WO2005085187A1 - Procede pour la production de compose de flurorure - Google Patents

Procede pour la production de compose de flurorure Download PDF

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WO2005085187A1
WO2005085187A1 PCT/JP2005/003888 JP2005003888W WO2005085187A1 WO 2005085187 A1 WO2005085187 A1 WO 2005085187A1 JP 2005003888 W JP2005003888 W JP 2005003888W WO 2005085187 A1 WO2005085187 A1 WO 2005085187A1
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general formula
represented
above general
fluoride
reaction
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PCT/JP2005/003888
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Japanese (ja)
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Hideo Saito
Nobuyuki Uematsu
Masanori Ikeda
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Asahi Kasei Kabushiki Kaisha
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Priority to JP2006510769A priority Critical patent/JP4993462B2/ja
Publication of WO2005085187A1 publication Critical patent/WO2005085187A1/fr

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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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/78—Halides of sulfonic acids
    • C07C309/79—Halides of sulfonic acids having halosulfonyl groups bound to acyclic carbon atoms
    • C07C309/80—Halides of sulfonic acids having halosulfonyl groups bound to acyclic carbon atoms of a saturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/78—Halides of sulfonic acids
    • C07C309/79—Halides of sulfonic acids having halosulfonyl groups bound to acyclic carbon atoms
    • C07C309/82—Halides of sulfonic acids having halosulfonyl groups bound to acyclic carbon atoms of a carbon skeleton substituted by singly-bound oxygen atoms

Definitions

  • the present invention relates to a method for producing ⁇ -fluorosulfol perfluoroalkyl alkyl ether, which is a raw material of a fluorine-based solid electrolyte polymer useful for a fuel cell and a salt electrolysis process, and a synthetic intermediate thereof.
  • Patent Document 1 JP-A-56-90054
  • Patent Document 2 US Pat. No. 6,624,328
  • Patent Document 3 WO2004Z60849
  • Non-Patent Document 1 Weiming Qiu and Donald J. Burton, Journal of Fluorine
  • the present invention relates to a novel ⁇ -fluorosulfol-perperfluoroalkylbutyl ether represented by the general formula (2) or (2 ′) and a synthetic intermediate thereof. It is an object of the present invention to provide a method for producing the compound in a high yield.
  • the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, the general formula (1) or Starting from the ⁇ -no, perfluoroalkylsulfur fluoride represented by the general formula (1,) as a raw material, the ⁇ -fluorosulfol-fluorofluoride represented by the general formula (2) or (2 ′) is used as a raw material.
  • Method for efficiently producing alkyl vinyl ether, and method for efficiently producing ⁇ -haloperfluoroalkylsulfur fluoride represented by the general formula (1) or (1 ′) or a synthetic intermediate thereof And completed the present invention.
  • the present invention is as follows.
  • R is a divalent perfluorocarbon group having 1 to 9 carbon atoms
  • X is selected from I or Br.
  • a halogen atom, Y is a fluorine atom, a perfluoroalkyl group having 1 to 3 carbon atoms, or
  • —CFY— R— is a divalent perfluorocarbon group having 3 to 10 carbon atoms.
  • Step (b ′) obtained by the above general formula (4 ′) Fluoride-sulfide compound represented by the above general formula (2) is converted to an ⁇ -fluorosulfol-perfluoroalkylbutyl ether represented by the general formula (2). Converting to.
  • R 1 is an alkyl group having 115 carbon atoms
  • R 2 is CH or CH.
  • P is 0-10
  • the mass ratio of the carboxylic acid di-tolyl solvent in the mixed solvent of the ether solvent represented by the general formula (6) and the carboxylic acid di-tolyl solvent is 30% by mass or more and 99% by mass.
  • This is a method for producing ⁇ -fluorosulfol-perfluoroalkyl ether represented by the following general formula (2 "), wherein ⁇ is a target product represented by the following general formula (2") —R is the number of moles of fluorosulfol-perfluoroalkylbutyl ether formed, and s is the number of moles of the acid fluoride conjugate represented by the above general formula (4 ′′) regenerated as a by-product.
  • the method is characterized in that the reaction is carried out at a production ratio of a by-product represented by [s] Z [r + s] of 0.1 or less.
  • Acid fluoride compound represented by the above general formula (4 ) The derived carboxylate is a potassium salt represented by the following general formula (7), and the carboxylate does not undergo thermal decomposition. 12. The method according to 11 above, which is performed in a solvent.
  • alkali metal salt type alkaline earth metal salt type, quaternary ammonium salt type, or quaternary phospho-dimethyl salt type
  • quaternary ammonium salt type quaternary phospho-dimethyl salt type
  • M is Ma, Mb, a quaternary ammo-radical or a quaternary phospho-dimethyl
  • Ma is an alkali metal and Mb is an alkaline earth metal.
  • X and m are the same as those in the general formula (1 ′).
  • step (ii) is at least the ⁇ - haloperfluoroalkylsulfinic acid salt represented by the general formula (9) obtained by the reaction of the step (i) and a by-product (1
  • step (ii) includes the following steps (ii 1) and (ii 2).
  • ⁇ -haloperfluoroalkylsulfinate represented by the general formula (9) is separated and removed, and then the reaction residue is treated with a chlorinating agent to represent the general formula (8).
  • a, ⁇ Dihaloperfluoroalkane and Z or ⁇ -C-perfluoroalkylsulfoylc chloride represented by the above general formula (10) are produced, and these are subjected to step (i) and Z or 14.
