Method for producing fluorine-containing polyether compounds, method for producing fluorine-containing divinyl polyether compounds, and fluorine-containing divinyl polyether compounds

Abstract

Provided is a production method in which a compound represented by (1) and a compound represented by (2) are reacted at a ratio at which the compound represented by (1) exceeds 1 mole with respect to a mole of the compound represented by (2) to thereby produce a compound represented by (3), after which the compound represented by (3) is fluorinated, and a fluorine-containing polyether compound represented by (4) is produced. (1): CF2=CR1-O-R2-O-CR1=CF2 (2): HO-R3-OH (3): CF2=CR1-O-R2-O-(CHR1-CF2-O-R3-O-CF2-CHR1-O-R2-O)a-CR1=CF2 (4): CF3-CFRF1-O-RF2-O-(CFRF1-CF2-O-RF3-O-CF2-CFRF1-O-RF2-O)a-CFRF1-CF3

Description

[Technical Field]

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

[0002] Fluorine-containing compounds exhibit high lubricity and water / oil repellency, etc., and are therefore used as surface treatment agents or lubricants, etc. Among fluorine-containing compounds, fluorine-containing polyether compounds having an ether bond have excellent lubricity and are used to form coatings for the purpose of protecting the read heads of magnetic disks, etc.

[0003] Fluorine-containing polyether compounds have been conventionally produced by various methods. For example, U.S. Patent No. 5,258,110 discloses a method for producing a fluorine-containing polyether compound by reacting tetrafluoroethylene with oxygen in the presence of a compound having a fluorooxy group. Furthermore, U.S. Pat. No. 4,845,268 discloses the production of a fluorine-containing polyether compound by ring-opening polymerization of 2,2,3,3-tetrafluorooxetane, and the production of a halogen-containing polyether compound by chlorinating and fluorinating the fluorine-containing polyether compound. In addition, in WO 2013 / 121984, a compound represented by CF2=CFO-CF2CF2CF2CH2OH and A 1 -OH(A 1 represents a methyl group, etc.) to form a primary alcohol represented by A 1 -O-(CF2CFHO-CF2CF2CF2CH2O) n+1 It is disclosed that a halogen-containing polyether compound represented by —H is produced. Summary of the Invention [Problem to be solved by the invention]

[0004] From the viewpoint of lubricity, it is preferable that the fluorine-containing polyether compound has a trifluoromethyl group (—CF3) at its terminal. However, in the production method disclosed in U.S. Pat. No. 5,258,110, it was difficult to produce a fluorine-containing polyether compound having trifluoromethyl groups at both terminals in high yield. Furthermore, the fluorine-containing polyether compounds obtained by the production methods disclosed in U.S. Pat. No. 4,845,268 and WO 2013 / 121984 have a functional group at at least one end, and the reaction of substituting the functional group with a trifluoromethyl group does not proceed easily, making it difficult to produce a fluorine-containing polyether compound having trifluoromethyl groups at both ends.

[0005] Furthermore, since the coating is required to have chemical resistance, heat resistance, etc., the fluorine-containing polyether compound used to form the coating is required to have a high molecular weight.

[0006] The present disclosure has been made in view of the above-mentioned demands, and an object of the present disclosure is to provide a method for producing a fluorinated polyether compound, which can produce a high molecular weight fluorinated polyether compound having trifluoromethyl groups at both ends in high yield. Another problem to be solved is to provide a method for producing a fluorine-containing divinyl polyether compound, which can easily produce a high-molecular-weight fluorine-containing divinyl polyether compound having vinyl groups at both ends in high yield, and a novel fluorine-containing divinyl polyether compound. [Means for solving the problem]

[0007] Specific means for achieving the above object are as follows: <1> A method for producing a fluorine-containing polyether compound, comprising reacting a fluorine-containing divinyl ether compound represented by the following general formula (1) with a diol compound represented by the following general formula (2) in a ratio of more than 1 mol of the fluorine-containing divinyl ether compound represented by the following general formula (1) per 1 mol of the diol compound represented by the following general formula (2) to produce a fluorine-containing divinyl polyether compound represented by the following general formula (3), and then fluorinating the fluorine-containing divinyl polyether compound represented by the following general formula (3) to produce a fluorine-containing polyether compound represented by the following general formula (4). CF2=CR 1 -OR 2 -O-CR 1 =CF2 (1) HO-R 3 -OH···(2) CF2=CR 1 -OR 2 -O-(CHR 1 -CF2-OR 3 -O-CF2-CHR 1 -OR 2 -O) a -CR 1 =CF2 (3) CF3-CFR F1 -OR F2 -O-(CFR F1 -CF2-OR F3 -O-CF2-CFR F1 -OR F2 -O) a -CFR F1 -CF3···(4)

[0008] (In general formulas (1) to (4), R 1 each independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having 1 to 3 carbon atoms, the hydrogen atom of which may be substituted with a fluorine atom; R 2 and R 3 each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may have a ring structure or a branched structure, which may have an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom; R F1 are each independently R 1 represents a fluorine atom, and R 1 represents a fluorine atom when R is a hydrogen atom; 1 represents a monovalent hydrocarbon group having 1 to 3 carbon atoms, a monovalent perfluorohydrocarbon group having 1 to 3 carbon atoms, R F2 are each independently R 2 represents a divalent perfluorohydrocarbon group having 1 to 20 carbon atoms, in which the divalent hydrocarbon group represented by the following formula is perfluorinated: R F3 are each independently R 3 represents a divalent perfluorohydrocarbon group having 1 to 20 carbon atoms, in which the divalent hydrocarbon group represented by the following formula is perfluorinated: a represents an integer of 1 or greater.) <2> a reaction of the fluorine-containing divinyl ether compound represented by the general formula (1) with the diol compound represented by the general formula (2) in the presence of an alkali catalyst; <1> 1. A method for producing a fluorine-containing polyether compound according to claim 1. <3> fluorination of the fluorinated divinyl polyether compound represented by the general formula (3) is carried out by introducing fluorine gas and the fluorinated divinyl polyether compound represented by the general formula (3) into a solvent, When the molar introduction rate of the fluorine-containing divinyl polyether compound represented by the general formula (3) into the solvent is taken as 1, the molar introduction rate of the fluorine gas is in the range of 1 to 10 times the rate obtained by multiplying the molar introduction rate of the fluorine-containing divinyl polyether compound represented by the general formula (3) by the number of hydrogen atoms that can be substituted with fluorine atoms by the fluorine gas contained in the fluorine-containing divinyl polyether compound represented by the general formula (3). <1> or <2> 1. A method for producing a fluorine-containing polyether compound according to claim 1. <4> a fluorine-containing divinyl ether compound represented by the general formula (1) and a diol compound represented by the general formula (2) are reacted in a ratio of 3 mol or less of the fluorine-containing divinyl ether compound represented by the general formula (1) to 1 mol of the diol compound represented by the general formula (2); <1> ~ <3> 1. A method for producing a fluorine-containing polyether compound according to any one of the above items. <5> A method for producing a fluorinated polyether compound, comprising reacting a fluorinated divinyl ether compound represented by the following general formula (1) with a fluorinated vinyl alcohol compound represented by the following general formula (5) in a ratio of more than 1 mol of the fluorinated vinyl alcohol compound represented by the following general formula (5) per 1 mol of the fluorinated divinyl ether compound represented by the following general formula (1) to produce a fluorinated divinyl polyether compound represented by the following general formula (6-1) or (6-2), and then fluorinating the fluorinated divinyl polyether compound represented by the following general formula (6-1) or (6-2) to produce a fluorinated polyether compound represented by the following general formula (7-1) or (7-2): CF2=CR 1 -OR 2 -O-CR 1 =CF2 (1) CF2=CR 1 -OR 4 -OH···(5) CF2=CR 1 -O-(R 4 -O-CF 2 -CHR 1 -O) b -R 4 -O-CF2-CHR 1 -OR 2 -O-CHR 1 -CF2-OR 4 -(O-CHR 1 -CF2-OR 4 ) c -O-CR 1 =CF2 (6-1) CF2=CR 1 -O-(R 4 -O-CF 2 -CHR 1 -O)d -R 4 -O-CF2-CHR 1 -OR 2 -O-CR 1 =CF2 (6-2) CF3-CFR F1 -O-(R F4 -O-CF 2 -CFR F1 -O) b -R F4 -O-CF2-CFR F1 -OR F2 -O-CFR F1 -CF2-OR F4 -(O-CFR F1 -CF2-OR F4 ) c -O-CFR F1 -CF3···(7-1) CF3-CFR F1 -O-(R F4 -O-CF 2 -CFR F1 -O) d -R F4 -O-CF2-CFR F1 -OR F2 -O-CFR F1 -CF3···(7-2)

[0009] (In the general formula (1), the general formula (5), the general formula (6-1), the general formula (6-2), the general formula (7-1) and the general formula (7-2), R 1 each independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having 1 to 3 carbon atoms, the hydrogen atom of which may be substituted with a fluorine atom; R 2 and R 4 each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may have a ring structure or a branched structure, which may have an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom; R F1 are each independently R 1 represents a fluorine atom, and R 1 represents a fluorine atom when R is a hydrogen atom;1 represents a monovalent hydrocarbon group having 1 to 3 carbon atoms, a monovalent perfluorohydrocarbon group having 1 to 3 carbon atoms, R F2 are each independently R 2 represents a divalent perfluorohydrocarbon group having 1 to 20 carbon atoms, in which the divalent hydrocarbon group represented by the following formula is perfluorinated: R F4 are each independently R 4 represents a divalent perfluorohydrocarbon group having 1 to 20 carbon atoms, in which the divalent hydrocarbon group represented by the following formula is perfluorinated: b, c, and d each independently represent an integer of 0 or 1 or more. <6> The reaction of the fluorinated divinyl ether compound represented by the general formula (1) with the fluorinated vinyl alcohol compound represented by the general formula (5) is carried out in the presence of an alkali catalyst. <5> 1. A method for producing a fluorine-containing polyether compound according to claim 1. <7> fluorination of the fluorine-containing divinyl polyether compound represented by the general formula (6-1) or (6-2) is carried out by introducing fluorine gas and the fluorine-containing divinyl polyether compound represented by the general formula (6-1) or (6-2) into a solvent, When the molar introduction rate of the fluorine-containing divinyl polyether compound represented by the general formula (6-1) or the general formula (6-2) into the solvent is taken as 1, the molar introduction rate of the fluorine gas is in the range of 1 to 10 times the rate obtained by multiplying the molar introduction rate of the fluorine-containing divinyl polyether compound represented by the general formula (6-1) or the general formula (6-2) by the number of hydrogen atoms that can be substituted by fluorine atoms by the fluorine gas contained in the fluorine-containing divinyl polyether compound represented by the general formula (6-1) or the general formula (6-2). <5> or <6> 1. A method for producing a fluorine-containing polyether compound according to claim 1. <8> The reaction of the fluorine-containing divinyl ether compound represented by the general formula (1) with the fluorine-containing vinyl alcohol compound represented by the general formula (5) is carried out in a ratio of 20 mol or less of the fluorine-containing vinyl alcohol compound represented by the general formula (5) per 1 mol of the fluorine-containing divinyl ether compound represented by the general formula (1). <5> ~ <7> 1. A method for producing a fluorine-containing polyether compound according to any one of the above items. <9> A method for producing a fluorine-containing divinyl polyether compound, comprising reacting a fluorine-containing divinyl ether compound represented by the following general formula (1) with a diol compound represented by the following general formula (2) in a ratio of more than 1 mol of the fluorine-containing divinyl ether compound represented by the following general formula (1) per 1 mol of the diol compound represented by the following general formula (2), to produce a fluorine-containing divinyl polyether compound represented by the following general formula (3): CF2=CR 1 -OR 2 -O-CR 1 =CF2 (1) HO-R 3 -OH···(2) CF2=CR 1 -OR 2 -O-(CHR 1 -CF2-OR 3 -O-CF2-CHR 1 -OR 2 -O) a -CR 1 =CF2 (3)

