Process for producing fluorine-containing polyether compound, process for producing fluorine-containing divinyl polyether compound, and fluorine-containing divinyl polyether compound

Abstract

A production method in which a compound represented by (1) is reacted with a compound represented by (2) at a ratio of more than 1 mol of the compound represented by (1) per 1 mol of the compound represented by (2), a compound represented by (3) is produced, and then fluorinated to produce a fluorine-containing polyether compound represented by (4). CF2=CR 1 -O-R 2 -O-CR 1 =CF2(1) HO-R 3 -OH(2) CF2=CR 1 -O-R 2 -O-(CHR 1 -CF2-O-R 3 -O-CF2-CHR 1 -O-R 2 -O) a -CR 1 =CF2(3) CF3-CFR F1 -O-R F2 -O-(CFR F1 -CF2-O-R F3 -O-CF2-CFR F1 -O-R F2 -O) a -CFR F1 -CF3(4).

Description

TECHNICAL FIELD

[0001] The present disclosure relates to a method for producing a fluorine-containing polyether compound, a method for producing a fluorine-containing divinyl polyether compound, and a fluorine-containing divinyl polyether compound. BACKGROUND

[0002] Fluorine-containing compounds are used for surface treatment agents or lubricants, etc. due to exhibiting high lubricity and water / oil repellency, etc. Among fluorine-containing compounds, fluorine-containing polyether compounds having ether bonds are excellent in lubricity and are used for coating film formation for the purpose of protecting a read / write head of a magnetic disk, etc.

[0003] Conventionally, fluorine-containing polyether compounds are produced by various methods. For example, in U.S. Patent No. 5258110, it is disclosed that a fluorine-containing polyether compound is produced by reacting tetrafluoroethylene in the presence of a compound having a fluoroxy group, etc. with oxygen.

[0004] Further, in U.S. Patent No. 4845268, it is disclosed that a fluorine-containing polyether compound is produced by ring-opening polymerization of 2,2,3,3-tetrafluorooxetane, and a halogen-containing polyether compound is produced by chlorination and fluorination of the fluorine-containing polyether compound.

[0005] Further, in International Publication No. 2013 / 121984, it is disclosed that a compound represented by CF2=CFO-CF2CF2CF2CH2OH is reacted with a primary alcohol represented by A 1 -OH (A 1 to produce A 1 -O-(CF2CFHO-CF2CF2CF2CH2O) n+1 -H. SUMMARY

[0006] PROBLEMS TO BE SOLVED BY THE INVENTION

[0007] From the viewpoint of lubricity, it is preferable that the fluorine-containing polyether compound has a trifluoromethyl group (-CF3) at the terminal, but in the production method disclosed in U.S. Patent No. 5258110, it is difficult to produce a fluorine-containing polyether compound having a trifluoromethyl group at both terminals with a high yield.

[0008] Further, the fluorine-containing polyether compound obtained by the production method disclosed in U.S. Patent No. 4845268 and International Publication No. 2013 / 121984 has a functional group at at least one terminal, and the reaction of replacing the functional group with a trifluoromethyl group is not easy to proceed, and it is difficult to produce a fluorine-containing polyether compound having a trifluoromethyl group at both terminals.

[0009] Further, since the above-mentioned coating film is required to have chemical resistance and heat resistance, etc., it is required that the fluorine-containing polyether compound used in the coating film formation has a high molecular weight.

[0010] The present disclosure was made in view of the above-described needs, and the problem to be solved by the present disclosure is to provide a method for producing a fluorine-containing polyether compound, which can produce a fluorine-containing polyether compound having a high molecular weight and a trifluoromethyl group at both terminals at a high yield.

[0011] In addition, the problem to be solved by the present disclosure is to provide a method for producing a fluorine-containing divinyl polyether compound, which can easily produce a fluorine-containing divinyl polyether compound having a high molecular weight and a vinyl group at both terminals at a high yield, and a novel fluorine-containing divinyl polyether compound.

[0012] Means for solving the problem

[0013] Specific means for achieving the above-described problem are as follows.

[0014] <1> A method for producing a fluorine-containing polyether compound, wherein a fluorine-containing divinyl ether compound represented by the following general formula (1) is reacted with a diol compound represented by the following general formula (2) at 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), a fluorine-containing divinyl polyether compound represented by the following general formula (3) is produced, and then the fluorine-containing divinyl polyether compound represented by the following general formula (3) is fluorinated to produce a fluorine-containing polyether compound represented by the following general formula (4).

[0015] CF2=CR 1 -O-R 2 -O-CR 1 =CF2 (1)

[0016] HO-R 3 -OH (2)

[0017] CF2=CR 1 -O-R 2 -O-(CHR 1 -CF2-O-R 3 -O-CF2-CHR 1 -O-R 2 -O) a -CR 1 =CF2 (3)

[0018] CF3-CFR F1 -O-R F2 -O-(CFR F1 -CF2-O-R F3 -O-CF2-CFR F1 -O-R F2 -O) a -CFR F1-CF3(4)

[0019] (in General Formula (1) to General Formula (4),

[0020] R 1 each independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having 1 to 3 carbons optionally substituted with a fluorine atom,

[0021] R 2 and R 3 each independently represents a divalent hydrocarbon group having 1 to 20 carbons, the divalent hydrocarbon group having 1 to 20 carbons optionally containing a ring structure, a branched structure, optionally containing an ether bond, and a hydrogen atom optionally substituted with a fluorine atom,

[0022] R 1 R F1 each independently represents a fluorine atom, R 1 R F1 each independently represents a fluorine atom, R 1 R F1 each independently represents a monovalent perfluorohydrocarbon group having 1 to 3 carbons,

[0023] R F2 each independently represents a divalent hydrocarbon group having 1 to 20 carbons, 2 a divalent perfluorohydrocarbon group having 1 to 20 carbons in which the divalent hydrocarbon group represented by R

[0024] R F3 each independently represents a divalent hydrocarbon group having 1 to 20 carbons, 3 a divalent perfluorohydrocarbon group having 1 to 20 carbons in which the divalent hydrocarbon group represented by R

[0025] a represents an integer of 1 or more.

[0026] <2> The method for producing a fluorine-containing polyether compound according to <1>, wherein the reaction of the fluorine-containing divinyl ether compound represented by General Formula (1) and the diol compound represented by General Formula (2) is performed in the presence of a base catalyst.

[0027] <3> The method for producing a fluorine-containing polyether compound according to <1> or <2>, wherein the fluorination of the fluorine-containing divinyl polyether compound represented by General Formula (3) is performed by introducing fluorine gas and the fluorine-containing divinyl polyether compound represented by General Formula (3) into a solvent,

[0028] When the introduction rate of the fluorine-containing divinyl polyether compound represented by the above general formula (3) into the above solvent is 1 on a molar basis, the introduction rate of the fluorine gas is in the range of 1 to 10 times the rate obtained by multiplying the introduction rate of the fluorine-containing divinyl polyether compound represented by the above general formula (3) on a molar basis by the number of hydrogen atoms included in the fluorine-containing divinyl polyether compound represented by the above general formula (3) that can be substituted with fluorine atoms by the above fluorine gas.

[0029] <4> The production method of a fluorine-containing polyether compound according to any one of <1> to <3>, wherein the fluorine-containing divinyl ether compound represented by the above general formula (1) is reacted with the diol compound represented by the above general formula (2) at a ratio of 3 mol or less of the fluorine-containing divinyl ether compound represented by the above general formula (1) per 1 mol of the diol compound represented by the above general formula (2).

[0030] <5> A production method of a fluorine-containing polyether compound, wherein a fluorine-containing divinyl ether compound represented by the following general formula (1) is reacted with a fluorine-containing vinyl alcohol compound represented by the following general formula (5) at a ratio of more than 1 mol of the fluorine-containing vinyl alcohol compound represented by the above general formula (5) per 1 mol of the fluorine-containing divinyl ether compound represented by the above general formula (1), a fluorine-containing divinyl polyether compound represented by the following general formula (6-1) or the following general formula (6-2) is produced, and then the fluorine-containing divinyl polyether compound represented by the above general formula (6-1) or the above general formula (6-2) is fluorinated to produce a fluorine-containing polyether compound represented by the following general formula (7-1) or the following general formula (7-2).

[0031] CF2=CR 1 -O-R 2 -O-CR 1 =CF2 (1)

[0032] CF2=CR 1 -O-R 4 -OH (5)

[0033] CF2=CR 1 -O-(R 4 -O-CF 2 -CHR 1 -O) b -R 4 -O-CF2-CHR 1 -O-R 2 -O-CHR 1 -CF2-O-R 4 -(O-CHR 1 -CF2-O-R 4 ) c -O-CR1 =CF2 (6-1)

[0034] CF2=CR 1 -O-(R 4 -O-CF 2 -CHR 1 -O) d -R 4 -O-CF2-CHR 1 -O-R 2 -O-CR 1 =CF2 (6-2)

[0035] CF3-CFR F1 -O-(R F4 -O-CF 2 -CFR F1 -O) b -R F4 -O-CF2-CFR F1 -O-R F2 -O-CFR F1 -CF2-O-R F4 -(O-CFR F1 -CF2-O-R F4 ) c -O-CFR F1 -CF3 (7-1)

[0036] CF3-CFR F1 -O-(R F4 -O-CF 2 -CFR F1 -O) d -R F4 -O-CF2-CFR F1 -O-R F2 -O-CFR F1 -CF3 (7-2)

[0037] (in General Formula (1), General Formula (5), General Formula (6-1), General Formula (6-2), General Formula (7-1), and General Formula (7-2),

[0038] R 1 each independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having a carbon number of 1 to 3, the monovalent hydrocarbon group having a carbon number of 1 to 3 being optionally substituted with a fluorine atom,

[0039] R 2 and R 4 each independently represents a divalent hydrocarbon group having a carbon number of 1 to 20, the divalent hydrocarbon group having a carbon number of 1 to 20 optionally containing a ring structure, a branched structure, optionally containing an ether bond, and a hydrogen atom being optionally substituted with a fluorine atom,

[0040] R 1 R F1 each independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having a carbon number of 1 to 3, 1 R F1 each independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having a carbon number of 1 to 3, 1 R F1 each independently represents a monovalent perfluorohydrocarbon group having a carbon number of 1 to 3,

[0041] R F2 each independently represents a monovalent hydrocarbon group having a carbon number of 1 to 3, 2 a divalent perfluorohydrocarbon group having a carbon number of 1 to 20 in which a divalent hydrocarbon group represented by the formula shown above is perfluorinated,

[0042] R F4 each independently represents a monovalent hydrocarbon group having a carbon number of 1 to 3, 4 a divalent perfluorohydrocarbon group having a carbon number of 1 to 20 in which a divalent hydrocarbon group represented by the formula shown above is perfluorinated,

[0043] b, c, and d each independently represent an integer of 0 or 1 or more.

[0044] <6> The method for producing a fluorine-containing polyether compound according to <5>, wherein the reaction of the fluorine-containing divinyl ether compound represented by the general formula (1) and the fluorine-containing vinyl alcohol compound represented by the general formula (5) is performed in the presence of a base catalyst.

[0045] <7> The method for producing a fluorine-containing polyether compound according to <5> or <6>, wherein the fluorination of the fluorine-containing divinyl polyether compound represented by the general formula (6-1) or the general formula (6-2) is performed 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.

[0046] When the introduction rate of the fluorine-containing divinyl polyether compound represented by the general formula (6-1) or the general formula (6-2) into the solvent is set to 1 on a molar basis, the introduction rate of the fluorine gas on a molar basis is in the range of 1 to 10 times the rate obtained by multiplying the introduction rate of the fluorine-containing divinyl polyether compound represented by the general formula (6-1) or the general formula (6-2) on a molar basis by the number of hydrogen atoms included in the fluorine-containing divinyl polyether compound represented by the general formula (6-1) or the general formula (6-2) which can be substituted with fluorine atoms by the fluorine gas.