  • reaction mixture represented by the general formula (8) ⁇ Dihaloperfluoroalkane and Z or ⁇ -haloperfluoroalkylsulfol-chloride represented by the above general formula (10) are produced, separated and subjected to step (i) and step (iv). ).
  • Oc ⁇ dihalo perflur represented by the above general formula (8), which comprises reacting perfluoroalkyl a, ⁇ bissulfol chloride represented by the above general formula (12) with iodine or bromine.
  • n or n is SO. 21. — Method described in item 1 of 22.
  • the ⁇ -fluorosulfol-leperfluoroalkylbutyl ether represented by the general formula (2) or (2 ′) and a synthetic intermediate thereof are produced in high yield.
  • a method is provided.
  • Steps (a)-(c) From the above, ⁇ -fluoroperfluoroalkylsulfur fluoride represented by the above general formula (1) is used as a raw material to obtain ⁇ -fluorosulfur-fluoride represented by the above general formula (2). According to the method for producing perfluoroalkylbutyl ether and the steps (a), (c), the ⁇ -noperoperfluoroalkylsulfurfluoride represented by the general formula (1) is used as a raw material. A method for producing ⁇ -fluorosulfol-perfluoroalkyl vinyl ether represented by the general formula (2) will be described.
  • step (a) and the step (a ') will be described.
  • R is a divalent perfluorocarbon group having 19 carbon atoms
  • X is a halogen atom selected from I or Br
  • Y represents a fluorine atom, a perfluoroalkyl group having 13 to 13 carbon atoms, or an f group linked to R (1 to 13 carbon atoms).
  • CF— is sometimes referred to as CFY—.
  • CFY— R— is a divalent perfluoro with 3-10 carbon atoms f
  • X is preferably I or Br, but I is more preferred in terms of reactivity! /.
  • CFY—R— is a divalent perfluorocarbon group having 3 to 10 carbon atoms.
  • It may have a structure, a branched structure, or a cyclic structure.
  • Synthesis and easiness of purification and represented by the above general formula (2) or general formula (2 ") derived from ⁇ -haloperfluoroalkylsulfur fluoride represented by the above general formula (1 ') M is more preferably 418, further preferably 416, and particularly preferably 4, from the viewpoint of the operability and functionality of the ⁇ -fluorosulfol-perfluoroalkyl vinyl ether to be obtained.
  • the ⁇ -fluorosulholi-rui dyad product represented by the following formula can be obtained.
  • R and ⁇ can be variously combined. Yes, for example
  • the ⁇ -fluorosulfonylui conjugate represented by the above general formula (3 ') is particularly preferable because of its high practicality.
  • m is more preferably 418, more preferably 416, for the same reason as in the above general formula (1 ′). And particularly preferably 4.
  • SO fuming sulfuric acid
  • C1SOH C1SOH
  • FSOH NO , O
  • catalysts and additives may be added to promote the reaction.
  • catalysts such as HgO and PO
  • chlorides such as pentaoxide, PC1, and SbCl may be used.
  • reaction temperature should be between 20 ° C and 150 ° C.
  • the concentration of SO in fuming sulfuric acid may vary.
  • the amount of fuming sulfuric acid is 0.1 mol based on the effective SO amount of fuming sulfuric acid per 1 mol of ⁇ - haloperfluoroalkylsulfur fluoride represented by the above general formula (1) or (1 ′). Preferred to use in the range from 1 to 100 moles 1 mole force 20
  • the reaction time is not particularly limited, and may be, for example, about 0.1 to 100 hours as long as the reaction proceeds to some extent.
  • the reaction method is not particularly limited.
  • the mixture of ⁇ -haloperfluoroalkylsulfur fluoride represented by the general formula (1) or (1 ′) and SO or fuming sulfuric acid may be heated to reflux,
  • a sulfol fluoride conjugate represented by the formula is contained in the reaction mixture.
  • the sulfonyl fluoride compound represented by the general formula (5) or (5 ′) is a target compound when brought into contact with an alkali metal salt, an alkaline earth metal salt, or a Lewis base. It can be converted to an ⁇ -fluorosulfonyl compound represented by (3) or the general formula (3 ′). Therefore, the SO dissolved in the reaction mixture is washed and removed with concentrated sulfuric acid.
  • the mixture After removal, the mixture is directly brought into contact with an alkali metal salt, an alkaline earth metal salt, or a Lewis base, and subjected to a distillation operation to obtain a target compound represented by the above general formula (3) or (3 ′) represented by the general formula (3 ′).
  • -Fluorosulfonyl ligated products can be obtained.
  • the target compound After washing and removing the SO dissolved in the reaction mixture with concentrated sulfuric acid, the target compound,
  • the sulfonylfluoride represented by the above general formula (5) or (5 ′) is separated.
  • the distillation residue containing the Doi-Dai-Gai product is brought into contact with an alkali metal salt, an alkaline earth metal salt, or a Lewis base to perform a distillation operation.
  • the ⁇ -fluorosulfonyl compound represented by the above general formula (3) or (3 ′) which is the target compound, can also be obtained.
  • Triethynoleamine, 1,8-diazabicyclo [5,4,0] indene, 1,5-diazabicyclo [4,3,0] non-5-ene, N, N-diisopropylethyla KF and N, N-diisopropylethylamine are preferable among the powers including min.
  • the amount of the alkali metal salt, alkaline earth metal salt or Lewis base to be used is 0.001 mol based on 1 mol of the sulfol fluoride compound represented by the general formula (5) or (5 ′). It is preferred to use in the range of from 5 to 5 mol! / ,.
  • the reaction time is not particularly limited, and may be, for example, about 0.1 to 100 hours.
