Classifications

• • 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
  • C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
  • C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
• • 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
  • C07C43/13—Saturated ethers containing hydroxy or O-metal groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
  • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
  • C07C69/734—Ethers
• • 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

• This disclosure relates to a method for producing a fluorine-containing polyether compound.
• Fluorine-containing polyether compounds are used as surface treatment agents or lubricants because they exhibit high lubricity, water repellency, oil repellency and the like. Fluorine-containing polyether compounds are produced by various methods.
• Patent Document 1 discloses that 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.
• Patent Document 2 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 to contain halogen. It is disclosed to produce a polyether compound.
• PFPE perfluoropolyether
• CF2-CF 2 O the structural units contained in PFPE
• CF 2 O the structural units can be freely selected.
• the structural unit included in PFPE cannot be freely selected.
• the present disclosure has been made in view of the above requirements, and the problem to be solved is a method for producing a fluorine-containing polyether compound having functional groups at both ends and having few restrictions when selecting a structural unit. Is to provide.
• the fluorine-containing diacyloxypolyether compound represented by the following general formula (4) is fluorinated to produce a perfluorodiacyloxypolyether compound represented by the following general formula (5).
• R 4 CO-O-CH 2 R 3 CH 2 -O- (CF 2 -CHR 1 -O-R 2 -O-CHR 1 -CF 2 -O-CH 2 R 3 CH 2 -O) a -CF 2 -CHR 1 -O-R 2 -O-CHR 1 -CF 2 -O-CH 2 R 3 CH 2 -O-COR 4 ...
• R 1 has independently, and the fluorine atom, the hydrogen atom, or the number of carbon atoms in which the hydrogen atom may be substituted by the fluorine atom is allowed. Represents 1 to 3 monovalent hydrocarbon groups.
• R 2 may independently contain a ring structure or a branched structure, may contain an ether bond, and may contain hydrogen.
• R 3 may independently contain a single bond, an ether bond, or a ring structure or a branched structure, or may contain an ether bond.
• R 4 may independently contain a ring structure or a branched structure, may contain an ether bond, and may have a hydrogen atom substituted with a fluorine atom. It represents a monovalent hydrocarbon group of the number 2 to 20.
• each of R 5 independently may contain a ring structure or a branched structure, may contain an ether bond, and may have a hydrogen atom substituted with a fluorine atom. It represents a monovalent hydrocarbon group of the number 1 to 20.
• 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
• the monovalent hydrocarbon group represented by R 1 represents a perfluoroylated monovalent perfluorohydrocarbon group having 1 to 3 carbon atoms.
• RF2 is a divalent perfluorocarbonated product having 1 to 20 carbon atoms in which a divalent hydrocarbon group represented by R2 is perfluorolated independently of each other. Represents a hydrogen group.
• RF3 independently represents a single bond when R 3 is a single bond, and represents an ether bond when R 3 is an ether bond.
• R 3 is a divalent hydrocarbon group
• the divalent hydrocarbon group represented by R 3 represents a perfluoroylated divalent perfluorohydrocarbon group having 1 to 20 carbon atoms.
• RF4 independently represents a divalent perfluorohydrocarbon group having 2 to 20 carbon atoms in which a divalent hydrocarbon group represented by R4 is perfluorolated.
• a represents an integer of 0 or 1 or more, and a in the general formulas (3) to (6) all represent the same value.
• Fluorination of the fluorine-containing diacyloxypolyether compound represented by the general formula (4) is introduced into a solvent by introducing a fluorine gas and a fluorine-containing diacyloxypolyether compound represented by the general formula (4) into a solvent.
• the introduction rate of the fluorine gas on the molar basis is the general formula (4).
• the introduction rate of the fluorine-containing diacyloxypolyether compound represented by 4) on a molar basis can be replaced with a fluorine atom by the fluorine gas contained in the fluorine-containing diacyloxypolyether compound represented by the general formula (4).
• the esterification of the hydroxyl group contained in the fluorine-containing dihydroxypolyether compound represented by the general formula (3) is represented by the acid fluoride represented by the following general formula (7) by the general formula (3).
• R 4 COF ... (7)
• R 4 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.
• the number of carbon atoms is 2 to 20.
• ⁇ 7> The method for producing a fluorine-containing polyether compound according to any one of ⁇ 1> to ⁇ 6>, wherein a in the general formula (3) to the general formula (6) is an integer of 1 or more. .. ⁇ 8>
• the reaction temperature at the time of reacting the fluorine-containing divinyl ether compound represented by the general formula (1) with the diol compound represented by the general formula (2) is 80 ° C to 160 ° C. 1>
• R 1 is a monovalent having 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. Represents the hydrocarbon group of.