[0047] <8> The method for producing a fluorine-containing polyether compound according to any one of <5> to <7>, wherein the reaction of the fluorine-containing divinyl ether compound represented by the above general formula (1) and the fluorine-containing vinyl alcohol compound represented by the above general formula (5) is performed at a ratio of 20 mol or less of the fluorine-containing vinyl alcohol compound represented by the above general formula (5) per 1 mol of the fluorine-containing divinyl ether compound represented by the above general formula (1).

[0048] <9> A method for producing a fluorine-containing divinyl polyether compound, wherein a fluorine-containing divinyl ether compound represented by the following general formula (1) is reacted with a diol compound represented by the following general formula (2) at a ratio of more than 1 mol of the fluorine-containing divinyl ether compound represented by the above general formula (1) per 1 mol of the diol compound represented by the above general formula (2), to produce a fluorine-containing divinyl polyether compound represented by the following general formula (3).

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

[0050] HO-R 3 -OH(2)

[0051] CF2=CR 1 -O-R 2 -O-(CHR 1 -CF2-O-R 3 -O-CF2-CHR 1 -O-R 2 -O) a -CR 1 =CF2 (3)

[0052] (in the general formula (1) to the general formula (3),

[0053] R 1 each independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having a carbon number of 1 to 3, the monovalent hydrocarbon group having a carbon number of 1 to 3 being optionally substituted with a fluorine atom,

[0054] R 2 and R 3 each independently represents a divalent hydrocarbon group having a carbon number of 1 to 20, the divalent hydrocarbon group having a carbon number of 1 to 20 optionally containing a ring structure, a branched structure, optionally containing an ether bond, and a hydrogen atom being optionally substituted with a fluorine atom,

[0055] a represents an integer of 1 or more.

[0056] <9> A method for producing a fluorine-containing divinyl polyether compound, wherein a fluorine-containing divinyl ether compound represented by the following general formula (1) is reacted with a fluorine-containing vinyl alcohol compound represented by the following general formula (5) at 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).

[0057] CF2=CR 1 -O-R 2 -O-CR 1 =CF2 (1)

[0058] CF2=CR 1 -O-R 4 -OH (5)

[0059] CF2=CR 1 -O-(R 4 -O-CF 2 -CHR 1 -O) b -R 4 -O-CF2-CHR 1 -O-R 2 -O-CHR 1 -CF2-O-R 4 -(O-CHR 1 -CF2-O-R 4 ) c -O-CR 1 =CF2 (6-1)

[0060] CF2=CR 1 -O-(R 4 -O-CF 2 -CHR 1 -O) d -R 4 -O-CF2-CHR 1 -O-R 2 -O-CR 1 =CF2 (6-2)

[0061] (in the general formula (1), the general formula (5), the general formula (6-1), and the general formula (6-2),

[0062] R 1 each independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having a carbon number of 1 to 3 which is optionally substituted with a fluorine atom,

[0063] R 2 and R 4each independently represents a divalent hydrocarbon group having a carbon number of 1 to 20, the divalent hydrocarbon group having a carbon number of 1 to 20 optionally contains a ring structure, a branched structure, optionally contains an ether bond, and a hydrogen atom is optionally substituted with a fluorine atom,

[0064] b, c, and d each independently represent an integer of 0 or more.

[0065] <10> A method for producing a fluorine-containing polyether compound, wherein a fluorine-containing divinyl polyether compound represented by the following general formula (3) is fluorinated to produce a fluorine-containing polyether compound represented by the following general formula (4).

[0066] CF2=CR 1 -O-R 2 -O-(CHR 1 -CF2-O-R 3 -O-CF2-CHR 1 -O-R 2 -O) a -CR 1 =CF2 (3)

[0067] CF3-CFR F1 -O-R F2 -O-(CFR F1 -CF2-O-R F3 -O-CF2-CFR F1 -O-R F2 -O) a -CFR F1 -CF3 (4)

[0068] (in General Formula (1) to General Formula (4),

[0069] R 1 each independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having a carbon number of 1 to 3 in which a hydrogen atom is optionally substituted with a fluorine atom,

[0070] R 2 and R 3 each independently represents a divalent hydrocarbon group having a carbon number of 1 to 20, the divalent hydrocarbon group having a carbon number of 1 to 20 optionally contains a ring structure, a branched structure, optionally contains an ether bond, and a hydrogen atom is optionally substituted with a fluorine atom,

[0071] each independently represents a fluorine atom when R 1 is a fluorine atom, each independently represents a hydrogen atom when R F1 each independently represents a fluorine atom, each independently represents a hydrogen atom when R 1 is a hydrogen atom, each independently represents a fluorine atom when R F1 is a monovalent hydrocarbon group having a carbon number of 1 to 3, each independently represents a monovalent perfluorohydrocarbon group having a carbon number of 1 to 3 when R 1 is a monovalent hydrocarbon group having a carbon number of 1 to 3, each independently represents a monovalent perfluorohydrocarbon group having a carbon number of 1 to 3 when R F1 is a monovalent hydrocarbon group having a carbon number of 1 to 3, each independently represents a monovalent perfluorohydrocarbon group having a carbon number of 1 to 3 when R

[0072] R F2 each independently represents R 2 the bivalent hydrocarbon group shown is replaced with a bivalent perfluorohydrocarbon group having a carbon number of 1 to 20 which is perfluorinated,

[0073] R F3 each independently represents R 3 the bivalent hydrocarbon group shown is replaced with a bivalent perfluorohydrocarbon group having a carbon number of 1 to 20 which is perfluorinated,

[0074] a represents an integer of 1 or more.

[0075] <11> A method for producing a fluorine-containing polyether compound, wherein a fluorine-containing divinyl polyether compound represented by the following general formula (6-1) or the following general formula (6-2) is fluorinated to produce a fluorine-containing polyether compound represented by the following general formula (7-1) or the following general formula (7-2).

[0076] CF2=CR 1 -O-R 2 -O-CR 1 =CF2 (1)

[0077] CF2=CR 1 -O-R 4 -OH (5)

[0078] CF2=CR 1 -O-(R 4 -O-CF 2 -CHR 1 -O) b -R 4 -O-CF2-CHR 1 -O-R 2 -O-CHR 1 -CF2-O-R 4 -(O-CHR 1 -CF2-O-R 4 ) c -O-CR 1 =CF2 (6-1)

[0079] CF2=CR 1 -O-(R 4 -O-CF 2 -CHR 1 -O) d -R 4 -O-CF2-CHR 1 -O-R 2 -O-CR 1 =CF2 (6-2)

[0080] CF3-CFRF1 -O-(R F4 -O-CF 2 -CFR F1 -O) b -R F4 -O-CF2-CFR F1 -O-R F2 -O-CFR F1 -CF2-O-R F4 -(O-CFR F1 -CF2-O-R F4 ) c -O-CFR F1 -CF3 (7-1)

[0081] CF3-CFR F1 -O-(R F4 -O-CF 2 -CFR F1 -O) d -R F4 -O-CF2-CFR F1 -O-R F2 -O-CFR F1 -CF3 (7-2)

[0082] in General Formula (1), General Formula (5), General Formula (6-1), General Formula (6-2), General Formula (7-1), and General Formula (7-2),

[0083] R 1 each independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having 1 to 3 carbons optionally substituted with a fluorine atom,

[0084] R 2 and R 4 each independently represents a divalent hydrocarbon group having 1 to 20 carbons, the divalent hydrocarbon group having 1 to 20 carbons optionally containing a ring structure, a branched structure, optionally containing an ether bond, and a hydrogen atom optionally substituted with a fluorine atom,

[0085] when R 1 is a fluorine atom, R F1 each independently represents a fluorine atom, when R 1 is a hydrogen atom, R F1 each independently represents a fluorine atom, when R 1 is a monovalent hydrocarbon group having 1 to 3 carbons, R F1 each independently represents a monovalent perfluorohydrocarbon group having 1 to 3 carbons,

[0086] R F2 each independently represents a divalent hydrocarbon group represented by R 2 is a divalent perfluorohydrocarbon group in which the divalent hydrocarbon group represented by R

[0087] R F4 each independently represents R 4 said divalent hydrocarbon group being perfluorinated,

[0088] b, c and d each independently represent an integer of 0 or more.

[0089] <12> A fluorine-containing divinyl polyether compound represented by the following general formula (3).

[0090] CF2=CR 1 -O-R 2 -O-(CHR 1 -CF2-O-R 3 -O-CF2-CHR 1 -O-R 2 -O) a -CR 1 =CF2 (3)

[0091] (in general formula (3),

[0092] R 1 each independently represents a fluorine atom, a hydrogen atom or a monovalent hydrocarbon group of carbon number 1 to 3 optionally substituted with a fluorine atom,

[0093] R 2 and R 3 each independently represents a divalent hydrocarbon group of carbon number 1 to 20 optionally containing a ring structure, a branched structure, optionally containing an ether bond, and a hydrogen atom optionally substituted with a fluorine atom,

[0094] a represents an integer of 1 or more.

[0095] <13> A fluorine-containing divinyl polyether compound represented by the following general formula (6-1).

[0096] CF2=CR 1 -O-(R 4 -O-CF 2 -CHR 1 -O) b -R 4 -O-CF2-CHR 1 -O-R 2 -O-CHR 1 -CF2-O-R 4 -(O-CHR 1 -CF2-O-R 4 ) c -O-CR 1 =CF2 (6-1)

[0097] (in General Formula (6-1),

[0098] R 1 each independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having a carbon number of 1 to 3, the monovalent hydrocarbon group having a carbon number of 1 to 3 being optionally substituted with a fluorine atom,

[0099] R 2 and R 4 each independently represents a divalent hydrocarbon group having a carbon number of 1 to 20, the divalent hydrocarbon group having a carbon number of 1 to 20 optionally containing a ring structure, a branched structure, optionally containing an ether bond, and a hydrogen atom being optionally substituted with a fluorine atom,

[0100] b and c each independently represent an integer of 0 or more.

[0101] <14> A fluorine-containing divinyl polyether compound represented by the following General Formula (6-2).

[0102] CF2=CR 1 -O-(R 4 -O-CF 2 -CHR 1 -O) d -R 4 -O-CF2-CHR 1 -O-R 2 -O-CR 1 =CF2 (6-2)

[0103] (in General Formula (6-2),

[0104] R 1 each independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having a carbon number of 1 to 3, the monovalent hydrocarbon group having a carbon number of 1 to 3 being optionally substituted with a fluorine atom,

[0105] R 2 and R 4 each independently represents a divalent hydrocarbon group having a carbon number of 1 to 20, the divalent hydrocarbon group having a carbon number of 1 to 20 optionally containing a ring structure, a branched structure, optionally containing an ether bond, and a hydrogen atom being optionally substituted with a fluorine atom,

[0106] d represents an integer of 0 or more.

[0107] Effects of the Invention

[0108] According to the present disclosure, a high molecular weight fluorine-containing polyether compound having a trifluoromethyl group at both terminals can be produced at a high yield, and a method for producing a fluorine-containing polyether compound.

[0109] Further, according to the present disclosure, there are provided a method for producing a fluorine-containing divinyl polyether compound having a high molecular weight and having a vinyl group at both terminals with a high yield, a method for producing a fluorine-containing divinyl polyether compound, and a novel fluorine-containing divinyl polyether compound. DETAILED DESCRIPTION

[0110] Hereinafter, modes for carrying out the present disclosure will be explained in detail. However, the present disclosure is not limited to the following embodiments. In the following embodiments, unless otherwise specified, the constituent elements (including element steps, etc.) are not essential. The same applies to numerical values and ranges thereof, and the present disclosure is not limited thereto.

[0111] In the present disclosure, a numerical range indicated by "~" includes the numerical values indicated before and after the "~" as the minimum value and the maximum value, respectively.

