Method for producing polyether composition, method for producing fluorine-containing polyether composition, and polyether composition

Abstract

A method for manufacturing a polyether composition containing a polyether compound through multiple polymerization reactions of the compound represented by the general formula (1) below and the compound represented by the general formula (2) below, the reactions involving: a first polymerization reaction wherein 1 mol of the compound represented by the general formula (2) is reacted with less than 1 mol of the compound represented by the general formula (1); and a second polymerization reaction following the first polymerization reaction.　(1): A-X-A (2): B-Y-B

Description

[Technical Field]

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

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

[0003] Fluorine-containing polyether compounds have been conventionally produced by various methods, for example, by fluorinating a polyether compound having an --OH group, a vinyl group or the like as a terminal group. For example, WO 2018 / 108866 discloses a method for producing a fluorine-containing polyether compound by producing a polyether compound from a vinyl ether compound and a diol compound, esterifying the —OH groups at both ends of the polyether compound to produce a diacyloxy polyether compound, and fluorinating the diacyloxy polyether compound. Furthermore, WO 2019 / 202076 discloses a method for producing a fluorine-containing polyether compound by polymerizing a vinyl ether compound and a diol compound in a solvent to produce a polyether compound, esterifying —OH groups at both ends of the polyether compound to produce a diacyloxy polyether compound, and fluorinating the diacyloxy polyether compound. Furthermore, WO 2018 / 108864, WO 2019 / 202079, and WO 2019 / 243404 disclose methods for producing a fluorinated polyether compound by polymerizing a diacyloxy compound and a difluoroacyl compound in a solvent to produce a polyether compound having a -C(=O)F group or an -OC(=O)F group as a terminal group, and fluorinating the polyether compound. Furthermore, WO 2019 / 243403 discloses a method for producing a fluorine-containing polyether compound by 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 ends of the polyether compound to produce a diacyloxy polyether compound, and fluorinating the diacyloxy polyether compound. Summary of the Invention [Problem to be solved by the invention]

[0004] From the viewpoint of heat resistance, it is preferable that the polyether compound used for producing a fluorinated polyether compound is a compound with a large number of repeating units. However, the polyether compounds produced by the production methods disclosed in WO 2018 / 108866 and WO 2019 / 202076 have a small number of repeating units, and the above polyether compounds and fluorinated polyether compounds produced by fluorinating the above polyether compounds have room for improvement in terms of heat resistance. Furthermore, WO 2018 / 108864 describes that the number average molecular weight of the polyether compound produced in the examples was about 2,200. However, in the production method disclosed in WO 2018 / 108864, a cyclic polyether compound is produced in addition to the polyether compound having the above-mentioned terminal group by reacting a diacyloxy compound with a difluoroacyl compound. Therefore, the cyclic polyether compound apparently has a large number average molecular weight value calculated from the integral ratio of the main chain to the terminal group using the NMR method, and the polyether compound having the above-mentioned terminal group that is actually obtained is a low molecular weight compound with a small number of repeating units. Therefore, the above-mentioned polyether compound and the fluorinated polyether compound produced by fluorinating the above-mentioned polyether compound have room for improvement in terms of heat resistance. In the production methods disclosed in WO 2019 / 202079 and WO 2019 / 243404, as in WO 2018 / 108864, a cyclic polyether compound is produced by reacting a diacyloxy compound with a difluoroacyl compound, and the polyether compounds having the above-mentioned terminal groups that are actually obtained are low-molecular-weight compounds with a small number of repeating units. Therefore, the above-mentioned polyether compounds and fluorinated polyether compounds produced by fluorinating the above-mentioned polyether compounds have room for improvement in terms of heat resistance. Furthermore, WO 2019 / 243403 describes in its examples that the number of repeating units of the polyether compound produced is 1 to 9. However, the polyether compound obtained by the production method according to WO 2019 / 243403 has an aromatic ring in the repeating unit, and there is room for improvement in terms of ease of fluorination.

[0005] The present disclosure has been made in view of the above-mentioned problems, and an object of the present disclosure is to provide a method for producing a polyether composition, which is capable of producing a polyether composition containing a polyether compound having excellent heat resistance. Another problem to be solved by the present disclosure is to provide a method for producing a fluorinated polyether composition, which is capable of producing a fluorinated polyether composition containing a fluorinated polyether compound having excellent heat resistance. Another problem to be solved by the present disclosure is to provide a polyether composition containing a polyether compound having excellent heat resistance. [Means for solving the problem]

[0006] Specific means for achieving the above object are as follows:

[0007] <1> A method for producing a polyether composition, comprising: a first polymerization reaction in which 1 mol of a compound represented by the following general formula (2) is reacted with less than 1 mol of a compound represented by the following general formula (1); and a second polymerization reaction following the first polymerization reaction, to produce a polyether composition containing a polyether compound by multiple polymerization reactions of a compound represented by the following general formula (1) and a compound represented by the following general formula (2): AXA···(1) BYB···(2)

[0008] (In general formula (1) and general formula (2), X and Y each independently represent a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain an ether bond and in which a hydrogen atom may be substituted with a fluorine atom; However, X and Y do not have an aromatic ring. Two A's contained in the compound represented by general formula (1) represent the same group, and are not -OCF=CF2, -O(CF2) m represents a group selected from the group comprising CF=CF2, -C(=O)F, -OH, -OC(=O)F, -OTs, -OTf and -OMs, A is -OCF=CF2, -O(CF2) m When CF=CF2, -OTs, -OTf or -OMs, B's both represent -OH; When A represents -C(=O)F, both B's represent -OC(=O)F; When A represents -OH, B represents both -OCF=CF2 and -O(CF2) m CF=CF2, -OTs, -OTf or -OMs; When A represents -OC(=O)F, both B's represent -C(=O)F. Here, Ts represents a p-toluenesulfonyl group, Tf represents a trifluoromethanesulfonyl group, Ms represents a methanesulfonyl group, and m represents an integer of 1 or more. <2> The multiple polymerization reactions are carried out 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 if the composition contains a solvent, the content of the solvent is 10 mass% or less. <1> A method for producing the polyether composition described in claim 1. <3> At least one of the multiple polymerization reactions is carried out in the presence of an alkali catalyst. <1> or <2> A method for producing the polyether composition described in claim 1. <4> the ratio of the time of the second polymerization reaction to the time of the first polymerization reaction is 1.1 to 3; <1> ~ <3> 10. A method for producing the polyether composition according to claim 9, wherein the polyether composition is a polyether having a molecular weight of 100 or more. <5> The first polymerization reaction is carried out by reacting 1 mol of the compound represented by general formula (2) with 0.1 mol to 0.9 mol of the compound represented by general formula (1). <1> ~ <4> 10. A method for producing the polyether composition according to claim 9, wherein the polyether composition is a polyether having a molecular weight of 100 or more. <6> the first polymerization reaction is carried out by introducing the compound represented by the general formula (2) into the compound represented by the general formula (1) at a rate of 0.01 to 100 times mol / hour per 1 mol of the compound represented by the general formula (1), and allowing them to react; <1> ~ <5> 10. A method for producing the polyether composition according to claim 9, wherein the polyether composition is a polyether having a molecular weight of 100 or more. <7> the first polymerization reaction is carried out by introducing the compound represented by the general formula (1) into the compound represented by the general formula (2) at a rate of 0.005 to 1.2 times mol / hour per 1 mol of the compound represented by the general formula (2), and reacting them; <1> ~ <5> 10. A method for producing the polyether composition according to claim 9, wherein the polyether composition is a polyether having a molecular weight of 100 or more. <8> the second polymerization reaction is carried out by reacting the compound represented by the general formula (1) with the composition obtained by the first polymerization reaction in a ratio of 0.1 mol to 1.2 mol per 1 mol of the compound represented by the general formula (2) charged in the first polymerization reaction. <1> ~ <7> 10. A method for producing the polyether composition according to claim 9, wherein the polyether composition is a polyether having a molecular weight of 100 or more. <9> the second polymerization reaction is carried out by introducing the compound represented by general formula (1) into the composition obtained by the first polymerization reaction at a rate of 0.5 to 360 times mol / hour relative to 1 mol of the compound represented by general formula (2) charged in the first polymerization reaction, and allowing the reaction to occur. <1> ~ <8> 10. A method for producing the polyether composition according to claim 9, wherein the polyether composition is a polyether having a molecular weight of 100 or more. <10> At least one of X in the general formula (1) and Y in the general formula (2) is a perfluorinated divalent hydrocarbon group having 1 to 20 carbon atoms which may contain an ether bond. <1> ~ <9> 10. A method for producing the polyether composition according to claim 9, wherein the polyether composition is a polyether having a molecular weight of 100 or more. <11> In the multiple polymerization reactions, the compound represented by the general formula (1) is reacted in a ratio of 0.6 mol to 1.4 mol per 1 mol of the compound represented by the general formula (2). <1> ~ <10> 10. A method for producing the polyether composition according to claim 9, wherein the polyether composition is a polyether having a molecular weight of 100 or more. <12> the proportion of the terminal group represented by A relative to the total content of terminal groups of the polyether compounds contained in the polyether composition (100 mol %) is 90 mol % or more; <1> ~ <11> 10. A method for producing the polyether composition according to claim 9, wherein the polyether composition is a polyether having a molecular weight of 100 or more. <13> <1> ~ <12> Fluorination of a polyether compound contained in a polyether composition produced by the method for producing a polyether composition according to any one of the above items 1 to 4, thereby producing a fluorinated polyether composition containing the fluorinated polyether compound. <14> A polyether composition comprising a polyether compound having a structure represented by the following general formula (3), wherein the proportion of terminal groups represented by A relative to the total of terminal groups possessed by all polyether compounds contained in the polyether composition (100 mol %) is 90 mol % or more: AX-(DYDX) n -A···(3)

