Process for producing fluorine-containing polyether compounds

Abstract

The manufacturing method of the present disclosure is a method of manufacturing a two-terminal functionalized fluorine-containing polyether compound by reacting a compound of formula (1) with a compound of formula (2) at a ratio of more than 1 mol of the compound of formula (2) per 1 mol of the compound of formula (1), manufacturing a compound of formula (3), performing esterification, performing fluorination, and then performing alcoholization. Here, R 1 represents a fluorine atom or the like, R 2 represents a fluorine atom or the like, and R 3 represents a divalent hydrocarbon group having a carbon number of 1 to 20 or the like. CF2=CR 1 -O-R 2 -O-CR 1 =CF2 (1) HO-CH2R 3 CH2-OH (2).

Description

Technical Field

[0001] This disclosure relates to a method for manufacturing fluorinated polyether compounds. Background Technology

[0002] Fluorinated polyether compounds are used as surface treatment agents or lubricants due to their high lubricity and water and oil repellency.

[0003] Fluorinated polyether compounds are manufactured by various methods. For example, Patent Document 1 discloses the manufacture of fluorinated polyether compounds by reacting tetrafluoroethylene with oxygen in the presence of a compound having a fluorooxy group.

[0004] In addition, Patent Document 2 discloses the manufacture of fluorinated polyether compounds by ring-opening polymerization of 2,2,3,3-tetrafluorooxetane, and the manufacture of halogenated polyether compounds by chlorination and fluorination of the fluorinated polyether compounds.

[0005] Furthermore, Patent Document 3 discloses a method for reacting the compound represented by CF2=CFO-CF2CF2CF2CH2OH with A. 1 -OH(A 1 The alcohol represented by methyl group, etc., is reacted to produce A. 1 -O-(CF2CFHO-CF2CF2CF2CH2O) n+1 -H represents a halogenated polyether compound.

[0006] Existing technology

[0007] Patent documents

[0008] Patent Document 1: US Patent No. 5,258,110

[0009] Patent Document 2: US Patent No. 4,845,268

[0010] Patent Document 3: International Publication No. 2013 / 121984 Summary of the Invention

[0011] The problem the invention aims to solve

[0012] The method described in Patent Document 1, which introduces tetrafluoroethylene and oxygen into a solvent, can obtain perfluoropolyethers (PFPEs) with esters or alcohols at both ends. However, the method described in Patent Document 1 produces PFPEs containing random polymers whose structural units are mainly (CF2-CF2O) and (CF2O), and the structural units cannot be freely selected.

[0013] Furthermore, the method described in Patent Document 2 does not allow for the free selection of structural units contained in the PFPE. Additionally, it is sometimes difficult to functionalize the two ends of the PFPE.

[0014] Furthermore, in the PFPE manufacturing method described in Patent Document 3, it is difficult to functionalize the two ends of PFPE.

[0015] This disclosure is made in view of the above requirements, and the problem it seeks to solve is to provide a method for manufacturing fluorinated polyether compounds having functional groups at both ends and with fewer restrictions on the selection of structural units.

[0016] Solution for solving the problem

[0017] The specific means to achieve the aforementioned goals are as follows.

[0018] <1> A method for manufacturing a fluorinated polyether compound, wherein a fluorinated divinyl ether compound of general formula (1) and a diol compound of general formula (2) are reacted at a ratio of the diol compound of general formula (2) to 1 mol of the fluorinated divinyl ether compound of general formula (1) exceeding 1 mol, to produce a fluorinated dihydroxy polyether compound of general formula (3).

[0019] The fluorinated dihydroxyl polyether compound represented by the following general formula (3) is prepared by esterifying the hydroxyl groups contained in the fluorinated dihydroxyl polyether compound represented by the following general formula (3).

[0020] Fluorination of the fluorinated diacyloxy polyether compound of general formula (4) below produces the perfluorodiacyloxy polyether compound of general formula (5) below.

[0021] The fluorinated dialkoxy carbonyl polyether compound of general formula (6) is prepared by reacting an alcohol with a perfluorodiacyloxy polyether compound of general formula (5).

[0022] CF2 = CR 1 -OR 2 -O-CR 1 =CF2 (1)

[0023] HO-CH2R 3 CH2-OH(2)

[0024] 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-CH2R3 CH2-OH(3)

[0025] 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)

[0026] 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)

[0027] 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)

[0028] (In general formulas (1), (3) and (4), R) 1 Each of the following groups independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group with 1 to 3 carbon atoms that is optionally replaced by a fluorine atom.

[0029] In general formulas (1), (3), and (4), R 2Each of the following groups independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, wherein the divalent hydrocarbon group having 1 to 20 carbon atoms may optionally include a ring structure, a branched structure, or an ether bond, and the hydrogen atom may optionally be replaced by a fluorine atom.

[0030] In general formulas (2) to (4), R 3 Each of the following can be independently represented as a single bond, an ether bond, or a divalent hydrocarbon group having 1 to 20 carbon atoms, wherein the divalent hydrocarbon group having 1 to 20 carbon atoms may optionally include a ring structure, a branched structure, may optionally include an ether bond, and the hydrogen atom may optionally be replaced by a fluorine atom.

[0031] In general formula (4), R 4 Each of the above independently represents a monovalent hydrocarbon group having 2 to 20 carbon atoms, wherein the monovalent hydrocarbon group having 2 to 20 carbon atoms may optionally include a ring structure, a branched structure, or an ether bond, and the hydrogen atom may optionally be replaced by a fluorine atom.

[0032] In general formula (6), R 5 Each of the above independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, wherein the monovalent hydrocarbon group having 1 to 20 carbon atoms may optionally include a ring structure, a branched structure, or an ether bond, and the hydrogen atom may optionally be replaced by a fluorine atom.

[0033] In general formulas (5) and (6), in R 1 When R is a fluorine atom F1 Each fluorine atom represents itself independently, in R 1 When R is a hydrogen atom F1 Each fluorine atom represents itself independently, in R 1 When R is a monovalent hydrocarbon group F1 Each represents R independently. 1 The monovalent hydrocarbon group shown is a monovalent perfluorinated hydrocarbon group with 1 to 3 carbon atoms.

[0034] In general formulas (5) and (6), R F2 Each represents R independently. 2 The divalent hydrocarbon group shown is a divalent perfluorinated hydrocarbon group with 1 to 20 carbon atoms.

[0035] In general formulas (5) and (6), in R 3 When R is a single bond F3 Each represents a single bond independently, in R 3 When R is an ether bond F3 Each independently represents an ether bond, in R 3 When R is a divalent hydrocarbon group F3 Each represents R independently. 3 The divalent hydrocarbon group shown is a divalent perfluorinated hydrocarbon group with 1 to 20 carbon atoms.

[0036] In general formula (5), R F4 Each represents R independently. 4The divalent hydrocarbon group shown is a divalent perfluorinated hydrocarbon group with 2 to 20 carbon atoms.

[0037] In general formulas (3) to (6), 'a' represents an integer greater than or equal to 0 or 1, and 'a' in general formulas (3) to (6) all represent the same value.

[0038] <2> according to <1> The method for manufacturing the fluorinated polyether compound includes a reaction of the fluorinated divinyl ether compound of general formula (1) and the diol compound of general formula (2) in the presence of an alkaline catalyst.

[0039] <3> according to <1> or <2> The method for manufacturing the fluorinated polyether compound, wherein, in the fluorination of the fluorinated diacyloxy polyether compound of the aforementioned general formula (4), fluorine gas is used at a ratio of 1.1 mol to 10 mol relative to 1 mol of fluorinated hydrogen atoms in the fluorinated diacyloxy polyether compound of the aforementioned general formula (4).

[0040] <4> according to <1> ~ <3> The method for manufacturing the fluorinated polyether compound according to any one of the above methods, wherein the fluorination of the fluorinated diacyloxy polyether compound of the above general formula (4) is carried out by introducing fluorine gas and the fluorinated diacyloxy polyether compound of the above general formula (4) into a solvent.

[0041] When the molar rate of the fluorinated diacyloxy polyether compound shown in the aforementioned general formula (4) into the aforementioned solvent is set to 1, the molar rate of the aforementioned fluorine gas is in the range of 1 to 10 times the rate obtained by multiplying the molar rate of the fluorinated diacyloxy polyether compound shown in the aforementioned general formula (4) by the number of hydrogen atoms in the fluorinated diacyloxy polyether compound shown in the aforementioned general formula (4) that can be replaced by the aforementioned fluorine gas as fluorine atoms.

[0042] <5> according to <1> ~ <4> The method for manufacturing the fluorinated polyether compound according to any one of the above general formulas (3) is wherein the esterification of the hydroxyl groups contained in the fluorinated dihydroxy polyether compound of the above general formula (3) is to cause the acyl fluoride of the above general formula (7) to act on the fluorinated dihydroxy polyether compound of the above general formula (3).

[0043] R 4 COF(7)

[0044] (In general formula (7), R) 4 The term "denotes a monovalent hydrocarbon group having 2 to 20 carbon atoms, wherein the monovalent hydrocarbon group having 2 to 20 carbon atoms optionally includes a ring structure, a branched structure, optionally includes an ether bond, and the hydrogen atom is optionally substituted with a fluorine atom."

[0045] <6> according to <1> ~ <5> The method for manufacturing the fluorinated polyether compound according to any one of the above methods, wherein the acidity of the diol compound represented by the aforementioned general formula (2) is 8 to 18.

[0046] <7> according to <1> ~ <6> The method for manufacturing a fluorinated polyether compound according to any one of the above general formulas (3) to (6) is an integer greater than or equal to 1.

[0047] <8> according to <1> ~ <7> The method for manufacturing the fluorinated polyether compound according to any one of the above methods, wherein the reaction temperature for reacting the fluorinated divinyl ether compound of the aforementioned general formula (1) with the diol compound of the aforementioned general formula (2) is 80°C to 160°C.

[0048] <9> A method for manufacturing a fluorinated polyether compound, wherein a fluorinated divinyl ether compound of general formula (1) and a diol compound of general formula (2) are reacted at a ratio of more than 1 mol of the diol compound of general formula (2) to 1 mol of the fluorinated divinyl ether compound of general formula (1) to produce a fluorinated dihydroxy polyether compound of general formula (3).

[0049] CF2 = CR 1 -OR 2 -O-CR 1 =CF2 (1)

[0050] HO-CH2R 3 CH2-OH(2)

[0051] 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)

[0052] (In general formulas (1) and (3), R) 1 Each of the following groups independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group with 1 to 3 carbon atoms that is optionally replaced by a fluorine atom.