[0112] In the present disclosure, the upper limit value or the lower limit value indicated in one numerical range can be replaced with the upper limit value or the lower limit value of another numerical range indicated in stages. In addition, in the present disclosure, the upper limit value or the lower limit value of the numerical range can be replaced with the value shown in the synthesis example.

[0113] In the present disclosure, "fluoroalkylene" includes perfluoroalkylene in which all hydrogen atoms are replaced with fluorine atoms, and fluoroalkylene in which a part of the hydrogen atoms are replaced with fluorine atoms. In addition, in the present disclosure, the "fluorocycloalkane" and the like also include not only perfluorocyclobutene in which all hydrogen atoms possessed by cyclobutene are replaced with fluorine atoms, but also cyclobutene in which a part of the hydrogen atoms are replaced with fluorine atoms.

[0114] In the present disclosure, each component can include a plurality of compounds that satisfy the conditions. For example, the mol ratio in the reaction of the fluorine-containing divinyl ether compound represented by General Formula (1) and the diol compound represented by General Formula (2) is calculated based on the total of the compounds corresponding to each component.

[0115] In the present disclosure, in the expression of a group (radical), for the expression of no substitution and no un-substitution, both the case of having no substituent and the case of having a substituent are included.

[0116] In the present disclosure, the carbon number refers to the total number of carbon atoms included in a certain group, and in the case where the group has no substituent, the number of carbon atoms forming the skeleton of the group is indicated, and in the case where the group has a substituent, the total number obtained by adding the number of carbon atoms in the substituent to the number of carbon atoms forming the skeleton of the group is indicated.

[0117] In the present disclosure, the "perfluorinated" of a monovalent or divalent hydrocarbon group means that the hydrocarbon group is fluorinated to the following state.

[0118] In the case where the monovalent or divalent hydrocarbon group is a saturated hydrocarbon group, the state where all of the fluorinatable hydrogen atoms bonded to the carbon atoms constituting the monovalent or divalent hydrocarbon group are fluorinated is referred to as the hydrocarbon group being "perfluorinated".

[0119] In the case where the monovalent or divalent hydrocarbon group is an unsaturated hydrocarbon group, the state where all of the fluorinatable hydrogen atoms bonded to the carbon atoms constituting the monovalent or divalent hydrocarbon group are fluorinated, and two carbon atoms each of which forms a carbon-carbon unsaturated bond such as a carbon-carbon double bond or a carbon-carbon triple bond, and to which a fluorine atom is added so as to eliminate the carbon-carbon unsaturated bond, is referred to as the hydrocarbon group being "perfluorinated". For example, >C=C< is changed to >CF-CF< if perfluorinated, and -C≡C- is changed to -CF2-CF2- if perfluorinated. In addition, the fluorinatable hydrogen atom can be bonded to a fluorinatable atomic group, for example, -CH=CH- is changed to -CF2-CF2- if perfluorinated.

[0120] 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 measurement based on GPC is performed under the following conditions according to the method described in Japanese Patent Application Laid-Open No. 2001-208736.

[0121] • Mobile phase: mixed solvent of R-225 (manufactured by AGC Inc., trade name: ASAHIKLIN (registered trademark) AK-225 SEC grade 1) and hexafluoroisopropyl alcohol (HFIP) (R-225:HFIP = 99:1 (volume ratio))

[0122] • Analysis column: two PLgel MIXED-E columns (manufactured by Polymer Laboratories) are connected in series

[0123] • Standard sample for molecular weight measurement: four perfluoropolyethers having a molecular weight distribution (Mw / Mn) of less than 1.1 and Mn of 2,000 to 10,000, and one perfluoropolyether having Mw / Mn of 1.1 or more and Mn of 1,300

[0124] • Flow rate of mobile phase: 1.0 mL / minute

[0125] • Column temperature: 37°C

[0126] • Detector: evaporative light scattering detector

[0127] (Method for producing fluorine-containing polyether compound of the first mode)

[0128] First, a method for producing a fluorine-containing polyether compound represented by General Formula (4) will be described. A fluorine-containing divinyl polyether compound represented by General Formula (3) and a method for producing the same will also be described together.

[0129] The first method for producing a fluorine-containing polyether compound is a method in which a fluorine-containing divinyl ether compound represented by the following general formula (1) (hereinafter, also referred to as a compound of formula (1)) is reacted with a diol compound represented by the following general formula (2) (hereinafter, also referred to as a compound of formula (2)) at a ratio of more than 1 mol of the compound of formula (1) per 1 mol of the compound of formula (2), to produce a fluorine-containing divinyl polyether compound represented by the following general formula (3) (hereinafter, also referred to as a compound of formula (3)), and then the compound of formula (3) is fluorinated to produce a fluorine-containing polyether compound represented by the following general formula (4) (hereinafter, also referred to as a compound of formula (4)).

[0130] CF2=CR 1 -O-R 2 -O-CR 1 =CF2 (1)

[0131] HO-R 3 -OH(2)

[0132] CF2=CR 1 -O-R 2 -O-(CHR 1 -CF2-O-R 3 -O-CF2-CHR 1 -O-R 2 -O) a -CR 1 =CF2 (3)

[0133] CF3-CFR F1 -O-R F2 -O-(CFR F1 -CF2-O-R F3 -O-CF2-CFR F1 -O-R F2 -O) a -CFR F1 -CF3(4)

[0134] 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 a carbon number of 1 to 3, which is optionally substituted with a fluorine atom.

[0135] In general formula (1) to general formula (3), R 2 and R 3 each independently represents a divalent hydrocarbon group having a carbon number of 1 to 20, which optionally contains a ring structure, a branched structure, optionally contains an ether bond, and a hydrogen atom is optionally substituted with a fluorine atom.

[0136] In general formula (4), in R 1R is a fluorine atom when R F1 each independently represents a fluorine atom, R 1 R is a hydrogen atom when R F1 each independently represents a fluorine atom, R 1 R is a monovalent hydrocarbon group having 1 to 3 carbons when R F1 each independently represents a monovalent perfluorohydrocarbon group having 1 to 3 carbons.

[0137] In General Formula (4), R F2 each independently represents R 2 a divalent perfluorohydrocarbon group having 1 to 20 carbons in which a divalent hydrocarbon group represented by the formula shown above is perfluorinated.

[0138] In General Formula (4), R F3 each independently represents R 3 a divalent perfluorohydrocarbon group having 1 to 20 carbons in which a divalent hydrocarbon group represented by the formula shown above is perfluorinated.

[0139] 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.

[0140] The production method of the fluorine-containing polyether compound by the first method can produce a high-molecular-weight fluorine-containing polyether compound having a trifluoromethyl group at both terminals at a high yield.

[0141] The reason for exerting the above effects is presumed as follows, but is not limited thereto.

[0142] In the reaction of the compound of Formula (1) and the compound of Formula (2), the reaction is performed at a ratio of more than 1 mol of the compound of Formula (1) with respect to 1 mol of the compound of Formula (2), and thus the polymerization reaction proceeds smoothly, and thus a high-molecular-weight compound of Formula (3) can be produced at a high yield.

[0143] Further, the compound of Formula (3) obtained by the above reaction has a vinyl group (CF2=CR 1 -) at both terminals, and the above vinyl group is easily fluorinated by contact with fluorine gas, and thus a high-molecular-weight compound of Formula (4) having a trifluoromethyl group at both terminals can be produced at a high yield.

[0144] Hereinafter, the production of the fluorine-containing divinyl polyether compound and the fluorination of the fluorine-containing divinyl polyether compound included in the production method of the fluorine-containing polyether compound by the first method will be described.

[0145] -Production of the fluorine-containing divinyl polyether compound-

[0146] By contacting both terminals of the compound of formula (3) manufactured by the reaction of the compound of formula (1) with the compound of formula (2) with fluorine gas or the like, the vinyl groups are easily fluorinated, and thus the compound of formula (4) having a trifluoromethyl group at both terminals can be manufactured.

[0147] In the reaction of the compound of formula (1) with the compound of formula (2), it is preferable to carry out the reaction at a ratio of 1.01 mol or more of the compound of formula (1) per 1 mol of the compound of formula (2), and more preferably at a ratio of 1.1 mol or more.

[0148] By carrying out the reaction of the compound of formula (1) with the compound of formula (2) at the above mol ratio, the polymerization reaction proceeds smoothly, and thus the compound of formula (3) having a high molecular weight can be manufactured at a high yield.

[0149] In the reaction of the compound of formula (1) with the compound of formula (2), it is preferable to carry out the reaction at a ratio of 3 mol or less of the compound of formula (1) per 1 mol of the compound of formula (2), and more preferably at a ratio of 2 mol or less.

[0150] By carrying out the reaction of the compound of formula (1) with the compound of formula (2) at the above mol ratio, the polymerization reaction proceeds smoothly, and thus the compound of formula (3) having a high molecular weight can be manufactured at a high yield.

[0151] The reaction of the compound of formula (1) with the compound of formula (2) is preferably carried out in the presence of a base catalyst. By carrying out the reaction of the compound of formula (1) with the compound of formula (2) in the presence of a base catalyst, the molecular weight and the yield of the manufactured compound of formula (3) can be further improved.

[0152] As the base catalyst, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, cesium fluoride, potassium carbonate, and the like can be given, and from the viewpoint of the molecular weight and the yield of the fluorine-containing divinyl polyether compound and the fluorine-containing polyether compound, potassium carbonate is preferable.

[0153] In addition, the reaction of the compound of formula (1) with the compound of formula (2) can be carried out in a solvent or without using a solvent. The solvent is not particularly limited, and when fluorination is carried out on the compound of formula (3), a solvent which is not fluorinated is preferable, and specifically, a fluorine-based solvent is preferable. As the fluorine-based solvent, fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkyl amines, and fluoroalcohols, and the like can be given.

[0154] From the viewpoint of the molecular weight and the yield of the compound of formula (3), the reaction temperature of the compound of formula (1) with the compound of formula (2) is preferably 80°C to 160°C, and more preferably 90°C to 140°C.

[0155] The reaction of the compound of formula (1) with the compound of formula (2) can be carried out in a batch manner or in a continuous manner, and can be carried out in a known manner as appropriate.

[0156] In the case where the reaction of the compound of formula (1) with the compound of formula (2) is carried out in a batch manner, for example, the compound of formula (2) is previously charged into a reactor, and the compound of formula (1) or a diluent thereof can be added to the reactor.

[0157] From the viewpoint of reactivity, in the case where the compound of formula (1) or a diluent thereof is added to the compound of formula (2) previously charged into a reactor, it is preferable to add the compound of formula (1) after the compound of formula (2) is heated to the above-mentioned reaction temperature to be in the state of an alkylene oxide.

[0158] From the viewpoint of the molecular weight and yield of the compound of formula (3), in the reaction of the compound of formula (1) with the compound of formula (2), the addition of the compound of formula (1) to the compound of formula (2) is preferably carried out at a rate of 0.01 times mol / hour to 10 times mol / hour relative to 1 mol of the compound of formula (2), and more preferably at a rate of 0.1 times mol / hour to 0.5 times mol / hour.

[0159] After the reaction of the compound of formula (1) with the compound of formula (2), at least one selected from the group consisting of a solvent, water, and an aqueous solution for adjusting to an appropriate acidity can be added and the mixture can be subjected to liquid separation, and then the organic phase can be concentrated. Alternatively, the reaction crude liquid obtained by concentrating the organic phase can be purified. The solvent is not particularly limited, and the above-mentioned fluorine-based solvent is preferable.

[0160] Hereinafter, the compound of formula (1), the compound of formula (2), and the compound of formula (3) will be described.

[0161] -- Compound of formula (1) --

[0162] In the following general formula (1), R 1 At least one is preferably a fluorine atom, and more preferably all are fluorine atoms.

