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WO2005073182A1 - Procédé de production de fluorure de sulfonyle insaturé contenant du fluor - Google Patents

Procédé de production de fluorure de sulfonyle insaturé contenant du fluor Download PDF

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Publication number
WO2005073182A1
WO2005073182A1 PCT/JP2005/001005 JP2005001005W WO2005073182A1 WO 2005073182 A1 WO2005073182 A1 WO 2005073182A1 JP 2005001005 W JP2005001005 W JP 2005001005W WO 2005073182 A1 WO2005073182 A1 WO 2005073182A1
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WO
WIPO (PCT)
Prior art keywords
formula
fluorine
chemical formula
sulfonyl fluoride
fluorinating agent
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2005/001005
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English (en)
Japanese (ja)
Inventor
Akinari Sugiyama
Kazuyoshi Ichihara
Noriyuki Shinoki
Toshiya Mantani
Masahiro Kondou
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Daikin Industries Ltd
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
Priority to JP2005517457A priority Critical patent/JP4379623B2/ja
Publication of WO2005073182A1 publication Critical patent/WO2005073182A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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 unsaturated sulfonyl fluoride.
  • perfluorofluorosulfonylalkyl vinyl ether is a compound useful as an industrial raw material such as an ion exchange membrane material.
  • a method for producing perfluorofluorosulfonylalkylbierether a method of reacting perfluorochlorosulfonylalkylvinylether with an alkali metal fluoride is known.
  • Patent Document 1 A method of using FCFSOF is known.
  • Patent Document 2 In this method, in order to obtain a fluorinated product in high yield, it is necessary to use sulfolane, formamide, or the like as a solvent. Even if it is fluorinated, the yield of CF SO F
  • Patent Document 1 US Patent No. 3,560,568
  • Patent Document 2 UK Patent No. 1,034,197
  • the present invention has been made in view of the above-mentioned state of the art, and the main object of the present invention is to reduce the cost of fluorine-containing sulfonyl fluoride having an unsaturated bond by an industrially advantageous method. Is also to provide a method which can be easily produced with high selectivity and high yield.
  • the present inventor has found that when a fluorine-containing sulfonyl chloride having at least one unsaturated bond is used as a raw material, hydrofluoric acid of a specific amine or pyridine compound is used. It has been found that the use of a salt as a fluorinating agent makes it possible to produce a fluorinated sulfonyl fluoride with a high selectivity and a high yield by a simple method. Reached.
  • the present invention provides the following method for producing a fluorinated sulfonyl fluoride.
  • R SO C1 (where R is a fluorine-containing f 2 f having at least one unsaturated bond)
  • R, R and R are the same or different and each represents an alkyl group or a cycloalkyl group
  • n is an integer of 1 to 9
  • R, R and R are the same or different and are a hydrogen atom or an alkyl group, and n is 1
  • R and R are the same or different and are each a hydrogen atom or an alkyl group, and n is 1
  • d e is an integer of 9 and m is an integer of 2 or more).
  • X is 0, S or NH
  • R is a group which may have a fluorine atom as a substituent.
  • the fluorinating agent has the chemical formula: [0015] [Formula 4]
  • R, R and R are the same or different and are a lower alkyl group, and n is 3)
  • a fluorine-containing unsaturated sulfonyl chloride represented by a chemical formula: RSOC1 is used as a raw material.
  • R is a fluorinated hydrocarbon having at least one unsaturated bond f
  • the fluorine-containing hydrocarbon group may contain at least one element selected from oxygen, nitrogen and zeolite.
  • the unsaturated bond may be a double bond or a triple bond, and both may be contained simultaneously.
  • the position of the unsaturated bond is not limited. Further, in the fluorinated hydrocarbon group, all hydrogen atoms may be substituted by fluorine atoms, or only some hydrogen atoms may be substituted.
  • the fluorine-containing hydrocarbon group represented by R includes the following formula:
  • X is ⁇ , S or NH
  • R is a divalent hydrocarbon group which may have a fluorine atom as a substituent
  • p is an integer of 0-4.
  • R include a linear or branched alkylene group, an arylene group, and g
  • Examples thereof include a divalent hydrocarbon group such as a group to which these are bonded.
  • the hydrocarbon group may further contain at least one element selected from oxygen, zeolite and nitrogen.
  • Examples of the alkylene group include groups having about 118 carbon atoms.
  • Examples of the arylene group include a phenylene group. These divalent hydrocarbon groups are In addition, some or all of the hydrogen atoms may be substituted or unsubstituted.
  • fluorine-containing hydrocarbon group represented by R include the following formula:
  • q is an integer of 0-3.
  • the fluorine-containing unsaturated sulfo-urquose is reacted with at least one kind of fluorinating agent selected from the compounds described in the following (i)-(iii) to obtain a fluorine-containing unsaturated sulfo-yoke.
  • a saturated sulfonyl fluoride can be obtained.
  • R, R and R are the same or different and each represents an alkyl group or a cycloalkyl group
  • n is an integer of 1 to 9
  • R, R and R are the same or different and are a hydrogen atom or an alkyl group, and n is 1
  • R and R are the same or different and are each a hydrogen atom or an alkyl group, and n is
