WO2007142266A1 - Procédé servant à produire un éther de fluorosulfonylalkyle et de vinyle fluoré - Google Patents

Procédé servant à produire un éther de fluorosulfonylalkyle et de vinyle fluoré Download PDF

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Publication number
WO2007142266A1
WO2007142266A1 PCT/JP2007/061456 JP2007061456W WO2007142266A1 WO 2007142266 A1 WO2007142266 A1 WO 2007142266A1 JP 2007061456 W JP2007061456 W JP 2007061456W WO 2007142266 A1 WO2007142266 A1 WO 2007142266A1
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WO
WIPO (PCT)
Prior art keywords
fluorine
weight
parts
vinyl ether
chemical formula
Prior art date
Application number
PCT/JP2007/061456
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English (en)
Japanese (ja)
Inventor
Yuuichi Hashikawa
Akinari Sugiyama
Kazuyoshi Ichihara
Original Assignee
Daikin Industries, Ltd.
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 Daikin Industries, Ltd. filed Critical Daikin Industries, Ltd.
Publication of WO2007142266A1 publication Critical patent/WO2007142266A1/fr

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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
    • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
    • C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups

Definitions

  • the present invention relates to a method for producing a fluorine-containing fluorosulfoalkyl alkyl ether.
  • the fluorine-containing fluorosulfoalkyl alkyl ether is a useful compound as an industrial raw material such as an ion exchange membrane material.
  • FC0CF (CF) 0CF CF SO F is used as a raw material, and its cyclized product
  • a method for converting to 3 2 2 2 2 2 groups is also known (see Patent Document 2 below).
  • CF CFO (CF CF (CF) 0) CF CF SO CI (where n is 0 or 1)
  • a fluorine-containing fluorosulfoalkyl alkyl ether can be obtained by reacting with a fluorine-containing agent using water as a solvent when the fluorine-containing chlorosulfoalkyl alkyl ether is used as a starting material (see below).
  • Patent Document 3 the target fluorine-containing fluorosulfoalkyl alkyl ether can be obtained in a relatively high yield, but HF adducts and hydrolysates are produced as by-products.
  • a method capable of producing a target fluorine-containing fluorosulfoalkyl vinyl ether with higher selectivity and good yield is desired.
  • Patent Document 1 British Patent 1, 034, 197
  • Patent Document 2 U.S. Pat.No. 3,560,568
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2004-244401
  • Non-Patent Document 1 S. Benefice—Malouet, H. Blancou, R. Teissedre and A. Commeyras, J. Fluorine Chem. 31 (1986) 319—332
  • the present invention has been made in view of the current state of the prior art described above, and the main object of the present invention is to easily and highly select fluorine-containing fluorosulfoalkyl alkyl ethers in an industrially advantageous manner. It is to provide a method that can be manufactured at a high yield with a high yield.
  • the inventor has conducted extensive research in view of the above-described problems. As a result, when a specific fluorine-containing chlorosulfoalkylalkyl ether was used as a raw material and reacted with a fluorinating agent, it was very limited to 0.05 to 9 parts by weight per 100 parts by weight of the raw material. Surprisingly, when a small amount of water is present, the selectivity is significantly improved and by-products are much less pure and highly pure than when water is used as a solvent or without water. The inventors have found that it is possible to obtain a fluorinated fluorosulfoalkyl alkyl ether, and have completed the present invention.
  • the present invention provides the following method for producing a fluorine-containing fluorosulfoalkyl alkyl ether.
  • Fluorine-containing chlorosulfoalkyl alkyl butyl ether represented by the following formula: MF '(HF) (wherein M is an alkali metal and X is 0 to 5)
  • MF '(HF) wherein M is an alkali metal and X is 0 to 5
  • CF CF (CF) 0 (CF CF (C)
  • a method for producing hole alkyl butyl ether comprising reacting in the presence of 0.05 to 9 parts by weight of water per 100 parts by weight of fluorine-containing chloroalkyl sulfone ether used as a raw material.
  • Key formula: CF CF (CF) 0 (CF CF (CF) 0) (CF) SO CI! /, A force ⁇ 0, b force or
  • Fluorinating agent power The method according to item 1 or 2, which is at least one selected from the group force consisting of a compound in which M is K and M is a compound in MF- (HF).
  • fluorine-containing chlorosulfoalkyl alkyl ethers compounds in which a is 0, b is 0 or 1, and c is an integer of 1 to 4 are used as raw materials for producing monomer components for fuel cell electrolyte polymers. It is highly useful.
  • a compound represented by the chemical formula: MF ′ (HF) (wherein M is an alkali metal and X is an integer of 0 to 5) is used as the fluorinating agent.
  • the fluorinating agent an alkali metal fluoride, an acid alkali metal fluoride or the like, which is a compound in which M is K or a compound in which M is Na in the above chemical formula, is preferable.
  • KF is preferable.
  • Fluorinating agents can be used alone or in combination of two or more.
  • the amount of the fluorinating agent used is usually about 0.5 to 10 mol, preferably about 1 to 5 mol, relative to 1 mol of the fluorinated chlorosulfuralkylalkyl ether.
  • the production method of the present invention comprises the use of the above-mentioned fluorine-containing chlorosulfoalkyl alkyl ether by reacting the fluorine-containing chlorosulfoalkyl alkyl ether with a fluorinating agent.
  • An important feature is the presence of a specific amount of water of 0.05 to 9 parts by weight per 100 parts by weight of rualkyl butyl ether.
  • the reaction proceeds in the presence of a specific proportion of water, which is a small amount relative to the raw material, thereby suppressing the formation of by-products and high yield with high selectivity.
  • a specific proportion of water which is a small amount relative to the raw material, thereby suppressing the formation of by-products and high yield with high selectivity.
  • This makes it possible to obtain the target fluorine-containing fluorosulfoalkyl alkyl ether. If the presence of water exceeds the above range, the by-product will increase!] And the selectivity will decrease, and if below, the reaction time will be significantly longer.
  • the amount of water is preferably about 0.1 to 6 parts by weight with respect to 100 parts by weight of the fluorine-containing chlorosulfoalkyl alkyl butyl ether. More preferably.
  • additives can be added as required.
  • additives include water-soluble organic solvents that do not participate in the reaction, such as sulfolane, dimethyl sulfoxide, dimethylformamide, and other phase transfer catalysts such as C H
  • Quaternary ammonium salts such as CH N (CH) .C1, quaternary phosphonium salts, etc., inclusion molecules, eg
  • a cyclic ether such as 18-crown-6 can be used.
  • the reaction rate can be improved by adding these additives.
  • the amount of the additive used for the aqueous organic solvent is preferably about 1 to 50 parts by weight with respect to 100 parts by weight of the fluorine-containing chlorosulfoalkyl alkyl ether used as a raw material.
  • the phase transfer catalyst is preferably about 0.1 to 10 parts by weight with respect to 100 parts by weight of the fluorine-containing chlorosulfonylalkyl vinyl ether used as a raw material.
  • the raw material and the fluorinating agent may be reacted in the presence of the specific amount of water described above.
  • the reaction temperature may be about 10 to 200 ° C, preferably about 15 to 100 ° C.
  • the reaction pressure may be any of reduced pressure, atmospheric pressure and increased pressure, but is preferably atmospheric pressure.
  • the reaction time is usually about 0.5 to 24 hours.
  • the obtained crude compound can be purified by a known method such as distillation or column chromatography.
  • the mixture is separated into two layers by adding water and stirring, and the lower layer becomes a fluorinated fluorosulfoalkyl alkyl ether represented by the above chemical formula and can be purified by the above method.
  • the fluorine-containing fluorosulfoalkyl alkyl ether obtained as described above is a substance useful as a monomer component for a fuel cell electrolyte polymer, for example.
  • the reactor was heated with stirring and refluxed at 95 ° C. During the reaction, the reflux temperature dropped and the reaction was stopped when it became constant at 75 ° C. The total reaction time was 2 hours.
  • CF CF ⁇ CF CF SO K has a selectivity of 0.1%, CF CHFOCF C
  • F SO F was produced with a selectivity of 0.1% and CF CHFOCF CF SO K with a selectivity of 0.5%.

