WO2022138510A1 - Procédé de production d'un composé de polyéther contenant du fluor, procédé de production d'un composé de polyéther divinyle contenant du fluor et composé de polyéther de divinyle contenant du fluor - Google Patents

Procédé de production d'un composé de polyéther contenant du fluor, procédé de production d'un composé de polyéther divinyle contenant du fluor et composé de polyéther de divinyle contenant du fluor Download PDF

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WO2022138510A1
WO2022138510A1 PCT/JP2021/046849 JP2021046849W WO2022138510A1 WO 2022138510 A1 WO2022138510 A1 WO 2022138510A1 JP 2021046849 W JP2021046849 W JP 2021046849W WO 2022138510 A1 WO2022138510 A1 WO 2022138510A1
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general formula
fluorine
compound represented
compound
hydrogen atom
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PCT/JP2021/046849
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English (en)
Japanese (ja)
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啓吾 松浦
誠人 宇野
元志 青山
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Ａｇｃ株式会社
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Priority to JP2022571415A priority Critical patent/JPWO2022138510A1/ja
Priority to CN202180086980.XA priority patent/CN116635359A/zh
Publication of WO2022138510A1 publication Critical patent/WO2022138510A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/22—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of halogens; by substitution of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/04—Saturated ethers
    • C07C43/12—Saturated ethers containing halogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
    • C08G65/323—Polymers modified by chemical after-treatment with inorganic compounds containing halogens
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives

Definitions

  • the present disclosure relates to a method for producing a fluorinated polyether compound, a method for producing a fluorinated divinyl polyether compound, and a fluorinated divinyl polyether compound.
  • Fluorine-containing compounds are used as surface treatment agents or lubricants because they exhibit high lubricity and water / oil repellency.
  • the fluorine-containing polyether compound having an ether bond has excellent lubricity and is used for forming a film for the purpose of protecting the reading head of a magnetic disk or the like.
  • a fluorine-containing polyether compound has been produced by various methods.
  • a fluorine-containing polyether compound is produced by reacting tetrafluoroethylene with oxygen in the presence of a compound having a fluorooxy group or the like.
  • a fluorine-containing polyether compound is produced by ring-opening polymerization of 2,2,3,3-tetrafluorooxetane, and the fluorine-containing polyether compound is chlorinated and fluorinated. It is disclosed to produce a halogen-containing polyether compound.
  • CF 2 CFO-CF 2 CF 2 CF 2 CH 2 OH and A 1 -OH (A 1 represents a methyl group or the like). It is disclosed that a halogen-containing polyether compound represented by A1 - O- (CF 2 CFHO-CF 2 CF 2 CF 2 CH 2 O) n + 1 -H is produced by reacting with a primary alcohol.
  • the fluorine-containing polyether compound has a trifluoromethyl group (-CF 3 ) at the end, but in the production method disclosed in US Pat. No. 5,258,110, the trifluoromethyl group is at both ends. It has been difficult to produce a fluorine-containing polyether compound having a high yield. Further, the fluorine-containing polyether compound obtained by the production method disclosed in US Pat. No. 4,845,268 and International Publication No. 2013/121984 has a functional group at at least one end, and the functional group is trifluoromethyl. The reaction of substituting with a group does not proceed easily, and it has been difficult to produce a fluorine-containing polyether compound having a trifluoromethyl group at both ends.
  • the fluorine-containing polyether compound used for film formation is required to have a high molecular weight.
  • the present disclosure has been made in view of the above requirements, and the problem to be solved thereof is that a high molecular weight fluorine-containing polyether compound having a trifluoromethyl group at both ends can be produced in a high yield.
  • the present invention is to provide a method for producing a fluoropolyether compound. Further, the problem to be solved is a method for producing a fluorine-containing divinyl polyether compound, which has vinyl groups at both ends and can easily produce a high-molecular-weight fluorine-containing divinyl polyether compound in a high yield, and a novel inclusion. It is to provide a fluorine divinyl polyether compound.
  • a fluorine-containing divinyl ether compound represented by the following general formula (1) and a diol compound represented by the following general formula (2) are added to 1 mol of the diol compound represented by the following general formula (2).
  • the fluorine-containing divinyl ether compound represented by the following general formula (1) is reacted at a ratio of more than 1 mol to produce the fluorine-containing divinyl polyether compound represented by the following general formula (3), and then the following general formula.
  • a method for producing a fluorine-containing polyether compound which comprises fluorinating the fluorine-containing divinyl polyether compound represented by (3) to produce a fluorine-containing polyether compound represented by the following general formula (4).
  • R 1 represents a monovalent hydrocarbon group having 1 to 3 carbon atoms, each of which may independently have a fluorine atom, a hydrogen atom or a hydrogen atom substituted with a hydrogen atom.
  • Each of R 2 and R 3 may independently contain a ring structure or a branched structure, may contain an ether bond, or may have a hydrogen atom substituted with a fluorine atom, and may have 1 to 1 carbon atoms.
  • R F1 independently represents a fluorine atom when R 1 is a fluorine atom, represents a fluorine atom when R 1 is a hydrogen atom, and R 1 has 1 carbon atom.
  • RF2 independently represents a divalent perfluorohydrocarbon group having 1 to 20 carbon atoms, in which the divalent hydrocarbon group represented by R2 is perfluorolated.
  • RF3 independently represents a divalent perfluorohydrocarbon group having 1 to 20 carbon atoms , in which the divalent hydrocarbon group represented by R3 is perfluorolated.
  • a represents an integer of 1 or more.
  • the introduction rate of the fluorine gas based on the molar is the general formula (3).
  • the hydrogen atom that can be replaced with a fluorine atom by the fluorine gas contained in the fluorine-containing divinyl polyether compound represented by the general formula (3) is in the range of 1 to 10 times the rate obtained by multiplying by a number.
  • the fluorine-containing divinyl ether compound represented by the general formula (1) and the diol compound represented by the general formula (2) are added to 1 mol of the diol compound represented by the general formula (2).
  • the fluorine-containing divinyl ether compound represented by the following general formula (1) and the fluorine-containing vinyl alcohol compound represented by the following general formula (5) are represented by the following general formula (1).
  • a fluorine-containing vinyl alcohol compound represented by the following general formula (5) is reacted with 1 mol of the divinyl ether compound at a ratio of more than 1 mol, and the following general formula (6-1) or the following general formula (6-2) is used.
  • the fluorinated divinyl polyether compound represented by the fluorinated divinyl polyether compound represented by the following general formula (6-1) or the following general formula (6-2) is fluorinated. 7-1) or a method for producing a fluorine-containing polyether compound, which comprises the following general formula (7-2).
  • CF 2 CR 1 -OR 4 -OH ...