[0053] In general formulas (1) and (3), R 2Each of the following groups independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, wherein the divalent hydrocarbon group having 1 to 20 carbon atoms may optionally include a ring structure, a branched structure, or an ether bond, and the hydrogen atom may optionally be replaced by a fluorine atom.

[0054] In general formulas (2) and (3), R 3 Each of the following can be independently represented as a single bond, an ether bond, or a divalent hydrocarbon group having 1 to 20 carbon atoms, wherein the divalent hydrocarbon group having 1 to 20 carbon atoms may optionally include a ring structure, a branched structure, may optionally include an ether bond, and the hydrogen atom may optionally be replaced by a fluorine atom.

[0055] In general formula (3), a represents an integer greater than or equal to 0 or 1.

[0056] <10> A method for manufacturing a fluorinated polyether compound, wherein a fluorinated divinyl ether compound of general formula (1) and a diol compound of general formula (2) are reacted at a ratio of the diol compound of general formula (2) to 1 mol of the fluorinated divinyl ether compound of general formula (1) exceeding 1 mol, to produce a fluorinated dihydroxy polyether compound of general formula (3).

[0057] The fluorinated dihydroxyl polyether compound represented by the following general formula (4) is prepared by esterifying the hydroxyl groups contained in the fluorinated dihydroxyl polyether compound represented by the following general formula (3).

[0058] CF2 = CR 1 -OR 2 -O-CR 1 =CF2 (1)

[0059] HO-CH2R 3 CH2-OH(2)

[0060] 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)

[0061] 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)

[0062] (In general formulas (1), (3) and (4), R) 1 Each of the following groups independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group with 1 to 3 carbon atoms that is optionally replaced by a fluorine atom.

[0063] In general formulas (1), (3), and (4), R 2 Each of the following groups independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, wherein the divalent hydrocarbon group having 1 to 20 carbon atoms may optionally include a ring structure, a branched structure, or an ether bond, and the hydrogen atom may optionally be replaced by a fluorine atom.

[0064] In general formulas (2) to (4), R 3 Each of the following can be independently represented as a single bond, an ether bond, or a divalent hydrocarbon group having 1 to 20 carbon atoms, wherein the divalent hydrocarbon group having 1 to 20 carbon atoms may optionally include a ring structure, a branched structure, may optionally include an ether bond, and the hydrogen atom may optionally be replaced by a fluorine atom.

[0065] In general formula (4), R 4 Each of the above independently represents a monovalent hydrocarbon group having 2 to 20 carbon atoms, wherein the monovalent hydrocarbon group having 2 to 20 carbon atoms may optionally include a ring structure, a branched structure, or an ether bond, and the hydrogen atom may optionally be replaced by a fluorine atom.

[0066] In general formulas (3) and (4), 'a' represents an integer greater than or equal to 0 or 1, and 'a' in both formulas (3) and (4) represents the same value.

[0067] <11> A method for manufacturing a fluorinated polyether compound, wherein a fluorinated divinyl ether compound of general formula (1) and a diol compound of general formula (2) are reacted at a ratio of the diol compound of general formula (2) to 1 mol of the fluorinated divinyl ether compound of general formula (1) exceeding 1 mol, to produce a fluorinated dihydroxy polyether compound of general formula (3).

[0068] The fluorinated dihydroxyl polyether compound represented by the following general formula (3) is prepared by esterifying the hydroxyl groups contained in the fluorinated dihydroxyl polyether compound represented by the following general formula (3).

[0069] Fluorination of the fluorinated diacyloxy polyether compound of general formula (4) is used to manufacture the perfluorodiacyloxy polyether compound of general formula (5).

[0070] CF2 = CR 1 -OR 2 -O-CR 1 =CF2 (1)

[0071] HO-CH2R 3 CH2-OH(2)

[0072] 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)

[0073] 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)

[0074] 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)

[0075] (In general formulas (1), (3) and (4), R) 1 Each of the following groups independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group with 1 to 3 carbon atoms that is optionally replaced by a fluorine atom.

[0076] In general formulas (1), (3), and (4), R 2 Each of the following groups independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, wherein the divalent hydrocarbon group having 1 to 20 carbon atoms may optionally include a ring structure, a branched structure, or an ether bond, and the hydrogen atom may optionally be replaced by a fluorine atom.

[0077] In general formulas (2) to (4), R 3 Each of the following can be independently represented as a single bond, an ether bond, or a divalent hydrocarbon group having 1 to 20 carbon atoms, wherein the divalent hydrocarbon group having 1 to 20 carbon atoms may optionally include a ring structure, a branched structure, may optionally include an ether bond, and the hydrogen atom may optionally be replaced by a fluorine atom.

[0078] In general formula (4), R 4 Each of the above independently represents a monovalent hydrocarbon group having 2 to 20 carbon atoms, wherein the monovalent hydrocarbon group having 2 to 20 carbon atoms may optionally include a ring structure, a branched structure, or an ether bond, and the hydrogen atom may optionally be replaced by a fluorine atom.

[0079] In general formula (5), in R 1 When R is a fluorine atom F1 Each fluorine atom represents itself independently, in R 1 When R is a hydrogen atom F1 Each fluorine atom represents itself independently, in R 1 When R is a monovalent hydrocarbon group F1 Each represents R independently. 1 The monovalent hydrocarbon group shown is a monovalent perfluorinated hydrocarbon group with 1 to 3 carbon atoms.

[0080] In general formula (5), R F2 Each represents R independently. 2 The divalent hydrocarbon group shown is a divalent perfluorinated hydrocarbon group with 1 to 20 carbon atoms.

[0081] In general formula (5), in R 3 When R is a single bond F3 Each represents a single bond independently, in R 3 When R is an ether bond F3 Each independently represents an ether bond, in R 3 When R is a divalent hydrocarbon group F3 Each represents R independently. 3 The divalent hydrocarbon group shown is a divalent perfluorinated hydrocarbon group with 1 to 20 carbon atoms.

[0082] In general formula (5), R F4 Each represents R independently.4 The divalent hydrocarbon group shown is a divalent perfluorinated hydrocarbon group with 2 to 20 carbon atoms.

[0083] In general formulas (3) to (5), 'a' represents an integer greater than or equal to 0 or 1, and 'a' in general formulas (3) to (5) all represent the same value.

[0084] The effects of the invention

[0085] According to this disclosure, a method for manufacturing a fluorinated polyether compound having functional groups at both ends and with few restrictions on the selection of structural units is provided. Detailed Implementation

[0086] The following describes in detail the methods for implementing this disclosure. However, this disclosure is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps, etc.) are not essential unless specifically stated otherwise. The same applies to numerical values ​​and their ranges; these are not limiting to this disclosure.

[0087] In this disclosure, the numerical range represented by “~” includes the values ​​recorded before and after “~” as the minimum and maximum values, respectively.

[0088] In the numerical ranges described in this disclosure in stages, the upper or lower limit value of one numerical range can be replaced by the upper or lower limit value of other numerical ranges described in stages. Furthermore, the upper or lower limit value of a numerical range described in this disclosure can be replaced by the value shown in the synthetic example.

[0089] In this disclosure, "fluoroalkylene" includes perfluoroalkylene in which all hydrogen atoms are replaced by fluorine atoms, and fluoroalkylene in which some hydrogen atoms are replaced by fluorine atoms. Furthermore, in this disclosure, the terms "fluorocycloalkanes" and the like not only include perfluorocycloalkanes in which all hydrogen atoms are replaced by fluorine atoms, but also cycloalkanes in which some hydrogen atoms are replaced by fluorine atoms.

[0090] Each component in this disclosure may comprise a variety of corresponding compounds. For example, the molar ratio in the reaction of the fluorinated divinyl ether compound of general formula (1) with the diol compound of general formula (2) is calculated based on the total of the compounds corresponding to each component.

[0091] In the description of groups (atomic groups) in this disclosure, the description of not specifying substitution and unsubstituent includes those without substituents and those with substituents.

[0092] In this disclosure, the carbon number refers to the total number of carbon atoms contained in a group as a whole. If the group does not have substituents, it represents the number of carbon atoms forming the skeleton of the group. If the group has substituents, it represents the total number of carbon atoms forming the skeleton of the group plus the number of carbon atoms in the substituents.

[0093] In this disclosure, "perfluorinated" means that the alkyl group is fluorinated to the following state.

[0094] When the monovalent or divalent hydrocarbon group is a saturated hydrocarbon group, the state in which all the fluorinated hydrogen atoms bonded to the carbon atoms constituting the monovalent or divalent hydrocarbon group are fluorinated is called "perfluorinated" hydrocarbon group.

[0095] When a monovalent or divalent hydrocarbon group is unsaturated, the state in which all fluorinated hydrogen atoms bonded to the carbon atoms constituting the monovalent or divalent hydrocarbon group are fluorinated, and fluorine atoms are added to each of the two carbon atoms forming carbon-carbon double or triple bonds, thus eliminating the carbon-carbon unsaturated bonds, is called "perfluorination" of the hydrocarbon group. For example, if >C=C< is perfluorinated, it becomes >CF-CF<, and if -C≡C- is perfluorinated, it becomes -CF2-CF2-. Additionally, fluorinated hydrogen atoms can bond to fluorinated radicals; for example, if -CH=CH- is perfluorinated, it becomes -CF2-CF2-.

[0096] In this disclosure, the number-average molecular weight (Mn) and mass-average molecular weight (Mw) are determined by gel permeation chromatography (hereinafter also referred to as "GPC"). The GPC-based determination is performed according to the method described in Japanese Patent Application Publication No. 2001-208736 under the following conditions.

[0097] • Mobile phase: A mixed solvent of R-225 (manufactured by AGC Corporation, trade name: ASAHIKLIN (registered trademark) AK-225 SEC grade 1) and hexafluoroisopropyl alcohol (HFIP) (R-225:HFIP = 99:1 (volume ratio))

[0098] • Analytical column: Two PLgel MIXED-E columns (manufactured by Polymer Laboratories) are connected in series.

[0099] • Standard samples for molecular weight determination: four types of perfluoropolyethers with a molecular weight distribution (Mw / Mn) less than 1.1 and Mn ranging from 2,000 to 10,000, and one type of perfluoropolyether with a Mw / Mn greater than 1.1 and Mn of 1,300.