  • the reaction temperature is preferably in the range of 10 ° C to 220 ° C, more preferably in the range of 20 ° C to 200 ° C, particularly preferably in the range of 30 ° C to 180 ° C.
  • the reaction method is not particularly limited, the alkali metal salt, alkaline earth metal salt, or Lewis base heated under normal pressure in the absence of a solvent or in the presence of a solvent may be added to the above-mentioned general formula (5) or (5 ′)
  • the reaction product may be distilled off at the same time as the dropwise addition of the sulfolfluoride conjugate represented by the general formula (5), or the sulfolfluoride conjugate represented by the above general formula (5) or (5 ′)
  • a mixture of the above-mentioned alkali metal salt, alkaline earth metal salt or Lewis base may be heated to reflux.
  • a mixture of the sulfonylfluoride conjugate represented by the general formula (5) or (5 ′) and the above alkali metal salt, alkaline earth metal salt, or Lewis base is added to a pressurized container. You can heat it.
  • ether solvents such as diglyme, triglyme and tetraglyme
  • amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone
  • polar solvents such as sulfolane A solvent
  • one kind may be used or a plurality of organic solvents may be combined.
  • m is an integer of 3-10, but more preferably 418 for the same reason as in the general formula (1 '). Yes, more preferably 416, and particularly preferably 4.
  • Patent Document 2 discloses that diglyme is used as a reaction solvent.
  • R 1 is an alkyl group having 115 carbon atoms
  • R 2 is CH or CH.
  • P is 0-10
  • Examples of the ether-based solvent represented by the general formula (6) include diethylene glycol dimethyl enoate, diethylene glycol olenoethyl enoate, diethylene glycol propylene dipropyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyole enoate, Ethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol dimethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, toluene propylene glycol dimethyl ether, tetrapropylene glycol dimethyl ether And the like.
  • Examples of the carboxylic acid di-tolyl-based solvent include saturated aliphatic dicarboxylic acids having 3 to 8 carbon atoms, such as adipo-tolyl.
  • the mass ratio of di-tolyl carboxylate in the mixed solvent of the ether-based solvent and di-tolyl carboxylate is preferably from 30% by mass to 99% by mass, more preferably from 40% by mass to 97% by mass. More preferred 50% by mass or more and 95% by mass or less is particularly preferred.
  • the amount of HFPO used depends on the amount of the ⁇ -fluorosulfol compound From 0.95 monoreca to HFPOi, 2 monoreca S is preferred, and from 0.98 monoreca to 1.8 monoreca is more preferably 1 mol to 1.5 mol.
  • reaction pressure there is no particular restriction on the reaction pressure.
  • the reaction may be performed under normal pressure or under pressure.
  • a pressurized reaction in a pressurized vessel is preferred.
  • the pressure in the pressurized reaction is not limited, but it is preferable to introduce HFPO within a range of 0.1 OlMPa force to 0.1 IMPa gauge pressure.
  • various fluoride ion-containing compounds such as alkali metal fluoride and quaternary ammonium fluoride are used as catalysts, and among them, KF and CsF are more preferable.
  • the amount of the fluorine ion-containing conjugate of the catalyst is not limited, it is usually about 0.001 to 1 mol per 1 mol of the ⁇ -fluorosulfonyl compound!
  • the reaction temperature is preferably in the range of 30 ° C to 50 ° C—more preferably in the range of 20 ° C to 30 ° C.
  • the reaction time is not particularly limited, and depends on the time during which HFPO is consumed, and is, for example, 0.5 hour and 72 hours.
  • the contents are divided into two layers (the upper layer is a mixed solvent of an ether-based solvent and a carboxylic acid dinitrile-based solvent, and the lower layer is a reaction mixture containing the acid fluoride conjugate represented by the above general formula (4 ")).
  • the lower layer portion is taken out, and the acid fluoride conjugate represented by the above general formula (4 ") can be obtained by a distillation operation.
  • ⁇ -fluorosulfol-perfluoroalkyl ethers Can be converted into ⁇ -fluorosulfol-perfluoroalkyl ethers, respectively.
  • the ⁇ -fluorosulfol-perperfluoroalkylbutyl ether represented by the general formula (2 ") has high practicability and is particularly preferable.
  • m is preferably an integer in the range of 3 to 10, but is more preferably 418, and still more preferably 416, from the viewpoint of ease of synthesis and purification and operability. Yes, especially 4
  • An acid fluoride compound represented by the above general formula (4) or the general formula (4 ') or the general formula (4 ") is introduced into silica or alumina or the like supporting an alkali metal or alkaline earth metal fluoride, By contacting, ⁇ -fluorosulfol-perfluorofluoroalkyl ether represented by the general formula (2), (2 ′) or (2 ′′) can be obtained.
  • the acid fluoride compound represented by the general formula (4) or (4 ′) or (4 ′′) is reacted with various basic compounds to form an alkali metal salt of carboxylic acid.
  • the carboxylate After being converted into a salt or an alkaline earth metal salt, the carboxylate is subjected to a heat decarboxylation reaction, whereby ⁇ -fluorosulfo- represented by the above general formula (2) or (2 ′) or (2 ′′) is obtained.
  • the method for obtaining ruperfluoroalkylbutyl ether will be described.
  • Examples of the basic compound used in the conversion reaction from the acid fluoride conjugate represented by the general formula (4) or (4 ′) or (4 ′′) to the carboxylate include: Alkali metal or alkaline earth metal carbonates and hydroxides are preferred, especially carbonates because of their good operability. Examples include lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, rubidium carbonate, calcium carbonate, barium carbonate, etc., and among them, sodium carbonate, potassium carbonate, and the like are preferred, such as sodium carbonate, potassium carbonate, and calcium carbonate. Particularly preferred is potassium carbonate.