  • R 1 represents a monovalent hydrocarbon group having 1 to 3 carbon atoms, each of which may independently have a fluorine atom, a hydrogen atom or a hydrogen atom substituted with a hydrogen atom.
  • R 2 and R 4 may independently contain a ring structure or a branched structure, may contain an ether bond, or may have a hydrogen atom substituted with a fluorine atom, and may have 1 to 1 carbon atoms.
  • R F1 independently represents a fluorine atom when R 1 is a fluorine atom, represents a fluorine atom when R 1 is a hydrogen atom, and R 1 has 1 carbon atom.
  • R 1 When it is a monovalent hydrocarbon group of 3 to 3, it represents a monovalent perfluorohydrocarbon group having 1 to 3 carbon atoms.
  • RF2 independently represents a divalent perfluorohydrocarbon group having 1 to 20 carbon atoms, in which the divalent hydrocarbon group represented by R2 is perfluorolated.
  • RF4 independently represents a divalent perfluorohydrocarbon group having 1 to 20 carbon atoms, in which the divalent hydrocarbon group represented by R4 is perfluorolated.
  • the introduction rate of the fluorine-containing divinyl polyether compound represented by the general formula (6-1) or the general formula (6-2) into the solvent is set to 1
  • the molar amount of the fluorine gas is set to 1.
  • the standard introduction rate is the same as the molar standard introduction rate of the fluorine-containing divinyl polyether compound represented by the general formula (6-1) or the general formula (6-2).
  • the fluorine-containing divinyl ether compound represented by the following general formula (1) is reacted at a ratio of more than 1 mol to produce a fluorine-containing divinyl polyether compound represented by the following general formula (3).
  • R 1 represents a monovalent hydrocarbon group having 1 to 3 carbon atoms, each of which may independently have a fluorine atom, a hydrogen atom or a hydrogen atom substituted with a hydrogen atom.
  • R 2 and R 3 may independently contain a ring structure or a branched structure, may contain an ether bond, or may have a hydrogen atom substituted with a fluorine atom, and may have 1 to 1 carbon atoms.
  • Represents 20 divalent hydrocarbon groups a represents an integer of 1 or more.
  • the fluorine-containing divinyl ether compound represented by the following general formula (1) and the fluorine-containing vinyl alcohol compound represented by the following general formula (5) are represented by the following general formula (1).
  • a fluorine-containing vinyl alcohol compound represented by the following general formula (5) is reacted with 1 mol of the divinyl ether compound at a ratio of more than 1 mol, and the following general formula (6-1) or the following general formula (6-2) is used.
  • a method for producing a fluorinated divinyl polyether compound which comprises producing the represented fluorinated divinyl polyether compound.
  • CF 2 CR 1 -OR 4 -OH ...
  • R 1 represents a monovalent hydrocarbon group having 1 to 3 carbon atoms, each of which may independently have a fluorine atom, a hydrogen atom or a hydrogen atom substituted with a hydrogen atom.
  • R 2 and R 4 may independently contain a ring structure or a branched structure, may contain an ether bond, or may have a hydrogen atom substituted with a fluorine atom, and may have 1 to 1 carbon atoms.
  • Represents 20 divalent hydrocarbon groups b, c and d independently represent an integer of 0 or 1 or more.
  • R 1 represents a monovalent hydrocarbon group having 1 to 3 carbon atoms, each of which may independently have a fluorine atom, a hydrogen atom or a hydrogen atom substituted with a hydrogen atom.
  • Each of R 2 and R 3 may independently contain a ring structure or a branched structure, may contain an ether bond, or may have a hydrogen atom substituted with a fluorine atom, and may have 1 to 1 carbon atoms.
  • R F1 independently represents a fluorine atom when R 1 is a fluorine atom, represents a fluorine atom when R 1 is a hydrogen atom, and R 1 has 1 carbon atom.
  • RF2 independently represents a divalent perfluorohydrocarbon group having 1 to 20 carbon atoms, in which the divalent hydrocarbon group represented by R2 is perfluorolated.
  • RF3 independently represents a divalent perfluorohydrocarbon group having 1 to 20 carbon atoms , in which the divalent hydrocarbon group represented by R3 is perfluorolated.
  • a represents an integer of 1 or more.
  • the fluorine-containing divinyl polyether compound represented by the following general formula (6-1) or the following general formula (6-2) is fluorinated, and the following general formula (7-1) or the following general formula (7-) is formed.
  • a method for producing a fluorine-containing polyether compound which comprises producing the fluorine-containing polyether compound represented by 2).
  • CF 2 CR 1 -OR 4 -OH ...
  • R 1 represents a monovalent hydrocarbon group having 1 to 3 carbon atoms, each of which may independently have a fluorine atom, a hydrogen atom or a hydrogen atom substituted with a hydrogen atom.
  • R 2 and R 4 may independently contain a ring structure or a branched structure, may contain an ether bond, or may have a hydrogen atom substituted with a fluorine atom, and may have 1 to 1 carbon atoms.
  • R F1 independently represents a fluorine atom when R 1 is a fluorine atom, represents a fluorine atom when R 1 is a hydrogen atom, and R 1 has 1 carbon atom.
  • R 1 When it is a monovalent hydrocarbon group of 3 to 3, it represents a monovalent perfluorohydrocarbon group having 1 to 3 carbon atoms.
  • RF2 independently represents a divalent perfluorohydrocarbon group having 1 to 20 carbon atoms, in which the divalent hydrocarbon group represented by R2 is perfluorolated.
  • RF4 independently represents a divalent perfluorohydrocarbon group having 1 to 20 carbon atoms, in which the divalent hydrocarbon group represented by R4 is perfluorolated.
  • b, c and d independently represent an integer of 0 or 1 or more.
  • R 1 represents a monovalent hydrocarbon group having 1 to 3 carbon atoms, each of which may independently have a fluorine atom, a hydrogen atom or a hydrogen atom substituted with a hydrogen atom.
  • R 2 and R 3 may independently contain a ring structure or a branched structure, may contain an ether bond, or may have a hydrogen atom substituted with a fluorine atom, and may have 1 to 1 carbon atoms.
  • Represents 20 divalent hydrocarbon groups a represents an integer of 1 or more.
  • 6-1 A fluorine-containing divinyl polyether compound represented by the following general formula (6-1).
  • R 1 represents a monovalent hydrocarbon group having 1 to 3 carbon atoms, each of which may independently have a fluorine atom, a hydrogen atom or a hydrogen atom substituted with a hydrogen atom.
  • Each of R 2 and R 4 may independently contain a ring structure or a branched structure, may contain an ether bond, or may have a hydrogen atom substituted with a fluorine atom, and may have 1 to 1 carbon atoms.
  • a fluorine-containing divinyl polyether compound represented by the following general formula (6-2).