[0009] (In general formula (3), X's each independently represent a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain an ether bond and in which a hydrogen atom may be substituted with a fluorine atom; Y's each independently represent a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain an ether bond and in which a hydrogen atom may be substituted with a fluorine atom; However, X and Y do not have an aromatic ring. A is the same group, and is -OCF=CF2, -O(CF2) m represents a group selected from the group comprising CF=CF2, -C(=O)F, -OH, -OC(=O)F, -OTs, -OTf and -OMs, D represents a divalent linking group; When A represents -OCF=CF2, all Ds represent *-OCFHCF2O-**, A is -O(CF2) m When CF=CF2, D is *-O(CF2) m CFHCF2O-**, When A represents -C(=O)F, each D represents **-OCF2-. If A represents -OC(=O)F, then all Ds represent *-OCF2-**. When A represents -OTs, -OTf or -OMs, D represents *-O-**; When A represents -OH, D is either **-OCFHCF2O-* or *-O(CF2) m CFHCF2O-** or *-O-**, n represents an integer of 6 or more, and m represents an integer of 1 or more. Here, Ts represents a p-toluenesulfonyl group, Tf represents a trifluoromethanesulfonyl group, Ms represents a methanesulfonyl group, * represents the bond to X, and ** represents the bond to Y. [Effects of the Invention]

[0010] According to the present disclosure, there is provided a method for producing a polyether composition that can produce a polyether composition containing a polyether compound having excellent heat resistance. The present disclosure also provides a method for producing a fluorinated polyether composition, which can produce a fluorinated polyether composition containing a fluorinated polyether compound having excellent heat resistance. Furthermore, the polyether composition according to the present disclosure can provide a polyether composition containing a polyether compound having excellent heat resistance. DETAILED DESCRIPTION OF THE INVENTION

[0011] Hereinafter, embodiments for carrying out the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments. In the following embodiments, components (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and do not limit the present disclosure.

[0012] In the present disclosure, numerical ranges indicated using "to" include the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In the numerical ranges described in stages in the present disclosure, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in the present disclosure, the upper or lower limit value of the numerical range may be replaced with the value shown in the synthesis examples.

[0013] In the present disclosure, the term "fluoroalkylene group" includes perfluoroalkylene groups in which all hydrogen atoms have been substituted with fluorine atoms and fluoroalkylene groups in which some hydrogen atoms have been substituted with fluorine atoms. Furthermore, in the present disclosure, the term "fluorocycloalkane" and the like also includes not only perfluorocycloalkanes in which all hydrogen atoms of a cycloalkane have been substituted with fluorine atoms, but also cycloalkanes in which some hydrogen atoms have been substituted with fluorine atoms.

[0014] In the present disclosure, each component may contain multiple corresponding compounds. For example, the molar ratio in the reaction between the compound represented by general formula (1) and the compound represented by general formula (2) is calculated based on the total amount of the compounds corresponding to each component.

[0015] In the representation of groups (atomic groups) in the present disclosure, a representation that does not specify whether substituted or unsubstituted encompasses both those that have no substituents and those that have a substituent.

[0016] In the present disclosure, the number of carbon atoms means the total number of carbon atoms contained in the entire group, and when the group does not have a substituent, it represents the number of carbon atoms forming the skeleton of the group, and when the group has a substituent, it represents the total number obtained by adding the number of carbon atoms forming the skeleton of the group to the number of carbon atoms in the substituent.

[0017] In the present disclosure, a monovalent or divalent hydrocarbon group is "perfluorinated" means that the hydrocarbon group has been fluorinated to the following state: When the monovalent or divalent hydrocarbon group is a saturated hydrocarbon group, the state in which all of the fluorinable hydrogen atoms bonded to carbon atoms constituting the monovalent or divalent hydrocarbon group are fluorinated is referred to as the hydrocarbon group being "perfluorinated." When a monovalent or divalent hydrocarbon group is an unsaturated hydrocarbon group, the hydrocarbon group is said to be "perfluorinated" when all fluorinable hydrogen atoms bonded to carbon atoms constituting the monovalent or divalent hydrocarbon group are fluorinated, and a fluorine atom is added to each of the two carbon atoms forming a carbon-carbon unsaturated bond such as a carbon-carbon double bond or a carbon-carbon triple bond, thereby eliminating the carbon-carbon unsaturated bond. For example, when >C=C< is perfluorinated, it becomes >CF-CF<, and when -C≡C- is perfluorinated, it becomes -CF-CF-. In addition, a fluorinable hydrogen atom may be bonded to the perfluorinable atomic group; for example, when -CH=CH- is perfluorinated, it becomes -CF-CF-.

[0018] In the present disclosure, the number average molecular weight (Mn) and the mass average molecular weight (Mw) are measured by gel permeation chromatography (hereinafter also referred to as "GPC"). Measurement by GPC was carried out according to the method described in paragraphs

[0010] to

[0030] of JP 2001-208736 A under the following conditions. Note that equivalent materials may be used for the mobile phase, etc. Mobile phase: a mixed solvent of R-225 (manufactured by AGC Corporation, product name: Asahiklin (registered trademark) AK-225SEC Grade 1) and hexafluoroisopropyl alcohol (HFIP) (R-225:HFIP = 99:1 (volume ratio)) Analytical column: Two PLgel MIXED-E columns (Polymer Laboratories) connected in series Standard samples for molecular weight measurement: Four types of perfluoropolyethers with a molecular weight distribution (Mw / Mn) of less than 1.1 and Mn of 2,000 to 10,000, and one type of perfluoropolyether with Mw / Mn of 1.1 or more and Mn of 1,300. ·Mobile phase flow rate: 1.0mL / min Column temperature: 37℃ Detector: Evaporative light scattering detector

[0019] (Method of producing polyether composition) The method for producing a polyether composition according to the present disclosure produces a polyether composition containing a polyether compound by multiple polymerization reactions of a compound represented by the following general formula (1) and a compound represented by the following general formula (2), including a first polymerization reaction in which 1 mol of a compound represented by the following general formula (2) is reacted with less than 1 mol of a compound represented by the following general formula (1), and a second polymerization reaction following the first polymerization reaction: AXA···(1) BYB···(2)

[0020] In general formula (1) and general formula (2), X and Y each independently represent a divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain an ether bond and in which a hydrogen atom may be substituted with a fluorine atom, provided that X and Y do not have an aromatic ring. In addition, two A's contained in the compound represented by general formula (1) represent the same group, and are not -OCF=CF2, -O(CF2) m represents a group selected from the group consisting of CF=CF2, -C(=O)F, -OH, -OC(=O)F, -OTs, -OTf and -OMs. A is -OCF=CF2, -O(CF2) m When A represents -CF=CF2, -OTs, -OTf or -OMs, both Bs represent -OH; when A represents -C(=O)F, both Bs represent -OC(=O)F; when A represents -OH, both Bs represent -OCF=CF2, -O(CF2) m CF=CF2, -OTs, -OTf or -OMs, and when A represents -OC(=O)F, both B's represent -C(=O)F. Here, Ts represents a p-toluenesulfonyl group, Tf represents a trifluoromethanesulfonyl group, Ms represents a methanesulfonyl group, and m represents an integer of 1 or more, preferably an integer of 1 to 6, and more preferably an integer of 1 to 3.

[0021] According to the method for producing a polyether composition according to the present disclosure, a polyether composition containing a polyether compound having excellent heat resistance can be produced.

[0022] The reason for the above effect is presumed to be as follows, but is not limited to this. In the method for producing a polyether composition according to the present disclosure, the polyether compound contained in the polyether composition is produced by multiple polymerization reactions of a compound represented by general formula (1) and a compound represented by general formula (2). By dividing the polymerization reaction into multiple steps and reacting the compound represented by general formula (1) in a ratio of less than 1 mol to 1 mol of the compound represented by general formula (2) in the first polymerization reaction, it is presumed that the self-cyclization reaction of the polymer can be suppressed in the polymerization reaction, a polyether compound with a large number of repeating units is produced, and the heat resistance of the polyether compound is improved.Furthermore, it is presumed that the fluorinated polyether compound produced by fluorinating the above polyether compound also has a large number of repeating units and is excellent in heat resistance.

