Process for producing a polyether composition, process for producing a fluorine-containing polyether composition, and polyether composition

Abstract

A method for producing a polyether composition, including: a first polymerization reaction of reacting a compound represented by the following general formula (1) with a compound represented by the following general formula (2) at a ratio of less than 1 mol per 1 mol of the compound represented by the following general formula (2); and a second polymerization reaction after the first polymerization reaction, to produce a polyether composition containing a polyether compound by a plurality of polymerization reactions of the compound represented by the following general formula (1) and the compound represented by the following general formula (2). A-X-A (1) B-Y-B (2).

Description

TECHNICAL FIELD

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

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

[0003] Conventionally, fluorine-containing polyether compounds are produced by various methods, for example, by fluorination of a polyether compound having an -OH group or a vinyl group, etc. as a terminal group.

[0004] For example, International Publication No. 2018 / 108866 discloses a method of producing a polyether compound from a vinyl ether compound and a diol compound, esterifying -OH groups at both terminals of the polyether compound to produce a diacyloxy polyether compound, and fluorinating the diacyloxy polyether compound to produce a fluorine-containing polyether compound.

[0005] Further, International Publication No. 2019 / 202076 discloses a method of polymerizing a vinyl ether compound and a diol compound in a solvent to produce a polyether compound, esterifying -OH groups at both terminals of the polyether compound to produce a diacyloxy polyether compound, and fluorinating the diacyloxy polyether compound to produce a fluorine-containing polyether compound.

[0006] Further, International Publication No. 2018 / 108864, International Publication No. 2019 / 202079, and International Publication No. 2019 / 243404 disclose a method of polymerizing a diacyloxy compound and a difluoroacyl compound in a solvent to produce a polyether compound having a -C(=O)F group or a -OC(=O)F group as a terminal group, and fluorinating the polyether compound to produce a fluorine-containing polyether compound.

[0007] Further, International Publication No. 2019 / 243403 discloses a method of reacting a vinyl ether compound and a diol compound in a solvent to produce a polyether compound having an aromatic ring, esterifying -OH groups at both terminals of the polyether compound to produce a diacyloxy polyether compound, and fluorinating the diacyloxy polyether compound to produce a fluorine-containing polyether compound. SUMMARY

[0008] PROBLEMS TO BE SOLVED BY THE INVENTION

[0009] From the viewpoint of heat resistance, the polyether compound used in the production of the fluorine-containing polyether compound is preferably a compound having a large number of repeating units. However, the polyether compound produced by the production method of International Publication No. 2018 / 108866 and International Publication No. 2019 / 202076 has a small number of repeating units, and the above-mentioned polyether compound and the fluorine-containing polyether compound produced by fluorination of the above-mentioned polyether compound have room for improvement from the viewpoint of heat resistance.

[0010] In addition, it is described in International Publication No. 2018 / 108864 that the number average molecular weight of the polyether compound produced in the examples thereof is about 2,200.

[0011] However, in the production method described in International Publication No. 2018 / 108864, a cyclic polyether compound is produced in addition to the polyether compound having the above-mentioned end group by the reaction of the diacyloxy compound and the difluoroacyl compound. Therefore, the above-mentioned cyclic polyether compound increases the value of the number average molecular weight calculated from the integral ratio of the main chain to the end group on the surface by NMR method, and the actually obtained polyether compound having the above-mentioned end group is a low molecular compound having a small number of repeating units. Therefore, the above-mentioned polyether compound and the fluorine-containing polyether compound produced by fluorination of the above-mentioned polyether compound have room for improvement from the viewpoint of heat resistance.

[0012] The production methods described in International Publication No. 2019 / 202079 and International Publication No. 2019 / 243404 also produce a cyclic polyether compound by the reaction of the diacyloxy compound and the difluoroacyl compound as in International Publication No. 2018 / 108864, and the actually obtained polyether compound having the above-mentioned end group is a low molecular compound having a small number of repeating units. Therefore, the above-mentioned polyether compound and the fluorine-containing polyether compound produced by fluorination of the above-mentioned polyether compound have room for improvement from the viewpoint of heat resistance.

[0013] In addition, it is described in International Publication No. 2019 / 243403 that the number of repeating units of the polyether compound produced in the examples thereof is 1 to 9. However, the polyether compound obtained by the production method described in International Publication No. 2019 / 243403 has an aromatic ring within the repeating unit, and has room for improvement from the viewpoint of ease of fluorination.

[0014] The present disclosure was made in view of the above-mentioned problems, and the problem to be solved by the present disclosure is to provide a production method of a polyether composition which can produce a polyether composition containing a polyether compound excellent in heat resistance.

[0015] In addition, the problem to be solved by the present disclosure is to provide a production method of a fluorine-containing polyether composition which can produce a fluorine-containing polyether composition containing a fluorine-containing polyether compound excellent in heat resistance.

[0016] Further, the present disclosure aims to provide a polyether composition containing a polyether compound having excellent heat resistance.

[0017] Means for solving the problem

[0018] Specific means for achieving the above object are as follows.

[0019] <1> A method for producing a polyether composition, comprising: a first polymerization reaction of reacting a compound represented by the following general formula (1) with a compound represented by the following general formula (2) at a ratio of less than 1 mol per 1 mol of the compound represented by the following general formula (2); and a second polymerization reaction after the first polymerization reaction, to produce a polyether composition containing a polyether compound, by a plurality of polymerization reactions of the compound represented by the following general formula (1) and the compound represented by the following general formula (2).

[0020] A-X-A (1)

[0021] B-Y-B (2)

[0022] (In the general formula (1) and the general formula (2),

[0023] X and Y each independently represent a divalent hydrocarbon group having a carbon number of 1 to 20, optionally containing an ether bond, and in which a hydrogen atom is optionally substituted with a fluorine atom,

[0024] X and Y do not have an aromatic ring.

[0025] The two As contained in the compound represented by the general formula (1) represent the same group, and represent a group selected from the group consisting of -OCF=CF2, -O(CF2) m CF=CF2, -C(=O)F, -OH, -OC(=O)F, -OTs, -OTf, and -OMs,

[0026] A represents -OCF=CF2, -O(CF2) m CF=CF2, -OTs, -OTf, or -OMs,

[0027] A represents -C(=O)F, B each represents -OC(=O)F,

[0028] A represents -OH, B each represents -OCF=CF2, -O(CF2) m CF=CF2, -OTs, -OTf, or -OMs,

[0029] A represents -OC(=O)F, B each represents -C(=O)F.

[0030] Here, Ts represents a p-tolylsulfonyl group, Tf represents a trifluoromethylsulfonyl group, Ms represents a methanesulfonyl group, and m represents an integer of 1 or more.

[0031] <2> The method for producing a polyether composition according to <1>, wherein the multiple polymerization reactions are performed in a composition containing at least a compound represented by the following general formula (1) and a compound represented by the following general formula (2), and the composition does not contain a solvent, or when the composition contains a solvent, the content of the solvent is 10% by mass or less.

[0032] <3> The method for producing a polyether composition according to <1> or <2>, wherein at least one of the multiple polymerization reactions is performed in the presence of a base catalyst.

[0033] <4> The method for producing a polyether composition according to any one of <1> to <3>, wherein the ratio of the time of the second polymerization reaction to the time of the first polymerization reaction is 1.1 to 3.

[0034] <5> The method for producing a polyether composition according to any one of <1> to <4>, wherein the first polymerization reaction is performed by reacting the compound represented by the following general formula (1) with the compound represented by the following general formula (2) at a ratio of 0.1 mol to 0.9 mol per 1 mol of the compound represented by the following general formula (2).

[0035] <6> The method for producing a polyether composition according to any one of <1> to <5>, wherein the first polymerization reaction is performed by introducing the compound represented by the following general formula (2) into the compound represented by the following general formula (1) at a rate of 0.01 times mol / hour to 100 times mol / hour per 1 mol of the compound represented by the following general formula (1), and allowing it to react.

[0036] <7> The method for producing a polyether composition according to any one of <1> to <5>, wherein the first polymerization reaction is performed by introducing the compound represented by the following general formula (1) into the compound represented by the following general formula (2) at a rate of 0.005 times mol / hour to 1.2 times mol / hour per 1 mol of the compound represented by the following general formula (2), and allowing it to react.

[0037] <8> The method for producing a polyether composition according to any one of <1> to <7>, wherein the second polymerization reaction is performed by reacting the compound represented by the following general formula (1) with the composition obtained by the first polymerization reaction at a ratio of 0.1 mol to 1.2 mol per 1 mol of the amount of the compound represented by the following general formula (2) introduced in the first polymerization reaction.

[0038] <9> The method for producing a polyether composition according to any one of <1> to <8>, wherein the second polymerization reaction is performed by introducing the compound represented by the general formula (1) into the composition obtained by the first polymerization reaction at a rate of 0.5 times mol / hour to 360 times mol / hour relative to 1 mol of the amount of the compound represented by the general formula (2) used in the first polymerization reaction, and allowing it to react.

[0039] <10> The method for producing a polyether composition according to any one of <1> to <9>, wherein at least one of X in the general formula (1) and Y in the general formula (2) is a divalent hydrocarbon group having a carbon number of 1 to 20, which is optionally fluorinated and optionally contains an ether bond.

[0040] <11> The method for producing a polyether composition according to any one of <1> to <10>, wherein the compound represented by the general formula (1) is allowed to react with the compound represented by the general formula (2) at a ratio of 0.6 mol to 1.4 mol relative to 1 mol of the compound represented by the general formula (2) by the multiple polymerization reaction.

[0041] <12> The method for producing a polyether composition according to any one of <1> to <11>, wherein the proportion of the terminal group represented by A is 90 mol% or more relative to the total content of the terminal groups possessed by the polyether compound contained in the polyether composition 100 mol%.

[0042] <13> A method for producing a fluorine-containing polyether composition comprising a fluorine-containing polyether compound, wherein the polyether compound contained in the polyether composition produced by the method for producing a polyether composition according to any one of <1> to <12> is fluorinated to produce a fluorine-containing polyether composition comprising a fluorine-containing polyether compound.

[0043] <14> A polyether composition comprising a polyether compound having a structure represented by the following general formula (3), and the proportion of the terminal group represented by A is 90 mol% or more relative to the total content of the terminal groups possessed by all the polyether compounds contained in the polyether composition 100 mol%.

[0044] A-X-(D-Y-D-X) n -A (3)

[0045] (in the general formula (3),

[0046] X each independently represents a divalent hydrocarbon group having a carbon number of 1 to 20, which is optionally fluorinated and optionally contains an ether bond,

[0047] Y each independently represents a divalent hydrocarbon group having a carbon number of 1 to 20, optionally containing an ether bond, and a hydrogen atom of which is optionally replaced with a fluorine atom,

[0048] wherein X and Y do not have an aromatic ring.

[0049] A is the same group, and represents a group selected from the group consisting of -OCF=CF2, -O(CF2) m CF=CF2, -C(=O)F, -OH, -OC(=O)F, -OTs, -OTf, and -OMs,

[0050] D represents a divalent linking group,

[0051] A represents -OCF=CF2, D each represents *-OCFHCF2O-**,

[0052] A represents -O(CF2) m CF=CF2, D each represents *-O(CF2) m CFHCF2O-**,

[0053] A represents -C(=O)F, D each represents **-OCF2-,

[0054] A represents -OC(=O)F, D each represents *-OCF2-**,

[0055] A represents -OTs, -OTf, or -OMs, D each represents *-O-**,

[0056] A represents -OH, D each represents **-OCFHCF2O-*, *-O(CF2) m CFHCF2O-** or *-O-**,

[0057] n represents an integer of 6 or more, and m represents an integer of 1 or more.

[0058] Here, Ts represents a p-toluenesulfonyl group, Tf represents a trifluoromethylsulfonyl group, Ms represents a methylsulfonyl group, * represents a bonding portion to X, and ** represents a bonding portion to Y.

[0059] Effects of the Invention

[0060] According to the present disclosure, it is possible to provide a method for producing a polyether composition, which can produce a polyether composition containing a polyether compound having excellent heat resistance.

[0061] In addition, according to the present disclosure, it is possible to provide a method for producing a fluorine-containing polyether composition, which can produce a fluorine-containing polyether composition containing a fluorine-containing polyether compound having excellent heat resistance.

[0062] Further, with the polyether composition of the present disclosure, a polyether composition containing a polyether compound excellent in heat resistance can be provided. DETAILED DESCRIPTION

[0063] Hereinafter, a mode 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.

[0064] In the present disclosure, a numerical range indicated by "~" contains the numerical values recited before and after "~" as the minimum value and the maximum value, respectively.

[0065] In the present disclosure, the upper limit value or the lower limit value recited in one numerical range can be replaced with the upper limit value or the lower limit value of another recited numerical range. Further, 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.

[0066] In the present disclosure, "fluoroalkylene" contains perfluoroalkylene in which all hydrogen atoms are replaced with fluorine atoms, and fluoroalkylene in which a part of hydrogen atoms are replaced with fluorine atoms. Further, in the present disclosure, the recitations such as "fluorocycloalkane" contain not only perfluorocycloalkane in which all hydrogen atoms possessed by cycloalkane are replaced with fluorine atoms, but also cycloalkane in which a part of hydrogen atoms are replaced with fluorine atoms.

[0067] In the present disclosure, each component can contain a plurality of compounds conforming thereto. For example, the mol ratio in the reaction of the compound represented by General Formula (1) and the compound represented by General Formula (2) is calculated based on the total of the compounds corresponding to each component.

[0068] In the present disclosure, in the recitations of groups (radicals), the recitations of "having no substitution" and "having no un-substitution" contain those having no substituent, and also contain those having a substituent.

[0069] In the present disclosure, the carbon number refers to the total number of carbon atoms contained in a certain group as a whole, 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 of carbon atoms forming the skeleton of the group plus the number of carbon atoms in the substituent is indicated.

[0070] In the present disclosure, the "perfluorination" of a 1-valent or 2-valent hydrocarbon group means that the hydrocarbon group is fluorinated to the following state.

