソシアネートが揮発しやすくなり、ビス（フルオロスルホニル）イミドの収率の低下を招くために好ましくない。
Furthermore, in the method for producing bis (fluorosulfonyl) imide of the present invention, 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. Here, it is not preferable that the reaction temperature is less than 50 degrees, because the reaction becomes slow. On the other hand, when 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.
本発明の反応機構は、以下のように説明される。上記式（２）で示される塩化合物（ＭＸ）の存在下で、フルオロ硫酸とフルオロスルホニルイソシアネートとを反応させることにより、下記反応式（Ｂ）で示すような化学反応が進む。その結果、ビス（フルオロスルホニル）イミドと、二酸化炭素（ＣＯ２）とが生成される。
本発明のメリットとしては、副生する二酸化炭素が気体であるため、反応系外への排出が容易であり、反応系に残存しないことが挙げられる。 The reaction mechanism of the present invention is explained as follows. 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. As a result, bis (fluorosulfonyl) imide and carbon dioxide (CO 2 ) are generated.
As an advantage of the present invention, since 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.
本発明のメリットとしては、副生する二酸化炭素が気体であるため、反応系外への排出が容易であり、反応系に残存しないことが挙げられる。 The reaction mechanism of the present invention is explained as follows. 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. As a result, bis (fluorosulfonyl) imide and carbon dioxide (CO 2 ) are generated.
As an advantage of the present invention, since 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.
以下に、本発明のビス（フルオロスルホニル）イミドの製造方法の第一の方法を説明する。上記第一の方法では、フルオロ硫酸とフルオロスルホニルイソシアネートとの反応系に、上記化学式（２）で示される塩化合物を直接添加する。
Hereinafter, the first method of producing the bis (fluorosulfonyl) imide of the present invention will be described. In the first method, the salt compound represented by the chemical formula (2) is directly added to the reaction system of fluorosulfuric acid and fluorosulfonyl isocyanate.
具体的説明すると、上記第一の方法は、フルオロ硫酸に上記化学式（２）で示される塩化合物を加えた混合液を調整する第一の工程と、この混合液にフルオロスルホニルイソシアネートを添加または滴下する第二の工程とを含む。
上記第一の方法では、上記第一の工程および第二の工程が終了した後、フルオロスルホニルイソシアネートを添加された混合液を加熱することで、フルオロ硫酸とフルオロスルホニルイソシアネートとを反応させても良い。
また、別法として、上記第一の工程で調製された、フルオロ硫酸および上記塩化合物を含む混合液を予め加熱し、そこへフルオロスルホニルイソシアネートを添加することで、フルオロ硫酸とフルオロスルホニルイソシアネートとを反応させても良い。 Specifically, 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.
In the first method, after the first step and the second step are completed, the mixed liquid to which fluorosulfonyl isocyanate is added may be heated to react fluorosulfuric acid with fluorosulfonyl isocyanate. .
As another method, 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.
上記第一の方法では、上記第一の工程および第二の工程が終了した後、フルオロスルホニルイソシアネートを添加された混合液を加熱することで、フルオロ硫酸とフルオロスルホニルイソシアネートとを反応させても良い。
また、別法として、上記第一の工程で調製された、フルオロ硫酸および上記塩化合物を含む混合液を予め加熱し、そこへフルオロスルホニルイソシアネートを添加することで、フルオロ硫酸とフルオロスルホニルイソシアネートとを反応させても良い。 Specifically, 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.
In the first method, after the first step and the second step are completed, the mixed liquid to which fluorosulfonyl isocyanate is added may be heated to react fluorosulfuric acid with fluorosulfonyl isocyanate. .
As another method, 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.
第一の方法における第一の工程では、上述したように、上記化学式（２）で示される塩化合物を、フルオロスルホニルイソシアネートと反応するフルオロ硫酸に対して、モル比で０．１～１０倍の範囲となるように調製することに留意する。
In the first step of the first method, as described above, 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.
第一の方法において、上記塩化合物存在下で、フルオロ硫酸およびフルオロスルホニルイソシアネートを反応させる工程では、上述したように、フルオロ硫酸とフルオロスルホニルイソシアネートとの反応温度を、５０～１７０℃の範囲となるように制御することに留意する。
In the first method, in the step of reacting fluorosulfuric acid and fluorosulfonyl isocyanate in the presence of the salt compound, the reaction temperature of fluorosulfuric acid and fluorosulfonyl isocyanate is in the range of 50 to 170 ° C. as described above. Note that control.
また、本発明のビス（フルオロスルホニル）イミドの製造方法の第二の方法としては、一方の原料であるフルオロ硫酸に所定の塩基を添加して当該フルオロ硫酸の一部と反応させることにより上記化学式（２）で示される塩化合物を生成する方法が挙げられる。
Further, as a second method of producing the bis (fluorosulfonyl) imide of the present invention, 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. The method of producing | generating the salt compound shown by (2) is mentioned.