[0163] CF2=CR 1 -O-R 2 -O-CR 1 =CF2 (1)

[0164] In general formula (1), R 2 represents a divalent hydrocarbon group having a carbon number of 1 to 20, and the divalent hydrocarbon group having a carbon number of 1 to 20 optionally contains a ring structure, a branched structure, optionally contains an ether bond, and a hydrogen atom is optionally substituted with a fluorine atom.

[0165] The carbon number of the divalent hydrocarbon group is preferably 15 or less, more preferably 10 or less. By setting the carbon number of the divalent hydrocarbon group to 15 or less, the polymerization reaction proceeds more smoothly, and thus a fluorine-containing polyether compound having a high molecular weight can be produced at a high yield.

[0166] From the viewpoint of suppressing the production of a cyclic compound in the polymerization reaction, the carbon number of the divalent hydrocarbon group is preferably 2 or more, more preferably 3 or more.

[0167] As the divalent hydrocarbon group represented by R 2 For example, the divalent hydrocarbon group represented by R

[0168] As the divalent hydrocarbon group represented by R 2 The divalent hydrocarbon group represented by R

[0169] As the divalent hydrocarbon group represented by R x As the divalent hydrocarbon group represented by R x ) n As the divalent hydrocarbon group represented by R

[0170] In General Formula (X), R x represents ethylene group, trimethylene group, propylene group, fluoroethylene group, fluorotrimethylene group, or fluoropropylene group, and n represents an integer of 1 or more.

[0171] Note that in General Formula (X), * represents a bonding portion to an oxygen atom.

[0172] As the divalent hydrocarbon group represented by R 2 The divalent hydrocarbon group represented by R

[0173] As the divalent hydrocarbon group represented by R b As the divalent hydrocarbon group represented by R a As the divalent hydrocarbon group represented by R b As the divalent hydrocarbon group represented by R

[0174] In General Formula (A), R a represents cycloalkanediyl group, fluorocycloalkanediyl group, or arylene group.

[0175] As the cycloalkanediyl group and the fluorocycloalkanediyl group, for example, cyclobutanediyl group, fluorocyclobutanediyl group, cyclopentanediyl group, fluorocyclopentanediyl group, cyclohexanediyl group, fluorocyclohexanediyl group, adamantanediyl group, norbornanediyl group, and the like can be given. The cycloalkanediyl group, the fluorocycloalkanediyl group, and the arylene group can have an alkyl group having a carbon number of 1 to 3, in which a hydrogen atom is optionally substituted with a fluorine atom, as a substituent.

[0176] In General Formula (A), R beach independently represents a divalent hydrocarbon group having a carbon number of 1 to 10, the divalent hydrocarbon group having a carbon number of 1 to 10 optionally containing a ring structure, a branched structure, and a hydrogen atom optionally being replaced with a fluorine atom.

[0177] Note that, in General Formula (A), * indicates a bonding portion to an oxygen atom.

[0178] As the hydrocarbon group satisfying General Formula (A), the following groups can be given, but are not limited thereto.

[0179]

[0180] In addition, R 2 The divalent hydrocarbon group represented by General Formula (A) can be a group represented by General Formulae (B) to (D) shown below.

[0181] *-R c -R a -R c -* (B)

[0182] *-R a -R c -R a -* (C)

[0183] *-R b -R d -R b -* (D)

[0184] Note that, in General Formulae (B) to (D), * indicates a bonding portion to an oxygen atom.

[0185] R a in General Formulae (B) to (D) is the same as in General Formula (A).

[0186] In addition, in General Formulae (B) and (C), R c each independently represents a single bond, or a divalent hydrocarbon group having a carbon number of 1 to 10, the divalent hydrocarbon group having a carbon number of 1 to 10 optionally containing a ring structure, a branched structure, and a hydrogen atom optionally being replaced with a fluorine atom.

[0187] In addition, in General Formula (D), R d represents a cycloalkane-1,1-diyl group having a carbon number of 3 to 6.

[0188] As the group satisfying any of General Formula (B) to General Formula (D), the following groups can be given, but are not limited thereto.

[0189]

[0190]

[0191]

[0192] The molecular weight of the compound of formula (1) is preferably 150 to 1000, more preferably 200 to 600. By making the molecular weight of the compound of formula (1) within the above numerical range, the reaction with the compound of formula (2) proceeds smoothly.

[0193] According to the above, as the compound of formula (1), the following compounds can be given, but are not limited thereto.

[0194]

[0195]

[0196]

[0197]

[0198] From the viewpoint of lubricity, in the compound of formula (1), R 1 are each fluorine, and R 2 is a perfluorinated divalent hydrocarbon group.

[0199] --Compound of formula (2)--

[0200] In the following general formula (2), R 3 represents a divalent hydrocarbon group having a carbon number of 1 to 20, which optionally contains a ring structure, a branched structure, optionally contains an ether bond, and a hydrogen atom is optionally substituted with a fluorine atom. The divalent hydrocarbon group can be selected from the same group as the divalent hydrocarbon group represented by R 2 . Therefore, the description is omitted here. In addition, R 2 and R 3 may be the same group, or can be different groups.

[0201] HO-R 3 -OH (2)

[0202] The molecular weight of the compound of formula (2) is preferably 50 to 400, more preferably 60 to 300. By making the molecular weight of the compound of formula (2) within the above numerical range, the reaction with the compound of formula (1) proceeds smoothly.

[0203] The acidity (pKa) of the compound of formula (2) is preferably 8 to 18, more preferably 9 to 15. By making the pKa of the compound of formula (2) within the above numerical range, the reaction with the compound of formula (1) proceeds smoothly.

[0204] In the present disclosure, pKa is a value in water at 25°C and is calculated by the method described in Chemical Pocket Reference Revised 5th Edition II-331 to II-343 (published by the Chemical Society of Japan, Maruzen Co., Ltd.).

[0205] As the compound of formula (2), the following compounds can be given, but are not limited thereto.

[0206]

[0207]

[0208]

[0209]

[0210]

[0211] From the viewpoint of reactivity, the compound of formula (1) and the compound of formula (2) are preferably selected from the combination of one or more compounds of formula (1) selected from the following Group A and the compound of formula (2) selected from the following Group B, more preferably the combination of one or more compounds of formula (1) selected from the following Group A' and the compound of formula (2) selected from the following Group B, but are not limited thereto.

[0212] Group A is as follows.

[0213]

[0214] Group A' is as follows.

[0215]

[0216] Group B is as follows.

[0217]

[0218]

[0219] --Compound of formula (3)--

[0220] A fluorine-containing divinyl polyether compound represented by the following general formula (3) is produced by the reaction of the compound of formula (1) and the compound of formula (2). In general formula (3), R 1 , R 2 and R 3 are as described above, and thus are omitted here.

[0221] CF2=CR 1 -O-R 2 -O-(CHR 1 -CF2-O-R 3-O-CF2-CHR 1 -O-R 2 -O) a -CR 1 =CF2 (3)

[0222] As the compound of formula (3), the following compounds can be given, but are not limited thereto. The divinyl groups at both terminals of the compound of formula (3) are easily fluorinated, and thus the compound of formula (4) having a trifluoromethyl group at both terminals can be produced at a high yield.

[0223]

[0224] Fluorination of fluorine-containing divinyl polyether compound

[0225] In the production method of the fluorine-containing polyether compound of the first mode, the fluorine-containing polyether compound represented by the following general formula (4) is produced by fluorinating the compound of formula (3).

[0226] CF3-CFR F1 -O-R F2 -O-(CFR F1 -CF2-O-R F3 -O-CF2-CFR F1 -O-R F2 -O) a -CFR F1 -CF3(4)

[0227] The method of fluorination of the compound of formula (3) is not particularly limited, and can be performed by a method known in the art. For example, the fluorination can be performed by contacting fluorine gas with the compound of formula (3).

[0228] The method of fluorination of the compound of formula (3) can be either a batch method or a continuous method. The fluorination reaction is preferably performed by the following <Method 1> or <Method 2>, and more preferably <Method 2> from the aspect of the yield of the compound of formula (4). In the case of performing in a batch method and in the case of performing in a continuous method, the fluorine gas can be used after being diluted with a non-reactive gas such as nitrogen.

[0229] <Method 1>

[0230] Method 1 is a method in which the compound of formula (3) and a solvent are charged into a reactor, and stirring is started. The reaction is performed under a prescribed reaction temperature and reaction pressure, while continuously supplying fluorine gas diluted with a non-reactive gas to the solvent.

[0231] <Method 2>

[0232] Method 2 is a method in which a solvent is charged to a reactor and stirred. Then, while supplying fluorine gas diluted with a non-reactive gas, the compound of formula (3), and the solvent to the fluorination reaction solvent continuously at a prescribed molar ratio, the reaction is carried out at a prescribed reaction temperature and reaction pressure.

[0233] <Method 3>

[0234] Method 3 is a method in which a solvent is continuously introduced into a tubular reactor so as to flow through the tubular reactor, then fluorine gas diluted with a non-reactive gas and a solution in which the compound of formula (3) is dissolved are continuously supplied to the solvent stream flowing through the tubular reactor at a ratio such that the fluorine gas and the compound of formula (3) become a prescribed molar ratio and are mixed, the fluorine gas and the compound of formula (3) are brought into contact with each other in the tubular reactor to carry out the reaction, and the solvent containing the reaction product is taken out of the tubular reactor. In this method, the solvent is circulated, and the reaction product is taken out of the circulating solvent, whereby the fluorination reaction can be carried out in a continuous manner.

[0235] As in the case of Method 3, in Method 2, it is preferable to supply the compound of formula (3) diluted with a solvent when the compound of formula (3) is supplied in order to improve the selectivity of the compound of formula (4) and suppress the amount of by-products. In addition, when the compound of formula (3) is diluted with a solvent, the amount of the solvent with respect to the compound of formula (3) is preferably set to 5 times or more, more preferably 7 times or more, on a mass basis.

[0236] As the non-reactive gas, there are rare gases such as helium, neon, argon, nitrogen, and the like, and nitrogen, helium are preferable, and nitrogen is more preferable from the viewpoint of economy. The proportion of fluorine gas (hereinafter, also referred to as "fluorine gas amount") is preferably 15% to 60% by volume in 100% by volume of the total of fluorine gas and non-reactive gas.

[0237] In the case where the fluorination of the compound of formula (3) is carried out in a solvent, in order to reduce the oxygen content in the solvent, the solvent can be subjected to nitrogen substitution in advance.

[0238] In addition, in the case where the compound of formula (3) is introduced into the solvent, the solvent can be subjected to nitrogen substitution in advance, and further subjected to fluorine substitution.

[0239] In the fluorination reaction, it is preferable that the amount of fluorine gas with which the fluorinatable hydrogen atoms in the compound of formula (3) are fluorinated is always set to an excess amount with respect to the total of the fluorinatable hydrogen atoms in the compound of formula (3), in both the batchwise manner and the continuous manner. The amount of fluorine gas is preferably 1.1 times or more, more preferably 1.3 times or more, of the theoretical amount required for fluorinating all of the fluorinatable hydrogen atoms.

[0240] In the case where the fluorination of the compound of formula (3) is carried out by introducing fluorine gas and the compound of formula (3) into a solvent, when the introduction rate of the compound of formula (3) into the solvent on a molar basis is set to 1, the introduction rate of fluorine gas on a molar basis can be in the range of 1 to 10 times, or in the range of 2 to 7 times, the rate obtained by multiplying the introduction rate of the compound of formula (3) on a molar basis by the number of hydrogen atoms in the compound of formula (3) which can be substituted with a fluorine atom by fluorine gas. By setting the relationship of the introduction rates within the above numerical range, the yield of the compound of formula (4) can be improved.

[0241] In order to efficiently carry out 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 ultraviolet rays to the solvent. These are preferably carried out in the later stage of the fluorination reaction. Thereby, the compound of formula (3) present in the solvent can be efficiently fluorinated, and the yield of the compound of formula (4) can be improved.

