WO2012105586A1 - Fluorure de perfluorobutane sulfonyle, sel perfluorobutane sulfonate de potassium, et procédé de fabrication de fluorure de perfluorobutane sulfonyle - Google Patents

Fluorure de perfluorobutane sulfonyle, sel perfluorobutane sulfonate de potassium, et procédé de fabrication de fluorure de perfluorobutane sulfonyle Download PDF

Info

Publication number
WO2012105586A1
WO2012105586A1 PCT/JP2012/052208 JP2012052208W WO2012105586A1 WO 2012105586 A1 WO2012105586 A1 WO 2012105586A1 JP 2012052208 W JP2012052208 W JP 2012052208W WO 2012105586 A1 WO2012105586 A1 WO 2012105586A1
Authority
WO
WIPO (PCT)
Prior art keywords
perfluorobutanesulfonyl fluoride
perfluorosulfolane
hydroxide
perfluorobutane
mass
Prior art date
Application number
PCT/JP2012/052208
Other languages
English (en)
Japanese (ja)
Inventor
博之 八柳
武志 神谷
常俊 本田
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
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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 WO2012105586A1 publication Critical patent/WO2012105586A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/42—Separation; Purification; Stabilisation; Use of additives
    • C07C303/44—Separation; Purification

Definitions

  • the present invention relates to high-purity perfluorobutanesulfonyl fluoride, a process for producing the same, and perfluorobutanesulfonic acid potassium salt produced using perfluorobutanesulfonyl fluoride. More specifically, the present invention relates to a method for producing perfluorobutanesulfonyl fluoride, perfluorobutanesulfonyl fluoride, and perfluorobutanesulfonic acid potassium salt, which can efficiently remove by-product perfluorosulfolane.
  • Perfluorobutane sulfonate (CF 3 CF 2 CF 2 CF 2 SO 3 M, where M is a cation) is a photoacid generator for photolithography used in the production of semiconductors and a flame retardant for polycarbonate resin It is used as a conductive agent for resins.
  • This perfluorobutane sulfonate is produced using perfluorobutanesulfonyl fluoride (CF 3 CF 2 CF 2 CF 2 SO 2 F) as a raw material.
  • Perfluorobutanesulfonyl fluoride is produced by electrolytic fluorination of sulfolane (tetrahydrothiophene-1,1-dioxide). This electrolytic fluorination (ECF) is represented by the following reaction formula (1).
  • perfluorosulfolane perfluorotetrahydrothiophene-1,1-dioxide
  • this impurity is contained in perfluorobutanesulfonyl fluoride. It is contained in several mass%.
  • Non-patent Document 1 As a method for removing perfluorosulfolane, a method using a buffered aqueous solution of dipotassium hydrogen phosphate and potassium phosphate has been reported (Non-patent Document 1). However, this method requires 4 days to remove perfluorosulfolane. Moreover, it cannot be said that the removal of perfluorosulfolane is sufficient, and further phosphorus resulting from the buffer aqueous solution used for the removal is mixed as a new impurity. For example, when used as a photoresist for semiconductor lithography, phosphorus as an impurity is not allowed, so the above removal method using a buffered aqueous solution is not appropriate.
  • An object of the present invention is to purify perfluorobutanesulfonyl fluoride to remove perfluorosulfolane to obtain high-purity perfluorobutanesulfonyl fluoride. Therefore, an object of the present invention is to provide a method for producing high-purity perfluorobutanesulfonyl fluoride, high-purity perfluorobutanesulfonic acid potassium salt, and high-purity perfluorobutanesulfonyl fluoride.
  • Perfluorobutanesulfonyl fluoride wherein the content of perfluorosulfolane is 100 ppm or less on a mass basis.