  • n is an integer of 2 or more).
  • R is the same or different.
  • the alkyl group include straight-chain or branched-chain alkyl groups having about 119 carbon atoms, such as methyl, ethyl, isopropyl, n-propyl, n-butyl, t-butyl, sec-butyl and the like.
  • a lower alkyl group having about 114 carbon atoms is preferable.
  • Examples of the cycloalkyl group include groups having about 5 to 8 carbon atoms, such as cyclopentyl, cyclohexyl, and cyclooctyl.
  • n is an integer from 1 to 9, preferably an integer from 2 to 9.
  • a and R are the same or different b c
  • a hydrogen atom or an alkyl group examples include the same groups as the alkyl groups of the alkylamine hydrofluoride described in (i) above.
  • n is an integer of 1 to 9, preferably an integer of 2 to 9.
  • n is an integer of 1 to 9, preferably an integer of 2 to 9.
  • m is an integer of 2 or more, and the weight average molecular weight is in the range of about 4 000 to 160,000.
  • the fluorinating agent comprising the compound described in the above (i) item (iii) can be used alone or in combination of two or more. By using these fluorinating agents, the desired fluorinated unsaturated sulfonyl fluoride can be obtained with high selectivity and high yield.
  • the fluorinated salt is used as the fluorinating agent
  • the desired fluorine-containing unsaturated sulfonyl fluoride can be obtained with a high conversion and a high selectivity, and the handling can be easily performed.
  • the method of reacting the fluorinated unsaturated sulfourukulide used as a raw material with a fluorinating agent is not particularly limited, and both may be charged at the same time and reacted, or either one of the raw material and the fluorinating agent The other may be dropped.
  • a method of dropping one of the raw material and the fluorinating agent with the other is advantageous in that the accumulation of reaction heat can be prevented.
  • the amount of the fluorinating agent to be used is preferably about 0.1 to 10 mol, and more preferably about 115 mol, per mol of the fluorinated unsaturated sulfo-uricide used as a raw material. .
  • the fluorinating agent is used in an amount of about 2 to 3 moles per mole of the fluorinated unsaturated sulfo-mouth compound, the desired product can be obtained at a high conversion rate.
  • the number of moles of the polyvinylpyridine hydrofluoride described in the above (m) is a structural unit represented by the following formula.
  • the reaction can be carried out without a solvent or in a solvent, but is preferably carried out without a solvent in terms of cost.
  • a solvent a polar solvent or a non-polar solvent that does not participate in the reaction can be used. Specific examples include CH CI, CHC1, CH CN, N, N-dimethylformamide (DMF)
  • the amount may be, for example, about 115 parts by weight with respect to 100 parts by weight of the fluorine-containing unsaturated sulfo-mouth compound.
  • the reaction temperature is preferably about -20 ° C to about 100 ° C, and more preferably about 10 ° C to about 40 ° C.
  • the reaction time is generally about 0.01 hour to 48 hours, preferably about 0.5 to 24 hours.
  • the reaction pressure may be any of reduced pressure, atmospheric pressure, and increased pressure, but it is preferable to carry out the reaction under atmospheric pressure.
  • the obtained crude product is usually separated into three phases.
  • the upper phase is the fluorinating agent
  • the lower phase is the desired fluorinated unsaturated sulfonyl fluoride phase
  • the middle phase is the hydrofluoric acid salt of the fluorinating agent, for example, when alkylamine hydrofluoride is used as the fluorinating agent.
  • alkylamine hydrochloride or pyridin hydrofluoride is used as a fluorinating agent
  • pyridine hydrochloride is used
  • polybutylpyridine hydrofluoride is used as a fluorinating agent
  • polybutylpyridine hydrochloride polybutylpyridine hydrochloride is used.
  • the desired fluorinated unsaturated sulfonyl fluoride can be purified by a known method such as filtration, distillation, column chromatography and the like.
  • a known method such as filtration, distillation, column chromatography and the like.
  • perfluoroalkylvinylsulfonyl fluoride is a substance useful as a monomer component for an electrolyte polymer.
  • anhydrous HF is added to the remaining two-phase mixture of the fluorinating agent and the hydrochloride of the fluorinating agent.
  • the hydrochloride of the fluorinating agent can be converted to hydrofluoric acid and regenerated as the fluorinating agent.
  • the amount of anhydrous HF used may be about 0.1 to 100 moles per mol of the hydrochloride of the fluorinating agent. It is preferred to use a molar excess of anhydrous HF.
  • the reaction temperature is preferably in the range of about -20 ° C to about 100 ° C, and is preferably in the range of about 0 ° C to about 40 ° C.
  • the reaction time is preferably about 0.01 to 48 hours, and preferably about 0.5 to 24 hours.
  • the reaction pressure may be any of reduced pressure, atmospheric pressure, and pressurized pressure, but it is preferable to carry out the reaction under atmospheric pressure or pressurized pressure up to about 5.0 MPa (gauge pressure).
  • the hydrochloride of the fluorinating agent can be converted to hydrofluoric acid and regenerated as the fluorinating agent.
  • the fluorinating agent used in the present invention can be regenerated and recycled by a simple method. Therefore, the method of the present invention can be said to be a production method with a low environmental load capable of reducing industrial waste.