[0242] As the C-H bond-containing compound, an aromatic hydrocarbon is preferable, and benzene and toluene and the like can be mentioned. The amount of the C-H bond-containing compound to be added is preferably in the range of 0.1 to 10 mol% relative to the hydrogen atoms in the compound of formula (3), and more preferably in the range of 0.1 to 5 mol%.

[0243] The C-H bond-containing compound is preferably added to the solvent in which fluorine gas is present. Furthermore, in the case where the C-H bond-containing compound is added, it is preferable to pressurize the reaction system. The reaction pressure at the time of pressurization is preferably in the range of 0.01 to 5 MPa (gauge pressure).

[0244] In the case where ultraviolet rays are irradiated to the reaction system, the irradiation time is preferably in the range of 0.1 to 3 hours.

[0245] After the fluorination reaction, at least one selected from the group consisting of a solvent, water, and an aqueous solution for adjusting to an appropriate acidity can be added to the reaction liquid, and the mixture can be subjected to liquid separation, and then the organic phase can be concentrated to obtain the compound of formula (4). Alternatively, the reaction crude liquid obtained by concentrating the organic phase can be purified to obtain the compound of formula (4).

[0246] Hereinafter, the compound of formula (4) will be described.

[0247] --Compound of Formula (4)--

[0248] In General Formula (4), R 1 is a fluorine atom, R F1 each independently represents a fluorine atom, R 1 is a hydrogen atom, R F1 each independently represents a fluorine atom, R 1 is a monovalent hydrocarbon group having a carbon number of 1 to 3, R F1each independently represents a monovalent perfluorohydrocarbon group having 1 to 3 carbons.

[0249] In General Formula (4), R F2 each independently represents R 2 a divalent hydrocarbon group shown by the formula: -C(R

[0250] In General Formula (4), R F3 each independently represents R 3 a divalent hydrocarbon group shown by the formula: -C(R

[0251] Note that R 2 and R 3 In the case where the above-mentioned divalent hydrocarbon group has an aromatic ring, the aromatic ring is perfluorinated to become a perfluorocycloalkyl ring.

[0252] The number average molecular weight (Mn) of the compound of Formula (4) obtained by the production method of the first aspect is preferably 1000 to 30000, more preferably 2000 to 20000, and further preferably 2000 to 10000. By setting the Mn of the compound of Formula (4) within the above numerical range, it is possible to suppress the viscosity of the compound of Formula (4) from becoming excessively high, and to make handling easier in production and use.

[0253] In addition, the molecular weight distribution (Mw / Mn) of the compound of Formula (4) is preferably 1 to 3, more preferably 1 to 2.5, and further preferably 1 to 1.5. By setting the Mw / Mn of the compound of Formula (4) within the above numerical range, it is possible to suppress volatilization of the compound of Formula (4) when used in a high-temperature environment.

[0254] In the production method of the fluorine-containing polyether compound of the first aspect, as the compound of Formula (4) obtained by fluorination of the compound of Formula (3), the following compounds can be given, but are not limited thereto.

[0255]

[0256] (Production method of fluorine-containing polyether compound of the second aspect)

[0257] Next, the production method of the fluorine-containing polyether compound represented by General Formula (7-1) or General Formula (7-2) will be described. The fluorine-containing divinyl polyether compound represented by General Formula (6-1) or General Formula (6-2) and the production method thereof will also be described together.

[0258] The method for producing a fluorine-containing polyether compound according to the second aspect is a method for producing a fluorine-containing polyether compound, in which a fluorine-containing divinyl ether compound represented by the following general formula (1) (hereinafter, also referred to as a compound of formula (1)) is reacted with a fluorine-containing vinyl alcohol compound represented by the following general formula (5) (hereinafter, also referred to as a compound of formula (5)) at a ratio of more than 1 mol of the compound of formula (5) per 1 mol of the compound of 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) (hereinafter, each is also referred to as a compound of formula (6-1) and a compound of formula (6-2)), and then the compound of formula (6-1) or the compound of formula (6-2) is fluorinated, to produce a fluorine-containing polyether compound represented by the following general formula (7-1) or the following general formula (7-2) (hereinafter, each is also referred to as a compound of formula (7-1) and a compound of formula (7-2)).

[0259] CF2=CR 1 -O-R 2 -O-CR 1 =CF2 (1)

[0260] CF2=CR 1 -O-R 4 -OH (5)

[0261] CF2=CR 1 -O-(R 4 -O-CF 2 -CHR 1 -O) b -R 4 -O-CF2-CHR 1 -O-R 2 -O-CHR 1 -CF2-O-R 4 -(O-CHR 1 -CF2-O-R 4 ) c -O-CR 1 =CF2 (6-1)

[0262] CF2=CR 1 -O-(R 4 -O-CF 2 -CHR 1 -O) d -R 4 -O-CF2-CHR 1 -O-R 2 -O-CR 1 =CF2(6-2)

[0263] CF3-CFR F1 -O-(R F4 -O-CF2 -CFR F1 -O) b -R F4 -O-CF2-CFR F1 -O-R F2 -O-CFR F1 -CF2-O-R F4 -(O-CFR F1 -CF2-O-R F4 ) c -O-CFR F1 -CF3 (7-1)

[0264] CF3-CFR F1 -O-(R F4 -O-CF 2 -CFR F1 -O) d -R F4 -O-CF2-CFR F1 -O-R F2 -O-CFR F1 -CF3 (7-2)

[0265] In General Formula (1), General Formula (5), General Formula (6-1), and General Formula (6-2), R 1 each independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having 1 to 3 carbons optionally substituted with a fluorine atom.

[0266] In General Formula (1), General Formula (5), General Formula (6-1), and General Formula (6-2), R 2 and R 4 each independently represents a divalent hydrocarbon group having 1 to 20 carbons, the divalent hydrocarbon group having 1 to 20 carbons optionally containing a ring structure, a branched structure, optionally containing an ether bond, and a hydrogen atom optionally substituted with a fluorine atom.

[0267] In General Formula (7-1) and General Formula (7-2), in the case where R 1 each independently represents a fluorine atom, in the case where R F1 each independently represents a fluorine atom, in the case where R 1 each independently represents a hydrogen atom, in the case where R F1 each independently represents a fluorine atom, in the case where R 1 each independently represents a monovalent perfluorohydrocarbon group having 1 to 3 carbons. F1 each independently represents a monovalent perfluorohydrocarbon group having 1 to 3 carbons.

[0268] In General Formula (7-1) and General Formula (7-2), R F2 each independently represents a divalent hydrocarbon group represented by R 2 each independently represents a divalent perfluorohydrocarbon group having 1 to 20 carbons in which the divalent hydrocarbon group represented by R

[0269] In General Formula (7-1) and General Formula (7-2), R F4 each independently represents R 4 each independently represents R

[0270] 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 an integer of 0 or more, preferably an integer of 3 or more, more preferably an integer of 5 or more.

[0271] The method for producing a fluorine-containing polyether compound according to the second aspect can produce a high-molecular-weight fluorine-containing polyether compound having a trifluoromethyl group at both terminals at a high yield.

[0272] The reason why the above effects are exerted is presumed as follows, but is not limited thereto.

[0273] In the reaction of the compound of Formula (1) and the compound of Formula (5), the reaction is performed at a ratio of more than 1 mol of the compound of Formula (5) per 1 mol of the compound of Formula (1), and thus the polymerization reaction proceeds smoothly, and thus a high-molecular-weight compound of Formula (6-1) or Formula (6-2) can be produced at a high yield.

[0274] Further, the compound of Formula (6-1) or Formula (6-2) obtained by the above reaction has a vinyl group (CF2=CR 1 -) at both terminals, and the above vinyl group is easily fluorinated by contact with fluorine gas, and thus a high-molecular-weight compound of Formula (7-1) or Formula (7-2) having a trifluoromethyl group at both terminals can be produced at a high yield.

[0275] Hereinafter, the production of a fluorine-containing divinyl polyether compound and the fluorination of the fluorine-containing divinyl polyether compound in the method for producing a fluorine-containing polyether compound according to the second aspect will be described.

[0276] -Production of a fluorine-containing divinyl polyether compound-

[0277] The vinyl groups at both terminals of the compound of Formula (6-1) or Formula (6-2) produced by the reaction of the compound of Formula (1) and the compound of Formula (5) are easily fluorinated by contact with fluorine gas or the like, and thus a compound of Formula (7-1) or Formula (7-2) having a trifluoromethyl group at both terminals can be produced.

[0278] In the reaction of the compound of Formula (1) and the compound of Formula (5), the reaction is preferably performed at a ratio of 2 mol or more of the compound of Formula (5) per 1 mol of the compound of Formula (1), and more preferably at a ratio of 5 mol or more.

[0279] By reacting the compound of formula (1) with the compound of formula (5) at the above-mentioned mol ratio, the polymerization reaction proceeds smoothly, and thus the compound of formula (6-1) or the compound of formula (6-2) can be produced at a high yield.

[0280] In addition, in the reaction of the compound of formula (1) with the compound of formula (5), it is preferable to react at a ratio of 20 mol or less of the compound of formula (5) per 1 mol of the compound of formula (1), and more preferable to react at a ratio of 15 mol or less.

[0281] By reacting the compound of formula (1) with the compound of formula (5) at the above-mentioned mol ratio, the 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 at a high yield.

[0282] As in the first method, the reaction of the compound of formula (1) with the compound of formula (5) is preferably performed in the presence of a base catalyst.

[0283] In addition, the above-mentioned reaction can be performed in a solvent or without using a solvent. The solvent is not particularly limited, and the above-mentioned fluorine-based solvent is preferable.

[0284] The reaction of the compound of formula (1) with the compound of formula (5) can be performed by adding a mixture of the compound of formula (1) and the compound of formula (5) to the above-mentioned solvent heated to the following reaction temperature. From the viewpoint of reactivity, the addition rate of the above-mentioned mixture is preferably 0.5 mass% / hour to 70 mass% / hour, and more preferably 1 mass% / hour to 50 mass% / hour, with respect to the total mass of the above-mentioned mixture.

[0285] From the viewpoint of the molecular weight and the yield of the compound of formula (6-1) and the compound of formula (6-2), the reaction temperature of the compound of formula (1) with the compound of formula (5) is preferably 80°C to 160°C, and more preferably 90°C to 140°C.

[0286] The reaction of the compound of formula (1) with the compound of formula (5) can be performed in a batch manner or in a continuous manner, and a publicly known method can be appropriately used.

[0287] After the reaction of 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 to an appropriate acidity can be added and the liquid can be separated, and then the organic phase can be concentrated. In addition, the reaction crude liquid obtained by concentrating the organic phase can be purified.

[0288] Hereinafter, the compound of formula (1), the compound of formula (5), the compound of formula (6-1), and the compound of formula (6-2) will be described.

[0289] --Compound of formula (5)--

[0290] In the following general formula (5), R 4 represents a divalent hydrocarbon group having 1 to 20 carbons, which optionally contains a ring structure, a branched structure, optionally contains an ether bond, and a hydrogen atom is optionally substituted with a fluorine atom. The divalent hydrocarbon group can be the same group as the divalent hydrocarbon group represented by R 2 and R 3 The same group as the divalent hydrocarbon group represented by R

[0291] CF2=CR 1 -O-R 4 -OH (5)

[0292] The molecular weight of the compound of formula (5) is preferably 90 to 800, more preferably 100 to 600. By making the molecular weight of the compound of formula (5) within the above numerical range, the reaction with the compound of formula (1) proceeds smoothly.

[0293] The pKa of the compound of formula (5) is preferably 8 to 16, more preferably 9 to 14. By making the pKa of the compound of formula (5) within the above numerical range, the reaction with the compound of formula (1) proceeds smoothly.

[0294] As the compound of formula (5), the following compounds can be given, but are not limited thereto. Note that the compound of formula (1) is as exemplified in the first mode.