[0100] • Mobile phase flow rate: 1.0 mL / min

[0101] Column temperature: 37℃

[0102] • Detector: Evaporative light scattering detector

[0103] <Method for manufacturing the first fluorinated polyether compound>

[0104] In the method for manufacturing the first fluorinated polyether compound of this disclosure (hereinafter, sometimes referred to as the first manufacturing method of this disclosure), a fluorinated divinyl ether compound of general formula (1) (hereinafter, sometimes referred to as compound (1)) is reacted with a diol compound of general formula (2) at a ratio of compound (2) to 1 mol of compound (1) of more than 1 mol to produce a fluorinated dihydroxy polyether compound of general formula (3) (hereinafter, sometimes referred to as...). Compound (3) is prepared by esterifying the hydroxyl groups contained in compound (3) to produce a fluorinated diacyloxy polyether compound of general formula (4) (hereinafter, sometimes referred to as compound (4)). Compound (4) is prepared by fluorinating the compound to produce a perfluorodiacyloxy polyether compound of general formula (5) (hereinafter, sometimes referred to as compound (5)). Compound (5) is prepared by reacting an alcohol with the compound to produce a fluorinated dialkoxy carbonyl polyether compound of general formula (6) (hereinafter, sometimes referred to as compound (6)).

[0105] CF2 = CR 1 -OR 2 -O-CR 1 =CF2 (1)

[0106] HO-CH2R 3 CH2-OH(2)

[0107] 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)

[0108] R 4 CO-O-CH2R 3 CH2-O-(CF2-CHR 1 -OR 2 -O-CHR 1 -CF2-O-CH2R 3CH2-O) a -CF2-CHR 1 -OR 2 -O-CHR 1 -CF2-O-CH2R 3 CH2-O-COR 4 (4)

[0109] 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)

[0110] 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)

[0111] In general formulas (1), (3), and (4), R 1 Each of the following groups independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group with 1 to 3 carbon atoms that is optionally replaced by a fluorine atom.

[0112] In general formulas (1), (3), and (4), R 2 Each of the following groups independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, wherein the divalent hydrocarbon group having 1 to 20 carbon atoms may optionally include a ring structure, a branched structure, or an ether bond, and the hydrogen atom may optionally be replaced by a fluorine atom.

[0113] In general formulas (2) to (4), R 3Each of the following can be independently represented as a single bond, an ether bond, or a divalent hydrocarbon group having 1 to 20 carbon atoms, wherein the divalent hydrocarbon group having 1 to 20 carbon atoms may optionally include a ring structure, a branched structure, may optionally include an ether bond, and the hydrogen atom may optionally be replaced by a fluorine atom.

[0114] In general formula (4), R 4 Each of the above independently represents a monovalent hydrocarbon group having 2 to 20 carbon atoms, wherein the monovalent hydrocarbon group having 2 to 20 carbon atoms may optionally include a ring structure, a branched structure, or an ether bond, and the hydrogen atom may optionally be replaced by a fluorine atom.

[0115] In general formula (6), R 5 Each of the above independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, wherein the monovalent hydrocarbon group having 1 to 20 carbon atoms may optionally include a ring structure, a branched structure, or an ether bond, and the hydrogen atom may optionally be replaced by a fluorine atom.

[0116] In general formulas (5) and (6), in R 1 When R is a fluorine atom F1 Each fluorine atom represents itself independently, in R 1 When R is a hydrogen atom F1 Each fluorine atom represents itself independently, in R 1 When R is a monovalent hydrocarbon group, F1 Each represents R independently. 1 The monovalent hydrocarbon group shown is a monovalent perfluorinated hydrocarbon group with 1 to 3 carbon atoms.

[0117] In general formulas (5) and (6), R F2 Each represents R independently. 2 The divalent hydrocarbon group shown is a divalent perfluorinated hydrocarbon group with 1 to 20 carbon atoms.

[0118] In general formulas (5) and (6), in R 3 When R is a single bond F3 Each represents a single bond independently, in R 3 When R is an ether bond F3 Each independently represents an ether bond, in R 3 When R is a divalent hydrocarbon group F3 Each represents R independently. 3 The divalent hydrocarbon group shown is a divalent perfluorinated hydrocarbon group with 1 to 20 carbon atoms.

[0119] In general formula (5), R F4 Each represents R independently. 4 The divalent hydrocarbon group shown is a divalent perfluorinated hydrocarbon group with 2 to 20 carbon atoms.

[0120] In general formulas (3) to (6), a represents an integer greater than or equal to 0 or 1, and a in general formulas (3) to (6) all represent the same value.

[0121] According to this disclosure, a method for manufacturing fluorinated polyether compounds having functional groups at both ends and with fewer restrictions on the selection of structural units can be provided.

[0122] As a reason for achieving the above-mentioned effect, for example, the following speculations can be made, but it is not limited to these.

[0123] In the first manufacturing method disclosed herein, compounds of formula (1) and formula (2) are used as monomers that serve as raw materials for fluorinated polyether compounds. By appropriately selecting the types of compounds of formula (1) and formula (2), the limitations in selecting structural units can be reduced compared to the methods described in Patent Documents 1 and 2.

[0124] Furthermore, in the first manufacturing method of this disclosure, when reacting the compound of formula (1) and the compound of formula (2) to obtain the compound of formula (3), the reaction is carried out at a ratio of more than 1 mol of the compound of formula (2) to 1 mol of the compound of formula (1), thus hydroxyl groups are easily generated at the end of the compound of formula (3). By chemically modifying the end of the compound of formula (3) containing hydroxyl groups, ester groups can be generated at both ends of the fluorinated polyether compound obtained by the first manufacturing method of this disclosure. Therefore, unlike the methods described in Patent Documents 2 and 3, the first manufacturing method of this disclosure can functionalize both ends of the fluorinated polyether compound.

[0125] The following describes in detail the various materials and reaction steps used in the first manufacturing method of this disclosure.

[0126] -Formula (1) Compound-

[0127] The compound of formula (1) used in this disclosure is a specific fluorinated divinyl ether compound represented by the following general formula (1).

[0128] CF2 = CR 1 -OR 2 -O-CR 1 =CF2 (1)

[0129] In general formula (1), R 1 Each of the groups independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having 1 to 3 carbon atoms, with the hydrogen atom optionally replaced by a fluorine atom. From the viewpoint of lubrication, at least one R group is preferred. 1 It is a fluorine atom, more preferably two R atoms. 1 It is a fluorine atom.

[0130] In general formula (1), R 2 The term represents a divalent hydrocarbon group having 1 to 20 carbon atoms, wherein the divalent hydrocarbon group having 1 to 20 carbon atoms optionally includes a ring structure, a branched structure, optionally includes an ether bond, and the hydrogen atom is optionally replaced by a fluorine atom.

[0131] R 2 The number of carbon atoms in the divalent hydrocarbon group shown is preferably 15 or less, more preferably 10 or less. By using R... 2 The number of carbon atoms in the divalent hydrocarbon group shown is set to 15 or less, so that the polymerization reaction proceeds better, and thus high molecular weight fluorinated polyether compounds can be produced in high yield.

[0132] From the perspective of preventing cyclization reactions, R 2 The number of carbon atoms in the divalent hydrocarbon group shown is preferably 3 or more, more preferably 4 or more.

[0133] As R 2 The divalent hydrocarbon groups shown include, for example, alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene and hexamethylene, and fluoroalkylene groups such as fluoromethylene, fluoroethylene, fluorotrimethylene, fluorotetramethylene, fluoropentamethylene and fluorohexamethylene.

[0134] R 2 The divalent hydrocarbon group shown can be a group represented by the following general formula (X).

[0135] *-R x -(OR x ) n -*(X)

[0136] In the general formula (X), R x The symbol represents ethylene, trimethylene, propylene, fluoroethylene, fluorotrimethylene, or fluoropropylene, and n represents an integer greater than or equal to 1.

[0137] It should be noted that in the general formula (X), * represents the part bonded to the oxygen atom.

[0138] R 2 The divalent hydrocarbon group shown can be a group represented by the following general formula (A).

[0139] *-R b -OR a -OR b -*(A)

[0140] In general formula (A), R a It indicates a cycloalkane dimethyl, a fluorocycloalkane dimethyl, or an aryl group.

[0141] As R a Examples of cycloalkane dimethyl and fluorocycloalkane dimethyl groups shown include cyclobutane dimethyl, fluorocyclobutane dimethyl, cyclopentane dimethyl, fluorocyclopentane dimethyl, cyclohexane dimethyl, fluorocyclohexane dimethyl, adamantane dimethyl, norbornene dimethyl, etc. The cycloalkane dimethyl, fluorocycloalkane dimethyl, and aryl group may have an alkyl group having 1 to 3 carbon atoms that are optionally replaced by fluorine atoms as substituents.

[0142] In general formula (A), R b Each can be independently represented as a divalent hydrocarbon group with 1 to 10 carbon atoms, which may contain a ring structure or a branched structure and whose hydrogen atoms may be substituted by fluorine atoms.

[0143] As R b Examples of divalent hydrocarbon groups shown include methylene, ethylene, trimethylene, tetramethylene, fluoromethylene, fluoroethylene, fluorotrimethylene, and fluorotetramethylene.

[0144] It should be noted that in general formula (A), * represents the part bonded to the oxygen atom.

[0145] Examples of divalent hydrocarbon groups represented by general formula (A) are listed below, but are not limited to these.

[0146]

[0147] Additionally, R 2 The divalent hydrocarbon group shown can be a group represented by the following general formulas (B) to (D).

[0148] *-R c -R a -R c -* (B)

[0149] *-R a -R c -R a -* (C)

[0150] *-R b -R d -R b -* (D)

[0151] R in general formulas (B) and (C) a The groups represented are the same as those in the above general formula (A).

[0152] R in general formula (D) b The groups represented are the same as those in the above general formula (A).

[0153] In addition, in general formulas (B) and (C), R c Each of the groups independently represents a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms, wherein the divalent hydrocarbon group having 1 to 10 carbon atoms may optionally include a ring structure or a branched structure, and the hydrogen atom may optionally be replaced by a fluorine atom.

[0154] As R c Examples of divalent hydrocarbon groups shown include methylene, ethylene, trimethylene, propylene, isopropylene, fluoromethylene, fluoroethylene, fluorotrimethylene, fluoropropylene, and fluoroisopropylene.

[0155] In addition, in general formula (D), R d It represents cycloalkanes with 3 to 6 carbon atoms, denoted as -1,1-dimethyl.