[0071] In the case where the 1-valent or 2-valent hydrocarbon group is a saturated hydrocarbon group, the state in which all fluorinatable hydrogen atoms bonded to the carbon atoms constituting the 1-valent or 2-valent hydrocarbon group are fluorinated is referred to as "perfluorination" of the hydrocarbon group.

[0072] 1 or 2 valent hydrocarbon group is referred to as "fully fluorinated" in the case where all of the fluorinatable hydrogen atoms bonded to the carbon atoms constituting the 1 or 2 valent hydrocarbon group are fluorinated, and a fluorine atom is added to each of the 2 carbon atoms forming an unsaturated bond between the carbon atoms such as a carbon-carbon double bond or a carbon-carbon triple bond, thereby eliminating the unsaturated bond between the carbon atoms. For example, >C=C< becomes >CF-CF< if fully fluorinated, and -C≡C- becomes -CF2-CF2- if fully fluorinated. In addition, the fluorinatable hydrogen atom can be bonded to a group that can be fully fluorinated, for example, -CH=CH- becomes -CF2-CF2- if fully fluorinated.

[0073] 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 in accordance with the method described in

[0010] to

[0030] of Japanese Patent Application Publication No. 2001-208736 and under the following conditions. Note that the same materials can also be used for the mobile phase and the like.

[0074] • Mobile phase: a 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))

[0075] • Analysis column: 2 PLgel MIXED-E columns (manufactured by Polymer Laboratories) connected in series

[0076] • Standard sample for molecular weight measurement: 4 kinds of perfluoropolyether having a molecular weight distribution (Mw / Mn) of less than 1.1 and a Mn of 2,000 to 10,000, and 1 kind of perfluoropolyether having a Mw / Mn of 1.1 or more and a Mn of 1,300

[0077] • Flow rate of mobile phase: 1.0 mL / minute

[0078] • Column temperature: 37°C

[0079] • Detector: Evaporative light scattering detector

[0080] (Method for producing polyether composition)

[0081] The production method of the polyether composition of the present disclosure includes: a first polymerization reaction in which a compound represented by the following general formula (1) is reacted with a compound represented by the following general formula (2) at a ratio of less than 1 mol per 1 mol of the compound represented by the following general formula (2); and a second polymerization reaction after the first polymerization reaction, and a polyether composition containing a polyether compound is produced by a plurality of polymerization reactions of the compound represented by the following general formula (1) and the compound represented by the following general formula (2).

[0082] A-X-A (1)

[0083] B-Y-B (2)

[0084] In general formula (1) and general formula (2), X and Y each independently represent a divalent hydrocarbon group having a carbon number of 1 to 20, optionally containing an ether bond, and in which a hydrogen atom is optionally substituted with a fluorine atom. Among them, X and Y do not have an aromatic ring.

[0085] In addition, the two A contained in the compound represented by general formula (1) represent the same group, and represent a group selected from the group consisting of -OCF=CF2, -O(CF2) m CF=CF2, -C(=O)F, -OH, -OC(=O)F, -OTs, -OTf, and -OMs.

[0086] A represents -OCF=CF2, -O(CF2) m CF=CF2, -OTs, -OTf, or -OMs, B each represents -OC(=O)F when A represents -C(=O)F, B each represents -OH when A represents -OH, B each represents -OCF=CF2, -O(CF2) m CF=CF2, -OTs, -OTf, or -OMs, B each represents -C(=O)F when A represents -OC(=O)F.

[0087] Note that Ts represents a p-toluenesulfonyl group, Tf represents a trifluoromethanesulfonyl group, Ms represents a methanesulfonyl group, m represents an integer of 1 or more, preferably represents an integer of 1 to 6, and more preferably represents an integer of 1 to 3.

[0088] By using the production method of the polyether composition of the present disclosure, it is possible to produce a polyether composition containing a polyether compound having excellent heat resistance.

[0089] The reason why the above effects are exerted is presumed as follows, but is not limited thereto.

[0090] In the production method of the polyether composition of the present disclosure, the polyether compound contained in the polyether composition is produced by a plurality of polymerization reactions of the compound represented by general formula (1) and the compound represented by general formula (2).

[0091] It is presumed that by dividing the polymerization into a plurality of times, and by causing the compound represented by General Formula (1) to react with the compound represented by General Formula (2) at a ratio of less than 1 mol per 1 mol of the compound represented by General Formula (2) in the first polymerization, the self-cyclization reaction of the polymer can be suppressed in the polymerization, and a polyether compound having a large number of repeating units can be produced, and the heat resistance of the polyether compound is improved. Also, it is presumed that the same applies to the fluorine-containing polyether compound produced by fluorinating the above-described polyether compound, and the number of repeating units is large, and the heat resistance is excellent.

[0092] The proportion of the terminal group represented by A with respect to the total content of the terminal groups possessed by the entire polyether compound contained in the polyether composition is preferably 90 mol% or greater, more preferably 92 mol% or greater, and further preferably 95 mol% or greater.

[0093] Hereinafter, the multiple polymerization reaction contained in the production method of the polyether composition of the present disclosure will be described.

[0094] - Multiple Polymerization Reaction -

[0095] In the production method of the polyether composition of the present disclosure, the multiple polymerization reaction includes at least a first polymerization reaction in which the compound represented by General Formula (1) is caused to react with the compound represented by General Formula (2) at a ratio of less than 1 mol per 1 mol of the compound represented by General Formula (2); and a second polymerization reaction after the above-described first polymerization reaction.

[0096] In the production method of the polyether composition of the present disclosure, the second polymerization reaction can be performed a plurality of times.

[0097] In the production method of the polyether composition of the present disclosure, the multiple polymerization reaction can be performed in a composition containing at least the compound represented by General Formula (1) and the compound represented by General Formula (2).

[0098] The content ratio of the solvent in the above-described composition is preferably 10 mass% or less, more preferably 5 mass% or less, further preferably 1 mass% or less, and particularly preferably the composition does not contain a solvent.

[0099] By causing the content ratio of the solvent in the composition to be 10 mass% or less, the above-described self-cyclization reaction can be more effectively suppressed, and a polyether composition containing a polyether compound having more excellent heat resistance can be produced. Also, by causing the content ratio of the solvent in the composition to be 10 mass% or less, the yield of the polyether compound having excellent heat resistance can be improved.

[0100] The solvent is not particularly limited, and examples thereof include acetonitrile, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, ethylene polyoxide dimethyl ether, dimethoxyethane, bis(2-methoxyethyl)ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether.

[0101] The compound represented by General Formula (1) is preferably reacted at a ratio of 0.6 mol to 1.4 mol, more preferably at a ratio of 0.7 mol to 1.3 mol, and further preferably at a ratio of 0.8 mol to 1.2 mol, per 1 mol of the compound represented by General Formula (2) in the multiple polymerization reactions. By setting the mol ratio in the multiple polymerization reactions within the above numerical range, a polyether composition containing a polyether compound having more excellent heat resistance can be produced.

[0102] Further, the production method of the polyether composition of the present disclosure makes it possible to adjust the presence ratio of A derived from General Formula (1) and B derived from General Formula (2) in the terminal of the polyether compound by setting the mol ratio in the reaction of the compound represented by General Formula (1) and the compound represented by General Formula (2) in the multiple polymerization reactions within the above numerical range. For example, a polyether compound having a terminal rich in A, a polyether compound having a terminal rich in B, and the like can be selectively produced.

[0103] Further, by setting the mol ratio in the reaction of the compound represented by General Formula (1) and the compound represented by General Formula (2) in the multiple polymerization reactions within the above numerical range, the content of the unreacted compound represented by General Formula (1) and the compound represented by General Formula (2) in the polyether composition produced by the polymerization reaction is reduced, and in some cases, purification and the like can be omitted.

[0104] In the production method of the polyether composition of the present disclosure, it is preferable that at least one of the polymerization reactions in the multiple polymerization reactions be performed in the presence of a base catalyst, and more preferable that all of the polymerization reactions be performed in the presence of a base catalyst.

[0105] By performing the polymerization reaction in the presence of a base catalyst, the polymerization reaction of the compound represented by General Formula (1) and the compound represented by General Formula (2) proceeds smoothly, and a polyether composition containing a polyether compound having more excellent heat resistance can be produced.

[0106] Further, by performing the polymerization reaction in the presence of a base catalyst, the yield of the polyether compound having excellent heat resistance can be improved.

[0107] As the base catalyst, for example, a carbonate and a metal fluoride salt, and the like can be appropriately used.

[0108] In General Formula (1), A represents -OCF=CF2, -O(CF2) mIn the case where CF = CF2, -OTs, -OTf, -OMs, or -OH, the base catalyst is preferably a carbonate, and in the case where A represents -C(=O)F or -OC(=O)F, the base catalyst is preferably a metal fluoride.

[0109] As the carbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, potassium bicarbonate, and cesium bicarbonate can be given. As the metal fluoride, cesium fluoride, sodium fluoride, and potassium fluoride can be given.

[0110] In the plurality of polymerization reactions, two or more of the compound represented by General Formula (1) and the compound represented by General Formula (2) can be used each.

[0111] In the case where two or more of the compound represented by General Formula (1) are used, the terminal groups represented by A are preferably all the same. In the case where two or more of the compound represented by General Formula (2) are used, the terminal groups represented by B are preferably all the same.

[0112] By making the terminal groups represented by A all the same and the terminal groups represented by B all the same, a polyether composition containing a polyether compound having more excellent heat resistance can be produced, and adjustment of the presence ratio of A derived from General Formula (1) and B derived from General Formula (2) in the terminal of the polyether compound becomes possible.

[0113] The ratio of the time of the second polymerization reaction (in the case of a plurality of times, the time of each of the second polymerization reactions) to the time of the first polymerization reaction is preferably 1.1 to 3, more preferably 1.3 to 2.5. By setting the ratio of the time of the second polymerization reaction to the time of the first polymerization reaction to the above numerical range, the polymerization reactions of the compound represented by General Formula (1) and the compound represented by General Formula (2) proceed smoothly, a polyether composition containing a polyether compound having more excellent heat resistance can be produced. Furthermore, adjustment of the presence ratio of A derived from General Formula (1) and B derived from General Formula (2) in the terminal of the polyether compound becomes possible.

[0114] In addition, by setting the ratio of the time of the second polymerization reaction to the time of the first polymerization reaction to the above numerical range, the yield of the polyether compound having excellent heat resistance can be improved.

[0115] Note that the time of the first polymerization reaction refers to the time from when the mixture of the compound represented by General Formula (1) and the compound represented by General Formula (2) is brought to the reaction temperature until the compound represented by General Formula (1) used in the second polymerization reaction is introduced.

[0116] In addition, the time for the second polymerization reaction, in the case of carrying out the second polymerization reaction once, refers to the time after the addition of the compound represented by the general formula (1) is introduced and the reaction temperature is reached, and the reaction system is cooled down until it reaches a temperature lower than the reaction temperature.

[0117] In addition, in the case of multiple second polymerization reactions, the time of the last second polymerization reaction (final polymerization reaction) in the multiple second polymerization reactions refers to the time after the addition of the compound represented by general formula (1) is introduced and the reaction temperature is reached, and the reaction system is cooled down until it reaches a temperature lower than the reaction temperature. The time of other second polymerization reactions refers to the time after the addition of the compound represented by general formula (1) is introduced and the reaction temperature is reached, until the compound represented by general formula (1) used in the next second polymerization reaction is introduced.

[0118] --First Polymerization Reaction--

[0119] The first polymerization reaction is preferably carried out by reacting 1 mol of the compound represented by general formula (1) with 0.1 mol to 0.9 mol of the compound represented by general formula (2), more preferably by reacting with 0.3 mol to 0.7 mol, and even more preferably by reacting with 0.4 mol to 0.6 mol. Using the method for manufacturing the polyether composition including the above-described first polymerization reaction, the above-described self-cyclization reaction can be suppressed more effectively, and a polyether composition containing a polyether compound with superior heat resistance can be manufactured.

[0120] Furthermore, by using the manufacturing method of the polyether composition including the first polymerization reaction described above, the yield of polyether compounds with excellent heat resistance can be improved.

[0121] In the first polymerization reaction, the compound represented by general formula (2) can be introduced into the compound represented by general formula (1) to carry out the reaction, the compound represented by general formula (1) can be introduced into the compound represented by general formula (2) to carry out the reaction, or the compound represented by general formula (1) and the compound represented by general formula (2) can be introduced into the container and then the reaction can be carried out.

[0122] When the first polymerization reaction is carried out by introducing the compound of general formula (2) into the compound of general formula (1), it is preferable to introduce the compound of general formula (2) at a rate of 0.01 times mol / h to 100 times mol / h relative to 1 mol of the compound of general formula (1), more preferably at a rate of 0.1 times mol / h to 10 times mol / h, and even more preferably at a rate of 0.5 times mol / h to 3 times mol / h.

[0123] In the case where the first polymerization reaction is performed by introducing the compound represented by General Formula (1) into the compound represented by General Formula (2) and reacting, the compound represented by General Formula (1) is preferably introduced at a rate of 0.005 times mol / hour to 1.2 times mol / hour relative to 1 mol of the compound represented by General Formula (2), more preferably at a rate of 0.01 times mol / hour to 0.9 times mol / hour, and further preferably at a rate of 0.1 times mol / hour to 0.5 times mol / hour.

[0124] The production method of the polyether composition including the above first polymerization reaction can more effectively suppress the above self-cyclization reaction, and can produce a polyether composition containing a polyether compound having more excellent heat resistance.

[0125] In addition, the production method of the polyether composition including the above first polymerization reaction can improve the yield of the polyether compound having excellent heat resistance.

[0126] The reaction temperature in the first polymerization reaction is preferably 20°C to 120°C, and more preferably 30°C to 100°C.

[0127] The production method of the polyether composition including the above first polymerization reaction can smoothly perform the polymerization reaction of the compound represented by General Formula (1) and the compound represented by General Formula (2), and can produce a polyether composition containing a polyether compound having more excellent heat resistance.

[0128] In addition, the production method of the polyether composition including the above first polymerization reaction can improve the yield of the polyether compound having excellent heat resistance.