[0010] (In general formulas (1) to (3), R 1 each independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having 1 to 3 carbon atoms, the hydrogen atom of which may be substituted with a fluorine atom; R 2 and R 3 each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may have a ring structure or a branched structure, which may have an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom; a represents an integer of 1 or greater.) <9> A method for producing a fluorine-containing divinyl polyether compound, comprising reacting a fluorine-containing divinyl ether compound represented by the following general formula (1) with a fluorine-containing vinyl alcohol compound represented by the following general formula (5) in a ratio of more than 1 mol of the fluorine-containing vinyl alcohol compound represented by the following general formula (5) per 1 mol of the fluorine-containing divinyl ether compound represented by the following general formula (1), to produce a fluorine-containing divinyl polyether compound represented by the following general formula (6-1) or (6-2): CF2=CR 1 -OR 2 -O-CR 1 =CF2 (1) CF2=CR 1 -OR 4 -OH···(5) CF2=CR 1 -O-(R 4 -O-CF 2 -CHR 1 -O) b -R 4 -O-CF2-CHR 1 -OR 2 -O-CHR 1 -CF2-OR 4 -(O-CHR 1 -CF2-OR 4 ) c -O-CR 1 =CF2 (6-1) CF2=CR 1 -O-(R 4 -O-CF 2 -CHR 1 -O) d -R 4 -O-CF2-CHR 1 -OR 2 -O-CR 1 =CF2 (6-2)

[0011] (In the general formula (1), the general formula (5), the general formula (6-1) and the general formula (6-2), R 1 each independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having 1 to 3 carbon atoms, the hydrogen atom of which may be substituted with a fluorine atom; R 2 and R 4 each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may have a ring structure or a branched structure, which may have an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom; b, c, and d each independently represent an integer of 0 or 1 or more. <10> A method for producing a fluorinated polyether compound, comprising fluorinating a fluorinated divinyl polyether compound represented by the following general formula (3) to produce a fluorinated polyether compound represented by the following general formula (4): CF2=CR 1 -OR 2 -O-(CHR 1 -CF2-OR 3 -O-CF2-CHR 1 -OR 2 -O) a -CR 1 =CF2 (3) CF3-CFR F1 -OR F2 -O-(CFR F1 -CF2-OR F3 -O-CF2-CFR F1 -OR F2 -O) a -CFR F1 -CF3···(4)

[0012] (In general formulas (1) to (4), R 1 each independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having 1 to 3 carbon atoms, the hydrogen atom of which may be substituted with a fluorine atom; R 2 and R 3 each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may have a ring structure or a branched structure, which may have an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom; R F1 are each independently R 1 represents a fluorine atom, and R 1represents a fluorine atom when R is a hydrogen atom; 1 represents a monovalent hydrocarbon group having 1 to 3 carbon atoms, a monovalent perfluorohydrocarbon group having 1 to 3 carbon atoms, R F2 are each independently R 2 represents a divalent perfluorohydrocarbon group having 1 to 20 carbon atoms, in which the divalent hydrocarbon group represented by the following formula is perfluorinated: R F3 are each independently R 3 represents a divalent perfluorohydrocarbon group having 1 to 20 carbon atoms, in which the divalent hydrocarbon group represented by the following formula is perfluorinated: a represents an integer of 1 or greater.) <11> A method for producing a fluorinated polyether compound, comprising fluorinating a fluorinated divinyl polyether compound represented by the following general formula (6-1) or (6-2) to produce a fluorinated polyether compound represented by the following general formula (7-1) or (7-2): CF2=CR 1 -OR 2 -O-CR 1 =CF2 (1) CF2=CR 1 -OR 4 -OH···(5) CF2=CR 1 -O-(R 4 -O-CF 2 -CHR 1 -O) b -R 4 -O-CF2-CHR 1 -OR 2 -O-CHR 1 -CF2-OR 4 -(O-CHR 1 -CF2-OR 4 ) c -O-CR 1 =CF2 (6-1) CF2=CR 1 -O-(R 4 -O-CF 2 -CHR 1 -O) d -R 4 -O-CF2-CHR1 -OR 2 -O-CR 1 =CF2 (6-2) CF3-CFR F1 -O-(R F4 -O-CF 2 -CFR F1 -O) b -R F4 -O-CF2-CFR F1 -OR F2 -O-CFR F1 -CF2-OR F4 -(O-CFR F1 -CF2-OR F4 ) c -O-CFR F1 -CF3···(7-1) CF3-CFR F1 -O-(R F4 -O-CF 2 -CFR F1 -O) d -R F4 -O-CF2-CFR F1 -OR F2 -O-CFR F1 -CF3···(7-2)

[0013] (In the general formula (1), the general formula (5), the general formula (6-1), the general formula (6-2), the general formula (7-1) and the general formula (7-2), R 1 each independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having 1 to 3 carbon atoms, the hydrogen atom of which may be substituted with a fluorine atom; R 2 and R 4 each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may have a ring structure or a branched structure, which may have an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom; R F1 are each independently R 1 represents a fluorine atom, and R 1 represents a fluorine atom when R is a hydrogen atom; 1represents a monovalent hydrocarbon group having 1 to 3 carbon atoms, a monovalent perfluorohydrocarbon group having 1 to 3 carbon atoms, R F2 are each independently R 2 represents a divalent perfluorohydrocarbon group having 1 to 20 carbon atoms, in which the divalent hydrocarbon group represented by the following formula is perfluorinated: R F4 are each independently R 4 represents a divalent perfluorohydrocarbon group having 1 to 20 carbon atoms, in which the divalent hydrocarbon group represented by the following formula is perfluorinated: b, c, and d each independently represent an integer of 0 or 1 or more. <12> A fluorine-containing divinyl polyether compound represented by the following general formula (3): CF2=CR 1 -OR 2 -O-(CHR 1 -CF2-OR 3 -O-CF2-CHR 1 -OR 2 -O) a -CR 1 =CF2 (3)

[0014] (In general formula (3), R 1 each independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having 1 to 3 carbon atoms, the hydrogen atom of which may be substituted with a fluorine atom; R 2 and R 3 each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may have a ring structure or a branched structure, which may have an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom; a represents an integer of 1 or greater.) <13> A fluorine-containing divinyl polyether compound represented by the following general formula (6-1): CF2=CR 1 -O-(R 4 -O-CF 2 -CHR 1 -O) b -R 4 -O-CF2-CHR1 -OR 2 -O-CHR 1 -CF2-OR 4 -(O-CHR 1 -CF2-OR 4 ) c -O-CR 1 =CF2 (6-1)

[0015] (In general formula (6-1), R 1 each independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having 1 to 3 carbon atoms, the hydrogen atom of which may be substituted with a fluorine atom; R 2 and R 4 each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may have a ring structure or a branched structure, which may have an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom; b and c each independently represent an integer of 0 or 1 or more. <14> A fluorine-containing divinyl polyether compound represented by the following general formula (6-2): CF2=CR 1 -O-(R 4 -O-CF 2 -CHR 1 -O) d -R 4 -O-CF2-CHR 1 -OR 2 -O-CR 1 =CF2 (6-2)

[0016] (In general formula (6-2), R 1 each independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having 1 to 3 carbon atoms, the hydrogen atom of which may be substituted with a fluorine atom; R 2 and R 4 each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may have a ring structure or a branched structure, which may have an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom; d represents an integer of 0 or 1 or more. [Effects of the Invention]

[0017] According to the present disclosure, there is provided a method for producing a fluorinated polyether compound, which can produce a high molecular weight fluorinated polyether compound having trifluoromethyl groups at both ends in high yield. The present disclosure also provides a method for producing a fluorine-containing divinyl polyether compound, which can produce a high-molecular-weight fluorine-containing divinyl polyether compound having vinyl groups at both ends in high yield, and a novel fluorine-containing divinyl polyether compound. DETAILED DESCRIPTION OF THE INVENTION

[0018] Hereinafter, embodiments for carrying out the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments. In the following embodiments, components (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and do not limit the present disclosure.

[0019] In the present disclosure, numerical ranges indicated using "to" include the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In the numerical ranges described in stages in the present disclosure, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in the present disclosure, the upper or lower limit value of the numerical range may be replaced with the value shown in the synthesis examples.

[0020] In the present disclosure, the term "fluoroalkylene group" includes perfluoroalkylene groups in which all hydrogen atoms have been substituted with fluorine atoms and fluoroalkylene groups in which some hydrogen atoms have been substituted with fluorine atoms. Furthermore, in the present disclosure, the term "fluorocycloalkane" and the like also includes not only perfluorocyclobutene in which all hydrogen atoms of cyclobutene have been substituted with fluorine atoms, but also cyclobutene in which some hydrogen atoms have been substituted with fluorine atoms.

[0021] In the present disclosure, each component may contain a plurality of corresponding compounds. For example, the molar ratio in the reaction of a fluorinated divinyl ether compound represented by general formula (1) with a diol compound represented by general formula (2) is calculated based on the total amount of compounds corresponding to each component.

[0022] In the representation of groups (atomic groups) in the present disclosure, a representation that does not specify whether substituted or unsubstituted encompasses both those that have no substituents and those that have a substituent.

[0023] In the present disclosure, the number of carbon atoms means the total number of carbon atoms contained in the entire group, and when the group does not have a substituent, it represents the number of carbon atoms forming the skeleton of the group, and when the group has a substituent, it represents the total number obtained by adding the number of carbon atoms forming the skeleton of the group to the number of carbon atoms in the substituent.