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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

Un procédé de production d’un fluorure de sulfonyle insaturé contenant du fluor représenté par la formule chimique : RfSO2F (dans laquelle Rf est tel que défini ci-après) est caractérisé en ce qu’un chlorure de sulfonyle insaturé contenant du fluor représenté par la formule chimique : RfSO2Cl (dans laquelle Rf est un groupe hydrocarboné contenant du fluor ayant au moins une liaison insaturée et peut contenir au moins un élément choisi parmi l’oxygène, l’azote et le soufre) est mis à réagir avec au moins un agent fluorant choisi parmi l’hydrofluorure d’alkylamine, l’hydrofluorure de pyridine et l’hydrofluorure de polyvinylpyridine. Par ce procédé, un fluorure de sulfonyle contenant du fluor ayant une liaison insaturée peut être avantageusement produit au niveau commercial à bas prix. Par ailleurs, ce procédé permet de produire simplement le fluorure de sulfonyle contenant du fluor avec une haute sélectivité et un haut rendement.
PCT/JP2005/001005 2004-02-02 2005-01-26 Procédé de production de fluorure de sulfonyle insaturé contenant du fluor Ceased WO2005073182A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2005517457A JP4379623B2 (ja) 2004-02-02 2005-01-26 含フッ素不飽和スルホニルフロライドの製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2004025768 2004-02-02
JP2004-025768 2004-02-02

Publications (1)

Publication Number Publication Date
WO2005073182A1 true WO2005073182A1 (fr) 2005-08-11

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JP (1) JP4379623B2 (fr)
WO (1) WO2005073182A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1149742A (ja) * 1997-08-01 1999-02-23 Daikin Ind Ltd ２−（トリフルオロメチルチオ）ビフェニルの製造方法、及びその合成中間体とその製造方法
JP2002531426A (ja) * 1998-11-30 2002-09-24 ゾルファイ フルーオル ウント デリヴァーテ ゲゼルシャフト ミット ベシュレンクテル ハフツング 酸塩化物から酸弗化物を製造するための方法
JP2003525286A (ja) * 2000-03-03 2003-08-26 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフトング Ｃｆ２ｏ結合を有する液晶の製造
JP2004018454A (ja) * 2002-06-14 2004-01-22 Daikin Ind Ltd 含フッ素フルオロスルフォニルアルキルビニルエーテル製造方法
JP2004018427A (ja) * 2002-06-14 2004-01-22 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
JP2004026728A (ja) * 2002-06-26 2004-01-29 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

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1149742A (ja) * 1997-08-01 1999-02-23 Daikin Ind Ltd ２−（トリフルオロメチルチオ）ビフェニルの製造方法、及びその合成中間体とその製造方法
JP2002531426A (ja) * 1998-11-30 2002-09-24 ゾルファイ フルーオル ウント デリヴァーテ ゲゼルシャフト ミット ベシュレンクテル ハフツング 酸塩化物から酸弗化物を製造するための方法
JP2003525286A (ja) * 2000-03-03 2003-08-26 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフトング Ｃｆ２ｏ結合を有する液晶の製造
JP2004018454A (ja) * 2002-06-14 2004-01-22 Daikin Ind Ltd 含フッ素フルオロスルフォニルアルキルビニルエーテル製造方法
JP2004018427A (ja) * 2002-06-14 2004-01-22 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
JP2004026728A (ja) * 2002-06-26 2004-01-29 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

Also Published As

Publication number Publication date
JP4379623B2 (ja) 2009-12-09
JPWO2005073182A1 (ja) 2007-09-06

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