• R 2 may independently contain a ring structure or a branched structure, may contain an ether bond, and the hydrogen atom is replaced by a fluorine atom.
• R 3 may independently contain a single bond, an ether bond, or a ring structure or a branched structure, or may contain an ether bond.
• a represents 0 or an integer of 1 or more.
• the fluorine-containing divinyl ether compound represented by the following general formula (1) and the diol compound represented by the following general formula (2) are combined with 1 mol of the fluorine-containing divinyl ether compound represented by the following general formula (1).
• the diol compound represented by the following general formula (2) was reacted at a ratio of more than 1 mol to produce a fluorine-containing dihydroxypolyether compound represented by the following general formula (3).
• R 4 CO-O-CH 2 R 3 CH 2 -O- (CF 2 -CHR 1 -O-R 2 -O-CHR 1 -CF 2 -O-CH 2 R 3 CH 2 -O) a -CF 2 -CHR 1 -O-R 2 -O-CHR 1 -CF 2 -O-CH 2 R 3 CH 2 -O-COR 4 ... (4)
• R 1 has independently, and the fluorine atom, the hydrogen atom, or the number of carbon atoms in which the hydrogen atom may be substituted by the fluorine atom is allowed. Represents 1 to 3 monovalent hydrocarbon groups.
• R 2 may independently contain a ring structure or a branched structure, may contain an ether bond, and may contain hydrogen.
• R 3 may independently contain a single bond, an ether bond, or a ring structure or a branched structure, or may contain an ether bond.
• R 4 may independently contain a ring structure or a branched structure, may contain an ether bond, and may have a hydrogen atom substituted with a fluorine atom. It represents a monovalent hydrocarbon group of the number 2 to 20.
• a represents an integer of 0 or 1 or more, and a in the general formula (3) and the general formula (4) both show the same value.
• the fluorine-containing divinyl ether compound represented by the following general formula (1) and the diol compound represented by the following general formula (2) are combined with 1 mol of the fluorine-containing divinyl ether compound represented by the following general formula (1).
• the diol compound represented by the following general formula (2) was reacted at a ratio of more than 1 mol to produce a fluorine-containing dihydroxypolyether compound represented by the following general formula (3).
• the hydroxyl group contained in the fluorine-containing dihydroxypolyester compound represented by the following general formula (3) is esterified to produce a fluorine-containing diacyloxypolyether compound represented by the following general formula (4).
• a method for producing a fluorine-containing polyether compound which comprises fluorinating a fluorine-containing diacyloxypolyether compound represented by the following general formula (4) to produce a perfluorodiacyloxypolyether compound represented by the following general formula (5).
• R 4 CO-O-CH 2 R 3 CH 2 -O- (CF 2 -CHR 1 -O-R 2 -O-CHR 1 -CF 2 -O-CH 2 R 3 CH 2 -O) a -CF 2 -CHR 1 -O-R 2 -O-CHR 1 -CF 2 -O-CH 2 R 3 CH 2 -O-COR 4 ...
• R 1 has independently, and the fluorine atom, the hydrogen atom, or the number of carbon atoms in which the hydrogen atom may be substituted by the fluorine atom is allowed. Represents 1 to 3 monovalent hydrocarbon groups.
• R 2 may independently contain a ring structure or a branched structure, may contain an ether bond, and may contain hydrogen.
• R 3 may independently contain a single bond, an ether bond, or a ring structure or a branched structure, or may contain an ether bond.
• R 4 may independently contain a ring structure or a branched structure, may contain an ether bond, and may have a hydrogen atom substituted with a fluorine atom. It represents a monovalent hydrocarbon group of the number 2 to 20.
• 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 is monovalent.
• the monovalent hydrocarbon group represented by R 1 represents a perfluoroylated monovalent perfluorohydrocarbon group having 1 to 3 carbon atoms.
• RF2 independently represents a divalent perfluorohydrocarbon group having 1 to 20 carbon atoms in which a divalent hydrocarbon group represented by R2 is perfluorolated.
• R F 3 independently represents a single bond when R 3 is a single bond, represents an ether bond when R 3 is an ether bond, and R 3 is divalent.
• the divalent hydrocarbon group represented by R3 represents a perfluoroylated divalent perfluorohydrocarbon group having 1 to 20 carbon atoms.
• RF4 independently represents a divalent perfluorohydrocarbon group having 2 to 20 carbon atoms in which a divalent hydrocarbon group represented by R4 is perfluorolated.