具体的説明すると、上記第二の方法は、フルオロ硫酸に、アンモニア、アミンからなる群から選ばれた化合物（塩基）のいずれか一種又は二種以上を添加して、反応液を生成する第一の工程と、この反応液にフルオロスルホニルイソシアネートを添加または滴下する第二の工程とを含む。
上記第二の方法では、上記第一の工程および第二の工程が終了した後、フルオロスルホニルイソシアネートを添加された反応液を加熱することで、フルオロ硫酸とフルオロスルホニルイソシアネートとを反応させても良い。
また、別法として、上記第一の工程で調製された、フルオロ硫酸および上記塩化合物を含む反応液を予め加熱し、そこへフルオロスルホニルイソシアネートを添加することで、フルオロ硫酸とフルオロスルホニルイソシアネートとを反応させても良い。 Specifically, in the second method, 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.
In the second method, after the first step and the second step are completed, the reaction liquid to which fluorosulfonyl isocyanate is added may be heated to react fluorosulfuric acid with fluorosulfonyl isocyanate. .
As another method, the 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.
上記第二の方法では、上記第一の工程および第二の工程が終了した後、フルオロスルホニルイソシアネートを添加された反応液を加熱することで、フルオロ硫酸とフルオロスルホニルイソシアネートとを反応させても良い。
また、別法として、上記第一の工程で調製された、フルオロ硫酸および上記塩化合物を含む反応液を予め加熱し、そこへフルオロスルホニルイソシアネートを添加することで、フルオロ硫酸とフルオロスルホニルイソシアネートとを反応させても良い。 Specifically, in the second method, 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.
In the second method, after the first step and the second step are completed, the reaction liquid to which fluorosulfonyl isocyanate is added may be heated to react fluorosulfuric acid with fluorosulfonyl isocyanate. .
As another method, the 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.
第二の方法における第一の工程では、先ず、フルオロ硫酸にアンモニア（ＮＨ３）、アミン（ＮＲ１Ｒ２Ｒ３）からなる群から選ばれた化合物のいずれか一種又は二種以上を添加する。
In the first step of the second method, first, one or more compounds selected from the group consisting of ammonia (NH 3 ) and amine (NR 1 R 2 R 3 ) are added to fluorosulfuric acid. .
フルオロ硫酸に上記化合物を添加することにより、フルオロ硫酸の一部と添加した上記化合物とが反応し、上記化学式（２）で示される化合物の一種であるフルオロ硫酸塩（ＦＳＯ３・Ｍ）が生成する。これにより、フルオロ硫酸と上記化合物との反応液である、フルオロ硫酸とフルオロ硫酸塩との混合物を含む反応液が生成される。
By adding the above compound to the fluorosulfuric acid, a part of the fluorosulfuric acid reacts with the added compound to produce a fluorosulfate (FSO 3 · M) which is a kind of the compound represented by the chemical formula (2). To do. As a result, a reaction liquid containing a mixture of fluorosulfuric acid and fluorosulfate, which is a reaction liquid of fluorosulfuric acid and the above compound, is generated.
第二の方法における第二の工程では、第一の工程で得られたフルオロ硫酸とフルオロ硫酸塩との混合物を含む反応液に、フルオロスルホニルイソシアネートを添加した後、加熱する。もしくは反応液を加熱し、その反応液にフルオロスルホニルイソシアネートを滴下する。これにより、第二の方法においても、フルオロ硫酸とフルオロスルホニルイソシアネートとを、上記化学式（２）で示される塩化合物の存在下で反応させることができる。
In the second step of the second method, fluorosulfonyl isocyanate is added to the reaction solution containing the mixture of fluorosulfuric acid and fluorosulfate obtained in the first step, followed by heating. Alternatively, the reaction solution is heated, and fluorosulfonyl isocyanate is added dropwise to the reaction solution. Thereby, also in the second method, fluorosulfuric acid and fluorosulfonyl isocyanate can be reacted in the presence of the salt compound represented by the chemical formula (2).
以上説明したように、本発明のビス（フルオロスルホニル）イミドの製造方法によれば、フルオロ硫酸とフルオロスルホニルイソシアネートとを化学式（２）で示される塩化合物の存在下で反応させることにより、ビス（フルオロスルホニル）イミドを生成する反応の速度を向上させることができる。これにより、反応速度が速く、簡便なビス（フルオロスルホニル）イミドの製造方法を提供することができる。
As described above, according to the method for producing bis (fluorosulfonyl) imide of the present invention, by reacting fluorosulfuric acid with fluorosulfonyl isocyanate in the presence of the salt compound represented by the chemical formula (2), bis ( The rate of the reaction to produce (fluorosulfonyl) imide can be improved. Thereby, the reaction rate is fast and a simple method for producing bis (fluorosulfonyl) imide can be provided.
したがって、本発明によれば、イオン伝導材料及びイオン液体のアニオンとして有用なビス（フルオロスルホニル）イミドを容易に製造することが可能となる。
Therefore, according to the present invention, it is possible to easily produce bis (fluorosulfonyl) imide useful as an anion of an ion conductive material and an ionic liquid.
以下、実施例によって本発明の効果をさらに詳細に説明する。なお、本発明は実施例によって、なんら限定されるものではない。
Hereinafter, the effects of the present invention will be described in more detail with reference to examples. In addition, this invention is not limited at all by the Example.
