WO2003106407A1 - Process for production of fluorine-containing fluoro- sulfonylalkyl vinyl ethers - Google Patents

Process for production of fluorine-containing fluoro- sulfonylalkyl vinyl ethers Download PDF

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Publication number
WO2003106407A1
WO2003106407A1 PCT/JP2003/006440 JP0306440W WO03106407A1 WO 2003106407 A1 WO2003106407 A1 WO 2003106407A1 JP 0306440 W JP0306440 W JP 0306440W WO 03106407 A1 WO03106407 A1 WO 03106407A1
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general formula
vinyl ether
cfo
integer
reaction
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PCT/JP2003/006440
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French (fr)
Japanese (ja)
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杉山　明平
大塚　達也
市原　一義
萬谷　聡哉
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ダイキン工業株式会社
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Priority to AU2003242416A priority Critical patent/AU2003242416A1/en
Publication of WO2003106407A1 publication Critical patent/WO2003106407A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C313/00—Sulfinic acids; Sulfenic acids; Halides, esters or anhydrides thereof; Amides of sulfinic or sulfenic acids, i.e. compounds having singly-bound oxygen atoms of sulfinic or sulfenic groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C313/02—Sulfinic acids; Derivatives thereof
    • 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
    • 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 fluorinated fluorosulfonylalkyl vinyl ether, and a method for producing an intermediate of the fluorinated fluorosulfonylalkyl vinyl ether.
  • Fluorinated Full O b sulfonyl alkyl vinyl ether of formula CF2 CFOCF2CF 2 S0 2 F is Ru compounds useful der as industrial raw materials such as an ion-exchange membrane material.
  • a sulfonyl vinyl ether such as the fluorinated fluorosulfonylalkyl vinyl ether
  • hexafluoropropylene oxide is added to FCOCF 2 S0
  • a method is described in which after addition to 2 F, the obtained acid fluoride derivative is thermally decomposed.
  • two or more molecules of hexafluoropropylene oxide are added,
  • CF 2 CFO (CF 2 CF (CF 3) ⁇ ) n CF 2 CF 2 S0 2 is Rukoto give sulfo ether represented by F are possible, the hexa full O b propylene O sulfoxide one molecular addition From the following formula
  • Japanese Patent Application Laid-Open No. 57-28025 describes a method in which a fluorene propylene oxide is added to FCOCF 2 SO 2 F and then thermally decomposed.
  • this method it is possible to obtain the above-mentioned fluorinated fluorosulfonylalkyl pinyl ether, but since the chloropentafluoropropylene oxide used as a raw material cannot be obtained in good yield, Fluorine-containing fluorosulfonyl alkyl vinyl ester One teller cannot be efficiently manufactured at low cost.
  • JP-A-61-30552 and JP-A-10-139745 disclose halogen-terminated vinyl ethers. how to convert halogens S0 2 F group, the JP 1 1 one 2 2 8 4 7 4 No. Gazette, a method for dechlorination with zinc CF 2 C1CFC10CF 2 CF 2 S0 2 F and the like are described ing.
  • the present invention has been made in view of the above situation, and a main object of the present invention is to provide a method capable of producing a fluorine-containing fluorosulfonylalkyl vinyl ether in an industrially advantageous manner with a good yield. That is.
  • Inventors of the present invention have conducted intensive studies in view of the above-mentioned problems, and as a result, have found that by reacting a fluorinated alkyl vinyl ether having a terminal octylogen atom with a dithionite and a neutralizing agent, a vinyl group is obtained. It has been found that a sulfinic acid salt of vinyl ether can be obtained as it is. By chlorinating and fluorinating the obtained sulfinate, it becomes possible to produce the desired fluorinated fluorosulfonylalkyl vinyl ether in a relatively simple process in a high yield. The present invention has been completed here.
  • the present invention provides the following fluorinated fluorosulfonylalkyl vinyl ether PC leakage 440
  • CF 2 CFO (CF 2 CF (CF 3 ) ⁇ ) n CF2 (CF 2 CF2) m CF2S0 2 F (1)
  • CF 2 CFO (CF 2 CF (CF 3 ) 0) n CF 2 (CF 2 CF 2 ) m CF2X (2)
  • CF 2 CFO (CF 2 CF (CF 3 ) ⁇ ) n CF 2 (CF 2 CF 2 ) m CF 2 S0 2 M (3) (where M is Ma or Mb 1/2 and Ma Is an alkali metal, Mb is an alkaline earth metal, m and n are the same as above, a process for producing a vinyl ether sulfinate represented by the following formula:
  • CF 2 CFO (CF 2 CF (CF 3 ) 0) n CF2 (CF 2 CF 2 ) m CF 2 X
  • CF 2 CFO (CF 2 CF (CF 3 ) ⁇ ) n CF 2 (CF2CF2) m CF 2 S0 2 M
  • M is Ma or Mb
  • Ma is an alkali metal
  • Mb is an alkaline earth metal
  • m and n are the same as described above.
  • CF 2 CFO (CF 2 CF (CF 3 ) ⁇ ) n CF 2 (CF 2 CF 2 ) m CF 2 S0 2 M
  • M is Ma or Mb 1/2
  • Ma is an alkali metal
  • Mb is an alkaline earth metal
  • M is an integer of 0-5
  • n is an integer of 0-10.
  • the vinyl ether sulphinate represented by the formula is chlorinated and then fluorinated, a general formula:
  • CF 2 CFO (CF 2 CF (CF 3 ) ⁇ ) n CF2 (CF 2 CF2) m CF 2 S02F
  • CF 2 CFO (CF 2 CF (CF 3 ) ⁇ ) n CF2 (CF2CF2) m CF 2 X (2)
  • CF 2 CFO (CF 2 CF (CF 3 ) 0) n CF2 (CF2CF2) m CF2S0 2 M (3)
  • M is M a or Mb 1/2, the M a is an alkali metal, Mb is force Li earth metals. M and n are the same. Above) Pinirue one Terusurufu represented by And phosphate.
  • the ⁇ -octalogenated pinyl ether of the general formula (2) used as a raw material is a known substance.
  • the fluorine-containing compound represented by) S0 3, C1S0 3 H is reacted with fuming sulfuric acid FOC (CF 2 CF 2) after the m CF 2 X
  • HFP0 hexafluoropropylene oxide
  • the dithionite alkali metal Ru used when Chiosuruhon the ⁇ - halogenated Biel ether of the general formula (2) for example, Li 2 S 2 0 4, Na 2 S 2 0 4, K 2 S 2 0 4, Cs 2 S 2 0 4 or the like can be mentioned, in particular, Na 2 S 2 0 4, etc. K 2 S 2 0 4 is preferred.
  • the amount of dithionite used must be at least 1 mol per 1 mol of the substrate, and preferably about 1 to 5 mol.
  • the neutralizing agent MaHC0 3, Mb 1/2 HC_ ⁇ 3 hydrogen carbonates such as, Ma 2 C_ ⁇ 3, carbonates such as MbC_ ⁇ 3, MAOH, M b E Bruno 2 ⁇ hydroxides such as H And various other bases can be used.
  • Ma indicates an alkali metal
  • Mb indicates an alkaline earth metal.
  • the amount of the neutralizing agent to be used is preferably about 1 to 20 times equivalent, more preferably about 1 to 10 times equivalent to the substrate.
  • the order of the reaction is not particularly limited, and for example, the general formula (2) Reacting the ⁇ -halogenated vinyl ether of the formula (2) with a dithionite and a neutralizing agent at the same time, reacting the ⁇ -halogenated vinyl ether of the general formula (2) with the dithionite, and then reacting with the neutralizing agent.