[0024] In the present disclosure, a monovalent or divalent hydrocarbon group is "perfluorinated" means that the hydrocarbon group has been fluorinated to the following state: When the monovalent or divalent hydrocarbon group is a saturated hydrocarbon group, the state in which all of the fluorinable hydrogen atoms bonded to carbon atoms constituting the monovalent or divalent hydrocarbon group are fluorinated is referred to as the hydrocarbon group being "perfluorinated." When a monovalent or divalent hydrocarbon group is an unsaturated hydrocarbon group, the hydrocarbon group is said to be "perfluorinated" when all fluorinable hydrogen atoms bonded to carbon atoms constituting the monovalent or divalent hydrocarbon group are fluorinated, and a fluorine atom is added to each of the two carbon atoms forming a carbon-carbon unsaturated bond such as a carbon-carbon double bond or a carbon-carbon triple bond, thereby eliminating the carbon-carbon unsaturated bond. For example, when >C=C< is perfluorinated, it becomes >CF-CF<, and when -C≡C- is perfluorinated, it becomes -CF-CF-. In addition, a fluorinable atomic group may have a perfluorinated hydrogen atom bonded thereto; for example, when -CH=CH- is perfluorinated, it becomes -CF-CF-.

[0025] In the present disclosure, the number average molecular weight (Mn) and the mass average molecular weight (Mw) are measured by gel permeation chromatography (hereinafter also referred to as "GPC"). The GPC measurement was carried out according to the method described in JP-A-2001-208736 under the following conditions. Mobile phase: a mixed solvent of R-225 (manufactured by AGC Corporation, product name: Asahiklin (registered trademark) AK-225SEC Grade 1) and hexafluoroisopropyl alcohol (HFIP) (R-225:HFIP = 99:1 (volume ratio)) Analytical column: Two PLgel MIXED-E columns (Polymer Laboratories) connected in series Standard samples for molecular weight measurement: Four types of perfluoropolyethers with a molecular weight distribution (Mw / Mn) of less than 1.1 and Mn of 2,000 to 10,000, and one type of perfluoropolyether with Mw / Mn of 1.1 or more and Mn of 1,300. ·Mobile phase flow rate: 1.0mL / min Column temperature: 37℃ Detector: Evaporative light scattering detector

[0026] (Method for producing a fluorinated polyether compound according to the first aspect) First, a method for producing a fluorine-containing polyether compound represented by general formula (4) will be explained, followed by a method for producing a fluorine-containing divinyl polyether compound represented by general formula (3) and a method for producing the same. In the method for producing a fluorine-containing polyether compound according to the first aspect, a fluorine-containing divinyl ether compound represented by the following general formula (1) (hereinafter also referred to as the formula (1) compound) is reacted with a diol compound represented by the following general formula (2) (hereinafter also referred to as the formula (2) compound) in a ratio of more than 1 mol of the formula (1) compound to 1 mol of the formula (2) compound to produce a fluorine-containing divinyl polyether compound represented by the following general formula (3) (hereinafter also referred to as the formula (3) compound), and then the formula (3) compound is fluorinated to produce a fluorine-containing polyether compound represented by the following general formula (4) (hereinafter also referred to as the formula (4) compound): CF2=CR1 -OR 2 -O-CR 1 =CF2 (1) HO-R 3 -OH···(2) CF2=CR 1 -OR 2 -O-(CHR 1 -CF2-OR 3 -O-CF2-CHR 1 -OR 2 -O) a -CR 1 =CF2 (3) CF3-CFR F1 -OR F2 -O-(CFR F1 -CF2-OR F3 -O-CF2-CFR F1 -OR F2 -O) a -CFR F1 -CF3···(4)

[0027] In general formula (1) and general formula (3), R 1 each independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having 1 to 3 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom. In general formulas (1) to (3), R 2 and R 3 each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may have a ring structure or a branched structure, may have an ether bond, and whose hydrogen atoms may be substituted with fluorine atoms. In general formula (4), R F1 are each independently R 1 represents a fluorine atom, and R 1 represents a fluorine atom when R is a hydrogen atom; 1 When is a monovalent hydrocarbon group having 1 to 3 carbon atoms, it represents a monovalent perfluorohydrocarbon group having 1 to 3 carbon atoms. In general formula (4), R F2 are each independently R 2The divalent hydrocarbon group represented by the following formula is perfluorinated, and represents a divalent perfluorohydrocarbon group having 1 to 20 carbon atoms. In general formula (4), R F3 are each independently R 3 The divalent hydrocarbon group represented by the following formula is perfluorinated, and represents a divalent perfluorohydrocarbon group having 1 to 20 carbon atoms. In general formula (3) and general formula (4), a represents an integer of 1 or more, preferably an integer of 3 or more, and more preferably an integer of 5 or more. In addition, a is preferably an integer of 15 or less.

[0028] According to the method for producing a fluorinated polyether compound according to the first aspect, a high molecular weight fluorinated polyether compound having trifluoromethyl groups at both ends can be produced in high yield.

[0029] The reason for the above effect is presumed to be as follows, but is not limited to this. In the reaction of the compound of formula (1) with the compound of formula (2), by reacting the compound of formula (1) in a ratio of more than 1 mol to 1 mol of the compound of formula (2), the polymerization reaction proceeds smoothly, and the compound of formula (3) having a high molecular weight can be produced in high yield. Furthermore, the compound of formula (3) obtained by the above reaction has vinyl groups (CF2=CR 1 -), and the vinyl group is easily fluorinated by contact with fluorine gas, so that a high molecular weight compound of formula (4) having trifluoromethyl groups at both ends can be produced in high yield.

[0030] The production of a fluorinated divinyl polyether compound and the fluorination of a fluorinated divinyl polyether compound, which are included in the method for producing a fluorinated polyether compound according to the first embodiment, will be described below.

[0031] -Production of Fluorine-Containing Divinyl Polyether Compounds- The vinyl groups at both ends of the compound of formula (3), which is produced by reacting the compound of formula (1) with the compound of formula (2), can be easily fluorinated by contacting with fluorine gas or the like, thereby producing the compound of formula (4), which has trifluoromethyl groups at both ends.

[0032] In the reaction of the compound of formula (1) with the compound of formula (2), the compound of formula (1) is preferably reacted at a ratio of 1.01 mol or more, more preferably 1.1 mol or more, per 1 mol of the compound of formula (2). By reacting the compound of formula (1) with the compound of formula (2) in the above molar ratio, the polymerization reaction proceeds smoothly, and the compound of formula (3) having a high molecular weight can be produced in high yield. In addition, in the reaction of the compound of formula (1) with the compound of formula (2), the compound of formula (1) is preferably reacted at a ratio of 3 mol or less, more preferably 2 mol or less, per 1 mol of the compound of formula (2). By reacting the compound of formula (1) with the compound of formula (2) in the above molar ratio, the polymerization reaction proceeds smoothly, and the compound of formula (3) having a high molecular weight can be produced in high yield.

[0033] The reaction of the compound of formula (1) with the compound of formula (2) is preferably carried out in the presence of an alkali catalyst. By reacting the compound of formula (1) with the compound of formula (2) in the presence of an alkali catalyst, the molecular weight and yield of the compound of formula (3) produced can be further improved. Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, sodium carbonate, cesium fluoride, and potassium carbonate, and from the viewpoints of the molecular weight and yield of the fluorine-containing divinyl polyether compound and the fluorine-containing polyether compound, potassium carbonate is preferred. The reaction between the compound of formula (1) and the compound of formula (2) may be carried out in a solvent or without a solvent. The solvent is not particularly limited, but a solvent that does not fluorinate when the compound of formula (3) is fluorinated is preferred, specifically, a fluorine-based solvent is preferred. Examples of the fluorine-based solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, and fluoroalcohols.

[0034] From the viewpoint of the molecular weight and yield of the compound of formula (3), the reaction temperature of the compound of formula (1) and the compound of formula (2) is preferably 80°C to 160°C, more preferably 90°C to 140°C.

[0035] The reaction of the compound of formula (1) with the compound of formula (2) may be carried out by a batch method or a continuous method, and any known method may be appropriately adopted. When the reaction of the compound of formula (1) with the compound of formula (2) is carried out by a batch method, for example, the compound of formula (2) may be placed in a reactor in advance, and the compound of formula (1) may be added to the reactor, or a diluted solution of the compound of formula (1) may be added to the reactor. From the viewpoint of reactivity, when the compound of formula (1) or a diluted solution thereof is added to the compound of formula (2) previously placed in a reactor, it is preferable to heat the compound of formula (2) to the above reaction temperature and convert it into an alkylene oxide before adding it. From the viewpoint of the molecular weight and yield of the compound of formula (3), in the reaction between the compound of formula (1) and the compound of formula (2), the compound of formula (1) is added to the compound of formula (2) at a rate of preferably 0.01 to 10 times mol / hour, and more preferably 0.1 to 0.5 times mol / hour, per 1 mol of the compound of formula (2).

[0036] After reacting the compound of formula (1) with the compound of formula (2), at least one selected from a solvent, water, and an aqueous solution for adjusting the acidity to an appropriate level may be added, followed by separation, and the organic phase may be concentrated. Alternatively, the crude reaction liquid obtained by concentrating the organic phase may be purified. The solvent is not particularly limited, but the above-mentioned fluorine-based solvents are preferred. The compounds of formula (1), formula (2) and formula (3) will be explained below.

[0037] --Formula (1) compound-- In the following general formula (1), R 1 From the viewpoint of lubricity, it is preferable that at least one of the groups be a fluorine atom, and it is more preferable that both of the groups be fluorine atoms. CF2=CR 1 -OR 2 -O-CR 1 =CF2 (1)

[0038] In general formula (1), R 2 represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain a ring structure or a branched structure, may contain an ether bond, and whose hydrogen atoms may be substituted with fluorine atoms. The number of carbon atoms in the divalent hydrocarbon group is preferably 15 or less, more preferably 10 or less. By making the number of carbon atoms in the divalent hydrocarbon group 15 or less, the polymerization reaction proceeds more smoothly, and a high molecular weight fluorine-containing polyether compound can be produced in high yield. From the viewpoint of suppressing the production of cyclized products in the polymerization reaction, the divalent hydrocarbon group preferably has 2 or more carbon atoms, and more preferably 3 or more carbon atoms.

[0039] R 2 Examples of the divalent hydrocarbon group represented by the formula (I) include alkylene groups such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group, and fluoroalkylene groups such as a fluoromethylene group, a fluoroethylene group, a fluorotrimethylene group, a fluorotetramethylene group, a fluoropentamethylene group, and a fluorohexamethylene group.

[0040] R 2 The divalent hydrocarbon group represented by the following formula (X) may be a group represented by the following formula (X): *-R x -(OR x ) n -*···(X) In general formula (X), R x represents an ethylene group, a trimethylene group, a propylene group, a fluoroethylene group, a fluorotrimethylene group, or a fluoropropylene group, and n represents an integer of 1 or more. In the general formula (X), * represents the bond to the oxygen atom.