[0156] It should be noted that in general formulas (B) to (D), * indicates the part bonded to the oxygen atom.

[0157] Examples of groups that satisfy any of the general formulas (B) to (D) are listed below, but are not limited to these.

[0158]

[0159]

[0160]

[0161] Based on the above R 2 The specific examples of the divalent hydrocarbon groups shown are, as specific examples of compounds of formula (1), the following compounds can be cited, but are not limited to these.

[0162]

[0163]

[0164]

[0165] Compound of formula (2)

[0166] The compounds of formula (2) used in this disclosure are specific diol compounds represented by the following general formula (2).

[0167] HO-CH2R 3 CH2-OH(2)

[0168] In general formula (2), R 3 The term represents a single bond, an ether bond, or a divalent hydrocarbon group having 1 to 20 carbon atoms, wherein the divalent hydrocarbon group having 1 to 20 carbon atoms optionally includes a ring structure, a branched structure, optionally includes an ether bond, and the hydrogen atom is optionally substituted by a fluorine atom.

[0169] The acidity (pKa) of the compound of formula (2) is preferably 8 to 18, more preferably 9 to 14. By making the pKa of the compound of formula (2) within the above-mentioned range, the reaction with the compound of formula (1) proceeds well.

[0170] In this disclosure, pKa is a value in water at 25°C, calculated using the method described in the Chemical Handbook Basics, Revised 5th Edition II-331 to II-343 (edited by the Chemical Society of Japan, published by Maruzen Co., Ltd.).

[0171] In general formula (2), R is included.3 "-CH2R" 3 The divalent hydrocarbon group indicated by "CH2-" (hereinafter sometimes referred to as "-CH2R") 3 The number of carbon atoms in the CH2-" group is preferably 15 or less, more preferably 10 or less. By using "-CH2R" 3 The number of carbon atoms in the CH2-" group is set to 15 or less, which allows the polymerization reaction to proceed more smoothly, thus enabling the production of high molecular weight fluorinated polyether compounds in high yield.

[0172] From a synthetic perspective, "-CH2R" 3 The number of carbons in the CH2-" group is preferably 2 or more, more preferably 3 or more.

[0173] As "-CH2R" 3 CH2-" groups, for example, include alkylene groups such as ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene, and fluoroalkylene groups such as fluorotrimethylene, fluorotetramethylene, fluoropentamethylene, and fluorohexamethylene. Among them, "-CH2R" 3 When the CH2-” group is a fluoroalkyl group, the two ends of the fluoroalkyl group are methylene structures.

[0174] -CH2R 3 The CH2-" group can be a group represented by the following general formula (X').

[0175] *-CH2R X1 -(OR X2 ) n1 -OR X1 CH2-*(X')

[0176] In the general formula (X'), R X1 This indicates a single bond, methylene, ethylene, methylmethylene, fluoromethylene, fluoroethylene, and fluoromethylmethylene.

[0177] In the general formula (X'), R X2 It can refer to ethylene, trimethylene, propylene, fluoroethylene, fluorotrimethylene, or fluoropropylene.

[0178] In the general formula (X'), n1 represents an integer greater than or equal to 0 or 1.

[0179] It should be noted that in the general formula (X'), * represents the part bonded to the oxygen atom.

[0180] Additionally, "-CH2R" 3 The CH2-" group can be a group represented by the following general formula (A').

[0181] *-R b2 -OR a -ORb2 -*(A')

[0182] In the general formula (A'), R a The specific examples of cycloalkane dimethyl, fluorocycloalkane dimethyl, or arylene are the same as those in general formula (A).

[0183] In the general formula (A'), R b2 Each of these groups independently represents a divalent hydrocarbon group with 1 to 10 carbon atoms, in which a hydrogen atom is optionally replaced by a fluorine atom. Wherein, R... b2 When a hydrogen atom is replaced by a fluorine atom in a divalent hydrocarbon group having 2 to 10 carbon atoms, R b2 The terminal end of the * side is a methylene structure. Additionally, R b2 When R is a hydrocarbon group with 1 carbon atom, b2 It is a methylene group.

[0184] It should be noted that in the general formula (A'), * represents the part bonded to the oxygen atom.

[0185] Examples of divalent hydrocarbon groups represented by the general formula (A') include, but are not limited to, the following groups.

[0186]

[0187] Additionally, "-CH2R" 3 The CH2-" group can be a group represented by the following general formula (B') or (D').

[0188] *-R c2 -R a -R c2 -* (B')

[0189] *-R b2 -R d -R b2 -* (D')

[0190] R in general formula (B') a The groups represented are the same as those in the above general formula (A).

[0191] In addition, in the general formula (B'), R c2 Each of the terms independently represents a straight-chain alkylene group having 1 to 10 carbon atoms, preferably a straight-chain alkylene group having 1 to 5 carbon atoms, and more preferably a straight-chain alkylene group having 1 to 2 carbon atoms.

[0192] R in general formula (D') b2 The groups represented are the same as those in the above general formula (A').

[0193] In addition, in the general formula (D'), R d It represents cycloalkanes with 3 to 6 carbon atoms, denoted as -1,1-dimethyl.

[0194] It should be noted that in general formulas (B') and (D'), * indicates the part bonded to the oxygen atom.

[0195] Examples of groups that satisfy either general formula (B') or general formula (D') include, but are not limited to, the following groups.

[0196]

[0197] Based on the above "-CH2R" 3 Specific examples of the CH2-" group, as specific examples of compounds of formula (2), can be given as the following compounds, but are not limited to them.

[0198]

[0199]

[0200]

[0201] -Preparation of compound (3)-

[0202] In the first manufacturing method disclosed herein, compound (3) is manufactured by reacting compound (1) with compound (2) at a ratio of compound (2) to 1 mol of compound (1) of more than 1 mol.

[0203] 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)

[0204] In general formula (3), R 1 R 2 and R 3 The details are as described above.

[0205] In general formula (3), a represents an integer of 0 or 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. In addition, 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.

[0206] The reaction between compound (1) and compound (2) can be carried out in a solvent or in a solvent-free state.

[0207] When the reaction between compound (1) and compound (2) is carried out in a solvent, fluorinated organic solvents are preferred, such as fluorinated alkanes, fluorinated aromatic compounds, and fluorinated alkyl ethers.

[0208] The ratio of compound (1) to compound (2) is preferably adjusted according to the molecular weight of the target fluorinated polyether compound. From the viewpoint of controlling the molecular weight, 1 mol of compound (2) is preferably 1.01 mol or more, more preferably 1.10 mol or more, relative to 1 mol of compound (1). On the other hand, from the viewpoint of controlling the molecular weight of the target fluorinated polyether compound and saving excess raw materials, the ratio of compound (1) to compound (2) is preferably 2.00 mol or less, more preferably 1.90 mol or less, further preferably 1.70 mol or less, and particularly preferably 1.50 mol or less, relative to 1 mol of compound (1).

[0209] The reaction of compound (1) with compound (2) is preferably carried out in the presence of a base catalyst. By reacting compound (1) with compound (2) in the presence of a base catalyst, the molecular weight and yield of the prepared compound (3) can be further increased.

[0210] Examples of alkaline catalysts include sodium hydroxide, potassium hydroxide, sodium carbonate, cesium fluoride, and potassium carbonate. From the viewpoint of the molecular weight and yield of the compound in formula (3), potassium carbonate is preferred.

[0211] 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℃~160℃, more preferably 90℃~140℃.

[0212] From the viewpoint of the molecular weight and yield of the compound of formula (3), the reaction time between 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.

[0213] The compound of formula (3) can be manufactured in batch or continuous manner, and can be manufactured in a known manner.

[0214] When manufacturing compound (3) in batches, for example, compound (2) is pre-contained in a reactor, compound (1) can be added directly to the reactor, or a dilution of compound (1) can be added.

[0215] From the viewpoint of the molecular weight and yield of compound (3), in the reaction between compound (1) and compound (2), the addition of compound (1) to compound (2) is preferably carried out at a rate of 0.01 to 10 times the mole of compound (2) relative to 1 mole of compound (2), more preferably at a rate of 0.1 to 0.5 times the mole of compound (2).

[0216] After reacting compound (1) with compound (2), at least one of an organic solvent, water, and an aqueous solution adjusted to a suitable acidity can be added to the reaction solution, and the mixture can be separated. The organic phase can then be concentrated to obtain compound (3). Alternatively, the crude reaction solution obtained by concentrating the organic phase can be purified to obtain compound (3).

[0217] There are no particular restrictions on the combination of compounds of formula (1) and formula (2) used in the manufacture of compound (3).

[0218] For example, the compound of formula (1) can be selected from perfluorodivinyl ether compounds.

[0219] -Preparation of compound (4)-

[0220] In the first manufacturing method disclosed herein, compound (4) is manufactured by esterifying the hydroxyl groups contained in compound (3).

[0221] 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)

[0222] In general formula (4), R 1 R 2 and R 3 The details of a are as described above.

[0223] In general formula (4), R 4 Details of the fluoride are described later along with the description of the acyl fluoride.

[0224] There are no particular limitations on the method for esterifying the hydroxyl group contained in the compound of formula (3), and conventionally known reactions can be used. For example, methods such as reacting a carboxylic acid compound with the hydroxyl group, reacting a carboxylic anhydride with the hydroxyl group, and reacting an acyl halide with the hydroxyl group can be cited.

[0225] From the viewpoint of high reactivity, the esterification of the hydroxyl group contained in the compound of formula (3) is preferably carried out by acting an acyl halide on the hydroxyl group, more preferably by acting an acyl fluoride on the hydroxyl group, and even more preferably by acting an acyl fluoride represented by the following general formula (7) (hereinafter sometimes referred to as the compound of formula (7)) on the compound of formula (3).

[0226] R 4 COF(7)

[0227] In general formula (7), R 4 The term represents a monovalent hydrocarbon group having 2 to 20 carbon atoms, wherein the monovalent hydrocarbon group having 2 to 20 carbon atoms may optionally include a ring structure, a branched structure, or an ether bond, and the hydrogen atom may optionally be replaced by a fluorine atom.

[0228] R 4 From the viewpoint of ease of purification, the number of carbon atoms in the monovalent hydrocarbon group shown is preferably 20 or less, more preferably 10 or less. On the other hand, R 4 From the viewpoint of suppressing side reactions during fluorination, the number of carbon atoms in the monovalent hydrocarbon group shown is preferably 3 or more, and more preferably 4 or more.

