Method for producing fluorine-containing polyether compound

Abstract

This production method of a fluorine-containing polyether compound involves producing the compound of formula (3) by reacting the compound of expression (1) and the compound of expression (2) in a ratio such that the compound of formula (2) exceeds 1 mol per 1 mol of the compound of expression (1), esterifying, fluorinating and subsequently reacting with an alcohol to produce a fluorine-containing polyether compound in which both terminals have been functionalized. Here, R1 represents a fluorine atom, etc., R2 and R3 represent a divalent hydrocarbon group of 1-20 carbons.　(1) ... CF2=CR1-O-R2-O-CR1=CF2, (2) ... HO-CH2R3CH2-OH

Description

[Technical Field]

[0001] The present disclosure relates to a method for producing a fluorinated polyether compound. [Background technology]

[0002] Fluorine-containing polyether compounds exhibit high lubricity and water and oil repellency, and are therefore used as surface treatment agents, lubricants, and the like. Fluorine-containing polyether compounds are produced by various methods. For example, Patent Document 1 discloses a method for producing a fluorine-containing polyether compound by reacting tetrafluoroethylene with oxygen in the presence of a compound having a fluorooxy group. Furthermore, Patent Document 2 discloses the production of a fluorine-containing polyether compound by ring-opening polymerization of 2,2,3,3-tetrafluorooxetane, and the production of a halogen-containing polyether compound by chlorinating and fluorinating this fluorine-containing polyether compound. In addition, in Patent Document 3, a compound represented by CF2=CFO-CF2CF2CF2CH2OH and A 1 -OH(A 1 represents a methyl group, etc.) to form a 1 -O-(CF2CFHO-CF2CF2CF2CH2O) n+1 It is disclosed that a halogen-containing polyether compound represented by —H is produced. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] U.S. Patent No. 5,258,110 [Patent Document 2] U.S. Patent No. 4,845,268 [Patent Document 3] International Publication No. 2013 / 121984 Summary of the Invention [Problem to be solved by the invention]

[0004] In the method described in Patent Document 1, perfluoropolyether (PFPE) in which both ends are esters or reduced alcohols can be obtained by introducing tetrafluoroethylene and oxygen into a solvent. However, in the method described in Patent Document 1, the structural units contained in PFPE are mainly random polymers such as (CF2-CF2O) and (CF2O), and the structural units cannot be freely selected. Furthermore, the structural units contained in the PFPE cannot be freely selected in the method described in Patent Document 2. Furthermore, it may be difficult to functionalize both ends of the PFPE. Furthermore, in the method for producing PFPE described in Patent Document 3, it is difficult to functionalize both ends of PFPE.

[0005] The present disclosure has been made in view of the above-mentioned demands, and an object of the present disclosure is to provide a method for producing a fluorinated polyether compound which has functional groups at both terminals and which has few restrictions on the selection of structural units. [Means for solving the problem]

[0006] Specific means for achieving the above object are as follows. <1> A fluorine-containing divinyl ether compound represented by the following general formula (1) is reacted with a diol compound represented by the following general formula (2) in a ratio of more than 1 mol of the diol compound represented by the following general formula (2) per 1 mol of the fluorine-containing divinyl ether compound represented by the following general formula (1), to produce a fluorine-containing dihydroxypolyether compound represented by the following general formula (3), esterifying a hydroxyl group contained in a fluorinated dihydroxypolyether compound represented by the following general formula (3) to produce a fluorinated diacyloxypolyether compound represented by the following general formula (4); A fluorinated diacyloxy polyether compound represented by the following general formula (4) is fluorinated to produce a perfluorodiacyloxy polyether compound represented by the following general formula (5), A method for producing a fluorine-containing polyether compound, comprising reacting a perfluorodiacyloxy polyether compound represented by the following general formula (5) with an alcohol to produce a fluorine-containing dialkoxycarbonyl polyether compound represented by the following general formula (6): CF2=CR 1 -OR 2 -O-CR 1 =CF2 (1) HO-CH2R 3 CH2-OH···(2) HO-CH2R 3 CH2-O-(CF2-CHR 1 -OR 2 -O-CHR 1 -CF2-O-CH2R 3 CH2-O) a -CF2-CHR 1 -OR 2 -O-CHR 1 -CF2-O-CH2R 3 CH2-OH···(3) R 4 CO-O-CH2R 3 CH2-O-(CF2-CHR 1 -OR 2 -O-CHR 1 -CF2-O-CH2R 3 CH2-O) a -CF2-CHR 1 -OR 2 -O-CHR 1 -CF2-O-CH2R 3 CH2-O-COR 4 ···(4) R F4 CO-O-CF2R F3 CF2-O-(CF2-CFR F1 -OR F2 -O-CFR F1 -CF2-O-CF2R F3 CF2-O) a -CF2-CFR F1 -ORF2 -O-CFR F1 -CF2-O-CF2R F3 CF2-O-COR F4 ···(5) R 5 -O-COR F3 CF2-O-(CF2-CFR F1 -OR F2 -O-CFR F1 -CF2-O-CF2R F3 CF2-O) a -CF2-CFR F1 -OR F2 -O-CFR F1 -CF2-O-CF2R F3 CO-OR 5 ···(6) (In general formula (1), general formula (3) and general formula (4), R 1 each independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having 1 to 3 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom. In general formula (1), general formula (3) and general formula (4), R 2 each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may have a ring structure or a branched structure, which may have an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom. In general formulas (2) to (4), R 3 each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain a single bond, an ether bond, or a ring structure or a branched structure, and which may contain an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom. In general formula (4), R 4 each independently represents a monovalent hydrocarbon group having 2 to 20 carbon atoms, which may have a ring structure or a branched structure, which may have an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom. In general formula (6), R 5 each independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, which may have a ring structure or a branched structure, which may have an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom. In the general formula (5) and the general formula (6), R F1 are each independently R 1 represents a fluorine atom, and R 1 When is a hydrogen atom, R represents a fluorine atom. 1 When is a monovalent hydrocarbon group, R 1 represents a perfluorinated monovalent perfluorohydrocarbon group having 1 to 3 carbon atoms. In the general formula (5) and the general formula (6), R F2 are each independently R 2 represents a perfluorinated divalent perfluorohydrocarbon group having 1 to 20 carbon atoms. In the general formula (5) and the general formula (6), R F3 are each independently R 3 represents a single bond, and R 3 represents an ether bond, and R 3 When is a divalent hydrocarbon group, R 3 represents a perfluorinated divalent perfluorohydrocarbon group having 1 to 20 carbon atoms. In general formula (5), R F4 are each independently R 4 represents a perfluorinated divalent perfluorohydrocarbon group having 2 to 20 carbon atoms. In general formulas (3) to (6), a represents 0 or an integer of 1 or more, and a in general formulas (3) to (6) all have the same value. <2> The reaction of the fluorine-containing divinyl ether compound represented by the general formula (1) with the diol compound represented by the general formula (2) is carried out in the presence of an alkali catalyst. <1> 1. A method for producing a fluorine-containing polyether compound according to claim 1. <3> In the fluorination of the fluorine-containing diacyloxy polyether compound represented by the general formula (4), fluorine gas is used in a ratio of 1.1 mol to 10 mol per 1 mol of hydrogen atoms to be substituted with fluorine in the fluorine-containing diacyloxy polyether compound represented by the general formula (4). <1> or <2> 1. A method for producing a fluorine-containing polyether compound according to claim 1. <4> fluorination of the fluorine-containing diacyloxy polyether compound represented by the general formula (4) is carried out by introducing fluorine gas and the fluorine-containing diacyloxy polyether compound represented by the general formula (4) into a solvent, When the molar introduction rate of the fluorine-containing diacyloxy polyether compound represented by the general formula (4) into the solvent is taken as 1, the molar introduction rate of the fluorine gas is in the range of 1 to 10 times the rate obtained by multiplying the molar introduction rate of the fluorine-containing diacyloxy polyether compound represented by the general formula (4) by the number of hydrogen atoms that can be substituted with fluorine atoms by the fluorine gas, which are contained in the fluorine-containing diacyloxy polyether compound represented by the general formula (4). <1> ~ <3> 10. A method for producing the fluorine-containing polyether compound according to any one of claims 1 to 9. <5> The esterification of the hydroxyl groups contained in the fluorinated dihydroxypolyether compound represented by the general formula (3) is carried out by allowing an acid fluoride represented by the following general formula (7) to act on the fluorinated dihydroxypolyether compound represented by the general formula (3): <1> ~ <4> 10. A method for producing the fluorine-containing polyether compound according to any one of claims 1 to 9. R 4 COF···(7) (In general formula (7), R 4 represents a monovalent hydrocarbon group having 2 to 20 carbon atoms, which may contain a ring structure or a branched structure, may contain an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom. <6> The acidity of the diol compound represented by the general formula (2) is 8 to 18. <1> ~ <5> 10. A method for producing the fluorine-containing polyether compound according to any one of claims 1 to 9. <7> In the general formulas (3) to (6), a is an integer of 1 or more. <1> ~ <6> 10. A method for producing the fluorine-containing polyether compound according to any one of claims 1 to 9. <8> the reaction temperature when 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> ~ <7> 10. A method for producing the fluorine-containing polyether compound according to any one of claims 1 to 9. <9> A method for producing a fluorine-containing polyether compound, comprising reacting a fluorine-containing divinyl ether compound represented by the following general formula (1) with a diol compound represented by the following general formula (2) in a ratio of more than 1 mol of the diol compound represented by the following general formula (2) to 1 mol of the fluorine-containing divinyl ether compound represented by the following general formula (1), to produce a fluorine-containing dihydroxypolyether compound represented by the following general formula (3): CF2=CR 1 -OR 2 -O-CR 1 =CF2 (1) HO-CH2R 3 CH2-OH···(2) HO-CH2R 3 CH2-O-(CF2-CHR 1 -OR 2 -O-CHR 1 -CF2-O-CH2R 3 CH2-O) a -CF2-CHR 1 -OR 2 -O-CHR 1 -CF2-O-CH2R 3 CH2-OH···(3) (In general formula (1) and general formula (3), R 1 each independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having 1 to 3 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom. In general formula (1) and general formula (3), R 2 each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may have a ring structure or a branched structure, which may have an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom. In general formula (2) and general formula (3), R 3 each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain a single bond, an ether bond, or a ring structure or a branched structure, and which may contain an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom. In the general formula (3), a represents 0 or an integer of 1 or more. <10> A fluorine-containing divinyl ether compound represented by the following general formula (1) is reacted with a diol compound represented by the following general formula (2) in a ratio of more than 1 mol of the diol compound represented by the following general formula (2) per 1 mol of the fluorine-containing divinyl ether compound represented by the following general formula (1), to produce a fluorine-containing dihydroxypolyether compound represented by the following general formula (3), A method for producing a fluorine-containing polyether compound, comprising esterifying a hydroxyl group contained in a fluorine-containing dihydroxypolyether compound represented by the following general formula (3) to produce a fluorine-containing diacyloxypolyether compound represented by the following general formula (4): CF2=CR 1 -OR 2 -O-CR 1 =CF2 (1) HO-CH2R 3 CH2-OH···(2) HO-CH2R 3 CH2-O-(CF2-CHR 1 -OR 2 -O-CHR 1 -CF2-O-CH2R 3 CH2-O) a -CF2-CHR 1 -OR 2 -O-CHR 1 -CF2-O-CH2R 3 CH2-OH···(3) R 4 CO-O-CH2R 3 CH2-O-(CF2-CHR 1 -OR 2 -O-CHR 1 -CF2-O-CH2R 3 CH2-O) a -CF2-CHR1 -OR 2 -O-CHR 1 -CF2-O-CH2R 3 CH2-O-COR 4 ···(4) (In general formula (1), general formula (3) and general formula (4), R 1 each independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having 1 to 3 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom. In general formula (1), general formula (3) and general formula (4), R 2 each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may have a ring structure or a branched structure, which may have an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom. In general formulas (2) to (4), R 3 each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain a single bond, an ether bond, or a ring structure or a branched structure, and which may contain an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom. In general formula (4), R 4 each independently represents a monovalent hydrocarbon group having 2 to 20 carbon atoms, which may have a ring structure or a branched structure, which may have an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom. In general formula (3) and general formula (4), a represents 0 or an integer of 1 or more, and a in general formula (3) and general formula (4) both have the same value. <11> A fluorine-containing divinyl ether compound represented by the following general formula (1) is reacted with a diol compound represented by the following general formula (2) in a ratio of more than 1 mol of the diol compound represented by the following general formula (2) per 1 mol of the fluorine-containing divinyl ether compound represented by the following general formula (1), to produce a fluorine-containing dihydroxypolyether compound represented by the following general formula (3), esterifying a hydroxyl group contained in a fluorinated dihydroxypolyether compound represented by the following general formula (3) to produce a fluorinated diacyloxypolyether compound represented by the following general formula (4); A method for producing a fluorinated polyether compound, comprising fluorinating a fluorinated diacyloxy polyether compound represented by the following general formula (4) to produce a perfluorodiacyloxy polyether compound represented by the following general formula (5): CF2=CR 1 -OR 2 -O-CR 1 =CF2 (1) HO-CH2R 3 CH2-OH···(2) HO-CH2R 3 CH2-O-(CF2-CHR 1 -OR 2 -O-CHR 1 -CF2-O-CH2R 3 CH2-O) a -CF2-CHR 1 -OR 2 -O-CHR 1 -CF2-O-CH2R 3 CH2-OH···(3) R 4 CO-O-CH2R 3 CH2-O-(CF2-CHR 1 -OR 2 -O-CHR 1 -CF2-O-CH2R 3 CH2-O) a -CF2-CHR 1 -OR 2 -O-CHR 1 -CF2-O-CH2R 3 CH2-O-COR 4 ···(4) R F4 CO-O-CF2R F3 CF2-O-(CF2-CFR F1 -OR F2 -O-CFR F1 -CF2-O-CF2R F3 CF2-O) a -CF2-CFR F1 -OR F2 -O-CFR F1 -CF2-O-CF2R F3 CF2-O-COR F4 ···(5) (In general formula (1), general formula (3) and general formula (4), R 1 each independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having 1 to 3 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom. In general formula (1), general formula (3) and general formula (4), R 2 each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may have a ring structure or a branched structure, which may have an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom. In general formulas (2) to (4), R 3 each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain a single bond, an ether bond, or a ring structure or a branched structure, and which may contain an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom. In general formula (4), R 4 each independently represents a monovalent hydrocarbon group having 2 to 20 carbon atoms, which may have a ring structure or a branched structure, which may have an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom. In general formula (5), R F1 are each independently R 1 represents a fluorine atom, and R 1 When is a hydrogen atom, R represents a fluorine atom. 1 When is a monovalent hydrocarbon group, R 1 represents a perfluorinated monovalent perfluorohydrocarbon group having 1 to 3 carbon atoms. In general formula (5), R F2 are each independently R 2 represents a perfluorinated divalent perfluorohydrocarbon group having 1 to 20 carbon atoms. In general formula (5), R F3 are each independently R 3 represents a single bond, and R 3 represents an ether bond, and R 3 When is a divalent hydrocarbon group, R 3represents a perfluorinated divalent perfluorohydrocarbon group having 1 to 20 carbon atoms. In general formula (5), R F4 are each independently R 4 represents a perfluorinated divalent perfluorohydrocarbon group having 2 to 20 carbon atoms. In general formulas (3) to (5), a represents 0 or an integer of 1 or more, and a in general formulas (3) to (5) all have the same value. [Effects of the Invention]