[0129] Note that the reaction temperature in the present disclosure refers to the internal temperature of a container in which the compound represented by General Formula (1) and the compound represented by General Formula (2) are reacted.

[0130] The time of the first polymerization reaction is preferably 0.5 hours to 10 hours, and more preferably 1 hour to 5 hours. The production method of the polyether composition including the above first polymerization reaction can smoothly perform the polymerization reaction of the compound represented by General Formula (1) and the compound represented by General Formula (2), and can produce a polyether composition containing a polyether compound having more excellent heat resistance.

[0131] In addition, the production method of the polyether composition including the above first polymerization reaction can improve the yield of the polyether compound having excellent heat resistance.

[0132] -- Second Polymerization Reaction --

[0133] A composition containing a polymer of a compound represented by General Formula (1) and a compound represented by General Formula (2) is produced by a first polymerization reaction. The composition can contain an unreacted compound represented by General Formula (2). In an embodiment of a second polymerization reaction, the above-mentioned polymer and the unreacted compound represented by General Formula (2) contained in the composition are reacted with a compound represented by General Formula (1) additionally introduced.

[0134] The second polymerization reaction is preferably performed so that the compound represented by General Formula (1) is reacted at a ratio of 0.1 mol to 1.2 mol per 1 mol of the amount of the compound represented by General Formula (2) introduced in the first polymerization reaction, more preferably at a ratio of 0.3 mol to 0.7 mol, and further preferably at a ratio of 0.3 mol to 0.6 mol. With the production method of the polyether composition including the above-mentioned second polymerization reaction, a polyether composition containing a polyether compound having more excellent heat resistance can be produced, and adjustment of the presence ratio of A derived from General Formula (1) and B derived from General Formula (2) in the terminal of the polyether compound becomes possible.

[0135] Further, with the production method of the polyether composition including the above-mentioned second polymerization reaction, the yield of the polyether compound having excellent heat resistance can be improved.

[0136] Note that, in the case where the second polymerization reaction is performed multiple times, each can be at a different reaction ratio or at the same reaction ratio.

[0137] In the second polymerization reaction as the final polymerization reaction, it is preferable to mix the compound represented by General Formula (1) at a ratio of 0.4 mol or more per 1 mol of the amount of the compound represented by General Formula (2) introduced in the first polymerization reaction into the composition obtained by the first polymerization reaction and allow it to react. With the production method of the polyether composition including the above-mentioned second polymerization reaction, adjustment of the presence ratio of A derived from General Formula (1) and B derived from General Formula (2) in the terminal of the polyether compound becomes possible.

[0138] Further, with the production method of the polyether composition including the above-mentioned second polymerization reaction, the yield of the polyether compound having excellent heat resistance can be improved.

[0139] In the second polymerization reaction, the compound represented by General Formula (1) is preferably introduced into the composition obtained by the first polymerization reaction at a rate of 0.5 times mol / hour to 360 times mol / hour relative to 1 mol of the amount of the compound represented by General Formula (2) introduced in the first polymerization reaction, more preferably at a rate of 0.8 times mol / hour to 300 times mol / hour, further preferably at a rate of 1 times mol / hour to 180 times mol / hour, and particularly preferably at a rate of 4 times mol / hour to 100 times mol / hour.

[0140] The production method of the polyether composition including the above-described second polymerization reaction can produce a polyether composition containing a polyether compound having more excellent heat resistance, and adjustment of the presence ratio of A derived from General Formula (1) and B derived from General Formula (2) in the terminal of the polyether compound is possible.

[0141] In addition, the production method of the polyether composition including the above-described second polymerization reaction can improve the yield of the polyether compound having excellent heat resistance.

[0142] Note that, in the case where the second polymerization reaction is performed multiple times, the respective rates of introduction can be different or the same.

[0143] The reaction temperature in the second polymerization reaction is preferably 20°C to 140°C, and more preferably 40°C to 130°C. The production method of the polyether composition including the above-described second polymerization reaction can smoothly perform the polymerization reaction of the compound represented by General Formula (1) and the compound represented by General Formula (2), can produce a polyether composition containing a polyether compound having more excellent heat resistance, and adjustment of the presence ratio of A derived from General Formula (1) and B derived from General Formula (2) in the terminal of the polyether compound is possible.

[0144] In addition, the production method of the polyether composition including the above-described second polymerization reaction can improve the yield of the polyether compound having excellent heat resistance.

[0145] Note that, in the case where the second polymerization reaction is performed multiple times, the respective reaction temperatures can be different or the same.

[0146] The time of the second polymerization reaction (in the case of multiple second polymerization reactions, the time of each second polymerization reaction) is preferably 1 hour to 30 hours, more preferably 2 hours to 20 hours. With the production method of the polyether composition including the above-described second polymerization reaction, the polymerization reaction of the compound represented by General Formula (1) and the compound represented by General Formula (2) proceeds smoothly, a polyether composition containing a polyether compound having more excellent heat resistance can be produced, and adjustment of the proportion of the presence of A derived from General Formula (1) and B derived from General Formula (2) in the terminal of the polyether compound is possible.

[0147] In addition, with the production method of the polyether composition including the above-described second polymerization reaction, the yield of the polyether compound having excellent heat resistance can be improved.

[0148] Note that in the case of multiple second polymerization reactions, each can be a different polymerization reaction time or the same polymerization reaction time.

[0149] In the production method of the polyether composition of the present disclosure, at least one selected from a solvent, water, and an aqueous solution for adjusting to an appropriate acidity can be added to the polyether composition obtained by the second polymerization reaction, and after the liquid separation, the organic phase can be concentrated. In addition, the concentrated organic phase can be purified. The solvent is not particularly limited, and a fluorine-based solvent is preferred. As the fluorine-based solvent, fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkyl amines, and fluoroalcohols, etc. can be given.

[0150] Hereinafter, the compound represented by General Formula (1), the compound represented by General Formula (2), and the polyether compound will be described.

[0151] --Compound represented by General Formula (1)--

[0152] In General Formula (1), X represents a divalent hydrocarbon group having a carbon number of 1 to 20, optionally containing an ether bond, and in which a hydrogen atom is optionally substituted with a fluorine atom. Here, X does not have an aromatic ring.

[0153] The carbon number of the divalent hydrocarbon group is preferably 15 or less, more preferably 13 or less. By setting the carbon number of the divalent hydrocarbon group to 15 or less, the polymerization reaction of the compound represented by General Formula (2) proceeds smoothly, and a polyether composition containing a polyether compound having more excellent heat resistance can be produced.

[0154] From the viewpoint of the balance of fluorination reactivity, heat resistance, etc., the divalent hydrocarbon group is preferably a hydrocarbon group optionally containing an ether bond which is perfluorinated.

[0155] In addition, from the viewpoint of the balance of fluorination reactivity, heat resistance, etc., at least one of X in General Formula (1) and Y in General Formula (2) described later is preferably a hydrocarbon group optionally containing an ether bond which is perfluorinated.

[0156] From the perspective of balancing fluorination reactivity, heat resistance, etc., it is preferable that X in general formula (1) and Y in general formula (2) both represent perfluorinated hydrocarbon groups. However, from the perspective of cost, it is preferable that X in general formula (1) or Y in general formula (2) represent perfluorinated hydrocarbon groups.

[0157] The divalent hydrocarbon group preferably has 4 or more carbon atoms, more preferably 5 or more. By making the divalent hydrocarbon group have 4 or more carbon atoms, it is possible to carry out the reaction with the compound shown in general formula (2) in the liquid state, and the adjustment of the reaction becomes easy.

[0158] Examples of divalent hydrocarbon groups represented by X include alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene, as well as fluoroalkylene groups such as fluoromethylene, fluoroethylene, fluorotrimethylene, fluorotetramethylene, fluoropentamethylene, and fluorohexamethylene.

[0159] The divalent hydrocarbon group shown in X can be a group represented by the following general formula (A).

[0160] *-R 1 -(OR 1 ) n’ -* (A)

[0161] In general formula (A), R 1 (CH2) n” Or (CF2) n” n' and n" are integers greater than or equal to 1, preferably integers from 1 to 12.

[0162] It should be noted that in general formula (A), * represents the bonded part with A in general formula (1).

[0163] The divalent hydrocarbon group shown in X can be a group represented by the following general formula (B).

[0164] *-CH(CH3)(CH2) n”’ CH(CH3)-* (B)

[0165] In general formula (B), n”’ is an integer greater than or equal to 1, preferably an integer from 1 to 8.

[0166] It should be noted that in general formula (B), * represents the bonding part with A in general formula (1).

[0167] The divalent hydrocarbon group shown in X can be a group represented by the following general formula (C).

[0168] *-R 3 -OR 2 -OR 3 -* (C)

[0169] In General Formula (C), R 2 represents a cycloalkanediyl group or a fluorocycloalkanediyl group.

[0170] As the cycloalkanediyl group and the fluorocycloalkanediyl group, for example, cyclobutanediyl, fluorocyclobutanediyl, cyclopentanediyl, fluorocyclopentanediyl, cyclohexanediyl, fluorocyclohexanediyl, adamantanediyl, norbornanediyl, and the like can be given. The cycloalkanediyl group and the fluorocycloalkanediyl 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.

[0171] In General Formula (C), R 3 each independently represents a divalent hydrocarbon group having a carbon number of 1 to 10, in which a hydrogen atom is optionally substituted with a fluorine atom. Among them, R 3 does not have an aromatic ring.

[0172] Note that, in General Formula (C), * indicates a bonding portion to A in General Formula (1).

[0173] As the divalent hydrocarbon group satisfying General Formula (C), the following groups can be given, but are not limited thereto.

[0174]

[0175]

[0176] Further, the divalent hydrocarbon group represented by X can be a group represented by General Formula (D) to (F) below.

[0177] *-R 4 -R 2 -R 4 *-R

[0178] *-R 2 -R 4 -R 2 *-R

[0179] *-R 3 -R 5 -R 3 *-R

[0180] Note that, in General Formulae (D) to (F), * indicates a bonding portion to A in General Formula (1).

[0181] Further, in General Formulae (D) and (E), R 4 each independently represents a single bond, or a divalent hydrocarbon group having a carbon number of 1 to 10, in which a hydrogen atom is optionally substituted with a fluorine atom. Among them, R 4 does not have an aromatic ring.

[0182] Further, in General Formula (F), R 5represents a cycloalkane-1,1-diyl group having a carbon number of 3 to 6.

[0183] Note that R 2 and R 3 represent the same groups as in the above general formula (C).

[0184] As the group satisfying any of the general formula (D) to the general formula (F), the following groups can be given, but are not limited thereto.

[0185]

[0186]

[0187]

[0188]

[0189] In the compound represented by the general formula (1), the two A's represent the same group, and represent a group selected from the group consisting of -OCF=CF2, -O(CF2) m CF=CF2, -C(=O)F, -OH, -OC(=O)F, -OTs, -OTf, and -OMs. In addition, -O(CF2) m In -O(CF2)

[0190] From the viewpoint of reactivity with the compound represented by the general formula (2), when A represents an -OH group, the compound represented by the general formula (1) is preferably a primary alcohol having a -CH2OH group at the terminal. In addition, when the compound represented by the general formula (1) is a primary alcohol, it is preferable that a hydrogen atom is substituted with a fluorine atom except for the -CH2OH group at the terminal.

[0191] The molecular weight of the compound represented by the general formula (1) is preferably 50 to 2000, more preferably 55 to 1000. By making the molecular weight of the compound represented by the general formula (1) within the above numerical range, the polymerization reaction with the compound represented by the general formula (2) proceeds smoothly, and a polyether compound having more excellent heat resistance can be produced.

[0192] In addition, by making the molecular weight of the compound represented by the general formula (1) within the above numerical range, the yield of the polyether compound having excellent heat resistance can be improved.

[0193] When A in General Formula (1) represents -OH, the acidity (pKa) of the compound of Formula (1) is preferably 8 to 18, more preferably 9 to 15. By making the pKa of the compound represented by General Formula (1) within the above numerical range, the polymerization reaction with the compound represented by General Formula (2) proceeds smoothly, and a polyether composition containing a polyether compound having more excellent heat resistance can be produced.

[0194] In addition, by making the pKa of the compound represented by General Formula (1) within the above numerical range, the yield of the polyether compound having excellent heat resistance can be improved.

[0195] In the present disclosure, the 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.).

[0196] According to the above, as the compound represented by General Formula (1), the following compounds can be given, but are not limited thereto. Note that A in the following compounds is as described above.

[0197]

[0198]

[0199]

[0200]

[0201]

[0202]

[0203]

[0204]

[0205]

[0206]

[0207] --Compound represented by General Formula (2)--

[0208] In General Formula (2), Y represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which optionally contains an ether bond and in which a hydrogen atom is optionally replaced with a fluorine atom. The divalent hydrocarbon group does not have an aromatic ring. The number of carbon atoms of the divalent hydrocarbon group is preferably 15 or less, more preferably 13 or less. By setting the number of carbon atoms of the divalent hydrocarbon group to 15 or less, the polymerization reaction with the compound represented by General Formula (1) proceeds smoothly, and a polyether compound having more excellent heat resistance can be produced. In addition, from the viewpoint of the balance of fluorination reactivity, heat resistance, and the like, the divalent hydrocarbon group is preferably a perfluorinated hydrocarbon group optionally containing an ether bond. The divalent hydrocarbon group can be the same group as the divalent hydrocarbon group represented by X, and thus specific description thereof is omitted here. In addition, X and Y can be the same group or different groups.

[0209] In addition, the number of carbon atoms of the divalent hydrocarbon group is preferably 4 or more, more preferably 5 or more. By setting the number of carbon atoms of the divalent hydrocarbon group to 4 or more, the reaction with the compound represented by General Formula (1) can be performed in a liquid state, and the adjustment of the reaction becomes easy.