[0229] R 4 When the hydrogen atoms in the monovalent hydrocarbon group shown are replaced by fluorine atoms, the fluorine atom content is preferably 50 mol% or more, more preferably 75 mol% or more, and even more preferably 100 mol% (perfluorocarbon group). The fluorine atom content is the proportion of hydrogen atoms in the hydrocarbon group that are replaced by fluorine atoms.

[0230] As specific examples of compounds of formula (7) that may be used in this disclosure, the following compounds may be cited, but are not limited thereto.

[0231] ·CF3CF2CF2-O-CF(CF3)COF

[0232] ·CF3CF2CF2-O-CF(CF3)CF2-O-CF(CF3)COF

[0233] ·CF3-CF(CF3)COF

[0234] The esterification of the hydroxyl groups contained in the compound of formula (3) can be carried out in a solvent or in a solvent-free state. When the esterification of the hydroxyl groups contained in the compound of formula (3) is carried out in a solvent, fluorinated organic solvents are preferred, such as fluorinated alkanes, fluorinated aromatic compounds, and fluoroalkyl ethers.

[0235] When the compound of formula (7) is reacted with the compound of formula (3), it is preferable to do so 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) can be further improved.

[0236] Examples of catalysts include sodium fluoride and triethylamine, with sodium fluoride being preferred from the viewpoint of ease of post-processing.

[0237] When compound (7) is reacted with compound (3), from the viewpoint of the yield of compound (4), the reaction temperature is preferably -10°C to 100°C, more preferably 0°C to 60°C.

[0238] When compound (7) is reacted with compound (3), from the viewpoint of the yield of compound (4), the reaction time of compound (3) and compound (7) is preferably 1 hour to 40 hours, more preferably 2 hours to 20 hours.

[0239] When compound (7) is reacted with compound (3), from the viewpoint of the yield of compound (4), the reaction pressure when compound (3) reacts with compound (7) is preferably atmospheric pressure to 2 MPa (gauge pressure).

[0240] The compound of formula (4) can be manufactured in batch or continuous manner, and can be manufactured in a known manner.

[0241] In the case of manufacturing compound (4) in batches, for example, compound (3) can be pre-contained in the reactor and compound (7) can be added directly into the reactor.

[0242] When compound (7) is applied to compound (3), from the viewpoint of suppressing the generation of byproducts, the addition of compound (7) to compound (3) is preferably carried out at a rate where the internal temperature of the reactor does not exceed 40°C, and more preferably at a rate where the internal temperature does not exceed 20°C.

[0243] If compound (7) is reacted with compound (3), hydrogen fluoride (HF) is produced through the reaction of compound (3) and compound (7). Therefore, it is preferable to have a hydrogen fluoride scavenger in the reaction system. Examples of hydrogen fluoride scavengers include alkali metal fluorides and trialkylamines. NaF or KF is preferred as an alkali metal fluoride. If no HF scavenger is used, it is preferable to carry out the reaction at a reaction temperature at which HF can be vaporized, and to vent HF out of the reaction system along with a nitrogen gas stream. The amount of HF scavenger is preferably 1 to 10 moles relative to compound (7).

[0244] After reacting compound (7) with compound (3), at least one of an organic solvent, water, and an aqueous solution adjusted to a suitable acidity can be added to the reaction solution and the mixture can be separated, or the reaction solution can be separated into solid and liquid phases and the organic phase can be concentrated to obtain compound (4). Alternatively, compound (4) can be obtained by purifying the crude reaction solution obtained by concentrating the organic phase.

[0245] -Preparation of compound (5)-

[0246] In the first manufacturing method disclosed herein, compound (5) is manufactured by fluorinating compound (4).

[0247] 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)

[0248] In general formula (5), in R 1 When R is a fluorine atom F1 Each fluorine atom represents itself independently, in R 1 When R is a hydrogen atom F1 Each fluorine atom represents itself independently, in R 1 When R is a monovalent hydrocarbon group F1 Each represents R independently. 1 The monovalent hydrocarbon group shown is a monovalent perfluorinated hydrocarbon group with 1 to 3 carbon atoms.

[0249] In general formula (5), R F2 Each represents R independently.2 The divalent hydrocarbon group shown is a divalent perfluorinated hydrocarbon group with 1 to 20 carbon atoms.

[0250] In general formula (5), in R 3 When R is a single bond F3 Each represents a single bond independently, in R 3 When R is an ether bond F3 Each independently represents an ether bond, in R 3 When R is a divalent hydrocarbon group F3 Each represents R independently. 3 The divalent hydrocarbon group shown is a divalent perfluorinated hydrocarbon group with 1 to 20 carbon atoms.

[0251] In general formula (5), R F4 Each represents R independently. 4 The divalent hydrocarbon group shown is a divalent perfluorinated hydrocarbon group with 2 to 20 carbon atoms.

[0252] In general formula (5), the details of a are as described above.

[0253] There are no particular limitations on the fluorination method of the compound of formula (4), and it can be carried out by methods known in the past. For example, fluorination can be carried out by contacting fluorine gas with the compound of formula (4).

[0254] The fluorination of compound (4) can be carried out in a batch or a continuous manner. The fluorination reaction is preferably carried out by either <Method 1> or <Method 2> described below, with <Method 2> being more preferred in terms of the reaction yield and selectivity of compound (5). In both the batch and continuous manner, the fluorine gas can be diluted with an inert gas such as nitrogen.

[0255] Method 1

[0256] Method 1 is as follows: the compound of formula (4) and solvent are added to the reactor, stirring is started, and then the reaction is carried out while fluorine gas diluted with inactive gas is continuously supplied to the solvent at the specified reaction temperature and reaction pressure.

[0257] Method 2

[0258] Method 2 is as follows: a solvent is added to the reactor and stirred, and then the reaction is carried out by continuously supplying fluorine gas diluted with an inactive gas, compound of formula (4) and solvent to the fluorination reaction solvent at a specified molar ratio under a specified reaction temperature and reaction pressure.

[0259] Method 3

[0260] Method 3 is as follows: A solvent is continuously introduced into a tubular reactor, allowing the solvent to flow within the reactor. Then, fluorine gas diluted with an inert gas and a solution containing the compound of formula (4) are continuously supplied to the solvent stream within the tubular reactor at a predetermined molar ratio of fluorine gas to the compound of formula (4) and mixed. The fluorine gas is then brought into contact with the compound of formula (4) within the tubular reactor to react. The solvent containing the reaction product is then removed from the tubular reactor. In this method, the solvent is circulated, and the reaction product is removed from the circulated solvent, enabling the fluorination reaction to proceed continuously.

[0261] Similar to Method 3, in Method 2, supplying a solvent-diluted compound of Formula (4) when supplying the compound of Formula (4) is preferable in terms of improving the selectivity of the compound of Formula (5) and suppressing the amount of byproducts. In addition, when diluting the compound of Formula (4) with a solvent, the amount of solvent relative to the compound of Formula (4) is preferably 5 times or more, more preferably 7 times or more, on a mass basis.

[0262] Examples of inert gases include rare gases such as helium, neon, and argon, as well as nitrogen. Nitrogen and helium are preferred, and nitrogen is more preferred from an economic perspective. The proportion of fluorine (hereinafter also referred to as "fluorine amount") is preferably 10% to 60% by volume in a total of 100% by volume of fluorine and inert gases.

[0263] The amount of fluorine gas used is preferably 1.1 mol to 10 mol, more preferably 1.2 mol to 5 mol, relative to 1 mol of fluorine-substituted hydrogen atoms in the compound of formula (4). By setting the ratio of the amount of fluorine gas used to the above values, the yield of the compound of formula (5) can be improved.

[0264] In the case of fluorination of compound (4) in a solvent, the solvent can be pre-purified with nitrogen in order to reduce the oxygen content in the solvent.

[0265] In addition, when the compound of formula (4) is introduced into the solvent, the solvent can be pre-nitrogen-replaced and then fluorine-replaced.

[0266] In the fluorination reaction, whether in a batch or continuous manner, it is preferable that the amount of fluorine gas used to fluorinate all the fluorinated hydrogen atoms in the compound of formula (4) is always in excess. The amount of fluorine gas is preferably at least 1.1 times the theoretical amount required to fluorinate all the fluorinated hydrogen atoms, more preferably at least 1.3 times the theoretical amount required to fluorinate all the fluorinated hydrogen atoms.

[0267] When fluorination of compound (4) is performed by introducing fluorine gas and compound (4) into a solvent, if the molar rate of introducing compound (4) into the solvent is set to 1, the molar rate of introducing fluorine gas can be in the range of 1 to 10 times, or 2 to 7 times, the rate obtained by multiplying the molar rate of introducing compound (4) by the number of hydrogen atoms in compound (4) that can be replaced by fluorine atoms. By setting the relationship of the introduction rates within the above-mentioned range, the yield of compound (5) can be improved.

[0268] To efficiently carry out the fluorination reaction of compound (4), it is preferable to add a CH-bonded compound other than compound (4) to the solvent, or to irradiate the solvent with ultraviolet light. These are preferably carried out in the later stages of the fluorination reaction. Thus, compound (4) present in the solvent can be fluorinated efficiently, and the yield of compound (5) can be increased.

[0269] As the CH-bonded compound, aromatic hydrocarbons are preferred, such as benzene and toluene. The amount of the CH-bonded compound added is preferably 0.1 mol% to 10 mol% relative to the hydrogen atoms in the compound of formula (4), more preferably 0.1 mol% to 5 mol%.

[0270] Compounds containing CH bonds are preferably added to a solvent in which fluorine gas is present. Furthermore, when adding a compound containing CH bonds, it is preferable to pressurize the reaction system. The reaction pressure during pressurization is preferably 0.01 MPa to 5 MPa (gauge pressure).

[0271] When the reaction system is irradiated with ultraviolet light, the irradiation time is preferably 0.1 hours to 3 hours.

[0272] After the fluorination reaction, the system can be purged with an inert gas such as nitrogen, and the organic phase can be concentrated to obtain compound (5). Alternatively, the crude reaction liquid obtained by concentrating the organic phase can be purified to obtain compound (5).

[0273] -Preparation of compound (6)-

[0274] In the first manufacturing method of this disclosure, compound (6) can be manufactured by reacting an alcohol with compound (5).

[0275] 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)

[0276] In general formula (6), R F1 R F2 R F3 and R F4 The details of a are as described above.