• a represents an integer of 0 or 1 or more, and a in the general formulas (3) to (5) all show the same value.
• a method for producing a fluorine-containing polyether compound which has functional groups at both ends and has few restrictions when selecting a structural unit.
• 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 examples.
• 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 the perfluorocycloalkane in which all the hydrogen atoms of the cycloalkane are replaced with the fluorine atom but also a part of the hydrogen atom is replaced with the fluorine atom in the description of "fluorocycloalkane” and the like. Cycloalkanes are 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 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
• it becomes -CF 2 -CF 2- when -C ⁇ C- is perfluorolated, it becomes -CF 2 -CF 2- .
• a hydrogen atom that can be fluorinated 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
• the method for producing the first fluorine-containing polyether compound of the present disclosure (hereinafter, may be referred to as the first production method of the present disclosure) is a fluorine-containing divinyl ether compound represented by the following general formula (1) (hereinafter, may be referred to as the first production method of the present disclosure).
• a compound of formula (1) may be referred to as a compound of formula (1)
• a diol compound represented by the following general formula (2) hereinafter, may be referred to as a compound of formula (2)).
• the compound of the formula (2) is reacted with 1 mol at a ratio of more than 1 mol, and the fluorine-containing dihydroxypolyester compound represented by the following general formula (3) (hereinafter, may be referred to as a compound of the formula (3)).
• the fluorine-containing dihydroxypolyester compound represented by the following general formula (3) (hereinafter, may be referred to as a compound of the formula (3)).
• the hydroxyl group contained in the compound of the formula (3) is esterified to obtain a fluorine-containing diacyloxypolyether compound represented by the following general formula (4) (hereinafter, may be referred to as a compound of the formula (4)).
• the compound of the formula (4) is fluorinated to produce a perfluorodiacyloxypolyether compound represented by the following general formula (5) (hereinafter, may be referred to as a compound of the formula (5)), and the formula (5) is produced.
• a fluorine-containing dialkoxycarbonylpolyether compound represented by the following general formula (6) (hereinafter, may be referred to as a compound of formula (6)) is produced by allowing an alcohol to act on the compound.
• R 4 CO-O-CH 2 R 3 CH 2 -O- (CF 2 -CHR 1 -O-R 2 -O-CHR 1 -CF 2 -O-CH 2 R 3 CH 2 -O) a -CF 2 -CHR 1 -O-R 2 -O-CHR 1 -CF 2 -O-CH 2 R 3 CH 2 -O-COR 4 ...
• R 1 has independently, and the fluorine atom, the hydrogen atom, or the hydrogen atom may be substituted with the fluorine atom.
• R 2 may independently contain a ring structure or a branched structure, may contain an ether bond, and may contain hydrogen.
• R 3 may independently contain a single bond, an ether bond, or a ring structure or a branched structure, or may contain an ether bond.
• R 4 may independently contain a ring structure or a branched structure, may contain an ether bond, and may have a hydrogen atom substituted with a fluorine atom. It represents a monovalent hydrocarbon group of the number 2 to 20.
• each of R 5 independently may contain a ring structure or a branched structure, may contain an ether bond, and may have a hydrogen atom substituted with a fluorine atom. It represents a monovalent hydrocarbon group of the number 1 to 20.
• 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
• the monovalent hydrocarbon group represented by R 1 represents a perfluoroylated monovalent perfluorohydrocarbon group having 1 to 3 carbon atoms.
• RF2 is a divalent perfluorocarbonated product having 1 to 20 carbon atoms in which a divalent hydrocarbon group represented by R2 is perfluorolated independently of each other. Represents a hydrogen group.
• RF3 independently represents a single bond when R 3 is a single bond, and represents an ether bond when R 3 is an ether bond.
• R 3 is a divalent hydrocarbon group
• the divalent hydrocarbon group represented by R 3 represents a perfluoroylated divalent perfluorohydrocarbon group having 1 to 20 carbon atoms.
• RF4 independently represents a divalent perfluorohydrocarbon group having 2 to 20 carbon atoms in which a divalent hydrocarbon group represented by R4 is perfluorolated.
• a represents an integer of 0 or 1 or more, and a in the general formulas (3) to (6) all represent the same value.
• the present disclosure it is possible to provide a method for producing a fluorine-containing polyether compound which has functional groups at both ends and has few restrictions when selecting a structural unit.
• the reason why the above effect is exhibited is presumed to be, for example, as follows, but is not limited to this.
• the compound of the formula (1) and the compound of the formula (2) are used as the monomer which is a raw material of the fluorine-containing polyether compound.