[0007] According to the present disclosure, there is provided a method for producing a fluorinated polyether compound which has functional groups at both ends and which has few restrictions on the selection of structural units. DETAILED DESCRIPTION OF THE INVENTION

[0008] Hereinafter, embodiments for carrying out the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments. In the following embodiments, components (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and do not limit the present disclosure.

[0009] In the present disclosure, numerical ranges indicated using "to" include the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In the numerical ranges described in stages in this disclosure, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in this disclosure, the upper or lower limit value of that numerical range may be replaced with a value shown in the examples.

[0010] In the present disclosure, the term "fluoroalkylene group" includes perfluoroalkylene groups in which all hydrogen atoms have been substituted with fluorine atoms and fluoroalkylene groups in which some hydrogen atoms have been substituted with fluorine atoms. Furthermore, in the present disclosure, the term "fluorocycloalkane" and the like also includes not only perfluorocycloalkanes in which all hydrogen atoms of a cycloalkane have been substituted with fluorine atoms, but also cycloalkanes in which some hydrogen atoms have been substituted with fluorine atoms.

[0011] In the present disclosure, each component may contain a plurality of corresponding compounds. For example, the molar ratio in the reaction of a fluorinated divinyl ether compound represented by general formula (1) with a diol compound represented by general formula (2) is calculated based on the total amount of compounds corresponding to each component.

[0012] In the representation of groups (atomic groups) in the present disclosure, a representation that does not specify whether substituted or unsubstituted encompasses both those that have no substituents and those that have a substituent.

[0013] In the present disclosure, 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 when the group has a substituent, it represents the total number obtained by adding the number of carbon atoms forming the skeleton of the group to the number of carbon atoms in the substituent.

[0014] In the present disclosure, a monovalent or divalent hydrocarbon group is "perfluorinated" means that the hydrocarbon group has been fluorinated to the following state: When the monovalent or divalent hydrocarbon group is a saturated hydrocarbon group, the state in which all of the fluorinable hydrogen atoms bonded to carbon atoms constituting the monovalent or divalent hydrocarbon group are fluorinated is referred to as the hydrocarbon group being "perfluorinated." When a monovalent or divalent hydrocarbon group is an unsaturated hydrocarbon group, a state in which all fluorinable hydrogen atoms bonded to carbon atoms constituting the monovalent or divalent hydrocarbon group are fluorinated, and a fluorine atom is added to each of two carbon atoms forming a carbon-carbon unsaturated bond such as a carbon-carbon double bond or a carbon-carbon triple bond, thereby eliminating the carbon-carbon unsaturated bond, is referred to as a "perfluorinated" hydrocarbon group. For example, perfluorination of >C=C< results in >CF-CF<, and perfluorination of -C≡C- results in -CF-CF-. Furthermore, a fluorinable atomic group may have a fluorinable hydrogen atom bonded thereto; for example, perfluorination of -CH=CH- results in -CF-CF-.