[0023] The proportion of the terminal group represented by A relative to the total content of terminal groups possessed by all polyether compounds contained in the polyether composition (100 mol %) is preferably 90 mol % or more, more preferably 92 mol % or more, and even more preferably 95 mol % or more.

[0024] Hereinafter, the multiple polymerization reactions involved in the method for producing a polyether composition according to the present disclosure will be described.

[0025] -Multiple polymerization reactions- In the method for producing a polyether composition according to the present disclosure, the multiple polymerization reactions include at least a first polymerization reaction in which 1 mol of the compound represented by general formula (2) is reacted with less than 1 mol of the compound represented by general formula (1), and a second polymerization reaction following the first polymerization reaction. In the method for producing the polyether composition according to the present disclosure, the second polymerization reaction may be carried out multiple times.

[0026] In the method for producing a polyether composition according to the present disclosure, multiple polymerization reactions can be carried out in a composition containing at least a compound represented by general formula (1) and a compound represented by general formula (2). The content of the solvent in the composition is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less, and it is particularly preferable that the composition does not contain any solvent. By controlling the solvent content in the composition to 10% by mass or less, the self-cyclization reaction can be more effectively suppressed, and a polyether composition containing a polyether compound with better heat resistance can be produced. Furthermore, by controlling the solvent content in the composition to 10% by mass or less, the yield of the polyether compound with better heat resistance can be improved. 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.

[0027] In the multiple polymerization reactions, the compound represented by general formula (1) is reacted in a ratio of preferably 0.6 mol to 1.4 mol, more preferably 0.7 mol to 1.3 mol, and even more preferably 0.8 mol to 1.2 mol per 1 mol of the compound represented by general formula (2). By setting the molar ratio in the multiple polymerization reactions within the above numerical range, a polyether composition containing a polyether compound having better heat resistance can be produced. Furthermore, in the method for producing a polyether composition according to the present disclosure, by setting the molar ratio in the reaction of the compound represented by general formula (1) and the compound represented by general formula (2) in multiple polymerization reactions within the above-mentioned range, it becomes possible to adjust the ratio of A derived from general formula (1) and B derived from general formula (2) at the terminals of the polyether compound. For example, it becomes possible to selectively produce polyether compounds having terminals rich in A, polyether compounds having terminals rich in B, etc. Furthermore, by setting the molar ratio in the reaction of the compound represented by general formula (1) and the compound represented by general formula (2) in multiple polymerization reactions within the above-mentioned numerical range, the content of unreacted compound represented by general formula (1) and 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.

[0028] In the method for producing a polyether composition according to the present disclosure, at least one of the multiple polymerization reactions is preferably carried out in the presence of an alkali catalyst, and it is more preferable that all of the polymerization reactions are carried out in the presence of an alkali catalyst. By carrying out the polymerization reaction in the presence of an alkali 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 better heat resistance can be produced. Furthermore, by carrying out the polymerization reaction in the presence of an alkali catalyst, the yield of the polyether compound having excellent heat resistance can be improved. As the alkali catalyst, for example, carbonates and metal fluoride salts can be suitably used. In the general formula (1), A is -OCF=CF2, -O(CF2) m When A represents CF═CF2, —OTs, —OTf, —OMs, or —OH, the alkali catalyst is preferably a carbonate, and when A represents —C(═O)F or —OC(═O)F, the alkali catalyst is preferably a metal fluoride. Examples of carbonates include sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate, etc. Examples of metal fluorides include cesium fluoride, sodium fluoride, potassium fluoride, etc.

[0029] In multiple polymerization reactions, two or more types of compounds represented by general formula (1) and two or more types of compounds represented by general formula (2) may be used. When two or more compounds represented by general formula (1) are used, it is preferable that all of the terminal groups represented by A are the same. When two or more compounds represented by general formula (2) are used, it is preferable that all of the terminal groups represented by B are the same. When all the terminal groups represented by A are the same and all the terminal groups represented by B are the same, a polyether composition containing a polyether compound having better heat resistance can be produced, and it becomes possible to adjust the ratio of A derived from general formula (1) and B derived from general formula (2) at the terminals of the polyether compound.

[0030] The ratio of the time of the second polymerization reaction to the time of the first polymerization reaction (when the reaction is carried out multiple times, this refers to the time of each second 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 within the above numerical range, 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 with better heat resistance can be produced. Furthermore, it becomes possible to adjust the ratio of A derived from general formula (1) and B derived from general formula (2) present at the terminal of the polyether compound. Furthermore, by setting the ratio of the time of the second polymerization reaction to the time of the first polymerization reaction within the above range, the yield of the polyether compound having excellent heat resistance can be improved. 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 when the compound represented by general formula (1) to be used in the second polymerization reaction is introduced. Furthermore, the time of the second polymerization reaction refers to the time, in the case where the second polymerization reaction is carried out once, from the time when the additional compound represented by general formula (1) is introduced and the reaction temperature is raised to the time when the reaction system is cooled to a temperature lower than the reaction temperature. Furthermore, when the second polymerization reaction is carried out multiple times, the time for the second polymerization reaction (final polymerization reaction) that is carried out last among the multiple second polymerization reactions refers to the time from introducing the additional compound represented by general formula (1), bringing the temperature to the reaction temperature, to lowering the temperature of the reaction system to a temperature lower than the reaction temperature, and the time for the other second polymerization reactions refers to the time from introducing the additional compound represented by general formula (1), bringing the temperature to the reaction temperature, to introducing the compound represented by general formula (1) to be used in the next second polymerization reaction.

[0031] --First polymerization reaction-- The first polymerization reaction is preferably carried out by reacting 1 mol of the compound represented by general formula (2) with 0.1 mol to 0.9 mol of the compound represented by general formula (1), more preferably with 0.3 mol to 0.7 mol, and even more preferably with 0.4 mol to 0.6 mol. According to the method for producing a polyether composition including the first polymerization reaction, the self-cyclization reaction can be more effectively suppressed, and a polyether composition containing a polyether compound having better heat resistance can be produced. Furthermore, according to the method for producing a polyether composition including the first polymerization reaction, the yield of a polyether compound having excellent heat resistance can be improved.

[0032] In the first polymerization reaction, the compound represented by general formula (2) may be introduced into the compound represented by general formula (1) and reacted with each other, the compound represented by general formula (1) may be introduced into the compound represented by general formula (2) and reacted with each other, or the compound represented by general formula (1) and the compound represented by general formula (2) may be introduced into a vessel and then reacted with each other. When the first polymerization reaction is carried out by introducing a compound represented by general formula (2) into a compound represented by general formula (1) and reacting them, the compound represented by general formula (2) is preferably introduced at a rate of 0.01 to 100 times mol / hour, more preferably 0.1 to 10 times mol / hour, and even more preferably 0.5 to 3 times mol / hour, per 1 mol of the compound represented by general formula (1). When the first polymerization reaction is carried out by introducing a compound represented by general formula (1) into a compound represented by general formula (2) and reacting them, the compound represented by general formula (1) is preferably introduced at a rate of 0.005 to 1.2 times mol / hour, more preferably 0.01 to 0.9 times mol / hour, and even more preferably 0.1 to 0.5 times mol / hour, per 1 mol of the compound represented by general formula (2). According to the method for producing a polyether composition including the first polymerization reaction, the self-cyclization reaction can be more effectively suppressed, and a polyether composition containing a polyether compound having better heat resistance can be produced. Furthermore, according to the method for producing a polyether composition including the first polymerization reaction, the yield of a polyether compound having excellent heat resistance can be improved.

[0033] The reaction temperature in the first polymerization reaction is preferably 20°C to 120°C, more preferably 30°C to 100°C. According to the method for producing a polyether composition including the first polymerization reaction, 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 better heat resistance can be produced. Furthermore, according to the method for producing a polyether composition including the first polymerization reaction, the yield of a polyether compound having excellent heat resistance can be improved. In the present disclosure, the reaction temperature refers to the internal temperature of a vessel in which the compound represented by general formula (1) and the compound represented by general formula (2) are reacted.

[0034] The time for the first polymerization reaction is preferably 0.5 to 10 hours, more preferably 1 to 5 hours. According to the method for producing a polyether composition including the first polymerization reaction, 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 better heat resistance can be produced. Furthermore, according to the method for producing a polyether composition including the first polymerization reaction, the yield of a polyether compound having excellent heat resistance can be improved.

[0035] --Second polymerization reaction-- The first polymerization reaction produces a composition containing a polymer of a compound represented by general formula (1) and a compound represented by general formula (2). The composition may contain unreacted compound represented by general formula (2). In one embodiment of the second polymerization reaction, the polymer and unreacted compound represented by general formula (2) contained in the composition react with an additionally introduced compound represented by general formula (1).