（実施例１）
撹拌機および温度計を備えた容量が１００ｍＬの反応器にフルオロ硫酸１４ｇ、フルオロ硫酸＝１，８－ジアザビシクロ[５，４，０]ウンデカ－７－エン塩３５ｇ、フルオロスルホニルイソシアネート１８ｇを仕込み加熱し、６時間反応させた。反応開始時では、反応器の温度計の測定値が７９℃になった時点でフルオロスルホニルイソシアネートの還流が確認された。そして、その後反応が進むにつれ原料のフルオロスルホニルイソシアネートが消費されたため、徐々に昇温し、４時間後には、反応器の温度計の測定値は１４０℃に達した。さらに、その状態のまま１４０℃で２時間反応させた後、反応を終了した。反応中は、二酸化炭素ガスの発生が確認された。
反応終了後、反応器内の反応液を水－アセトン混合液に溶解し、１９Ｆ－ＮＭＲにて分析を行なった。その結果、ビス（フルオロスルホニル）イミドの存在を示す５１．９ｐｐｍのピークが確認された。また、内部標準添加法により、ビス（フルオロスルホニル）イミドのフルオロスルホニルイソシアネート基準の収率は、６４％であった。 Example 1
A reactor having a capacity of 100 mL equipped with a stirrer and a thermometer was charged with 14 g of fluorosulfuric acid, 35 g of fluorosulfuric acid = 1,8-diazabicyclo [5,4,0] undec-7-ene salt, and 18 g of fluorosulfonyl isocyanate. And allowed to react for 6 hours. At the start of the reaction, the reflux of the fluorosulfonyl isocyanate was confirmed when the measured value of the thermometer in the reactor reached 79 ° C. Then, since the raw material fluorosulfonyl isocyanate was consumed as the reaction proceeded, the temperature was gradually raised, and after 4 hours, the measured value of the reactor thermometer reached 140 ° C. Furthermore, after making it react at 140 degreeC for 2 hours with the state, reaction was complete | finished. During the reaction, generation of carbon dioxide gas was confirmed.
After completion of the reaction, the reaction solution in the reactor was dissolved in a water-acetone mixed solution and analyzed by 19 F-NMR. As a result, a 51.9 ppm peak indicating the presence of bis (fluorosulfonyl) imide was confirmed. Further, the yield based on fluorosulfonyl isocyanate of bis (fluorosulfonyl) imide by the internal standard addition method was 64%.
撹拌機および温度計を備えた容量が１００ｍＬの反応器にフルオロ硫酸１４ｇ、フルオロ硫酸＝１，８－ジアザビシクロ[５，４，０]ウンデカ－７－エン塩３５ｇ、フルオロスルホニルイソシアネート１８ｇを仕込み加熱し、６時間反応させた。反応開始時では、反応器の温度計の測定値が７９℃になった時点でフルオロスルホニルイソシアネートの還流が確認された。そして、その後反応が進むにつれ原料のフルオロスルホニルイソシアネートが消費されたため、徐々に昇温し、４時間後には、反応器の温度計の測定値は１４０℃に達した。さらに、その状態のまま１４０℃で２時間反応させた後、反応を終了した。反応中は、二酸化炭素ガスの発生が確認された。
反応終了後、反応器内の反応液を水－アセトン混合液に溶解し、１９Ｆ－ＮＭＲにて分析を行なった。その結果、ビス（フルオロスルホニル）イミドの存在を示す５１．９ｐｐｍのピークが確認された。また、内部標準添加法により、ビス（フルオロスルホニル）イミドのフルオロスルホニルイソシアネート基準の収率は、６４％であった。 Example 1
A reactor having a capacity of 100 mL equipped with a stirrer and a thermometer was charged with 14 g of fluorosulfuric acid, 35 g of fluorosulfuric acid = 1,8-diazabicyclo [5,4,0] undec-7-ene salt, and 18 g of fluorosulfonyl isocyanate. And allowed to react for 6 hours. At the start of the reaction, the reflux of the fluorosulfonyl isocyanate was confirmed when the measured value of the thermometer in the reactor reached 79 ° C. Then, since the raw material fluorosulfonyl isocyanate was consumed as the reaction proceeded, the temperature was gradually raised, and after 4 hours, the measured value of the reactor thermometer reached 140 ° C. Furthermore, after making it react at 140 degreeC for 2 hours with the state, reaction was complete | finished. During the reaction, generation of carbon dioxide gas was confirmed.
After completion of the reaction, the reaction solution in the reactor was dissolved in a water-acetone mixed solution and analyzed by 19 F-NMR. As a result, a 51.9 ppm peak indicating the presence of bis (fluorosulfonyl) imide was confirmed. Further, the yield based on fluorosulfonyl isocyanate of bis (fluorosulfonyl) imide by the internal standard addition method was 64%.