[0277] In general formula (6), R 5 Each of the above independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, wherein the monovalent hydrocarbon group having 1 to 20 carbon atoms may optionally include a ring structure, a branched structure, or an ether bond, and the hydrogen atom may optionally be replaced by a fluorine atom.

[0278] By reacting an alcohol with the compound of formula (5), the end of the compound of formula (5) is esterified to obtain the compound of formula (6).

[0279] There are no particular limitations on the alcohols that act on the compound of formula (5). Examples of alcohols include methanol, ethanol, and isopropanol.

[0280] The reaction of compound (5) with alcohol can be carried out in a solvent or in a solvent-free state.

[0281] When the reaction of the compound of formula (5) with the alcohol is carried out in a solvent, a fluorinated organic solvent is preferred, such as fluorinated alkanes, fluorinated aromatic compounds, fluorinated alkyl ethers, etc.

[0282] Regarding the amount of alcohol relative to the compound of formula (5), relative to 1 mol of the compound of formula (5), the alcohol 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.

[0283] From the viewpoint of the yield of compound (6), the reaction temperature of compound (5) with alcohol is preferably -10°C to 60°C, more preferably 0°C to 40°C.

[0284] From the viewpoint of the yield of compound (6), the reaction time of compound (5) with alcohol is preferably 0.5 hours to 48 hours, more preferably 1 hour to 24 hours.

[0285] From the viewpoint of suppressing the generation of byproducts, in the reaction of compound (5) with alcohol, the addition of alcohol to compound (5) is preferably carried out at a rate where the internal temperature of the reactor does not exceed 40°C, and more preferably at a rate where the internal temperature does not exceed 20°C.

[0286] After reacting the compound of formula (5) with an alcohol, at least one of an organic solvent, water, and an aqueous solution adjusted to a suitable acidity can be added to the reaction solution, and the mixture can be separated. The organic phase can then be concentrated to obtain the compound of formula (6). Alternatively, the crude reaction solution obtained by concentrating the organic phase can be purified to obtain the compound of formula (6).

[0287] The number-average molecular weight (Mn) of the compound of formula (6) obtained by the first manufacturing method of this disclosure is preferably 1,000 to 30,000, more preferably 1,500 to 20,000, and even more preferably 2,000 to 10,000.

[0288] Furthermore, the molecular weight distribution (Mw / Mn) of the compound of formula (6) obtained by the first manufacturing method of this disclosure is preferably 1 to 3, more preferably 1 to 2.5, and even more preferably 1 to 2.

[0289] <Second Method for Manufacturing Fluorinated Polyether Compounds>

[0290] In the method for manufacturing the second fluorinated polyether compound of this disclosure (hereinafter, sometimes referred to as the second manufacturing method of this disclosure), compound (1) and compound (2) are reacted at a ratio of compound (2) to 1 mol of compound (1) of more than 1 mol to produce compound (3).

[0291] The details of compounds of formula (1) to (3) in the second manufacturing method of this disclosure, as well as the details of the synthesis steps of compound (3), are the same as those in the first manufacturing method of this disclosure.

[0292] <Method for manufacturing the third fluorinated polyether compound>

[0293] In the method for manufacturing the third fluorinated polyether compound of the present disclosure (hereinafter, sometimes referred to as the third manufacturing method of the present disclosure), the compound of formula (1) and the compound of formula (2) are reacted at a ratio of more than 1 mol of the compound of formula (2) to 1 mol of the compound of formula (1) to produce the compound of formula (3), and the hydroxyl groups contained in the compound of formula (3) are esterified to produce the compound of formula (4).

[0294] The details of compounds of formula (1) to (4) in the third manufacturing method of this disclosure, as well as the details of the synthesis steps of compounds of formula (3) and (4), are the same as those of the first manufacturing method of this disclosure.

[0295] <Method for manufacturing the fourth fluorinated polyether compound>

[0296] In the method for manufacturing the fourth fluorinated polyether compound of this disclosure (hereinafter, sometimes referred to as the fourth manufacturing method of this disclosure), compound (1) and compound (2) are reacted at a ratio of compound (2) to 1 mol of compound (1) of more than 1 mol to produce compound (3), hydroxyl groups contained in compound (3) are esterified to produce compound (4), compound (4) is fluorinated to produce compound (5).

[0297] The details of compounds of formula (1) to (5) in the fourth manufacturing method of this disclosure, as well as the details of the synthesis steps of compounds of formula (3) to (5), are the same as those of the first manufacturing method of this disclosure.

[0298] Example

[0299] The above embodiments will be described in more detail below through examples, but the above embodiments are not limited to these examples.

[0300] Synthetic Examples 1-1 to 3-4 are examples, and Synthetic Example 4 is a comparative example.

[0301] [Evaluation Method]

[0302] (GPC Analysis)

[0303] Number-average molecular weight (Mn) and mass-average molecular weight (Mw) were determined by GPC.

[0304] The GPC-based measurements were performed using the methods described above.

[0305] (Synthesis Example 1-1)

[0306] In a 200 mL flask, add 4.1 g of ethylene glycol and 4 g of potassium carbonate, which are equivalent to the compound of formula (2). Stir the flask while keeping the temperature inside at 120 °C. Add 20 g of compound A-1, which is equivalent to the compound of formula (1), over 4 hours (0.21 moles per hour relative to 1 mole of compound of formula (2)). Stir for 2 hours at 120 °C.

[0307] Subsequently, the temperature inside the flask was restored to 25°C, and 20g each of a fluorinated organic solvent (manufactured by AGC Corporation, ASAHIKLIN AC-2000, 1H-tridecylfluorohexane, hereinafter referred to as AC-2000) and hydrochloric acid were added, resulting in a crude reaction solution separated into an organic phase and an aqueous phase. The crude reaction solution was then separated, and the organic phase was concentrated.

[0308] The crude reaction solution obtained by concentrating the organic phase was purified by column chromatography to obtain 14 g of compound A-2 (yield 58%), which is equivalent to compound (3). The average value of a is 6.

[0309] CF2=CF-O-CF2CF2CF2-O-CF=CF2 A-1

[0310]

[0311] (Synthesis Example 1-2)

[0312] In a 200 mL flask, add 14 g of compound A-2, 1.5 g of sodium fluoride, and 20 mL of AC-2000. Stir while chilled, then add 5.0 g of compound A-3, equivalent to compound (7). Afterward, restore to 25 °C and stir for 15 hours.

[0313] Subsequently, the solid and liquid were separated by filtration, and the resulting liquid was concentrated and purified by column chromatography to obtain 16g of compound A-4 equivalent to compound (4) (yield 94%).

[0314] CF3CF2CF2-O-CF(CF3)COF A-3

[0315]

[0316] (Synthesis Example 1-3)

[0317] Add 250 mL of CFE-419 (ClCF2CFClCF2OCF2CF2Cl) to a 500 mL nickel reactor and purge with nitrogen gas (bubbling).

[0318] After the dissolved oxygen concentration has sufficiently decreased, 20% (v / v) fluorine gas diluted with nitrogen is blown in for 1 hour. A CFE-419 solution of compound A-4 (concentration: 10% (w / w), compound A-4: 17 g) is added over 3 hours. Simultaneously with the addition of the CFE-419 solution of compound A-4, fluorine gas is introduced into the reactor. When the molar rate of compound A-4 introduced into the solvent is set to 1, the molar rate of fluorine gas introduced is set to twice the rate obtained by multiplying the molar rate of compound A-4 by the number of hydrogen atoms in compound A-4 that can be replaced by fluorine atoms.

[0319] After the addition of the CFE-419 solution of compound A-4 was completed, the CFE-419 solution of benzene (concentration: 0.1% by mass, benzene: 0.1g) was added intermittently.

[0320] After the addition of the benzene CFE-419 solution, fluorine gas was purged in for 1 hour, and finally the reactor was completely replaced with nitrogen. The solvent was removed by distillation to obtain 20g of compound A-5 (yield 94%), which is equivalent to the compound of formula (5).

[0321]

[0322] (Synthesis Example 1-4)

[0323] In a 200 mL pear-shaped flask, add 20 g of compound A-5 and 20 mL of AC-2000, stir while chilled, and then add 1.5 g of methanol. Afterward, restore the temperature to 25 °C and stir for 15 hours.

[0324] Subsequently, 30 ml of water was added to obtain a crude reaction solution separated into an organic phase and an aqueous phase. The crude reaction solution was separated, and then the organic phase was concentrated to obtain 16 g of compound A-6 (yield 98%), equivalent to compound (6). It should be noted that Me in compound A-6 refers to the methyl group.

[0325]

[0326] The compound A-6 has an Mn of 3700 and an Mw / Mn ratio of 1.7.

[0327] (Synthesis example 2-1)

[0328] In a 200 mL flask, add 9.4 g of 1,4-benzyl alcohol and 4 g of potassium carbonate, which are equivalent to the compound of formula (2). Stir the flask while keeping the temperature inside at 120 °C. Add 20 g of compound A-1, which is equivalent to the compound of formula (1), over a period of 7 hours (0.12 times the molar ratio of 1 mole of compound (2)). Stir for 2 hours at 120 °C.

[0329] Subsequently, the temperature inside the flask was restored to 25°C, and 20g each of AC-2000 and hydrochloric acid were added, resulting in a crude reaction solution separated into an organic phase and an aqueous phase. The crude reaction solution was then separated, and the organic phase was concentrated.

[0330] The crude reaction solution obtained by concentrating the organic phase was purified by column chromatography to obtain 25 g of compound B-1 equivalent to compound (3) (yield 85%). The average value of a is 5.

[0331]

[0332] (Synthesis example 2-2)

[0333] In a 200 mL flask, add 24 g of compound B-1, 2.5 g of sodium fluoride, and 30 mL of AC-2000. Stir under ice conditions, then add 7.5 g of compound A-3, equivalent to compound (7). Afterward, restore to 25 °C and stir for 15 hours.

[0334] Subsequently, the solid and liquid were separated by filtration, and the resulting liquid was concentrated and purified by column chromatography to obtain 29g of compound B-2 equivalent to compound (4) (yield 98%). The average value of a is 5.

[0335]

[0336] (Synthesis example 2-3)

[0337] Add 250 mL of CFE-419 to a 500 mL nickel reactor and purge with nitrogen gas (bubbling).