[0210] A in General Formula (1) represents -OCF=CF2, -O(CF2) m When B in General Formula (2) represents -OH when A in General Formula (1) represents -C(=O)F, B in General Formula (2) represents -OC(=O)F, and when A in General Formula (1) represents -OH, B in General Formula (2) represents -OCF=CF2, -O(CF2) m When B in General Formula (2) represents -OH when A in General Formula (1) represents -C(=O)F, B in General Formula (2) represents -OC(=O)F, and when A in General Formula (1) represents -OH, B in General Formula (2) represents -OCF=CF2, -O(CF2) m CF=CF2, m is as described above, and thus the description thereof is omitted here.

[0211] From the viewpoint of the reactivity with the compound represented by General Formula (1), when B represents an -OH group, the compound represented by General Formula (2) is preferably a primary alcohol. In addition, when the compound represented by General Formula (2) is a primary alcohol, it is preferable that a hydrogen atom be replaced with a fluorine atom except for the terminal -CH2OH group.

[0212] The molecular weight of the compound represented by General Formula (2) is preferably 50 to 2000, more preferably 55 to 1000. By setting the molecular weight of the compound represented by General Formula (2) to the above numerical range, the polymerization reaction with the compound represented by General Formula (1) proceeds smoothly, and a polyether composition containing a polyether compound having more excellent heat resistance can be produced.

[0213] In addition, by setting the molecular weight of the compound represented by General Formula (2) to the above numerical range, the yield of the polyether compound having excellent heat resistance can be improved.

[0214] When B in General Formula (2) represents -OH, the pKa of the compound of Formula (2) is preferably 8 to 18, more preferably 9 to 15. By making the pKa of the compound represented by General Formula (2) within the above numerical range, the polymerization reaction with the compound represented by General Formula (1) proceeds smoothly, and a polyether composition containing a polyether compound having more excellent heat resistance can be produced.

[0215] In addition, by making the pKa of the compound represented by General Formula (2) within the above numerical range, the yield of the polyether compound having excellent heat resistance can be improved.

[0216] Specific examples of the compound represented by General Formula (2) are compounds in which the terminal group A of the specific examples of the compound represented by General Formula (1) described above is replaced with the terminal group B, and thus specific descriptions thereof are omitted here.

[0217] From the viewpoint of reactivity, as the preferred combination of the terminal group A in General Formula (1) and the terminal group B in General Formula (2), there can be mentioned a combination in which A represents -OCF=CF2and B represents -OH; a combination in which A represents -C(=O)F and B represents -OC(=O)F; a combination in which A represents -OH and B represents -O(CF2) m CF=CF2; and a combination in which A represents -OC(=O)F and B represents -C(=O)F.

[0218] The polyether composition produced by the production method of the polyether composition of the present disclosure can contain a polyether compound having a structure represented by General Formula (3).

[0219] A-X-(D-Y-D-X) n -A(3)

[0220] In General Formula (3), each X independently represents a divalent hydrocarbon group having a carbon number of 1 to 20, which optionally contains an ether bond and in which a hydrogen atom is optionally substituted with a fluorine atom. Among them, X does not have an aromatic ring.

[0221] In General Formula (3), each Y independently represents a divalent hydrocarbon group having a carbon number of 1 to 20, which optionally contains an ether bond and in which a hydrogen atom is optionally substituted with a fluorine atom. Among them, Y does not have an aromatic ring.

[0222] In General Formula (3), D is a divalent linking group, and when A represents -OCF=CF2, D all represent *-OCFHCF2O-**, and when A represents -O(CF2) m CF=CF2, D all represent *-O(CF2) mCFHCF2O-**, A represents -C(=O)F, D all represent **-OCF2-*, A represents -OC(=O)F, D all represent *-OCF2-**, A represents -OTs, -OTf or -OMs, D all represent *-O-, A represents -OH, D all represent **-OCFHCF2O-*, *-O(CF2) m CFHCF2O-** or *-O-**. * represents a bonding portion to X, and ** represents a bonding portion to Y. In addition, -O(CF2) m CFHCF2O-**, A represents -C(=O)F, D all represent **-OCF2-*, A represents -OC(=O)F, D all represent *-OCF2-**, A represents -OTs, -OTf or -OMs, D all represent *-O-, A represents -OH, D all represent **-OCFHCF2O-*, *-O(CF2)

[0223] In General Formula (3), n represents an integer of 6 or more, preferably an integer of 7 or more, and more preferably an integer of 8 or more.

[0224] From the viewpoint of flowability of the polyether composition and solubility of the polyether compound, the average of the number average molecular weight (Mn) of the polyether compound contained in the polyether composition is preferably 10,000 to 20,000, more preferably 1,500 to 10,000, and further preferably 1,500 to 7,000.

[0225] In addition, from the viewpoint of flowability of the polyether composition and solubility of the polyether compound, the average of the molecular weight distribution (Mw / Mn) of the polyether compound contained in the polyether composition is preferably 1.0 to 2.5, more preferably 1.0 to 2.3, and further preferably 1.0 to 2.0.

[0226] As the polyether compound having the structure represented by General Formula (3) above, the following compounds can be given, but are not limited to these.

[0227]

[0228]

[0229] In the case where the polyether composition contains the polyether compound having the structure represented by General Formula (3), the polyether composition can contain at least one of the polyether compound having the structure represented by General Formula (3') below and the polyether compound having the structure represented by General Formula (3') below.

[0230] B-Y-(D-X-D-Y) n -B (3')

[0231] A-X-(D-Y-D-X) n -D-Y-B (3")

[0232] As for X, Y, A, B, D and n in General Formula (3') and General Formula (3"), the above description applies.

[0233] From the viewpoint of heat resistance, the content of polyether compound in the polyether composition is preferably 60% to 100% by mass, and more preferably 80% to 100% by mass.

[0234] The polyether composition may contain one polyether compound or two or more.

[0235] From the viewpoint of heat resistance, the content of the polyether compound having the structure shown in general formula (3) in the polyether composition is preferably 50% to 100% by mass.

[0236] --Polyether Composition--

[0237] The polyether composition disclosed herein comprises a polyether compound having the structure shown in the above general formula (3), and the proportion of the terminal group shown in A is 90 mol% or more relative to 100 mol% of the total number of terminal groups of all polyether compounds contained in the polyether composition. The proportion of A is preferably 92 mol%, more preferably 95 mol%.

[0238] Regarding the preferred content of the polyether compound in the polyether composition, etc., as described above.

[0239] When the polyether composition contains a polyether compound having the structure shown in general formula (3), the polyether composition may contain at least one of a polyether compound having the structure shown in general formula (3') and a polyether compound having the structure shown in general formula (3').

[0240] (Method for manufacturing fluorinated polyether compositions)

[0241] The present disclosure discloses a method for manufacturing fluorinated polyether compositions by fluorinating a polyether compound contained in a polyether composition manufactured by the above-described method for manufacturing polyether compositions, thereby manufacturing a fluorinated polyether composition containing a fluorinated polyether compound.

[0242] Using the method for manufacturing the fluorinated polyether composition disclosed herein, it is possible to manufacture fluorinated polyether compositions containing fluorinated polyether compounds with superior heat resistance.

[0243] The following describes specific examples of methods for manufacturing fluorinated polyether compositions, but are not limited to these examples.

[0244] -Specific example A of the manufacturing method of fluorinated polyether composition-

[0245] The polyether composition contains two ends having -OCF=CF2 groups or -O(CF2). m In the case of CF=CF2-based polyether compounds, fluorination of the polyether compound can produce a fluorinated polyether composition containing the fluorinated polyether compound.

[0246] The above method is preferably a method in which the total of the -OCF=CF2groups or -O(CF2) m The proportion of the CF=CF2groups is preferably 90 mol% or more.

[0247] The method of fluorination of the polyether compound is not particularly limited and can be carried out based on a method known in the art. The method of fluorination can be a batch method or a continuous method. The fluorination reaction is preferably carried out by the following <Method 1> or <Method 2>, and more preferably <Method 2> from the viewpoint of the yield of the fluorine-containing polyether compound. As for fluorine gas, in the case of carrying out in a batch method and in the case of carrying out in a continuous method, it can be used after being diluted with a non-active gas such as nitrogen.

[0248] <Method 1>

[0249] Method 1 is a method in which a polyether compound and a solvent are charged into a reactor and stirring is started. The reaction is carried out under a prescribed reaction temperature and reaction pressure while continuously supplying fluorine gas diluted with a non-active gas to the solvent.

[0250] <Method 2>

[0251] Method 2 is a method in which a solvent is charged into a reactor and stirring is carried out. Subsequently, the reaction is carried out under a prescribed reaction temperature and reaction pressure while continuously supplying fluorine gas diluted with a non-active gas, a polyether compound, and a solvent to the fluorination reaction solvent at a prescribed molar ratio.

[0252] <Method 3>

[0253] Method 3 is a method in which a solvent is continuously introduced into a tubular reactor so that the solvent flows through the tubular reactor, and then fluorine gas diluted with a non-active gas and a solution in which a polyether compound is dissolved are continuously supplied to the solvent flow in the tubular reactor at a ratio at which the fluorine gas and the polyether compound become a prescribed molar ratio and are mixed, so that the fluorine gas and the polyether compound contact and react in the tubular reactor, and the solvent containing the reaction product is taken out of the tubular reactor. In this method, the fluorination reaction can be carried out in a continuous method by circulating the solvent and taking out the reaction product from the circulated solvent.

[0254] As in the case of Method 3, in Method 2, it is preferable to supply a polyether compound diluted with a solvent when the polyether compound is supplied from the viewpoint of improving the selective production of the fluorine-containing polyether compound and suppressing the amount of by-products. In addition, when the polyether compound is diluted with a solvent, the amount of the solvent with respect to the polyether compound is preferably 5 times or more, and more preferably 7 times or more, on a mass basis.

[0255] As the non-reactive gas, rare gases such as helium, neon, argon, nitrogen, and the like can be mentioned, and nitrogen, helium are preferred, and nitrogen is more preferred from the economical aspect. 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.

[0256] In the case where fluorination of the polyether compound is carried out in a solvent, in order to reduce the oxygen content in the solvent, the solvent can be previously subjected to nitrogen substitution.

[0257] Further, in the case where the polyether compound is introduced into the solvent, the solvent can be previously subjected to nitrogen substitution, and further, the solvent can be subjected to fluorine substitution.

[0258] In the fluorination reaction, in either the batchwise or continuous mode, the amount of fluorine gas with which the fluorination of all of the hydrogen atoms that can be fluorinated in the polyether compound is carried out is preferably always set to an excess amount. 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 the fluorination of all of the hydrogen atoms that can be fluorinated.

[0259] In the case where fluorination of the polyether compound is carried out by introducing fluorine gas and the polyether compound into a solvent, when the introduction rate of the polyether compound 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 polyether compound by the number of hydrogen atoms in the polyether compound that can be replaced with fluorine atoms by fluorine gas. By setting the relationship of the introduction rates within the above numerical range, the yield of the fluorine-containing polyether compound can be improved.

[0260] In order to efficiently carry out the fluorination reaction of the polyether compound, it is preferred to introduce a C-H bond-containing compound other than the polyether compound into the solvent, or to irradiate ultraviolet rays to the solvent. These are preferably carried out in the later stage of the fluorination reaction. By this, the polyether compound present in the solvent can be efficiently fluorinated, and the yield of the fluorine-containing polyether compound can be improved.

[0261] As the C-H bond-containing compound, an aromatic hydrocarbon is preferred, and benzene, toluene, and the like can be mentioned. The introduction amount of the C-H bond-containing compound is preferably in the range of 0.1 to 10 mole%, more preferably in the range of 0.1 to 5 mole%, relative to the hydrogen atoms in the polyether compound.

[0262] The C-H bond-containing compound is preferably introduced into the solvent in which fluorine gas is present. Further, in the case where the C-H bond-containing compound is added, the reaction system is preferably pressurized. The reaction pressure at the time of pressurization is preferably in the range of 0.01 to 5 MPa (gauge pressure).

[0263] When the reaction system is irradiated with ultraviolet rays, the irradiation time is preferably 0.1 hour to 3 hours.

[0264] After the fluorination reaction, at least one selected from a solvent, water, and an aqueous solution for adjusting to an appropriate acidity can be added to the reaction solution, and after the liquid is separated, the organic phase is concentrated to obtain a fluorine-containing polyether compound. Alternatively, the reaction crude liquid obtained by concentrating the organic phase can be purified to obtain a fluorine-containing polyether compound.

[0265] When the polyether compound has the structure represented by the above formula (3) and has -OCF=CF2 groups at both terminals, a fluorine-containing polyether compound having the structure represented by the following general formula (4-1) is obtained by fluorination of the polyether compound.

[0266] CF3CF2O-X F -(D 1F -Y F -D 1F -X F n -OCF2CF3 (4-1)

[0267] When the polyether compound has the structure represented by the above formula (3) and has -O(CF2) m CF=CF2 groups at both terminals, a fluorine-containing polyether compound having the structure represented by the following general formula (4-2) is obtained by fluorination of the polyether compound.

[0268] CF3CF2(CF2) m O-X F -(D 1F -Y F -D 1F -X F n -O(CF2) m CF2CF3 (4-2)

[0269] In general formula (4-1) and general formula (4-2), X F each independently represents a divalent perfluorohydrocarbon group in which a divalent hydrocarbon group represented by X is perfluorinated.

[0270] In general formula (4-1) and general formula (4-2), Y F each independently represents a divalent perfluorohydrocarbon group in which a divalent hydrocarbon group represented by Y is perfluorinated.

[0271] In general formula (4-1) and general formula (4-2), D 1F represents a divalent linking group in which a divalent linking group represented by D is perfluorinated, and each represents *-OCF2CF2O-** or *-O(CF2)​​m CF2CF2O-**. * indicates a bonding portion to X F F CF2CF2O-**. * indicates a bonding portion to X m CF2CF2O-**. * indicates a bonding portion to X

[0272]

[0273] As the compound having the structure represented by General Formula (4-1) or General Formula (4-2), the following compounds can be given, but are not limited to these.