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

Abstract

L'invention concerne un procédé servant à produire un éther de fluorosulfonylalkyle et de vinyle fluoré représenté par la formule chimique suivante : CF2=CF(CF2)aO(CF2CF(CF3)O)b(CF2)cSO2F (dans laquelle a, b et c sont tels que définis ci-dessous) en faisant réagir un éther de chlorosulfonylalkyle et de vinyle fluoré représenté par la formule chimique suivante : CF2=CF(CF2)aO(CF2CF(CF3)O)b(CF2)cSO2Cl (dans laquelle a représente 0 ou 1, b représente un nombre entier de 0-5 et c représente un nombre entier de 1-10) avec un agent de fluoration représenté par la formule chimique suivante : MF•(HF)x (dans laquelle M représente un métal alcalin et x représente un nombre entier de 0-5). Ce procédé servant à produire un éther de fluorosulfonylalkyle et de vinyle fluoré est caractérisé en ce qu'on effectue la réaction en présence de 0,05-9 parties en poids d'eau pour 100 parties en poids de l'éther de chlorosulfonylalkyle et de vinyle fluoré servant de matière première. Ce procédé permet de produire de façon industriellement avantageuse un éther de fluorosulfonylalkyle et de vinyle fluoré avec une sélectivité élevée et un rendement de production élevé par un procédé simple.
PCT/JP2007/061456 2006-06-07 2007-06-06 Procédé servant à produire un éther de fluorosulfonylalkyle et de vinyle fluoré WO2007142266A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006-158231 2006-06-07
JP2006158231 2006-06-07

Publications (1)

Publication Number Publication Date
WO2007142266A1 true WO2007142266A1 (fr) 2007-12-13

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7565809B2 (ja) 2021-01-22 2024-10-11 旭化成株式会社 含フッ素ビニルスルホン酸フルオリド、又は含フッ素ビニルスルホン酸塩の製造方法、及び分離方法。

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003221378A (ja) * 2002-01-03 2003-08-05 Ausimont Spa ２−（２−フルオロスルホニル）−ペルフルオロエチレンオキシ３−ハロゲン−プロピオン酸のアルキルエステル及びその製造方法
JP2004244401A (ja) * 2002-12-19 2004-09-02 Daikin Ind Ltd 含フッ素フルオロスルホニルアルキルビニルエーテルの製造方法
WO2005003082A1 (fr) * 2003-07-04 2005-01-13 Asahi Glass Company, Limited Procede de production de fluorures de sulfonyle fluore

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003221378A (ja) * 2002-01-03 2003-08-05 Ausimont Spa ２−（２−フルオロスルホニル）−ペルフルオロエチレンオキシ３−ハロゲン−プロピオン酸のアルキルエステル及びその製造方法
JP2004244401A (ja) * 2002-12-19 2004-09-02 Daikin Ind Ltd 含フッ素フルオロスルホニルアルキルビニルエーテルの製造方法
WO2005003082A1 (fr) * 2003-07-04 2005-01-13 Asahi Glass Company, Limited Procede de production de fluorures de sulfonyle fluore

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7565809B2 (ja) 2021-01-22 2024-10-11 旭化成株式会社 含フッ素ビニルスルホン酸フルオリド、又は含フッ素ビニルスルホン酸塩の製造方法、及び分離方法。

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