  • a reaction method can be adopted. The above reaction is usually performed in a solvent.
  • the solvent used in the reaction is not particularly limited, and examples thereof include water, ketones such as acetone, esters such as ethyl acetate, dioxane, acetonitrile, dimethylformamide, dimethylsulfoxide, and tetrahydrofuran. These can be used alone or in combination of two or more.
  • the vinyl ether sulfide of the general formula (3) can be obtained in high yield. Can be obtained.
  • the concentration of the ⁇ -halogenated vinyl ether compound of the general formula (2) in the solvent is not particularly limited, but may be usually about 10 to 80% by mass.
  • the reaction temperature is preferably about ⁇ 20 to 90, more preferably about 0 to 50 ° C. for the reaction with the neutralizing agent and the reaction with the ditite.
  • the reaction time may be set according to the reaction conditions to be actually employed until the desired reaction has progressed sufficiently. Usually, the total time is about 0.5 to 48 hours depending on the reaction conditions. Can be performed within a range.
  • CF 2 CFO (CF 2 CF (CF 3 ) ⁇ ) n CF2 (CF2CF 2 ) m CF2S0 2 M (3)
  • examples of the alkali metal include Na, K, Li, and Cs
  • examples of the alkaline earth metal include Ca and Mg.
  • the vinyl ether sulfinate is a novel substance useful as an intermediate for producing a fluorinated fluorosulfonyl alkyl vinyl ether of the general formula (1).
  • CF 2 CFO (CF 2 CF (CF 3 ) ⁇ ) n CF2 (CF 2 CF2) m CF2S0 2 F (1)
  • the chlorination reaction can be performed according to a conventional method using a known chlorinating agent. Specifically, for example, after dissolving or dispersing the vinyl ether sulfinate of the general formula (3) in water, an organic solvent, or the like, performing a chlorination reaction by adding a chlorinating agent thereto. Can be.
  • the organic solvent used in the decarboxylation reaction may be present as it is during the chlorination reaction, or may be removed.
  • an acid such as hydrochloric acid, sulfuric acid, formic acid, or acetic acid may be contained in the solvent depending on the type of the chlorinating agent used.
  • an acid such as hydrochloric acid, sulfuric acid, formic acid, or acetic acid
  • hydrochloric acid generated by the reaction is contained in water.
  • copper chloride used as the chlorinating agent
  • an aqueous solution containing formic acid can be used as the solvent.
  • the concentration of the acid in these cases is not particularly limited as long as it does not adversely affect the chlorination reaction.
  • the organic solvent can be appropriately selected and used as long as it does not adversely affect the reaction.
  • the chlorinating agent is not particularly limited, and a known chlorinating agent can be used.
  • a known chlorinating agent can be used.
  • chlorine, sulfuryl chloride, copper (II) chloride, etc. are used as chlorinating agents.
  • chlorine is preferably used.
  • chlorination reaction is performed in water using chlorine, the obtained chlorinated product is separated into an organic layer, so that it can be easily collected and industrially implemented.
  • the conditions of the chlorination reaction are not particularly limited, and may be appropriately determined depending on the type of the chlorinating agent to be used so that a desired chlorinated product is formed.
  • the chlorination reaction may be carried out by supplying chlorine gas into an aqueous solution in which the vinyl ether sulfinate of the general formula (3) is dissolved. Is about 0 to 50 ° C, and the amount of chlorine to be charged is about 1 to 5 mol, preferably about 1.2 to 3 mol, per 1 mol of bierether sulfinate of the general formula (3). .
  • the reaction time varies depending on the specific reaction conditions, but is usually within a range of about 0.5 to 48 hours.
  • the concentration of the pinyl monotersulfinate of the general formula (3) in the aqueous solution is not particularly limited, but may be generally about 0.5 to 50% by mass.
  • CF 2 CFO (CF 2 CF (CF 3 ) ⁇ ) n CF2 (CF 2 CF2) m CF2S02F (1)
  • the fluorination reaction can be performed according to a known method.
  • the chlorinated product and the fluorinating agent may be reacted in a solvent for the fluorination reaction or without a solvent.
  • the solvent is not particularly limited, and may be any solvent that does not participate in the reaction, and examples thereof include organic solvents such as sulfolane, dimethylsulfoxide, and dimethylformamide, and water.
  • the fluorinating agent a known fluorinating agent can be used.
  • NaF, KF and the like can be suitably used.
  • the reaction temperature may be about 20 to 200 ° C
  • the reaction time may be about 0.5 to 48 hours
  • the amount of the fluorinating agent used may be 1 mole of chlorinated product.
  • the amount may be about 1 to 5 moles.
  • concentration of chlorinated substances in the solvent 3/06440
  • the obtained crude compound may be purified by a known method such as extraction, distillation, recrystallization, and column chromatography.
  • the fluorine-containing sulfonylalkyl vinyl ether represented by the general formula (1) obtained by the method of the present invention is a useful substance as a monomer component for a polymer used for an electrolyte membrane or an ion exchange membrane.
  • This electrolyte membrane or ion exchange membrane is used, for example, for an electrolyte membrane of a solid polymer electrolyte fuel cell, a membrane for a lithium battery, a membrane for salt electrolysis, a membrane for water electrolysis, a membrane for hydrohalogen oxyacid electrolysis, and an oxygen concentrator. Used as membrane, humidity sensor membrane, gas sensor membrane, etc.
  • the desired fluorinated fluorosulfonyl ether can be produced at low cost and with high yield by an industrially advantageous method without requiring complicated operations.

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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

A process for the production of fluorine-containing fluorosulfonylalkyl vinyl ethers represented by the general formula: CF2=CFO(CF2CF(CF3)O)nCF2(CF2CF2)mCF2SO2F (wherein m is an integer of 0 to 5 and n is an integer of 0 to 10), characterized by reacting an ω-halogenated vinyl ether represented by the general formula: CF2=CFO(CF2CF(CF3)O)nCF2(CF2CF2)mCF2X (wherein X is I or Br, and m and n are each as defined above) with an alkali metal dithionite and a neutralizing agent to form a vinyl ether sulfinate represented by the general formula: CF2=CFO(CF2CF(CF3)O)nCF2(CF2CF2)mCF2SO2M (wherein M is Ma or Mb1/2; Ma is an alkali metal; Mb is an alkaline earth metal; and m and n are each as defined above), chlorinating the vinyl ether sulfinate, and then fluorinating the obtained compound. According to the process, fluorine-containing fluorosulfonyl- alkyl vinyl ethers can be industrially advantageously produced in high yield.

Description

明 細 書  Specification
含フッ素フルォロスルホニルアルキルビニルエーテルの製造方法  Method for producing fluorine-containing fluorosulfonylalkyl vinyl ether
技 術 分 野  Technical field
本発明は、 含フッ素フルォロスルホニルアルキルビニルエーテルの製造方法、 及び該含フッ素フルォロスルホニルアルキルビニルエーテルの中間体の製造方法 に関する。  The present invention relates to a method for producing a fluorinated fluorosulfonylalkyl vinyl ether, and a method for producing an intermediate of the fluorinated fluorosulfonylalkyl vinyl ether.
背 景 技 術  Background technology
化学式 CF2=CFOCF2CF2S02F で表される含フッ素フルォロスルホニルアルキ ルビニルエーテルは、 イオン交換膜材料などの工業原料として有用な化合物であ る。 Fluorinated Full O b sulfonyl alkyl vinyl ether of formula CF2 = CFOCF2CF 2 S0 2 F is Ru compounds useful der as industrial raw materials such as an ion-exchange membrane material.