[0274]

[0275] Specific Example B of the method for producing a fluorine-containing polyether composition

[0276] In the case where the polyether composition contains a polyether compound having -OH groups at both terminals, a diacyloxy polyether compound can be produced by esterifying the -OH groups, and a fluorine-containing polyether composition containing a fluorine-containing polyether compound having ester groups at both terminals can be produced by fluorinating the diacyloxy polyether compound.

[0277] The above method is preferable in the case where the proportion of -OH groups is 90 mol% or more relative to 100 mol% of the total of terminal groups possessed by all of the polyether compounds contained in the polyether composition.

[0278] Further, a fluorine-containing polyether composition containing a fluorine-containing polyether compound having -OH groups at both terminals can be produced by reacting an alcohol with the above fluorine-containing polyether compound to produce a fluorine-containing diacylalkyloxycarbonyl polyether compound, and reducing the fluorine-containing diacylalkyloxycarbonyl polyether compound.

[0279] Note that in the case where the polyether compound has -OTs groups, -OTf groups, or -OMs groups at both terminals, -OH groups are formed at both terminals by a method known in the art using a cleavage reaction, and a fluorine-containing polyether composition containing a fluorine-containing polyether compound having ester groups at both terminals and a fluorine-containing polyether composition containing a fluorine-containing polyether compound having -OH groups at both terminals can be produced by the above method.

[0280] For the esterification of -OH groups, a method in which an acyl halide is allowed to act on a hydroxyl group is preferable from the viewpoint of reactivity, a method in which an acyl fluoride is allowed to act on a hydroxyl group is more preferable, and a method in which a polyether compound is allowed to act on an acyl fluoride represented by the following General Formula (5) is further preferable.

[0281] R 6 C(=O)F (5)​​

[0282] In General Formula (5), R 6 represents a monovalent hydrocarbon group having a carbon number of 2 to 20, which optionally contains an ether bond, and in which a hydrogen atom is optionally substituted with a fluorine atom.

[0283] R 6 The carbon number of the monovalent hydrocarbon group represented by R 6 The carbon number of the monovalent hydrocarbon group represented by R

[0284] R 6 In the case where a hydrogen atom in the monovalent hydrocarbon group represented by R

[0285] As specific examples of the acyl fluoride represented by General Formula (5), the following compounds can be given, but are not limited thereto.

[0286] • CF3CF2CF2OCF(CF3)C(=0)F

[0287] • CF3CF2CF2OCF(CF3)CF2OCF(CF3)C(=0)F

[0288] • CF3CF(CF3)C(=0)F

[0289] The esterification of the -OH group possessed by the polyether compound can be performed in a solvent or in a solventless state without using a solvent. In the case where the esterification of the -OH group possessed by the polyether compound is performed in a solvent, as the solvent, a fluorine-based organic solvent is preferred, and fluorinated alkanes, fluorinated aromatic compounds, and fluoroalkyl ethers, etc. can be given.

[0290] In the case where the acyl fluoride is allowed to react with the polyether compound, it is preferred to perform in the presence of a hydrogen fluoride (HF) replenisher. HF is generated by the reaction of the polyether compound with the acyl fluoride, and thus it is preferred to allow an HF trapping agent to exist in the reaction system. As the HF trapping agent, metal fluoride salts and trialkyl amines, etc. can be given. As the metal fluoride salt, sodium fluoride or potassium fluoride is preferred.

[0291] In the case where the HF trapping agent is not used, it is preferred to perform the reaction at a reaction temperature at which HF is vaporizable, and to allow the HF to be discharged to the outside of the reaction system along with a nitrogen gas stream. The amount of the HF trapping agent used is preferably 1 to 10 times the molar amount relative to the acyl fluoride.

[0292] The polyether compound having the structure represented by the above formula (3) and having -OH groups at both terminals is subjected to esterification to obtain a diacyloxy polyether compound having the structure represented by the following general formula (6).

[0293] R 6 C(=O)O-X-(D 2 -Y-D 2 -X) n -OC(=O)R 6 (6)

[0294] In the general formula (6), D 2 represents a divalent linking group, and each of them represents **-OCFHCF2O-*, *-O(CF2) m CFHCF2O-** or *-O-**. * represents a bonding portion to X, and ** represents a bonding portion to Y. In addition, -O(CF2) m CF=CF2, m is as described above, and thus the description thereof is omitted here.

[0295] In the general formula (6), X, Y, R 6 and n are as described above, and thus the description thereof is omitted here.

[0296] The method for fluorinating the diacyloxy polyether compound is not particularly limited, and can be performed by the above-described method, and thus the description thereof is omitted here.

[0297] The diacyloxy polyether compound is represented by the above general formula (6), and the diacyloxy polyether compound is subjected to fluorination to obtain a fluorine-containing polyether compound having the structure represented by the following general formula (7).

[0298] R 6F C(=O)O-X F -(D 2F -Y F -D 2F -X F ) n -OC(=O)R 6F (7)

[0299] In the general formula (7), R 6F each independently represents R 6 a monovalent perfluorohydrocarbon group having a carbon number of 2 to 20 in which a monovalent hydrocarbon group represented by R

[0300] In the general formula (7), D 2F represents a divalent linking group, and each of them represents **-OCF2CF2O-*, *-O(CF2) 2 CFHCF2O-** or *-O-**. * represents a bonding portion to X, and ** represents a bonding portion to Y. In addition, -O(CF2) mCF2CF2O-** or *-O-**. * indicates a bonding portion to X F ** indicates a bonding portion to Y F In addition, -O(CF2) m CF=CF2, m is as described above, and thus the description is omitted here.

[0301] In General Formula (7), X F , Y F , and n are as described above, and thus the description is omitted here.

[0302] As the compound having the structure represented by General Formula (7), the following compounds can be given, but are not limited to these.

[0303]

[0304] The fluorine-containing diacyloxy polyether compound produced by fluorinating the diacyloxy polyether compound is then reacted with an alcohol to produce a fluorine-containing diacylalkyloxycarbonyl polyether compound. The alcohol is not particularly limited, and for example, methanol, ethanol, isopropanol, and the like can be given.

[0305] As for the amount of the alcohol used with respect to the fluorine-containing diacyloxy polyether compound, with respect to 1 mol of the fluorine-containing diacyloxy polyether compound, the alcohol is preferably 2 mol to 10 mol, more preferably 2.1 mol to 5 mol, and further preferably 2.2 mol to 4 mol.

[0306] The reaction of the fluorine-containing diacyloxy polyether compound with the alcohol can be performed in a solvent or in a solventless state without using a solvent.

[0307] In the case where the reaction of the fluorine-containing diacyloxy polyether compound with the alcohol is performed in a solvent, as the solvent, a fluorine-based organic solvent is preferred, and fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, and the like can be given.

[0308] From the viewpoint of the yield of the fluorine-containing diacylalkyloxycarbonyl polyether compound, the reaction temperature of the fluorine-containing diacyloxy polyether compound with the alcohol is preferably 0°C to 60°C, and more preferably 0°C to 40°C.

[0309] From the viewpoint of the yield of the fluorine-containing diacylalkyloxycarbonyl polyether compound, the reaction time of the fluorine-containing diacyloxy polyether compound with the alcohol is preferably 0.5 hours to 48 hours, and more preferably 0.5 hours to 24 hours.

[0310] The fluorine-containing diacylalkyloxycarbonyl polyether compound having the structure represented by General Formula (8) is obtained by reacting the fluorine-containing polyether compound having the structure represented by General Formula (7) described above with an alcohol.

[0311] R 7 OC(=O)-XF-1 -(D 2F -Y F -D 2F -X F ) n-1 -D 2F -Y F -D 2F -X F-1 -C(=O)OR 7 (8)

[0312] In General Formula (8), X F-1 each independently represents a bivalent perfluorohydrocarbon group having a carbon number of 1 to 19 obtained by subtracting one carbon number from the bivalent perfluorohydrocarbon group represented by X F It should be noted that the above-mentioned reduction of the carbon number is caused by the reaction of the bivalent perfluorohydrocarbon group represented by X F with an alcohol to form a -C(=O)OR 7 group.

[0313] In General Formula (8), R 7 each independently represents a monovalent hydrocarbon group having a carbon number of 1 to 20, which optionally contains an ether bond, and in which a hydrogen atom is optionally replaced with a fluorine atom. It should be noted that R 7 is a group derived from an alcohol which reacts with a fluorine-containing diacyloxy polyether compound.

[0314] In General Formula (8), X F , Y F , D 2F and n are as described above, and thus the description thereof is omitted here.

[0315] By reducing the fluorine-containing diacylalkyloxycarbonyl polyether compound, it is possible to produce a fluorine-containing polyether compound having -OH groups at both terminal ends.

[0316] The reducing agent is not particularly limited, and examples thereof include sodium borohydride (NaBH4), sodium cyanoborohydride (NaBH3CN), lithium borohydride (LiBH4), lithium aluminum hydride (LAH) and diisobutylaluminum hydride (DIBAL), and the like.

[0317] The amount of the reducing agent used with respect to the fluorine-containing diacylalkyloxycarbonyl polyether compound is preferably 0.25 mol to 10 mol, more preferably 0.5 mol to 8 mol, and further preferably 0.6 mol to 5 mol, with respect to 1 mol of the fluorine-containing diacylalkyloxycarbonyl polyether compound.

[0318] The reaction temperature of the fluorine-containing diacylalkyloxycarbonyl polyether compound with the reducing agent is preferably -20°C to 60°C, and more preferably 0°C to 40°C from the viewpoint of the yield of the fluorine-containing polyether compound.

[0319] The reaction time of the fluorine-containing diacylalkoxycarbonyl polyether compound with the reducing agent is preferably 0.5 hours to 48 hours, more preferably 1 hour to 24 hours, from the viewpoint of the yield of the fluorine-containing polyether compound.

[0320] The fluorine-containing polyether compound having the structure represented by the general formula (9) is obtained by reducing the fluorine-containing diacylalkoxycarbonyl polyether compound having the structure represented by the general formula (8).

[0321] HOCH2-X F-1 -(D 2F -Y F -D 2F -X F ) n-1 -D 2F -Y F -D 2F -X F1 -CH2OH (9)

[0322] In the general formula (9), X F , X F-1 , Y F , D 2F and n are as described above, and thus the description thereof is omitted here.

[0323] As the compound having the structure represented by the general formula (9), the following compounds can be given, but are not limited thereto.

[0324]

[0325] Specific example C of the method for producing a fluorine-containing polyether composition

[0326] In the case where the polyether composition contains a polyether compound having a -C(=O)F group, -OC(=O)F group, -OTs group, -OTf group or -OMs group at both terminals, a fluorine-containing polyether composition containing a fluorine-containing polyether compound having a -C(=O)F group, -OC(=O)F group, -OTs group, -OTf group or -OMs group at both terminals can be produced by fluorinating the polyether compound.

[0327] The above method is preferred in the case where the proportion of the -C(=O)F group, -OC(=O)F group, -OTs group, -OTf group or -OMs group is 90 mol% or more, relative to the total of 100 mol% of the terminal groups possessed by the entire polyether compound contained in the polyether composition.

[0328] In addition, a fluorine-containing diacylalkoxycarbonyl polyether compound is produced by reacting an alcohol with the above fluorine-containing polyether compound, and a fluorine-containing polyether compound having -OH groups at both terminals can be produced by reducing the fluorine-containing diacylalkoxycarbonyl polyether compound.

[0329] The polyether compound has the structure represented by the above formula (3), and in the case where -C(=O)F group, -OC(=O)F group, -OTs group, -OTf group or -OMs group is present at both terminals, a fluorine-containing polyether compound having the structure represented by the following general formula (10-1) or the following general formula (10-2) is obtained by fluorination of the polyether compound.

[0330] FC(=O)-X F -(D 3 -Y F -D 3 -X F n -C(=O)F (10-1)

[0331] E-X F -(D 3 -Y F -D 3 -X F n -E (10-2)

[0332] In the general formula (10-1), D 3 represents a divalent linking group, and each represents **-OCF2-* or *-O-**. * represents a bonding portion to X F , and ** represents a bonding portion to Y F .

[0333] In the general formula (10-2), D 3 represents a divalent linking group, and each represents *-OCF2-** or **-O-*. * represents a bonding portion to X F , and ** represents a bonding portion to Y F .

[0334] In the general formula (10-1) and the general formula (10-2), E represents -OC(=O)F group, -OTs group, -OTf group or -OMs group.

[0335] In the general formula (10-1) and the general formula (10-2), X F , Y F and n are as described above, and thus the description thereof is omitted here.

[0336] As the fluorine-containing polyether compound having the structure represented by the above general formula (10-1) or the general formula (10-2), the following compounds can be given, but are not limited thereto.​​

[0337]

[0338] There are no particular limitations on the method for fluorinating polyether compounds; it can be carried out using the methods described above, so the details are omitted here.

[0339] By reacting an alcohol with a fluorinated polyether compound having the structure shown in the above general formula (10-1), a fluorinated diacylalkoxycarbonyl polyether compound having the structure shown in the following general formula (11-1) is obtained.

[0340] R 7 OC(=O)-X F -(D 3 -Y F -D 3 -X F ) n -C(=O)OR 7 (11-1)

[0341] By reacting an alcohol with a fluorinated polyether compound having the structure shown in the above general formula (10-2), a fluorinated diacylalkoxycarbonyl polyether compound having the structure shown in the following general formula (11-2) is obtained.

[0342] R 7 OC(=O)-X F-1 -(D 3 -Y F -D 3 -X F ) n-1 -D 3 -Y F -D 3 -X F-1 -C(=O)OR 7 (11-2)

[0343] In general formulas (11-1) and (11-2), X F X F-1 Y F D 3 R 7 As mentioned above, n is omitted here.

[0344] Furthermore, the reaction between fluorinated polyether compounds and alcohols is not particularly limited and can be carried out by the above method, so it is omitted here.

[0345] By reducing a fluorinated diacylalkoxycarbonyl polyether compound having the structure shown in general formula (11-1), a fluorinated polyether compound having the structure shown in general formula (12-1) is obtained.