  • Perfluorobutanesulfonic acid potassium salt characterized in that the content of 1,1,2,2,3,3,4,4-octafluorobutanesulfonic acid potassium salt is 100 ppm or less on a mass basis.
  • high-purity perfluorobutanesulfonyl fluoride can be provided.
  • it is difficult to produce such high-purity perfluorobutanesulfonyl fluoride.
  • high-purity perfluorobutanesulfonyl fluoride can be easily produced, for example, in a short time of about 1 to 2 hours.
  • the unit% which shows content is the mass%.
  • the perfluorobutanesulfonyl fluoride of this embodiment is characterized in that the content of perfluorosulfolane is 100 ppm or less on a mass basis. Further, the perfluorobutanesulfonic acid potassium salt of the present embodiment produced using perfluorobutanesulfonyl fluoride as a raw material is 1,1,2,2,3,3,4,4-octafluorobutanesulfonic acid potassium salt The content of is characterized by being 100 ppm or less on a mass basis.
  • Perfluorosulfolane in perfluorobutanesulfonyl fluoride is produced by the above-described reaction formula (2).
  • perfluorobutane sulfonyl fluoride When perfluorobutane sulfonyl fluoride is reacted with, for example, potassium hydroxide to produce potassium perfluorobutane sulfonate, the perfluorosulfolane present in the perfluorobutane sulfonyl fluoride also reacts with potassium hydroxide.
  • one CF 2 —S bond in perfluorosulfolane is cleaved to generate impurities.
  • This impurity is 1,1,2,2,3,3,4,4-octafluorobutanesulfonic acid potassium salt (HCF 2 CF 2 CF 2 CF 2 SO 3 K).
  • 1,1,2,2,3,3,4,4-Octafluorobutanesulfonic acid potassium salt in perfluorobutanesulfonic acid potassium salt is derived from perfluorosulfolane present in perfluorobutanesulfonyl fluoride used as a raw material . Therefore, by inhibiting the formation of perfluorosulfolane in perfluorobutanesulfonyl fluoride, 1,1,2,2,3,3,4,4-octafluorobutanesulfonic acid potassium salt in perfluorobutanesulfonic acid potassium salt Can be prevented.
  • perfluorobutanesulfonic acid potassium salt When the content of 1,1,2,2,3,3,4,4-octafluorobutanesulfonic acid potassium salt is 100 ppm or less, perfluorobutanesulfonic acid potassium salt has an impurity content used during semiconductor production. It is useful as a raw material for a photoacid generator for photolithography with a small size.
  • 1,1,2,2,3,3,4,4-octafluorobutanesulfonic acid potassium salt is quantified by 19F-NMR or LC-MS. Further, when analyzing perfluorosulfolane, it is performed by gas chromatography (GC).
  • the method for producing perfluorobutanesulfonyl fluoride according to this embodiment is characterized in that an aqueous solution of an alkali metal hydroxide is added to perfluorobutanesulfonyl fluoride for purification.
  • this production method purification method
  • the content of perfluorosulfolane in perfluorobutanesulfonyl fluoride can be reduced to 100 ppm or less in 1 to 2 hours.
  • Both perfluorobutanesulfonyl fluoride and perfluorosulfolane are insoluble in water.
  • an aqueous solution of potassium hydroxide is added, at a reaction temperature of 0 to 50 ° C. (preferably 20 to 30 ° C.)
  • perfluorobutanesulfonyl fluoride does not react with potassium hydroxide and does not change.
  • perfluorosulfolan reacts with potassium hydroxide to produce water-soluble 1,1,2,2,3,3,4,4-octafluorobutanesulfonic acid potassium salt by the above reaction formula (3). Dissolve in an aqueous solution of potassium hydroxide.
  • the alkali metal hydroxide is preferably at least one selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide. Also good.