  • R 1 represents a monovalent hydrocarbon group having 1 to 3 carbon atoms, each of which may independently have a fluorine atom, a hydrogen atom or a hydrogen atom substituted with a hydrogen atom.
  • R 2 and R 4 may independently contain a ring structure or a branched structure, may contain an ether bond, or may have a hydrogen atom substituted with a fluorine atom, and may have 1 to 1 carbon atoms.
  • Represents 20 divalent hydrocarbon groups d represents an integer of 0 or 1 or more.
  • a method for producing a fluorine-containing polyether compound capable of producing a high molecular weight fluorine-containing polyether compound having a trifluoromethyl group at both ends in a high yield.
  • a method for producing a fluorine-containing divinyl polyether compound and a novel fluorine-containing divinyl polyether which can produce a high-molecular-weight fluorine-containing divinyl polyether compound having vinyl groups at both ends in a high yield, and a novel fluorine-containing divinyl polyether. The compound is provided.
  • the numerical range indicated by using “-" includes the numerical values before and after "-" as the minimum value and the maximum value, respectively.
  • the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described in another stepwise description. .. Further, in the numerical range described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the synthesis example.
  • the "fluoroalkylene group” includes a perfluoroalkylene group in which all hydrogen atoms are substituted with fluorine atoms and a fluoroalkylene group in which a part of hydrogen atoms is substituted with fluorine atoms. Further, in the present disclosure, not only perfluorocyclobutene in which all hydrogen atoms contained in cyclobutene are substituted with fluorine atoms but also cyclobutene in which some hydrogen atoms are substituted with fluorine atoms are also described in the description of "fluorocycloalkane" and the like. Is also included.
  • each component may contain a plurality of applicable compounds.
  • the mol ratio in the reaction between the fluorine-containing divinyl ether compound represented by the general formula (1) and the diol compound represented by the general formula (2) is calculated based on the total of the compounds corresponding to each component.
  • the notation that does not describe substitution or non-substitution includes those having no substituent as well as those having a substituent.
  • the number of carbon atoms means the total number of carbon atoms contained in the entire group, and when the group does not have a substituent, it represents the number of carbon atoms forming the skeleton of the group, and the group. When has a substituent, it represents the total number of carbon atoms forming the skeleton of the group plus the number of carbon atoms in the substituent.
  • perfluorocarbonated of a monovalent or divalent hydrocarbon group means that the hydrocarbon group has been fluorinated to the following states.
  • the monovalent or divalent hydrocarbon group is a saturated hydrocarbon group, all the fluorinated hydrogen atoms bonded to the carbon atoms constituting the monovalent or divalent hydrocarbon group are fluorinated.
  • Hydrocarbon groups are referred to as "perfluoroylated”.
  • the monovalent or divalent hydrocarbon group is an unsaturated hydrocarbon group
  • all the fluorinated hydrogen atoms bonded to the carbon atoms constituting the monovalent or divalent hydrocarbon group are fluorinated and , A fluorine atom was added to each of the two carbon atoms forming a carbon-carbon unsaturated bond such as a carbon-carbon double bond or a carbon-carbon triple bond, and the carbon-carbon unsaturated bond disappeared.
  • the state is referred to as the hydrocarbon group being "perfluoroylated".
  • -C ⁇ C- perfluorolated
  • a hydrogen atom that can be perfluorolated may be bonded to the atom group that can be fluorinated.
  • the number average molecular weight (Mn) and the mass average molecular weight (Mw) are measured by gel permeation chromatography (hereinafter, also referred to as “GPC”).
  • GPC gel permeation chromatography
  • a fluorine-containing divinyl ether compound represented by the following general formula (1) (hereinafter, also referred to as a compound of formula (1)) and the following general formula (hereinafter, also referred to as a compound)
  • the diol compound represented by 2) (hereinafter, also referred to as the compound of the formula (2)) is reacted with 1 mol of the compound of the formula (2) at a ratio of more than 1 mol of the compound of the formula (1), and the following general
  • the compound of the formula (3) is fluorinated and represented by the following general formula (4).
  • a fluorine-containing polyether compound (hereinafter, also referred to as a compound of formula (4)) is produced.
  • R 1 is a monovalent of 1 to 3 carbon atoms in which a fluorine atom, a hydrogen atom or a hydrogen atom may be substituted with a fluorine atom independently of each other.
  • R 2 and R 3 may independently contain a ring structure or a branched structure, may contain an ether bond, and the hydrogen atom is fluorine.
  • RF1 independently represents a fluorine atom when R 1 is a fluorine atom, and represents a fluorine atom when R 1 is a hydrogen atom.
  • R 1 is a monovalent hydrocarbon group having 1 to 3 carbon atoms, it represents a monovalent perfluorohydrocarbon group having 1 to 3 carbon atoms.
  • RF2 independently represents a divalent perfluorohydrocarbon group having 1 to 20 carbon atoms, in which the divalent hydrocarbon group represented by R2 is perfluorolated.
  • RF3 independently represents a divalent perfluorohydrocarbon group having 1 to 20 carbon atoms , in which the divalent hydrocarbon group represented by R3 is perfluorolated.
  • a represents an integer of 1 or more, preferably an integer of 3 or more, and more preferably an integer of 5 or more. Further, a is preferably an integer of 15 or less.
  • a high-molecular-weight fluorine-containing polyether compound having a trifluoromethyl group at both ends can be produced in a high yield.
  • the compound of formula (1) In the reaction between the compound of formula (1) and the compound of formula (2), it is preferable to react the compound of formula (1) at a ratio of 1.01 mol or more with respect to 1 mol of the compound of formula (2), preferably at a ratio of 1.1 mol or more. It is more preferable to react with.
  • the polymerization reaction proceeds smoothly, so that the compound of the formula (3) having a high molecular weight can be produced in a high yield.
  • the compound of the formula (1) in the reaction between the compound of the formula (1) and the compound of the formula (2), it is preferable to react the compound of the formula (1) at a ratio of 3 mol or less with respect to 1 mol of the compound of the formula (2), and react at a ratio of 2 mol or less. It is more preferable to let them.
  • the polymerization reaction proceeds smoothly, so that the compound of the formula (3) having a high molecular weight can be produced in a high yield.
  • the reaction between the compound of formula (1) and the compound of formula (2) is preferably carried out in the presence of an alkaline catalyst.
  • an alkaline catalyst By reacting the compound of the formula (1) with the compound of the formula (2) in the presence of an alkaline catalyst, the molecular weight and yield of the produced compound of the formula (3) can be further improved.
  • the alkaline catalyst include sodium hydroxide, potassium hydroxide, sodium carbonate, cesium fluoride, potassium carbonate and the like, and from the viewpoint of the molecular weight and yield of the fluorine-containing divinyl polyether compound and the fluorine-containing polyether compound. , Potassium carbonate is preferred.