[0015] In the present disclosure, 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"). Measurement by GPC is performed according to the method described in JP 2001-208736 A under the following conditions. Mobile phase: a mixed solvent of R-225 (manufactured by AGC Corporation, product name: Asahiklin (registered trademark) AK-225SEC Grade 1) and hexafluoroisopropyl alcohol (HFIP) (R-225:HFIP = 99:1 (volume ratio)) Analytical column: Two PLgel MIXED-E columns (Polymer Laboratories) connected in series Standard samples for molecular weight measurement: Four types of perfluoropolyethers with a molecular weight distribution (Mw / Mn) of less than 1.1 and Mn of 2,000 to 10,000, and one type of perfluoropolyether with Mw / Mn of 1.1 or more and Mn of 1,300. ·Mobile phase flow rate: 1.0mL / min Column temperature: 37℃ Detector: Evaporative light scattering detector

[0016] <Method for producing first fluorinated polyether compound> The first method for producing a fluorinated polyether compound of the present disclosure (hereinafter may be referred to as the first production method of the present disclosure) comprises reacting a fluorinated divinyl ether compound represented by the following general formula (1) (hereinafter may be referred to as the compound of formula (1)) with a diol compound represented by the following general formula (2) (hereinafter may be referred to as the compound of formula (2)) in a ratio of more than 1 mol of the compound of formula (2) to 1 mol of the compound of formula (1), to produce a fluorinated dihydroxypolyether compound represented by the following general formula (3) (hereinafter may be referred to as the compound of formula (3)), The hydroxyl groups contained in the compound of formula (3) are esterified to produce a fluorine-containing diacyloxy polyether compound represented by the following general formula (4) (hereinafter, sometimes referred to as the compound of formula (4)), the compound of formula (4) is fluorinated to produce a perfluorodiacyloxy polyether compound represented by the following general formula (5) (hereinafter, sometimes referred to as the compound of formula (5)), and the compound of formula (5) is reacted with an alcohol to produce a fluorine-containing dialkoxycarbonyl polyether compound represented by the following general formula (6) (hereinafter, sometimes referred to as the compound of formula (6)).

[0017] CF2=CR 1 -OR 2 -O-CR 1 =CF2 (1) HO-CH2R 3 CH2-OH···(2) HO-CH2R 3 CH2-O-(CF2-CHR 1 -OR 2 -O-CHR 1 -CF2-O-CH2R 3 CH2-O) a -CF2-CHR 1 -OR 2 -O-CHR 1 -CF2-O-CH2R 3 CH2-OH···(3) R 4 CO-O-CH2R 3 CH2-O-(CF2-CHR 1 -OR 2 -O-CHR 1 -CF2-O-CH2R3 CH2-O) a -CF2-CHR 1 -OR 2 -O-CHR 1 -CF2-O-CH2R 3 CH2-O-COR 4 ···(4) R F4 CO-O-CF2R F3 CF2-O-(CF2-CFR F1 -OR F2 -O-CFR F1 -CF2-O-CF2R F3 CF2-O) a -CF2-CFR F1 -OR F2 -O-CFR F1 -CF2-O-CF2R F3 CF2-O-COR F4 ···(5) R 5 -O-COR F3 CF2-O-(CF2-CFR F1 -OR F2 -O-CFR F1 -CF2-O-CF2R F3 CF2-O) a -CF2-CFR F1 -OR F2 -O-CFR F1 -CF2-O-CF2R F3 CO-OR 5 ···(6)

[0018] In general formula (1), general formula (3) and general formula (4), R 1 each independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having 1 to 3 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom. In general formula (1), general formula (3) and general formula (4), R 2 each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may have a ring structure or a branched structure, which may have an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom. In general formulas (2) to (4), R 3each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain a single bond, an ether bond, or a ring structure or a branched structure, and which may contain an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom. In general formula (4), R 4 each independently represents a monovalent hydrocarbon group having 2 to 20 carbon atoms, which may have a ring structure or a branched structure, which may have an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom. In general formula (6), R 5 each independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, which may have a ring structure or a branched structure, which may have an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom. In the general formula (5) and the general formula (6), R F1 are each independently R 1 represents a fluorine atom, and R 1 When is a hydrogen atom, R represents a fluorine atom. 1 When is a monovalent hydrocarbon group, R 1 represents a perfluorinated monovalent perfluorohydrocarbon group having 1 to 3 carbon atoms. In the general formula (5) and the general formula (6), R F2 are each independently R 2 represents a perfluorinated divalent perfluorohydrocarbon group having 1 to 20 carbon atoms. In the general formula (5) and the general formula (6), R F3 are each independently R 3 represents a single bond, and R 3 represents an ether bond, and R 3 When is a divalent hydrocarbon group, R 3 represents a perfluorinated divalent perfluorohydrocarbon group having 1 to 20 carbon atoms. In general formula (5), R F4 are each independently R 4 represents a perfluorinated divalent perfluorohydrocarbon group having 2 to 20 carbon atoms. In the general formulas (3) to (6), a represents 0 or an integer of 1 or more, and a in the general formulas (3) to (6) all have the same value.

[0019] According to the present disclosure, there is provided a method for producing a fluorinated polyether compound which has functional groups at both ends and which has few restrictions on the selection of structural units. The reason why the above effects are achieved is presumed to be, for example, as follows, but is not limited to this. In the first production method of the present disclosure, a compound of formula (1) and a compound of formula (2) are used as raw material monomers for the fluorinated polyether compound. By appropriately selecting the types of the compound of formula (1) and the compound of formula (2), restrictions on the selection of structural units can be reduced compared to the methods described in Patent Documents 1 and 2. Furthermore, in the first production method of the present disclosure, when the compound of formula (1) and the compound of formula (2) are reacted to obtain the compound of formula (3), the ratio of the compound of formula (2) to 1 mol of the compound of formula (1) is greater than 1 mol, which makes it easy to generate hydroxyl groups at the terminals of the compound of formula (3). By chemically modifying the terminals of the compound of formula (3) that have hydroxyl groups, ester groups can be generated at both terminals of the fluorinated polyether compound obtained by the first production method of the present disclosure. Therefore, unlike the methods described in Patent Documents 2 and 3, the first production method of the present disclosure makes it possible to functionalize both terminals of the fluorinated polyether compound.

[0020] Hereinafter, the various materials and reaction steps used in the first production method of the present disclosure will be described in detail.

[0021] -Formula (1) compound- 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). CF2=CR 1 -OR 2 -O-CR 1 =CF2 (1) In general formula (1), R 1each independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having 1 to 3 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom, and from the viewpoint of lubricity, R 1 Preferably, at least one of R is a fluorine atom. 1 It is more preferable that both of the groups are fluorine atoms.

[0022] In general formula (1), R 2 represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may have a ring structure or a branched structure, may contain an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom. R 2 The number of carbon atoms in the divalent hydrocarbon group represented by R is preferably 15 or less, and more preferably 10 or less. 2 By making the number of carbon atoms in the divalent hydrocarbon group represented by the formula: 15 or less, the polymerization reaction proceeds more smoothly, and a high molecular weight fluorine-containing polyether compound can be produced in high yield. R 2 From the viewpoint of preventing a cyclization reaction, the number of carbon atoms in the divalent hydrocarbon group represented by the following formula is preferably 3 or more, and more preferably 4 or more.

[0023] R 2 Examples of the divalent hydrocarbon group represented by the formula (I) include alkylene groups such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group, and fluoroalkylene groups such as a fluoromethylene group, a fluoroethylene group, a fluorotrimethylene group, a fluorotetramethylene group, a fluoropentamethylene group, and a fluorohexamethylene group.

[0024] R 2 The divalent hydrocarbon group represented by the following formula (X) may be a group represented by the following formula (X): *-R x -(OR x ) n -*···(X) In general formula (X), R xrepresents an ethylene group, a trimethylene group, a propylene group, a fluoroethylene group, a fluorotrimethylene group, or a fluoropropylene group, and n represents an integer of 1 or more. In the general formula (X), * represents the bond to the oxygen atom.

[0025] R 2 The divalent hydrocarbon group represented by the following formula (A) may be a group represented by the following formula (A): *-R b -OR a -OR b -*···(A) In general formula (A), R a represents a cycloalkanediyl group, a fluorocycloalkanediyl group, or an arylene group. R a Examples of the cycloalkanediyl group and fluorocycloalkanediyl group represented by the formula (I) include a cyclobutanediyl group, a fluorocyclobutanediyl group, a cyclopentanediyl group, a fluorocyclopentanediyl group, a cyclohexanediyl group, a fluorocyclohexanediyl group, an adamantanediyl group, and a norbornanediyl group. The cycloalkanediyl group, the fluorocycloalkanediyl group, and the arylene group may have, as a substituent, an alkyl group having 1 to 3 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom. In general formula (A), R b each independently represents a divalent hydrocarbon group having 1 to 10 carbon atoms, which may have a ring structure or a branched structure, and in which a hydrogen atom may be substituted with a fluorine atom. R b Examples of the divalent hydrocarbon group represented by the formula (I) include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a fluoromethylene group, a fluoroethylene group, a fluorotrimethylene group, and a fluorotetramethylene group. In the general formula (A), * represents the bond to the oxygen atom.

[0026] Examples of the divalent hydrocarbon group represented by general formula (A) include, but are not limited to, the following groups:

[0027] [ka]

[0028] Also, R 2 The divalent hydrocarbon group represented by the formula (I) may be a group represented by the following general formulas (B) to (D). *-R c -R a -R c -*···(B) *-R a -R c -R a -*···(C) *-R b -R d -R b -*···(D) R in general formulas (B) and (C) a The group represented by is the same as in the above general formula (A). R in general formula (D) b The group represented by is the same as in the above general formula (A). In addition, in the general formulas (B) and (C), R c each independently represents a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms which may contain a ring structure or a branched structure and in which a hydrogen atom may be substituted with a fluorine atom. R c Examples of the divalent hydrocarbon group represented by the formula (I) include a methylene group, an ethylene group, a trimethylene group, a propylidene group, an isopropylidene group, a fluoromethylene group, a fluoroethylene group, a fluorotrimethylene group, a fluoropropylidene group, and a fluoroisopropylidene group. In addition, in the general formula (D), R d represents a cycloalkane-1,1-diyl group having 3 to 6 carbon atoms. In the general formulae (B) to (D), * represents the bond to the oxygen atom.

[0029] Examples of groups satisfying any one of general formulas (B) to (D) include, but are not limited to, the following groups.