[0041] R 2 The divalent hydrocarbon group represented by the following formula (A) may be a group represented by the following formula (A): *-R b -OR a -OR b -*···(A) In general formula (A), R a represents a cycloalkanediyl group, a fluorocycloalkanediyl group, or an arylene group. Examples of cycloalkanediyl groups and fluorocycloalkanediyl groups include cyclobutanediyl groups, fluorocyclobutanediyl groups, cyclopentanediyl groups, fluorocyclopentanediyl groups, cyclohexanediyl groups, fluorocyclohexanediyl groups, adamantanediyl groups, norbornanediyl groups, etc. The cycloalkanediyl groups, fluorocycloalkanediyl groups, and arylene groups may have, as a substituent, an alkyl group having 1 to 3 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom. In general formula (A), R b each independently represents a divalent hydrocarbon group having 1 to 10 carbon atoms, which may have a ring structure or a branched structure, and in which a hydrogen atom may be substituted with a fluorine atom. In the general formula (A), * represents the bond to the oxygen atom.

[0042] Examples of hydrocarbon groups satisfying general formula (A) include, but are not limited to, the following groups:

[0043] [ka]

[0044] Also, R 2 The divalent hydrocarbon group represented by the formula (I) may be a group represented by the following general formulas (B) to (D). *-R c -R a -R c -*···(B) *-R a -R c -R a -*···(C) *-R b -R d -R b -*···(D) In the general formulae (B) to (D), * represents the bond to the oxygen atom. R in the above general formulas (B) to (D) a The group represented by is the same as in the above general formula (A). In addition, in the general formulas (B) and (C), R c each independently represents a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms which may contain a ring structure or a branched structure and in which a hydrogen atom may be substituted with a fluorine atom. In addition, in the general formula (D), R d represents a cycloalkane-1,1-diyl group having 3 to 6 carbon atoms.

[0045] Examples of groups satisfying any one of the general formulae (B) to (D) include, but are not limited to, the following groups.

[0046] [ka]

[0047] [ka]

[0048] [ka]

[0049] The molecular weight of the compound of formula (1) is preferably 150 to 1000, more preferably 200 to 600. When the molecular weight of the compound of formula (1) is within the above range, the reaction with the compound of formula (2) proceeds smoothly.

[0050] From the above, examples of the compound of formula (1) include, but are not limited to, the following compounds:

[0051] [ka]

[0052] [ka]

[0053] [ka]

[0054] [ka]

[0055] From the viewpoint of lubricity, the compound of formula (1) is 1 are both fluorine and R 2 may be a perfluorinated divalent hydrocarbon group.

[0056] --Formula (2) compound-- In the following general formula (2), R 3 represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain a ring structure or a branched structure, may contain an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom. 2Since the same groups as the divalent hydrocarbon group represented by R can be selected, the description is omitted here. 2 and R 3 may be the same group or different groups. HO-R 3 -OH···(2)

[0057] The molecular weight of the compound of formula (2) is preferably 50 to 400, more preferably 60 to 300. When the molecular weight of the compound of formula (2) is within the above range, the reaction with the compound of formula (1) proceeds smoothly.

[0058] The acidity (pKa) of the compound of formula (2) is preferably 8 to 18, more preferably 9 to 15. When the pKa of the compound of formula (2) is within the above range, the reaction with the compound of formula (1) proceeds smoothly. In the present disclosure, pKa is a value in water at 25° C., and is calculated according to the method described in Chemistry Handbook, Basic Edition, 5th Revised Edition, II-331 to II-343 (edited by the Chemical Society of Japan, published by Maruzen Co., Ltd.).

[0059] Examples of the compound of formula (2) include, but are not limited to, the following compounds:

[0060] [ka]

[0061] [ka]

[0062] [ka]

[0063] [ka]

[0064] [ka]

[0065] From the viewpoint of reactivity, the formula (1) compound and the formula (2) compound are preferably a combination of one or more formula (1) compounds selected from the following Group A with a formula (2) compound selected from the following Group B, and more preferably a combination of one or more formula (1) compounds selected from the following Group A' with a formula (2) compound selected from the following Group B, but are not limited thereto.

[0066] Group A is as follows:

[0067] [ka]

[0068] Group A' is as follows: [ka]

[0069] Group B is as follows:

[0070] [ka]

[0071] [ka]

[0072] --Formula (3) compound-- By reacting the compound of formula (1) with the compound of formula (2), a fluorine-containing divinyl polyether compound represented by the following general formula (3) is produced. 1 , R 2 and R 3 Since this has been described above, the description will be omitted here. CF2=CR 1 -OR 2 -O-(CHR 1 -CF2-OR 3 -O-CF2-CHR 1 -OR 2 -O) a -CR 1 =CF2 (3)

[0073] Examples of the compound of formula (3) include, but are not limited to, the following compounds: The divinyl groups at both ends of the compound of formula (3) are easily fluorinated, so that the compound of formula (4) having a high molecular weight and trifluoromethyl groups at both ends can be produced in high yield.

[0074] [ka]

[0075] [ka]

[0076] [ka]

[0077] [ka]

[0078] -Fluorination of fluorine-containing divinyl polyether compounds- In the method for producing a fluorinated polyether compound according to the first embodiment, a compound of formula (3) is fluorinated to produce a fluorinated polyether compound represented by the following general formula (4). CF3-CFR F1 -OR F2 -O-(CFR F1 -CF2-OR F3 -O-CF2-CFR F1 -OR F2 -O) a -CFR F1 -CF3···(4)

[0079] The method for fluorinating the compound of formula (3) is not particularly limited, and can be carried out by a conventionally known method. For example, the fluorination can be carried out by contacting the compound of formula (3) with fluorine gas. The method for fluorinating the compound of formula (3) may be a batch system or a continuous system. The fluorination reaction is preferably carried out by the following <Method 1> or <Method 2>, with <Method 2> being more preferred from the viewpoint of the yield of the compound of formula (4). Whether the reaction is carried out by the batch system or the continuous system, the fluorine gas may be diluted with an inert gas such as nitrogen gas before use.

[0080] <Method 1> In Method 1, the compound of formula (3) and a solvent are charged into a reactor, and stirring is initiated. The reaction is carried out at a predetermined reaction temperature and pressure while continuously supplying fluorine gas diluted with an inert gas into the solvent. <Method 2> In Method 2, a solvent is charged into a reactor and stirred, and then fluorine gas diluted with an inert gas, the compound of formula (3), and the solvent are continuously fed into the fluorination reaction solvent at a predetermined molar ratio to cause a reaction at a predetermined reaction temperature and pressure. <Method 3> In method 3, a solvent is continuously introduced into a tubular reactor and circulated through the reactor, and then fluorine gas diluted with an inert gas and a solution of the compound of formula (3) are continuously supplied to the solvent flow in the tubular reactor and mixed in proportions such that the fluorine gas and the compound of formula (3) have a predetermined molar ratio, and the fluorine gas and the compound of formula (3) are brought into contact with each other in the tubular reactor to react with each other, and the solvent containing the reaction product is removed from the tubular reactor. In this method, the solvent is circulated and the reaction product is removed from the circulating solvent, thereby allowing the fluorination reaction to proceed in a continuous manner.

[0081] As in the case of Method 3, in Method 2, when the compound of formula (3) is supplied, it is preferable to supply the compound of formula (3) diluted with a solvent, in order to improve the selectivity of the compound of formula (4) and to suppress the amount of by-products. When the compound of formula (3) is diluted with a solvent, the amount of the solvent relative to the compound of formula (3) is preferably 5 times or more, more preferably 7 times or more, by mass.

[0082] Examples of inert gases include rare gases such as helium gas, neon gas, and argon gas, and nitrogen gas, with nitrogen gas and helium gas being preferred, and nitrogen gas being more preferred from the viewpoint of economical advantages. The proportion of fluorine gas (hereinafter also referred to as "fluorine gas amount") is preferably 15 to 60% by volume out of 100% by volume of the total of fluorine gas and inert gas.

[0083] When the fluorination of the compound of formula (3) is carried out in a solvent, the solvent may be previously substituted with nitrogen in order to reduce the oxygen content in the solvent. When the compound of formula (3) is introduced into a solvent, the solvent may be substituted with nitrogen in advance, and then with fluorine.

[0084] In the fluorination reaction, whether in a batch system or a continuous system, it is preferable that the amount of fluorine gas used to fluorinate all of the fluorinatable hydrogen atoms in the compound of formula (3) is always in excess, preferably 1.1 equivalents or more, more preferably 1.3 equivalents or more, of the theoretical amount required to fluorinate all of the fluorinatable hydrogen atoms.

[0085] When the fluorination of the compound of formula (3) is carried out by introducing fluorine gas and the compound of formula (3) into a solvent, the molar introduction rate of the fluorine gas may be in the range of 1 to 10 times, or may be in the range of 2 to 7 times, the rate obtained by multiplying the molar introduction rate of the compound of formula (3) by the number of hydrogen atoms that can be substituted with fluorine atoms by the fluorine gas contained in the compound of formula (3), assuming that the molar introduction rate of the compound of formula (3) into the solvent is 1. By keeping the introduction rate relationship within the above numerical range, the yield of the compound of formula (4) can be improved.

[0086] To efficiently proceed with the fluorination reaction of the compound of formula (3), it is preferable to add a C-H bond-containing compound other than the compound of formula (3) to the solvent or to irradiate the solvent with ultraviolet light. These steps are preferably carried out at the later stage of the fluorination reaction. This allows the compound of formula (3) present in the solvent to be efficiently fluorinated, thereby improving the yield of the compound of formula (4). The C-H bond-containing compound is preferably an aromatic hydrocarbon, such as benzene or toluene. The amount of the C-H bond-containing compound added is preferably 0.1 mol % to 10 mol %, more preferably 0.1 mol % to 5 mol %, based on the hydrogen atoms in the compound of formula (3). The C-H bond-containing compound is preferably added to a solvent in which fluorine gas is present. Furthermore, when the C-H bond-containing compound is added, it is preferable to pressurize the reaction system. The reaction pressure when pressurized is preferably 0.01 MPa to 5 MPa (gauge pressure). When the reaction system is irradiated with ultraviolet light, the irradiation time is preferably 0.1 to 3 hours.

[0087] After the fluorination reaction, at least one selected from a solvent, water, and an aqueous solution for adjusting the acidity to an appropriate level may be added to the reaction mixture, followed by separation, and the organic phase may be concentrated to obtain the compound of formula (4). Alternatively, the crude reaction liquid obtained by concentrating the organic phase may be purified to obtain the compound of formula (4). The compound of formula (4) will be described below.