該含フッ素フルォロスルホニルアルキルビニルエーテル等のスルホ二ルビニル エーテルの製造方法としては、 例えば、 英国特許 1 , 0 3 4 , 1 9 7号公報に、 へキサフルォロプロピレンォキシドを FCOCF2S02Fに付加させた後、得られた酸 フロリ ド誘導体を熱分解する方法が記載されている。 しかしながら、 この方法で は、 へキサフルォロプロピレンォキシドを 2分子以上付加したものからは、As a method for producing a sulfonyl vinyl ether such as the fluorinated fluorosulfonylalkyl vinyl ether, for example, in British Patent No. 1,034,1977, hexafluoropropylene oxide is added to FCOCF 2 S0 A method is described in which after addition to 2 F, the obtained acid fluoride derivative is thermally decomposed. However, in this method, two or more molecules of hexafluoropropylene oxide are added,
CF2=CFO (CF2CF (CF3) θ) n CF2CF2S02F で表されるスルホビニルエーテルを得 ることは可能であるが、 へキサフルォロプロピレンォキシドを 1分子付加したも のからは、 下記式 CF 2 = CFO (CF 2 CF (CF 3) θ) n CF 2 CF 2 S0 2 is Rukoto give sulfo ether represented by F are possible, the hexa full O b propylene O sulfoxide one molecular addition From the following formula
Figure imgf000003_0001
Figure imgf000003_0001
で表される環化体が主生成物として生じ、化学式 CF2=CFOCF2CF2S02Fで表され る含フッ素フルォロスルホニルアルキルビニルエーテルをほとんど得ることがで きない。 In occur as cyclized main product represented by the chemical formula CF2 = CFOCF2CF 2 S0 2 no Ki out that most obtain fluorinated full O b sulfonyl vinyl ether, which you express by F.
また、 特開昭 5 7 - 2 8 0 2 5号公報には、 クロ口ペン夕フルォロプロピレン ォキシドを FCOCF2S02Fに付加させた後、 熱分解する方法が記載されている。 こ の方法では、 上記した含フッ素フルォロスルホニルアルキルピニルェ一テルを得 ることは可能であるが、 原料とするクロロペンタフルォロプロピレンォキシドが 収率よく得られないために、 上記含フッ素フルォロスルホニルアルキルビニルェ 一テルを安価に効率良く製造することができない。 Further, Japanese Patent Application Laid-Open No. 57-28025 describes a method in which a fluorene propylene oxide is added to FCOCF 2 SO 2 F and then thermally decomposed. In this method, it is possible to obtain the above-mentioned fluorinated fluorosulfonylalkyl pinyl ether, but since the chloropentafluoropropylene oxide used as a raw material cannot be obtained in good yield, Fluorine-containing fluorosulfonyl alkyl vinyl ester One teller cannot be efficiently manufactured at low cost.
また、 米国特許第 3,560,568号には、 FCOCF (CF3) OCF2CF2S02Fを原料として 用 い 、 その環化体 を 形成 し た後、 CH3ONa を用 いて 開環 さ せて CF2=CFOCF2CF2S03Naとし、 その後、 末端の S03Na基を塩素化し、 更に、 フッ 素化して S02F基に変換する方法が記載されている。 しかしながら、 この方法は、 CF2=CFOCF2CF2S03Na の塩素化の反応性が極めて低いために非常に効率の悪い 方法であり、 しかも、 系内に水分が存在すると H C 1ガスを発生する等の問題が ある。 更に、 塩素化反応の前に、 N a F等の不純物をほぼ完全に除去する必要が あり、 製造工程が非常に煩雑であり、 工業的実施は困難である。 Also, U.S. Pat. No. 3,560,568, FCOCF (CF 3) have use a OCF 2 CF 2 S0 2 F as starting materials, and their after forming a cyclized, by ring-opening with have use the CH 3 ONa CF 2 = a CFOCF 2 CF2S0 3 Na, then the S0 3 Na group of the terminal chlorinated, further, a method of converting the S0 2 F group to fluorination is described. However, this method, CF2 = CFOCF a 2 CF 2 S0 3 Na very inefficient way to very low reactivity chlorination of, moreover, generates a HC 1 gas when moisture is present in the system And so on. Further, it is necessary to remove impurities such as NaF almost completely before the chlorination reaction, so that the production process is very complicated and industrially difficult.
その他に、 スルホ二ルビ二ルェ一テルを製造する方法として、 特開昭 6 1— 3 0 5 5 2号公報及び特開平 1 0— 1 3 9 7 4 5号公報には、 ハロゲン末端ビニル エーテルのハロゲンを S02F基に変換する方法、 特開平 1 1一 2 2 8 4 7 4号公 報には、 CF2C1CFC10CF2CF2S02F を亜鉛で脱塩素化する方法等が記載されてい る。 In addition, as a method for producing sulfonyl vinyl ether, JP-A-61-30552 and JP-A-10-139745 disclose halogen-terminated vinyl ethers. how to convert halogens S0 2 F group, the JP 1 1 one 2 2 8 4 7 4 No. Gazette, a method for dechlorination with zinc CF 2 C1CFC10CF 2 CF 2 S0 2 F and the like are described ing.
しかしながら、 これらのいずれの方法も、 目的物であるスルホ二ルビニルエー テルの収率が低いか、 廃棄物の多さから工業的な製造方法としては満足のいくも のではない。  However, none of these methods is satisfactory as an industrial production method because the yield of the target product, sulfonyl vinyl ether, is low or the amount of waste is large.
発 明 の 開 示  Disclosure of the invention
本発明は、 上記した現状に鑑みてなされたものであり、 その主な目的は、 含フ ッ素フルォロスルホニルアルキルビニルエーテルを工業的に有利な方法で収率良 く製造できる方法を提供することである。  The present invention has been made in view of the above situation, and a main object of the present invention is to provide a method capable of producing a fluorine-containing fluorosulfonylalkyl vinyl ether in an industrially advantageous manner with a good yield. That is.
本発明者は、 上記した問題点に鑑みて鋭意研究を重ねた結果、 末端に八ロゲン 原子を有する含フッ素アルキルビニルエーテルを亜ジチオン酸塩及び中和剤と反 応させることによって、 ビニル基を有したままでビニルエーテルのスルフィン酸 塩を得ることができることを見出した。 そして、 得られたスルフィン酸塩を塩素 化及びフッ素化することによって、 目的とする含フッ素フルォロスルホニルアル キルビニルエーテルを比較的簡単な工程により高収率で製造することが可能とな ることを見出し、 ここに本発明を完成するに至った。  Inventors of the present invention have conducted intensive studies in view of the above-mentioned problems, and as a result, have found that by reacting a fluorinated alkyl vinyl ether having a terminal octylogen atom with a dithionite and a neutralizing agent, a vinyl group is obtained. It has been found that a sulfinic acid salt of vinyl ether can be obtained as it is. By chlorinating and fluorinating the obtained sulfinate, it becomes possible to produce the desired fluorinated fluorosulfonylalkyl vinyl ether in a relatively simple process in a high yield. The present invention has been completed here.