[0030] [ka]

[0031] [ka]

[0032] [ka]

[0033] The above-mentioned R 2 Taking into account specific examples of the divalent hydrocarbon group represented by the formula (1), specific examples of the compound of formula (1) include, but are not limited to, the following compounds:

[0034] [ka]

[0035] [ka]

[0036] [ka]

[0037] [ka]

[0038] -Formula (2) compound- The compound of formula (2) used in the present disclosure is a specific diol compound represented by the following general formula (2). HO-CH2R 3 CH2-OH···(2) In general formula (2), R 3represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain a single bond, an ether bond, or a ring structure or a branched structure, and which may contain an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom. The acidity (pKa) of the compound of formula (2) is preferably 8 to 18, more preferably 9 to 14. When the pKa of the compound of formula (2) is within the above range, the reaction with the compound of formula (1) proceeds smoothly. In the present disclosure, pKa is a value in water at 25° C., and is calculated according to the method described in Chemistry Handbook, Basic Edition, 5th Revised Edition, II-331 to II-343 (edited by the Chemical Society of Japan, published by Maruzen Co., Ltd.).

[0039] In general formula (2), R 3 Contains "-CH2R 3 A divalent hydrocarbon group represented by "-CH2R 3 The number of carbon atoms in "-CHR" is preferably 15 or less, and more preferably 10 or less. 3 By making the number of carbon atoms in the CH2-" group 15 or less, the polymerization reaction proceeds more smoothly, and a high molecular weight fluorine-containing polyether compound can be produced in high yield. "-CH2R 3 The number of carbon atoms in the CH2-" group is preferably 2 or more, more preferably 3 or more, from the viewpoint of synthetic handling.

[0040] "-CH2R 3 Examples of the "-CH-" group include alkylene groups such as ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene, and fluoroalkylene groups such as fluorotrimethylene, fluorotetramethylene, fluoropentamethylene, and fluorohexamethylene. 3 When the CH2-" group is a fluoroalkylene group, both ends of the fluoroalkylene group have methylene structures.

[0041] "-CH2R 3 The CH2-" group may be a group represented by the following general formula (X'): *-CH2R X1 -(OR X2 ) n1 -OR X1 CH2-*···(X') In general formula (X'), R X1 represents a single bond, a methylene group, an ethylene group, a methylmethylene group, a fluoromethylene group, a fluoroethylene group, or a fluoromethylmethylene group. In general formula (X'), R X2 represents an ethylene group, a trimethylene group, a propylene group, a fluoroethylene group, a fluorotrimethylene group, or a fluoropropylene group. In the general formula (X'), n1 represents 0 or an integer of 1 or more. In the general formula (X'), * represents the bond to the oxygen atom.

[0042] Also, "-CH2R 3 The CH2-" group may be a group represented by the following general formula (A'): *-R b2 -OR a -OR b2 -*···(A') In general formula (A'), R a represents a cycloalkanediyl group, a fluorocycloalkanediyl group, or an arylene group, and specific examples thereof are the same as those in the case of general formula (A). In general formula (A'), R b2 each independently represents a divalent hydrocarbon group having 1 to 10 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom, provided that R b2 is a divalent hydrocarbon group having 2 to 10 carbon atoms in which a hydrogen atom is substituted with a fluorine atom, R b2 The terminal on the * side of R is a methylene structure. b2 is a hydrocarbon group having one carbon atom, R b2 is considered to be a methylene group. In the general formula (A'), * represents the bond to the oxygen atom.

[0043] Examples of the divalent hydrocarbon group represented by general formula (A') include, but are not limited to, the following groups:

[0044] [ka]

[0045] Also, "-CH2R 3 The CH2-" 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') R in general formula (B') a The group represented by is the same as in the above general formula (A). In addition, in the general formula (B'), R c2 are each independently a linear alkylene group having 1 to 10 carbon atoms, preferably a linear alkylene group having 1 to 5 carbon atoms, and more preferably a linear alkylene group having 1 or 2 carbon atoms. R in general formula (D') b2 The group represented by is the same as that represented by general formula (A') above. In addition, 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 the bond to the oxygen atom.

[0046] Examples of the group satisfying either the general formula (B') or the general formula (D') include, but are not limited to, the following groups.

[0047] [ka]

[0048] [ka]

[0049] The above-mentioned "-CH2R 3 Taking into account specific examples of the CH2- group, specific examples of the compound of formula (2) include, but are not limited to, the following compounds:

[0050] [ka]

[0051] [ka]

[0052] [ka]

[0053] [ka]

[0054] -Production of Compound of Formula (3)- In the first production method of the present disclosure, the compound of formula (3) is produced by reacting the compound of formula (1) with the compound of formula (2) in a ratio of more than 1 mol of the compound of formula (2) to 1 mol of the compound of formula (1). HO-CH2R 3 CH2-O-(CF2-CHR 1 -OR 2 -O-CHR 1 -CF2-O-CH2R 3 CH2-O) a -CF2-CHR 1 -OR 2 -O-CHR 1 -CF2-O-CH2R 3 CH2-OH···(3) In general formula (3), R 1 , R 2 and R 3 The details are as described above. In general formula (3), 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 even more preferably an integer of 5 or more. Furthermore, 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.

[0055] The reaction of the compound of formula (1) with the compound of formula (2) may be carried out in a solvent or in the absence of a solvent. When the reaction between the compound of formula (1) and the compound of formula (2) is carried out in a solvent, the solvent is preferably a fluorine-based organic solvent, and examples thereof include fluorinated alkanes, fluorinated aromatic compounds, and fluoroalkyl ethers. The ratio of the compound of formula (1) to the compound of formula (2) is preferably adjusted according to the molecular weight of the target fluorine-containing polyether compound, and from the viewpoint of controlling the molecular weight, the compound of formula (2) is preferably 1.01 mol or more, more preferably 1.10 mol or more, per mol of the compound of formula (1). On the other hand, the ratio of the compound of formula (1) to the compound of formula (2) is preferably 2.00 mol or less, more preferably 1.90 mol or less, even more preferably 1.70 mol or less, particularly preferably 1.50 mol or less, per mol of the compound of formula (1), from the viewpoint of saving excess raw materials while controlling the molecular weight of the target fluorine-containing polyether compound.

[0056] The reaction of the compound of formula (1) with the compound of formula (2) is preferably carried out in the presence of an alkali catalyst. By reacting the compound of formula (1) with the compound of formula (2) in the presence of an alkali catalyst, the molecular weight and yield of the compound of formula (3) produced can be further improved. Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, sodium carbonate, cesium fluoride, and potassium carbonate, and from the viewpoints of the molecular weight and yield of the compound of formula (3), potassium carbonate is preferred.

[0057] From the viewpoint of the molecular weight and yield of the compound of formula (3), the reaction temperature of the compound of formula (1) and the compound of formula (2) is preferably 80°C to 160°C, more preferably 90°C to 140°C. From the viewpoint of the molecular weight and yield of the compound of formula (3), the reaction time of the compound of formula (1) and the compound of formula (2) is preferably 1 hour to 72 hours, more preferably 2 hours to 48 hours.

[0058] The compound of formula (3) may be produced by a batch method or a continuous method, and known methods can be appropriately adopted. When the compound of formula (3) is produced by a batch method, for example, the compound of formula (2) may be placed in a reactor in advance, and the compound of formula (1) may be added directly to the reactor, or a diluted solution of the compound of formula (1) may be added to the reactor. From the viewpoint of the molecular weight and yield of the compound of formula (3), in the reaction between the compound of formula (1) and the compound of formula (2), the compound of formula (1) is added to the compound of formula (2) at a rate of preferably 0.01 to 10 moles / hour, and more preferably 0.1 to 0.5 moles / hour, per mole of the compound of formula (2).

[0059] After reacting the compound of formula (1) with the compound of formula (2), at least one selected from an organic solvent, water, and an aqueous solution for adjusting the acidity to an appropriate level may be added to the reaction mixture, followed by separation, and the organic phase may be concentrated to obtain the compound of formula (3). Alternatively, the crude reaction liquid obtained by concentrating the organic phase may be purified to obtain the compound of formula (3).

[0060] There is no particular limitation on the combination of the compound of formula (1) and the compound of formula (2) used in producing the compound of formula (3). For example, the compound of formula (1) may be selected from perfluorodivinyl ether compounds.

[0061] -Production of Compound of Formula (4)- In the first production method of the present disclosure, the compound of formula (4) is produced by esterifying the hydroxyl group contained in the compound of formula (3). R 4 CO-O-CH2R 3 CH2-O-(CF2-CHR 1 -OR 2 -O-CHR 1-CF2-O-CH2R 3 CH2-O) a -CF2-CHR 1 -OR 2 -O-CHR 1 -CF2-O-CH2R 3 CH2-O-COR 4 ···(4) In general formula (4), R 1 , R 2 and R 3 The details of a are as described above. In general formula (4), R 4 The details will be described later together with the explanation of acid fluorides.

[0062] The method for esterifying the hydroxyl group contained in the compound of formula (3) is not particularly limited, and a conventionally known reaction may be used, such as a method of reacting a carboxylic acid compound with the hydroxyl group, a method of reacting a carboxylic acid anhydride with the hydroxyl group, or a method of reacting an acid halide with the hydroxyl group.