  • Alkaline metal hydroxide aqueous solution The amount of the alkali metal hydroxide is preferably 0.1 to 20 parts by mass, more preferably 1 to 5 parts by mass with respect to 100 parts by mass. When the ratio of the alkali metal hydroxide is less than 0.1 parts by mass, no purification effect is observed. When the ratio of the alkali metal hydroxide exceeds 20 parts by mass, decomposition of perfluorobutanesulfonyl fluoride occurs, which is not preferable.
  • the addition amount (ratio) of alkali metal hydroxide is preferably 1 to 10 mol, more preferably 2 to 5 mol, per mol of perfluorosulfolane.
  • the ratio of the alkali metal hydroxide is less than 1 mol, the reaction of the reaction formula (3) is not completed and the purification effect cannot be obtained. Even if the ratio of the alkali metal hydroxide exceeds 10 mol, a remarkable effect cannot be obtained.
  • an aqueous solution of an alkali metal hydroxide to perfluorobutanesulfonyl fluoride may be performed by a known method and is not particularly limited. However, in order to easily take out the lower layer perfluorobutanesulfonyl fluoride separated after the purification, it is preferable to use, for example, a separatory funnel.
  • An example of the reaction conditions is a reaction for 1 to 2 hours at room temperature while appropriately stirring the mixed solution. The reaction conditions may be appropriately determined depending on the amount of perfluorosulfolane contained in the perfluorobutanesulfonyl fluoride, the size of the batch to be reacted (amount of raw material), the strength of stirring, and the like.
  • perfluorobutanesulfonic acid potassium salt By using perfluorobutanesulfonyl fluoride as a raw material, perfluorobutanesulfonic acid potassium salt can be produced by the following reaction formula (4).
  • reaction formula (4) C 4 F 9 SO 2 F + 2KOH ⁇ C 4 F 9 SO 3 K + KF + H 2 O (4)
  • perfluorobutanesulfonyl fluoride is reacted with an aqueous potassium hydroxide solution, and the produced potassium perfluorobutanesulfonate is cooled and crystallized.
  • the crystallized perfluorobutanesulfonic acid potassium salt is filtered and dried. As described above, potassium perfluorobutanesulfonate can be obtained.
  • Perfluorobutanesulfonyl fluoride The molar ratio of potassium hydroxide to 1 mol is preferably 2 to 3 mol, and particularly preferably 2 mol.
  • Potassium hydroxide aqueous solution The amount of potassium hydroxide is preferably 20 to 70 parts by mass, particularly preferably 20 parts by mass with respect to 100 parts by mass.
  • the reaction temperature of the reaction formula (4) is 50 to 100 ° C., particularly preferably 80 ° C.
  • the reaction time of the reaction formula (4) is 10 to 50 hours, whereby the reaction can be completed.
  • a method for cooling the produced potassium perfluorosulfonic acid and crystallizing the potassium perfluorosulfonic acid, and a method for filtering and drying the crystallized perfluorobutanesulfonic acid potassium salt may be a publicly known method. It is not limited.
  • the perfluorobutanesulfonic acid potassium salt of this embodiment can be produced.
  • Example 1 Perfluorobutanesulfonyl fluoride containing 1% by mass of perfluorosulfolane: 50 g was put in a 100 cm 3 polyethylene bottle. Next, 21 g of a 1% by mass potassium hydroxide aqueous solution was added. The mixture was stirred at room temperature for 1 hour, and then the lower layer was separated to obtain 49 g of perfluorobutanesulfonyl fluoride.
  • the obtained perfluorobutanesulfonyl fluoride was analyzed by gas chromatography (GC). As a result, the content of perfluorosulfolane was less than 100 ppm. In addition, 100 ppm is a detection lower limit value of perfluorosulfolane in GC.