  • a solvent When converting the acid fluoride conjugate represented by the general formula (4), (4 ′) or (4 ′′) into an alkali metal salt or an alkaline earth metal salt of the carboxylic acid, a solvent is required.
  • a solvent for example, a solvent such as acetonitrile or propio-tolyl, or a tolyl solvent or an ether such as monoglyme, diglyme, triglyme, or tetraglyme may be used.
  • a system solvent is used, and a reaction temperature in the range of 0 ° C to 80 ° C is particularly preferred!
  • the above-mentioned general formula (2) or general formula (2 ′) or general formula (2 ′′) is obtained by heat decarboxylation reaction.
  • the conversion may be carried out with or without a solvent, but it is better to carry out the conversion without a solvent. Easy to achieve reaction grade! /, So more preferred.
  • Conditions for performing the decarboxylation reaction in the presence of a solvent include, for example, performing the decarboxylation reaction in the range of 80 ° C to 180 ° C using an ethereal solvent such as diglyme, triglyme, or tetraglyme.
  • the ⁇ -fluorosulfol-perperfluoroalkylbutyl ether represented by the general formula (2), (2 ′) or (2 ′′) can be produced.
  • the solvent used in the neutralization reaction is once distilled off by distillation or the like, and then the decarboxylation reaction is performed in the range of 100 ° C to 250 ° C, preferably in the range of 150 ° C to 230 ° C.
  • the ⁇ -fluorosulfol-perfluorofluoroalkyl ether represented by the general formula (2), (2 ′) or (2 ′′) can be obtained.
  • the reaction products It is desirable to carry out the reaction while continuously and quickly distilling the product out of the reaction system. If the reaction product stays in the reactor, by-products are likely to be generated, and the ⁇ full represented by the above-mentioned general formula (2), general formula (2 ′) or general formula (2 ′′), which is the target product, The yield of olosulfonyl perfluoroalkyl butyl ether is reduced.
  • the present inventors have converted the particularly useful ⁇ -fluorosulfol-leperfluoroalkylbutyl ether represented by the above general formula (2 ′′) to the acid fluoridyl ether represented by the above general formula (4 ′′).
  • the acid fluoridyl ether represented by the above general formula (4 ′′).
  • the present inventors have proposed a method for producing an acid fluoridation compound represented by the above general formula (4 ") and a method for producing ⁇ -fluorosulfol perfluoroalkyl alkyl ether represented by the above general formula (2"). , Including the method described in Patent Document 2.
  • the method via sodium salt described in Patent Document 2 is not an industrially advantageous production method due to the generation of many difficult-to-separate by-products. It has been found that high quality products can be produced with high yield by employing the method very efficiently.
  • Patent Document 2 having these problems cannot be said to be an industrially advantageous production method.
  • the present inventors have conducted intensive studies on a reaction method for minimizing the side reaction as described above. As a result, there are salts such as potassium salts which do not melt even during the heating decarboxylation reaction. In the thermal decarboxylation reaction, it was found that the amount of the by-product acid fluoride compound represented by the above general formula (4 ") was extremely reduced, and the target product of high purity was obtained in high yield.
  • the value of [s] Z [r + s] is preferably 0.1 or less, more preferably 0.08 or less, further preferably 0.06 or less, and particularly preferably. 0.04 or less.
  • the lower limit of [s] Z [r + s] is not particularly limited, but may be 0.001 or 0.0001, or may be lower than the detection limit of the measuring instrument.
  • the carboxylate derived from the acid fluoride compound represented by ") is represented by the following general formula (7)
  • thermal decomposition of the carboxylate is carried out without a solvent.
  • the thermal decomposition of the carboxylate is carried out during decarboxylation by heating. This is performed while keeping the carboxylate in a solid phase state.
  • the effect of the potassium salt will be specifically described by comparing the reaction results of the sodium salt and the potassium salt when the carboxylate is thermally decomposed with a medium.
  • the carboxylate is a sodium salt
  • the heating temperature is set to 180 ° C. or higher
  • the sodium salt is in a molten state at the time of thermal decomposition as described above, and is represented by the above general formula (4 ′′) as a by-product.
  • the acid fluoride compound is produced in a large amount, and the desired product, ⁇ -fluorosulfol-perfluoroalkylalkyl ether represented by the above general formula (2 ′′), is obtained in low yield, and the [ s ] Z [r + s] was 0.19.
  • the carboxylate is a potassium salt
  • the potassium salt is in a solid phase upon thermal decomposition, and is an acid fluoride represented by the general formula (4 "), which is a by-product described above.
  • the formation of the compound was slight, and the desired product, ⁇ -fluorosulfol-perperfluoroalkylbutyl ether represented by the above general formula (2 "), was obtained in high yield, and [s] Z [r + s] was 0.01.
  • alkali metal or alkaline earth metal carbonates used include lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, and carbonate. Rubidium, calcium carbonate, barium carbonate and the like can be mentioned. Among them, potassium carbonate, which is more preferably sodium carbonate, potassium carbonate, calcium carbonate and the like, is particularly preferable.
  • a silyl ester of carboxylic acid is produced by reacting the silanol compound with a siloxane compound using the catalyst as a catalyst.
  • siloxane conjugates include, for example, disiloxane conjugates such as hexamethinoresisiloxane, hexethinoresisiloxane, and hexafeninoresisiloxane, and siloxane polymers such as cyclic siloxane compounds and polymethylsiloxane.