[0063] For the esterification of the hydroxyl group contained in the compound of formula (3), from the viewpoint of high reactivity, a method of reacting an acid halide with the hydroxyl group is preferred, a method of reacting an acid fluoride with the hydroxyl group is more preferred, and a method of reacting an acid fluoride represented by the following general formula (7) (hereinafter, sometimes referred to as the compound of formula (7)) with the compound of formula (3) is even more preferred. R 4 COF···(7) In general formula (7), R 4 represents a monovalent hydrocarbon group having 2 to 20 carbon atoms, which may have a ring structure or a branched structure, may contain an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom. R 4 From the viewpoint of ease of purification, the number of carbon atoms in the monovalent hydrocarbon group represented by R is preferably 20 or less, and more preferably 10 or less. 4 The number of carbon atoms in the monovalent hydrocarbon group represented by the following formula is preferably 3 or more, more preferably 4 or more, from the viewpoint of suppressing side reactions during fluorination. R 4In the case where hydrogen atoms in the monovalent hydrocarbon group represented by the formula (I) are substituted with fluorine atoms, the fluorine atom content is preferably 50 mol % or more, more preferably 75 mol % or more, and even more preferably 100 mol % (perfluorohydrocarbon group), where the fluorine atom content refers to the proportion of hydrogen atoms in the hydrocarbon group that have been substituted with fluorine atoms.

[0064] Specific examples of compounds of formula (7) that can be used in the present disclosure include, but are not limited to, the following compounds: CF3CF2CF2-O-CF(CF3)COF ·CF3CF2CF2-O-CF(CF3)CF2-O-CF(CF3)COF CF3-CF(CF3)COF

[0065] The esterification of the hydroxyl group contained in the compound of formula (3) may be carried out in a solvent or in a solvent-free state without using a solvent. When the esterification of the hydroxyl group contained in the compound of formula (3) is carried out in a solvent, the solvent is preferably a fluorine-based organic solvent, and examples thereof include a fluorinated alkane, a fluorinated aromatic compound, and a fluoroalkyl ether.

[0066] When the compound of formula (7) is reacted with the compound of formula (3), it is preferable to carry out the reaction in the presence of a catalyst. By reacting the compound of formula (7) with the compound of formula (3) in the presence of a catalyst, the yield of the compound of formula (4) produced can be further improved. Examples of the catalyst include sodium fluoride and triethylamine, and sodium fluoride is preferred from the viewpoint of ease of post-treatment.

[0067] When the compound of formula (7) is reacted with the compound of formula (3), the reaction temperature is preferably from -10°C to 100°C, more preferably from 0°C to 60°C, from the viewpoint of the yield of the compound of formula (4). When the compound of formula (7) is reacted with the compound of formula (3), from the viewpoint of the yield of the compound of formula (4), the reaction time between the compound of formula (3) and the compound of formula (7) is preferably 1 hour to 40 hours, more preferably 2 hours to 20 hours. When the compound of formula (7) is allowed to act on the compound of formula (3), from the viewpoint of the yield of the compound of formula (4), the reaction pressure when reacting the compound of formula (3) with the compound of formula (7) is preferably atmospheric pressure to 2 MPa (gauge pressure).

[0068] The compound of formula (4) may be produced by a batch method or a continuous method, and known methods can be appropriately adopted. When the compound of formula (4) is produced by a batch method, for example, the compound of formula (3) may be placed in a reactor in advance, and the compound of formula (7) may be added directly to the reactor. When the compound of formula (7) is allowed to react with the compound of formula (3), from the viewpoint of suppressing the generation of by-products, the compound of formula (7) is preferably added to the compound of formula (3) at a rate that does not cause the internal temperature of the reactor to exceed 40°C, and more preferably at a rate that does not cause the internal temperature to exceed 20°C.

[0069] When the compound of formula (7) is allowed to act on the compound of formula (3), hydrogen fluoride (HF) is generated by the reaction between the compound of formula (3) and the compound of formula (7), so it is preferable to have a hydrogen fluoride scavenger present in the reaction system. Examples of hydrogen fluoride scavenger include alkali metal fluorides and trialkylamines. As the alkali metal fluoride, NaF or KF is preferred. When an HF scavenger is not used, it is preferable to carry out the reaction at a reaction temperature at which HF can be vaporized, and to discharge the HF to the outside of the reaction system by entraining it in a nitrogen stream. The amount of the HF scavenger used is preferably 1 to 10 times the molar amount of the compound of formula (7).

[0070] After reacting the compound of formula (7) with the compound of formula (3), at least one selected from an organic solvent, water, and an aqueous solution for adjusting the acidity to an appropriate level may be added to the reaction solution to separate the liquids, or the reaction solution may be subjected to solid-liquid separation, and the organic phase may be concentrated to obtain the compound of formula (4). Alternatively, the crude reaction liquid obtained by concentrating the organic phase may be purified to obtain the compound of formula (4).

[0071] -Production of Compound of Formula (5)- In the first production method of the present disclosure, the compound of formula (5) is produced by fluorinating the compound of formula (4). R F4 CO-O-CF2R F3 CF2-O-(CF2-CFR F1 -OR F2 -O-CFR F1 -CF2-O-CF2R F3 CF2-O) a -CF2-CFR F1 -OR F2 -O-CFR F1 -CF2-O-CF2R F3 CF2-O-COR F4 ···(5) In general formula (5), R F1 are each independently R 1 represents a fluorine atom, and R 1 When is a hydrogen atom, R represents a fluorine atom. 1 When is a monovalent hydrocarbon group, R 1 represents a perfluorinated monovalent perfluorohydrocarbon group having 1 to 3 carbon atoms. In general formula (5), R F2 are each independently R 2 represents a perfluorinated divalent perfluorohydrocarbon group having 1 to 20 carbon atoms. In general formula (5), R F3 are each independently R 3 represents a single bond, and R 3 represents an ether bond, and R 3 When is a divalent hydrocarbon group, R 3 represents a perfluorinated divalent perfluorohydrocarbon group having 1 to 20 carbon atoms. In general formula (5), R F4 are each independently R 4 represents a perfluorinated divalent perfluorohydrocarbon group having 2 to 20 carbon atoms. In the general formula (5), the details of a are as described above.

[0072] The method for fluorinating the compound of formula (4) is not particularly limited, and can be carried out by a conventionally known method. For example, the fluorination can be carried out by contacting the compound of formula (4) with fluorine gas. The method for fluorinating the compound of formula (4) may be a batch system or a continuous system. The fluorination reaction is preferably carried out by the following <Method 1> or <Method 2>, with <Method 2> being more preferred from the viewpoint of the reaction yield and selectivity of the compound of formula (5). Whether the reaction is carried out by the batch system or the continuous system, the fluorine gas may be diluted with an inert gas such as nitrogen gas before use.

[0073] <Method 1> In Method 1, a reaction vessel is charged with the compound of formula (4) and a solvent, stirring is initiated, and then the reaction is carried out at a predetermined reaction temperature and pressure while continuously supplying fluorine gas diluted with an inert gas into the solvent. <Method 2> Method 2 is a method in which a solvent is charged into a reactor, the mixture is stirred, and then fluorine gas diluted with an inert gas, the compound of formula (4), and the solvent are reacted at a predetermined reaction temperature and pressure while being continuously supplied to the fluorination reaction solvent in a predetermined molar ratio. <Method 3> In method 3, a solvent is continuously introduced into a tubular reactor and circulated through the reactor, and then fluorine gas diluted with an inert gas and a solution of the compound of formula (4) are continuously supplied to the solvent flow in the tubular reactor and mixed in proportions such that the fluorine gas and the compound of formula (4) have a predetermined molar ratio, and the fluorine gas and the compound of formula (4) are brought into contact with each other in the tubular reactor to react with each other, and the solvent containing the reaction product is removed from the tubular reactor. In this method, the solvent is circulated and the reaction product is removed from the circulating solvent, thereby allowing the fluorination reaction to proceed in a continuous manner.

[0074] As in the case of Method 3, in Method 2, when the compound of formula (4) is supplied, it is preferable to supply the compound of formula (4) diluted with a solvent, in order to improve the selectivity of the compound of formula (5) and to suppress the amount of by-products. Furthermore, when the compound of formula (4) is diluted with a solvent, the amount of the solvent relative to the compound of formula (4) is preferably 5 times or more, more preferably 7 times or more, by mass.

[0075] Examples of inert gases include rare gases such as helium gas, neon gas, and argon gas, and nitrogen gas, with nitrogen gas and helium gas being preferred, and nitrogen gas being more preferred from the viewpoint of economical advantages. The proportion of fluorine gas (hereinafter also referred to as "fluorine gas amount") is preferably 10 to 60% by volume out of 100% by volume of the total of fluorine gas and inert gas.

[0076] The amount of fluorine gas used is preferably 1.1 mol to 10 mol, more preferably 1.2 mol to 5 mol, per mol of hydrogen atoms to be substituted with fluorine in the compound of formula (4). By keeping the ratio of the amount of fluorine gas used within the above range, the yield of the compound of formula (5) can be improved.

[0077] When the fluorination of the compound of formula (4) is carried out in a solvent, the solvent may be previously substituted with nitrogen in order to reduce the oxygen content in the solvent. When the compound of formula (4) is introduced into a solvent, the solvent may be substituted with nitrogen in advance, and then with fluorine.

[0078] In the fluorination reaction, whether in a batch system or a continuous system, it is preferable that the amount of fluorine gas used to fluorinate all of the fluorinatable hydrogen atoms in the compound of formula (4) is always in excess, preferably 1.1 times or more equivalents, and more preferably 1.3 times or more equivalents, of the theoretical amount required to fluorinate all of the fluorinatable hydrogen atoms.

[0079] When the fluorination of the compound of formula (4) is carried out by introducing fluorine gas and the compound of formula (4) into a solvent, the molar introduction rate of the fluorine gas may be in the range of 1 to 10 times, or may be in the range of 2 to 7 times, the rate obtained by multiplying the molar introduction rate of the compound of formula (4) by the number of hydrogen atoms that can be substituted with fluorine atoms by the fluorine gas contained in the compound of formula (4), assuming that the molar introduction rate of the compound of formula (4) into the solvent is 1. By keeping the introduction rate relationship within the above numerical range, the yield of the compound of formula (5) can be improved.