• the compound of the formula (2) when the compound of the formula (1) and the compound of the formula (2) are reacted to obtain the compound of the formula (3), the compound of the formula (2) is obtained with respect to 1 mol of the compound of the formula (1). Is reacted at a ratio of more than 1 mol, so that a hydroxyl group is likely to be generated at the terminal of the compound of the formula (3).
• ester groups can be generated at both ends of the fluorine-containing polyether compound obtained by the first production method of the present disclosure. Therefore, unlike the methods described in Patent Documents 2 and 3, in the first production method of the present disclosure, both ends of the fluorine-containing polyether compound can be functionalized.
• the compound of formula (1) used in the present disclosure is a specific fluorine-containing divinyl ether compound represented by the following general formula (1).
• R 1 independently represents a monovalent hydrocarbon group having 1 to 3 carbon atoms in which a fluorine atom, a hydrogen atom, or a hydrogen atom may be substituted with a fluorine atom. From the viewpoint of lubricity, it is preferable that at least one of R 1 is a hydrogen atom, and it is more preferable that both of R 1 are hydrogen atoms.
• R 2 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 20 carbon atoms.
• the number of carbon atoms of the divalent hydrocarbon group represented by R2 is preferably 15 or less, more preferably 10 or less.
• the number of carbon atoms of the divalent hydrocarbon group represented by R2 is preferably 3 or more, and more preferably 4 or more, from the viewpoint of preventing a cyclization reaction.
• 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 represented by Ra include a cyclobutanediyl group, a fluorocyclobutanediyl group, a cyclopentanediyl group, a fluorocyclopentanediyl group, a cyclohexanediyl group, and a fluorocyclohexanediyl group. Examples thereof include an adamantandiyl group and a norbornandyl group.
• 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.
• Examples of the divalent hydrocarbon group represented by R b include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a fluoromethylene group, a fluoroethylene group, a fluorotrimethylene group, a fluorotetramethylene group and the like. Be done.
• * represents a bonding portion with an oxygen atom.
• Examples of the divalent hydrocarbon group represented by the general formula (A) 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).
• the group represented by Ra in the general formulas (B) and (C) is the same as the above general formula ( A ).
• the group represented by R b in the general formula (D) is the same as that in 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.
• Examples of the divalent hydrocarbon group represented by R c include a methylene group, an ethylene group, a trimethylene group, a propyridene group, an isopropyridene group, a fluoromethylene group, a fluoroethylene group, a fluorotrimethylene group and a fluoropropyridene group. , Fluoroisopropylidene group and the like.
• R d represents a cycloalkane-1,1-diyl group having 3 to 6 carbon atoms.
• * represents a bonding portion with an oxygen atom.
• Examples of the group satisfying any of the general formulas (B) to (D) include, but are not limited to, the following groups.
• the compound of formula (2) used in the present disclosure is a specific diol compound represented by the following general formula (2). HO-CH 2 R 3 CH 2 -OH ... (2)
• R 3 may contain a single bond, an ether bond, a ring structure or a branched structure, may contain an ether bond, or the hydrogen atom may be substituted with a fluorine atom.
• the acidity (pKa) of the compound of the formula (2) is preferably 8 to 18, and more preferably 9 to 14. When the pKa of the compound of the formula (2) is within the above numerical range, the reaction with the compound of the formula (1) proceeds satisfactorily.
• 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.).
• a divalent hydrocarbon group represented by "-CH 2 R 3 CH 2- " including R 3 (hereinafter referred to as "-CH 2 R 3 CH 2- " group may be referred to.
• the number of carbon atoms in (1) is preferably 15 or less, more preferably 10 or less.
• the carbon number of the "-CH 2 R 3 CH 2- " group is preferably 2 or more, and more preferably 3 or more, from the viewpoint of synthetic handling.
• Examples of the "-CH 2 R 3 CH 2- " group include an alkylene group such as an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group and a hexamethylene group, a fluorotrimethylene group, a fluorotetramethylene group and a fluoropenta. Fluoroalkylene groups such as a methylene group and a fluorohexamethylene group, and the like can be mentioned. However, when the "-CH 2 R 3 CH 2- " group is a fluoroalkylene group, both ends of the fluoroalkylene group have a methylene structure.
• the "-CH 2 R 3 CH 2- " group may be a group represented by the following general formula (X'). * -CH 2 R X1- (OR X2 ) n1 -OR X1 CH 2- * ... (X')
• RX1 represents a single bond, a methylene group, an ethylene group, a methylmethylene group, a fluoromethylene group, a fluoroethylene group, and a fluoromethylmethylene group.
• RX2 represents an ethylene group, a trimethylene group, a propylene group, a fluoroethylene group, a fluorotrimethylene group, or a fluoropropylene group.