[0295]

[0296]

[0297]

[0298]

[0299] As the compound of formula (1) and the compound of formula (5), from the viewpoint of reactivity, 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.

[0300] Group C is as follows.

[0301]

[0302] --Compounds of formula (6-1) and formula (6-2)--

[0303] A fluorine-containing divinyl polyether compound represented by the following general formula (6-1) or the following general formula (6-2) is produced by the reaction of the compound of formula (1) and the compound of formula (5). In the general formula (3), R 1 , R 2and R 4 In the above description, therefore, the description is omitted here.

[0304] CF2=CR 1 -O-(R 4 -O-CF 2 -CHR 1 -O) b -R 4 -O-CF2-CHR 1 -O-R 2 -O-CHR 1 -CF2-O-R 4 -(O-CHR 1 -CF2-O-R 4 ) c -O-CR 1 =CF2 (6-1)

[0305] CF2=CR 1 -O-(R 4 -O-CF 2 -CHR 1 -O) d -R 4 -O-CF2-CHR 1 -O-R 2 -O-CR 1 =CF2 (6-2)

[0306] As the compound of formula (6-1) and the compound of formula (6-2), the following compounds can be given, but are not limited thereto. The divinyl groups at both terminals of the compound of formula (6-1) and the compound of formula (6-2) are easily fluorinated, and thus a high molecular weight fluorine-containing polyether compound having a trifluoromethyl group at both terminals can be produced at a high yield.

[0307]

[0308] Fluorination of fluorine-containing divinyl polyether compound

[0309] In the production method of the fluorine-containing polyether compound of the second aspect, a fluorine-containing polyether compound represented by the following general formula (7-1) or the following general formula (7-2) is produced by fluorinating the compound of formula (6-1) or the compound of formula (6-2).

[0310] CF3-CFR F1 -O-(R F4 -O-CF 2 -CFR F1 -O) b -R F4 -O-CF2-CFR F1 -O-RF2 -O-CFR F1 -CF2-O-R F4 -(O-CFR F1 -CF2-O-R F4 ) c -O-CFR F1 -CF3(7-1)

[0311] CF3-CFR F1 -O-(R F4 -O-CF 2 -CFR F1 -O) d -R F4 -O-CF2-CFR F1 -O-R F2 -O-CFR F1 -CF3(7-2)

[0312] The method of fluorination of the compound of formula (6-1) or the compound of formula (6-2) is not particularly limited and can be performed by a method known in the art. For example, the fluorination can be performed by contacting fluorine gas with the compound of formula (6-1) or the compound of formula (6-2). The method of fluorination is the same as in the first method, and thus the description is omitted here.

[0313] In the case where the fluorination of the compound of formula (6-1) or the compound of formula (6-2) is performed by introducing fluorine gas and the compound of formula (6-1) or the compound of formula (6-2) into a solvent, when the introduction rate of the fluorination of the compound of formula (6-1) or the compound of formula (6-2) into the solvent is set to 1 on a molar basis, the introduction rate of fluorine gas can be in the range of 1 to 10 times, or in the range of 2 to 7 times, the rate obtained by multiplying the introduction rate of the fluorination of the compound of formula (6-1) or the compound of formula (6-2) by the number of hydrogen atoms included in the fluorination of the compound of formula (6-1) or the compound of formula (6-2) which can be substituted with fluorine atoms by fluorine gas. By setting the relationship of the introduction rates to be in the above numerical range, the yield of the fluorination of the compound of formula (7-1) or the compound of formula (7-2) can be improved.

[0314] Hereinafter, the compound of formula (7-1) and the compound of formula (7-2) will be described.

[0315] --Compound of formula (7-1) and compound of formula (7-2)--

[0316] In general formula (7-1) and general formula (7-2), R F4 each independently represents R 4 a divalent hydrocarbon group having 1 to 20 carbon atoms which is perfluorinated by a divalent perfluorohydrocarbon group having 1 to 20 carbon atoms. R 4In the case where the above 2-valent hydrocarbon group has an aromatic ring, the aromatic ring is perfluorinated to become a perfluorocycloalkyl ring.

[0317] R F1 R F2 The groups represented by the above formulae are the same as in the first embodiment, and thus the description thereof is omitted here.

[0318] In the production method of the fluorine-containing polyether compound of the second embodiment, as the compound of formula (7-1) or formula (7-2) obtained by fluorination of the compound of formula (6-1) or formula (6-2), the following compounds can be given, but are not limited thereto.

[0319]

[0320] Examples

[0321] Hereinafter, the above embodiments will be described more specifically by synthesis examples, but the above embodiments are not limited to these synthesis examples.

[0322] [Evaluation method]

[0323] (NMR analysis)

[0324] NMR analysis was performed under the following conditions.

[0325] 1 The reference substance for H-NMR (300.4 MHz) was nitrobenzene at 7.5 ppm.

[0326] 19 The reference substance for F-NMR (282.7 MHz) was perfluorobenzene at -162.5 ppm.

[0327] The solvent for NMR was a mixed solvent of deuterated chloroform and hexafluorobenzene or a mixed solvent of deuterated chloroform and 1,4-bistrifluoromethylbenzene.

[0328] (GPC analysis)

[0329] The number average molecular weight (Mn) and the mass average molecular weight (Mw) were measured by GPC. The measurement based on GPC was performed according to the above-described method.

[0330] (Synthesis Example 1-1)

[0331] In a 200 mL eggplant-type flask, 3.3 g of ethylene glycol (pKa: 14.22) and 4 g of potassium carbonate satisfying the above general formula (2) were placed, and the internal temperature of the flask was set to 120°C, and stirring was performed.

[0332] ​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 times mol / hour relative to 1 mol of ethylene glycol while the internal temperature of the flask was maintained at 120°C, and stirring was performed for 2 hours.

[0333] Note that the reaction was performed at a ratio of 1.11 mol of the fluorine-containing divinyl ether compound (1A) relative to 1 mol of ethylene glycol.

[0334] CF2=CF-O-CF2CF2CF2-O-CF=CF2 (1A)

[0335] Thereafter, the internal temperature of the flask was maintained at 25°C, and 20 g each of a fluorine-based solvent (ASAHI KLIN (registered trademark) AC-2000, 1H-tridecafluorohexane, hereinafter referred to as AC-2000) and hydrochloric acid were added, and a reaction crude liquid was obtained which was separated into an organic phase and an aqueous phase. The obtained reaction crude liquid was subjected to liquid separation, and then the organic phase was concentrated.

[0336] The reaction crude liquid obtained by concentrating the organic phase was purified by column chromatography, and 15 g (yield 65%) of the following fluorine-containing divinyl polyether compound (3A) satisfying the above general formula (3) was obtained. The average value of the number of repeating units a was 9.

[0337] Hereinafter, the fluorine-containing divinyl polyether compound (3A) is described.

[0338]

[0339] Into a 500 mL nickel reactor, 250 mL of CFE-419 was placed, and then nitrogen gas was blown (bubbling).

[0340] After confirming that the dissolved oxygen concentration was sufficiently reduced, 20% by volume of fluorine gas diluted with nitrogen gas was blown for 1 hour (bubbling).

[0341] Next, a 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% by mass, and the amount of the fluorine-containing divinyl polyether compound (3A) was 15 g. The CFE-419 solution was added while bubbling fluorine gas into the CFE-419.

[0342] Note that when the introduction rate of the fluorine-containing divinyl polyether compound (3A) into the solvent was set to 1 on a molar basis, the introduction rate of the fluorine gas was set to twice the rate obtained by multiplying the introduction rate of the fluorine-containing divinyl polyether compound (3A) on a molar basis by the number of hydrogen atoms in the fluorine-containing divinyl polyether compound (3A) which can be replaced with fluorine atoms by fluorine gas.

[0343] After the addition of the CFE-419 solution of the fluorochemical divinyl polyether compound and the blowing of fluorine gas, the CFE-419 solution of benzene was added intermittently. The concentration of benzene in the CFE-419 solution was 0.1 mass%, and the amount of benzene was 0.1 g.

[0344] After the addition of the CFE-419 solution of benzene, fluorine gas was blown for 1 hour, and finally the inside of the reactor was sufficiently replaced with nitrogen gas. The solvent was distilled off, and the following fluorochemical polyether compound (4A) satisfying the above general formula (4) was obtained in 17 g (yield 90%).

[0345] The structure of the fluorochemical polyether compound (4A) was determined by 1 H-NMR method and 19 F-NMR method. In addition, the Mn of the fluorochemical polyether compound (4A) was 5000, and the Mw / Mn was 1.8.

[0346] The following fluorochemical polyether compound (4A) was synthesized.

[0347]

[0348] (Synthesis Example 1-2)

[0349] In a 200 mL eggplant-type flask, 5.9 g of 1,4-benzene diol (pKa: 9.8) satisfying the above general formula (2) and 4 g of potassium carbonate were placed, and the inside of the flask was made 120°C, and stirring was performed.

[0350] Next, 20 g of the following fluorochemical divinyl ether compound (1A) satisfying the above general formula (1) was added at a rate of 0.27 times mol / hour with respect to 1 mol of 1,4-benzene diol, the inside of the flask was made 120°C, and stirring was performed for 2 hours.

[0351] Note that the reaction was performed at a ratio of 1.08 mol of the fluorochemical divinyl ether compound (1A) with respect to 1 mol of 1,4-benzene diol.

[0352] Next, the inside of the flask was made 25°C, 20 g each of the above AC-2000 and hydrochloric acid were placed, and a reaction crude liquid was obtained which was separated into an organic phase and an aqueous phase. The obtained reaction crude liquid was subjected to liquid separation, and then the organic phase was concentrated.

[0353] The reaction crude liquid obtained by concentrating the organic phase was purified by column chromatography, and the following fluorochemical divinyl polyether compound (3B) satisfying the above general formula (3) was obtained in 20 g (yield 79%). The average value of the number of repeating units a was 12.

[0354] The following fluorochemical divinyl polyether compound (3B) was synthesized.

[0355]

[0356] Into a 500 mL reactor made of nickel was put 250 mL of CFE-419, and then nitrogen gas was bubbled.

[0357] After confirming that the dissolved oxygen concentration was sufficiently reduced, 20 volume% of fluorine gas diluted with nitrogen gas was bubbled for 1 hour.

[0358] In addition, 20 g of the fluorine-containing divinyl polyether compound (3B) 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. The CFE-419 solution was added while bubbling fluorine gas into the CFE-419.

[0359] Note that when the introduction rate of the fluorine-containing divinyl polyether compound (3B) into the solvent on a molar basis was set to 1, the introduction rate of fluorine gas on a molar basis was set to 3 times the rate obtained by multiplying the introduction rate of the fluorine-containing divinyl polyether compound (3B) on a molar basis by the number of hydrogen atoms included in the fluorine-containing divinyl polyether compound (3B) that can be substituted with fluorine atoms by fluorine gas.

[0360] After the addition of the CFE-419 solution of the fluorine-containing divinyl polyether compound, the above-described CFE-419 solution of benzene was added intermittently.

[0361] After the addition of the CFE-419 solution of benzene, fluorine gas was blown in for 1 hour, and finally the inside of the reactor was sufficiently replaced with nitrogen gas. The solvent was distilled off, and 24 g (yield 81%) of the following fluorine-containing polyether compound (4B) satisfying the above general formula (4) was obtained.

[0362] The structure of the fluorine-containing polyether compound (4B) was determined by1H-NMR method and19F-NMR method. In addition, the Mn of the fluorine-containing polyether compound (4B) was about 8000, and the Mw / Mn was 1.8. 1 H-NMR method and 19 F-NMR method. In addition, the Mn of the fluorine-containing polyether compound (4B) was about 8000, and the Mw / Mn was 1.8.

[0363] The fluorine-containing polyether compound (4B) is described below.