  • the silyl ester of the carboxylic acid thus produced is subjected to a desilyl fluoride reaction in a liquid or gaseous phase using an alkali metal fluoride such as KF or NaF as a catalyst to obtain the above general formula (2) or general formula (2 ′)
  • ⁇ -fluorosulfonylperfluoroalkylbutyl ether represented by the general formula (2 ") can be obtained.
  • the temperature at which the desilyl fluoride reaction is performed is, for example, a reaction in a liquid phase. In this case, the reaction temperature is in the range of 25 ° C to 175 ° C, and when the reaction is performed in the gas phase, it is in the range of 140 ° C to 250 ° C.
  • the ⁇ -fluorosulfol-perperfluoroalkylbutyl ether represented by the general formula (2), (2 ′) or (2 ′′) obtained by the above-mentioned various methods is obtained by a method such as distillation. Can be purified.
  • ⁇ -haloperfluoroalkylsulfonylfluoride represented by the above general formula (1) which is a raw material for synthesizing ⁇ -fluorosulfol-perperfluoroalkylbutyl ether represented by the above general formula (2).
  • the metal can be used in the method of the present invention whatever is manufactured by any method.
  • the production method shown in the above scheme 2 has been reported. However, it is not an industrially advantageous production method.
  • highly pure ⁇ -haloperfluoroalkylsulfur fluoride is efficiently produced. It is practically particularly preferable because it can be manufactured.
  • step (i) will be described.
  • M is Ma, Mb, quaternary ammom-radical or quaternary phospho-mradica
  • Ma is an alkali metal and Mb is an alkaline earth metal.
  • X and m are the same as those in the above general formula (1 ′).
  • Alkali metal salt type such as O, KSO, CsSO, alkaline earth metal salt type such as CaSO
  • Quaternary ammonium salt forms such as ((CH) N) SO and ((n-Bu) N) SO, ((CH) P
  • a, ⁇ -dihaloperfluoroalkane represented by the above general formula (8) and an alkali metal salt type, an alkaline earth metal salt type, a quaternary ammonium salt type, or a quaternary ammonium salt type In the reaction of dithionite selected from any of the lower phospho-dum salt forms, in addition to the ⁇ -haloperfluoroalkylsulfinate represented by the general formula (9), by-products
  • the amount of the dithionite used is preferably from 0.1 to 3 equivalents to the a, ⁇ dihaloperfluoroalkane represented by the general formula (8). 0.1 to 2.0 equivalents Is more preferably 0.2 to 1.5 equivalents. At less than 0.1 equivalent, the reaction of the substrate hardly progresses, and at more than 3.0 equivalent, the amount of perfluoroalkyl ⁇ , ⁇ bissulfinate represented by the above general formula (11) increases. This is not preferred.
  • Solvents used in the above reaction include, for example, ketone solvents such as acetone and methyl ethyl ketone, -tolyl solvents such as acetonitrile and propio-tolyl, and linear or cyclic solvents such as tetrahydrofuran, dioxane and diglyme.
  • Ether solvents amide solvents such as ⁇ , ⁇ -dimethylformamide and ⁇ , ⁇ -dimethylacetamide, and various polar solvents such as dimethyl sulfoxide.
  • ketone solvents such as acetone and methyl ethyl ketone
  • -tolyl solvents such as acetonitrile and propio-tolyl
  • acetone and acetonitrile are preferred.
  • These organic solvents are preferably used as a mixed solvent with water, and one kind of organic solvent may be used, or a combination of a plurality of organic solvents may be used.
  • the amount of the organic solvent to be used with respect to water is preferably 0.1 times or more and 100 times or less, more preferably 1 time or more and 50 times or less with respect to the volume of water. It is particularly preferable that the ratio be from 20 to 20 times. If the amount of water used is more than 100 times, the reaction of the substrate hardly proceeds, which is not preferable.
  • the amount of water relative to the substrate is preferably from 0.1 to 200 equivalents, more preferably from 1 to 150 equivalents, particularly preferably from 5 to 100 equivalents, based on the substrate.
  • a neutralizing agent or a buffer may be added.
  • the neutralizing agent include hydrogen carbonate such as lithium hydrogen carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate; carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate; and phosphorus such as sodium hydrogen phosphate and potassium hydrogen phosphate.
  • Hydrogen salts, phosphates such as sodium phosphate and potassium phosphate, and hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and the like can be used. It comes out.
  • Reaction temperatures are preferably in the range of 30 ° C to 90 ° C—more preferably in the range of 10 ° C to 60 ° C.
  • the reaction time is not particularly limited as long as the dithionite is sufficiently consumed depending on the reaction conditions, but practically, the range is about 0.1 to 48 hours. .
  • step (ii) will be described.
  • the target compound represented by the above general formula (9) is obtained by reacting a, ⁇ dihaloperfluoroalkane represented by the above general formula (8) with dithionite.
  • a, ⁇ dihaloperfluoroalkane represented by the above general formula (8) with dithionite.
  • Oroalkyl ⁇ , ⁇ bissulfinates are formed as by-products.
  • an inorganic iodide or an inorganic bromide generated by the reaction also exists in the reaction system.
  • inorganic iodide or inorganic bromide When a suspension in which inorganic iodide or inorganic bromide is precipitated and formed in the reaction system is formed, inorganic iodide or inorganic bromide may be removed by filtration and separation and purification may be performed. .
  • the removal method can be adopted.
  • Specific examples of the removal method include, for example, removal by distillation, extraction and removal with a fluorine atom-containing organic solvent, or ⁇ -haloperfluoroalkylsulfinate represented by the general formula (9) and Examples of the method include removal by phase separation from an aqueous medium containing a perfluoroalkyl ⁇ , ⁇ bissulfinate represented by the general formula (11).