  • the reaction between the compound of the formula (1) and the compound of the formula (2) may be carried out in a solvent or without using a solvent.
  • the solvent is not particularly limited, but when the compound of the formula (3) is fluorinated, a solvent that does not fluorinate is preferable, and specifically, a fluorinated solvent is preferable.
  • a fluorinated solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines and fluoroalcohols.
  • the reaction temperature of the compound of the formula (1) and the compound of the formula (2) is preferably 80 ° C to 160 ° C, more preferably 90 ° C to 140 ° C.
  • the reaction between the compound of the formula (1) and the compound of the formula (2) may be carried out by a batch method, a continuous method, or a known method may be appropriately adopted.
  • the reaction of the compound of the formula (1) and the compound of the formula (2) is carried out by a batch method, for example, the compound of the formula (2) is previously contained in a reactor, and the compound of the formula (1) is added into the reactor. Alternatively, a diluted solution of the compound of formula (1) may be added.
  • the formula (1) compound or a diluted solution thereof is added to the formula (2) compound previously stored in the reactor from the viewpoint of reactivity, the formula (2) compound is heated to the above reaction temperature to obtain an alkylene oxide state. It is preferable to add it later.
  • the addition of the compound of the formula (1) to the compound of the formula (2) is carried out by the formula (2). It is preferable to carry out the reaction at a rate of 0.01 times mol / hour to 10 times mol / hour, and more preferably at a rate of 0.1 times mol / hour to 0.5 times mol / hour with respect to 1 mol of the compound. ..
  • the compound of formula (1) After reacting the compound of formula (1) with the compound of formula (2), at least one selected from a solvent, water and an aqueous solution for adjusting to an appropriate acidity is added and the liquid is separated, and then the organic phase is added. May be concentrated. Further, the reaction crude liquid obtained by concentrating the organic phase may be purified.
  • the solvent is not particularly limited, but the above-mentioned fluorine-based solvent is preferable.
  • R 2 may contain a ring structure or a branched structure, may contain an ether bond, or may have a hydrogen atom substituted with a fluorine atom, and may have 1 to 20 carbon atoms.
  • the number of carbon atoms of the divalent hydrocarbon group is preferably 15 or less, more preferably 10 or less.
  • the polymerization reaction proceeds more smoothly, so that a high molecular weight fluorine-containing polyether compound can be produced in high yield.
  • the number of carbon atoms of the divalent hydrocarbon group is preferably 2 or more, and more preferably 3 or more.
  • Examples of the divalent hydrocarbon group represented by R 2 include an alkylene group such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group and a hexamethylene group, a fluoromethylene group and a fluoroethylene group.
  • Examples thereof include fluoroalkylene groups such as fluorotrimethylene group, fluorotetramethylene group, fluoropentamethylene group and fluorohexamethylene group.
  • the divalent hydrocarbon group represented by R 2 may be a group represented by the following general formula (X). * -R x- (OR x ) n- * ... (X)
  • R x represents an ethylene group, a trimethylene group, a propylene group, a fluoroethylene group, a fluorotrimethylene group or a fluoropropylene group
  • n represents an integer of 1 or more.
  • * represents a bonding portion with an oxygen atom.
  • the divalent hydrocarbon group represented by R 2 may be a group represented by the following general formula (A). * -R b -OR a -OR b- * ... (A)
  • Ra represents a cycloalkanediyl group, a fluorocycloalkandyl group or an arylene group.
  • Examples of the cycloalkanediyl group and the fluorocycloalkanediyl group include a cyclobutanediyl group, a fluorocyclobutanediyl group, a cyclopentanediyl group, a fluorocyclopentanediyl group, a cyclohexanediyl group, a fluorocyclohexanediyl group, an adamantandiyl group, and a norbornandyl.
  • the basis etc. can be mentioned.
  • the cycloalkandyl group, the fluorocycloalkandyl group and the arylene group may have an alkyl group having 1 to 3 carbon atoms in which the hydrogen atom may be substituted with a fluorine atom as a substituent.
  • R b may independently contain a ring structure or a branched structure, and the hydrogen atom may be substituted with a fluorine atom, which is a divalent group having 1 to 10 carbon atoms. Represents a hydrocarbon group.
  • * represents a bonding portion with an oxygen atom.
  • hydrocarbon group satisfying the general formula (A) examples include, but are not limited to, the following groups.
  • the divalent hydrocarbon group represented by R 2 may be a group represented by the following general formulas (B) to (D).
  • * represents a bonding portion with an oxygen atom.
  • the group represented by Ra in the general formulas (B) to (D) is the same as the general formula ( A ).
  • R c may independently contain a single bond, a ring structure or a branched structure, and the hydrogen atom may be substituted with a fluorine atom.
  • R d represents a cycloalkane-1,1-diyl group having 3 to 6 carbon atoms.
  • Examples of the group satisfying any of the general formula (B) to the general formula (D) include, but are not limited to, the following groups.
  • the molecular weight of the compound of the formula (1) is preferably 150 to 1000, more preferably 200 to 600. When the molecular weight of the compound of the formula (1) is within the above numerical range, the reaction with the compound of the formula (2) proceeds smoothly.
  • examples of the compound of formula (1) include, but are not limited to, the following compounds.
  • the compound of the formula (1) may have R 1 being both fluorine and R 2 being a perfluoroylated divalent hydrocarbon group.
  • R 3 may contain a ring structure or a branched structure, may contain an ether bond, and a hydrogen atom may be substituted with a fluorine atom, and has 1 to 1 carbon atoms.
  • the divalent hydrocarbon group the same group as the divalent hydrocarbon group represented by R 2 can be selected, and thus the description thereof is omitted here. Further, R 2 and R 3 may be the same group or different groups. HO-R 3 -OH ... (2)
  • the molecular weight of the compound of the formula (2) is preferably 50 to 400, more preferably 60 to 300. When the molecular weight of the compound of the formula (2) is within the above numerical range, the reaction with the compound of the formula (1) proceeds smoothly.
  • the acidity (pKa) of the compound of the formula (2) is preferably 8 to 18, and more preferably 9 to 15.
  • pKa is a numerical value in water at 25 ° C., and is calculated by the method described in Revised 5th Edition II-331 to II-343 (edited by The Chemical Society of Japan, published by Maruzen Co., Ltd.).
  • Examples of the compound of the formula (2) include, but are not limited to, the following compounds.
  • the formula (1) compound and the formula (2) compound are one or more formula (1) compounds selected from the following group A and the formula (2) compound selected from the following group B.
  • the combination is preferable, and a combination of one or more formula (1) compounds selected from the following group A'and a compound of formula (2) selected from the following group B is more preferable, but the combination is not limited thereto. ..
  • Group A is as follows.
  • the A'group is as follows.
  • Group B is as follows.