[0088] --Formula (4) compound-- In general formula (4), R F1 are each independently R 1 represents a fluorine atom, and R 1 represents a fluorine atom when R is a hydrogen atom; 1 When is a monovalent hydrocarbon group having 1 to 3 carbon atoms, it represents a monovalent perfluorohydrocarbon group having 1 to 3 carbon atoms. In general formula (4), R F2 are each independently R 2 The divalent hydrocarbon group represented by the following formula is perfluorinated, and represents a divalent perfluorohydrocarbon group having 1 to 20 carbon atoms. In general formula (4), R F3 are each independently R 3 The divalent hydrocarbon group represented by the following formula is perfluorinated, and represents a divalent perfluorohydrocarbon group having 1 to 20 carbon atoms. In addition, R 2 and R 3 When the divalent hydrocarbon group represented by the formula (I) has an aromatic ring, the aromatic ring is perfluorinated to form a perfluorocycloalkyl ring.

[0089] The number average molecular weight (Mn) of the compound of formula (4) obtained by the production method according to the first aspect is preferably 1000 to 30000, more preferably 2000 to 20000, and even more preferably 2000 to 10000. By setting the Mn of the compound of formula (4) within the above range, it is possible to prevent the viscosity of the compound of formula (4) from becoming too high, and the compound becomes easy to handle in production and use.

[0090] The molecular weight distribution (Mw / Mn) of the compound of formula (4) is preferably 1 to 3, more preferably 1 to 2.5, and even more preferably 1 to 1.5. By setting the Mw / Mn of the compound of formula (4) within the above range, volatilization of the compound of formula (4) can be suppressed when used in a high-temperature environment.

[0091] In the method for producing a fluorinated polyether compound according to the first aspect, examples of the compound of formula (4) obtained by fluorination of the compound of formula (3) include, but are not limited to, the following compounds:

[0092] [ka]

[0093] [ka]

[0094] [ka]

[0095] [ka]

[0096] (Method for producing a fluorinated polyether compound according to the second aspect) Next, a method for producing a fluorinated polyether compound represented by general formula (7-1) or general formula (7-2) will be described. In addition, a fluorinated divinyl polyether compound represented by general formula (6-1) or general formula (6-2) and a method for producing the same will also be described. The method for producing a fluorinated polyether compound according to the second aspect comprises reacting a fluorinated divinyl ether compound represented by the following general formula (1) (hereinafter also referred to as the formula (1) compound) with a fluorinated vinyl alcohol compound represented by the following general formula (5) (hereinafter also referred to as the formula (5) compound) in a ratio of more than 1 mol of the formula (5) compound to 1 mol of the formula (1) compound to produce a fluorinated divinyl polyether compound represented by the following general formula (6-1) or the following general formula (6-2) (hereinafter also referred to as the formula (6-1) compound and the formula (6-2) compound, respectively), and then fluorinating the formula (6-1) compound or the formula (6-2) compound to produce a fluorinated polyether compound represented by the following general formula (7-1) or the following general formula (7-2) (hereinafter also referred to as the formula (7-1) compound and the formula (7-2) compound, respectively). CF2=CR 1 -OR 2 -O-CR 1 =CF2 (1) CF2=CR 1 -OR 4 -OH···(5) CF2=CR 1 -O-(R 4 -O-CF 2 -CHR 1 -O) b -R 4 -O-CF2-CHR 1 -OR 2 -O-CHR 1 -CF2-OR 4 -(O-CHR 1 -CF2-OR 4 ) c -O-CR 1 =CF2 (6-1) CF2=CR 1 -O-(R 4 -O-CF 2 -CHR 1 -O) d -R 4 -O-CF2-CHR 1 -OR 2 -O-CR 1 =CF2 (6-2) CF3-CFR F1 -O-(RF4 -O-CF 2 -CFR F1 -O) b -R F4 -O-CF2-CFR F1 -OR F2 -O-CFR F1 -CF2-OR F4 -(O-CFR F1 -CF2-OR F4 ) c -O-CFR F1 -CF3···(7-1) CF3-CFR F1 -O-(R F4 -O-CF 2 -CFR F1 -O) d -R F4 -O-CF2-CFR F1 -OR F2 -O-CFR F1 -CF3···(7-2)

[0097] In the general formula (1), the general formula (5), the general formula (6-1) and the general formula (6-2), R 1 each independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having 1 to 3 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom. In the general formula (1), the general formula (5), the general formula (6-1) and the general formula (6-2), R 2 and R 4 each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may have a ring structure or a branched structure, may have an ether bond, and whose hydrogen atoms may be substituted with fluorine atoms. In the general formula (7-1) and the general formula (7-2), R F1 are each independently R 1 represents a fluorine atom, and R 1 represents a fluorine atom when R is a hydrogen atom; 1 When is a monovalent hydrocarbon group having 1 to 3 carbon atoms, it represents a monovalent perfluorohydrocarbon group having 1 to 3 carbon atoms. In the general formula (7-1) and the general formula (7-2), R F2are each independently R 2 The divalent hydrocarbon group represented by the following formula is perfluorinated, and represents a divalent perfluorohydrocarbon group having 1 to 20 carbon atoms. In the general formula (7-1) and the general formula (7-2), R F4 are each independently R 4 The divalent hydrocarbon group represented by the following formula is perfluorinated, and represents a divalent perfluorohydrocarbon group having 1 to 20 carbon atoms. In general formula (6-1), general formula (6-2), general formula (7-1) and general formula (7-2), b, c and d each independently represent 0 or an integer of 1 or more, preferably an integer of 3 or more, more preferably an integer of 5 or more.

[0098] According to the method for producing a fluorinated polyether compound according to the second aspect, a high molecular weight fluorinated polyether compound having trifluoromethyl groups at both ends can be produced in high yield.

[0099] The reason for the above effect is presumed to be as follows, but is not limited to this. In the reaction of the compound of formula (1) with the compound of formula (5), by reacting the compound of formula (5) in a ratio of more than 1 mol to 1 mol of the compound of formula (1), the polymerization reaction proceeds smoothly, and the compound of formula (6-1) or (6-2) having a high molecular weight can be produced in high yield. Furthermore, the compound of formula (6-1) or the compound of formula (6-2) obtained by the above reaction has vinyl groups (CF2=CR 1 -), and the vinyl group is easily fluorinated by contact with fluorine gas, so that a high molecular weight compound of formula (7-1) or formula (7-2) having trifluoromethyl groups at both ends can be produced in high yield.

[0100] The production of a fluorinated divinyl polyether compound and the fluorination of the produced fluorinated divinyl polyether compound, which are included in the production method of a fluorinated polyether compound according to the second embodiment, will be described below.

[0101] -Production of Fluorine-Containing Divinyl Polyether Compounds- The vinyl groups at both ends of the compound of formula (6-1) or the compound of formula (6-2), which is produced by the reaction of the compound of formula (1) with the compound of formula (5), can be easily fluorinated by contacting with fluorine gas or the like, thereby producing the compound of formula (7-1) or the compound of formula (7-2), which has trifluoromethyl groups at both ends.

[0102] In the reaction between the compound of formula (1) and the compound of formula (5), the compound of formula (5) is preferably reacted in a ratio of 2 mol or more, more preferably 5 mol or more, per 1 mol of the compound of formula (1). By reacting the compound of formula (1) with the compound of formula (5) in the above molar ratio, the polymerization reaction proceeds smoothly, and the compound of formula (6-1) or (6-2) having a high molecular weight can be produced in high yield. In addition, in the reaction between the compound of formula (1) and the compound of formula (5), the compound of formula (5) is preferably reacted at a ratio of 20 mol or less, more preferably 15 mol or less, per 1 mol of the compound of formula (1). By reacting the compound of formula (1) with the compound of formula (5) in the above molar ratio, homopolymerization of the compound of formula (5) can be prevented, and the compound of formula (6-1) or the compound of formula (6-2) can be produced in high yield.

[0103] As in the first embodiment, the reaction of the compound of formula (1) with the compound of formula (5) is preferably carried out in the presence of an alkali catalyst. The reaction may be carried out in a solvent or without the use of a solvent. The solvent is not particularly limited, but the above-mentioned fluorine-containing solvents are preferred. The reaction of the compound of formula (1) with the compound of formula (5) can be carried out by adding a mixture of the compound of formula (1) and the compound of formula (5) to the solvent heated to the following reaction temperature: From the viewpoint of reactivity, the addition rate of the mixture is preferably 0.5% by mass / hour to 70% by mass / hour, more preferably 1% by mass / hour to 50% by mass / hour, based on the total mass of the mixture.

[0104] From the viewpoint of the molecular weight and yield of the compound of formula (6-1) and the compound of formula (6-2), the reaction temperature of the compound of formula (1) and the compound of formula (5) is preferably 80 to 160°C, more preferably 90 to 140°C.

[0105] The reaction of the compound of formula (1) with the compound of formula (5) may be carried out by a batch method or a continuous method, and any known method may be appropriately adopted.

[0106] After reacting the compound of formula (1) with the compound of formula (5), at least one selected from the above-mentioned solvents, water, and an aqueous solution for adjusting the acidity to an appropriate level may be added, followed by liquid separation, and the organic phase may be concentrated. Alternatively, the reaction crude liquid obtained by concentrating the organic phase may be purified. The compounds of formula (1), formula (5), formula (6-1) and formula (6-2) will be explained below.

[0107] --Formula (5) compound-- In the following general formula (5), R 4 represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain a ring structure or a branched structure, may contain an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom. 2 and R 3 Since the same groups as the divalent hydrocarbon group represented by can be selected, the description thereof is omitted here. CF2=CR 1 -OR 4 -OH···(5)

[0108] The molecular weight of the compound of formula (5) is preferably 90 to 800, more preferably 100 to 600. When the molecular weight of the compound of formula (5) is within the above range, the reaction with the compound of formula (1) proceeds smoothly.

[0109] The pKa of the compound of formula (5) is preferably 8 to 16, and more preferably 9 to 14. When the pKa of the compound of formula (5) is within the above range, the reaction with the compound of formula (1) proceeds smoothly.

[0110] Examples of the compound of formula (5) include, but are not limited to, the following compounds: The compound of formula (1) is as exemplified in the first embodiment.

[0111] [ka]

[0112] [ka]

[0113] [ka]

[0114] [ka]

[0115] With regard to the compounds of formula (1) and formula (5), a combination of one or more compounds of formula (1) selected from the above Group A and a compound of formula (5) selected from the following Group C is preferred from the viewpoint of reactivity, but is not limited thereto.

[0116] Group C is as follows: [ka]

[0117] --Compound of formula (6-1) and compound of formula (6-2)-- By reacting the compound of formula (1) with the compound of formula (5), a fluorine-containing divinyl polyether compound represented by the following general formula (6-1) or (6-2) is produced. 1 , R 2 and R 4 Since this has been described above, the description will be omitted here. CF2=CR 1 -O-(R 4 -O-CF 2 -CHR 1 -O) b -R 4 -O-CF2-CHR 1 -OR 2 -O-CHR 1 -CF2-OR 4 -(O-CHR 1 -CF2-OR 4 ) c -O-CR 1 =CF2 (6-1) CF2=CR 1 -O-(R 4 -O-CF 2 -CHR 1 -O) d -R 4 -O-CF2-CHR 1 -OR 2 -O-CR 1 =CF2 (6-2)

[0118] Examples of the compounds of formula (6-1) and formula (6-2) include, but are not limited to, the following compounds: The divinyl groups at both ends of the compounds of formula (6-1) and formula (6-2) are easily fluorinated, and therefore high-molecular-weight fluorine-containing polyether compounds having trifluoromethyl groups at both ends can be produced in high yield.