[0346] HOCH2-X F -(D 3 -Y F -D 3 -X F ) n -CH2OH(12-1)

[0347] The fluorine-containing polyether compound having the structure represented by the following general formula (12-2) is obtained by reducing the fluorine-containing diacylalkoxycarbonyl polyether compound having the structure represented by the general formula (11-2).

[0348] HOCH2-X F-1 -(D 3 -Y F -D 3 -X F ) n-1 -D 3 -Y F -D 3 -X F-1 -CH2OH(12-2)

[0349] In the general formula (12-1) and the general formula (12-2), X F , X F-1 , Y F , D 3 and n are as described above, and thus the description thereof is omitted here.

[0350] As the fluorine-containing polyether compound having the structure represented by the general formula (12-1) or the general formula (12-2), the following compounds can be given, but are not limited thereto.

[0351]

[0352] The reduction of the fluorine-containing diacylalkoxycarbonyl polyether compound is not particularly limited, and can be performed by the above-described method, and thus the description thereof is omitted here.

[0353] From the viewpoint of heat resistance, the content ratio of the fluorine-containing polyether compound in the fluorine-containing polyether composition is preferably 60% by mass to 100% by mass, and more preferably 80% by mass to 100% by mass.

[0354] The fluorine-containing polyether composition can contain one kind of fluorine-containing polyether compound, or two or more kinds thereof.

[0355] Example

[0356] Hereinafter, the above-described embodiments will be described more specifically by synthesis examples, but the above-described embodiments are not limited to the synthesis examples. Synthesis Examples 1-1 to 1-5, Synthesis Examples 2-1 to 2-2, and Synthesis Examples 3-1 to 3-4 are examples, and Synthesis Example 4-1 and Synthesis Examples 5-1 to 5-2 are comparative examples.

[0357] [evaluation method]

[0358] (NMR analysis)

[0359] NMR analysis was performed under the following conditions.

[0360] 1 The reference substance for H-NMR (300.4 MHz) was nitrobenzene at 7.5 ppm.

[0361] 19 The reference substance for F-NMR (282.7 MHz) was perfluorobenzene at -162.5 ppm.

[0362] The solvent for NMR was CFE-419 (ClCF2CFClCF2OCF2CF2Cl).

[0363] (GPC analysis)

[0364] The number average molecular weight (Mn) and the mass average molecular weight (Mw) were measured by GPC. The measurement based on GPC was performed by the above-described method.

[0365] The abbreviations in the examples mean the following.

[0366] (HFPO)2: CF3CF2CF2-O-CF(CF3)C(=O)F

[0367] PTFE: polytetrafluoroethylene

[0368] AC-2000: fluorine-based solvent, manufactured by AGC Inc., ASAHIKLIN (registered trademark) AC-2000

[0369] (Synthesis Example 1-1)

[0370] In a three-necked flask equipped with a stirring blade, a thermometer, and a reflux condenser, 31 g of ethylene glycol (0.5 mol, pKa: 14.22) represented by the following formula (1-1) and 138 g of an alkaline catalyst (K2CO3) were introduced, and the three-necked flask was heated to 40°C, and the mixture was stirred for 10 minutes.

[0371] Next, 344 g of divinyl ether represented by the following formula (2-1) (1.0 mol) was introduced into the three-necked flask at a rate of 1 mol / hour relative to 1 mol of ethylene glycol. After the introduction of the divinyl ether, the internal temperature of the three-necked flask was heated to 70°C, and the mixture was stirred and reacted to obtain a first polymerization composition.

[0372] HOCH2CH2OH (1-1)

[0373] CF2=CFOCF2CF2CF2OCF=CF2 (2-1)

[0374] Next, 344 g of divinyl ether represented by the following formula (2-1) (1.0 mol) was introduced into the three-necked flask at a rate of 1 mol / hour relative to 1 mol of ethylene glycol. After the introduction of the divinyl ether, the internal temperature of the three-necked flask was heated to 70°C, and the mixture was stirred and reacted to obtain a first polymerization composition.

[0375] In the first polymerization reaction, the time from when the internal temperature of the three-necked flask reached 70°C to when the ethylene glycol used in the second polymerization reaction was introduced (the time of the first polymerization reaction) was 3 hours.

[0376] In the second polymerization reaction, the time from when the ethylene glycol was introduced and the internal temperature of the three-necked flask reached 70°C to when the internal temperature of the three-necked flask reached 25°C (the time of the second polymerization reaction) was 5 hours.

[0377] After the second polymerization reaction, hydrochloric acid was added to the second polymerization composition, and the mixture was stirred 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 308 g of the organic phase (polyether composition A) was recovered.

[0378] By 1 H-NMR method and 19 F-NMR method, it was confirmed that the polyether composition A contained a polyether compound a represented by the following formula (3-1), a polyether compound b represented by the following formula (3-2), and a polyether compound c represented by the following formula (3-3). In the formulas (3-1) to (3-3), the average value of n was 8.

[0379] The yield of the polyether compound was 76%.

[0380] In addition, by 1 H-NMR method and 19 F-NMR method, it was confirmed that the polyether compound contained in the polyether composition A had a ratio of terminal groups of 94 mol% of -OH and 6 mol% of -OCF=CF2 relative to the total of 100 mol% of -OH and -OCF=CF2.

[0381] In addition, the Mw / Mn of the polyether compound contained in the polyether composition A was 1.55.

[0382] NMR spectrum of the polyether composition A

[0383] 1 H-NMR δ (ppm): 2.8 ppm (1.88H), 3.7 ppm (3.76H), 3.8 ppm (32.24H), 3.9 ppm (3.76H), 6.0 ppm (16.12H)

[0384] 19 F-NMR δ (ppm): -84 ppm (32.24F), -87 ppm (32.12F), -114 ppm (0.06F), -122 ppm (0.06F), -128 ppm (16.12F), -135 ppm (0.06F), -145 ppm (16.06F)

[0385] The following polyether compound a represented by Chemical Formula (3-1) was described.

[0386]

[0387] The following polyether compound b represented by Chemical Formula (3-2) was described.

[0388]

[0389] The following polyether compound c represented by Chemical Formula (3-3) was described.

[0390]

[0391] (Synthesis Example 1-2)

[0392] In a three-necked flask equipped with a stirring blade, a thermometer, and a reflux condenser, which was prepared separately, 280 g of the polyether composition A obtained in Synthesis Example 1-1, 35.5 g of sodium fluoride (HF trapping agent), and 280 g of (HFPO)2were introduced.

[0393] The internal temperature of the three-necked flask was heated to 50°C, and the contents were stirred and mixed for 20 hours. After the stirring and mixing, the internal temperature of the three-necked flask was cooled to 25°C, and the HF replenisher was filtered from the contents using a PTFE membrane filter.

[0394] The low-boiling components were distilled away from the filtered contents under vacuum at 60°C to obtain a crude product A-1 in an oil form.

[0395] By the H-NMR method and the F-NMR method 1 H-NMR method and the F-NMR method 19The F-NMR method confirmed that the crude product A-1 contained the diacyloxy polyether compound a represented by the following formula (6-1), the acyloxy polyether compound a represented by the following formula (6-2), and the polyether compound b represented by the above formula (3-2). In the formula (6-1), the formula (6-2), and the formula (3-2), the average value of n was 8.

[0396] In addition, by 1 The H-NMR method and 19 The F-NMR method confirmed the proportion of the terminal groups possessed by the compound contained in the crude product A-1. As a result, with respect to the total of 100 mol% of -OC(=O)CF(CF3)-OC3F7 and -OCF=CF2, the proportion of -OC(=O)CF(CF3)-OC3F7 was 94 mol%, and the proportion of -OCF=CF2 was 6 mol%.

[0397] In addition, the Mw / Mn of the compound contained in the crude product A-1 was 1.52.

[0398] The diacyloxy polyether compound a represented by the following formula (6-1) is described below.

[0399]

[0400] The acyloxy polyether compound a represented by the following formula (6-2) is described below.

[0401]

[0402] (Synthesis Example 1-3)

[0403] Into a 3000 mL nickel autoclave, 2800 g of CFE-419 was introduced and stirred, and the internal temperature of the flask was cooled to 20°C. Note that a condenser that maintains the internal temperature of the flask at 20°C was provided at the gas outlet of the autoclave.

[0404] Next, nitrogen gas was blown into the CFE-419 at a rate of 155 L / hour for 1 hour (bubbling).

[0405] After the bubbling of the nitrogen gas, 20% by volume of fluorine gas diluted with nitrogen gas (hereinafter referred to as 20% by volume fluorine gas) was bubbled into the CFE-419 at a rate of 155 L / hour, and a solution obtained by diluting 315 g of the crude product A-1 obtained in Synthesis Example 1-2 with CFE-419 was introduced for 6 hours.

[0406] After the introduction of the solution, a solution obtained by diluting benzene with CFE-419 (hereinafter referred to as CFE-419 solution) was intermittently introduced. The concentration of benzene in the CFE-419 solution was set to 0.1% by mass, and the amount of benzene was set to 0.3 g.

[0407] After the introduction of the CFE-419 solution of benzene, 20 vol% fluorine gas was bubbled for 1 hour, and then nitrogen gas was blown for 1 hour to sufficiently replace the autoclave.

[0408] The recovered material from the autoclave was concentrated to obtain 378 g of a crude product A-2 (fluorine-containing polyether composition) as an oil.

[0409] The crude product A-2 was analyzed by 1 H-NMR method and 19 F-NMR method, and it was confirmed that the crude product A-2 contained a fluorine-containing polyether compound a represented by the following formula (7-1), a fluorine-containing polyether compound b represented by the following formula (7-2), and a fluorine-containing polyether compound c represented by the following formula (7-3). In the formulas (7-1) to (7-3), the average value of n was 8.

[0410] In addition, the proportion of the terminal groups possessed by the compounds contained in the crude product A-2 was determined by 1 H-NMR method and 19 F-NMR method, and as a result, with respect to the total of 100 mol% of -OC(=O)CF(CF3)-OC3F7 and -OCF2CF3, the proportion of -OC(=O)CF(CF3)-OC3F7 was 94 mol%, and the proportion of -OCF2CF3 was 6 mol%.

[0411] In addition, the Mw / Mn of the compounds contained in the crude product A-2 was 1.62.

[0412] The fluorine-containing polyether compound a represented by the following formula (7-1) is described below.

[0413]

[0414] The fluorine-containing polyether compound b represented by the following formula (7-2) is described below.

[0415]

[0416] The fluorine-containing polyether compound c represented by the following formula (7-3) is described below.

[0417]

[0418] (Synthetic Example 1-4)

[0419] In a 500 mL flask, 370 g of the crude product A-2 obtained in Synthetic Example 1-3, 32 g of sodium fluoride (HF trapping agent), and 24 g of methanol were introduced, and the inside of the flask was cooled to 0°C, and the mixture was stirred for 2 hours.

[0420] ​After the stirring mixture, the internal temperature of the flask was heated to 25°C, and the contents were filtered using a PTFE membrane filter.

[0421] The low boiling components were distilled off from the filtered contents under vacuum at 60°C to obtain 321 g of a crude product A-3 as an oil.

[0422] The crude product A-3 was analyzed by 1 H-NMR method and 19 F-NMR method, and it was confirmed that the crude product A-3 contained a fluorine-containing diacylalkoxycarbonyl polyether compound a represented by the following formula (8-1), a fluorine-containing acylalkoxycarbonyl polyether compound a represented by the following formula (8-2), and the above-mentioned fluorine-containing polyether compound b represented by the following formula (7-2). In the formula (8-1), the formula (8-2), and the formula (7-2), the average value of n was 8.

[0423] In addition, the crude product A-3 was analyzed by 1 H-NMR method and 19 F-NMR method, and the proportion of the terminal groups possessed by the compounds contained in the crude product A-3 was determined. As a result, with respect to the total of -C(=O)OCH3 and -OCF2CF3, the proportion of -C(=O)OCH3 was 94 mol%, and the proportion of -O-CF2CF3 was 6 mol%.

[0424] In addition, the Mw / Mn of the compounds contained in the crude product A-3 was 1.56.

[0425] The fluorine-containing diacylalkoxycarbonyl polyether compound a represented by the following formula (8-1) is described below.

[0426]

[0427] The fluorine-containing acylalkoxycarbonyl polyether compound a represented by the following formula (8-2) is described below.

[0428]

[0429] (Synthesis Example 1-5)

[0430] In a 1000 mL three-necked flask, 5.7 g of NaBH4 powder (reducing agent) was introduced. Subsequently, 640 g of AC-2000 and 70 g of ethanol were introduced into the three-necked flask, and the internal temperature of the three-necked flask was cooled to 0°C, and then stirring mixture was performed.

[0431] 320 g of the crude product A-3 obtained in Synthesis Example 1-4 was introduced into the three-necked flask, and stirring mixture was performed for 2 hours while maintaining the internal temperature of the three-necked flask at 0°C.

[0432] After the mixture was stirred, hydrochloric acid was introduced into the flask until the contents of the flask became acidic, 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 the organic phase was recovered. The organic phase was concentrated, and low-boiling components were distilled off, and a crude product A-4 (fluorine-containing polyether composition) was obtained as an oil.

[0433] By 1 H-NMR method and 19 F-NMR method, it was confirmed that the crude product A-4 contained a fluorine-containing polyether compound d represented by the following formula (9-1), a fluorine-containing divinyl polyether compound e represented by the following formula (9-2), and a fluorine-containing polyether compound b represented by the following formula (7-2). In the formula (9-1), the formula (9-2), and the formula (7-2), the average value of n was 8.

[0434] In addition, by 1 H-NMR method and 19 F-NMR method, the proportion of the terminal groups possessed by the compounds contained in the crude product A-4 was determined, and as a result, with respect to the total of -OH and -OCF2CF3, the proportion of -OH was 94 mol%, and the proportion of -O-CF2CF3 was 6 mol%.

[0435] In addition, the Mw / Mn of the compounds contained in the crude product A-4 was 1.50.