  • the unreacted a, ⁇ dihaloperfluoroalkane represented by the above general formula (8) is reacted with the used organic solvent by distillation or the like from the solution or suspension after the reaction. Can be excluded.
  • a removal method by phase separation for example, after distilling off the organic solvent used by a method such as distillation, water is added to separate into two layers, and a, ⁇ dihalo perfluoro represented by the above general formula (8) is obtained. Since the lower alkane is separated into the lower layer, the lower layer The a, ⁇ dihaloperfluoroalkane represented by the general formula (8) can be obtained.
  • the method of extraction and removal using a fluorine atom-containing organic solvent is as follows.
  • the reaction mixture obtained in step (i) is mixed with a fluorine atom-containing organic solvent such as HFC43-10mee and perfluorohexane, and the above formula (8) is used.
  • a fluorine atom-containing organic solvent such as HFC43-10mee and perfluorohexane
  • an aqueous dispersion in which the ⁇ -haloperfluoroalkylsulfinate represented by the general formula (9) and the perfluoroalkyl ⁇ , ⁇ bissulfinate represented by the general formula (11) are dissolved From the liquid or the solid mixture containing both components, the ⁇ -haloperfluoroalkylsulfinate represented by the above general formula (9) can be extracted.
  • Reaction mixture in which the ⁇ -haloperfluoroalkyl sulfinate represented by the general formula (9) and the perfluoroalkyl a, ⁇ bis sulfinate represented by the general formula (11) are dissolved As a method for extracting the ⁇ -haloperfluoroalkyl sulfinate represented by the above general formula (9), for example, ester solvents such as ethyl acetate, ether solvents such as ethyl ether, etc. And extracting the ⁇ -noperoperfluoroalkylsulfinate represented by the above general formula (9) into the organic layer by adding the poorly water-soluble organic solvent.
  • ester solvents such as ethyl acetate
  • ether solvents such as ethyl ether
  • the perfluoroalkyl ⁇ , ⁇ -bissulfinate represented by the general formula (11) and the inorganic iodide or inorganic bromide such as an inorganic iodide or an inorganic bromide generated in the step (i) are used.
  • the salt is separated on the aqueous layer side.
  • the organic solvent is distilled off to obtain a highly pure compound represented by the above general formula (9).
  • ⁇ -haloperfluoroalkyl sulfinate can be isolated.
  • the organic layer contains almost no perfluoroalkyl a, ⁇ bissulfinate represented by the general formula (11)! /.
  • an ester solvent such as ethyl acetate or an ether solvent such as getyl ether is used.
  • the perfluoroalkyl ⁇ , ⁇ bissulfinate represented by the general formula (11) and inorganic salts such as inorganic iodide or inorganic bromide, which are insoluble in the organic solvent, are removed by filtration. be able to.
  • the organic solvent is distilled off from the filtrate by distillation or the like, a high-purity ⁇ -no, perfluoroalkylsulfinate represented by the above general formula (9) is obtained in a high yield.
  • step (iii) will be described.
  • the ⁇ -haloperfluoroalkylsulfojuruku mouth represented by the formula can be obtained. Specifically, after dissolving or dispersing the ⁇ -haloperfluoroalkylsulfinate represented by the general formula (9) in water, an organic solvent or a mixed solvent thereof, a chlorinating agent is added. With this, a chlorination reaction can be performed.
  • This step can be carried out in various media, but considering the ease and safety of the reaction operation, it is preferable to use water or an aqueous solution containing an acid as the solvent.
  • the chloridizing agent is not particularly limited as long as it can convert —SO M to SO C1.
  • chloridizing agents For example, the ability to use chlorine, sulfuryl chloride or the like as a chlorine-containing agent, particularly preferably chlorine.
  • chlorine sulfuryl chloride or the like
  • the target compound ⁇ -haloperfluoroalkylsulfuric acid mouth lid represented by the above general formula (10)
  • the conditions for 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 the desired chlorinated product is produced.
  • chlorine gas is supplied to an aqueous solution in which the ⁇ -noperoperfluoroalkyl sulfinate of the above general formula (9) is dissolved to perform the chlorination reaction.
  • the reaction temperature is preferably 0-50 ° C, and the amount of chlorine charged is preferably about 115 mol per mol of ⁇ - haloperfluoroalkyl sulfinic acid salt of the above general formula (9).
  • the range of 1.2 to 3 moles is more preferable.
  • the concentration of the ⁇ -noperoperfluoroalkyl sulfinate of the above general formula (9) in the aqueous solution is not particularly limited, but may be usually about 0.5 to 50% by mass.
  • the compound represented by the general formula (1 ′) is obtained.
  • ⁇ -haloperfluoroalkylsulfur fluoride can be obtained.
  • the reaction with the fluoride ion-containing compound can be carried out according to a known method, and in a solvent or without a solvent, the ⁇ -haloperfluoroalkylsulfonyl chloride represented by the above general formula (10) and fluorine ion What is necessary is just to make the contained dangling product react.
  • the solvent is not particularly limited, and various solvents can be used.
  • a polar organic solvent such as acetonitrile, sulfolane, dimethyl sulfoxide, ⁇ , ⁇ -dimethylformamide, water, or a mixed solvent thereof can be used. .
  • the fluorine ion-containing compound used is one that can convert SO C1 to SO F.
  • Any known fluorine ion-containing conjugate can be used without particular limitation.
  • Examples include alkali metal fluorides such as NaF and KF.
  • the reaction temperature may be in the range of 0 to 200 ° C, and the reaction time may be about 0.1 hour, about 48 hours.