即ち、 本発明は、 下記の含フッ素フルォロスルホニルアルキルビニルエーテル PC漏裏 440 That is, the present invention provides the following fluorinated fluorosulfonylalkyl vinyl ether PC leakage 440
3 Three
の製造方法、 該含フッ素フルォロスルホニルアルキルビニルェ一テルの中間体と して有用な化合物の製造方法を提供するものである。 And a process for producing a compound useful as an intermediate of the fluorinated fluorosulfonylalkyl vinyl ether.
1. 下記 （ i ) 及び （ii) の工程を含むことを特徴とする一般式 （1)  1. General formula (1) characterized by including the following steps (i) and (ii):
CF2=CFO (CF2CF (CF3) θ) nCF2(CF2CF2)mCF2S02F ( 1 ) CF 2 = CFO (CF 2 CF (CF 3 ) θ) n CF2 (CF 2 CF2) m CF2S0 2 F (1)
(式中、 mは 0~ 5の整数、 nは 0~ 1 0の整数である。 ） で表される含フッ素 フルォロスルホニルアルキルビニルエーテルの製造方法：  (Wherein, m is an integer of 0 to 5, and n is an integer of 0 to 10.) A method for producing a fluorinated fluorosulfonylalkyl vinyl ether represented by the following formula:
( i ) 下記一般式 （2) ：  (i) The following general formula (2):
CF2=CFO (CF2CF (CF3) 0) nCF2(CF2CF2)mCF2X (2) CF 2 = CFO (CF 2 CF (CF 3 ) 0) n CF 2 (CF 2 CF 2 ) m CF2X (2)
(式中、 Xは Iまたは Brであり、 m及び nは上記に同じ。 ）で表される ω-八ロゲ ン化ビニルエーテルを、 アルカリ金属の亜ジチオン酸塩及び中和剤と反応させて 下記一般式 （3) ： (Wherein X is I or Br, and m and n are the same as described above). The following reaction is carried out by reacting the ω-octalogenated vinyl ether represented by the formula with an alkali metal dithionite and a neutralizing agent. General formula (3):
CF2=CFO (CF2CF (CF3) θ) nCF2(CF2CF2)mCF2S02M (3) (式中、 Mは、 M a又は Mb 1 /2であり、 Maはアルカリ金属、 Mbはアル力 リ土類金属である。 m及び nは上記に同じ。 ） で表されるビニルエーテルスルフ イン酸塩を製造する工程、 CF 2 = CFO (CF 2 CF (CF 3 ) θ) n CF 2 (CF 2 CF 2 ) m CF 2 S0 2 M (3) (where M is Ma or Mb 1/2 and Ma Is an alkali metal, Mb is an alkaline earth metal, m and n are the same as above, a process for producing a vinyl ether sulfinate represented by the following formula:
(ϋ) 工程 （ i ) で得られたビニルエーテルスルフィン酸塩を塩素化した後、 フッ素化して、 上記一般式 （1) で表される含フッ素フルォロスルホニルアルキ ルビニルエーテルを製造する工程。  (ii) a step of chlorinating and fluorinating the vinyl ether sulfinate obtained in the step (i) to produce a fluorinated fluorosulfonylalkyl vinyl ether represented by the general formula (1).
2. 一般式：  2. General formula:
CF2=CFO (CF2CF (CF3) 0) nCF2(CF2CF2)mCF2X CF 2 = CFO (CF 2 CF (CF 3 ) 0) n CF2 (CF 2 CF 2 ) m CF 2 X
(式中、 Xは Iまたは Brであり、 mは 0〜 5の整数、 nは 0~ 1 0の整数である。） で表される ω-ハロゲン化ビニルエーテルを、アル力リ金属の亜ジチオン酸塩'及び 中和剤と反応させることを特徴とする、 一般式  (Wherein X is I or Br, m is an integer of 0 to 5, and n is an integer of 0 to 10). The ω-halogenated vinyl ether represented by the following formula: Acid salt 'and a neutralizing agent, characterized by the general formula
CF2=CFO (CF2CF (CF3) θ) nCF2(CF2CF2)mCF2S02M CF 2 = CFO (CF 2 CF (CF 3 ) θ) n CF 2 (CF2CF2) m CF 2 S0 2 M
(式中、 Mは、 Ma又は Mb であり、 Maはアルカリ金属、 Mbはアル力 リ土類金属である。 m及ぴ nは上記に同じ。 ） で表されるビニルエーテルスルフ ィン酸塩の製造方法。  (Wherein, M is Ma or Mb, Ma is an alkali metal, Mb is an alkaline earth metal, and m and n are the same as described above.) Manufacturing method.
3. 一般式：  3. General formula:
CF2=CFO (CF2CF (CF3) θ) nCF2(CF2CF2)mCF2S02M (式中、 Mは、 Ma又は Mb 1 /2であり、 Maはアルカリ金属、 Mbはアル カリ土類金属である。 mは 0~ 5の整数、 nは 0〜1 0の整数である。 ） で表さ れるビ二ルェ一テルスルフィン酸塩を塩素化した後、 フッ素化することを特徴と する、 一般式： CF 2 = CFO (CF 2 CF (CF 3 ) θ) n CF 2 (CF 2 CF 2 ) m CF 2 S0 2 M (Wherein, M is Ma or Mb 1/2 , Ma is an alkali metal, Mb is an alkaline earth metal. M is an integer of 0-5, and n is an integer of 0-10.) Wherein the vinyl ether sulphinate represented by the formula is chlorinated and then fluorinated, a general formula:
CF2=CFO (CF2CF (CF3) θ) nCF2(CF2CF2)mCF2S02F CF 2 = CFO (CF 2 CF (CF 3 ) θ) n CF2 (CF 2 CF2) m CF 2 S02F
(式中、 m及び nは前記に同じ。 ）で表される含フッ素フルォロスルホニルアルキ ルビ二ルェ一テルの製造方法。 本発明の含フッ素フルォロスルホニルアルキルビニルエーテルの製造方法で は、 まず、 一般式 （2) ：  (Wherein, m and n are the same as above.) A method for producing a fluorinated fluorosulfonylalkylvinyl ether represented by the formula: In the method for producing a fluorinated fluorosulfonylalkyl vinyl ether of the present invention, first, a general formula (2):
CF2=CFO (CF2CF (CF3) θ) nCF2(CF2CF2)mCF2X (2) CF 2 = CFO (CF 2 CF (CF 3 ) θ) n CF2 (CF2CF2) m CF 2 X (2)
(式中、 Xは Iまたは Brであり、 mは 0〜 5の整数、 nは 0〜 1 0の整数である。） で表される ω-ハロゲン化ビエルエーテルをアル力リ金属の亜ジチオン酸塩及び 中和剤と反応させて、 下記一般式 （3) ： (Wherein, X is I or Br, m is an integer of 0 to 5, and n is an integer of 0 to 10). Reacting with an acid salt and a neutralizing agent to obtain the following general formula (3):
CF2=CFO(CF2CF(CF3)0)nCF2(CF2CF2)mCF2S02M (3)CF 2 = CFO (CF 2 CF (CF 3 ) 0) n CF2 (CF2CF2) m CF2S0 2 M (3)
(式中、 Mは、 M a又は Mb 1 /2であり、 M aはアルカリ金属、 Mbはアル力 リ土類金属である。 m及び nは上記に同じ。 ） で表されるピニルェ一テルスルフ ィン酸塩とする。 (Wherein, M is M a or Mb 1/2, the M a is an alkali metal, Mb is force Li earth metals. M and n are the same. Above) Pinirue one Terusurufu represented by And phosphate.