[0119] [ka]

[0120] [ka]

[0121] [ka]

[0122] [ka]

[0123] -Fluorination of fluorine-containing divinyl polyether compounds- In the method for producing a fluorinated polyether compound according to the second aspect, a fluorinated polyether compound represented by the following general formula (7-1) or (7-2) is produced by fluorinating a compound of formula (6-1) or (6-2). CF3-CFR F1 -O-(R F4 -O-CF 2 -CFR F1 -O) b -R F4 -O-CF2-CFR F1 -OR F2 -O-CFR F1 -CF2-OR F4 -(O-CFR F1 -CF2-OR F4 ) c -O-CFR F1 -CF3···(7-1) CF3-CFR F1 -O-(R F4 -O-CF 2 -CFR F1 -O) d -R F4 -O-CF2-CFR F1 -OR F2 -O-CFR F1 -CF3···(7-2)

[0124] The method for fluorinating the compound of formula (6-1) or the compound of formula (6-2) is not particularly limited, and can be carried out by a conventionally known method. For example, the fluorination can be carried out by contacting the compound of formula (6-1) or the compound of formula (6-2) with fluorine gas. The specific fluorination method is the same as that in the first embodiment, and therefore will not be described here.

[0125] When the fluorination of the compound of Formula (6-1) or Formula (6-2) is carried out by introducing fluorine gas and the fluorine compound of Formula (6-1) or Formula (6-2) into a solvent, the molar introduction rate of the fluorine gas into the solvent may be 1 to 10 times, or may be 2 to 7 times, the molar introduction rate of the fluorine compound of Formula (6-1) or Formula (6-2) multiplied by the number of hydrogen atoms that can be substituted with fluorine atoms by the fluorine gas contained in the fluorine compound of Formula (6-1) or Formula (6-2), assuming that the molar introduction rate of the fluorine compound into the solvent is 1. By keeping the introduction rate relationship within the above numerical range, the yield of the fluorination of the compound of Formula (7-1) or Formula (7-2) can be improved. The compounds of formula (7-1) and formula (7-2) will be explained below.

[0126] --Compound of formula (7-1) and compound of formula (7-2)-- In the general formula (7-1) and the general formula (7-2), R F4 are each independently R 4 R represents a divalent perfluorohydrocarbon group having 1 to 20 carbon atoms, in which a divalent hydrocarbon group represented by the following formula is perfluorinated. 4 When the divalent hydrocarbon group represented by the formula (I) has an aromatic ring, the aromatic ring is perfluorinated to form a perfluorocycloalkyl ring. R F1 and R F2 The group represented by is the same as in the first embodiment, and therefore description thereof will be omitted here.

[0127] In the method for producing a fluorinated polyether compound according to the second aspect, examples of the compound of formula (7-1) or (7-2) obtained by fluorination of the compound of formula (6-1) or (6-2) include, but are not limited to, the following compounds:

[0128] [ka]

[0129] [ka]

[0130] [ka]

[0131] [ka] [Example]

[0132] The above embodiment will be specifically described below using synthesis examples, but the above embodiment is not limited to these synthesis examples.

[0133] [Evaluation method] (NMR analysis) The NMR analysis was carried out under the following conditions. 1 Nitrobenzene (7.5 ppm) was used as the reference substance for H-NMR (300.4 MHz). · 19 Perfluorobenzene at −162.5 ppm was used as the reference substance for F-NMR (282.7 MHz). The solvent used for NMR was a mixed solvent of deuterated chloroform and hexafluorobenzene or a mixed solvent of deuterated chloroform and 1,4-bistrifluoromethylbenzene.

[0134] (GPC analysis) The number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured by GPC, which was carried out by the method described above.

[0135] (Synthesis Example 1-1) In a 200 mL recovery flask, 3.3 g of ethylene glycol (pKa: 14.22) satisfying the above general formula (2) and 4 g of potassium carbonate were placed, and the internal temperature of the flask was raised to 120° C., followed by stirring. Next, 20 g of the following fluorine-containing divinyl ether compound (1A) satisfying the above general formula (1) was added at a rate of 0.37 moles / hour per mole of ethylene glycol, and the internal temperature of the flask was raised to 120°C, followed by stirring for 2 hours. The fluorine-containing divinyl ether compound (1A) was reacted in a ratio of 1.11 mol per 1 mol of ethylene glycol. CF2=CF-O-CF2CF2CF2-O-CF=CF2...(1A)

[0136] The internal temperature of the flask was then adjusted to 25°C, and 20 g each of a fluorine-based solvent (manufactured by AGC Corporation, Asahiklin (registered trademark) AC-2000, 1H-tridecafluorohexane, hereinafter referred to as AC-2000) and hydrochloric acid were added, resulting in a reaction crude liquid separated into an organic phase and an aqueous phase. The resulting reaction crude liquid was separated, and then the organic phase was concentrated. The organic phase was concentrated and the resulting crude reaction liquid was purified by column chromatography to obtain 15 g (yield 65%) of the following fluorine-containing divinyl polyether compound (3A) which satisfies the general formula (3). The average number of repeating units a was 9.

[0137] The fluorine-containing divinyl polyether compound (3A) is described below. [ka]

[0138] 250 mL of CFE-419 was placed in a 500 mL nickel reactor, and then nitrogen gas was bubbled through. After confirming that the dissolved oxygen concentration had sufficiently decreased, 20% by volume of fluorine gas diluted with nitrogen gas was blown in (bubbling) for 1 hour. Next, the CFE-419 solution of the fluorine-containing divinyl polyether compound (3A) was added to the CFE-419 in the reactor over 3 hours. The concentration of the fluorine-containing divinyl polyether compound (3A) in the CFE-419 solution was 10 mass %, and the amount of the fluorine-containing divinyl polyether compound (3A) was 15 g. Simultaneously with the addition of the CFE-419 solution, fluorine gas was bubbled into the CFE-419. When the molar introduction rate of the fluorine-containing divinyl polyether compound (3A) into the solvent was taken as 1, the molar introduction rate of the fluorine gas was set to twice the rate obtained by multiplying the molar introduction rate of the fluorine-containing divinyl polyether compound (3A) by the number of hydrogen atoms that can be substituted with fluorine atoms by the fluorine gas contained in the fluorine-containing divinyl polyether compound (3A).

[0139] After the addition of the CFE-419 solution of the fluorine-containing divinyl polyether compound and the fluorine gas were blown in, the CFE-419 solution of benzene was intermittently added. The benzene concentration in the CFE-419 solution was 0.1 mass %, and the amount of benzene was 0.1 g. After the addition of the benzene solution of CFE-419, fluorine gas was blown in over 1 hour, and finally the atmosphere in the reactor was thoroughly replaced with nitrogen gas. The solvent was distilled off to obtain 17 g (yield 90%) of the following fluorine-containing polyether compound (4A) which satisfies the above general formula (4). The structure of the fluorine-containing polyether compound (4A) is 1 H-NMR method and 19 The Mn of the fluorine-containing polyether compound (4A) was determined by F-NMR, and the Mw / Mn was 5,000 and 1.8, respectively.

[0140] The fluorine-containing polyether compound (4A) is described below. [ka]

[0141] (Synthesis Example 1-2) In a 200 mL recovery flask, 5.9 g of 1,4-benzenediol (pKa: 9.8) satisfying the above general formula (2) and 4 g of potassium carbonate were placed, and the internal temperature of the flask was raised to 120° C., followed by stirring. Next, 20 g of the following fluorine-containing divinyl ether compound (1A) satisfying the above general formula (1) was added at a rate of 0.27 moles / hour per mole of 1,4-benzenediol, and the internal temperature of the flask was raised to 120°C, followed by stirring for 2 hours. The fluorine-containing divinyl ether compound (1A) was reacted in a ratio of 1.08 mol per 1 mol of 1,4-benzenediol.

[0142] Next, the internal temperature of the flask was adjusted to 25°C, and 20 g each of the AC-2000 and hydrochloric acid were added to obtain a crude reaction liquid separated into an organic phase and an aqueous phase. The resulting crude reaction liquid was separated, and then the organic phase was concentrated. The organic phase was concentrated and the resulting crude reaction liquid was purified by column chromatography to obtain 20 g (yield 79%) of the following fluorine-containing divinyl polyether compound (3B) which satisfies the general formula (3). The average number of repeating units a was 12.

[0143] The fluorine-containing divinyl polyether compound (3B) is described below. [ka]

[0144] In a 500 mL nickel reactor, 250 mL of CFE-419 was placed, and then nitrogen gas was bubbled through. After confirming that the dissolved oxygen concentration had dropped sufficiently, 20% by volume of fluorine gas diluted with nitrogen gas was bubbled through the solution for 1 hour. Furthermore, a solution of the fluorine-containing divinyl polyether compound (3B) in CFE-419 was added to the CFE-419 in the reactor over 3 hours. The concentration of the fluorine-containing divinyl polyether compound (3B) in the CFE-419 solution was 10 mass %, and the amount of the fluorine-containing divinyl polyether compound (3B) was 20 g. Simultaneously with the addition of the CFE-419 solution, fluorine gas was bubbled into the CFE-419. When the molar introduction rate of the fluorine-containing divinyl polyether compound (3B) into the solvent was taken as 1, the molar introduction rate of the fluorine gas was set to three times the rate obtained by multiplying the molar introduction rate of the fluorine-containing divinyl polyether compound (3B) by the number of hydrogen atoms that can be substituted with fluorine atoms by the fluorine gas contained in the fluorine-containing divinyl polyether compound (3B).

[0145] After the addition of the CFE-419 solution of the fluorine-containing divinyl polyether compound, the above CFE-419 solution in benzene was intermittently added. After the addition of the benzene solution of CFE-419, fluorine gas was blown in over 1 hour, and finally the atmosphere in the reactor was thoroughly replaced with nitrogen gas. The solvent was distilled off to obtain 24 g (yield 81%) of the following fluorine-containing polyether compound (4B) which satisfies the above general formula (4). The structure of the fluorine-containing polyether compound (4B) is 1 H-NMR method and 19 The Mn of the fluorine-containing polyether compound (4B) was approximately 8000, and the Mw / Mn was 1.8.