（実施例２）
撹拌機および温度計を備えた容量が２００ｍＬの反応器にフルオロ硫酸１９ｇ、フルオロ硫酸＝トリエチルアミン塩３７ｇ、フルオロスルホニルイソシアネート２３ｇを仕込み加熱し、１１時間反応させた。反応開始時では、反応器の温度計の測定値が８２℃になった時点でフルオロスルホニルイソシアネートの還流が確認された。そして、その後反応が進むにつれ原料のフルオロスルホニルイソシアネートが消費されたため、徐々に昇温し、５時間後には、反応器の温度計の測定値は１４０℃に達した。さらに、その状態のまま１４０℃で６時間反応させた後、反応を終了した。反応中は、二酸化炭素ガスの発生が確認された。
反応終了後、反応内の反応液を１９Ｆ－ＮＭＲにて分析を行なった。その結果、ビス（フルオロスルホニル）イミドの存在を示す５１．９ｐｐｍのピークが確認された。また、内部標準添加法により、ビス（フルオロスルホニル）イミドのフルオロスルホニルイソシアネート基準の収率は、８５％であった。 (Example 2)
In a reactor having a capacity of 200 mL equipped with a stirrer and a thermometer, 19 g of fluorosulfuric acid, 37 g of fluorosulfuric acid = triethylamine salt, and 23 g of fluorosulfonyl isocyanate were charged and heated for 11 hours. At the start of the reaction, the reflux of the fluorosulfonyl isocyanate was confirmed when the measured value of the thermometer in the reactor reached 82 ° C. Then, since the raw material fluorosulfonyl isocyanate was consumed as the reaction proceeded, the temperature was gradually raised, and after 5 hours, the measured value of the reactor thermometer reached 140 ° C. Furthermore, after making it react at 140 degreeC for 6 hours with the state, reaction was complete | finished. During the reaction, generation of carbon dioxide gas was confirmed.
After completion of the reaction, the reaction solution in the reaction was analyzed by 19 F-NMR. As a result, a 51.9 ppm peak indicating the presence of bis (fluorosulfonyl) imide was confirmed. Further, according to the internal standard addition method, the yield of bis (fluorosulfonyl) imide based on fluorosulfonyl isocyanate was 85%.
撹拌機および温度計を備えた容量が２００ｍＬの反応器にフルオロ硫酸１９ｇ、フルオロ硫酸＝トリエチルアミン塩３７ｇ、フルオロスルホニルイソシアネート２３ｇを仕込み加熱し、１１時間反応させた。反応開始時では、反応器の温度計の測定値が８２℃になった時点でフルオロスルホニルイソシアネートの還流が確認された。そして、その後反応が進むにつれ原料のフルオロスルホニルイソシアネートが消費されたため、徐々に昇温し、５時間後には、反応器の温度計の測定値は１４０℃に達した。さらに、その状態のまま１４０℃で６時間反応させた後、反応を終了した。反応中は、二酸化炭素ガスの発生が確認された。
反応終了後、反応内の反応液を１９Ｆ－ＮＭＲにて分析を行なった。その結果、ビス（フルオロスルホニル）イミドの存在を示す５１．９ｐｐｍのピークが確認された。また、内部標準添加法により、ビス（フルオロスルホニル）イミドのフルオロスルホニルイソシアネート基準の収率は、８５％であった。 (Example 2)
In a reactor having a capacity of 200 mL equipped with a stirrer and a thermometer, 19 g of fluorosulfuric acid, 37 g of fluorosulfuric acid = triethylamine salt, and 23 g of fluorosulfonyl isocyanate were charged and heated for 11 hours. At the start of the reaction, the reflux of the fluorosulfonyl isocyanate was confirmed when the measured value of the thermometer in the reactor reached 82 ° C. Then, since the raw material fluorosulfonyl isocyanate was consumed as the reaction proceeded, the temperature was gradually raised, and after 5 hours, the measured value of the reactor thermometer reached 140 ° C. Furthermore, after making it react at 140 degreeC for 6 hours with the state, reaction was complete | finished. During the reaction, generation of carbon dioxide gas was confirmed.
After completion of the reaction, the reaction solution in the reaction was analyzed by 19 F-NMR. As a result, a 51.9 ppm peak indicating the presence of bis (fluorosulfonyl) imide was confirmed. Further, according to the internal standard addition method, the yield of bis (fluorosulfonyl) imide based on fluorosulfonyl isocyanate was 85%.
（実施例３）
撹拌機および温度計を備えた容量が５０ｍＬのガラス製反応器に塩化アンモニウム３．２ｇを仕込み、室温でフルオロ硫酸１５．０ｇを滴下した。フルオロ硫酸の滴下と同時に、塩化水素ガスの発生が確認された。
その後、１２０℃に温度を保ちながらフルオロスルホニルイソシアネート１８．８ｇを２２時間かけて反応器内へ滴下し、滴下終了後さらに６時間反応させた後、反応を終了した。反応中は、二酸化炭素ガスの発生が確認された。
反応終了後、反応器内の反応液を１９Ｆ－ＮＭＲにて分析を行なった。その結果、ビス（フルオロスルホニル）イミドの存在を示す５１．９ｐｐｍのピークが確認された。また、内部標準添加法により、ビス（フルオロスルホニル）イミドのフルオロスルホニルイソシアネート基準の収率は、７８％であった。 (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.