  • Example 2 Perfluorobutanesulfonyl fluoride: 49 g was obtained in the same manner as in Example 1 except that 11 g of a 1% by mass aqueous potassium hydroxide solution was used. The obtained perfluorobutanesulfonyl fluoride was analyzed by GC. As a result, the content of perfluorosulfolane was less than 100 ppm.
  • Example 3 Perfluorobutanesulfonyl fluoride: 49 g was obtained in the same manner as in Example 1 except that 1% by mass of potassium hydroxide aqueous solution: 31 g was used. The obtained perfluorobutanesulfonyl fluoride was analyzed by GC. As a result, the content of perfluorosulfolane was less than 100 ppm.
  • Example 4 49 g of perfluorobutanesulfonyl fluoride was obtained in the same manner as in Example 1 except that 15 g of 1 wt% sodium hydroxide aqueous solution was used instead of 1 wt% potassium hydroxide aqueous solution.
  • the obtained perfluorobutanesulfonyl fluoride was analyzed by GC. As a result, the content of perfluorosulfolane was less than 100 ppm.
  • Example 5 Perfluorobutanesulfonyl fluoride: 49 g was obtained in the same manner as in Example 1 except that 1% by mass of potassium hydroxide aqueous solution: 42 g was used. The obtained perfluorobutanesulfonyl fluoride was analyzed by GC. As a result, the content of perfluorosulfolane was less than 100 ppm.
  • Example 6 20 mass% aqueous potassium hydroxide solution: 15 g and perfluorobutanesulfonyl fluoride having a perfluorosulfolane content of Example 1 of less than 100 ppm: 8 g were put into a 100 cm 3 flask. The mixture was stirred at 80 ° C. for 24 hours. Then, it cooled to 20 degreeC and filtered the crystal
  • Example 6 using perfluorobutanesulfonyl fluoride having a perfluorosulfolane content of less than 100 ppm, the content of 1,1,2,2,3,3,4,4-octafluorobutanesulfonic acid potassium salt was It was 100 ppm or less.
  • Comparative Example 4 using perfluorobutanesulfonyl fluoride having a perfluorosulfolane content of 10,000 ppm contained 1,1,2,2,3,3,4,4-octafluorobutanesulfonic acid potassium salt. The amount was 9000 ppm.
  • the perfluorobutanesulfonyl fluoride can be removed in a short time by the method for producing perfluorobutanesulfonyl fluoride of the present embodiment, and high-purity perfluorobutanesulfonyl fluoride can be obtained. For this reason, in this embodiment, the highly purified perfluorobutane sulfonyl fluoride and the highly purified perfluorobutane sulfonate synthesized from this perfluorobutane sulfonyl fluoride can be provided.
  • the perfluorobutane sulfonate of the present embodiment is highly pure, it is used for a raw material of a photoacid generator for photolithography used at the time of manufacturing a semiconductor, a flame retardant for a polycarbonate resin, a conductive agent for a resin, etc. Very useful.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Ce fluorure de perfluorobutane sulfonyle a une teneur en perfluorosulfolane de 100 ppm ou moins sur une base en masse. Ce sel perfluorobutane sulfonate de potassium a une teneur en sel 1,1,2,2,3,3,4,4-octafluorobutane sulfonate de potassium de 100 ppm ou moins sur une base en masse. Dans ce procédé de fabrication de fluorure de perfluorobutane sulfonyle, le perfluorosulfolane est retiré par addition d'une solution aqueuse d'un hydroxyde de métal alcalin dans le fluorure de perfluorobutane sulfonyle.
PCT/JP2012/052208 2011-02-04 2012-02-01 Fluorure de perfluorobutane sulfonyle, sel perfluorobutane sulfonate de potassium, et procédé de fabrication de fluorure de perfluorobutane sulfonyle WO2012105586A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011-022587 2011-02-04
JP2011022587 2011-02-04