[0338] After the dissolved oxygen concentration has sufficiently decreased, 20% (v / v) fluorine gas diluted with nitrogen is blown in for 1 hour. A CFE-419 solution of compound B-2 (concentration: 10% (w / w), compound B-2: 17 g) is added over 3 hours. Simultaneously with the addition of the CFE-419 solution of compound B-2, fluorine gas is introduced into the reactor. When the molar rate of compound B-2 introduction into the solvent is set to 1, the molar rate of fluorine gas introduction is set to three times the rate obtained by multiplying the molar rate of compound B-2 introduction by the number of hydrogen atoms in compound B-2 that can be replaced by fluorine atoms.

[0339] After the addition of the CFE-419 solution of compound B-2 was completed, the CFE-419 solution of benzene (concentration: 0.1% by mass, benzene: 0.1g) was added intermittently.

[0340] After the addition of the benzene CFE-419 solution, fluorine gas was purged in for 1 hour, and finally the reactor was completely purged with nitrogen. The solvent was removed by distillation to obtain 16 g of compound B-3 equivalent to compound (5) (yield 70%). The average value of a is 5.

[0341]

[0342] (Synthesis example 2-4)

[0343] In a 200 mL flask, add 16 g of compound B-3 and 20 mL of AC-2000, stir while chilled, and then add 1.5 g of methanol. Afterward, restore the temperature to 25 °C and stir for 15 hours.

[0344] Subsequently, 30 ml of water was added to obtain a crude reaction solution separated into an organic phase and an aqueous phase. The crude reaction solution was separated, and then the organic phase was concentrated to obtain 14 g of compound B-4 equivalent to compound (6) (yield 98%). The average value of a is 5. It should be noted that Me in compound B-4 refers to methyl.

[0345]

[0346] The compound B-4 has an Mn of 4000 and an Mw / Mn ratio of 2.

[0347] (Synthesis example 3-1)

[0348] In a 200 mL eggplant-shaped flask, add 13.6 g of tetraethylene glycol and 4 g of potassium carbonate, which are equivalent to the compound of formula (2). Stir the flask while keeping the temperature inside at 120 °C. Add 20 g of compound A-1, which is equivalent to the compound of formula (1), over 2 hours (0.4 times the molar ratio of 1 mole of compound of formula (2)). Stir at 120 °C for 2 hours.

[0349] Subsequently, the temperature inside the flask was restored to 25°C, and 20g each of AC-2000 and hydrochloric acid were added, resulting in a crude reaction solution separated into an organic phase and an aqueous phase. The crude reaction solution was then separated, and the organic phase was concentrated.

[0350] The crude reaction solution obtained by concentrating the organic phase was purified by column chromatography to obtain 26 g of compound C-1 (yield 78%), equivalent to compound (3). The average value of a is 4. In the formula, * represents the portion bonded to oxygen atoms, and ** represents the portion bonded to carbon atoms.

[0351]

[0352] (Synthesis example 3-2)

[0353] In a 200 mL flask, add 26 g of compound C-1, 2.5 g of sodium fluoride, and 30 mL of AC-2000. Stir while chilled, then add 9 g of compound A-3, equivalent to compound (7). Afterward, restore to 25 °C and stir for 15 hours.

[0354] Subsequently, the solid and liquid were separated by filtration. The resulting liquid was concentrated and purified by column chromatography to obtain 30g of compound C-2 equivalent to compound (4) (yield 93%). The average value of a is 4. In the formula, * represents the bonded portion with oxygen atoms, and ** represents the bonded portion with carbon atoms.

[0355]

[0356] (Synthesis example 3-3)

[0357] Add 250 mL of CFE-419 to a 500 mL nickel reactor and purge with nitrogen gas (bubbling).

[0358] After the dissolved oxygen concentration has sufficiently decreased, 20% (v / v) fluorine gas diluted with nitrogen is blown in for 1 hour. A CFE-419 solution of compound C-2 (concentration: 10% (w / w), compound C-2: 30 g) is added over 3 hours. Simultaneously with the addition of the CFE-419 solution of compound C-2, fluorine gas is introduced into the reactor. When the molar rate of compound C-2 introduced into the solvent is set to 1, the molar rate of fluorine gas introduced is set to twice the rate obtained by multiplying the molar rate of compound C-2 by the number of hydrogen atoms in compound C-2 that can be replaced by fluorine atoms.

[0359] After the addition of the CFE-419 solution of compound C-2 was completed, the CFE-419 solution of benzene (concentration: 0.1% by mass, benzene: 0.1g) was added intermittently.

[0360] After the addition of the benzene CFE-419 solution, fluorine gas was purged for 1 hour, and finally the reactor was completely purged with nitrogen. The solvent was removed by distillation to obtain 44g of compound C-3 equivalent to compound (5) (yield 96%). The average value of a is 4. In the formula, * represents the bonded portion with oxygen atoms, and ** represents the bonded portion with carbon atoms.

[0361]

[0362] (Synthesis Example 3-4)

[0363] In a 200 mL pear-shaped flask, add 44 g of compound C-3 and 20 mL of AC-2000, stir while chilled, and then add 3 g of methanol. Afterward, restore the temperature to 25 °C and stir for 15 hours.

[0364] Subsequently, 30 ml of water was added to obtain a crude reaction solution separated into an organic phase and an aqueous phase. The crude reaction solution was separated, and then the organic phase was concentrated to obtain 38 g of compound C-4 equivalent to compound (6) (yield 98%). The average value of a is 4. It should be noted that Me in compound C-4 refers to methyl. In the formula, * represents the bonded portion with oxygen atoms, and ** represents the bonded portion with carbon atoms.

[0365]

[0366] (Synthesis Example 4)

[0367] When ethylene glycol equivalent to compound (2) is reacted with less than 1 mol of compound A-1 equivalent to compound (1), a polymer with terminal hydroxyl groups is not obtained, and no further reaction is carried out.

[0368] As can be seen from the above embodiments, according to this disclosure, a method for manufacturing fluorinated polyether compounds with functional groups at both ends and fewer restrictions on the selection of structural units can be provided.

[0369] All documents, patent applications, and technical standards described herein, and the specific details thereof, are incorporated herein by reference to each document, patent application, and technical standard to the same extent.

Claims

1. A method for manufacturing a fluorinated polyether compound, wherein, A fluorinated divinyl ether compound of general formula (1) is reacted with a diol compound of general formula (2) at a ratio of more than 1 mol of the diol compound of general formula (2) to 1 mol of the fluorinated divinyl ether compound of general formula (1) to produce a fluorinated dihydroxy polyether compound of general formula (3). The fluorinated dihydroxyl polyether compound represented by the following general formula (3) is prepared by esterifying the hydroxyl groups contained in the fluorinated dihydroxyl polyether compound represented by the following general formula (3). Fluorination of the fluorinated diacyloxy polyether compound of general formula (4) below produces the perfluorodiacyloxy polyether compound of general formula (5) below. The fluorinated dialkoxy carbonyl polyether compound of general formula (6) is prepared by reacting an alcohol with a perfluorodiacyloxy polyether compound of general formula (5). CF2=CR 1 -O-R 2 -O-CR 1 =CF2 (1) HO-CH2R 3 CH2-OH(2) HO-CH2R 3 CH2-O-(CF2-CHR 1 -O-R 2 -O-CHR 1 -CF2-O-CH2R 3 CH2-O) a -CF2-CHR 1 -O-R 2 -O-CHR 1 -CF2-O-CH2R 3 CH2-OH(3) R 4 CO-O-CH2R 3 CH2-O-(CF2-CHR 1 -O-R 2 -O-CHR 1 -CF2-O-CH2R 3 CH2-O) a -CF2-CHR 1 -O-R 2 -O-CHR 1 -CF2-O-CH2R 3 CH2-O-COR 4 (4) R F4 CO-O-CF2R F3 CF2-O-(CF2-CFR F1 -O-R F2 -O-CFR F1 -CF2-O-CF2R F3 CF2-O) a -CF2-CFR F1 -O-R F2 -O-CFR F1 -CF2-O-CF2R F3 CF2-O-COR F4 (5) R 5 -O-COR F3 CF2-O-(CF2-CFR F1 -O-R F2 -O-CFR F1 -CF2-O-CF2R F3 CF2-O) a -CF2-CFR F1 -O-R F2 -O-CFR F1 -CF2-O-CF2R F3 CO-O-R 5 (6) In general formulas (1), (3), and (4), R 1 Each of these groups independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group with 1 to 3 carbon atoms, in which a hydrogen atom is optionally replaced by a fluorine atom. In general formulas (1), (3), and (4), R 2 Each of the following groups independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, wherein the divalent hydrocarbon group having 1 to 20 carbon atoms optionally includes a ring structure, a branched structure, optionally includes an ether bond, and the hydrogen atom is optionally replaced by a fluorine atom. In general formulas (2) to (4), R 3 Each of the following can independently represent a single bond, an ether bond, or a divalent hydrocarbon group having 1 to 20 carbon atoms, wherein the divalent hydrocarbon group having 1 to 20 carbon atoms may optionally include a ring structure, a branched structure, or an ether bond, and the hydrogen atom may optionally be replaced by a fluorine atom. In general formula (4), R 4 Each of the above independently represents a monovalent hydrocarbon group having 2 to 20 carbon atoms, wherein the monovalent hydrocarbon group having 2 to 20 carbon atoms optionally includes a ring structure, a branched structure, optionally includes an ether bond, and the hydrogen atom is optionally replaced by a fluorine atom. In general formula (6), R 5 Each of the above independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, wherein the monovalent hydrocarbon group having 1 to 20 carbon atoms optionally includes a ring structure, a branched structure, optionally includes an ether bond, and the hydrogen atom is optionally replaced by a fluorine atom. In general formulas (5) and (6), in R 1 When R is a fluorine atom F1 Each fluorine atom represents itself independently, in R 1 When R is a hydrogen atom F1 Each fluorine atom represents itself independently, in R 1 When R is a monovalent hydrocarbon group F1 Each represents R independently. 1 The monovalent hydrocarbon group shown is a perfluorinated monovalent perfluorocarbon group with 1 to 3 carbon atoms. In general formulas (5) and (6), R F2 Each represents R independently. 2 The divalent hydrocarbon group shown is a perfluorinated divalent perfluorocarbon group with 1 to 20 carbon atoms. In general formulas (5) and (6), in R 3 When R is a single bond F3 Each represents a single bond independently, in R 3 When R is an ether bond F3 Each independently represents an ether bond, in R 3 When R is a divalent hydrocarbon group F3 Each represents R independently. 3 The divalent hydrocarbon group shown is a perfluorinated divalent perfluorocarbon group with 1 to 20 carbon atoms. In general formula (5), R F4 Each represents R independently. 4 The divalent hydrocarbon group shown is a perfluorinated divalent perfluorocarbon group with 2 to 20 carbon atoms. In general formulas (3) to (6), a represents an integer greater than or equal to 0 or 1, and a in general formulas (3) to (6) all represent the same value.