After completion of the reaction, the reaction solution in the reactor was analyzed by 19 F-NMR. As a result, a 51.9 ppm peak indicating the presence of bis (fluorosulfonyl) imide was confirmed. In addition, according to the internal standard addition method, the yield of bis (fluorosulfonyl) imide based on fluorosulfonyl isocyanate was 78%.
撹拌機および温度計を備えた容量が５０ｍＬのガラス製反応器に塩化アンモニウム３．２ｇを仕込み、室温でフルオロ硫酸１５．０ｇを滴下した。フルオロ硫酸の滴下と同時に、塩化水素ガスの発生が確認された。
その後、１２０℃に温度を保ちながらフルオロスルホニルイソシアネート１８．８ｇを２２時間かけて反応器内へ滴下し、滴下終了後さらに６時間反応させた後、反応を終了した。反応中は、二酸化炭素ガスの発生が確認された。
反応終了後、反応器内の反応液を１９Ｆ－ＮＭＲにて分析を行なった。その結果、ビス（フルオロスルホニル）イミドの存在を示す５１．９ｐｐｍのピークが確認された。また、内部標準添加法により、ビス（フルオロスルホニル）イミドのフルオロスルホニルイソシアネート基準の収率は、７８％であった。 (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.
After completion of the reaction, the reaction solution in the reactor was analyzed by 19 F-NMR. As a result, a 51.9 ppm peak indicating the presence of bis (fluorosulfonyl) imide was confirmed. In addition, according to the internal standard addition method, the yield of bis (fluorosulfonyl) imide based on fluorosulfonyl isocyanate was 78%.
（実施例４）
撹拌機および温度計を備えた容量が１００ｍＬの反応器にフルオロ硫酸１５ｇを仕込み、そこに、反応器の温度計の測定値を５℃以上１５℃以下に保ちながら、1－メチルイミダゾール１２ｇを１時間かけて滴下し、フルオロ硫酸＝１－メチルイミダゾリウム塩２７ｇを得た。
そして、得られたフルオロ硫酸＝１－メチルイミダゾリウム塩２７ｇにフルオロ硫酸１５ｇを添加し、１２０℃に加熱した。そこに、反応器の温度計の測定値を１２０℃に保ちながらフルオロスルホニルイソシアネート１９ｇを７．５時間かけて滴下し、滴下終了後さらに３．５時間反応させた後、反応を終了した。反応中は、二酸化炭素ガスの発生が確認された。
反応終了後、反応液を水－アセトン混合液に溶解し、１９Ｆ－ＮＭＲにて分析を行なった。その結果、ビス（フルオロスルホニル）イミドの存在を示す５１．９ｐｐｍのピークが確認された。また、内部標準添加法により、ビス（フルオロスルホニル）イミドのフルオロスルホニルイソシアネート基準の収率は、５５％であった。 Example 4
A reactor equipped with a stirrer and a thermometer having a capacity of 100 mL was charged with 15 g of fluorosulfuric acid. While maintaining the measured value of the thermometer of the reactor at 5 ° C. or more and 15 ° C. or less, 1 g of 1-methylimidazole was added by 1 The solution was added dropwise over a period of time to obtain 27 g of fluorosulfuric acid = 1-methylimidazolium salt.
Then, 15 g of fluorosulfuric acid was added to 27 g of the obtained fluorosulfuric acid = 1-methylimidazolium salt and heated to 120 ° C. Thereto, 19 g of fluorosulfonyl isocyanate was added dropwise over 7.5 hours while keeping the measured value of the thermometer of the reactor at 120 ° C., and the reaction was further completed for 3.5 hours after completion of the addition. During the reaction, generation of carbon dioxide gas was confirmed.
After completion of the reaction, the reaction solution was dissolved in a water-acetone mixed solution and analyzed by 19 F-NMR. As a result, a 51.9 ppm peak indicating the presence of bis (fluorosulfonyl) imide was confirmed. Further, according to the internal standard addition method, the yield of bis (fluorosulfonyl) imide based on fluorosulfonyl isocyanate was 55%.
撹拌機および温度計を備えた容量が１００ｍＬの反応器にフルオロ硫酸１５ｇを仕込み、そこに、反応器の温度計の測定値を５℃以上１５℃以下に保ちながら、1－メチルイミダゾール１２ｇを１時間かけて滴下し、フルオロ硫酸＝１－メチルイミダゾリウム塩２７ｇを得た。
そして、得られたフルオロ硫酸＝１－メチルイミダゾリウム塩２７ｇにフルオロ硫酸１５ｇを添加し、１２０℃に加熱した。そこに、反応器の温度計の測定値を１２０℃に保ちながらフルオロスルホニルイソシアネート１９ｇを７．５時間かけて滴下し、滴下終了後さらに３．５時間反応させた後、反応を終了した。反応中は、二酸化炭素ガスの発生が確認された。
反応終了後、反応液を水－アセトン混合液に溶解し、１９Ｆ－ＮＭＲにて分析を行なった。その結果、ビス（フルオロスルホニル）イミドの存在を示す５１．９ｐｐｍのピークが確認された。また、内部標準添加法により、ビス（フルオロスルホニル）イミドのフルオロスルホニルイソシアネート基準の収率は、５５％であった。 Example 4
A reactor equipped with a stirrer and a thermometer having a capacity of 100 mL was charged with 15 g of fluorosulfuric acid. While maintaining the measured value of the thermometer of the reactor at 5 ° C. or more and 15 ° C. or less, 1 g of 1-methylimidazole was added by 1 The solution was added dropwise over a period of time to obtain 27 g of fluorosulfuric acid = 1-methylimidazolium salt.