[0036] The second polymerization reaction is preferably carried out by reacting the compound represented by general formula (1) in a ratio of 0.1 mol to 1.2 mol, more preferably 0.3 mol to 0.7 mol, and even more preferably 0.3 mol to 0.6 mol, with 1 mol of the compound represented by general formula (2) charged in the first polymerization reaction. The method for producing a polyether composition including the second polymerization reaction can produce a polyether composition containing a polyether compound with better heat resistance, and can adjust the ratio of A derived from general formula (1) and B derived from general formula (2) present at the terminal of the polyether compound. Furthermore, according to the method for producing a polyether composition including the second polymerization reaction, the yield of a polyether compound having excellent heat resistance can be improved. When the second polymerization reaction is carried out multiple times, the reaction ratios may be different or the same.

[0037] In the second polymerization reaction, which is the final polymerization reaction, it is preferable to mix the compound represented by general formula (1) with the composition obtained by the first polymerization reaction in a ratio of 0.4 mol or more per 1 mol of the compound represented by general formula (2) charged in the first polymerization reaction, and then allow the reaction to proceed. The method for producing a polyether composition including the second polymerization reaction makes it possible to adjust the ratio of A derived from general formula (1) and B derived from general formula (2) at the terminal of the polyether compound. Furthermore, according to the method for producing a polyether composition including the second polymerization reaction, the yield of a polyether compound having excellent heat resistance can be improved.

[0038] 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 to 360 times mol / hour relative to 1 mol of the compound represented by general formula (2) charged in the first polymerization reaction, and reacted therewith, more preferably at a rate of 0.8 to 300 times mol / hour, even more preferably at a rate of 1 to 180 times mol / hour, and particularly preferably at a rate of 4 to 100 times mol / hour. According to the method for producing a polyether composition including the second polymerization reaction, a polyether composition containing a polyether compound having better heat resistance can be produced, and it becomes possible to adjust the ratio of A derived from general formula (1) and B derived from general formula (2) present at the terminal of the polyether compound. Furthermore, according to the method for producing a polyether composition including the second polymerization reaction, the yield of a polyether compound having excellent heat resistance can be improved. When the second polymerization reaction is carried out a plurality of times, the introduction rates may be different or the same for each time.

[0039] The reaction temperature in the second polymerization reaction is preferably 20° C. to 140° C., more preferably 40° C. to 130° C. According to the method for producing a polyether composition including the second polymerization reaction, the polymerization reaction of the compound represented by general formula (1) and the compound represented by general formula (2) proceeds smoothly, making it possible to produce a polyether composition containing a polyether compound with better heat resistance, and also making it possible to adjust the ratio of A derived from general formula (1) and B derived from general formula (2) present at the terminal of the polyether compound. Furthermore, according to the method for producing a polyether composition including the second polymerization reaction, the yield of a polyether compound having excellent heat resistance can be improved. When the second polymerization reaction is carried out a plurality of times, the reaction temperatures may be different from each other or may be the same.

[0040] The time for the second polymerization reaction (when carried out multiple times, this refers to the time for each second polymerization reaction) is preferably 1 hour to 30 hours, more preferably 2 hours to 20 hours. According to the method for producing a polyether composition including the second polymerization reaction, the polymerization reaction of the compound represented by general formula (1) and the compound represented by general formula (2) proceeds smoothly, making it possible to produce a polyether composition containing a polyether compound with better heat resistance, and also making it possible to adjust the ratio of A derived from general formula (1) and B derived from general formula (2) present at the terminal of the polyether compound. Furthermore, according to the method for producing a polyether composition including the second polymerization reaction, the yield of a polyether compound having excellent heat resistance can be improved. When the second polymerization reaction is carried out a plurality of times, the polymerization reaction times may be different or the same.

[0041] In the method for producing a polyether composition according to the present disclosure, at least one selected from a solvent, water, and an aqueous solution for adjusting the acidity to an appropriate level may be added to the polyether composition obtained by the second polymerization reaction, followed by liquid separation, and then the organic phase may be concentrated. The concentrated organic phase may also be purified. The solvent is not particularly limited, but a fluorine-based solvent is preferred. Examples of the fluorine-based solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, and fluoroalcohols.

[0042] The compound represented by general formula (1), the compound represented by general formula (2), and the polyether compound will be described below.

[0043] --Compound represented by general formula (1)-- In general formula (1), X represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain an ether bond and in which a hydrogen atom may be substituted with a fluorine atom, provided that X does not have an aromatic ring. The number of carbon atoms in the divalent hydrocarbon group is preferably 15 or less, more preferably 13 or less. By making the number of carbon atoms in the divalent hydrocarbon group 15 or less, the polymerization reaction with the compound represented by general formula (2) proceeds smoothly, and a polyether composition containing a polyether compound having better heat resistance can be produced. From the viewpoint of a balance between fluorination reactivity, heat resistance, etc., the divalent hydrocarbon group is preferably a perfluorinated hydrocarbon group which may contain an ether bond. From the viewpoint of a balance between fluorination reactivity, heat resistance, etc., it is preferable that at least one of X in general formula (1) and Y in general formula (2) described later is a perfluorinated hydrocarbon group which may contain an ether bond. From the viewpoint of a balance between fluorination reactivity, heat resistance, etc., it is preferable that X in general formula (1) and Y in general formula (2) both represent a perfluorinated hydrocarbon group. However, from the viewpoint of cost, it is preferable that X in general formula (1) or Y in general formula (2) represent a perfluorinated hydrocarbon group. The number of carbon atoms in the divalent hydrocarbon group is preferably 4 or more, and more preferably 5 or more. When the number of carbon atoms in the divalent hydrocarbon group is 4 or more, the reaction with the compound represented by general formula (2) can be carried out in a liquid state, making it easy to adjust the reaction.

[0044] Examples of the divalent hydrocarbon group represented by X include alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene, and fluoroalkylene groups such as fluoromethylene, fluoroethylene, fluorotrimethylene, fluorotetramethylene, fluoropentamethylene, and fluorohexamethylene.

[0045] The divalent hydrocarbon group represented by X may be a group represented by the following general formula (A). *-R 1 -(OR 1 ) n’ -*···(A) In general formula (A), R 1is (CH2) n’’ or (CF2) n’’ where n′ and n″ are integers of 1 or more, and preferably integers of 1 to 12. In general formula (A), * represents the bonding site with A in general formula (1).

[0046] The divalent hydrocarbon group represented by X may be a group represented by the following general formula (B): *-CH(CH3)(CH2) n’’’ CH(CH3)-*···(B) In general formula (B), n''' is an integer of 1 or more, and is preferably an integer of 1 to 8. In general formula (B), * represents the bonding site to A in general formula (1).

[0047] The divalent hydrocarbon group represented by X may be a group represented by the following general formula (C): *-R 3 -OR 2 -OR 3 -*···(C) In general formula (C), R 2 represents a cycloalkanediyl group or a fluorocycloalkanediyl group. Examples of cycloalkanediyl groups and fluorocycloalkanediyl groups include cyclobutanediyl groups, fluorocyclobutanediyl groups, cyclopentanediyl groups, fluorocyclopentanediyl groups, cyclohexanediyl groups, fluorocyclohexanediyl groups, adamantanediyl groups, and norbornanediyl groups. The cycloalkanediyl groups and fluorocycloalkanediyl groups may have, as a substituent, an alkyl group having 1 to 3 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom. In general formula (C), R 3 each independently represents a divalent hydrocarbon group having 1 to 10 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom. 3 does not have an aromatic ring. In general formula (C), * represents the bond to A in general formula (1).

[0048] Examples of divalent hydrocarbon groups satisfying general formula (C) include, but are not limited to, the following groups:

[0049] [ka]

[0050] [ka]

[0051] The divalent hydrocarbon group represented by X may also be a group represented by the following general formulas (D) to (F). *-R 4 -R 2 -R 4 -*···(D) *-R 2 -R 4 -R 2 -*···(E) *-R 3 -R 5 -R 3 -*···(F) In the general formulae (D) to (F), * represents the bonding site with A in the general formula (1). In addition, in the general formulas (D) and (E), R 4 each independently represents a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom. 4 does not have an aromatic ring. In addition, in general formula (F), R 5 represents a cycloalkane-1,1-diyl group having 3 to 6 carbon atoms. In addition, R in the above general formulas (D) to (F) 2 and R 3 The group represented by is the same as that represented by general formula (C) above.

[0052] Examples of groups satisfying any of the general formulae (D) to (F) include, but are not limited to, the following groups.