  • Examples of the compound of formula (3) include, but are not limited to, the following compounds. Since the divinyl groups at both ends of the compound of formula (3) are easily fluorinated, a high molecular weight compound of formula (4) having trifluoromethyl groups at both ends can be produced in high yield.
  • the fluorine-containing polyether compound represented by the following general formula (4) is produced by fluorinating the compound of the formula (3).
  • CF 3 -CFR F1 -OR F2 -O- (CFR F1 -CF 2 -OR F3 -O-CF 2 -CFR F1 -OR F2 -O) a -CFR F1 -CF 3 ...
  • the method for fluorinating the compound of the formula (3) is not particularly limited, and can be carried out by a conventionally known method.
  • fluorination can be performed by contacting the compound of formula (3) with a fluorine gas.
  • the method for fluorinating the compound of the formula (3) may be a batch method or a continuous method.
  • the fluorination reaction is preferably carried out by the following ⁇ Method 1> or ⁇ Method 2>, and ⁇ Method 2> is more preferable from the viewpoint of the yield of the compound of the formula (4).
  • the fluorine gas may be diluted with an inert gas such as nitrogen gas before use in either the batch method or the continuous method.
  • Method 1 In the method 1, the compound of formula (3) and the solvent are charged in the reactor, and stirring is started. This is a method of reacting while continuously supplying a fluorine gas diluted with an inert gas into a solvent under a predetermined reaction temperature and reaction pressure.
  • Method 2 In method 2, a solvent is charged in the reactor and stirred. Next, under a predetermined reaction temperature and reaction pressure, a method of reacting while continuously supplying a fluorine gas diluted with an inert gas, a compound of formula (3) and a solvent into a fluorination reaction solvent at a predetermined molar ratio. Is.
  • a solvent is continuously introduced into the tubular reactor and circulated in the tubular reactor, and then a fluorine gas diluted with an inert gas and a solution in which the compound of the formula (3) is dissolved are mixed with the fluorine gas.
  • the compound of formula (3) are continuously supplied to the solvent flow in the tubular reactor and mixed at a ratio of a predetermined molar ratio, and the fluorine gas and the compound of formula (3) are mixed in the tubular reactor.
  • a solvent containing a reaction product is taken out from a tubular reactor by contacting and reacting.
  • the fluorination reaction can be carried out in a continuous manner by circulating the solvent and extracting the reaction product from the circulating solvent.
  • the amount of the solvent with respect to the compound of the formula (3) is preferably 5 times or more, more preferably 7 times or more on a mass basis.
  • the inert gas examples include rare gases such as helium gas, neon gas, and argon gas, and nitrogen gas. Nitrogen gas and helium gas are preferable, and nitrogen gas is more preferable because it is economically advantageous.
  • the ratio of the fluorine gas (hereinafter, also referred to as “fluorine gas amount”) is preferably 15% by volume to 60% by volume in the total 100% by volume of the fluorine gas and the inert gas.
  • the solvent When the fluorination of the compound of the formula (3) is carried out in a solvent, the solvent may be previously substituted with nitrogen in order to reduce the oxygen content in the solvent. Further, when the compound of the formula (3) is introduced into the solvent, the solvent may be substituted with nitrogen in advance, and then the solvent may be further substituted with fluorine.
  • the amount of the fluorine gas that fluorinated these hydrogen atoms in the compound of formula (3) should always be excessive with respect to all the hydrogen atoms that can be fluorinated. Is preferable.
  • the amount of fluorine gas is preferably 1.1 times equivalent or more, more preferably 1.3 times equivalent or more, the theoretical amount required for fluorinating all hydrogen atoms that can be fluorinated.
  • the fluorination of the compound of the formula (3) is carried out by introducing a fluorine gas and the compound of the formula (3) into the solvent
  • the molar-based introduction rate of the compound of the formula (3) into the solvent is 1.
  • the molar-based introduction rate of fluorine gas was obtained by multiplying the molar-based introduction rate of the compound of formula (3) by the number of hydrogen atoms that could be replaced by fluorine atoms by the fluorine gas contained in the compound of formula (3). It may be in the range of 1 to 10 times the speed, or may be in the range of 2 to 7 times the speed.
  • a CH bond-containing compound other than the compound of formula (3) to the solvent or to irradiate the solvent with ultraviolet rays. .. These are preferably performed in the latter stage of the fluorination reaction.
  • the compound of the formula (3) existing in the solvent can be efficiently fluorinated, and the yield of the compound of the formula (4) can be improved.
  • aromatic hydrocarbons are preferable, and examples thereof include benzene and toluene.
  • the amount of the CH bond-containing compound added is preferably 0.1 mol% to 10 mol%, preferably 0.1 mol% to 5 mol%, based on the hydrogen atom in the compound of formula (3). Is more preferable.
  • the CH bond-containing compound is preferably added in a solvent in which fluorine gas is present. Further, when the CH bond-containing compound is added, it is preferable to pressurize the reaction system.
  • the reaction pressure during pressurization is preferably 0.01 MPa to 5 MPa (gauge pressure).
  • the irradiation time is preferably 0.1 hour to 3 hours.
  • the fluorination reaction After the fluorination reaction, at least one selected from a solvent, water and an aqueous solution for adjusting to an appropriate acidity is added to the reaction solution to separate the layers, and then the organic phase is concentrated to obtain the compound of the formula (4). You may get it. Further, the reaction crude liquid obtained by concentrating the organic phase may be purified to obtain the compound of the formula (4).
  • the compound of formula (4) will be described.
  • RF1 independently represents a fluorine atom when R 1 is a fluorine atom, and represents a fluorine atom when R 1 is a hydrogen atom.
  • R 1 is a monovalent hydrocarbon group having 1 to 3 carbon atoms, it represents a monovalent perfluorohydrocarbon group having 1 to 3 carbon atoms.
  • RF2 independently represents a divalent perfluorohydrocarbon group having 1 to 20 carbon atoms, in which the divalent hydrocarbon group represented by R2 is perfluorolated.
  • RF3 independently represents a divalent perfluorohydrocarbon group having 1 to 20 carbon atoms , in which the divalent hydrocarbon group represented by R3 is perfluorolated.
  • the divalent hydrocarbon group represented by R 2 and R 3 has an aromatic ring, the aromatic ring is perfluorolated to become a perfluorocycloalkyl ring.
  • the number average molecular weight (Mn) of the compound of the formula (4) obtained by the production method according to the first aspect is preferably 1000 to 30,000, more preferably 2000 to 20000, and even more preferably 2000 to 10000.
  • the molecular weight distribution (Mw / Mn) of the compound of the formula (4) is preferably 1 to 3, more preferably 1 to 2.5, and even more preferably 1 to 1.5.
  • examples of the compound of the formula (4) obtained by fluorination of the compound of the formula (3) include, but are not limited to, the following compounds. ..