原料として用いる一般式 （2) の ω-八ロゲン化ピニルエーテルは、 公知物質で あり、 例えば、 公知物質である一般式 CFX2(CF2CF2)mCF2X (式中、 Xは Iまたは Brであり、 mは 0〜 5の整数である。）で表される含フッ素化合物を S03、C1S03H、 発煙硫酸等と反応させて FOC(CF2CF2)mCF2X とした後、 公知の方法でへキサ フルォロプロピレンォキサイ ド （以後 HFP0 と略す） とオリゴメリ反応を 行い、 中和及ぴ脱炭酸反応を行なう ことにより得ることができる。 The ω-octalogenated pinyl ether of the general formula (2) used as a raw material is a known substance. For example, a known substance of the general formula CFX 2 (CF 2 CF2) m CF 2 X (where X is I or Br in and, m is an integer of 0-5. the fluorine-containing compound represented by) S0 3, C1S0 3 H, is reacted with fuming sulfuric acid FOC (CF 2 CF 2) after the m CF 2 X It can be obtained by carrying out an oligomerization reaction with hexafluoropropylene oxide (hereinafter abbreviated as HFP0) by a known method, followed by neutralization and decarboxylation.
一般式 （ 2 ) の ω-ハロゲン化ビエルエーテルをチォスルホン化する際に用い るアルカリ金属の亜ジチオン酸塩としては、 例えば、 Li2S204、 Na2S204、 K2S204、 Cs2S204等を挙げることができ、 特に、 Na2S204、 K2S204などが好ましい。 The dithionite alkali metal Ru used when Chiosuruhon the ω- halogenated Biel ether of the general formula (2), for example, Li 2 S 2 0 4, Na 2 S 2 0 4, K 2 S 2 0 4, Cs 2 S 2 0 4 or the like can be mentioned, in particular, Na 2 S 2 0 4, etc. K 2 S 2 0 4 is preferred.
亜ジチオン酸塩の使用量は、 基質 1モルに対して 1モル以上必要であり、 好ま しくは、 1〜 5モル程度とすればよい。 中和剤としては、 MaHC03、 Mb 1/2HC〇3等の炭酸水素塩、 Ma2 C〇3、 MbC〇 3等の炭酸塩、 MaOH、 M bェノ 2〇 H等の水酸化物等の各種 塩基を用いることができる。 ここで、 Maはアルカリ金属を示し、 Mbはアル力 リ土類金属を示す。 これらの塩基としては、 特に、 炭酸塩、 炭酸水素塩等を用い ることが好ましい。 The amount of dithionite used must be at least 1 mol per 1 mol of the substrate, and preferably about 1 to 5 mol. As the neutralizing agent, MaHC0 3, Mb 1/2 HC_〇 3 hydrogen carbonates such as, Ma 2 C_〇 3, carbonates such as MbC_〇 3, MAOH, M b E Bruno 2 〇 hydroxides such as H And various other bases can be used. Here, Ma indicates an alkali metal, and Mb indicates an alkaline earth metal. As these bases, it is particularly preferable to use carbonates, hydrogencarbonates and the like.
中和剤の使用量は、基質に対して 1〜 2 0倍当量程度とすることが好ま しく、 1 ~ 1 0倍当量程度とすることがより好ましい。  The amount of the neutralizing agent to be used is preferably about 1 to 20 times equivalent, more preferably about 1 to 10 times equivalent to the substrate.
一般式 （ 2 ) の ω-ノ、ロゲン化ビニルエーテルとアルカリ金属の亜ジチオン酸 塩及び中和剤との反応工程では、 反応の順序については特に限定的ではなく、 例 えば、 一般式 （ 2 ) の ω-ハロゲン化ビニルェ一テルと亜ジチオン酸塩及び中和 剤とを同時に反応させる方法、 一般式 （ 2 ) の ω-ハロゲン化ビニルエーテルを 亜ジチオン酸塩と反応させた後、 中和剤と反応させる方法などを採用できる。 上記反応は、 通常、 溶媒中で行う。 反応に用いる溶媒としては、 特に限定はな く、 例えば、 水、 アセトンなどのケトン類、 酢酸ェチル等のエステル類等の他、 ジォキサン、 ァセトニトリル、 ジメチルホルムアミ ド、 ジメチルスルホキシド、 テトラヒドロフランなどを例示でき、 これらを一種単独又は二種以上混合して用 いることができる。  In the reaction step of the ω-no of the general formula (2), the hydrogenated vinyl ether with the alkali metal dithionite and the neutralizing agent, the order of the reaction is not particularly limited, and for example, the general formula (2) Reacting the ω-halogenated vinyl ether of the formula (2) with a dithionite and a neutralizing agent at the same time, reacting the ω-halogenated vinyl ether of the general formula (2) with the dithionite, and then reacting with the neutralizing agent. A reaction method can be adopted. The above reaction is usually performed in a solvent. The solvent used in the reaction is not particularly limited, and examples thereof include water, ketones such as acetone, esters such as ethyl acetate, dioxane, acetonitrile, dimethylformamide, dimethylsulfoxide, and tetrahydrofuran. These can be used alone or in combination of two or more.
特に、 原料とする一般式 （ 2 ) の ω-ハロゲン化ビエルエーテルと亜ジチォ ン酸塩が完全に溶解する様に溶媒を選択することにより、高収率で一般式（ 3 ) のビニルエーテルスルフィ ン酸塩を得ることができる。  In particular, by selecting a solvent so that the ω-halogenated beer ether of the general formula (2) and the dithionite used as raw materials are completely dissolved, the vinyl ether sulfide of the general formula (3) can be obtained in high yield. Can be obtained.
溶媒中における一般式 （2) の ω-ハロゲン化ビニルエーテル体の濃度について は、 特に限定的ではないが、 通常、 10〜80質量％程度とすればよい。  The concentration of the ω-halogenated vinyl ether compound of the general formula (2) in the solvent is not particularly limited, but may be usually about 10 to 80% by mass.
反応温度は、 中和剤との反応及び亜ジチン酸塩との反応について、 いずれも、 - 20- 90で程度とすることが好ましく、 0〜50°C程度とすることがより好 ましい。  The reaction temperature is preferably about −20 to 90, more preferably about 0 to 50 ° C. for the reaction with the neutralizing agent and the reaction with the ditite.
反応時間については、 実際に採用する反応条件に応じて、 目的とする反応が十 分に進行するまで行えば良く、 通常、 反応条件に応じて、 合計時間として、 0. 5〜48時間程度の範囲内で行うことができる。  The reaction time may be set according to the reaction conditions to be actually employed until the desired reaction has progressed sufficiently. Usually, the total time is about 0.5 to 48 hours depending on the reaction conditions. Can be performed within a range.
上記した方法で亜ジチオン酸塩と反応させてスルフィン化を行うことによつ て、 高い収率で一般式 （3 ) ： By performing sulfination by reacting with dithionite according to the method described above, And a high yield of the general formula (3):
CF2=CFO (CF2CF (CF3) θ) nCF2(CF2CF2)mCF2S02M ( 3 ) CF 2 = CFO (CF 2 CF (CF 3 ) θ) n CF2 (CF2CF 2 ) m CF2S0 2 M (3)
(式中、 M、 m及び nは上記に同じ。 ） で表されるビニルエーテルスルフィン酸塩 を得ることができる。 上記一般式において、 アルカリ金属としては、 N a、 K、 L i、 C s等を例示でき、 アルカリ土類金属としては C a、 M g等を例示できる。 該ビニルエーテルスルフィン酸塩は、 一般式 （1 ) の含フッ素フルォロスルホニ ルアルキルビニルエーテル製造用の中間体として有用な新規物質である。  (Wherein, M, m and n are the same as described above). In the above general formula, examples of the alkali metal include Na, K, Li, and Cs, and examples of the alkaline earth metal include Ca and Mg. The vinyl ether sulfinate is a novel substance useful as an intermediate for producing a fluorinated fluorosulfonyl alkyl vinyl ether of the general formula (1).