• n1 represents 0 or an integer greater than or equal to 1.
• * represents a bonding portion with an oxygen atom.
• the "-CH 2 R 3 CH 2- " group may be a group represented by the following general formula (A'). * -R b2 -OR a -OR b2- * ... (A')
• Ra represents a cycloalkanediyl group, a fluorocycloalkanediyl group, or an arylene group, and specific examples thereof and the like are the same as in the case of the general formula (A).
• R b2 independently represents a divalent hydrocarbon group having 1 to 10 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom.
• R b2 is a divalent hydrocarbon group having 2 to 10 carbon atoms in which a hydrogen atom is substituted with a fluorine atom
• the end on the * side of R b2 has a methylene structure.
• R b2 is a hydrocarbon group having 1 carbon atom
• R b2 is a methylene group.
• * represents a bonding portion with an oxygen atom.
• Examples of the divalent hydrocarbon group represented by the general formula (A') include, but are not limited to, the following groups.
• the "-CH 2 R 3 CH 2- " group may be a group represented by the following general formula (B') or (D'). * -R c2 -R a -R c2- * ... (B') * -R b2 -R d -R b2- * ... (D')
• the group represented by Ra in the general formula (B') is the same as that in the general formula ( A ).
• R c2 independently represents a linear alkylene group having 1 to 10 carbon atoms, preferably a linear alkylene group having 1 to 5 carbon atoms, and preferably 1 to 2 carbon atoms.
• the straight chain alkylene group of is more preferable.
• R b2 in the general formula (D') is the same as the above general formula (A'). Further, in the general formula (D'), R d represents a cycloalkane-1,1-diyl group having 3 to 6 carbon atoms. In the general formula (B') and the general formula (D'), * represents a bonding portion with an oxygen atom.
• Examples of the group satisfying either the general formula (B') or the general formula (D') include, but are not limited to, the following groups.
• a represents 0 or an integer of 1 or more, preferably an integer of 1 or more, more preferably an integer of 3 or more, and further preferably an integer of 5 or more. Further, a is preferably an integer of 20 or less, more preferably an integer of 15 or less, and even more preferably an integer of 12 or less.
• the reaction between the compound of formula (1) and the compound of formula (2) may be carried out in a solvent or in a solvent-free state without using a solvent.
• the solvent is preferably a fluorinated organic solvent, and examples thereof include a fluorinated alkane, a fluorinated aromatic compound, and a fluoroalkyl ether. ..
• the ratio of the compound of the formula (1) to the compound of the formula (2) is preferably adjusted according to the molecular weight of the target fluorine-containing polyether compound, but from the viewpoint of controlling the molecular weight, the ratio is relative to 1 mol of the compound of the formula (1).
• the compound of the formula (2) is preferably 1.01 mol or more, more preferably 1.10 mol or more.
• the ratio of the compound of the formula (1) to the compound of the formula (2) is based on 1 mol of the compound of the formula (1) from the viewpoint of saving extra raw materials while controlling the molecular weight of the target fluorine-containing polyether compound.
• the compound of the formula (2) is preferably 2.00 mol or less, more preferably 1.90 mol or less, further preferably 1.70 mol or less, and particularly preferably 1.50 mol or less.
• 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 formula (1) with the compound of formula (2) in the presence of an alkaline catalyst, the molecular weight and yield of the produced compound of formula (3) can be further improved.
• the alkaline catalyst include sodium hydroxide, potassium hydroxide, sodium carbonate, cesium fluoride, potassium carbonate and the like, and potassium carbonate is preferable from the viewpoint of the molecular weight and yield of the compound of the formula (3).
• 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 time of the compound of the formula (1) and the compound of the formula (2) is preferably 1 hour to 72 hours, more preferably 2 hours to 48 hours.
• the compound of the formula (3) may be produced by a batch method or a continuous method, and a known method can be appropriately adopted.
• the compound of formula (3) is produced by a batch method, for example, the compound of formula (2) may be previously contained in a reactor and the compound of formula (1) may be directly added into the reactor, or the compound of formula (1) may be added directly to the reactor.
• a diluted solution of the compound may be added.
• the addition of the compound of the formula (1) to the compound of the formula (2) is carried out by the formula (2).
• the reaction solution After reacting the compound of formula (1) and the compound of formula (2), at least one selected from an organic solvent, water and an aqueous solution for adjusting to an appropriate acidity is added to the reaction solution and separated. , The organic phase may be concentrated to obtain the compound of formula (3). Further, the reaction crude liquid obtained by concentrating the organic phase may be purified to obtain the compound of the formula (3).