[0080] To efficiently proceed with the fluorination reaction of the compound of formula (4), it is preferable to add a C-H bond-containing compound other than the compound of formula (4) to the solvent or to irradiate the solvent with ultraviolet light. These steps are preferably carried out at the later stage of the fluorination reaction. This allows the compound of formula (4) present in the solvent to be efficiently fluorinated, thereby improving the yield of the compound of formula (5). The C-H bond-containing compound is preferably an aromatic hydrocarbon, such as benzene, toluene, etc. The amount of the C-H bond-containing compound added is preferably 0.1 mol % to 10 mol %, more preferably 0.1 mol % to 5 mol %, based on the hydrogen atoms in the compound of formula (4). The C-H bond-containing compound is preferably added to a solvent in which fluorine gas is present. Furthermore, when the C-H bond-containing compound is added, it is preferable to pressurize the reaction system. The reaction pressure when pressurized is preferably 0.01 MPa to 5 MPa (gauge pressure). When the reaction system is irradiated with ultraviolet light, the irradiation time is preferably 0.1 to 3 hours.

[0081] After the fluorination reaction, the atmosphere in the system may be purged with an inert gas such as nitrogen gas, and the organic phase may be concentrated to obtain the compound of formula (5). Alternatively, the compound of formula (5) may be obtained by purifying the reaction crude liquid obtained by concentrating the organic phase.

[0082] -Production of Compound of Formula (6)- In the first production method of the present disclosure, a compound of formula (6) is produced by reacting a compound of formula (5) with an alcohol. R 5 -O-COR F3 CF2-O-(CF2-CFR F1 -OR F2 -O-CFR F1 -CF2-O-CF2R F3 CF2-O) a -CF2-CFR F1 -OR F2 -O-CFR F1 -CF2-O-CF2R F3 CO-OR 5 ···(6) In general formula (6), R F1 , R F2 , R F3 and R F4 The details of a are as described above. In general formula (6), R 5 each independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, which may have a ring structure or a branched structure, which may have an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom.

[0083] By reacting an alcohol with the compound of formula (5), the terminal of the compound of formula (5) is esterified to obtain a compound of formula (6). The alcohol to be reacted with the compound of formula (5) is not particularly limited, and examples of the alcohol include methanol, ethanol, and isopropanol.

[0084] The reaction of the compound of formula (5) with the alcohol may be carried out in a solvent or in the absence of a solvent. When the reaction of the compound of formula (5) with an alcohol is carried out in a solvent, the solvent is preferably a fluorine-based organic solvent, and examples thereof include fluorinated alkanes, fluorinated aromatic compounds, and fluoroalkyl ethers. The amount of alcohol used relative to the compound of formula (5) is preferably 2 mol to 20 mol, more preferably 2.1 mol to 15 mol, and even more preferably 2.2 mol to 10 mol, relative to 1 mol of the compound of formula (5).

[0085] From the viewpoint of the yield of the compound of formula (6), the reaction temperature of the compound of formula (5) and the alcohol is preferably from -10°C to 60°C, more preferably from 0°C to 40°C. From the viewpoint of the yield of the compound of formula (6), the reaction time of the compound of formula (5) with the alcohol is preferably 0.5 to 48 hours, more preferably 1 to 24 hours.

[0086] From the viewpoint of suppressing the generation of by-products, in the reaction of the compound of formula (5) with an alcohol, the addition of the alcohol to the compound of formula (5) is preferably carried out at a rate that does not cause the internal temperature of the reactor to exceed 40°C, more preferably at a rate that does not cause the internal temperature to exceed 20°C.

[0087] After reacting the compound of formula (5) with the alcohol, at least one selected from an organic solvent, water, and an aqueous solution for adjusting the acidity to an appropriate level may be added to the reaction mixture, followed by separation, and the organic phase may be concentrated to obtain the compound of formula (6). Alternatively, the crude reaction liquid obtained by concentrating the organic phase may be purified to obtain the compound of formula (6).

[0088] The number average molecular weight (Mn) of the compound of formula (6) obtained by the first production method of the present disclosure is preferably 1,000 to 30,000, more preferably 1,500 to 20,000, and even more preferably 2,000 to 10,000. The molecular weight distribution (Mw / Mn) of the compound of formula (6) obtained by the first production method of the present disclosure is preferably 1-3, more preferably 1-2.5, and even more preferably 1-2.

[0089] <Method for producing second fluorinated polyether compound> The second method for producing a fluorinated polyether compound of the present disclosure (hereinafter, may be referred to as the second production method of the present disclosure) comprises reacting a compound of formula (1) with a compound of formula (2) in a ratio of more than 1 mol of the compound of formula (2) to 1 mol of the compound of formula (1) to produce a compound of formula (3). In the second production method of the present disclosure, the details of the compounds of formula (1) to formula (3) and the details of the synthesis process of the compound of formula (3) are the same as those in the first production method of the present disclosure.

[0090] <Third method for producing fluorine-containing polyether compound> The third production method of a fluorinated polyether compound of the present disclosure (hereinafter may be referred to as the third production method of the present disclosure) comprises reacting a compound of formula (1) with a compound of formula (2) in a ratio of more than 1 mol of the compound of formula (2) to 1 mol of the compound of formula (1) to produce a compound of formula (3), and esterifying a hydroxyl group contained in the compound of formula (3) to produce a compound of formula (4). In the third production method of the present disclosure, details of the compounds of formula (1) to formula (4), as well as details of the synthesis steps of the compounds of formula (3) and formula (4), are the same as in the first production method of the present disclosure.

[0091] <Fourth method for producing fluorine-containing polyether compound> The fourth production method of a fluorinated polyether compound of the present disclosure (hereinafter, may be referred to as the fourth production method of the present disclosure) comprises reacting a compound of formula (1) with a compound of formula (2) in a ratio of more than 1 mol of the compound of formula (2) to 1 mol of the compound of formula (1) to produce a compound of formula (3), esterifying a hydroxyl group contained in the compound of formula (3) to produce a compound of formula (4), and fluorinating the compound of formula (4) to produce a compound of formula (5). In the fourth production method of the present disclosure, the details of the compounds of formula (1) to formula (5) and the details of the synthesis steps of the compounds of formula (3) to formula (5) are the same as in the first production method of the present disclosure. [Example]

[0092] The above embodiment will be specifically described below using examples, but the above embodiment is not limited to these examples. Synthesis Examples 1-1 to 3-4 are working examples, and Synthesis Example 4 is a comparative example.

[0093] [Evaluation method] (GPC analysis) The number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured by GPC. The GPC measurement was carried out by the method described above.

[0094] (Synthesis Example 1-1) To a 200 mL recovery flask were added 4.1 g of ethylene glycol corresponding to the compound of formula (2) and 4 g of potassium carbonate, and the temperature inside the flask was kept at 120°C while stirring the contents of the flask. 20 g of compound A-1 corresponding to the compound of formula (1) was added over 4 hours (0.21 moles / hour relative to 1 mole of the compound of formula (2)) and the mixture was stirred at 120°C for 2 hours. The temperature inside the flask was then returned to 25°C, and 20 g each of a fluorine-based organic solvent (manufactured by AGC Corporation, Asahiklin (registered trademark) AC-2000, 1H-tridecafluorohexane, hereinafter referred to as AC-2000) and hydrochloric acid were added, obtaining a reaction crude liquid separated into an organic phase and an aqueous phase. The obtained reaction crude liquid was separated, and then the organic phase was concentrated. The organic phase was concentrated and the resulting crude reaction liquid was purified by column chromatography to obtain 14 g (yield 58%) of the following compound A-2, which corresponds to the compound of formula (3). The average of a was 6. CF2=CF-O-CF2CF2CF2-O-CF=CF2A-1

[0095] [ka]

[0096] (Synthesis Example 1-2) 14 g of compound A-2, 1.5 g of sodium fluoride, and 20 ml of AC-2000 were added to a 200 mL recovery flask and stirred under ice cooling, and 5.0 g of compound A-3 corresponding to the compound of formula (7) was added, and then the temperature was returned to 25°C and stirred for 15 hours. Thereafter, the solid and liquid were separated by filtration, and the resulting liquid was concentrated and then purified by column chromatography to obtain 16 g (yield 94%) of compound A-4 corresponding to the compound of formula (4). CF3CF2CF2-O-CF(CF3)COF A-3

[0097] [ka]

[0098] (Synthesis Example 1-3) 250 mL of CFE-419 (ClCF2CFClCF2OCF2CF2Cl) was added to a 500 mL nickel reactor, and nitrogen gas was introduced (bubbling). After the dissolved oxygen concentration had sufficiently decreased, 20% by volume fluorine gas diluted with nitrogen gas was blown in for 1 hour. A CFE-419 solution of compound A-4 (concentration: 10% by mass, compound A-4: 17 g) was added over 3 hours. Fluorine gas was introduced into the reactor simultaneously with the addition of the CFE-419 solution of compound A-4. When the molar introduction rate of compound A-4 into the solvent was set to 1, the molar introduction rate of fluorine gas was set to twice the rate obtained by multiplying the molar introduction rate of compound A-4 by the number of hydrogen atoms that could be substituted for fluorine atoms by the fluorine gas contained in compound A-4. After the addition of the CFE-419 solution of compound A-4 was completed, a CFE-419 solution of benzene (concentration: 0.1% by mass, benzene: 0.1 g) was intermittently added. After the addition of the benzene solution of CFE-419, fluorine gas was blown in over 1 hour, and finally the atmosphere in the reactor was thoroughly replaced with nitrogen gas. The solvent was distilled off, yielding 20 g (yield 94%) of compound A-5, which corresponds to the compound of formula (5).