Then, 15 g of fluorosulfuric acid was added to 27 g of the obtained fluorosulfuric acid = 1-methylimidazolium salt and heated to 120 ° C. Thereto, 19 g of fluorosulfonyl isocyanate was added dropwise over 7.5 hours while keeping the measured value of the thermometer of the reactor at 120 ° C., and the reaction was further completed for 3.5 hours after completion of the addition. During the reaction, generation of carbon dioxide gas was confirmed.
After completion of the reaction, the reaction solution was dissolved in a water-acetone mixed solution and analyzed by 19 F-NMR. As a result, a 51.9 ppm peak indicating the presence of bis (fluorosulfonyl) imide was confirmed. Further, according to the internal standard addition method, the yield of bis (fluorosulfonyl) imide based on fluorosulfonyl isocyanate was 55%.
（比較例１）
撹拌機および温度計を備えた容量が５０ｍＬのガラス製反応器にフルオロ硫酸１５．０ｇとフルオロスルホニルイソシアネート１８．８ｇとを仕込み、反応器を加熱し６３時間反応させた後、反応を終了した。反応開始時では、反応器の温度計の測定値が７７℃になった時点ででフルオロスルホニルイソシアネートの還流が確認された。そして、その後反応が進むにつれ原料のフルオロスルホニルイソシアネートが消費されたため、徐々に昇温し、反応終了時の反応器の温度計の測定値は１４８℃であった。反応中は、穏やかな二酸化炭素ガスの発生が確認された。
反応終了後、反応器内の反応液を水に溶解し、１９Ｆ－ＮＭＲにて分析を行なった。その結果、ビス（フルオロスルホニル）イミドの存在を示す５１．９ｐｐｍのピークが確認された。また、内部標準添加法により、ビス（フルオロスルホニル）イミドのフルオロスルホニルイソシアネート基準の収率は、５４％であった。 (Comparative Example 1)
A glass reactor equipped with a stirrer and a thermometer having a capacity of 50 mL was charged with 15.0 g of fluorosulfuric acid and 18.8 g of fluorosulfonyl isocyanate, heated to react for 63 hours, and then the reaction was terminated. At the start of the reaction, the reflux of the fluorosulfonyl isocyanate was confirmed when the measured value of the thermometer in the reactor reached 77 ° C. Then, since the raw material fluorosulfonyl isocyanate was consumed as the reaction proceeded, the temperature was gradually raised, and the measured value of the thermometer of the reactor at the end of the reaction was 148 ° C. During the reaction, generation of mild carbon dioxide gas was confirmed.
After completion of the reaction, the reaction solution in the reactor was dissolved in water and analyzed by 19 F-NMR. As a result, a 51.9 ppm peak indicating the presence of bis (fluorosulfonyl) imide was confirmed. In addition, according to the internal standard addition method, the yield of bis (fluorosulfonyl) imide based on fluorosulfonyl isocyanate was 54%.
撹拌機および温度計を備えた容量が５０ｍＬのガラス製反応器にフルオロ硫酸１５．０ｇとフルオロスルホニルイソシアネート１８．８ｇとを仕込み、反応器を加熱し６３時間反応させた後、反応を終了した。反応開始時では、反応器の温度計の測定値が７７℃になった時点ででフルオロスルホニルイソシアネートの還流が確認された。そして、その後反応が進むにつれ原料のフルオロスルホニルイソシアネートが消費されたため、徐々に昇温し、反応終了時の反応器の温度計の測定値は１４８℃であった。反応中は、穏やかな二酸化炭素ガスの発生が確認された。
反応終了後、反応器内の反応液を水に溶解し、１９Ｆ－ＮＭＲにて分析を行なった。その結果、ビス（フルオロスルホニル）イミドの存在を示す５１．９ｐｐｍのピークが確認された。また、内部標準添加法により、ビス（フルオロスルホニル）イミドのフルオロスルホニルイソシアネート基準の収率は、５４％であった。 (Comparative Example 1)
A glass reactor equipped with a stirrer and a thermometer having a capacity of 50 mL was charged with 15.0 g of fluorosulfuric acid and 18.8 g of fluorosulfonyl isocyanate, heated to react for 63 hours, and then the reaction was terminated. At the start of the reaction, the reflux of the fluorosulfonyl isocyanate was confirmed when the measured value of the thermometer in the reactor reached 77 ° C. Then, since the raw material fluorosulfonyl isocyanate was consumed as the reaction proceeded, the temperature was gradually raised, and the measured value of the thermometer of the reactor at the end of the reaction was 148 ° C. During the reaction, generation of mild carbon dioxide gas was confirmed.