  • the amount of the fluoride ion-containing compound to be used is preferably 1 mol or more and 10 mol or less with respect to 1 mol of the ⁇ -halofluoroalkylsulfonyl chloride represented by the above general formula (10). It is more preferably at least 5 mol and at most 5 mol.
  • the concentration of ⁇ -haloperfluoroalkylsulfol chloride represented by the above general formula (10) is not particularly limited, but is usually 10 to 100% by mass.
  • the method for separating the ⁇ -haloperfluoroalkylsulfonyl fluoride represented by the above general formula (1 ′) obtained by the above method may be appropriately changed depending on the solvent used in the reaction.
  • ⁇ -noperoperfluoroalkylsulfonyl fluoride represented by the above general formula (1 ′) can be separated by distillation, and the above general formula can be obtained by removing water depending on the type of solvent.
  • the ⁇ -haloperfluoroalkylsulfur-fluoride represented by the formula (1) can be separated as an organic layer.
  • step (ii 2) the by-product perfluoroalkyl a, ⁇ bissulfinate represented by the above general formula (11), which is separated by the above step (ii 2), is converted into the above general formula (8)
  • a method for producing the ⁇ , ⁇ dihaloperfluoroalkane and ⁇ or the ⁇ -haloperfluoroalkylsulfol-chloride represented by the general formula (10) will be described.
  • the processing solution or purified residue separated in step (ii 2) contains by-products perfluoroalkyl a, ⁇ bissulfinate represented by the general formula (11) and inorganic iodide or Inorganic bromide power Contains at least one selected inorganic salt.
  • the perfluoroalkyl, ⁇ bissulfinate represented by the general formula (11) is represented by the general formula (12)
  • Perfluoroalkyl ⁇ , ⁇ -bissulfol-chloride is formed, while inorganic iodide or inorganic bromide forms iodine or bromine.
  • the reaction of the perfluoroalkyl a, ⁇ bissulfol chloride represented by the above general formula (12) with iodine or bromine causes ⁇ , ⁇ represented by the above general formula (8).
  • Dihaloperfluoroalkanes and ⁇ -haloperfluoroalkyl sulfides represented by the general formula (10) can be obtained.
  • the formation ratio of the ⁇ , ⁇ dihalo perfluoroalkane represented by the general formula (8) and the ⁇ -haloperfluoroalkyl sulfonyl chloride represented by the general formula (10) is determined by the above-mentioned general formula It is determined by the ratio of perfluoroalkylalkyl ⁇ , ⁇ -bissulfoyl chloride represented by (12) and coexisting iodine or bromine.
  • a solvent capable of simultaneously dissolving iodine or bromine and both the perfluoroalkyl ⁇ , ⁇ bissulfoulyl chloride compound represented by the general formula (12) is added, whereby the compound represented by the general formula (8) is added.
  • Examples of the solvent for simultaneously dissolving iodine or bromine and both the perfluoroalkyl ⁇ , ⁇ -bissulfoyl chloride compound represented by the above general formula (12) include, for example, ethyl acetate, butyl acetate and the like.
  • Examples include polar solvents such as ester solvents, ether solvents such as monoglyme and diglyme, -tolyl solvents such as acetonitrile and propio-tolyl, and ketone solvents such as acetone and methyl ethyl ketone. It is more preferable to use a poorly water-soluble organic solvent such as ethyl acetate or butyl acetate as the solvent, because the product can be extracted simultaneously with the reaction.
  • polar solvents such as ester solvents, ether solvents such as monoglyme and diglyme, -tolyl solvents such as acetonitrile and propio-tolyl, and ketone solvents such as acetone and methyl ethyl ketone.
  • polar solvents such as ester solvents, ether solvents such as monoglyme and diglyme, -tolyl solvents such as acetonitrile and propio-tolyl, and ketone solvent
  • the treatment solution or the purified residue is reacted with a chlorinating agent to form a perfluoroalkyl a, ⁇ bissulfol chloride represented by the general formula (12), and the acid chloride is converted to Isolation by filtration, solvent extraction, or the like, followed by reaction with iodine or bromine in a solvent, gives ⁇ , ⁇ dihaloperfluoroalkane represented by the above general formula (8) and Z or ⁇ -haloperfluoroalkylsulfoyl chloride represented by the above general formula (10) can also be obtained.
  • the ratio is determined by the amount of iodine or bromine added.
  • the solvent in this step include ester solvents such as ethyl acetate and butyl acetate, ether solvents such as monodalaim and diglyme, -tolyl solvents such as acetonitrile and propio-tolyl, acetone, and methyl ethyl ketone. And the like.
  • chlorinating agent used in the first step a publicly known chlorinating agent without particular limitation can be used.
  • a publicly known chlorinating agent without particular limitation can be used.
  • chlorine, sulfuryl chloride and the like can be used as a chlorinating agent, and chlorine is particularly preferred.
  • the a, ⁇ -dihaloperfluoroalkane represented by the general formula (8) obtained by the above operation can be reused in the reaction with the dithionite in the step (i). .
  • the ⁇ -haloperfluoroalkylsulfonyl chloride represented by the above general formula (10) obtained by the above operation is reused in the reaction with the fluorine ion-containing conjugate in the above step (iv).
  • it can be used after being converted to ⁇ -no and perfluoroalkylsulfur fluoride represented by the above general formula (1,).
  • the ⁇ -fluorosulfonylperfluoroalkylvinyl ether represented by the above general formula (2) or (2 ′) according to the production method of the present invention can be used for various solid electrolyte materials or ion exchange membranes. It is a useful substance as a monomer component for polymers.