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

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

4. The method for manufacturing the fluorinated polyether compound according to claim 1 or 2, wherein, The fluorination of the fluorinated diacyloxy polyether compound of general formula (4) is carried out by introducing fluorine gas and the fluorinated diacyloxy polyether compound of general formula (4) into the solvent. When the molar rate of the fluorinated diacyloxy polyether compound of general formula (4) into the solvent is set to 1, the molar rate of the fluorine gas is in the range of 1 to 10 times the rate obtained by multiplying the molar rate of the fluorinated diacyloxy polyether compound of general formula (4) by the number of hydrogen atoms in the fluorinated diacyloxy polyether compound of general formula (4) that can be replaced by the fluorine gas as fluorine atoms.

5. The method for manufacturing the fluorinated polyether compound according to claim 1 or 2, wherein, The esterification of the hydroxyl groups contained in the fluorinated dihydroxy polyether compound of general formula (3) is such that the acyl fluoride of general formula (7) below acts on the fluorinated dihydroxy polyether compound of general formula (3). R 4 COF(7) In general formula (7), R 4 The term represents a monovalent hydrocarbon group having 2 to 20 carbon atoms, wherein the monovalent hydrocarbon group having 2 to 20 carbon atoms may optionally include a ring structure, a branched structure, may optionally include an ether bond, and the hydrogen atom may optionally be replaced by a fluorine atom.

6. The method for manufacturing the fluorinated polyether compound according to claim 1 or 2, wherein, The acidity of the diol compound represented by the general formula (2) is 8 to 18.

7. The method for manufacturing the fluorinated polyether compound according to claim 1 or 2, wherein, In the general formulas (3) to (6), a is an integer greater than or equal to 1.

8. The method for manufacturing the fluorinated polyether compound according to claim 1 or 2, wherein, The reaction temperature for reacting the fluorinated divinyl ether compound of general formula (1) with the diol compound of general formula (2) is 80°C to 160°C.

9. A method for manufacturing a fluorinated polyether compound, wherein, A fluorinated divinyl ether compound of general formula (1) is reacted with a diol compound of general formula (2) at a ratio of more than 1 mol of the diol compound of general formula (2) to 1 mol of the fluorinated divinyl ether compound of general formula (1) to produce a fluorinated dihydroxy polyether compound of general formula (3). CF2=CR 1 -O-R 2 -O-CR 1 =CF2 (1) HO-CH2R 3 CH2-OH(2) HO-CH2R 3 CH2-O-(CF2-CHR 1 -O-R 2 -O-CHR 1 -CF2-O-CH2R 3 CH2-O) a -CF2-CHR 1 -O-R 2 -O-CHR 1 -CF2-O-CH2R 3 CH2-OH(3) In general formulas (1) and (3), R 1 Each of these groups independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group with 1 to 3 carbon atoms, in which a hydrogen atom is optionally replaced by a fluorine atom. In general formulas (1) and (3), R 2 Each of the following groups independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, wherein the divalent hydrocarbon group having 1 to 20 carbon atoms optionally includes a ring structure, a branched structure, optionally includes an ether bond, and the hydrogen atom is optionally replaced by a fluorine atom. In general formulas (2) and (3), R 3 Each of the following can independently represent a single bond, an ether bond, or a divalent hydrocarbon group having 1 to 20 carbon atoms, wherein the divalent hydrocarbon group having 1 to 20 carbon atoms may optionally include a ring structure, a branched structure, or an ether bond, and the hydrogen atom may optionally be replaced by a fluorine atom. In general formula (3), a represents an integer greater than or equal to 0 or 1.

10. A method for manufacturing a fluorinated polyether compound, wherein, A fluorinated divinyl ether compound of general formula (1) is reacted with a diol compound of general formula (2) at a ratio of more than 1 mol of the diol compound of general formula (2) to 1 mol of the fluorinated divinyl ether compound of general formula (1) to produce a fluorinated dihydroxy polyether compound of general formula (3). The fluorinated dihydroxyl polyether compound represented by the following general formula (3) is prepared by esterifying the hydroxyl groups contained in the fluorinated dihydroxyl polyether compound represented by the following general formula (3). CF2=CR 1 -O-R 2 -O-CR 1 =CF2 (1) HO-CH2R 3 CH2-OH(2) HO-CH2R 3 CH2-O-(CF2-CHR 1 -O-R 2 -O-CHR 1 -CF2-O-CH2R 3 CH2-O) a -CF2-CHR 1 -O-R 2 -O-CHR 1 -CF2-O-CH2R 3 CH2-OH(3) R 4 CO-O-CH2R 3 CH2-O-(CF2-CHR 1 -O-R 2 -O-CHR 1 -CF2-O-CH2R 3 CH2-O) a -CF2-CHR 1 -O-R 2 -O-CHR 1 -CF2-O-CH2R 3 CH2-O-COR 4 (4) In general formulas (1), (3), and (4), R 1 Each of these groups independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group with 1 to 3 carbon atoms, in which a hydrogen atom is optionally replaced by a fluorine atom. In general formulas (1), (3), and (4), R 2 Each of the following groups independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, wherein the divalent hydrocarbon group having 1 to 20 carbon atoms optionally includes a ring structure, a branched structure, optionally includes an ether bond, and the hydrogen atom is optionally replaced by a fluorine atom. In general formulas (2) to (4), R 3 Each of the following can independently represent a single bond, an ether bond, or a divalent hydrocarbon group having 1 to 20 carbon atoms, wherein the divalent hydrocarbon group having 1 to 20 carbon atoms may optionally include a ring structure, a branched structure, or an ether bond, and the hydrogen atom may optionally be replaced by a fluorine atom. In general formula (4), R 4 Each of the above independently represents a monovalent hydrocarbon group having 2 to 20 carbon atoms, wherein the monovalent hydrocarbon group having 2 to 20 carbon atoms optionally includes a ring structure, a branched structure, optionally includes an ether bond, and the hydrogen atom is optionally replaced by a fluorine atom. In general formulas (3) and (4), a represents an integer greater than or equal to 0 or 1, and a in general formulas (3) and (4) represents the same value.

11. A method for manufacturing a fluorinated polyether compound, wherein, A fluorinated divinyl ether compound of general formula (1) is reacted with a diol compound of general formula (2) at a ratio of more than 1 mol of the diol compound of general formula (2) to 1 mol of the fluorinated divinyl ether compound of general formula (1) to produce a fluorinated dihydroxy polyether compound of general formula (3). The fluorinated dihydroxyl polyether compound represented by the following general formula (3) is prepared by esterifying the hydroxyl groups contained in the fluorinated dihydroxyl polyether compound represented by the following general formula (3). Fluorination of the fluorinated diacyloxy polyether compound of general formula (4) below produces the perfluorodiacyloxy polyether compound of general formula (5) below. CF2=CR 1 -O-R 2 -O-CR 1 =CF2 (1) HO-CH2R 3 CH2-OH(2) HO-CH2R 3 CH2-O-(CF2-CHR 1 -O-R 2 -O-CHR 1 -CF2-O-CH2R 3 CH2-O) a -CF2-CHR 1 -O-R 2 -O-CHR 1 -CF2-O-CH2R 3 CH2-OH(3) R 4 CO-O-CH2R 3 CH2-O-(CF2-CHR 1 -O-R 2 -O-CHR 1 -CF2-O-CH2R 3 CH2-O) a -CF2-CHR 1 -O-R 2 -O-CHR 1 -CF2-O-CH2R 3 CH2-O-COR 4 (4) R F4 CO-O-CF2R F3 CF2-O-(CF2-CFR F1 -O-R F2 -O-CFR F1 -CF2-O-CF2R F3 CF2-O) a -CF2-CFR F1 -O-R F2 -O-CFR F1 -CF2-O-CF2R F3 CF2-O-COR F4 (5) In general formulas (1), (3), and (4), R 1 Each of these groups independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group with 1 to 3 carbon atoms, in which a hydrogen atom is optionally replaced by a fluorine atom. In general formulas (1), (3), and (4), R 2 Each of the following groups independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, wherein the divalent hydrocarbon group having 1 to 20 carbon atoms optionally includes a ring structure, a branched structure, optionally includes an ether bond, and the hydrogen atom is optionally replaced by a fluorine atom. In general formulas (2) to (4), R 3 Each of the following can independently represent a single bond, an ether bond, or a divalent hydrocarbon group having 1 to 20 carbon atoms, wherein the divalent hydrocarbon group having 1 to 20 carbon atoms may optionally include a ring structure, a branched structure, or an ether bond, and the hydrogen atom may optionally be replaced by a fluorine atom. In general formula (4), R 4 Each of the above independently represents a monovalent hydrocarbon group having 2 to 20 carbon atoms, wherein the monovalent hydrocarbon group having 2 to 20 carbon atoms optionally includes a ring structure, a branched structure, optionally includes an ether bond, and the hydrogen atom is optionally replaced by a fluorine atom. In general formula (5), in R 1 When R is a fluorine atom F1 Each fluorine atom represents itself independently, in R 1 When R is a hydrogen atom F1 Each fluorine atom represents itself independently, in R 1 When R is a monovalent hydrocarbon group F1 Each represents R independently. 1 The monovalent hydrocarbon group shown is a perfluorinated monovalent perfluorocarbon group with 1 to 3 carbon atoms. In general formula (5), R F2 Each represents R independently. 2 The divalent hydrocarbon group shown is a perfluorinated divalent perfluorocarbon group with 1 to 20 carbon atoms. In general formula (5), in R 3 When R is a single bond F3 Each represents a single bond independently, in R 3 When R is an ether bond F3 Each independently represents an ether bond, in R 3 When R is a divalent hydrocarbon group F3 Each represents R independently. 3 The divalent hydrocarbon group shown is a perfluorinated divalent perfluorocarbon group with 1 to 20 carbon atoms. In general formula (5), R F4 Each represents R independently. 4 The divalent hydrocarbon group shown is a perfluorinated divalent perfluorocarbon group with 2 to 20 carbon atoms. In general formulas (3) to (5), a represents an integer greater than or equal to 0 or 1, and a in general formulas (3) to (5) all represent the same value.

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