  • the method for producing a fluorine-containing polyether compound represented by the general formula (7-1) or the general formula (7-2) will be described.
  • a fluorine-containing divinyl polyether compound represented by the general formula (6-1) or the general formula (6-2) and a method for producing the same will also be described.
  • the method for producing a fluorine-containing polyether compound according to the second aspect is a fluorine-containing divinyl ether compound represented by the following general formula (1) (hereinafter, also referred to as a compound of formula (1)) and the following general formula (5).
  • a compound (hereinafter, also referred to as a compound of formula (7-1) and a compound of formula (7-2), respectively) is produced.
  • CF 2 CR 1 -OR 4 -OH ...
  • R 1 is independently composed of a fluorine atom, a hydrogen atom or a hydrogen atom depending on the fluorine atom. It represents a monovalent hydrocarbon group having 1 to 3 carbon atoms which may be substituted.
  • R 2 and R 4 each independently include a ring structure and a branched structure. It may also contain an ether bond, and the hydrogen atom may be substituted with a fluorine atom, and represents a divalent hydrocarbon group having 1 to 20 carbon atoms.
  • RF1 independently represents a fluorine atom when R 1 is a fluorine atom, and R 1 is a hydrogen atom. In some cases, it represents a fluorine atom, and when R 1 is a monovalent hydrocarbon group having 1 to 3 carbon atoms, it represents a monovalent perfluorohydrocarbon group having 1 to 3 carbon atoms.
  • RF2 has 1 to 20 carbon atoms in which the divalent hydrocarbon group represented by R 2 is perfluorolated independently of each other. Represents a divalent perfluorohydrocarbon group.
  • RF4 has 1 to 20 carbon atoms in which the divalent hydrocarbon group represented by R4 is perfluorolated independently of each other. Represents a divalent perfluorohydrocarbon group.
  • b, c and d are independently 0 or 1 or more. It represents an integer, preferably an integer of 3 or more, and more preferably an integer of 5 or more.
  • a high-molecular-weight fluorine-containing polyether compound having a trifluoromethyl group at both ends can be produced in a high yield.
  • the polymerization reaction proceeds smoothly by reacting the compound of the formula (5) with a ratio of more than 1 mol with respect to 1 mol of the compound of the formula (1). Therefore, a high molecular weight compound of formula (6-1) or compound of formula (6-2) can be produced in high yield.
  • the compound of the formula (1) In the reaction between the compound of the formula (1) and the compound of the formula (5), it is preferable to react the compound of the formula (5) with 1 mol of the compound of the formula (1) at a ratio of 2 mol or more, preferably at a ratio of 5 mol or more. It is more preferable to react.
  • the polymerization reaction proceeds smoothly, so that the compound of the formula (6-1) or the formula (6-2) having a high molecular weight is used. ) The compound can be produced in high yield.
  • the compound of the formula (5) it is preferable to react the compound of the formula (5) with respect to 1 mol of the compound of the formula (1) at a ratio of 20 mol or less, preferably 15 mol or less. It is more preferable to react at a ratio.
  • the reaction between the compound of formula (1) and the compound of formula (5) is preferably carried out in the presence of an alkaline catalyst. Further, the above reaction may be carried out in a solvent or without using a solvent.
  • the solvent is not particularly limited, but the above-mentioned fluorine-based solvent is preferable.
  • the reaction between the compound of the formula (1) and the compound of the formula (5) can be carried out by adding a mixture of the compound of the formula (1) and the compound of the formula (5) to the solvent heated to the following reaction temperature. From the viewpoint of reactivity, the addition rate of the mixture is preferably 0.5% by mass / hour to 70% by mass / hour with respect to the total mass of the mixture, more preferably 1% by mass / hour to 50% by mass / hour. preferable.
  • the reaction temperature between the compound of the formula (1) and the compound of the formula (5) is preferably 80 ° C. to 160 ° C., 90 ° C. ° C to 140 ° C is more preferable.
  • reaction between the compound of the formula (1) and the compound of the formula (5) may be carried out by a batch method, a continuous method, or a known method may be appropriately adopted.
  • R 4 may contain a ring structure or a branched structure, may contain an ether bond, or a hydrogen atom may be substituted with a fluorine atom, and has 1 to 1 carbon atoms.
  • the divalent hydrocarbon group the same group as the divalent hydrocarbon group represented by R 2 and R 3 can be selected, and thus the description thereof is omitted here.
  • CF 2 CR 1 -OR 4 -OH ... (5)
  • the molecular weight of the compound of the formula (5) is preferably 90 to 800, more preferably 100 to 600. When the molecular weight of the compound of the formula (5) is within the above numerical range, the reaction with the compound of the formula (1) proceeds smoothly.
  • the pKa of the compound of the formula (5) is preferably 8 to 16, and more preferably 9 to 14. When the pKa of the compound of the formula (5) is within the above numerical range, the reaction with the compound of the formula (1) proceeds smoothly.
  • Examples of the compound of the formula (5) include, but are not limited to, the following compounds.
  • the compound of formula (1) is as exemplified in the first aspect.
  • the combination of one or more compounds of the formula (1) selected from the above group A and the compound of the formula (5) selected from the following group C is reactive. It is preferable from the viewpoint, but is not limited to this.
  • Group C is as follows.
  • Examples of the compound of the formula (6-1) and the compound of the formula (6-2) include, but are not limited to, the following compounds. Since the divinyl groups at both ends of the compound of formula (6-1) and the compound of formula (6-2) are easily fluorinated, a high molecular weight fluorine-containing polyether compound having trifluoromethyl groups at both ends. Can be produced in high yield.
  • the method for fluorinating the compound of the formula (6-1) or the compound of the formula (6-2) is not particularly limited, and can be carried out by a conventionally known method.
  • fluorination can be performed by contacting the compound of the formula (6-1) or the compound of the formula (6-2) with a fluorine gas. Since the specific method of fluorination is the same as that of the first aspect, the description thereof is omitted here.
  • Fluorination of the compound of formula (6-1) or the compound of formula (6-2) is carried out by introducing fluorine gas and fluorination of the compound of formula (6-1) or the compound of formula (6-2) into a solvent.
  • the molar-based introduction rate of the fluorinated compound of the formula (6-1) or the formula (6-2) into the solvent is 1, the molar-based introduction rate of the fluorine gas is the formula (6).
  • RF4 has 1 to 20 carbon atoms in which the divalent hydrocarbon group represented by R4 is perfluorolated independently of each other. Represents a divalent perfluorohydrocarbon group.
  • the divalent hydrocarbon group represented by R 4 has an aromatic ring, the aromatic ring is perfluorolated to become a perfluorocycloalkyl ring. Since the groups represented by RF1 and RF2 are the same as those in the first aspect, the description thereof will be omitted here.
  • Examples of the compound include, but are not limited to, the following compounds.