[0436] NMR spectrum of the crude product A-4

[0437] 1 H-NMR δ (ppm): 4.0 ppm (3.76H)

[0438] 19 F-NMR δ (ppm): -76 ppm (3.76F), -86 ppm (32F), -89 ppm (0.18F), -92 ppm (95.76F), -93 ppm (0.12F), -128 ppm (16F)

[0439] The fluorine-containing polyether compound d represented by the following formula (9-1) is described below.

[0440]

[0441] The fluorine-containing polyether compound e represented by the following formula (9-2) is described below.

[0442]

[0443] The crude product A-4 was purified by column chromatography, and the fluorine-containing polyether compound d was obtained. The Mw / Mn of the fluorine-containing polyether compound d was 1.48. In addition, by 1H-NMR method and 19 F-NMR method, and the NMR spectrum of the fluorine-containing polyether compound d was obtained. As a result, it was confirmed that the average value of n was 8 in the compound represented by the above formula (9-1).

[0444] NMR spectrum of the fluorine-containing polyether compound d

[0445] 1 H-NMR δ (ppm): 4.0 ppm (4H)

[0446] 19 F-NMR δ (ppm): -76 ppm (4F), -86 ppm (32F), -92 ppm (96F), -128 ppm (16F)

[0447] (Synthesis Example 2-1)

[0448] In a three-necked flask equipped with a stirring blade, a thermometer, and a reflux condenser, 62 g of ethylene glycol (1.0 mol, pKa: 14.22) and 138 g of potassium carbonate (base catalyst) were introduced, and the three-necked flask was heated to 40°C, and the mixture was stirred for 10 minutes.

[0449] Next, 172 g of the divinyl ether represented by the above formula (2-1) (0.5 mol) was introduced into the three-necked flask at a rate of 0.25 times mol / hour with respect to 1 mol of ethylene glycol. After the introduction of the divinyl ether, the internal temperature of the flask was heated to 70°C, and the mixture was stirred to perform a first polymerization reaction, and a first polymerization composition was obtained.

[0450] 172 g of the divinyl ether represented by the above formula (2-1) (0.5 mol) was introduced into the first polymerization composition at a rate of 20 times mol / hour with respect to 1 mol of the amount of ethylene glycol used in the first polymerization reaction, and the internal temperature of the flask was maintained at 70°C, and the mixture was stirred to perform a second polymerization reaction. The internal temperature of the flask was cooled to 25°C, and a second polymerization composition was obtained.

[0451] Note that the time of the first polymerization reaction was 3 hours, and the time of the second polymerization reaction was 5 hours.

[0452] After the second polymerization reaction, hydrochloric acid was added to the second polymerization composition, and the mixture was stirred 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 333 g of the organic phase (polyether composition B) was recovered.

[0453] By 1 H-NMR method and 19The F-NMR method confirmed that the polyether composition B contained the polyether compound a represented by the above formula (3-1), the polyether compound b represented by the above formula (3-2), and the polyether compound c represented by the above formula (3-3), and the average value of n in the formulas (3-1) to (3-3) was 8.

[0454] The yield of the polyether compound was 82%.

[0455] In addition, by 1 The H-NMR method and 19 The F-NMR method confirmed that the polyether compound contained in the polyether composition B had a ratio of terminal groups of 2 mol% of -OH and 98 mol% of -OCH=CH2 with respect to the total of 100 mol% of -OH and -OCH=CH2.

[0456] In addition, the Mw / Mn of the compound contained in the polyether composition B was 1.55.

[0457] NMR spectrum of the polyether composition B

[0458] 1 H-NMR δ (ppm): 2.8 ppm (0.02H), 3.7 ppm (0.04H), 3.87 ppm (32H), 3.9 ppm (0.04H), 6.0 ppm (16.02H)

[0459] 19 F-NMR δ (ppm): -84 ppm (36F), -87 ppm (32.04F), -114 ppm (1.96F), -122 ppm (1.96F), -128 ppm (17.96F), -135 ppm (1.96F), -145 ppm (8.16F)

[0460] (Synthesis Example 2-2)

[0461] Into a 3000 mL nickel autoclave, 2800 g of CFE-419 was introduced, and stirring was performed, and the internal temperature of the flask was cooled to 20°C. Note that a condenser maintained at 20°C was provided at the gas outlet of the autoclave.

[0462] Next, nitrogen was bubbled into the CFE-419 at a rate of 178 L / hour for 1 hour.

[0463] After the nitrogen bubbling, 20% by volume fluorine gas was bubbled into the CFE-419 at a rate of 178 L / hour, and a solution in which 330 g of the polyether composition B obtained in Synthesis Example 1-2 was diluted with CFE-419 was introduced for 6 hours.

[0464] After the introduction of the solution, the CFE-419 solution was intermittently introduced. After the introduction of the CFE-419 solution in benzene, 20 vol% fluorine gas was bubbled for 1 hour at an introduction rate of 178 L / hour, and finally nitrogen gas was blown in for 1 hour to sufficiently replace the inside of the reactor.

[0465] The recovered material from the autoclave was concentrated, and as a result, 404 g of a crude product B-1 (fluorine-containing polyether composition) in the form of an oil was obtained.

[0466] By 1 H-NMR method and 19 The fluorine-containing polyether composition was confirmed to contain a fluorine-containing polyether compound f represented by the following formula (4-1), a fluorine-containing polyether compound g represented by the following formula (4-2), and a fluorine-containing polyether compound h represented by the following formula (4-3) by F-NMR method, and the average value of n in the formulas (4-1) to (4-3) was 8.

[0467] In addition, the Mw / Mn of the compound contained in the fluorine-containing polyether composition was 1.52.

[0468] The fluorine-containing polyether compound f represented by the following formula (4-1) is described below.

[0469]

[0470] The fluorine-containing polyether compound g represented by the following formula (4-2) is described below.

[0471]

[0472] The fluorine-containing polyether compound h represented by the following formula (4-3) is described below.

[0473]

[0474] NMR spectrum of the fluorine-containing polyether composition

[0475] 19 F-NMR δ (ppm): -86 ppm (36F), -90 ppm (6F), -92 ppm (96F), -93 ppm (4F), -128 ppm (18F)

[0476] (Synthesis Example 3-1)

[0477] Into a 500 mL autoclave made of Hastelloy, 83 g of cesium fluoride (base catalyst) was introduced.

[0478] Next, 100 g of a difluorinated acyloxy compound represented by the following formula (2-2) (0.55 mol) was introduced into the autoclave, the inside of the autoclave was made into an N2 atmosphere, and the inside temperature was made -196°C, and vacuum degassing was performed.

[0479] FC(=O)OCH2CH2CH2CH2OC(=O)F (2-2)

[0480] After degassing, 81 g of the difluorinated acyl compound represented by the following formula (1-2) (0.27 mol) was introduced into the autoclave at a rate of 0.17 times mol / hour per 1 mol of the acyloxy difluorinated compound. After the introduction of the difluorinated acyl compound, the internal temperature of the autoclave was heated to 80°C, and the mixture was stirred and subjected to the first polymerization reaction.

[0481] FC(=O)CF2CF2CF2CF2C(=O)F (1-2)

[0482] Next, 81 g of the difluorinated acyl compound represented by the above formula (1-2) (0.27 mol) was introduced into the autoclave at a rate of 5 times mol / hour per 1 mol of the acyloxy difluorinated compound used in the first polymerization reaction, the internal temperature of the autoclave was heated to 120°C, and the mixture was stirred and subjected to the second polymerization. The internal temperature of the flask was cooled to 25°C, and a crude product C-1 was obtained.

[0483] Note that the time of the first polymerization reaction was 3 hours, and the time of the second polymerization reaction was 8 hours.

[0484] After the second polymerization, the alkali catalyst was filtered from the crude product C-1 using a PTFE membrane filter.

[0485] Into the crude product C-1 from which cesium fluoride was filtered, 160 g of cesium fluoride was introduced, and the internal temperature of the autoclave was heated to 180°C, and the mixture was stirred and mixed for 30 hours.

[0486] After the stirring and mixing, nitrogen was blown into the autoclave to purge the by-produced HF and the like, and the by-products such as HF in the autoclave were sufficiently replaced with nitrogen (nitrogen purge).

[0487] The recovered material from the autoclave was filtered using a PTFE membrane filter, and 160 g of a viscous polyether composition C was obtained.

[0488] By 1 H-NMR method and 19 F-NMR method, it was confirmed that the polyether composition C contained a polyether compound d represented by the following formula (3-4), a polyether compound e represented by formula (3-5), and a polyether compound f represented by formula (3-6). In formulas (3-4) to (3-6), the average value of n was 8.

[0489] The yield of the polyether compound was 83%.

[0490] In addition, by 1 H-NMR method and 19The F-NMR method was used to determine the proportion of terminal groups possessed by the polyether compound contained in the polyether composition C, and the results were that the proportion of -OC(=O)F was 4 mol% and the proportion of -C(=O)F was 96 mol% relative to the total of 100 mol% of -OC(=O)F and -C(=O)F.

[0491] In addition, the Mw / Mn of the polyether compound contained in the polyether composition C was 1.58.

[0492] NMR spectrum of the polyether composition C

[0493] 1 H-NMR δ (ppm): 1.6 ppm (0.08H), 1.8 ppm (32.08H), 3.4 ppm (32.08H), 4.2 ppm (0.08H)

[0494] 19 F-NMR δ (ppm): 14 ppm (0.96F), -11 ppm (0.04F), -86 ppm (16.32F), -118 ppm (3.84F), -121 ppm (31.92F), -122 ppm (33.92F), -126 ppm (33.92F)

[0495] The polyether compound d represented by Chemical Formula (3-4) is described below.

[0496]

[0497] The polyether compound e represented by Chemical Formula (3-5) is described below.

[0498]

[0499] The polyether compound f represented by Chemical Formula (3-6) is described below.

[0500]

[0501] (Synthesis Example 3-2)

[0502] Into a 500 mL autoclave made of nickel, 300 g of CFE-419 was introduced, and stirring was performed, and the internal temperature of the autoclave was cooled to 20°C. Note that a condenser maintained at 20°C was provided at the gas outlet of the autoclave.

[0503] Next, nitrogen gas was bubbled into the CFE-419 at a rate of 63 L / hour for 1 hour.

[0504] After the bubbling of the nitrogen gas, 20% by volume of fluorine gas was bubbled into the CFE-419 at a rate of 63 L / hour.

[0505] After the bubbling of fluorine gas, a solution of 120 g of the polyether composition C obtained in Synthesis Example 3-1 diluted with CFE-419 was introduced into CFE-419 over 1 hour, and 20 vol% fluorine gas was bubbled into CFE-419 at a rate of 63 L / hour.

[0506] After the introduction of the solution, the CFE-419 solution was intermittently introduced.

[0507] After the introduction of the CFE-419 solution of benzene, 20 vol% fluorine gas was bubbled at a rate of 63 L / hour over 1 hour, and finally nitrogen gas was blown in over 1 hour to sufficiently replace the autoclave.

[0508] The recovered material from the autoclave was concentrated, and as a result, 151 g of crude product C-2 (fluorine-containing polyether composition) was obtained.

[0509] By 1 H-NMR method and 19 F-NMR method, it was confirmed that the crude product C-2 contained a fluorine-containing polyether compound j represented by Chemical Formula (10-1), a fluorine-containing polyether compound k represented by Chemical Formula (10-2), and a fluorine-containing polyether compound 1 represented by Chemical Formula (10-3), and in Chemical Formulas (10-1) to (10-3), the average value of n was 8.

[0510] In addition, by 1 H-NMR method and 19 F-NMR method, the proportion of terminal groups possessed by the fluorine-containing polyether compound contained in the crude product C-2 was determined, and as a result, with respect to 100 mol% of the total of -OC(=O)F and -C(=O)F, the proportion of -OC(=O)F was 4 mol%, and the proportion of -C(=O)F was 96 mol%.

[0511] In addition, the Mw / Mn of the fluorine-containing polyether compound contained in the crude product C-2 was 1.60.

[0512] The fluorine-containing polyether compound j represented by Chemical Formula (10-1) is described below.

[0513]

[0514] The fluorine-containing polyether compound k represented by Chemical Formula (10-2) is described below.

[0515]

[0516] The fluorine-containing polyether compound 1 represented by Chemical Formula (10-3) is described below.

[0517]

[0518] (Synthetic Example 3-3)

[0519] Into a 500 mL flask, 150 g of the above-mentioned crude product C-2, 14 g of sodium fluoride (HF trapping agent), 11 g of methanol, and 150 g of AC-2000 were introduced, and the inside of the flask was cooled to 0°C, and then stirred for 2 hours.

[0520] After the stirring and mixing, the inside of the flask was warmed to 25°C, and the contents were filtered using a PTFE membrane filter to remove the HF supplement.

[0521] The filtered contents were concentrated under vacuum at 60°C to obtain 144 g of a crude product C-3.

[0522] The crude product C-3 was analyzed by 1 H-NMR method and 19 F-NMR method, and it was confirmed that the crude product C-3 contained a fluorine-containing diacylalkoxycarbonyl polyether compound d represented by the following formula (11-1), a fluorine-containing diacylalkoxycarbonyl polyether compound e represented by the following formula (11-2), and a fluorine-containing diacylalkoxycarbonyl polyether compound f represented by the following formula (11-3), and the average value of n in the formulas (11-1) to (11-3) was 8.

[0523] The fluorine-containing diacylalkoxycarbonyl polyether compound d represented by the following formula (11-1) is described below.

[0524]

[0525] The fluorine-containing diacylalkoxycarbonyl polyether compound e represented by the following formula (11-2) is described below.

[0526]

[0527] The fluorine-containing diacylalkoxycarbonyl polyether compound f represented by the following formula (11-3) is described below.

[0528]

[0529] (Synthetic Example 3-4)

[0530] Into a 1000 mL three-necked flask, 2.3 g of NaBH4 powder (reducing agent) was introduced. Subsequently, 280 g of AC-2000 and 28 g of ethanol were introduced into the three-necked flask, and the inside of the three-necked flask was cooled to 0°C, and then stirred and mixed.

[0531] Into the three-necked flask, 140 g of the crude product C-3 obtained in the above-mentioned Synthetic Example 3-3 was introduced, and the inside of the three-necked flask was maintained at 0°C, and then stirred and mixed for 2 hours.