After completion of the reaction, the reaction solution in the reactor was dissolved in water and analyzed by 19 F-NMR. As a result, a 51.9 ppm peak indicating the presence of bis (fluorosulfonyl) imide was confirmed. In addition, according to the internal standard addition method, the yield of bis (fluorosulfonyl) imide based on fluorosulfonyl isocyanate was 54%.
なお、上記実施例１～４及び比較例１においては経時的にサンプリングを行い、１９Ｆ－ＮＭＲの内部標準添加法で収率の確認を行なった。図１に、実施例１～４及び比較例１におけるビス（フルオロスルホニル）イミドの収率の変化を示す。図１において、横軸は反応開始からの経過時間（ｈｏｕｒ）を示しており、縦軸は内部標準添加法による、ビス（フルオロスルホニル）イミドのフルオロスルホニルイソシアネート基準の収率（％）を示している。
図１に示される結果から以下のことが示された。すなわち、本発明の実施例１～４では、比較例１と比べ、早い反応速度でかつ高い収率で、ビス（フルオロスルホニル）イミドが生産された。 In Examples 1 to 4 and Comparative Example 1, sampling was performed over time, and the yield was confirmed by the internal standard addition method of 19 F-NMR. FIG. 1 shows changes in the yield of bis (fluorosulfonyl) imide in Examples 1 to 4 and Comparative Example 1. In FIG. 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.
図１に示される結果から以下のことが示された。すなわち、本発明の実施例１～４では、比較例１と比べ、早い反応速度でかつ高い収率で、ビス（フルオロスルホニル）イミドが生産された。 In Examples 1 to 4 and Comparative Example 1, sampling was performed over time, and the yield was confirmed by the internal standard addition method of 19 F-NMR. FIG. 1 shows changes in the yield of bis (fluorosulfonyl) imide in Examples 1 to 4 and Comparative Example 1. In FIG. 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.
本発明のビス（フルオロスルホニル）イミドの製造方法によれば、フルオロ硫酸とフルオロスルホニルイソシアネートとを所定の塩の存在下で反応させることにより、反応速度を向上させることができる。したがって、反応速度が速く、簡便な方法で生産が可能なビス（フルオロスルホニル）イミドの製造方法を提供することができる。
According to the method for producing bis (fluorosulfonyl) imide of the present invention, 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.
Claims (10)
- ビス（フルオロスルホニル）イミドの製造方法であって、
フルオロ硫酸とフルオロスルホニルイソシアネートとを、下記化学式（１）で示される塩化合物のいずれか一種又は二種以上の存在下で反応させるビス（フルオロスルホニル）イミド生成工程を備え、
下記化学式（１）の、記号Ｍは、アルカリ金属、アルカリ土類金属、オニウムカチオンのいずれか一種のカチオンであり、
下記化学式（１）の、記号Ｘは、Ｆ－，Ｃｌ－，Ｂｒ－，Ｉ－，ＳＯ４ ２－，ＦＳＯ３ －，（ＦＳＯ２）２Ｎ－のいずれか一種のアニオンであるビス（フルオロスルホニル）イミドの製造方法。
ＭＸ （１） A method for producing bis (fluorosulfonyl) imide, comprising:
Comprising a bis (fluorosulfonyl) imide production step in which 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 symbol M in the following chemical formula (1) is a cation of any one of an alkali metal, an alkaline earth metal, and an onium cation.
In the following chemical formula (1), the symbol X represents bis (fluoro) which is an anion of any one of F − , Cl − , Br − , I − , SO 4 2− , FSO 3 − , (FSO 2 ) 2 N −. (Sulfonyl) imide production method.