  • NMR analysis The NMR analysis was performed under the following conditions. 1 7.5 ppm nitrobenzene was used as the reference material for 1 H-NMR (300.4 MHz). -162.5 ppm of perfluorobenzene was used as the reference material for 19 F-NMR (282.7 MHz).
  • NMR solvent a mixed solvent of deuterated chloroform and hexafluorobenzene or a mixed solvent of deuterated chloroform and 1,4-bistrifluoromethylbenzene was used.
  • the internal temperature of the flask was set to 25 ° C., and 20 g each of a fluorine-based solvent (manufactured by AGC Inc., Asahiclin (registered trademark) AC-2000, 1H-tridecafluorohexane, hereinafter referred to as AC-2000) and hydrochloric acid was added.
  • the mixture was added to obtain a crude reaction solution separated into an organic phase and an aqueous phase.
  • the obtained crude reaction solution was separated, and then the organic phase was concentrated.
  • the crude reaction solution in which the organic phase was concentrated was purified by column chromatography to obtain 15 g (yield 65%) of the following fluorine-containing divinyl polyether compound (3A) satisfying the above general formula (3).
  • the average value of the number of repeating units a was 9.
  • the fluorine-containing divinyl polyether compound (3A) is described below.
  • CFE-419 250 mL of CFE-419 was placed in a 500 mL nickel reactor and then blown with nitrogen gas (bubbling). After confirming that the dissolved oxygen concentration was sufficiently lowered, 20% by volume of fluorine gas diluted with nitrogen gas was blown in for 1 hour (bubbling). Then, a solution of CFE-419 of the fluorine-containing divinyl polyether compound (3A) was added to CFE-419 in the reactor over 3 hours. The concentration of the fluorine-containing divinyl polyether compound (3A) in the CFE-419 solution was 10% by mass, and the amount of the fluorine-containing divinyl polyether compound (3A) was 15 g. Fluorine gas was bubbled to CFE-419 with the addition of CFE-419 solution.
  • the molar-based introduction rate of the fluorine-containing divinyl polyether compound (3A) into the solvent is 1
  • the molar-based introduction rate of the fluorine gas is set to the molar-based introduction rate of the fluorine-containing divinyl polyether compound (3A).
  • the introduction rate was multiplied by the number of hydrogen atoms that could be replaced with fluorine atoms by the fluorine gas contained in the fluorine-containing divinyl polyether compound (3A) to obtain twice the rate.
  • the structure of the fluorine-containing polyether compound (4A) was determined by 1 H-NMR method and 19 F-NMR method.
  • the Mn of the fluorine-containing polyether compound (4A) was 5000, and the Mw / Mn was 1.8.
  • the fluorine-containing polyether compound (4A) is described below.
  • the internal temperature of the flask was set to 25 ° C., and 20 g of each of the above AC-2000 and hydrochloric acid was added to obtain a crude reaction solution separated into an organic phase and an aqueous phase.
  • the obtained crude reaction solution was separated, and then the organic phase was concentrated.
  • the crude reaction solution in which the organic phase was concentrated was purified by column chromatography to obtain 20 g (yield 79%) of the following fluorine-containing divinyl polyether compound (3B) satisfying the above general formula (3).
  • the average value of the number of repeating units a was 12.
  • the fluorine-containing divinyl polyether compound (3B) is described below.
  • CFE-419 250 mL of CFE-419 was placed in a 500 mL nickel reactor and then bubbled with nitrogen gas. After confirming that the dissolved oxygen concentration was sufficiently lowered, 20% by volume of fluorine gas diluted with nitrogen gas was bubbled for 1 hour. Moreover, the CFE-419 solution of the fluorine-containing divinyl polyether compound (3B) was added to CFE-419 in the reactor over 3 hours. The concentration of the fluorine-containing divinyl polyether compound (3B) in the CFE-419 solution was 10% by mass, and the amount of the fluorine-containing divinyl polyether compound (3B) was 20 g. Fluorine gas was bubbled to CFE-419 with the addition of CFE-419 solution.
  • the molar-based introduction rate of the fluorine-containing divinyl polyether compound (3B) into the solvent is 1
  • the molar-based introduction rate of the fluorine gas is set to the molar-based introduction rate of the fluorine-containing divinyl polyether compound (3B).
  • the introduction rate was multiplied by the number of hydrogen atoms that could be replaced with fluorine atoms by the fluorine gas contained in the fluorine-containing divinyl polyether compound (3B) to obtain 3 times the rate obtained.
  • the CFE-419 solution of the fluorine-containing divinyl polyether compound was added intermittently. After adding the CFE-419 solution of benzene, fluorine gas was blown over for 1 hour, and finally the inside of the reactor was sufficiently replaced with nitrogen gas. The solvent was distilled off to obtain 24 g (yield 81%) of the following fluorine-containing polyether compound (4B) satisfying the above general formula (4).
  • the structure of the fluorine-containing polyether compound (4B) was determined by 1 H-NMR method and 19 F-NMR method.
  • the Mn of the fluorine-containing polyether compound (4B) was about 8000, and the Mw / Mn was 1.8.
  • the fluorine-containing polyether compound (4B) is described below.
  • the internal temperature of the flask was set to 25 ° C., and 20 g of each of the above AC-2000 and hydrochloric acid was added to obtain a crude reaction solution separated into an organic phase and an aqueous phase.
  • the obtained crude reaction solution was separated, and then the organic phase was concentrated.
  • the crude reaction solution in which the organic phase was concentrated was purified by column chromatography to obtain 21 g (yield 72%) of the following fluorine-containing divinyl polyether compound (3C) satisfying the above general formula (3).
  • the average value of the number of repeating units a was 6.
  • the fluorine-containing divinyl polyether compound (3C) is described below.
  • CFE-419 250 mL of CFE-419 was placed in a 500 mL nickel reactor and then bubbled with nitrogen gas. After confirming that the dissolved oxygen concentration was sufficiently lowered, 20% by volume of fluorine gas diluted with nitrogen gas was bubbled for 1 hour. Then, a solution of CFE-419 of the fluorine-containing divinyl polyether compound (3C) was added to CFE-419 in the reactor over 3 hours. The concentration of the fluorine-containing divinyl polyether compound (3C) in the CFE-419 solution was 10% by mass, and the amount of the fluorine-containing divinyl polyether compound (3C) was 21 g. Fluorine gas was bubbled to CFE-419 with the addition of CFE-419 solution.
  • the molar-based introduction rate of the fluorine-containing divinyl polyether compound (3C) into the solvent is 1
  • the molar-based introduction rate of the fluorine gas is set to the molar-based introduction rate of the fluorine-containing divinyl polyether compound (3C).
  • the introduction rate was multiplied by the number of hydrogen atoms that could be replaced with fluorine atoms by the fluorine gas contained in the fluorine-containing divinyl polyether compound (3C) to obtain twice the rate.