[0053] [ka]

[0054] [ka]

[0055] [ka]

[0056] [ka]

[0057] Two A's contained in the compound represented by general formula (1) represent the same group, and are not -OCF=CF2, -O(CF2) m represents a group selected from the group including CF=CF2, -C(=O)F, -OH, -OC(=O)F, -OTs, -OTf and -OMs. Also, -O(CF2) m In CF=CF2, m represents an integer of 1 or more, preferably an integer of 1 to 6, and more preferably an integer of 1 to 3. From the viewpoint of reactivity with the compound represented by general formula (2), when A represents an -OH group, the compound represented by general formula (1) is preferably a primary alcohol having a terminal -CH2OH group. When the compound represented by general formula (1) is a primary alcohol, it is preferable that hydrogen atoms, except for the terminal -CH2OH group, are substituted with fluorine atoms.

[0058] The molecular weight of the compound represented by general formula (1) is preferably 50 to 2000, more preferably 55 to 1000. When the molecular weight of the compound represented by general formula (1) is within the above numerical range, the polymerization reaction with the compound represented by general formula (2) proceeds smoothly, and a polyether compound having better heat resistance can be produced. Furthermore, when the molecular weight of the compound represented by general formula (1) is within the above numerical range, the yield of the polyether compound having excellent heat resistance can be improved.

[0059] 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. When the pKa of the compound represented by general formula (1) is within the above-mentioned range, the polymerization reaction with the compound represented by general formula (2) proceeds smoothly, and a polyether composition containing the polyether compound having better heat resistance can be produced. Furthermore, when the pKa of the compound represented by general formula (1) is within the above range, the yield of the polyether compound having excellent heat resistance can be improved. In the present disclosure, pKa is a value in water at 25° C., and is calculated according to the method described in Chemistry Handbook, Basic Edition, 5th Revised Edition, II-331 to II-343 (edited by the Chemical Society of Japan, published by Maruzen Co., Ltd.).

[0060] From the above, examples of compounds represented by general formula (1) include, but are not limited to, the following compounds: In the following compounds, A is as defined above.

[0061] [ka]

[0062] [ka]

[0063] [ka]

[0064] [ka]

[0065] [ka]

[0066] [ka]

[0067] [ka]

[0068] [ka]

[0069] [ka]

[0070] [ka]

[0071] --Compound represented by general formula (2)-- In general formula (2), Y represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain an ether bond and in which a hydrogen atom may be substituted with a fluorine atom. However, Y does not have an aromatic ring. The divalent hydrocarbon group preferably has 15 or fewer carbon atoms, more preferably 13 or fewer carbon atoms. By controlling the carbon number of the divalent hydrocarbon group to 15 or fewer, the polymerization reaction with the compound represented by general formula (1) proceeds smoothly, and a polyether compound with better heat resistance can be produced. Furthermore, from the viewpoint of a balance between fluorination reactivity, heat resistance, etc., the divalent hydrocarbon group is preferably a perfluorinated hydrocarbon group which may contain an ether bond. The divalent hydrocarbon group can be selected from the same groups as the divalent hydrocarbon group represented by X, and therefore a detailed description thereof will be omitted here. Furthermore, X and Y may be the same group or different groups. The number of carbon atoms in the divalent hydrocarbon group is preferably 4 or more, and more preferably 5 or more. When the number of carbon atoms in the divalent hydrocarbon group is 4 or more, the reaction with the compound represented by general formula (1) can be carried out in a liquid state, making it easier to control the reaction.

[0072] In the general formula (1), A is -OCF=CF2, -O(CF2) m When A in general formula (1) represents -C(=O)F, both Bs in general formula (2) represent -OC(=O)F, and when A in general formula (1) represents -OH, both Bs in general formula (2) represent -OCF=CF2, -O(CF2) m CF=CF2, -OTs, -OTf or -OMs, and when A represents -OC(=O)F, both B's represent -C(=O)F. Also, -O(CF2) m In CF=CF2, m is as described above and will not be described here. From the viewpoint of 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. Furthermore, when the compound represented by general formula (2) is a primary alcohol, it is preferable that hydrogen atoms, except for the terminal -CHOH group, are substituted with fluorine atoms.

[0073] The molecular weight of the compound represented by general formula (2) is preferably 50 to 2000, more preferably 55 to 1000. When the molecular weight of the compound represented by general formula (2) is 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 better heat resistance can be produced. Furthermore, when the molecular weight of the compound represented by general formula (2) is within the above range, the yield of the polyether compound having excellent heat resistance can be improved.

[0074] 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. When the pKa of the compound represented by general formula (2) is within the above-mentioned range, the polymerization reaction with the compound represented by general formula (1) proceeds smoothly, and a polyether composition containing the polyether compound having better heat resistance can be produced. Furthermore, when the pKa of the compound represented by general formula (2) is within the above range, the yield of the polyether compound having excellent heat resistance can be improved.

[0075] Specific examples of the compound represented by general formula (2) are compounds in which the terminal group A of the specific example of the compound represented by general formula (1) described above is replaced with the terminal group B, and therefore a detailed description thereof will be omitted here.

[0076] From the viewpoint of reactivity, preferred combinations of the terminal group A in the general formula (1) and the terminal group B in the general formula (2) include a combination in which A represents -OCF=CF2 and 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 Examples of the combination include a combination where A represents -CF=CF2, and a combination where A represents -OC(=O)F and B represents -C(=O)F.

[0077] The polyether composition produced by the method for producing a polyether composition according to the present disclosure can contain a polyether compound having a structure represented by general formula (3). AX-(DYDX) n -A···(3)

[0078] In general formula (3), each X independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain an ether bond and in which a hydrogen atom may be substituted with a fluorine atom, provided that X does not have an aromatic ring. In general formula (3), each Y independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain an ether bond and in which a hydrogen atom may be substituted with a fluorine atom, provided that Y does not have an aromatic ring. In the general formula (3), D is a divalent linking group, and when A represents -OCF=CF2, D represents *-OCFHCF2O-**, and when A represents -O(CF2) m When CF=CF2, D is *-O(CF2) m When A represents -C(=O)F, all Ds represent **-OCF2-*, when A represents -OC(=O)F, all Ds represent *-OCF2-**, when A represents -OTs, -OTf or -OMs, all Ds represent *-O-**, when A represents -OH, all Ds represent **-OCFHCF2O-*, *-O(CF2) m CFHCF2O-** or *-O-**. * represents the bond to X, and ** represents the bond to Y. Also, -O(CF2) m In CFHCF2O-, m is as defined above and will not be described here. 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.

[0079] From the viewpoint of the fluidity of the polyether composition and the solubility of the polyether compound, the average value 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 even more preferably 1,500 to 7,000.

[0080] Furthermore, from the viewpoint of the fluidity of the polyether composition and the solubility of the polyether compound, the average 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 even more preferably 1.0 to 2.0.

[0081] Examples of polyether compounds having a structure represented by the above general formula (3) include, but are not limited to, the following compounds:

[0082] [ka]

[0083] [ka]

[0084] [ka]

[0085] [ka]

[0086] When the polyether composition contains a polyether compound having a structure represented by general formula (3), the polyether composition may contain at least one of a polyether compound having a structure represented by the following general formula (3') and a polyether compound having a structure represented by the following general formula (3'): BY-(DXDY) n -B···(3') AX-(DYDX) n -DYB···(3'')

[0087] X, Y, A, B, D and n in the general formula (3') and the general formula (3'') are as described above.

[0088] From the viewpoint of heat resistance, the content of the polyether compound in the polyether composition is preferably 60% by mass to 100% by mass, and more preferably 80% by mass to 100% by mass. The polyether composition may contain one type of polyether compound or two or more types of polyether compounds. From the viewpoint of heat resistance, the content of the polyether compound having the structure represented by general formula (3) in the polyether composition is preferably 50% by mass to 100% by mass.

[0089] --Polyether composition-- The polyether composition according to the present disclosure contains a polyether compound having a structure represented by general formula (3) above, and the proportion of terminal groups represented by A relative to the total of terminal groups possessed by all polyether compounds contained in the polyether composition (100 mol %) is 90 mol % or more. The proportion of A is preferably 92 mol %, more preferably 95 mol %. The preferred content of the polyether compound in the polyether composition is as described above.

[0090] When the polyether composition contains a polyether compound having a structure represented by general formula (3), the polyether composition may contain at least one of a polyether compound having a structure represented by the above general formula (3') and a polyether compound having a structure represented by the above general formula (3').

[0091] (Method of producing fluorinated polyether composition) The production of the fluorinated polyether composition according to the present disclosure involves fluorinating a polyether compound contained in the polyether composition produced by the above-mentioned method for producing a polyether composition, to produce a fluorinated polyether composition containing the fluorinated polyether compound.

[0092] According to the method for producing a fluorinated polyether composition according to the present disclosure, a fluorinated polyether composition containing a fluorinated polyether compound having better heat resistance can be produced.

[0093] Specific examples of the method for producing a fluorinated polyether composition will be described below, but the present invention is not limited to these.