• the combination of the formula (1) compound and the formula (2) compound used when producing the formula (3) compound is not particularly limited.
• the compound of formula (1) may be selected from the perfluorodivinyl ether compound.
• the compound of formula (4) is produced by esterifying the hydroxyl group contained in the compound of formula (3).
• R 4 CO-O-CH 2 R 3 CH 2 -O- (CF 2 -CHR 1 -O-R 2 -O-CHR 1 -CF 2 -O-CH 2 R 3 CH 2 -O) a -CF 2 -CHR 1 -O-R 2 -O-CHR 1 -CF 2 -O-CH 2 R 3 CH 2 -O-COR 4 ...
• the details of R 1 , R 2 , R 3 and a in the general formula (4) are as described above. In the general formula (4), the details of R4 will be described later together with the description of acid fluoride.
• the method for esterifying the hydroxyl group contained in the compound of the formula (3) is not particularly limited, and a conventionally known reaction may be used.
• a method of allowing a carboxylic acid compound to act on a hydroxyl group a method of allowing a carboxylic acid anhydride to act on a hydroxyl group, a method of allowing an acid halide to act on a hydroxyl group, and the like can be mentioned.
• a method of allowing an acid halide to act on the hydroxyl group is preferable from the viewpoint of high reactivity, a method of allowing an acid halide to act on the hydroxyl group is more preferable, and the acid fluoride is described below.
• a method in which an acid halide represented by the general formula (7) (hereinafter, may be referred to as a compound of the formula (7)) is allowed to act on the compound of the formula (3) is more preferable.
• R 4 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 2 to 20 carbon atoms.
• the carbon number of the monovalent hydrocarbon group represented by R4 is preferably 20 or less, more preferably 10 or less, from the viewpoint of ease of purification.
• the carbon number of the monovalent hydrocarbon group represented by R4 is preferably 3 or more, and more preferably 4 or more, from the viewpoint of suppressing side reactions during fluorination.
• the fluorine atom content is preferably 50 mol% or more, more preferably 75 mol% or more, and 100 mol% ( Perfluorohydrocarbon groups) are more preferred.
• the fluorine atom content is the ratio at which the hydrogen atom contained in the hydrocarbon group is replaced with the fluorine atom.
• the esterification of the hydroxyl group contained in the compound of the formula (3) may be carried out in a solvent or in a solvent-free state without using a solvent.
• the solvent is preferably a fluorinated organic solvent, and examples thereof include fluorinated alkanes, fluorinated aromatic compounds, and fluoroalkyl ethers.
• the compound of formula (7) When the compound of formula (7) is allowed to act on the compound of formula (3), it is preferably carried out in the presence of a catalyst. By allowing the compound of formula (7) to act on the compound of formula (3) in the presence of a catalyst, the yield of the produced compound of formula (4) can be further improved.
• the catalyst include sodium fluoride, triethylamine and the like, and sodium fluoride is preferable from the viewpoint of ease of post-treatment.
• the reaction temperature is preferably ⁇ 10 ° C. to 100 ° C., more preferably 0 ° C. to 60 ° C. from the viewpoint of the yield of the compound of the formula (4).
• the reaction time between the compound of formula (3) and the compound of formula (7) is 1 hour to 40 hours from the viewpoint of the yield of the compound of formula (4). Is preferable, and 2 hours to 20 hours are more preferable.
• the reaction pressure when reacting the compound of formula (3) with the compound of formula (7) is large from the viewpoint of the yield of the compound of formula (4). Atmospheric pressure to 2 MPa (gauge pressure) is preferable.
• the compound of the formula (4) may be produced by a batch method or a continuous method, and a known method can be appropriately adopted.
• the compound of formula (4) is produced by a batch method, for example, the compound of formula (3) may be previously contained in a reactor and the compound of formula (7) may be directly added into the reactor.
• the internal temperature of the reactor is 40 when the compound of formula (7) is added to the compound of formula (3) from the viewpoint of suppressing the generation of by-products. It is preferably performed at a rate not exceeding ° C., and more preferably performed at a rate at which the internal temperature does not exceed 20 ° C.
• hydrogen fluoride is generated by the reaction between the compound of formula (3) and the compound of formula (7), so that hydrogen fluoride is generated in the reaction system.
• a scavenger present.
• the hydrogen fluoride scavenger include alkali metal fluorides and trialkylamines.
• NaF or KF is preferable.
• the HF scavenger it is preferable to carry out the reaction at a reaction temperature at which the HF can be vaporized, and to accompany the HF with a nitrogen stream and discharge the HF out of the reaction system.