[0146] The fluorine-containing polyether compound (4B) will be described below. [ka]

[0147] (Synthesis Example 1-3) In a 200 mL recovery flask were placed 9.7 g of tetraethylene glycol (pKa: 14.1) satisfying the above general formula (2) and 4 g of potassium carbonate, and the internal temperature of the flask was raised to 120° C. and the mixture was stirred. Next, 20 g of the following fluorine-containing divinyl ether compound (1A) satisfying the above general formula (1) was added at a rate of 0.29 moles / hour per mole of tetraethylene glycol, and the internal temperature of the flask was raised to 120°C, followed by stirring for 2 hours. The fluorine-containing divinyl ether compound (1A) was reacted in a ratio of 1.16 mol to 1 mol of tetraethylene glycol.

[0148] Next, the internal temperature of the flask was adjusted to 25°C, and 20 g each of the AC-2000 and hydrochloric acid were added to obtain a crude reaction liquid separated into an organic phase and an aqueous phase. The resulting crude reaction liquid was separated, and then the organic phase was concentrated. The organic phase was concentrated and the resulting crude reaction liquid was purified by column chromatography to obtain 21 g (yield 72%) of the following fluorine-containing divinyl polyether compound (3C) which satisfies the general formula (3). The average number of repeating units a was 6.

[0149] The fluorine-containing divinyl polyether compound (3C) is described below. [ka]

[0150] In a 500 mL nickel reactor, 250 mL of CFE-419 was placed, and then nitrogen gas was bubbled through. After confirming that the dissolved oxygen concentration had dropped sufficiently, 20% by volume of fluorine gas diluted with nitrogen gas was bubbled through the solution for 1 hour. Next, the CFE-419 solution of the fluorine-containing divinyl polyether compound (3C) was added to the CFE-419 in the reactor over 3 hours. The concentration of the fluorine-containing divinyl polyether compound (3C) in the CFE-419 solution was 10 mass %, and the amount of the fluorine-containing divinyl polyether compound (3C) was 21 g. Simultaneously with the addition of the CFE-419 solution, fluorine gas was bubbled into the CFE-419. When the molar introduction rate of the fluorine-containing divinyl polyether compound (3C) into the solvent was taken as 1, the molar introduction rate of the fluorine gas was set to twice the rate obtained by multiplying the molar introduction rate of the fluorine-containing divinyl polyether compound (3C) by the number of hydrogen atoms that can be substituted with fluorine atoms by the fluorine gas contained in the fluorine-containing divinyl polyether compound (3C).

[0151] After the addition of the CFE-419 solution of the fluorine-containing divinyl polyether compound, the above CFE-419 solution in benzene was intermittently added. After the addition of the CFE-419 solution in benzene, fluorine gas was blown into the reactor over 1 hour, and finally the atmosphere in the reactor was thoroughly replaced with nitrogen gas. The solvent was distilled off to obtain 33 g (yield 98%) of the following fluorine-containing polyether compound (4C) which satisfies the above general formula (4). The structure of the fluorine-containing polyether compound (4C) is 1 H-NMR method and 19 The Mn of the fluorine-containing polyether compound (4C) was determined by F-NMR, and the Mw / Mn was 5000 and 1.6, respectively.

[0152] The fluorine-containing polyether compound (4C) is described below. [ka]

[0153] (Synthesis Example 2-1) In a 200 mL recovery flask were placed 2 g of a fluorine-based solvent (manufactured by AGC Corporation, Asahiklin (registered trademark) AC-6000, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane) and 2 g of potassium carbonate, and the internal temperature of the flask was raised to 120° C. and stirred. Next, a mixture of 5 g of the above fluorine-containing divinyl ether compound (1A) and 40 g of the following fluorine-containing vinyl alcohol compound (5A) (pKa: 12.5) satisfying the above general formula (5) was added over 8 hours, the internal temperature of the flask was raised to 120°C, and the mixture was stirred for 2 hours. The fluorine-containing vinyl alcohol compound (5A) was reacted in a ratio of 9.92 mol per 1 mol of the fluorine-containing divinyl ether compound (1A). CF2=CF-O-CF2CF2CF2CH2-OH (5A)

[0154] The internal temperature of the flask was adjusted to 25°C, and 20 g each of the AC-2000 and hydrochloric acid were added to obtain a crude reaction liquid separated into an organic phase and an aqueous phase. The crude reaction liquid obtained was separated, and then the organic phase was concentrated. The organic phase was concentrated and the crude reaction solution was purified by column chromatography to obtain 25 g (yield 56%) of the following fluorine-containing divinyl polyether compound (6-1A) satisfying the general formula (6-1). The average number of repeating units b+c was 7.

[0155] The fluorine-containing divinyl polyether compound (6-1A) is described below. [ka]

[0156] In a 500 mL nickel reactor, 250 mL of CFE-419 was placed, and then nitrogen gas was bubbled through. After confirming that the dissolved oxygen concentration had dropped sufficiently, 20% by volume of fluorine gas diluted with nitrogen gas was bubbled through the solution for 1 hour. Furthermore, a solution of fluorine-containing divinyl polyether compound (6-1A) in CFE-419 was added to the CFE-419 in the reactor over 3 hours. The concentration of fluorine-containing divinyl polyether compound (6-1A) in the CFE-419 solution was 10 mass %, and the amount of fluorine-containing divinyl polyether compound (6-1A) was 25 g. Simultaneously with the addition of the CFE-419 solution, fluorine gas was bubbled into the CFE-419. When the molar introduction rate of the fluorine-containing divinyl polyether compound (6-1A) into the solvent was taken as 1, the molar introduction rate of the fluorine gas was set to twice the rate obtained by multiplying the molar introduction rate of the fluorine-containing divinyl polyether compound (6-1A) by the number of hydrogen atoms that can be substituted with fluorine atoms by the fluorine gas contained in the fluorine-containing divinyl polyether compound (6-1A).

[0157] After the addition of the CFE-419 solution of the fluorine-containing divinyl polyether compound, the above CFE-419 solution in benzene was intermittently added. After the addition of the CFE-419 solution in benzene, fluorine gas was blown into the reactor over 1 hour, and finally the atmosphere in the reactor was thoroughly purged with nitrogen gas. The solvent was distilled off to obtain 30 g (yield 98%) of the following fluorine-containing polyether compound (7-1A) which satisfies the above general formula (7-1). The structure of the fluorine-containing polyether compound (7-1A) is: 1 H-NMR method and 19 The Mn of the fluorine-containing polyether compound (7-1A) was determined by F-NMR, and the Mw / Mn was 3,500 and 1.6, respectively.

[0158] The fluorine-containing polyether compound (7-1A) is described below. [ka]

[0159] (Synthesis Example 3-1) When an attempt is made to produce a fluorine-containing polyether compound (4A) in the same manner as in Synthesis Example 1-1, except that 1 mol of fluorine-containing divinyl ether compound (1-1) is reacted with 1 mol of ethylene glycol in a ratio of 1 mol or less, a fluorine-containing polyether compound having trifluoromethyl groups at both ends cannot be produced.

[0160] (Synthesis Example 3-2) When an attempt is made to produce a fluorine-containing polyether compound (6-1A) in the same manner as in Synthesis Example 2-1, except that 1 mol of a fluorine-containing vinyl alcohol compound (5A) is reacted with 1 mol or less of a fluorine-containing divinyl ether compound (1A), a fluorine-containing polyether compound (6-1A) having a sufficient molecular weight cannot be produced.

[0161] In the above synthesis examples, it was shown that the method for producing a fluorinated polyether compound of the present disclosure makes it possible to produce a high molecular weight fluorinated polyether compound having trifluoroalkyl groups (-CF3) at both ends in high yield.

[0162] The disclosure of Japanese Patent Application No. 2020-217942, filed on December 25, 2020, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A method for producing a fluorinated polyether compound, comprising reacting a fluorinated divinyl ether compound represented by the following general formula (1) with a diol compound represented by the following general formula (2) in a ratio of more than 1 mol of the fluorinated divinyl ether compound represented by the following general formula (1) to 1 mol of the diol compound represented by the following general formula (2) to produce a fluorinated divinyl polyether compound represented by the following general formula (3), and then fluorinating the fluorinated divinyl polyether compound represented by the following general formula (3) to produce a fluorinated polyether compound represented by the following general formula (4), wherein the acidity of the diol compound represented by the general formula (2) is 8 to 18. CF ２ =CR １ -O-R ２ -O-CR １ =CF ２ ・・・(1) HO-R ３ -OH・・・(2) CF ２ =CR １ -O-R ２ -O-(CHR １ -CF ２ -O-R ３ -O-CF ２ -CHR １ -O-R ２ -O) ａ -CR １ =CF ２ ・・・(3) CF ３ -CFR Ｆ１ -O-R Ｆ２ -O-(CFR Ｆ１ -CF ２ -O-R Ｆ３ -O-CF ２ -CFR Ｆ１ -O-R Ｆ２ -O) ａ -CFR Ｆ１ -CF ３ ・・・(4) (In general formulas (1) to (4), R １ represents a fluorine atom, R ２ and R ３ each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may have a ring structure or a branched structure, which may have an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom; R Ｆ１ represents a fluorine atom, R Ｆ２ are each independently R ２ represents a divalent perfluorohydrocarbon group having 1 to 20 carbon atoms, in which a divalent hydrocarbon group represented by the following formula is perfluorinated: R Ｆ３ are each independently R ３ represents a divalent perfluorohydrocarbon group having 1 to 20 carbon atoms, in which a divalent hydrocarbon group represented by the following formula is perfluorinated: a represents an integer of 1 or more.

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

3. fluorination of the fluorinated divinyl polyether compound represented by the general formula (3) is carried out by introducing fluorine gas and the fluorinated divinyl polyether compound represented by the general formula (3) into a solvent, 3. The method for producing a fluorine-containing polyether compound according to claim 1 or 2, wherein, when the molar introduction rate of the fluorine-containing divinyl polyether compound represented by the general formula (3) into the solvent is taken as 1, the molar introduction rate of the fluorine gas is in the range of 1 to 10 times the rate obtained by multiplying the molar introduction rate of the fluorine-containing divinyl polyether compound represented by the general formula (3) by the number of hydrogen atoms that can be substituted with fluorine atoms by the fluorine gas contained in the fluorine-containing divinyl polyether compound represented by the general formula (3).

4. The method for producing a fluorinated polyether compound according to any one of claims 1 to 3, wherein the fluorinated divinyl ether compound represented by the general formula (1) is reacted with the diol compound represented by the general formula (2) in a ratio of 3 mol or less of the fluorinated divinyl ether compound represented by the general formula (1) per 1 mol of the diol compound represented by the general formula (2).