次いで、 一般式 （3 ) のビニルエーテルスルフィン酸塩を塩素化した後、 フッ 素化することによって、 目的とする一般式 （1 ) ：  Next, the vinyl ether sulfinate of the general formula (3) is chlorinated and then fluorinated to obtain the desired general formula (1):
CF2=CFO (CF2CF (CF3) θ) nCF2(CF2CF2)mCF2S02F ( 1 )CF 2 = CFO (CF 2 CF (CF 3 ) θ) n CF2 (CF 2 CF2) m CF2S0 2 F (1)
(式中、 m及び nは上記に同じ。 ） で表される含フッ素フルォロスルホニルアル キルビニルエーテルを得ることができる。 (Wherein, m and n are the same as above.) Can be obtained.
塩素化反応は、 公知の塩素化剤を用いて、 常法に従って行うことができる。 具 体的には、 例えば、 一般式 （3 ) のビニルエーテルスルフィン酸塩を水、 有機溶 媒等に溶解又は分散させた後、 これに塩素化剤を添加することによって塩素化反 応を行うことができる。 末端ハロゲン化カルボン酸塩の脱炭酸反応を有機溶媒中 で行った場合には、 脱炭酸反応で使用した有機溶媒については、 塩素化反応時に そのまま存在させても良く、 或いは除去しても良い。  The chlorination reaction can be performed according to a conventional method using a known chlorinating agent. Specifically, for example, after dissolving or dispersing the vinyl ether sulfinate of the general formula (3) in water, an organic solvent, or the like, performing a chlorination reaction by adding a chlorinating agent thereto. Can be. When the decarboxylation reaction of the terminal halogenated carboxylate is performed in an organic solvent, the organic solvent used in the decarboxylation reaction may be present as it is during the chlorination reaction, or may be removed.
塩素化反応における溶媒として水を用いる場合には、 使用する塩素化剤の種類 に応じて、 溶媒中に塩酸、 硫酸、 蟻酸、 酢酸などの酸が含まれても良い。 例えば、 塩素化剤として塩素を用いる場合には、 反応により生じた塩酸が水中に含まれる ことになる。 また、 塩素化剤として、 塩化銅を用いる場合には、 蟻酸を含む水溶 液を溶媒として用いることができる。 これらの場合の酸の濃度については、 特に 限定はなく、塩素化反応に悪影響がない範囲内であればよい。有機溶媒としても、 反応に悪影響を与えないものであれば、 適宜遒択して用いることができる。  When water is used as the solvent in the chlorination reaction, an acid such as hydrochloric acid, sulfuric acid, formic acid, or acetic acid may be contained in the solvent depending on the type of the chlorinating agent used. For example, when chlorine is used as a chlorinating agent, hydrochloric acid generated by the reaction is contained in water. When copper chloride is used as the chlorinating agent, an aqueous solution containing formic acid can be used as the solvent. The concentration of the acid in these cases is not particularly limited as long as it does not adversely affect the chlorination reaction. The organic solvent can be appropriately selected and used as long as it does not adversely affect the reaction.
本発明では、 反応操作の容易さや安全性等を考慮すると、 水又は酸を含む水溶 液を溶媒とすることが好ましい。  In the present invention, it is preferable to use water or an aqueous solution containing an acid as a solvent in consideration of ease of reaction operation and safety.
塩素化剤としては、 特に限定的ではなく、 公知の塩素化剤を用いることが可能 である。 例えば、 塩素、 塩化スルフリル、 塩化銅 （II) 等を塩素化剤として用い ることができ、 特に塩素が好適に用いられる。 塩素を用いて水中で塩素化反応を 行う場合には、 得られた塩素化物は、 有機層となって分離するため回収が容易と なり、 工業的な実施が容易となる。 The chlorinating agent is not particularly limited, and a known chlorinating agent can be used. For example, chlorine, sulfuryl chloride, copper (II) chloride, etc. are used as chlorinating agents. In particular, chlorine is preferably used. When chlorination reaction is performed in water using chlorine, the obtained chlorinated product is separated into an organic layer, so that it can be easily collected and industrially implemented.
塩素化反応の条件については、 特に限定的ではなく、 使用する塩素化剤の種類 に応じて、 目的とする塩素化物が形成されるように適宜決めれば良い。 例えば、 塩素化剤として塩素を用いる場合には、 一般式 （3 ) のビニルエーテルスルフィ ン酸塩を溶解した水溶液中に塩素ガスを供給して塩素化反応を行えば良く、 例え ば、 反応温度は 0〜 5 0 °C程度、 塩素の仕込量は、 一般式 （3 ) のビエルエーテ ルスルフィン酸塩 1モルに対して 1 ~ 5モル程度、 好ましくは 1 . 2 ~ 3モル程 度とすればよい。 反応時間は、 具体的な反応条件によって異なるが、 通常、 0 . 5〜4 8時間程度の範囲内とすればよい。 水溶液中における一般式 （3 ) のピニ ルェ一テルスルフィン酸塩の濃度については、 特に限定的ではないが、 通常、 0 . 5 - 5 0質量％程度とすればよい。  The conditions of the chlorination reaction are not particularly limited, and may be appropriately determined depending on the type of the chlorinating agent to be used so that a desired chlorinated product is formed. For example, when chlorine is used as the chlorinating agent, the chlorination reaction may be carried out by supplying chlorine gas into an aqueous solution in which the vinyl ether sulfinate of the general formula (3) is dissolved. Is about 0 to 50 ° C, and the amount of chlorine to be charged is about 1 to 5 mol, preferably about 1.2 to 3 mol, per 1 mol of bierether sulfinate of the general formula (3). . The reaction time varies depending on the specific reaction conditions, but is usually within a range of about 0.5 to 48 hours. The concentration of the pinyl monotersulfinate of the general formula (3) in the aqueous solution is not particularly limited, but may be generally about 0.5 to 50% by mass.
次 い で 、 上 記 方 法 で 得 ら れ た 塩 素 化 物 (CF2=CFO (CF2CF (CF3) θ) nCF2(CF2CF2)mCF2S02Cl ) をフッ素化することによ つて、 目的とする一般式 （1 ) ： Next, the chloride (CF 2 = CFO (CF 2 CF (CF 3 ) θ) n CF 2 (CF 2 CF 2 ) m CF 2 S0 2 Cl) obtained by the above method is converted to fluorine. The desired general formula (1):
CF2=CFO (CF2CF (CF3) θ) nCF2(CF2CF2)mCF2S02F ( 1 )CF 2 = CFO (CF 2 CF (CF 3 ) θ) n CF2 (CF 2 CF2) m CF2S02F (1)
(式中、 m及び nは上記に同じ。 ） で表される含フッ素フルォロスルホニルアル キルビニルエーテルを得ることができる。 (Wherein, m and n are the same as above.) Can be obtained.