MX (1) - 請求項１に記載されたビス（フルオロスルホニル）イミドの製造方法であって、
フルオロ硫酸に前記塩化合物を加えることにより混合液を調製する混合液調製工程と、
前記混合液調製工程後に、前記混合液にフルオロスルホニルイソシアネートを添加する添加工程とをさらに備えるビス（フルオロスルホニル）イミドの製造方法。 A process for producing a bis (fluorosulfonyl) imide according to claim 1,
A mixed solution preparation step of preparing a mixed solution by adding the salt compound to fluorosulfuric acid;
A method for producing bis (fluorosulfonyl) imide, further comprising an addition step of adding fluorosulfonyl isocyanate to the mixed solution after the mixed solution preparing step. - 請求項２に記載されたビス（フルオロスルホニル）イミドの製造方法であって、
前記添加工程後にフルオロスルホニルイソシアネートが添加された前記混合液を加熱することにより、前記ビス（フルオロスルホニル）イミド生成工程を行うビス（フルオロスルホニル）イミドの製造方法。 A method for producing a bis (fluorosulfonyl) imide according to claim 2,
The manufacturing method of the bis (fluoro sulfonyl) imide which performs the said bis (fluoro sulfonyl) imide production | generation process by heating the said liquid mixture with which the fluoro sulfonyl isocyanate was added after the said addition process. - 請求項２に記載されるビス（フルオロスルホニル）イミドの製造方法であって、
前記混合液調製工程と前記添加工程との間に、前記混合液を加熱し、前記添加工程にて、加熱された前記混合液にフルオロスルホニルイソシアネートを滴下することにより、前記ビス（フルオロスルホニル）イミド生成工程を行うビス（フルオロスルホニル）イミドの製造方法。 A process for producing a bis (fluorosulfonyl) imide according to claim 2,
The bis (fluorosulfonyl) imide is heated by heating the mixed liquid between the mixed liquid preparing step and the adding step, and dropping fluorofluoroisocyanate into the heated mixed liquid in the adding step. The manufacturing method of the bis (fluoro sulfonyl) imide which performs a production | generation process. - 請求項１に記載されるビス（フルオロスルホニル）イミドの製造方法であって
フルオロ硫酸に、アンモニア、アミンからなる群から選ばれた化合物のいずれか一種又は二種以上を添加して、前記化学式（１）で示される塩化合物を含む反応液を生成する反応液調製工程と、
前記反応液調製工程後に、前記反応液にフルオロスルホニルイソシアネートを添加する添加工程とをさらに備えるビス（フルオロスルホニル）イミドの製造方法。 The method for producing bis (fluorosulfonyl) imide according to claim 1, wherein one or more compounds selected from the group consisting of ammonia and amine are added to fluorosulfuric acid, and the chemical formula ( A reaction solution preparation step for producing a reaction solution containing the salt compound represented by 1);
A method for producing bis (fluorosulfonyl) imide, further comprising an addition step of adding fluorosulfonyl isocyanate to the reaction solution after the reaction solution preparation step. - 請求項５に記載されるビス（フルオロスルホニル）イミドの製造方法であって、
前記添加工程後にフルオロスルホニルイソシアネートが添加された前記反応液を加熱することにより、前記ビス（フルオロスルホニル）イミド生成工程を行うビス（フルオロスルホニル）イミドの製造方法。 A method for producing a bis (fluorosulfonyl) imide according to claim 5,
The manufacturing method of the bis (fluoro sulfonyl) imide which performs the said bis (fluoro sulfonyl) imide production | generation process by heating the said reaction liquid to which fluoro sulfonyl isocyanate was added after the said addition process. - 請求項５に記載されるビス（フルオロスルホニル）イミドの製造方法であって、
前記反応液調製工程と前記添加工程との間に、前記反応液を加熱し、前記添加工程にて、加熱された前記反応液にフルオロスルホニルイソシアネートを滴下することにより、前記ビス（フルオロスルホニル）イミド生成工程を行うビス（フルオロスルホニル）イミドの製造方法。 A method for producing a bis (fluorosulfonyl) imide according to claim 5,
By heating the reaction liquid between the reaction liquid preparation step and the addition step, and dropping fluorosulfonyl isocyanate into the reaction liquid heated in the addition step, the bis (fluorosulfonyl) imide The manufacturing method of the bis (fluoro sulfonyl) imide which performs a production | generation process. - 請求項１から７のいずれか一項に記載されるビス（フルオロスルホニル）イミドの製造方法であって、
前記フルオロスルホニルイソシアネートと反応する前記フルオロ硫酸に対する、前記化学式（１）で示される塩化合物の量が、モル比で０．１～１０倍の範囲内であるビス（フルオロスルホニル）イミドの製造方法。 A method for producing a bis (fluorosulfonyl) imide according to any one of claims 1 to 7,
A method for producing bis (fluorosulfonyl) imide, wherein the amount of the salt compound represented by the chemical formula (1) with respect to the fluorosulfuric acid reacting with the fluorosulfonyl isocyanate is within a range of 0.1 to 10 times in terms of molar ratio. - 請求項１から７のいずれか一項に記載されるビス（フルオロスルホニル）イミドの製造方法であって、
前記フルオロ硫酸と前記フルオロスルホニルイソシアネートとの反応温度が、５０～１７０℃の範囲内であるビス（フルオロスルホニル）イミドの製造方法。 A method for producing a bis (fluorosulfonyl) imide according to any one of claims 1 to 7,
A process for producing bis (fluorosulfonyl) imide, wherein the reaction temperature between the fluorosulfuric acid and the fluorosulfonyl isocyanate is in the range of 50 to 170 ° C. - 請求項８に記載されるビス（フルオロスルホニル）イミドの製造方法であって、
前記フルオロ硫酸と前記フルオロスルホニルイソシアネートとの反応温度が、５０～１７０℃の範囲内であるビス（フルオロスルホニル）イミドの製造方法。 A method for producing a bis (fluorosulfonyl) imide according to claim 8,
A process for producing bis (fluorosulfonyl) imide, wherein the reaction temperature between the fluorosulfuric acid and the fluorosulfonyl isocyanate is in the range of 50 to 170 ° C.
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| 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 (en) * | 2022-03-19 | 2022-06-10 | 珠海市赛纬电子材料股份有限公司 | Preparation method of lithium bis (fluorosulfonyl) imide and application of lithium bis (fluorosulfonyl) imide |
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