[0094] -Specific Example A of Method for Producing Fluorinated Polyether Composition- The polyether composition has -OCF=CF2 groups or -O(CF2) groups at both ends. m When a polyether compound having a CF=CF2 group is contained, a fluorine-containing polyether composition containing the fluorine-containing polyether compound can be produced by fluorinating the polyether compound. The method involves adding -OCF=CF2 groups or -O(CF2) groups to a total of 100 mol% of the terminal groups of all polyether compounds contained in the polyether composition. m It is preferred if the proportion of CF=CF2 groups is 90 mol % or more. The method for fluorinating a polyether compound is not particularly limited and can be carried out based on a conventionally known method. The fluorination method may be a batch method or a continuous method. The fluorination reaction is preferably carried out by the following <Method 1> or <Method 2>, with <Method 2> being more preferred from the viewpoint of the yield of the fluorinated polyether compound. Whether carried out by a batch method or a continuous method, the fluorine gas may be diluted with an inert gas such as nitrogen gas before use.

[0095] <Method 1> In Method 1, a polyether compound and a solvent are charged into a reactor, and stirring is initiated. The reaction is carried out at a predetermined reaction temperature and pressure while continuously supplying fluorine gas diluted with an inert gas into the solvent. <Method 2> In Method 2, a solvent is charged into a reactor and stirred, and then fluorine gas diluted with an inert gas, a polyether compound, and a solvent are continuously fed into the fluorination reaction solvent at a predetermined molar ratio to cause a reaction at a predetermined reaction temperature and pressure. <Method 3> In method 3, a solvent is continuously introduced into a tubular reactor and circulated through the reactor, and then fluorine gas diluted with an inert gas and a solution of a polyether compound are continuously supplied to the solvent flow in the tubular reactor at a predetermined molar ratio between the fluorine gas and the polyether compound, and mixed therewith, so that the fluorine gas and the polyether compound are brought into contact with each other in the tubular reactor and reacted, and the solvent containing the reaction product is removed from the tubular reactor. In this method, the fluorination reaction can be carried out continuously by circulating the solvent and removing the reaction product from the circulating solvent.

[0096] As in Method 3, in Method 2, when supplying the polyether compound, it is preferable to supply the polyether compound diluted with a solvent, in order to improve the selective production of the fluorinated polyether compound and to suppress the amount of by-products. When diluting the polyether compound with a solvent, the amount of the solvent relative to the polyether compound is preferably 5 times or more, more preferably 7 times or more, by mass.

[0097] Examples of inert gases include rare gases such as helium gas, neon gas, and argon gas, and nitrogen gas, with nitrogen gas and helium gas being preferred, and nitrogen gas being more preferred from the viewpoint of economical advantages. The proportion of fluorine gas (hereinafter also referred to as "fluorine gas amount") is preferably 15 to 60% by volume out of 100% by volume of the total of fluorine gas and inert gas.

[0098] When the fluorination of the polyether compound is carried out in a solvent, the solvent may be previously substituted with nitrogen in order to reduce the oxygen content in the solvent. When the polyether compound is introduced into a solvent, the solvent may be substituted with nitrogen in advance and then with fluorine.

[0099] In the fluorination reaction, whether in a batch system or a continuous system, it is preferable that the amount of fluorine gas used to fluorinate all of the fluorinatable hydrogen atoms in the polyether compound is always in excess, preferably 1.1 equivalents or more, more preferably 1.3 equivalents or more, of the theoretical amount required to fluorinate all of the fluorinatable hydrogen atoms.

[0100] When the fluorination of a polyether compound is carried out by introducing fluorine gas and the polyether compound into a solvent, the molar introduction rate of the fluorine gas may be in the range of 1 to 10 times, or may be in the range of 2 to 7 times, the rate obtained by multiplying the molar introduction rate of the polyether compound by the number of hydrogen atoms that can be substituted with fluorine atoms by the fluorine gas contained in the polyether compound, when the molar introduction rate of the polyether compound into the solvent is taken as 1. By keeping the introduction rate relationship within the above numerical range, the yield of the fluorine-containing polyether compound can be improved.

[0101] In order to efficiently proceed with the fluorination reaction of the polyether compound, it is preferable to introduce a C-H bond-containing compound other than the polyether compound into the solvent or to irradiate the solvent with ultraviolet light. These are preferably carried out at the later stage of the fluorination reaction. This allows the polyether compound present in the solvent to be efficiently fluorinated, thereby improving the yield of the fluorinated polyether compound. The C-H bond-containing compound is preferably an aromatic hydrocarbon, such as benzene or toluene, etc. The amount of the C-H bond-containing compound introduced is preferably 0.1 mol % to 10 mol %, more preferably 0.1 mol % to 5 mol %, based on the hydrogen atoms in the polyether compound. The C-H bond-containing compound is preferably introduced into a solvent in which fluorine gas is present. Furthermore, when the C-H bond-containing compound is added, it is preferable to pressurize the reaction system. The reaction pressure when pressurized is preferably 0.01 MPa to 5 MPa (gauge pressure). When the reaction system is irradiated with ultraviolet light, the irradiation time is preferably 0.1 to 3 hours.

[0102] After the fluorination reaction, at least one selected from a solvent, water, and an aqueous solution for adjusting the acidity to an appropriate level may be added to the reaction liquid to separate the liquids, and the organic phase may be concentrated to obtain a fluorinated polyether compound. Alternatively, the reaction crude liquid obtained by concentrating the organic phase may be purified to obtain a fluorinated polyether compound.

[0103] When a polyether compound has a structure represented by the above formula (3) and has -OCF=CF2 groups at both ends, fluorination of the polyether compound gives a fluorinated polyether compound having a structure represented by the following general formula (4-1): CF3CF2O-X F -(D 1F -Y F -D 1F -X F ) n -OCF2CF3···(4-1) The polyether compound has a structure represented by the above formula (3) and has -O(CF2) at both ends. m When the polyether compound has a CF=CF2 group, the fluorination of the polyether compound gives a fluorine-containing polyether compound having a structure represented by the following general formula (4-2). CF3CF2(CF2) m OX F -(D 1F -Y F -D 1F -X F ) n -O(CF2) m CF2CF3···(4-2)

[0104] In the general formula (4-1) and the general formula (4-2), X Feach independently represents a divalent perfluorohydrocarbon group having 1 to 20 carbon atoms, which is a divalent hydrocarbon group represented by X that has been perfluorinated. In the general formula (4-1) and the general formula (4-2), Y F each independently represents a divalent perfluorohydrocarbon group having 1 to 20 carbon atoms, which is a divalent hydrocarbon group represented by Y that has been perfluorinated. In the general formula (4-1) and the general formula (4-2), D 1F represents a divalent linking group in which the divalent linking group represented by D is perfluorinated, and both are *-OCF2CF2O-** or *-O(CF2) m CF2CF2O-**. * is X F represents the bond to Y F Also, -O(CF2) m In CF2CF2O-, m is as defined above and will not be described here. In the general formula (4-1) and the general formula (4-2), n is as defined above, and therefore will not be described here.

[0105] Compounds having a structure represented by general formula (4-1) or general formula (4-2) include, but are not limited to, the following compounds:

[0106] [ka]

[0107] [ka]

[0108] -Specific Example B of Method for Producing Fluorinated Polyether Composition- When the polyether composition contains a polyether compound having —OH groups at both ends, the —OH groups are esterified to produce a diacyloxy polyether compound, and the diacyloxy polyether compound is fluorinated, thereby producing a fluorinated polyether composition containing a fluorinated polyether compound having ester groups at both ends. The above method is preferable when the proportion of —OH groups relative to the total of 100 mol % of terminal groups possessed by all polyether compounds contained in the polyether composition is 90 mol % or more. Alternatively, the above-mentioned fluorine-containing polyether compound can be reacted with an alcohol to produce a fluorine-containing diacylalkoxycarbonyl polyether compound, and the fluorine-containing diacylalkoxycarbonyl polyether compound can be reduced to produce a fluorine-containing polyether composition containing a fluorine-containing polyether compound having —OH groups at both ends. When the polyether compound has an -OTs group, an -OTf group or an -OMs group at both ends, both ends can be converted to -OH groups by elimination reaction using a conventionally known method, and a fluorine-containing polyether composition containing a fluorine-containing polyether compound having ester groups at both ends and a fluorine-containing polyether composition containing a fluorine-containing polyether compound having -OH groups at both ends can be produced by the above-mentioned method.