Publications (1)

Publication Number Publication Date
WO2012105586A1 true WO2012105586A1 (fr) 2012-08-09

Family

ID=46602793

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/052208 WO2012105586A1 (fr) 2011-02-04 2012-02-01 Fluorure de perfluorobutane sulfonyle, sel perfluorobutane sulfonate de potassium, et procédé de fabrication de fluorure de perfluorobutane sulfonyle

Country Status (2)

Country Link
JP (1) JP6023432B2 (fr)
WO (1) WO2012105586A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111170898A (zh) * 2020-02-13 2020-05-19 内蒙古三爱富万豪氟化工有限公司 全氟丁磺酸钾的制备方法
CN113980748A (zh) * 2021-11-15 2022-01-28 安徽冠宇光电科技有限公司 一种太阳能单多晶硅片清洗液及其制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002038288A (ja) * 2000-06-28 2002-02-06 Bayer Ag 完全フッ素置換有機化合物を電気化学的フッ素置換で製造する方法
JP2009179836A (ja) * 2008-01-30 2009-08-13 Mitsubishi Materials Corp ペルフルオロアルカンスルホニルフロリドの吸収方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3919295A (en) * 1973-04-16 1975-11-11 Bayer Ag Preparation of inorganic fluoride-free perfluoroalkane sulphonates
JP3030661B2 (ja) * 1991-03-06 2000-04-10 株式会社トーケムプロダクツ ペルフルオロアルキルスルホン酸フッ化物の抽出方法
JP2001322975A (ja) * 2000-05-16 2001-11-20 Dainippon Ink & Chem Inc パーフルオロアルキルスルホン酸塩の製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002038288A (ja) * 2000-06-28 2002-02-06 Bayer Ag 完全フッ素置換有機化合物を電気化学的フッ素置換で製造する方法
JP2009179836A (ja) * 2008-01-30 2009-08-13 Mitsubishi Materials Corp ペルフルオロアルカンスルホニルフロリドの吸収方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111170898A (zh) * 2020-02-13 2020-05-19 内蒙古三爱富万豪氟化工有限公司 全氟丁磺酸钾的制备方法
CN113980748A (zh) * 2021-11-15 2022-01-28 安徽冠宇光电科技有限公司 一种太阳能单多晶硅片清洗液及其制备方法
CN113980748B (zh) * 2021-11-15 2024-01-26 安徽冠宇光电科技有限公司 一种太阳能单多晶硅片清洗液及其制备方法

Also Published As

Publication number Publication date
JP2012176944A (ja) 2012-09-13
JP6023432B2 (ja) 2016-11-09

Similar Documents

Publication Publication Date Title
CN107416782A (zh) 一种双氟磺酰亚胺锂盐的制备方法
CN102105444B (zh) 全氟烷基亚磺酸盐的制造方法
JP4341055B2 (ja) Ｎ−（シクロヘキシルチオ）フタルイミドの製造方法
JP2008195547A (ja) 六フッ化リン酸塩の製造方法
JP6218598B2 (ja) 高純度次亜塩素酸ナトリウム５水和物および次亜塩素酸ナトリウム水溶液の製造方法
JP6023432B2 (ja) ペルフルオロブタンスルホニルフルオリド、ペルフルオロブタンスルホン酸カリウム塩、およびペルフルオロブタンスルホニルフルオリドの製造方法
JP2014024786A (ja) パーフルオロアルキルスルホン酸金属塩の製造方法及びパーフルオロアルキルスルホン酸金属塩、これを利用したリチウムイオン電池用の電解質並びに樹脂用の導電性付与剤
JP2017137221A (ja) フッ化水素酸と硝酸の回収方法
JP5756999B2 (ja) ビス（ペルフルオロアルカンスルホン）イミド塩の製造方法
WO2010128649A1 (fr) Mélange de sels de diaryliodonium et son procédé de production, et procédé de production d'un composé de diaryliodonium
JP2017218328A (ja) ビス（フルオロスルホニル）イミドアルカリ金属塩の製造方法
CN108633276B (zh) 1,2,3,5,6-五硫杂环庚烷的制造方法
WO2011148971A1 (fr) Procédé pour la préparation de composés sulfonylimide contenant du fluor
JPH0499743A (ja) 高品質テトラブロモビスフェノールａの製法
JP5497799B2 (ja) ペルフルオロブタンスルホン酸塩の製造方法
US5540818A (en) Process for the production of high purity methanesulphonyl fluoride at an improved yield
JP5485583B2 (ja) ジアリールヨードニウム化合物の製造方法
JP5811671B2 (ja) フルオロアルカンスルホン酸の製造方法
JP2007145815A (ja) トリフルオロメタンスルホン酸無水物の製造方法。
EP4242173A1 (fr) Purification d'hydrogène bis(fluorosulfonyl)imide
WO2006059774A1 (fr) Procédé servant à purifier un composé diallylbisphénol
JP2022036383A (ja) ２－アミノエチルスルホン酸の製造方法
JP2007186438A (ja) Ｎ−（シクロヘキシルチオ）フタルイミドの製造方法
JPH04334335A (ja) 高品質テトラブロモビスフェノ−ルａの製造方法
JP2010280656A (ja) ジアリールヨードニウム塩混合物とその製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12742656

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12742656

Country of ref document: EP

Kind code of ref document: A1