[0364]

[0365] (Synthesis Example 1-3)

[0366] Into a 200 mL flask made of glass, 9.7 g of tetraethylene glycol (pKa: 14.1) satisfying the above general formula (2) and 4 g of potassium carbonate were put, and the inside of the flask was made to be 120°C, and stirring was performed.

[0367] 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 times mol / hour with respect to 1 mol of tetraethylene glycol while the internal temperature of the flask was maintained at 120°C, and stirring was performed for 2 hours.

[0368] Note that the reaction was performed at a ratio of 1.16 mol of the fluorine-containing divinyl ether compound (1A) with respect to 1 mol of tetraethylene glycol.

[0369] Next, the internal temperature of the flask was maintained at 25°C, and 20 g each of the above AC-2000 and hydrochloric acid were added to obtain a reaction crude liquid separated into an organic phase and an aqueous phase. The obtained reaction crude liquid was subjected to liquid separation, and then the organic phase was concentrated.

[0370] The reaction crude liquid obtained by concentrating the organic phase was purified by column chromatography to obtain 21 g (yield 72%) of the following fluorine-containing divinyl polyether compound (3C) satisfying the above general formula (3). The average value of the number of repeating units a was 6.

[0371] The following describes the fluorine-containing divinyl polyether compound (3C).

[0372]

[0373] Into a 500 mL nickel reactor, 250 mL of CFE-419 was placed, and then nitrogen gas was bubbled.

[0374] After confirming that the dissolved oxygen concentration was sufficiently reduced, 20% by volume of fluorine gas diluted with nitrogen gas was bubbled for 1 hour.

[0375] Next, a 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% by mass, and the amount of the fluorine-containing divinyl polyether compound (3C) was 21 g. The CFE-419 solution was added while bubbling fluorine gas into the CFE-419.

[0376] Note that when the introduction rate of the fluorine-containing divinyl polyether compound (3C) into the solvent was set to 1 on a molar basis, the introduction rate of the fluorine gas was set to twice the rate obtained by multiplying the introduction rate of the fluorine-containing divinyl polyether compound (3C) on a molar basis by the number of hydrogen atoms in the fluorine-containing divinyl polyether compound (3C) that can be replaced with fluorine atoms by fluorine gas.

[0377] After the addition of the CFE-419 solution of the fluorine-containing divinyl polyether compound, the above CFE-419 solution of benzene was added intermittently.

[0378] After the addition of the benzene CFE-419 solution, fluorine gas was blown in for 1 hour, and finally the reactor was sufficiently replaced with nitrogen gas. The solvent was distilled off, and the following fluorine-containing polyether compound (4C) satisfying the above general formula (4) was obtained in 33 g (yield 98 %).

[0379] The structure of the fluorine-containing polyether compound (4C) was determined by 1 H-NMR method and 19 F-NMR method. In addition, the Mn of the fluorine-containing polyether compound (4C) was 5000, and the Mw / Mn was 1.6.

[0380] The fluorine-containing polyether compound (4C) is described below.

[0381]

[0382] (Synthesis Example 2-1)

[0383] In a 200 mL eggplant-type flask, 2 g of a fluorine-based solvent (manufactured by AGC Inc., 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 were placed, and the internal temperature of the flask was made 120°C, and stirring was performed.

[0384] 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) satisfying the above general formula (5) (pKa: 12.5) was added over 8 hours, the internal temperature of the flask was made 120°C, and stirring was performed for 2 hours.

[0385] Note that the reaction was performed at a ratio of 9.92 mol of the fluorine-containing vinyl alcohol compound (5A) per 1 mol of the fluorine-containing divinyl ether compound (1A).

[0386] CF2=CF-O-CF2CF2CF2CH2-OH (5A)

[0387] The internal temperature of the flask was made 25°C, 20 g each of the above AC-2000 and hydrochloric acid were placed, and a reaction crude liquid was obtained which was separated into an organic phase and an aqueous phase. The obtained reaction crude liquid was subjected to liquid separation, and then the organic phase was concentrated.

[0388] The reaction crude liquid obtained by concentrating the organic phase was purified by column chromatography, and the following fluorine-containing divinyl polyether compound (6-1A) satisfying the above general formula (6-1) was obtained in 25 g (yield 56 %). The average value of the number of repeating units b + c was 7.

[0389] The fluorine-containing divinyl polyether compound (6-1A) is described below.

[0390]

[0391] Into a 500 mL reactor made of nickel was put 250 mL of CFE-419, and then nitrogen gas was bubbled.

[0392] After confirming that the dissolved oxygen concentration was sufficiently reduced, 20 volume% of fluorine gas diluted with nitrogen gas was bubbled for 1 hour.

[0393] In addition, 3 hours were required to add a CFE-419 solution of the fluorine-containing divinyl polyether compound (6-1A) to the CFE-419 in the reactor. The concentration of the fluorine-containing divinyl polyether compound (6-1A) in the CFE-419 solution was 10 mass%, and the amount of the fluorine-containing divinyl polyether compound (6-1A) was 25 g. The CFE-419 solution was added while bubbling fluorine gas into the CFE-419.

[0394] Note that when the introduction rate of the fluorine-containing divinyl polyether compound (6-1A) into the solvent on a molar basis was set to 1, the introduction rate of fluorine gas on a molar basis was set to twice the rate obtained by multiplying the introduction rate of the fluorine-containing divinyl polyether compound (6-1A) on a molar basis by the number of hydrogen atoms included in the fluorine-containing divinyl polyether compound (6-1A) that can be substituted with fluorine atoms by fluorine gas.

[0395] After the addition of the CFE-419 solution of the fluorine-containing divinyl polyether compound, the above-described CFE-419 solution of benzene was added intermittently.

[0396] After the addition of the CFE-419 solution of benzene, fluorine gas was blown in for 1 hour after the addition of the CFE-419 solution of benzene, and finally the inside of the reactor was sufficiently replaced with nitrogen gas. The solvent was distilled off, and 30 g (yield 98%) of the following fluorine-containing polyether compound (7-1A) satisfying the above general formula (7-1) was obtained.

[0397] The structure of the fluorine-containing polyether compound (7-1A) was determined by 1 H-NMR method and 19 F-NMR method. In addition, the Mn of the fluorine-containing polyether compound (7-1A) was 3500, and the Mw / Mn was 1.6.

[0398] The fluorine-containing polyether compound (7-1A) is described below.

[0399]

[0400] (Synthesis Example 3-1)

[0401] The reaction was carried out with a ratio of 1 mol to less than 1 mol of ethylene glycol, and the procedure was the same as in Synthesis Example 1-1. The aim was to produce a fluorinated polyether compound (4A), but it was not possible to produce a fluorinated polyether compound with trifluoromethyl groups at both ends.

[0402] (Synthesis example 3-2)

[0403] The reaction was carried out at a ratio of less than 1 mol of fluorinated vinyl alcohol compound (5A) to 1 mol of fluorinated divinyl ether compound (1A). Otherwise, the same procedure as in Synthesis Example 2-1 was followed to produce fluorinated polyether compound (6-1A), but it was not possible to produce fluorinated polyether compound (6-1A) with a sufficient molecular weight.

[0404] The above synthesis examples demonstrate that, using the method for manufacturing fluorinated polyether compounds disclosed herein, it is possible to produce high-molecular-weight fluorinated polyether compounds with trifluoroalkyl (-CF3) ends in high yield.

[0405] The entire disclosure of Japanese Patent Application No. 2020-217942, filed on December 25, 2020, is incorporated herein by reference. All documents, patent applications, and technical standards described herein, and their specific and individual descriptions, are also incorporated herein by reference to the extent described herein.

Claims

1. A method for producing a fluorine-containing polyether compound, wherein, A fluorine-containing divinyl ether compound represented by the following general formula (1) is reacted with a diol compound represented by the following general formula (2) at 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), a fluorine-containing divinyl polyether compound represented by the following general formula (3) is produced, and the fluorine-containing divinyl polyether compound represented by the following general formula (3) is fluorinated to produce a fluorine-containing polyether compound represented by the following general formula (4), CF2=CR 1 -O-R 2 -O-CR 1 =CF2 (1) HO-R 3 -OH(2) CF2=CR 1 -O-R 2 -O-(CHR 1 -CF2-O-R 3 -O-CF2-CHR 1 -O-R 2 -O) a -CR 1 =CF2 (3) CF3-CFR F1 -O-R F2 -O-(CFR F1 -CF2-O-R F3 -O-CF2-CFR F1 -O-R F2 -O) a -CFR F1 -CF3(4) in the general formula (1) to the general formula (4), R 1 each independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having a carbon number of 1 to 3, which hydrogen atom is optionally substituted with a fluorine atom, R 2 and R 3 each independently represents a divalent hydrocarbon group having a carbon number of 1 to 20, the divalent hydrocarbon group having a carbon number of 1 to 20 optionally containing a ring structure, a branched structure, optionally containing an ether bond, and a hydrogen atom being optionally substituted with a fluorine atom, In R 1 When R is a fluorine atom F1 Each fluorine atom represents itself independently, in R 1 When R is a hydrogen atom F1 Each fluorine atom represents itself independently, in R 1 When R is a monovalent hydrocarbon group with 1 to 3 carbon atoms F1 Each of these groups independently represents a monovalent perfluorocarbon group having 1 to 3 carbon atoms. R F2 each independently represents R 2 the bivalent hydrocarbon group represented by the formula shown above is a bivalent perfluorohydrocarbon group having a carbon number of 1 to 20 which is perfluorinated, R F3 each independently represents R 3 the bivalent hydrocarbon group represented by the formula shown above is a bivalent perfluorohydrocarbon group having a carbon number of 1 to 20 which is perfluorinated, a represents an integer of 1 or more.

2. The method for producing a fluorine-containing polyether compound according to claim 1, wherein, The reaction of the fluorine-containing divinyl ether compound represented by the general formula (1) and the diol compound represented by the general formula (2) is performed in the presence of a base catalyst.

3. The method for producing a fluorine-containing polyether compound according to claim 1 or 2, wherein, The fluorination of the fluorine-containing divinyl polyether compound represented by the general formula (3) is performed by introducing fluorine gas and the fluorine-containing divinyl polyether compound represented by the general formula (3) into a solvent, When the introduction rate of the fluorine-containing divinyl polyether compound represented by the general formula (3) into the solvent is 1 on a molar basis, the introduction rate of the fluorine gas is in the range of 1 to 10 times the introduction rate of the fluorine-containing divinyl polyether compound represented by the general formula (3) on a molar basis multiplied by the number of hydrogen atoms included in the fluorine-containing divinyl polyether compound represented by the general formula (3) which can be substituted with fluorine atoms by the fluorine gas.

4. The method for producing a fluorine-containing polyether compound according to claim 1 or 2, wherein, The fluorine-containing divinyl ether compound represented by the general formula (1) is reacted with the diol compound represented by the general formula (2) at a ratio of 3 mol or less of the fluorine-containing divinyl ether compound represented by the general formula (1) per 1 mol of the diol compound represented by the general formula (2).

5. The method for producing a fluorine-containing polyether compound according to claim 3, wherein, The fluorine-containing divinyl ether compound represented by the general formula (1) is reacted with the diol compound represented by the general formula (2) at a ratio of 3 mol or less of the fluorine-containing divinyl ether compound represented by the general formula (1) per 1 mol of the diol compound represented by the general formula (2).