フッ素化反応は公知の方法に従って行うことができる。 通常は、 塩素化物を分 液後、 フッ素化反応用の溶媒中又は無溶媒で該塩素化物とフッ素化剤とを反応さ せればよい。 溶媒としては、 特に限定的ではなく、 反応に関与しない溶媒であれ ば良く、 例えば、 スルホラン、 ジメチルスルホキシド、 ジメチルホルムアミド等 の有機溶媒、 水などを用いることができる。  The fluorination reaction can be performed according to a known method. In general, after the chlorinated product is separated, the chlorinated product and the fluorinating agent may be reacted in a solvent for the fluorination reaction or without a solvent. The solvent is not particularly limited, and may be any solvent that does not participate in the reaction, and examples thereof include organic solvents such as sulfolane, dimethylsulfoxide, and dimethylformamide, and water.
フッ素化剤としては、 公知のフッ素化剤を用いることができる。 例えば、 N a F、 K F等を好適に用いることができる。  As the fluorinating agent, a known fluorinating agent can be used. For example, NaF, KF and the like can be suitably used.
フッ素化反応条件の一例を示すと、反応温度 2 0〜 2 0 0 °C程度、反応時間 0 . 5 ~ 4 8時間程度とすれば良く、 フッ素化剤の使用量は、 塩素化物 1モルに対し て 1〜 5モル程度とすればよい。 また、 溶媒中での塩素化物の濃度については、 3/06440 As an example of the fluorination reaction conditions, the reaction temperature may be about 20 to 200 ° C, the reaction time may be about 0.5 to 48 hours, and the amount of the fluorinating agent used may be 1 mole of chlorinated product. The amount may be about 1 to 5 moles. Also, regarding the concentration of chlorinated substances in the solvent, 3/06440
8 8
特に限定的ではないが、 通常、 1 0 ~ 1 0 0質量％程度とすればよい。 Although not particularly limited, usually, it may be about 10 to 100% by mass.
以上の方法によって、 一般式 （1 ) の含フッ素フルォロスルホニルアルキルビ ニルエーテルを得ることができる。  By the above method, the fluorinated fluorosulfonylalkylvinyl ether of the general formula (1) can be obtained.
得られた粗化合物は、 抽出、 蒸留、 再結晶、 カラムクロマトグラフィーなどの 公知の方法で精製すればよい。  The obtained crude compound may be purified by a known method such as extraction, distillation, recrystallization, and column chromatography.
本発明方法によって得られる一般式 （1 ) で表される含フッ素スルホニルアル キルビニルエーテルは、 電解質膜又はイオン交換膜等に用いるポリマー用のモノ マ一成分として有用な物質である。  The fluorine-containing sulfonylalkyl vinyl ether represented by the general formula (1) obtained by the method of the present invention is a useful substance as a monomer component for a polymer used for an electrolyte membrane or an ion exchange membrane.
この電解質膜又はイオン交換膜は、 例えば固体高分子電解質型燃料電池の電解 質用膜、 リチウム電池用膜、 食塩電解用膜、 水電解用膜、 八ロゲン化水素酸電解 用膜、 酸素濃縮器用膜、 湿度センサー用膜、 ガスセンサ一用膜等として使用され る。  This electrolyte membrane or ion exchange membrane is used, for example, for an electrolyte membrane of a solid polymer electrolyte fuel cell, a membrane for a lithium battery, a membrane for salt electrolysis, a membrane for water electrolysis, a membrane for hydrohalogen oxyacid electrolysis, and an oxygen concentrator. Used as membrane, humidity sensor membrane, gas sensor membrane, etc.
以上の通り、 本発明方法によれば、 煩雑な操作を要することなく工業的に有利 な方法により、 目的とする含フッ素フルォロスルホニルエーテルを、 安価に高収 率で製造することができる。  As described above, according to the method of the present invention, the desired fluorinated fluorosulfonyl ether can be produced at low cost and with high yield by an industrially advantageous method without requiring complicated operations.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
以下、 実施例を挙げて本発明を更に詳細に説明する。  Hereinafter, the present invention will be described in more detail with reference to Examples.
実施例 1  Example 1
スルフィン化工程  Sulfination process
5 0 m 1のガラスフラスコに、 水 8ml とァセトニトリル 10ml を投入し、 さら に、 Na 2 S 204を 2. lgと NaHC03を 2. 0g仕込んだ。 To 5 0 m 1 glass flask, water 8ml and Asetonitoriru 10ml were charged, in addition, a 2. lg and NaHCO 3 and Na 2 S 2 0 4 2. charged 0 g.
そこに滴下口一卜で CF2=CFOCF2CF2Iを 1. 34g滴下し、 反応温度 20 で炭酸ガス の発泡がなくなるまで反応させた。 反応終了後、 減圧下に溶媒を留去し、 メタノ ール 10mlを加えて不溶物をろ過して除去した後、濾液を乾固乾燥して固体を l . Og 回収した。 この固体は IR、 NMR測定結果より CF2=CFOCF2CF2S02Naであることが確 認できた。 収率は NMR測定より、 86. 2%であった。 Then, 1.34 g of CF 2 = CFOCF 2 CF 2 I was added dropwise at a dropping port, and the reaction was carried out at a reaction temperature of 20 until carbon dioxide gas generation was stopped. After completion of the reaction, the solvent was distilled off under reduced pressure, 10 ml of methanol was added, and insolubles were removed by filtration. The filtrate was dried and dried to collect l.Og. The solid IR, that by NMR measurement results is CF 2 = CFOCF 2 CF 2 S0 2 Na was confirmed. The yield was 86.2% from NMR measurement.
スルフィン化反応による生成物（CF2=CFOCF2CF2S02Na) の分析結果を以下に 示す。 Product by sulfination reaction analysis of the (CF 2 = CFOCF 2 CF2S0 2 Na) are shown below.
19F NMR (282.4 MHz, D20, CFC13) 6 -83.34 (m， 2F) , -112.36 (dd, J = 86.13, JP03/06440 19 F NMR (282.4 MHz, D 2 0, CFC1 3) 6 -83.34 (m, 2F), -112.36 (dd, J = 86.13, JP03 / 06440
9 9
63.76 Hz, IF) , -120.57 (ddt, J = 111.17, 86.13, 5.45 Hz, IF) , -133.24 (s, 2F) , -134.22 (ddt, J = 111.17， 63.76, 6.54 Hz, IF)  63.76 Hz, IF), -120.57 (ddt, J = 111.17, 86.13, 5.45 Hz, IF), -133.24 (s, 2F), -134.22 (ddt, J = 111.17, 63.76, 6.54 Hz, IF)
塩素化工程  Chlorination process
50mlフラスコに、 上記工程で得られた CF2=CFOCF2CF2S02Naを l.Ogと水を 30ml仕込んだ。 フラスコを氷浴につけ、 Cl2ガスを 10ml/分で 8分間流した。 反応 終了後、 水層と有機層に分液した。 窒素ブローして残留する C 1 2をブローした 後、下層を回収し、 さらに水層を塩化メチレンで抽出した。両者をあわせて G.C.、 GC/MS、 NMR分析を行なったところ CF2=CF0CF2CF2S02C1であることがわかつ た。 収率は NMR測定より 89.4%であった。 In 50ml flask was charged 30ml of l.Og and water and the resulting CF 2 = CFOCF 2 CF 2 S0 2 Na in the above Step. The flask was placed in an ice bath and Cl 2 gas was flowed at 10 ml / min for 8 minutes. After completion of the reaction, the mixture was separated into an aqueous layer and an organic layer. After the C 1 2 remaining nitrogen blown by blow, the lower layer was collected and then the aqueous layer was extracted with methylene chloride. GC together both, GC / MS, to be CF 2 = CF0CF 2 CF 2 S0 2 C1 was subjected to NMR analysis divide. The yield was 89.4% from NMR measurement.