[0099] [ka]

[0100] (Synthesis Example 1-4) 20 g of Compound A-5 and 20 ml of AC-2000 were added to a 200 mL recovery flask, and the mixture was stirred under ice cooling, followed by the addition of 1.5 g of methanol, and then the mixture was returned to 25° C. and stirred for 15 hours. Then, 30 ml of water was added, and a crude reaction liquid was obtained, separated into an organic phase and an aqueous phase. The crude reaction liquid obtained was separated, and then the organic phase was concentrated to obtain 16 g (yield 98%) of compound A-6, which corresponds to the compound of formula (6). In compound A-6, Me means a methyl group.

[0101] [ka]

[0102] Compound A-6 had an Mn of 3700 and an Mw / Mn of 1.7.

[0103] (Synthesis Example 2-1) To a 200 mL recovery flask were added 9.4 g of 1,4-benzenedimethanol corresponding to the compound of formula (2) and 4 g of potassium carbonate, and the contents of the flask were stirred while the temperature inside the flask was kept at 120°C. 20 g of compound A-1 corresponding to the compound of formula (1) was added over 7 hours (0.12 moles / hour relative to 1 mole of the compound of formula (2)) and the mixture was stirred at 120°C for 2 hours. Thereafter, the temperature inside the flask was returned to 25°C, and 20 g each of AC-2000 and hydrochloric acid were added to obtain a crude reaction liquid separated into an organic phase and an aqueous phase. The obtained crude reaction liquid was separated, and then the organic phase was concentrated. The organic phase was concentrated and the resulting crude reaction liquid was purified by column chromatography to obtain 25 g (yield 85%) of compound B-1, which corresponds to the compound of formula (3). The average of a was 5.

[0104] [ka]

[0105] (Synthesis Example 2-2) 24 g of compound B-1, 2.5 g of sodium fluoride, and 30 ml of AC-2000 were added to a 200 mL recovery flask and stirred under ice cooling, followed by the addition of 7.5 g of compound A-3 corresponding to the compound of formula (7). The mixture was then returned to 25°C and stirred for 15 hours. The solid and liquid were then separated by filtration, and the resulting liquid was concentrated and purified by column chromatography to obtain 29 g (98% yield) of compound B-2, which corresponds to the compound of formula (4). The average a was 5.

[0106] [ka]

[0107] (Synthesis Example 2-3) 250 mL of CFE-419 was added to a 500 mL nickel reactor, and nitrogen gas was bubbled into the reactor. After the dissolved oxygen concentration had sufficiently decreased, 20% by volume fluorine gas diluted with nitrogen gas was blown in for 1 hour. A CFE-419 solution of compound B-2 (concentration: 10% by mass, 17 g of compound B-2) was added over 3 hours. Fluorine gas was introduced into the reactor simultaneously with the addition of the CFE-419 solution of compound B-2. When the molar introduction rate of compound B-2 into the solvent was set to 1, the molar introduction rate of fluorine gas was set to three times the rate obtained by multiplying the molar introduction rate of compound B-2 by the number of hydrogen atoms that could be substituted with fluorine atoms by the fluorine gas contained in compound B-2. After the addition of the CFE-419 solution of compound B-2 was completed, a CFE-419 solution of benzene (concentration: 0.1% by mass, benzene: 0.1 g) was intermittently added. After the addition of the benzene CFE-419 solution, fluorine gas was blown into the reactor over 1 hour, and finally the atmosphere in the reactor was thoroughly replaced with nitrogen gas. The solvent was distilled off, yielding 16 g (70% yield) of compound B-3, which corresponds to the compound of formula (5). The average a was 5.

[0108] [ka]

[0109] (Synthesis Example 2-4) In a 200 mL recovery flask, 16 g of compound B-3 and 20 ml of AC-2000 were added, and the mixture was stirred under ice cooling, and 1.5 g of methanol was added, and then the mixture was returned to 25° C. and stirred for 15 hours. Then, 30 ml of water was added, and a crude reaction liquid was obtained, separated into an organic phase and an aqueous phase. The crude reaction liquid obtained was separated, and then the organic phase was concentrated to obtain 14 g (98% yield) of compound B-4, which corresponds to the compound of formula (6). The average of a was 5. In addition, Me in compound B-4 means a methyl group.

[0110] [ka]

[0111] Compound B-4 had an Mn of 4,000 and an Mw / Mn of 2.

[0112] (Synthesis Example 3-1) In a 200 mL recovery flask, 13.6 g of tetraethylene glycol corresponding to the compound of formula (2) and 4 g of potassium carbonate were added, and the temperature inside the flask was kept at 120°C while stirring the contents of the flask. 20 g of compound A-1 corresponding to the compound of formula (1) was added over 2 hours (0.4 moles / hour relative to 1 mole of the compound of formula (2)) and the mixture was stirred at 120°C for 2 hours. Thereafter, the temperature inside the flask was returned to 25°C, and 20 g each of AC-2000 and hydrochloric acid were added to obtain a crude reaction liquid separated into an organic phase and an aqueous phase. The obtained crude reaction liquid was separated, and then the organic phase was concentrated. The organic phase was concentrated and the resulting crude reaction liquid was purified by column chromatography to obtain 26 g (78% yield) of the following compound C-1, which corresponds to the compound of formula (3). The average of a was 4. In the formula, * represents the bond to the oxygen atom, and ** represents the bond to the carbon atom.

[0113] [ka]

[0114] (Synthesis Example 3-2) 26 g of compound C-1, 2.5 g of sodium fluoride, and 30 ml of AC-2000 were added to a 200 mL recovery flask and stirred under ice cooling, followed by the addition of 9 g of compound A-3 corresponding to the compound of formula (7). The mixture was then returned to 25°C and stirred for 15 hours. The solid and liquid were then separated by filtration, and the resulting liquid was concentrated and purified by column chromatography to obtain 30 g (93% yield) of compound C-2, which corresponds to the compound of formula (4). The average value of a was 4. In the formula, * represents the bond to the oxygen atom, and ** represents the bond to the carbon atom.

[0115] [ka]

[0116] (Synthesis Example 3-3) 250 mL of CFE-419 was added to a 500 mL nickel reactor, and nitrogen gas was bubbled into the reactor. After the dissolved oxygen concentration had sufficiently decreased, 20% by volume fluorine gas diluted with nitrogen gas was blown in for 1 hour. A CFE-419 solution of compound C-2 (concentration: 10% by mass, 30 g of compound C-2) was added over 3 hours. Fluorine gas was introduced into the reactor simultaneously with the addition of the CFE-419 solution of compound C-2. When the molar introduction rate of compound C-2 into the solvent was set to 1, the molar introduction rate of fluorine gas was set to twice the rate obtained by multiplying the molar introduction rate of compound C-2 by the number of hydrogen atoms that could be substituted for fluorine atoms by the fluorine gas contained in compound C-2. After the addition of the CFE-419 solution of compound C-2 was completed, a CFE-419 solution of benzene (concentration: 0.1% by mass, benzene: 0.1 g) was intermittently added. After the addition of the benzene CFE-419 solution was completed, fluorine gas was bubbled in over 1 hour, and finally the atmosphere in the reactor was thoroughly replaced with nitrogen gas. The solvent was distilled off, yielding 44 g (96% yield) of compound C-3, which corresponds to the compound of formula (5). The average value of a was 4. In the formula, * represents the bond to the oxygen atom, and ** represents the bond to the carbon atom.

[0117] [ka]

[0118] (Synthesis Example 3-4) 44 g of compound C-3 and 20 ml of AC-2000 were added to a 200 mL recovery flask, and the mixture was stirred under ice cooling, followed by the addition of 3 g of methanol. The mixture was then returned to 25° C. and stirred for 15 hours. Then, 30 ml of water was added, and a crude reaction liquid was obtained, separated into an organic phase and an aqueous phase. The crude reaction liquid obtained was separated, and the organic phase was then concentrated to obtain 38 g (98% yield) of compound C-4, which corresponds to the compound of formula (6). The average of a was 4. In compound C-4, Me means a methyl group. In the formula, * represents the bond to the oxygen atom, and ** represents the bond to the carbon atom.

[0119] [ka]

[0120] (Synthesis Example 4) When 1 mol of compound A-1 corresponding to the compound of formula (1) is reacted with 1 mol or less of ethylene glycol corresponding to the compound of formula (2), a polymer having a hydroxyl group at the end is not obtained, and the subsequent reaction cannot proceed.

[0121] From the above examples, it can be seen that the present disclosure provides a method for producing a fluorinated polyether compound which has functional groups at both ends and which has few restrictions on the selection of structural units.