5. A method for producing a fluorine-containing polyether compound, comprising reacting a fluorine-containing divinyl ether compound represented by the following general formula (1) with a fluorine-containing vinyl alcohol compound represented by the following general formula (5) in a ratio of more than 1 mol of the fluorine-containing vinyl alcohol compound represented by the following general formula (5) per 1 mol of the fluorine-containing divinyl ether compound represented by the following general formula (1) to produce a fluorine-containing divinyl polyether compound represented by the following general formula (6-1) or the following general formula (6-2), and then fluorinating the fluorine-containing divinyl polyether compound represented by the following general formula (6-1) or the following general formula (6-2) to produce a fluorine-containing polyether compound represented by the following general formula (7-1) or the following general formula (7-2), wherein the acidity of the fluorine-containing vinyl alcohol compound represented by the general formula (5) is 8 to 16. CF ２ =CR １ -O-R ２ -O-CR １ =CF ２ ・・・(1) CF ２ =CR １ -O-R ４ -OH・・・(5) CF ２ =CR １ -O-(R ４ -O-CF ２ -CHR １ -O) ｂ -R ４ -O-CF ２ -CHR １ -O-R ２ -O-CHR １ -CF ２ -O-R ４ -(O-CHR １ -CF ２ -O-R ４ ) ｃ -O-CR １ =CF ２ ・・・(6-1) CF ２ =CR １ -O-(R ４ -O-CF ２ -CHR １ -O) ｄ -R ４ -O-CF ２ -CHR １ -O-R ２ -O-CR １ =CF ２ ・・・(6-2) CF ３ -CFR Ｆ１ -O-(R Ｆ４ -O-CF ２ -CFR Ｆ１ -O) ｂ -R Ｆ４ -O-CF ２ -CFR Ｆ１ -O-R Ｆ２ -O-CFR Ｆ１ -CF ２ -O-R Ｆ４ -(O-CFR Ｆ１ -CF ２ -O-R Ｆ４ ) ｃ -O-CFR Ｆ１ -CF ３ ・・・(7-1) CF ３ -CFR Ｆ１ -O-(R Ｆ４ -O-CF ２ -CFR Ｆ１ -O) ｄ -R Ｆ４ -O-CF ２ -CFR Ｆ１ -O-R Ｆ２ -O-CFR Ｆ１ -CF ３ ・・・(7-2) (In the general formula (1), the general formula (5), the general formula (6-1), the general formula (6-2), the general formula (7-1) and the general formula (7-2), R １ represents a fluorine atom, R ２ and R ４ each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may have a ring structure or a branched structure, which may have an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom; R Ｆ１ represents a fluorine atom, R Ｆ２ are each independently R ２ represents a divalent perfluorohydrocarbon group having 1 to 20 carbon atoms, in which a divalent hydrocarbon group represented by the following formula is perfluorinated: R Ｆ４ are each independently R ４ represents a divalent perfluorohydrocarbon group having 1 to 20 carbon atoms, in which a divalent hydrocarbon group represented by the following formula is perfluorinated: b, c, and d each independently represent an integer of 0 or 1 or more.

6. 6. The method for producing a fluorinated polyether compound according to claim 5, wherein the reaction of the fluorinated divinyl ether compound represented by the general formula (1) with the fluorinated vinyl alcohol compound represented by the general formula (5) is carried out in the presence of an alkali catalyst.

7. fluorination of the fluorine-containing divinyl polyether compound represented by the general formula (6-1) or the general formula (6-2) is carried out by introducing fluorine gas and the fluorine-containing divinyl polyether compound represented by the general formula (6-1) or the general formula (6-2) into a solvent, 7. The method for producing a fluorine-containing polyether compound according to claim 5 or 6, wherein, when the molar introduction rate of the fluorine-containing divinyl polyether compound represented by the general formula (6-1) or the general formula (6-2) into the solvent is taken as 1, the molar introduction rate of the fluorine gas is in the range of 1 to 10 times the rate obtained by multiplying the molar introduction rate of the fluorine-containing divinyl polyether compound represented by the general formula (6-1) or the general formula (6-2) by the number of hydrogen atoms that can be substituted by fluorine atoms by the fluorine gas contained in the fluorine-containing divinyl polyether compound represented by the general formula (6-1) or the general formula (6-2).

8. The method for producing a fluorinated polyether compound according to any one of claims 5 to 7, wherein the reaction of the fluorinated divinyl ether compound represented by the general formula (1) with the fluorinated vinyl alcohol compound represented by the general formula (5) is carried out in a ratio of 20 mol or less of the fluorinated vinyl alcohol compound represented by the general formula (5) per 1 mol of the fluorinated divinyl ether compound represented by the general formula (1).

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

10. A method for producing a fluorine-containing divinyl polyether compound, comprising reacting a fluorine-containing divinyl ether compound represented by the following general formula (1) with a fluorine-containing vinyl alcohol compound represented by the following general formula (5) in a ratio of more than 1 mol of the fluorine-containing vinyl alcohol compound represented by the following general formula (5) per 1 mol of the fluorine-containing divinyl ether compound represented by the following general formula (1), to produce a fluorine-containing divinyl polyether compound represented by the following general formula (6-1) or (6-2), wherein the acidity of the fluorine-containing vinyl alcohol compound represented by the general formula (5) is 8 to 16. CF ２ =CR １ -O-R ２ -O-CR １ =CF ２ ・・・(1) CF ２ =CR １ -O-R ４ -OH・・・(5) CF ２ =CR １ -O-(R ４ -O-CF ２ -CHR １ -O) ｂ -R ４ -O-CF ２ -CHR １ -O-R ２ -O-CHR １ -CF ２ -O-R ４ -(O-CHR １ -CF ２ -O-R ４ ) ｃ -O-CR １ =CF ２ ・・・(6-1) CF ２ =CR １ -O-(R ４ -O-CF ２ -CHR １ -O) ｄ -R ４ -O-CF ２ -CHR １ -O-R ２ -O-CR １ =CF ２ ・・・(6-2) (In the general formula (1), the general formula (5), the general formula (6-1) and the general formula (6-2), R １ represents a fluorine atom, R ２ and R ４ each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may have a ring structure or a branched structure, which may have an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom; b, c, and d each independently represent an integer of 0 or 1 or more.

11. A method for producing a fluorinated polyether compound, comprising fluorinating a fluorinated divinyl polyether compound represented by the following general formula (3) to produce a fluorinated polyether compound represented by the following general formula (4): CF ２ =CR １ -O-R ２ -O-(CHR １ -CF ２ -O-R ３ -O-CF ２ -CHR １ -O-R ２ -O) ａ -CR １ =CF ２ ・・・(3) CF ３ -CFR Ｆ１ -O-R Ｆ２ -O-(CFR Ｆ１ -CF ２ -O-R Ｆ３ -O-CF ２ -CFR Ｆ１ -O-R Ｆ２ -O) ａ -CFR Ｆ１ -CF ３ ・・・(4) (In general formulas (1) to (4), R １ represents a fluorine atom, R ２ and R ３ each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may have a ring structure or a branched structure, which may have an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom; R Ｆ１ represents a fluorine atom, R Ｆ２ are each independently R ２ represents a divalent perfluorohydrocarbon group having 1 to 20 carbon atoms, in which a divalent hydrocarbon group represented by the following formula is perfluorinated: R Ｆ３ are each independently R ３ represents a divalent perfluorohydrocarbon group having 1 to 20 carbon atoms, in which a divalent hydrocarbon group represented by the following formula is perfluorinated: a represents an integer of 1 or more.

12. A method for producing a fluorinated polyether compound, which comprises fluorinating a fluorinated divinyl polyether compound represented by the following general formula (6-1) or (6-2) to produce a fluorinated polyether compound represented by the following general formula (7-1) or (7-2), wherein the fluorinated vinyl alcohol compound represented by the general formula (5) has an acidity of 8 to 16. CF ２ =CR １ -O-R ２ -O-CR １ =CF ２ ・・・(1) CF ２ =CR １ -O-R ４ -OH・・・(5) CF ２ =CR １ -O-(R ４ -O-CF ２ -CHR １ -O) ｂ -R ４ -O-CF ２ -CHR １ -O-R ２ -O-CHR １ -CF ２ -O-R ４ -(O-CHR １ -CF ２ -O-R ４ ) ｃ -O-CR １ =CF ２ ・・・(6-1) CF ２ =CR １ -O-(R ４ -O-CF ２ -CHR １ -O) ｄ -R ４ -O-CF ２ -CHR １ -O-R ２ -O-CR １ =CF ２ ・・・(6-2) CF ３ -CFR Ｆ１ -O-(R Ｆ４ -O-CF ２ -CFR Ｆ１ -O) ｂ -R Ｆ４ -O-CF ２ -CFR Ｆ１ -O-R Ｆ２ -O-CFR Ｆ１ -CF ２ -O-R Ｆ４ -(O-CFR Ｆ１ -CF ２ -O-R Ｆ４ ) ｃ -O-CFR Ｆ１ -CF ３ ・・・(7-1) CF ３ -CFR Ｆ１ -O-(R Ｆ４ -O-CF ２ -CFR Ｆ１ -O) ｄ -R Ｆ４ -O-CF ２ -CFR Ｆ１ -O-R Ｆ２ -O-CFR Ｆ１ -CF ３ ・・・(7-2) (In the general formula (1), the general formula (5), the general formula (6-1), the general formula (6-2), the general formula (7-1) and the general formula (7-2), R １ represents a fluorine atom, R ２ and R ４ each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may have a ring structure or a branched structure, which may have an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom; R Ｆ１ represents a fluorine atom, R Ｆ２ are each independently R ２ represents a divalent perfluorohydrocarbon group having 1 to 20 carbon atoms, in which a divalent hydrocarbon group represented by the following formula is perfluorinated: R Ｆ４ are each independently R ４ represents a divalent perfluorohydrocarbon group having 1 to 20 carbon atoms, in which a divalent hydrocarbon group represented by the following formula is perfluorinated: b, c, and d each independently represent an integer of 0 or 1 or more.

13. A fluorine-containing divinyl polyether compound represented by the following general formula (3): CF ２ =CR １ -O-R ２ -O-(CHR １ -CF ２ -O-R ３ -O-CF ２ -CHR １ -O-R ２ -O) ａ -CR １ =CF ２ ・・・(3)

14. A fluorine-containing divinyl polyether compound represented by the following general formula (6-1): CF ２ =CR １ -O-(R ４ -O-CF ２ -CHR １ -O) ｂ -R ４ -O-CF ２ -CHR １ -O-R ２ -O-CHR １ -CF ２ -O-R ４ -(O-CHR １ -CF ２ -O-R ４ ) ｃ -O-CR １ =CF ２ ・・・(6-1) (In general formula (6-1), R １ represents a fluorine atom, R ２ and R ４ each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may have a ring structure or a branched structure, which may have an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom; b and c each independently represent an integer of 0 or 1 or more.

15. A fluorine-containing divinyl polyether compound represented by the following general formula (6-2): CF ２ =CR １ -O-(R ４ -O-CF ２ -CHR １ -O) ｄ -R ４ -O-CF ２ -CHR １ -O-R ２ -O-CR １ =CF ２ ・・・(6-2) (In general formula (6-2), R １ represents a fluorine atom, R ２ and R ４ each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may have a ring structure or a branched structure, which may have an ether bond, and in which a hydrogen atom may be substituted with a fluorine atom; d represents 0 or an integer of 1 or more.

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