フッ素化工程  Fluorination process
撹拌機と 5段精留塔を備えた 50m l のガラスフラスコ中に、上記工程で 得られた CF2 = CF0CF2CF2S02C 1 を 33g と、 NaF ( 1 3. Og) 及びスルホラン ( 1 9. Og) を仕込んだ後、 加熱し約 75 °Cの留分を抜き出した。 その結果、 2 8 . O gの液体が得られた。 この液体について、 G. 、 GC/MS、 匪 R分 析を行なった結果、 CF2 = CFOCF2CF2S02Fであることがわかった。 収率は、 NMR測定より 90. 9%であった。 In a 50 ml glass flask equipped with a stirrer and a 5-stage rectification column, 33 g of CF 2 = CF0CF 2 CF 2 S0 2 C 1 obtained in the above step, NaF (1 3.Og) and sulfolane ( After charging 1 9. Og), it was heated and a distillate of about 75 ° C was extracted. As a result, a liquid of 28. O g was obtained. The liquid was analyzed by G., GC / MS, and R-band analysis, and it was found that CF 2 = CFOCF 2 CF 2 S0 2 F. The yield was 90.9% based on NMR measurement.

Claims

請 求 の 範 囲 The scope of the claims
1. 下記 （ i ) 及び （ii) の工程を含むことを特徴とする一般式 （1)  1. General formula (1) characterized by including the following steps (i) and (ii):
CF2=CFO (CF2CF (CF3) θ) nCF2(CF2CF2)mCF2S02F ( 1 ) (式中、 mは 0〜5の整数、 nは 0〜10の整数である。 ） で表される含フッ素 フルォロスルホニルアルキルビニルエーテルの製造方法： CF 2 = CFO (CF 2 CF (CF 3) θ) n CF 2 (CF 2 CF2) mCF2S0 2 F (1) ( wherein, m is an integer of 0 to 5, n represents an integer of 0. A method for producing a fluorine-containing fluorosulfonylalkyl vinyl ether represented by the following formula:
( i ) 下記一般式 （ 2 ) ：  (i) The following general formula (2):
CF2=CFO (CF2CF (CF3) θ) nCF2(CF2CF2)mCF2X (2) CF 2 = CFO (CF 2 CF (CF 3 ) θ) n CF 2 (CF 2 CF2) m CF 2 X (2)
(式中、 Xは Iまたは Brであり、 m及び nは上記に同じ。 ）で表される ω-ハロゲ ン化ビニルエーテルを、 アルカリ金属の亜ジチオン酸塩及び中和剤と反応させて 下記一般式 （3) ： (Wherein X is I or Br, and m and n are the same as above), and reacted with an alkali metal dithionite and a neutralizing agent to obtain Equation (3):
CF2=CFO (CF2CF (CF3) θ) nCF2(CF2CF2)mCF2S02M (3) CF 2 = CFO (CF 2 CF (CF 3 ) θ) n CF 2 (CF2CF 2 ) mCF2S0 2 M (3)
(式中、 Mは、 M a又は Mb 1 / 2であり、 Maはアルカリ金属、 Mbはアル力 リ土類金属である。 m及び nは上記に同じ。 ） で表されるビニルエーテルスルフ ィン酸塩を製造する工程、 (In the formula, M is Ma or Mb 1/2 , Ma is an alkali metal, Mb is an alkaline earth metal, and m and n are the same as described above.) A process for producing phosphate
(ii) 工程 （ i ) で得られたビニルエーテルスルフィン酸塩を塩素化した後、 フッ素化して、 上記一般式 （1) で表される含フッ素フルォロスルホニルアルキ ルビニルエーテルを製造する工程。  (ii) a step of chlorinating and fluorinating the vinyl ether sulfinate obtained in the step (i) to produce a fluorinated fluorosulfonylalkyl vinyl ether represented by the general formula (1).
2. 一般式： 2. General formula:
CF2=CFO (CF2CF (CF3) θ) nCF2(CF2CF2)mCF2X CF 2 = CFO (CF 2 CF (CF 3 ) θ) n CF2 (CF 2 CF2) m CF 2 X
(式中、 Xは Iまたは Brであり、 mは 0~ 5の整数、 nは 0〜10の整数である。） で表される ω-ハロゲン化ビニルエーテルを、アル力リ金属の亜ジチオン酸塩及び 中和剤と反応させることを特徴とする、 一般式 (Wherein X is I or Br, m is an integer of 0 to 5, and n is an integer of 0 to 10). The ω-halogenated vinyl ether represented by the following formula: A general formula characterized by reacting with a salt and a neutralizing agent
CF2=CFO (CF2CF (CF3) θ) nCF2(CF2CF2)mCF2S02M CF 2 = CFO (CF 2 CF (CF 3 ) θ) n CF 2 (CF 2 CF2) m CF 2 S0 2 M
(式中、 Mは、 M a又は Mb 1 / 2であり、 Maはアルカリ金属、 Mbはアル力 リ土類金属である。 m及び nは上記に同じ。 ） で表されるビニルエーテルスルフ ィン酸塩の製造方法。 (In the formula, M is Ma or Mb 1/2 , Ma is an alkali metal, Mb is an alkaline earth metal, and m and n are the same as described above.) Production method of phosphate.
3. 一般式：  3. General formula:
CF2=CFO (CF2CF(CF3) θ) n CF2(CF2CF2)mCF2S02M CF 2 = CFO (CF 2 CF (CF 3 ) θ) n CF2 (CF 2 CF 2 ) m CF 2 S0 2 M
(式中、 Mは、 Ma又は Mb 1 /2であり、 Maはアルカリ金属、 Mbはアル カリ土類金属である。 mは 0 ~ 5の整数、 nは 0〜 1 0の整数である。 ） で表さ れるビニルエーテルスルフィン酸塩を塩素化した後、 フッ素化することを特徴と する、 一般式： (Wherein, M is Ma or Mb 1/2 , Ma is an alkali metal, and Mb is Potassium earth metal. m is an integer of 0 to 5, and n is an integer of 0 to 10. Chlorinating and then fluorinating the vinyl ether sulfinate represented by the general formula:
CF2=CFO (CF2CF (CF3) θ) nCF2(CF2CF2)mCF2S02F CF 2 = CFO (CF 2 CF (CF 3 ) θ) n CF2 (CF 2 CF2) m CF2S0 2 F
(式中、 m及び nは前記に同じ。 ）で表される含フッ素フルォロスルホニルアルキ ルビニルエーテルの製造方法。  (Wherein m and n are the same as described above.) A method for producing a fluorinated fluorosulfonylalkyl vinyl ether represented by the formula:
PCT/JP2003/006440 2002-06-14 2003-05-23 Process for production of fluorine-containing fluoro- sulfonylalkyl vinyl ethers WO2003106407A1 (en)

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JP4379623B2 (en) * 2004-02-02 2009-12-09 ダイキン工業株式会社 Method for producing fluorine-containing unsaturated sulfonyl fluoride
US8946465B2 (en) * 2010-12-17 2015-02-03 3M Innovative Properties Company Preparation of oligomers and co-oligomers of highly fluorinated sulfinic acids and salts thereof
CN110759805B (en) * 2018-07-26 2021-12-14 中国科学院上海有机化学研究所 Preparation method of fluoroalkyl iodide

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JPS6130552A (en) * 1984-07-24 1986-02-12 Asahi Glass Co Ltd Preparation of perfluorovinyl ether having functional group
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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