• the amount of the HF scavenger used is preferably 1 to 10 times by mole with respect to the compound of the formula (7).
• the reaction solution After allowing the compound of formula (7) to act on the compound of formula (3), at least one selected from an organic solvent, water and an aqueous solution for adjusting to an appropriate acidity is added to the reaction solution and the solution is separated.
• the reaction solution may be solid-liquid separated and then the organic phase may be concentrated to obtain the compound of formula (4). 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 (5) is produced by fluorinating the compound of formula (4).
• 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 is monovalent.
• the monovalent hydrocarbon group represented by R 1 represents a perfluoroylated monovalent perfluorohydrocarbon group having 1 to 3 carbon atoms.
• RF2 independently represents a divalent perfluorohydrocarbon group having 1 to 20 carbon atoms in which a divalent hydrocarbon group represented by R2 is perfluorolated.
• R F 3 independently represents a single bond when R 3 is a single bond, represents an ether bond when R 3 is an ether bond, and R 3 is divalent.
• the divalent hydrocarbon group represented by R3 represents a perfluoroylated divalent perfluorohydrocarbon group having 1 to 20 carbon atoms.
• RF4 independently represents a divalent perfluorohydrocarbon group having 2 to 20 carbon atoms in which a divalent hydrocarbon group represented by R4 is perfluorolated. The details of a in the general formula (5) are as described above.
• the method for fluorinating the compound of the formula (4) is not particularly limited, and can be carried out by a conventionally known method.
• fluorination can be performed by contacting the compound of formula (4) with a fluorine gas.
• the method for fluorinating the compound of the formula (4) 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 reaction yield and selectivity of the compound of the formula (5).
• 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 the compound of formula (4) and a solvent are charged into a reactor, stirring is started, and then, under a predetermined reaction temperature and reaction pressure, a fluorine gas diluted with an inert gas is continuously added to the solvent. It is a method of reacting while supplying.
• Method 2 the solvent is charged into the reactor, stirred, and then the fluorine gas diluted with the inert gas, the compound of formula (4), and the solvent are continuously mixed at a predetermined molar ratio under a predetermined reaction temperature and reaction pressure. This is a method of reacting while supplying the gas to the fluorination reaction solvent.
• 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 (4) is dissolved are mixed with the fluorine gas.
• the compound of formula (4) are continuously supplied to the flow of the solvent in the tubular reactor and mixed at a ratio of a predetermined molar ratio, and the fluorine gas and the compound of formula (4) 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 (4) 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 10% by volume to 60% by volume in the total 100% by volume of the fluorine gas and the inert gas.
• the amount of the fluorine gas used is preferably 1.1 mol to 10 mol, more preferably 1.2 mol to 5 mol, with respect to 1 mol of the hydrogen atom to be substituted with fluorine in the compound of the formula (4).
• 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 (4) 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 fluorination of the compound of the formula (4) is carried out by introducing a fluorine gas and the compound of the formula (4) into the solvent
• the molar-based introduction rate of the compound of the formula (4) 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 (4) by the number of hydrogen atoms that could be replaced by fluorine atoms by the fluorine gas contained in the compound of formula (4). 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 the formula (4) it is preferable to add a CH bond-containing compound other than the compound of the formula (4) 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 (4) existing in the solvent can be efficiently fluorinated, and the yield of the compound of the formula (5) can be improved.
• the CH bond-containing compound aromatic hydrocarbons are preferable, and benzene, toluene and the like can be mentioned.
• 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 (4). 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 inside of the system may be replaced with an inert gas such as nitrogen gas, and then the organic phase may be concentrated to obtain the compound of formula (5). Further, the reaction crude liquid obtained by concentrating the organic phase may be purified to obtain the compound of the formula (5).
• the compound of formula (6) is produced by allowing an alcohol to act on the compound of formula (5).
• the details of RF1 , RF2, RF3, RF4 and a in the general formula (6) are as described above.
• each of R 5 independently may contain a ring structure or a branched structure, may contain an ether bond, and may have a hydrogen atom substituted with a fluorine atom.
• the terminal of the compound of formula (5) is esterified to obtain the compound of formula (6).
• the alcohol acting on the compound of formula (5) is not particularly limited. Examples of the alcohol include methanol, ethanol, isopropanol and the like.
• the reaction of the compound of the formula (5) with an alcohol may be carried out in a solvent or in a solvent-free state without using a solvent.
• the solvent is preferably a fluorinated organic solvent, and examples thereof include fluorinated alkane, a fluorinated aromatic compound, and a fluoroalkyl ether.