  • the solid electrolyte polymer examples include an electrolyte membrane for a solid polymer electrolyte fuel cell, a catalyst binder, a membrane for a lithium battery, a membrane for salt electrolysis, a membrane for water electrolysis, a membrane for hydrohalic acid electrolysis, and a membrane for oxygen concentrator. It is used as a film for temperature sensors and films for gas sensors.
  • the ⁇ -fluorosulfo-leperfluoroalkylbutyl ether represented by the general formula (2) or (2 ′) and a synthetic intermediate thereof can be produced at a high yield. Can be manufactured.
  • the 19 F-NMR spectrum was measured using a GSX-400 nuclear magnetic resonance device manufactured by JEOL Japan as a measuring device, double-mouthed form as a solvent, and Freon 11 (CFC1) as a reference material.
  • the test was performed under the following apparatus and conditions.
  • the test was performed under the following apparatus and conditions.
  • the vessel was cooled in an ice bath.
  • 287 g of Na 2 S O is calorie divided into 5 times in 15 minutes.
  • reaction mixture was 19 F-NMR, 57 mol I (CF) I % Remaining, 36 mol% of I (CF) SONa and 7 mol% of NaOS (CF) SONa
  • the obtained liquid was purified by distillation (bp 54 ° C, 40 kPa) to obtain FOC (CF) SO F 2.67 kg
  • the flask was placed in an ice bath, 19 g of Na 2 S 2 O was added little by little, and the mixture was stirred at room temperature for 2 hours.
  • Recol dimethyl ether was distilled off under reduced pressure, and the residue was further heated to 120 ° C. and dried under reduced pressure. Dried residue containing CF CF (CO Na) 0 (CF) SO F to 200 ° C
  • Example 1 In a 200 mL three-necked flask equipped with a distillation tower and a dropping funnel, 33.2 g of sulfolane and 6.05 g of KF were placed, and while heating to 50 ° C, the FSO 0 (CF) SOF obtained in Example 1 was heated.
  • reaction mixture Upon heating at 60 ° C. for 19 hours, the reaction mixture separated into two layers and reached a conversion of 91%. After separating the upper layer and washing with concentrated sulfuric acid, distillation and purification yielded 34.lg of liquid.
  • reaction mixture power is also ethylene glyco
  • the reaction was carried out in the same manner as in Example 1. That is, after the reaction of I (CF) I and NaSO is completed, After acetone was distilled off from the mixture, water was added to separate the mixture into two layers. When the lower layer was separated, 546 g of I (CF) I was recovered. Ethyl acetate is added to the upper layer and extracted three times with ethyl acetate.
  • Example 1 In a 1 L four-necked flask equipped with a gas injection tube, NaO S (CF) separated in Example 1 was placed.
  • the solid formed is iodine and CIO S (CF) SOCI.

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

Abstract

Il est divulgué un procédé pour la production d'un éther vinylique ω-fluorosulfonyle perfluoroalkyl représentée par la formule générale ci-dessous (2) par des étapes spécifiques (a)-(c) á partir d'un fluorure ω-haloperfluoroalkyl sulfonyl representé par la formule générale (1) utilisée comme matériau brut. (1) (Dans la formule, Rf représente un groupe divalent de perfluorocarbone ayant 1 à 9 atomes de carbone; X représente un atome d'halogène sélectionné par I et Br; Y représente un atome de fluorure, un groupe de perfluoroalkyl ayant 1-3 atomes de carbone ou un groupe de liaison avec Rf (ayant 1-3 atomes de carbone; et CFY-Rf- représente un groupe divalent de perfluorocarbone ayant 3-10 atomes de carbone.). (2): CF2=CFO(CF2CF(CF3)O)n-CFY-Rf-SO2F (dans la formule, n est un nombre entier de 0-2, et Rf et Y sont défini comme dans la formule générale (1) ci-dessus.)
PCT/JP2005/003888 2004-03-08 2005-03-07 Procede pour la production de compose de flurorure WO2005085187A1 (fr)

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JP2006248907A (ja) * 2005-03-08 2006-09-21 Daikin Ind Ltd 含フッ素ハロゲン化物の製造方法
US7399887B1 (en) 2007-08-06 2008-07-15 E. I. Du Pont De Nemours And Company Fluorinated sulfonate surfactants
JP2011203029A (ja) * 2010-03-25 2011-10-13 Hitachi-Ge Nuclear Energy Ltd フッ化化合物の処理方法

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JP2002241980A (ja) * 2001-02-13 2002-08-28 Asahi Kasei Corp フッ素化モノマーの製造法
JP4143810B2 (ja) * 2002-06-14 2008-09-03 ダイキン工業株式会社 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
JP4143809B2 (ja) * 2002-06-14 2008-09-03 ダイキン工業株式会社 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
WO2003106515A1 (fr) * 2002-06-14 2003-12-24 ダイキン工業株式会社 Monomere fluore possedant un groupe fonctionnel sulfonate, copolymere fluore comprenant celui-ci et membrane echangeuse d'ions

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US6624328B1 (en) * 2002-12-17 2003-09-23 3M Innovative Properties Company Preparation of perfluorinated vinyl ethers having a sulfonyl fluoride end-group

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006248907A (ja) * 2005-03-08 2006-09-21 Daikin Ind Ltd 含フッ素ハロゲン化物の製造方法
US7399887B1 (en) 2007-08-06 2008-07-15 E. I. Du Pont De Nemours And Company Fluorinated sulfonate surfactants
JP2011203029A (ja) * 2010-03-25 2011-10-13 Hitachi-Ge Nuclear Energy Ltd フッ化化合物の処理方法

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