6. A method for producing a fluorine-containing polyether compound, wherein, A fluorine-containing divinyl ether compound represented by the following general formula (1) is reacted with a fluorine-containing vinyl alcohol compound represented by the following general formula (5) at a ratio of more than 1 mol 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), a fluorine-containing divinyl polyether compound represented by the following general formula (6-1) or the following general formula (6-2) is produced, and the fluorine-containing divinyl polyether compound represented by the general formula (6-1) or the general formula (6-2) is fluorinated to produce a fluorine-containing polyether compound represented by the following general formula (7-1) or the following general formula (7-2), CF2=CR 1 -O-R 2 -O-CR 1 =CF2 (1) CF2=CR 1 -O-R 4 -OH (5) CF2=CR 1 -O-(R 4 -O-CF 2 -CHR 1 -O) b -R 4 -O-CF2-CHR 1 -O-R 2 -O-CHR 1 -CF2-O-R 4 -(O-CHR 1 -CF2-O-R 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 -O-R 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 -O-R F2 -O-CFR F1 -CF2-O-R F4 -(O-CFR F1 -CF2-O-R 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 -O-R F2 -O-CFR F1 -CF3(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 each independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having a carbon number of 1 to 3, which hydrogen atom is optionally substituted with a fluorine atom, R 2 and R 4 each independently represents a divalent hydrocarbon group having a carbon number of 1 to 20, the divalent hydrocarbon group having a carbon number of 1 to 20 optionally containing a ring structure, a branched structure, optionally containing an ether bond, and a hydrogen atom being optionally substituted with a fluorine atom, In R 1 When R is a fluorine atom F1 Each fluorine atom represents itself independently, in R 1 When R is a hydrogen atom F1 Each fluorine atom represents itself independently, in R 1 When R is a monovalent hydrocarbon group with 1 to 3 carbon atoms F1 Each of these groups independently represents a monovalent perfluorocarbon group having 1 to 3 carbon atoms. R F2 each independently represents R 2 the bivalent hydrocarbon group shown is a bivalent perfluorohydrocarbon group having a carbon number of 1 to 20 which is perfluorinated, R F4 each independently represents R 4 the bivalent hydrocarbon group represented by the formula shown above is a bivalent perfluorohydrocarbon group having a carbon number of 1 to 20 which is perfluorinated, b, c, and d each independently represent 0 or an integer of 1 or more.

7. The method for producing a fluoropolylether compound according to claim 6, wherein, The reaction of the fluorine-containing divinyl ether compound represented by the general formula (1) and the fluorine-containing vinyl alcohol compound represented by the general formula (5) is performed in the presence of a base catalyst.

8. The method for producing a fluoropolylether compound according to claim 6 or 7, wherein, The fluorination of the fluorine-containing divinyl polyether compound represented by the general formula (6-1) or the general formula (6-2) is performed 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, When the introduction rate of the fluorine-containing divinyl polyether compound represented by the general formula (6-1) or the general formula (6-2) into the solvent is 1 on a molar basis, the introduction rate of the fluorine gas is in the range of 1 to 10 times the introduction rate of the fluorine-containing divinyl polyether compound represented by the general formula (6-1) or the general formula (6-2) on a molar basis multiplied by the number of hydrogen atoms in the fluorine-containing divinyl polyether compound represented by the general formula (6-1) or the general formula (6-2) which can be substituted with fluorine atoms by the fluorine gas.

9. The method for producing a fluoropolylether compound according to claim 6 or 7, wherein, The reaction of the fluorine-containing divinyl ether compound represented by the general formula (1) and the fluorine-containing vinyl alcohol compound represented by the general formula (5) is performed at a ratio of 20 mol or less of the fluorine-containing vinyl alcohol compound represented by the general formula (5) to 1 mol of the fluorine-containing divinyl ether compound represented by the general formula (1).

10. The method for producing a fluorine-containing polyether compound according to claim 8, wherein, The reaction of the fluorine-containing divinyl ether compound represented by the general formula (1) and the fluorine-containing vinyl alcohol compound represented by the general formula (5) is performed at a ratio of 20 mol or less of the fluorine-containing vinyl alcohol compound represented by the general formula (5) to 1 mol of the fluorine-containing divinyl ether compound represented by the general formula (1).

11. A method for producing a fluorine-containing divinyl polyether compound, wherein, The fluorine-containing divinyl ether compound represented by the general formula (1) and the diol compound represented by the general formula (2) are reacted at a ratio of more than 1 mol 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), to produce the fluorine-containing divinyl polyether compound represented by the general formula (3), CF2=CR 1 -O-R 2 -O-CR 1 =CF2 (1) HO-R 3 -OH(2) CF2=CR 1 -O-R 2 -O-(CHR 1 -CF2-O-R 3 -O-CF2-CHR 1 -O-R 2 -O) a -CR 1 =CF2 (3) In the general formula (1) to the general formula (3), R 1 each independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having a carbon number of 1 to 3, which hydrogen atom is optionally substituted with a fluorine atom, R 2 and R 3 each independently represents a divalent hydrocarbon group having a carbon number of 1 to 20, the divalent hydrocarbon group having a carbon number of 1 to 20 optionally containing a ring structure, a branched structure, optionally containing an ether bond, and a hydrogen atom being optionally substituted with a fluorine atom, a represents an integer of 1 or more.

12. A method for producing a fluorine-containing divinyl polyether compound, wherein, The fluorine-containing divinyl ether compound represented by the general formula (1) and the fluorine-containing vinyl alcohol compound represented by the general formula (5) are reacted at a ratio of more than 1 mol of the fluorine-containing vinyl alcohol compound represented by the general formula (5) to 1 mol of the fluorine-containing divinyl ether compound represented by the general formula (1), to produce the fluorine-containing divinyl polyether compound represented by the general formula (6-1) or the general formula (6-2). CF2=CR 1 -O-R 2 -O-CR 1 =CF2 (1) CF2=CR 1 -O-R 4 -OH (5) CF2=CR 1 -O-(R 4 -O-CF 2 -CHR 1 -O) b -R 4 -O-CF2-CHR 1 -O-R 2 -O-CHR 1 -CF2-O-R 4 -(O-CHR 1 -CF2-O-R 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 -O-R 2 -O-CR 1 =CF2 (6-2) 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 each independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having a carbon number of 1 to 3, which hydrogen atom is optionally substituted with a fluorine atom, R 2 and R 4 each independently represents a divalent hydrocarbon group having a carbon number of 1 to 20, the divalent hydrocarbon group having a carbon number of 1 to 20 optionally containing a ring structure, a branched structure, optionally containing an ether bond, and a hydrogen atom being optionally substituted with a fluorine atom, b, c, and d each independently represent 0 or an integer of 1 or more.

13. A method for producing a fluorine-containing polyether compound, wherein, The fluorine-containing divinyl polyether compound represented by the general formula (3) is fluorinated to produce the fluorine-containing polyether compound represented by the general formula (4), CF2=CR 1 -O-R 2 -O-(CHR 1 -CF2-O-R 3 -O-CF2-CHR 1 -O-R 2 -O) a -CR 1 =CF2 (3) CF3-CFR F1 -O-R F2 -O-(CFR F1 -CF2-O-R F3 -O-CF2-CFR F1 -O-R F2 -O) a -CFR F1 -CF3(4) In the general formula (1) to the general formula (4), R 1 each independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having a carbon number of 1 to 3, which hydrogen atom is optionally substituted with a fluorine atom, R 2 and R 3 each independently represents a divalent hydrocarbon group having a carbon number of 1 to 20, the divalent hydrocarbon group having a carbon number of 1 to 20 optionally containing a ring structure, a branched structure, optionally containing an ether bond, and a hydrogen atom being optionally substituted with a fluorine atom, In R 1 When R is a fluorine atom F1 Each fluorine atom represents itself independently, in R 1 When R is a hydrogen atom F1 Each fluorine atom represents itself independently, in R 1 When R is a monovalent hydrocarbon group with 1 to 3 carbon atoms F1 Each of these groups independently represents a monovalent perfluorocarbon group having 1 to 3 carbon atoms. R F2 each independently represents R 2 the bivalent hydrocarbon group represented by the formula shown above is a bivalent perfluorohydrocarbon group having a carbon number of 1 to 20 which is perfluorinated, R F3 each independently represents R 3 the bivalent hydrocarbon group represented by the formula shown above is a bivalent perfluorohydrocarbon group having a carbon number of 1 to 20 which is perfluorinated, a represents an integer of 1 or more.

14. A method for producing a fluorine-containing polyether compound, wherein, The fluorine-containing divinyl polyether compound represented by the general formula (6-1) or the general formula (6-2) is fluorinated to produce the fluorine-containing polyether compound represented by the general formula (7-1) or the general formula (7-2). CF2=CR 1 -O-R 2 -O-CR 1 =CF2 (1) CF2=CR 1 -O-R 4 -OH (5) CF2=CR 1 -O-(R 4 -O-CF 2 -CHR 1 -O) b -R 4 -O-CF2-CHR 1 -O-R 2 -O-CHR 1 -CF2-O-R 4 -(O-CHR 1 -CF2-O-R 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 -O-R 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 -O-R F2 -O-CFR F1 -CF2-O-R F4 -(O-CFR F1 -CF2-O-R 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 -O-R F2 -O-CFR F1 -CF3(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 each independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having a carbon number of 1 to 3, which hydrogen atom is optionally substituted with a fluorine atom, R 2 and R 4 each independently represents a divalent hydrocarbon group having a carbon number of 1 to 20, the divalent hydrocarbon group having a carbon number of 1 to 20 optionally containing a ring structure, a branched structure, optionally containing an ether bond, and a hydrogen atom being optionally substituted with a fluorine atom, In R 1 When R is a fluorine atom F1 Each fluorine atom represents itself independently, in R 1 When R is a hydrogen atom F1 Each fluorine atom represents itself independently, in R 1 When R is a monovalent hydrocarbon group with 1 to 3 carbon atoms F1 Each of these groups independently represents a monovalent perfluorocarbon group having 1 to 3 carbon atoms. R F2 each independently represents R 2 the bivalent hydrocarbon group shown is a bivalent perfluorohydrocarbon group having a carbon number of 1 to 20 which is perfluorinated, R F4 each independently represents R 4 the bivalent hydrocarbon group shown is a bivalent perfluorohydrocarbon group having a carbon number of 1 to 20 which is perfluorinated, b, c and d each independently represent an integer of 0 or more.

15. A fluorine-containing di-vinyl polyether compound represented by the following general formula (3), CF2=CR 1 -O-R 2 -O-(CHR 1 -CF2-O-R 3 -O-CF2-CHR 1 -O-R 2 -O) a -CR 1 =CF2 (3) In the general formula (3), R 1 each independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having a carbon number of 1 to 3, which hydrogen atom is optionally substituted with a fluorine atom, R 2 and R 3 each independently represents a divalent hydrocarbon group having a carbon number of 1 to 20, the divalent hydrocarbon group having a carbon number of 1 to 20 optionally containing a ring structure, a branched structure, optionally containing an ether bond, and a hydrogen atom being optionally substituted with a fluorine atom, a represents an integer of 1 or more.

16. A fluorine-containing di-vinyl 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-CHR 1 -O-R 2 -O-CHR 1 -CF2-O-R 4 -(O-CHR 1 -CF2-O-R 4 ) c -O-CR 1 =CF2 (6-1) In the general formula (6-1), R 1 each independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having a carbon number of 1 to 3, which hydrogen atom is optionally substituted with a fluorine atom, R 2 and R 4 each independently represents a divalent hydrocarbon group having a carbon number of 1 to 20, the divalent hydrocarbon group having a carbon number of 1 to 20 optionally containing a ring structure, a branched structure, optionally containing an ether bond, and a hydrogen atom being optionally substituted with a fluorine atom, b and c each independently represent an integer of 0 or more.

17. A fluorine-containing di-vinyl 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 -O-R 2 -O-CR 1 =CF2 (6-2) In the general formula (6-2), R 1 each independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having a carbon number of 1 to 3, which hydrogen atom is optionally substituted with a fluorine atom, R 2 and R 4 each independently represents a divalent hydrocarbon group having a carbon number of 1 to 20, the divalent hydrocarbon group having a carbon number of 1 to 20 optionally containing a ring structure, a branched structure, optionally containing an ether bond, and a hydrogen atom being optionally substituted with a fluorine atom, d represents an integer of 0 or more.

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