[0532] After the stirring mixture, hydrochloric acid was added dropwise to the three-necked flask until the contents of the three-necked flask became acidic, 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 the organic phase was recovered. The organic phase was concentrated, and low-boiling components were removed by distillation, to obtain a crude product C-4 (fluorine-containing polyether composition) as an oil.

[0533] The crude product C-4 was purified by column chromatography, and 113 g of a fluorine-containing polyether composition was recovered.

[0534] The fluorine-containing polyether composition was analyzed by 1 H-NMR method and 19 F-NMR method, and it was confirmed that the fluorine-containing polyether composition contained a fluorine-containing polyether compound m represented by the following formula (12-1), a fluorine-containing polyether compound n represented by the following formula (12-2), and a fluorine-containing polyether compound o represented by the following formula (12-3), and the average value of n was 8.

[0535] The Mw / Mn of the fluorine-containing polyether compound contained in the fluorine-containing polyether composition was 1.58.

[0536] The fluorine-containing polyether compound m represented by the following formula (12-1) is described below.

[0537]

[0538] The fluorine-containing polyether compound n represented by the following formula (12-2) is described below.

[0539]

[0540] The fluorine-containing polyether compound o represented by the following formula (12-3) is described below.

[0541]

[0542] NMR spectrum of the fluorine-containing diol polyether composition

[0543] 1 H-NMR δ (ppm): 4.0 ppm (4H)

[0544] 19 F-NMR δ (ppm): -86 ppm (64F), -121 ppm (4F), -122 ppm (18F), -123 ppm (18F), -125 ppm (64F)

[0545] (Synthesis Example 4-1)

[0546] A crude product D-1 containing a fluorine-containing polyether compound n represented by the following formula (15-1) was obtained according to the method described in paragraphs

[0104] to

[0109] of International Publication No. 2018 / 108866.

[0547] The following describes the fluorinated polyether compound n represented by chemical formula (15-1).

[0548]

[0549] The crude product D-1 was purified by column chromatography to obtain fluorinated polyether compound n. 1 H-NMR method and 19 F-NMR confirmed that the fluorinated glycol polyether compound n has the structure shown in the above chemical formula, and the average value of n is 2.

[0550] (Synthesis Example 5-1)

[0551] The crude product E-1 was obtained by means of the method described in paragraphs

[0106] to

[0109] of International Publication No. 2019 / 202079.

[0552] pass 1 H-NMR method and 19 F-NMR confirmed that the crude product E-1 contained the following fluorinated polyether compound p (chemical formula (16-1), compound q (chemical formula (16-2)) and compound r (chemical formula (16-3)). The average value of n in chemical formulas (16-1) to (16-3) is 4.

[0553] In addition, through 1 H-NMR method and 19 F-NMR was used to determine the proportion of terminal groups of the fluorinated polyether compound contained in the crude product E-1. The results showed that, relative to the total of -CF3 and -C(=O)OCH2CH3 (100 mol%), the proportion of -CF3 was 56 mol% and the proportion of -C(=O)OCH2CH3 was 44 mol%.

[0554] The following describes the fluorinated polyether compound p represented by chemical formula (16-1).

[0555]

[0556] The following describes the fluorinated polyether compound q represented by chemical formula (16-2).

[0557]

[0558] The following describes the fluorinated polyether compound r represented by chemical formula (16-3).

[0559]

[0560] (Synthesis example 5-2)

[0561] In a 300 mL three-necked flask, 2.2 g of NaBH4 powder (reducing agent) was added. Then, 100 g of AC-2000 and 26.3 g of ethanol were added to the flask. After cooling the internal temperature of the flask to 0 °C, the mixture was stirred.

[0562] 50g of the crude product E-1 obtained in Synthesis Example 6-1 was introduced into a three-necked flask, and the mixture was stirred for 2 hours while maintaining the temperature inside the three-necked flask at 0°C.

[0563] After stirring and mixing, hydrochloric acid was introduced into a three-necked flask until the contents of the flask became acidic, resulting in a crude reaction solution separated into an organic phase and an aqueous phase. The crude reaction solution was separated, and the organic phase was recovered. The organic phase was concentrated, and low-boiling components were removed by distillation to obtain an oily crude product E-2.

[0564] pass 1 H-NMR method and 19 F-NMR analysis confirmed that the crude product E-2 contained fluorinated polyether compound p as shown in formula (16-1), fluorinated polyether compound s as shown in formula (17-1), and fluorinated polyether compound t as shown in formula (17-3). The average value of n in formulas (16-1), (17-1), and (17-2) is 4.

[0565] In addition, through 1 H-NMR method and 19 F-NMR was used to determine the proportion of terminal groups of the fluorinated polyether compound contained in the crude product E-2. The results showed that, relative to the total of -CF3 and -CH2OH (100 mol%), the proportion of -CF3 was 56 mol% and the proportion of -CH2OH was 44 mol%.

[0566] The following describes fluorinated polyether compounds s represented by chemical formula (17-1).

[0567]

[0568] The following describes the fluorinated polyether compound t represented by chemical formula (17-2).

[0569]

[0570] The crude product F-2 was purified by column chromatography to obtain the fluorinated polyether compound S. 1 H-NMR method and 19 The NMR spectrum of the fluorinated polyether compound s was obtained by F-NMR method, and the results confirmed that it is a compound represented by the above chemical formula (17-1) with an average value of 3 for n.

[0571] NMR spectra of fluorinated polyether compounds

[0572] 1 H-NMR δ (ppm): 4.0 ppm (4H)

[0573] 19 F-NMR δ (ppm): -86 ppm (28F), -124 ppm (4F), -128 ppm (12F)

[0574] <<Heat resistance evaluation>>

[0575] Each 10 mg of the fluorine-containing polyether compound d obtained in the above Synthesis Example 1-5, the fluorine-containing polyether composition obtained in the above Synthesis Example 2-2, the fluorine-containing polyether composition obtained in the above Synthesis Example 3-4, the fluorine-containing polyether compound n obtained in the above Synthesis Example 4-1, and the fluorine-containing polyether compound s obtained in the above Synthesis Example 5-2 was prepared.

[0576] The above fluorine-containing polyether compounds and fluorine-containing polyether compositions were set in a thermogravimetric / differential thermal analysis device (model name: TG / DTA6200, manufactured by Hitachi High-Tech Science Corporation), and heated from a starting temperature of 25°C to 500°C at a temperature increase rate of 10°C / minute, and the temperature at which the weight of each fluorine-containing polyether compound and fluorine-containing polyether composition became half of the introduced weight (weight reduction temperature) was measured. Based on the following evaluation criteria, the heat resistance of the fluorine-containing polyether compounds and fluorine-containing polyether compositions was evaluated, and summarized in Table 1.

[0577] (Evaluation criteria)

[0578] A: The weight reduction temperature was 210°C or higher.

[0579] B: The weight reduction temperature was 200°C or higher and lower than 210°C.

[0580] C: The weight reduction temperature was lower than 200°C.

[0581] [Table 1]

[0582] Heat resistance evaluation Synthesis example 1-5 A Synthesis example 2-2 B Synthesis example 3-4 A Synthesis example 4-1 C Synthesis example 5-2 C

[0583] In the above Synthesis Examples, it was shown that using the production method of the polyether composition of the present disclosure, a polyether composition containing a polyether compound having a large number of repeating units and excellent heat resistance could be produced, and by using the polyether compound contained in the above polyether composition, a fluorine-containing polyether composition containing a fluorine-containing polyether compound having excellent heat resistance could be produced.

[0584] The disclosure of Japanese Patent Application No. 2020-217941 filed on December 25, 2020 is incorporated herein by reference in its entirety. All of the documents, patent applications, and technical standards cited in the present specification are hereby incorporated by reference to the same extent as if each individual document, patent application, or technical standard were specifically and individually indicated to be incorporated by reference.

Claims

1. A method for producing a polyether composition, comprising: subjecting a compound represented by the following general formula (1) to a first polymerization reaction with a compound represented by the following general formula (2) at a ratio of less than 1 mol per 1 mol of the compound represented by the general formula (2); and a second polymerization reaction after the first polymerization reaction, the second polymerization reaction is performed by subjecting the compound represented by the general formula (1) to a composition obtained by the first polymerization reaction at a ratio of 0.3 mol to 0.7 mol per 1 mol of the amount of the compound represented by the general formula (2) charged in the first polymerization reaction; a polyether composition containing a polyether compound is produced by a plurality of polymerization reactions of a compound represented by the following general formula (1) and a compound represented by the following general formula (2), A-X-A··· (1) B-Y-B··· (2) in the general formula (1) and the general formula (2), X and Y each independently represent a divalent hydrocarbon group having a carbon number of 1 to 20, optionally containing an ether bond, and a hydrogen atom of which is optionally substituted with a fluorine atom, wherein X and Y do not have an aromatic ring, when A represents -C(=O)F, B each represents -OC(=O)F, The 2 A's in the compound of formula (1) represent the same group and represent a group selected from the group comprising -OCF=CF2, -O(CF2) m CF=CF2, -C(=O)F, -OH, -OC(=O)F, -OTs, -OTf and -OMs. A represents -OCF=CF2, -O(CF2) m CF=CF2, -OTs, -OTf or -OMs, B all represent -OH, when A represents -OC(=O)F, B each represents -C(=O)F, A represents -OH, B represents -OCF=CF2, -O(CF2) m CF=CF2, -OTs, -OTf or -OMs, wherein Ts represents a p-toluenesulfonyl group, Tf represents a trifluoromethylsulfonyl group, Ms represents a methanesulfonyl group, and m represents an integer of 1 or more. the plurality of polymerization reactions are performed in a composition containing at least the compound represented by the general formula (1) and the compound represented by the general formula (2), 2. The method of manufacturing a polyether composition according to claim 1, wherein, the composition does not contain a solvent, or when the composition contains a solvent, the content rate of the solvent is 10% by mass or less. at least one of the plurality of polymerization reactions is performed in the presence of a base catalyst.

3. The method of producing a polyether composition according to claim 1 or 2, wherein, the ratio of the time of the second polymerization reaction to the time of the first polymerization reaction is 1.1 to 3.

4. The method for producing a polyether composition according to claim 1 or 2, wherein, the first polymerization reaction is performed by subjecting the compound represented by the general formula (1) to the compound represented by the general formula (2) at a ratio of 0.1 mol to 0.9 mol per 1 mol of the compound represented by the general formula (2).

5. The method for producing a polyether composition according to claim 1 or 2, wherein, the first polymerization reaction is performed by introducing the compound represented by the general formula (2) to the compound represented by the general formula (1) at a rate of 0.01 times mol / hour to 100 times mol / hour per 1 mol of the compound represented by the general formula (1), and allowing it to react.

6. The method of producing a polyether composition according to claim 1 or 2, wherein, the first polymerization reaction is performed by introducing the compound represented by the general formula (1) to the compound represented by the general formula (2) at a rate of 0.005 times mol / hour to 1.2 times mol / hour per 1 mol of the compound represented by the general formula (2), and allowing it to react.

7. The method of producing a polyether composition according to claim 1 or 2, wherein, the second polymerization reaction is performed by introducing the compound represented by the general formula (1) to a composition obtained by the first polymerization reaction at a rate of 0.5 times mol / hour to 360 times mol / hour per 1 mol of the amount of the compound represented by the general formula (2) charged in the first polymerization reaction, and allowing it to react.

8. The method of producing a polyether composition according to claim 1 or 2, wherein, ​ 9. The method of producing a polyether composition according to claim 1 or 2, wherein, At least one of X in the general formula (1) and Y in the general formula (2) is a divalent hydrocarbon group having 1 to 20 carbon atoms which is optionally fluorinated and optionally contains an ether bond.

10. The method of producing a polyether composition according to claim 1 or 2, wherein, The compound represented by the general formula (1) is reacted with the compound represented by the general formula (2) at a ratio of 0.6 to 1.4 mol per 1 mol of the compound represented by the general formula (2) through the plurality of polymerization reactions.

11. The method of manufacturing a polyether composition according to claim 1 or 2, wherein, The proportion of the terminal group A is 90 mol% or more relative to the total content of the terminal groups possessed by the polyether compound contained in the polyether composition.

12. A method of manufacturing a fluorine-containing polyether composition, wherein, A fluorine-containing polyether composition containing a fluorine-containing polyether compound is produced by fluorinating the polyether compound contained in the polyether composition produced by the production method of the polyether composition according to any one of claims 1 to 11.

13. A polyether composition produced by the production method of the polyether composition according to any one of claims 1 to 11, which contains a polyether compound having a structure represented by the following general formula (3), and the proportion of the terminal group A is 90 mol% or more relative to the total 100 mol% of the terminal groups possessed by the entire polyether compound contained in the polyether composition, A-X-(D-Y-D-X) n -A (3) In the general formula (3), X each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms which optionally contains an ether bond and in which a hydrogen atom is optionally substituted with a fluorine atom, Y each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms which optionally contains an ether bond and in which a hydrogen atom is optionally substituted with a fluorine atom, wherein X and Y do not have an aromatic ring, A is the same group and represents a group selected from the group comprising -OCF=CF2, -O(CF2) m CF=CF2, -C(=0)F, -OH, -OC(=0)F, -OTs, -OTf and -OMs, D represents a divalent linking group, A represents -OCF=CF2, D all represent -OCFHCF2O- , A represents -O(CF2) m CF=CF2, D each represents -O(CF2) m CFHCF2O- , A represents -C(=O)F, D all represent -OCF2-, A represents -OC(=0)F, D all represent -OCF2- , A represents -OTs, -OTf or -OMs, D all represent -O- , A represents -OH, D all represent -OCFHCF2O- , -O(CF2) m CFHCF2O- or -O- , n represents an integer of 6 or more, and m represents an integer of 1 or more, wherein Ts represents a p-toluenesulfonyl group, Tf represents a trifluoromethylsulfonyl group, Ms represents a methanesulfonyl group, represents a bonding portion to X, represents a bonding portion to Y.

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