  • the CFE-419 solution of the fluorine-containing divinyl polyether compound was added intermittently. After adding the CFE-419 solution of benzene, the CFE-419 solution of benzene was added, fluorine gas was blown over for 1 hour, and finally the inside of the reactor was sufficiently replaced with nitrogen gas. The solvent was distilled off to obtain 33 g (yield 98%) of the following fluorine-containing polyether compound (4C) satisfying the above general formula (4).
  • the structure of the fluorine-containing polyether compound (4C) was determined by 1 H-NMR method and 19 F-NMR method.
  • the Mn of the fluorine-containing polyether compound (4C) was 5000, and the Mw / Mn was 1.6.
  • the fluorine-containing polyether compound (4C) is described below.
  • the internal temperature of the flask was set to 120 ° C., and the mixture was stirred for 2 hours.
  • the fluorine-containing vinyl alcohol compound (5A) was reacted at a ratio of 9.92 mol to 1 mol of the fluorine-containing divinyl ether compound (1A).
  • CF 2 CF-O-CF 2 CF 2 CF 2 CH 2 -OH ...
  • the internal temperature of the flask was set to 25 ° C., and 20 g of each of the above AC-2000 and hydrochloric acid was added to obtain a crude reaction solution separated into an organic phase and an aqueous phase. The obtained crude reaction solution was separated, and then the organic phase was concentrated. The crude reaction solution in which the organic phase was concentrated was purified by column chromatography to obtain 25 g (yield 56%) of the following fluorine-containing divinyl polyether compound (6-1A) satisfying the above general formula (6-1). The average value of the number of repeating units b + c was 7.
  • the fluorine-containing divinyl polyether compound (6-1A) is described below.
  • CFE-419 250 mL of CFE-419 was placed in a 500 mL nickel reactor and then bubbled with nitrogen gas. After confirming that the dissolved oxygen concentration was sufficiently lowered, 20% by volume of fluorine gas diluted with nitrogen gas was bubbled for 1 hour. Further, a solution of CFE-419 of the fluorine-containing divinyl polyether compound (6-1A) was added to CFE-419 in the reactor over 3 hours. The concentration of the fluorine-containing divinyl polyether compound (6-1A) in the CFE-419 solution was 10% by mass, and the amount of the fluorine-containing divinyl polyether compound (6-1A) was 25 g. Fluorine gas was bubbled to CFE-419 with the addition of CFE-419 solution.
  • the introduction rate of the fluorine gas on the molar basis is set to the fluorine-containing divinyl polyether compound (6-1A).
  • the CFE-419 solution of the fluorine-containing divinyl polyether compound was added intermittently. After adding the CFE-419 solution of benzene, the CFE-419 solution of benzene was added, fluorine gas was blown over for 1 hour, and finally the inside of the reactor was sufficiently replaced with nitrogen gas. The solvent was distilled off to obtain 30 g (yield 98%) of the following fluorine-containing polyether compound (7-1A) satisfying the above general formula (7-1).
  • the structure of the fluorine-containing polyether compound (7-1A) was determined by 1 H-NMR method and 19 F-NMR method.
  • the Mn of the fluorine-containing polyether compound (7-1A) was 3500, and the Mw / Mn was 1.6.
  • the fluorine-containing polyether compound (7-1A) is described below.
  • both ends are trifluoroalkyl groups (-CF 3 ), and a high-molecular-weight fluorine-containing polyether compound is produced in high yield. It was shown that it can be done.

Abstract

L'invention concerne un procédé de production dans lequel un composé représenté par (1) et un composé représenté par (2) sont mis à réagir à un rapport auquel le composé représenté par (1) dépasse 1 mole par rapport à une mole du composé représenté par (2) pour ainsi produire un composé représenté par (3), après quoi le composé représenté par (3) est fluoré, et un composé polyéther contenant du fluor représenté par (4) est produit. (1) : CF2 = CR1-O-R2-O-CR1 = CF2 (2) : HO-R3-OH (3) : CF2 = CR1-O-R2-O-(CHR1-CF2-O-R3-O-CF2-CHR1-O-R2-O)a-CR1 = CF2 (4) : CF3-CFRF1-O-RF2-O-(CFRF1-CF2-O-RF3-O-CF2-CFRF1-O-RF2-O)a-CFRF1-CF3
PCT/JP2021/046849 2020-12-25 2021-12-17 Procédé de production d'un composé de polyéther contenant du fluor, procédé de production d'un composé de polyéther divinyle contenant du fluor et composé de polyéther de divinyle contenant du fluor WO2022138510A1 (fr)

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Citations (7)

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Publication number Priority date Publication date Assignee Title
GB1108128A (en) * 1965-06-02 1968-04-03 Du Pont Perfluoro (polyethylene glycol divinyl ethers) and polymers thereof
US3397191A (en) * 1965-06-02 1968-08-13 Du Pont Fluorocarbon ethers
JPH04500827A (ja) * 1988-09-28 1992-02-13 エクスフルアー・リサーチ・コーポレーシヨン アセタール、ケタールおよびオルトエステルのフツ素化
JP2006131514A (ja) * 2004-11-04 2006-05-25 Yunimatekku Kk 末端水酸基を有する含フッ素ビニルエーテルおよびその製造法
JP2010077222A (ja) * 2008-09-24 2010-04-08 Fujifilm Corp 含フッ素重合体、反射防止膜、反射防止フィルムおよび画像表示装置
JP2010535792A (ja) * 2007-08-06 2010-11-25 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー フッ素化非イオン性界面活性剤
JP2012506458A (ja) * 2008-10-21 2012-03-15 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー フッ化ポリオキシアルキレングリコールジエステル界面活性剤

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1108128A (en) * 1965-06-02 1968-04-03 Du Pont Perfluoro (polyethylene glycol divinyl ethers) and polymers thereof
US3397191A (en) * 1965-06-02 1968-08-13 Du Pont Fluorocarbon ethers
JPH04500827A (ja) * 1988-09-28 1992-02-13 エクスフルアー・リサーチ・コーポレーシヨン アセタール、ケタールおよびオルトエステルのフツ素化
JP2006131514A (ja) * 2004-11-04 2006-05-25 Yunimatekku Kk 末端水酸基を有する含フッ素ビニルエーテルおよびその製造法
JP2010535792A (ja) * 2007-08-06 2010-11-25 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー フッ素化非イオン性界面活性剤
JP2010077222A (ja) * 2008-09-24 2010-04-08 Fujifilm Corp 含フッ素重合体、反射防止膜、反射防止フィルムおよび画像表示装置
JP2012506458A (ja) * 2008-10-21 2012-03-15 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー フッ化ポリオキシアルキレングリコールジエステル界面活性剤

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