[0109] For the esterification of the -OH group, from the viewpoint of reactivity, a method of reacting an acid halide with the hydroxyl group is preferred, a method of reacting an acid fluoride with the hydroxyl group is more preferred, and a method of reacting an acid fluoride represented by the following general formula (5) with a polyether compound is even more preferred. R 6 C(=O)F (5)

[0110] In general formula (5), R 6 represents a monovalent hydrocarbon group having 2 to 20 carbon atoms which may contain an ether bond and in which a hydrogen atom may be substituted with a fluorine atom. R 6 From the viewpoint of ease of purification, the number of carbon atoms in the monovalent hydrocarbon group represented by R is preferably 20 or less, and more preferably 10 or less.6 The number of carbon atoms in the monovalent hydrocarbon group represented by the following formula is preferably 3 or more, more preferably 4 or more, from the viewpoint of suppressing side reactions during fluorination. R 6 In the case where hydrogen atoms in the monovalent hydrocarbon group represented by the formula (I) are substituted with fluorine atoms, the fluorine atom content is preferably 50 mol % or more, more preferably 75 mol % or more, and even more preferably 100 mol % (perfluorohydrocarbon group), where the fluorine atom content refers to the proportion of hydrogen atoms in the hydrocarbon group that have been substituted with fluorine atoms.

[0111] Specific examples of the acid fluoride represented by the general formula (5) include, but are not limited to, the following compounds: CF3CF2CF2OCF(CF3)C(=O)F ·CF3CF2CF2OCF(CF3)CF2OCF(CF3)C(=O)F CF3CF(CF3)C(=O)F

[0112] The esterification of the -OH groups of the polyether compound may be carried out in a solvent or in a solvent-free state without using a solvent. When the esterification of the -OH groups of the polyether compound is carried out in a solvent, the solvent is preferably a fluorine-based organic solvent, and examples thereof include a fluorinated alkane, a fluorinated aromatic compound, and a fluoroalkyl ether.

[0113] When acid fluoride is reacted with a polyether compound, it is preferable to carry out the reaction in the presence of a hydrogen fluoride (HF) scavenger. HF is generated by the reaction between the polyether compound and acid fluoride, so it is preferable to have an HF scavenger present in the reaction system. Examples of HF scavengers include metal fluoride salts and trialkylamines. As metal fluoride salts, sodium fluoride or potassium fluoride is preferable. When no HF scavenger is used, it is preferable to carry out the reaction at a reaction temperature at which HF can be vaporized and to discharge HF from the reaction system by entraining it in a nitrogen stream. The amount of the HF scavenger used is preferably 1 to 10 times the molar amount of the acid fluoride.

[0114] When a polyether compound has a structure represented by the above formula (3) and has —OH groups at both ends, a diacyloxy polyether compound having a structure represented by the following general formula (6) is obtained by esterification of the polyether compound. R 6 C(=O)OX-(D 2 -YD 2 -X) n -OC(=O)R 6 ···(6)

[0115] In general formula (6), D 2 represents a divalent linking group, and both are **-OCFHCF2O-* and *-O(CF2) m CFHCF2O-** or *-O-**. * represents the bond to X, and ** represents the bond to Y. Also, -O(CF2) m In CF=CF2, m is as described above and will not be described here. In general formula (6), X, Y, R 6 and n are as described above, and therefore will not be described here.

[0116] The method for fluorinating the diacyloxy polyether compound is not particularly limited, and can be carried out by the above-mentioned method, so the description thereof will be omitted here.

[0117] When the diacyloxy polyether compound is represented by the above general formula (6), a fluorinated polyether compound having a structure represented by the following general formula (7) can be obtained by fluorination of the diacyloxy polyether compound. R 6F C(=O)OX F -(D 2F -Y F -D 2F -X F ) n -OC(=O)R 6F ···(7)

[0118] In general formula (7), R 6F are each independently R6 represents a perfluorinated monovalent hydrocarbon group having 2 to 20 carbon atoms. In general formula (7), D 2F is D 2 represents a perfluorinated divalent linking group, and both are **-OCF2CF2O-* and *-O(CF2) m CF2CF2O-** or *-O-**. * is X F represents the bond to Y F Also, -O(CF2) m In CF=CF2, m is as described above and will not be described here. In general formula (7), X F , Y F and n are as described above, and therefore will not be described here.

[0119] Compounds having a structure represented by general formula (7) include, but are not limited to, the following compounds:

[0120] [ka]

[0121] The fluorinated diacyloxy polyether compound is then reacted with an alcohol to produce a fluorinated diacylalkoxycarbonyl polyether compound. The alcohol is not particularly limited, and examples thereof include methanol, ethanol, and isopropanol. The amount of alcohol used relative to the fluorine-containing diacyloxy polyether compound is preferably 2 mol to 10 mol, more preferably 2.1 mol to 5 mol, and even more preferably 2.2 mol to 4 mol, of alcohol relative to 1 mol of the fluorine-containing diacyloxy polyether compound.

[0122] The reaction of the fluorine-containing diacyloxy polyether compound with the alcohol may be carried out in a solvent or in the absence of a solvent. When the reaction of the fluorine-containing diacyloxy polyether compound with the alcohol is carried out in a solvent, the solvent is preferably a fluorine-containing organic solvent, and examples thereof include fluorinated alkanes, fluorinated aromatic compounds, and fluoroalkyl ethers.

[0123] From the viewpoint of the yield of the fluorine-containing diacylalkoxycarbonyl polyether compound, the reaction temperature of the fluorine-containing diacyloxy polyether compound and the alcohol is preferably from 0 to 60°C, more preferably from 0 to 40°C. From the viewpoint of the yield of the fluorine-containing diacylalkoxycarbonyl polyether compound, the reaction time of the fluorine-containing diacyloxy polyether compound with the alcohol is preferably from 0.5 to 48 hours, more preferably from 0.5 to 24 hours.

[0124] A fluorine-containing diacylalkoxycarbonyl polyether compound having a structure represented by the following general formula (8) can be obtained by reacting a fluorine-containing polyether compound having a structure represented by the above general formula (7) with an alcohol. R 7 OC(=O)-X F-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)

[0125] In general formula (8), X F-1 are each independently, X F It represents a divalent perfluorohydrocarbon group having 1 to 19 carbon atoms, which is obtained by reducing the number of carbon atoms by one from the divalent perfluorohydrocarbon group represented by the formula: FThe divalent perfluorohydrocarbon group represented by the formula: reacts with alcohol to form -C(=O)OR 7 This is due to the formation of a group. In general formula (8), R 7 R each independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain an ether bond and in which a hydrogen atom may be substituted with a fluorine atom. 7 is a group derived from an alcohol reacted with a fluorine-containing diacyloxy polyether compound. In general formula (8), X F , Y F , D 2F and n are as described above, and therefore will not be described here.

[0126] A fluorine-containing polyether compound having —OH groups at both ends can be produced by reducing a fluorine-containing diacylalkoxycarbonyl polyether compound. 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). The amount of the reducing agent used relative to the fluorine-containing diacylalkoxycarbonyl polyether compound is preferably 0.25 mol to 10 mol, more preferably 0.5 mol to 8 mol, and even more preferably 0.6 mol to 5 mol, per 1 mol of the fluorine-containing diacylalkoxycarbonyl polyether compound.

[0127] From the viewpoint of the yield of the fluorine-containing polyether compound, the reaction temperature of the fluorine-containing diacylalkoxycarbonyl polyether compound and the reducing agent is preferably from -20°C to 60°C, more preferably from 0°C to 40°C. From the viewpoint of the yield of the fluorinated polyether compound, the reaction time of the fluorinated diacylalkoxycarbonyl polyether compound with the reducing agent is preferably from 0.5 to 48 hours, more preferably from 1 to 24 hours.

[0128] A fluorine-containing polyether compound having a structure represented by the following general formula (9) can be obtained by reducing a fluorine-containing diacylalkoxycarbonyl polyether compound having a structure represented by the following general formula (8). HOCH2-X F-1 -(D 2F -Y F -D 2F -X F ) n-1 -D 2F -Y F -D 2F -X F1 -CH2OH···(9)

[0129] In general formula (9), X F , X F-1 , Y F , D 2F and n are as described above, and therefore will not be described here.

[0130] Compounds having a structure represented by general formula (9) include, but are not limited to, the following compounds:

[0131] [ka]

[0132] -Specific Example C of Method for Producing Fluorinated Polyether Composition- When the polyether composition contains a polyether compound having a -C(=O)F group, a -OC(=O)F group, a -OTs group, a -OTf group or a -OMs group at both terminals, the polyether compound can be fluorinated to produce a fluorinated polyether composition containing a fluorinated polyether compound having a -C(=O)F group, a -OC(=O)F group, a -OTs group, a -OTf group or a -OMs group at both terminals. The above method is preferred when the proportion of the -C(=O)F group, the -OC(=O)F group, the -OTs group, the -OTf group, or the -OMs group relative to the total 100 mol% of the terminal groups of all the polyether compounds contained in the polyether composition is 90 mol% or more. Alternatively, the above-mentioned fluorine-containing polyether compound can be reacted with an alcohol to produce a fluorine-containing diacylalkoxycarbonyl polyether compound, and the fluorine-containing diacylalkoxycarbonyl polyether compound can be reduced to produce a fluorine-containing polyether composition containing a fluorine-containing polyether compound having —OH groups at both ends.