• the amount of alcohol used for the compound of formula (5) is preferably 2 mol to 20 mol, more preferably 2.1 mol to 15 mol, still more preferably 2.2 mol to 10 mol, relative to 1 mol of the compound of formula (5).
• the reaction temperature of the compound of the formula (5) and the alcohol is preferably ⁇ 10 ° C. to 60 ° C., more preferably 0 ° C. to 40 ° C.
• the reaction time of the compound of the formula (5) with the alcohol is preferably 0.5 hours to 48 hours, more preferably 1 hour to 24 hours.
• the addition of alcohol to the compound of formula (5) should be carried out at a rate at which the internal temperature of the reactor does not exceed 40 ° C. Is preferable, and it is more preferable to carry out at a rate at which the internal temperature does not exceed 20 ° C.
• the reaction solution After reacting the compound of formula (5) with an alcohol, at least one selected from an organic 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 obtained.
• the compound of formula (6) may be obtained by concentration. Further, the reaction crude liquid obtained by concentrating the organic phase may be purified to obtain the compound of the formula (6).
• the number average molecular weight (Mn) of the compound of formula (6) obtained by the first production method of the present disclosure is preferably 1000 to 30,000, more preferably 1500 to 20000, and even more preferably 2000 to 10000. Further, the molecular weight distribution (Mw / Mn) of the compound of the formula (6) obtained by the first production method of the present disclosure is preferably 1 to 3, more preferably 1 to 2.5, still more preferably 1 to 2.
• the method for producing the second fluorine-containing polyether compound of the present disclosure (hereinafter, may be referred to as the second production method of the present disclosure) is a formula (1) compound and a formula (2) compound. 1) The compound of the formula (2) is reacted with 1 mol of the compound at a ratio of more than 1 mol to produce the compound of the formula (3).
• the details of the formula (1) to the compound (3) and the step of synthesizing the compound of the formula (3) in the second production method of the present disclosure are the same as those of the first production method of the present disclosure. Is.
• the method for producing the third fluorine-containing polyether compound of the present disclosure (hereinafter, may be referred to as the third production method of the present disclosure) is a formula (1) compound and a formula (2) compound. 1) The compound of the formula (2) is reacted with 1 mol of the compound at a ratio of more than 1 mol to produce the compound of the formula (3), and the hydroxyl group contained in the compound of the formula (3) is esterified to obtain the compound of the formula (4). It is manufactured.
• the formula (1) compound and the formula (2) compound are expressed in the formula (1).
• the compound of the formula (2) is reacted with 1 mol of the compound at a ratio of more than 1 mol to produce the compound of the formula (3), and the hydroxyl group contained in the compound of the formula (3) is esterified to obtain the compound of the formula (4). It is produced and the compound of the formula (4) is fluorinated to produce the compound of the formula (5).
• the details of the formula (1) to the compound (5) and the details of the steps for synthesizing the formula (3) to the compound (5) in the fourth production method of the present disclosure are described in the first of the present disclosure. This is the same as in the case of the manufacturing method.
• Synthesis Examples 1-1 to 3-4 are examples, and synthesis example 4 is a comparative example.
• the molar-based introduction rate of compound A-4 into the solvent is 1
• the molar-based introduction rate of fluorine gas is set to the molar-based introduction rate of compound A-4, and the fluorine contained in compound A-4.
• the rate was doubled by multiplying the number of hydrogen atoms that could be replaced by fluorine atoms by the gas.
• the CFE-419 solution of compound A-4 was completed, the CFE-419 solution of benzene (concentration: 0.1% by mass, benzene: 0.1 g) was added intermittently.
• 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 20 g (yield 94%) of compound A-5 corresponding to the compound of formula (5).
• the Mn of compound A-6 was 3700, and the Mw / Mn was 1.7.
• the obtained crude reaction solution was separated, and then the organic phase was concentrated.
• the reaction crude solution obtained by concentrating the organic phase was purified by column chromatography to obtain 25 g (yield 85%) of compound B-1 corresponding to the compound of formula (3).
• the average of a was 5.
• the Mn of compound B-4 was 4000, and the Mw / Mn was 2.
• the rate was doubled by multiplying the number of hydrogen atoms that could be replaced by fluorine atoms by the gas.
• the CFE-419 solution of compound C-2 was completed, the CFE-419 solution of benzene (concentration: 0.1% by mass, benzene: 0.1 g) was added intermittently.
• 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 44 g (yield 96%) of the compound C-3 corresponding to the compound of the formula (5).
• the average of a was 4.
• * represents a bond with an oxygen atom
• ** represents a bond with a carbon atom.

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