[0122] All publications, patent applications, and technical standards mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent application, or technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A fluorine-containing divinyl ether compound represented by the following general formula (1) is reacted with a diol compound represented by the following general formula (2) in a ratio of more than 1 mol of the diol compound represented by the following general formula (2) to 1 mol of the fluorine-containing divinyl ether compound represented by the following general formula (1), to produce a fluorine-containing dihydroxypolyether compound represented by the following general formula (3), esterifying a hydroxyl group contained in a fluorinated dihydroxypolyether compound represented by the following general formula (3) to produce a fluorinated diacyloxypolyether compound represented by the following general formula (4); A fluorinated diacyloxy polyether compound represented by the following general formula (4) is fluorinated to produce a perfluorodiacyloxy polyether compound represented by the following general formula (5), A method for producing a fluorine-containing polyether compound, which comprises reacting a perfluorodiacyloxy polyether compound represented by the following general formula (5) with an alcohol to produce a fluorine-containing dialkoxycarbonyl polyether compound represented by the following general formula (6), wherein the acidity of the diol compound represented by the general formula (2) is 8 to 18. CF ２ =CR １ -O-R ２ -O-CR １ =CF ２ ・・・(1) HO-CH ２ R ３ CH ２ -OH・・・(2) HO-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 -OH・・・(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 Ｆ４ CO-O-CF ２ R Ｆ３ CF ２ -O-(CF ２ -CFR Ｆ１ -O-R Ｆ２ -O-CFR Ｆ１ -CF ２ -O-CF ２ R Ｆ３ CF ２ -O) ａ -CF ２ -CFR Ｆ１ -O-R Ｆ２ -O-CFR Ｆ１ -CF ２ -O-CF ２ R Ｆ３ CF ２ -O-COR Ｆ４ ・・・(5) R ５ -O-COR Ｆ３ CF ２ -O-(CF ２ -CFR Ｆ１ -O-R Ｆ２ -O-CFR Ｆ１ -CF ２ -O-CF ２ R Ｆ３ CF ２ -O) ａ -CF ２ -CFR Ｆ１ -O-R Ｆ２ -O-CFR Ｆ１ -CF ２ -O-CF ２ R Ｆ３ CO-O-R ５ ・・・(6) (In general formula (1), general formula (3) and general formula (4), R １ represents a fluorine atom. In general formula (1), general formula (3) and general formula (4), R ２ each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may have a ring structure or a branched structure, which may have an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom. In general formulas (2) to (4), R ３ each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain a single bond, an ether bond, or a ring structure or a branched structure, and which may contain an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom. In general formula (4), R ４ each independently represents a monovalent hydrocarbon group having 2 to 20 carbon atoms, which may have a ring structure or a branched structure, which may have an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom. In general formula (6), R ５ each independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, which may have a ring structure or a branched structure, may contain an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom. In the general formula (5) and the general formula (6), R Ｆ１ represents a fluorine atom. In the general formula (5) and the general formula (6), R Ｆ２ are each independently R ２ represents a perfluorinated divalent hydrocarbon group having 1 to 20 carbon atoms. In the general formula (5) and the general formula (6), R Ｆ３ are each independently R ３ represents a single bond, and R ３ represents an ether bond, and R ３ When R is a divalent hydrocarbon group, ３ represents a perfluorinated divalent hydrocarbon group having 1 to 20 carbon atoms. In general formula (5), R Ｆ４ are each independently R ４ represents a perfluorinated divalent hydrocarbon group having 2 to 20 carbon atoms. In general formulas (3) to (6), a represents 0 or an integer of 1 or more, and a in general formulas (3) to (6) all have the same value.

2. 2. The method for producing a fluorinated polyether compound according to claim 1, wherein the reaction of the fluorinated divinyl ether compound represented by the general formula (1) with the diol compound represented by the general formula (2) is carried out in the presence of an alkali catalyst.

3. 3. The method for producing a fluorine-containing polyether compound according to claim 1 or 2, wherein in the fluorination of the fluorine-containing diacyloxy polyether compound represented by the general formula (4), fluorine gas is used in a ratio of 1.1 mol to 10 mol per 1 mol of hydrogen atoms to be fluorinated in the fluorine-containing diacyloxy polyether compound represented by the general formula (4).

4. fluorination of the fluorine-containing diacyloxy polyether compound represented by the general formula (4) is carried out by introducing fluorine gas and the fluorine-containing diacyloxy polyether compound represented by the general formula (4) into a solvent, 4. The method for producing a fluorine-containing polyether compound according to claim 1, wherein, when the molar introduction rate of the fluorine-containing diacyloxy polyether compound represented by the general formula (4) into the solvent is taken as 1, the molar introduction rate of the fluorine gas is in the range of 1 to 10 times the rate obtained by multiplying the molar introduction rate of the fluorine-containing diacyloxy polyether compound represented by the general formula (4) by the number of hydrogen atoms that can be substituted with fluorine atoms by the fluorine gas, contained in the fluorine-containing diacyloxy polyether compound represented by the general formula (4).

5. The method for producing a fluorinated polyether compound according to any one of claims 1 to 4, wherein the esterification of the hydroxyl groups contained in the fluorinated dihydroxypolyether compound represented by the general formula (3) is carried out by reacting an acid fluoride represented by the following general formula (7) with the fluorinated dihydroxypolyether compound represented by the general formula (3): R ４ COF・・・(7) (In general formula (7), R ４ represents a monovalent hydrocarbon group having 2 to 20 carbon atoms, which may contain a ring structure or a branched structure, may contain an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom.

6. The method for producing a fluorinated polyether compound according to any one of claims 1 to 5, wherein a in said general formulas (3) to (6) is an integer of 1 or more.

7. The method for producing a fluorinated polyether compound according to any one of claims 1 to 6, wherein the reaction temperature when reacting the fluorinated 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.

8. A method for producing a fluorinated polyether compound, comprising reacting a fluorinated divinyl ether compound represented by the following general formula (1) with a diol compound represented by the following general formula (2) in a ratio of more than 1 mol of the diol compound represented by the following general formula (2) per 1 mol of the fluorinated divinyl ether compound represented by the following general formula (1), to produce a fluorinated dihydroxy polyether compound represented by the following general formula (3), wherein the acidity of the diol compound represented by the general formula (2) is 8 to 18. CF ２ =CR １ -O-R ２ -O-CR １ =CF ２ ・・・(1) HO-CH ２ R ３ CH ２ -OH・・・(2) HO-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 -OH・・・(3) (In general formula (1) and general formula (3), R １ represents a fluorine atom. In the general formula (1) and the general formula (3), R ２ each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may have a ring structure or a branched structure, which may have an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom. In the general formula (2) and the general formula (3), R ３ each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain a single bond, an ether bond, or a ring structure or a branched structure, and which may contain an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom. In the general formula (3), a represents 0 or an integer of 1 or more.

9. A fluorine-containing divinyl ether compound represented by the following general formula (1) is reacted with a diol compound represented by the following general formula (2) in a ratio of more than 1 mol of the diol compound represented by the following general formula (2) to 1 mol of the fluorine-containing divinyl ether compound represented by the following general formula (1), to produce a fluorine-containing dihydroxypolyether compound represented by the following general formula (3), A method for producing a fluorine-containing polyether compound, comprising esterifying a hydroxyl group contained in a fluorine-containing dihydroxypolyether compound represented by the following general formula (3) to produce a fluorine-containing diacyloxypolyether compound represented by the following general formula (4), wherein the acidity of the diol compound represented by the general formula (2) is 8 to 18. CF ２ =CR １ -O-R ２ -O-CR １ =CF ２ ・・・(1) HO-CH ２ R ３ CH ２ -OH・・・(2) HO-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 -OH・・・(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) (In general formula (1), general formula (3) and general formula (4), R １ represents a fluorine atom. In general formula (1), general formula (3) and general formula (4), R ２ each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may have a ring structure or a branched structure, which may have an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom. In general formulas (2) to (4), R ３ each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain a single bond, an ether bond, or a ring structure or a branched structure, and which may contain an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom. In general formula (4), R ４ each independently represents a monovalent hydrocarbon group having 2 to 20 carbon atoms, which may have a ring structure or a branched structure, which may have an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom. In general formula (3) and general formula (4), a represents 0 or an integer of 1 or more, and a in general formula (3) and general formula (4) both have the same value.

10. A fluorine-containing divinyl ether compound represented by the following general formula (1) is reacted with a diol compound represented by the following general formula (2) in a ratio of more than 1 mol of the diol compound represented by the following general formula (2) to 1 mol of the fluorine-containing divinyl ether compound represented by the following general formula (1), to produce a fluorine-containing dihydroxypolyether compound represented by the following general formula (3), esterifying a hydroxyl group contained in a fluorinated dihydroxypolyether compound represented by the following general formula (3) to produce a fluorinated diacyloxypolyether compound represented by the following general formula (4); A method for producing a fluorinated polyether compound, which comprises fluorinating a fluorinated diacyloxy polyether compound represented by the following general formula (4) to produce a perfluorodiacyloxy polyether compound represented by the following general formula (5), wherein the acidity of the diol compound represented by the general formula (2) is 8 to 18. CF ２ =CR １ -O-R ２ -O-CR １ =CF ２ ・・・(1) HO-CH ２ R ３ CH ２ -OH・・・(2) HO-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 -OH・・・(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 Ｆ４ CO-O-CF ２ R Ｆ３ CF ２ -O-(CF ２ -CFR Ｆ１ -O-R Ｆ２ -O-CFR Ｆ１ -CF ２ -O-CF ２ R Ｆ３ CF ２ -O) ａ -CF ２ -CFR Ｆ１ -O-R Ｆ２ -O-CFR Ｆ１ -CF ２ -O-CF ２ R Ｆ３ CF ２ -O-COR Ｆ４ ・・・(5) (In general formula (1), general formula (3) and general formula (4), R １ represents a fluorine atom. In general formula (1), general formula (3) and general formula (4), R ２ each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may have a ring structure or a branched structure, which may have an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom. In general formulas (2) to (4), R ３ each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain a single bond, an ether bond, or a ring structure or a branched structure, and which may contain an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom. In general formula (4), R ４ each independently represents a monovalent hydrocarbon group having 2 to 20 carbon atoms, which may have a ring structure or a branched structure, which may have an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom. In general formula (5), R Ｆ１ represents a fluorine atom. In general formula (5), R Ｆ２ are each independently R ２ represents a perfluorinated divalent hydrocarbon group having 1 to 20 carbon atoms. In general formula (5), R Ｆ３ are each independently R ３ represents a single bond, and R ３ represents an ether bond, and R ３ When R is a divalent hydrocarbon group, ３ represents a perfluorinated divalent hydrocarbon group having 1 to 20 carbon atoms. In general formula (5), R Ｆ４ are each independently R ４ represents a perfluorinated divalent hydrocarbon group having 2 to 20 carbon atoms. In general formulas (3) to (5), a represents 0 or an integer of 1 or more, and a in general formulas (3) to (5) all have the same value.

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