[0133] When a polyether compound has a structure represented by the above formula (3) and has a -C(=O)F group, a -OC(=O)F group, a -OTs group, a -OTf group or a -OMs group at both ends, fluorination of the polyether compound gives a fluorinated polyether compound having a structure represented by the following general formula (10-1) or the following general formula (10-2): FC(=O)-X F -(D 3 -Y F -D 3 -X F ) n -C(=O)F···(10-1) EX F -(D 3 -Y F -D 3 -X F ) n -E···(10-2)

[0134] In general formula (10-1), D 3 represents a divalent linking group, and each represents **-OCF2-* or *-O-**. * represents X F represents the bond to Y F represents the binding site to In general formula (10-2), D 3 represents a divalent linking group, and each represents *-OCF2-** or **-O-*. * represents X F represents the bond to Y F represents the binding site to In the general formulae (10-1) and (10-2), E represents an -OC(=O)F group, an -OTs group, an -OTf group, or an -OMs group. In the general formula (10-1) and the general formula (10-2), X F , Y Fand n are as described above, and therefore will not be described here.

[0135] Examples of the fluorine-containing polyether compound having a structure represented by the above general formula (10-1) or general formula (10-2) include, but are not limited to, the following compounds:

[0136] [ka]

[0137] [ka]

[0138] The method for fluorinating the polyether compound is not particularly limited, and can be carried out by the above-mentioned method, so the description thereof will be omitted here.

[0139] By reacting a fluorine-containing polyether compound having a structure represented by the above general formula (10-1) with an alcohol, a fluorine-containing diacylalkoxycarbonyl polyether compound having a structure represented by the following general formula (11-1) can be obtained. R 7 OC(=O)-X F -(D 3 -Y F -D 3 -X F ) n -C(=O)OR 7 (11-1)

[0140] By reacting a fluorine-containing polyether compound having a structure represented by the above general formula (10-2) with an alcohol, a fluorine-containing diacylalkoxycarbonyl polyether compound having a structure represented by the following general formula (11-2) can be obtained. R 7 OC(=O)-X F-1 -(D 3 -Y F -D 3 -XF ) n-1 -D 3 -Y F -D 3 -X F-1 -C(=O)OR 7 (11-2)

[0141] In the general formula (11-1) and the general formula (11-2), X F , X F-1 , Y F , D 3 , R 7 and n are as described above, and therefore will not be described here. The reaction between the fluorine-containing polyether compound and the alcohol is not particularly limited and can be carried out by the above-mentioned method, so the description thereof will be omitted here.

[0142] A fluorine-containing polyether compound having a structure represented by the following general formula (12-1) can be obtained by reducing a fluorine-containing diacylalkoxycarbonyl polyether compound having a structure represented by the following general formula (11-1). HOCH2-X F -(D 3 -Y F -D 3 -X F ) n -CH2OH···(12-1)

[0143] A fluorine-containing polyether compound having a structure represented by the following general formula (12-2) can be obtained by reducing a fluorine-containing diacylalkoxycarbonyl polyether compound having a structure represented by the following general formula (11-2). 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)

[0144] In the general formula (12-1) and the general formula (12-2), XF , X F-1 , Y F , D 3 and n are as described above, and therefore will not be described here.

[0145] Examples of the fluorine-containing polyether compound having a structure represented by the above general formula (12-1) or general formula (12-2) include, but are not limited to, the following compounds:

[0146] [ka]

[0147] [ka]

[0148] [ka]

[0149] The reduction of the fluorine-containing diacylalkoxycarbonyl polyether compound is not particularly limited and can be carried out by the above-mentioned method, so the description thereof will be omitted here.

[0150] From the viewpoint of heat resistance, the content of the fluorinated polyether compound in the fluorinated polyether composition is preferably from 60 to 100% by mass, and more preferably from 80 to 100% by mass. The fluorine-containing polyether composition may contain one kind of fluorine-containing polyether compound or two or more kinds of fluorine-containing polyether compounds. [Example]

[0151] The above embodiment will be specifically described below using synthesis examples, but the above embodiment is not limited to these synthesis examples. Synthesis examples 1-1 to 1-5, 2-1 to 2-2, and 3-1 to 3-4 are working examples, and synthesis examples 4-1, 5-1, and 5-2 are comparative examples.

[0152] [Evaluation method] (NMR analysis) The NMR analysis was carried out under the following conditions. 1 Nitrobenzene (7.5 ppm) was used as the reference substance for H-NMR (300.4 MHz). 19 Perfluorobenzene at −162.5 ppm was used as the reference substance for F-NMR (282.7 MHz). The solvent used for NMR was CFE-419 (ClCF2CFClCF2OCF2CF2Cl).

[0153] (GPC analysis) The number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured by GPC, which was carried out by the method described above.

[0154] The abbreviations in the examples have the following meanings: (HFPO)2:CF3CF2CF2-O-CF(CF3)C(=O)F PTFE: Polytetrafluoroethylene AC-2000: Fluorine-based solvent, manufactured by AGC Corporation, Asahiklin (registered trademark) AC-2000

[0155] (Synthesis Example 1-1) Into 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 chemical formula (1-1) and 138 g of an alkali catalyst (K2CO3) were introduced, heated until the temperature inside the three-necked flask reached 40°C, and stirred and mixed for 10 minutes. Next, 344 g of divinyl ether (1.0 mol) represented by the following chemical formula (2-1) was introduced into the three-necked flask at a rate of 1 mole / hour per 1 mole of ethylene glycol. After the introduction of the divinyl ether, the three-necked flask was heated until the internal temperature reached 70°C, and the contents were stirred and mixed to carry out a first polymerization reaction, thereby obtaining a first polymer composition. HOCH2CH2OH···(1-1) CF2=CFOCF2CF2CF2OCF=CF2...(2-1)

[0156] To the first polymer composition, 31 g of ethylene glycol (0.5 mol) was introduced at a rate of 6 mol / hour relative to 1 mol of the divinyl ether charged in the first polymerization reaction, and the internal temperature of the three-neck flask was maintained at 70°C, followed by stirring and mixing to carry out a second polymerization reaction.The flask was then cooled until the internal temperature reached 25°C, yielding a second polymer composition. In the first polymerization reaction, the time from when the reaction temperature was raised to 70° C. until the ethylene glycol used in the second polymerization reaction was introduced (first polymerization reaction time) was 3 hours. In the second polymerization reaction, after ethylene glycol was introduced and the reaction temperature was raised to 70°C, it took 5 hours for the internal temperature of the flask to reach 25°C (second polymerization reaction time).

[0157] After the second polymerization reaction, hydrochloric acid was added to the second polymerization composition and stirred and mixed to obtain a reaction crude liquid separated into an organic phase and an aqueous phase. The obtained reaction crude liquid was separated, and 308 g of the organic phase (polyether composition A) was recovered. 1 H-NMR method and 19 F-NMR analysis confirmed that polyether composition A contains polyether compound a represented by the following chemical formula (3-1), polyether compound b represented by the following chemical formula (3-2), and polyether compound c represented by the following chemical formula (3-3), and that the average value of n in the chemical formulas (3-1) to (3-3) is 8. The yield of the polyether compound was 76%. Also, 1 H-NMR method and 19The proportions of the terminal groups of the polyether compound contained in polyether composition A were determined by F-NMR. The proportion of -OH was 94 mol% and the proportion of -OCF=CF2 was 6 mol%, with the total of -OH and -OCF=CF2 being 100 mol%. The Mw / Mn of the polyether compound contained in Polyether Composition A was 1.55.

[0158] NMR spectrum of polyether composition A 1 H-NMR δ(ppm):2.8ppm(1.88H), 3.7ppm(3.76H), 3.8ppm(32.24H), 3.9ppm(3.76H), 6.0ppm(16.12H) 19 F-NMR δ(ppm): -84ppm(32.24F), -87ppm(32.12F), -114ppm(0.06F), -122ppm(0.06F), -128ppm(16.12F), -135ppm(0.06F), -145ppm(16.06F)

[0159] The polyether compound a represented by the chemical formula (3-1) is described below. [ka]

[0160] The polyether compound b represented by the chemical formula (3-2) is shown below. [ka]

[0161] The polyether compound c represented by the chemical formula (3-3) is shown below. [ka]

[0162] (Synthesis Example 1-2) Into a separately prepared three-neck flask equipped with a stirring blade, a thermometer, and a reflux condenser, 280 g of the polyether composition A obtained in Synthesis Example 1-1, 35.5 g of sodium fluoride (HF scavenger), and 280 g of (HFPO) were introduced.

[0163] The three-necked flask was heated until the internal temperature reached 50°C, and the contents were stirred and mixed for 20 hours. After stirring and mixing, the three-necked flask was cooled until the internal temperature reached 25°C, and the HF scavenger was filtered out of the contents using a PTFE membrane filter.

[0164] Low boiling components were distilled off from the filtered content at 60° C. under vacuum to obtain an oily crude product A-1. 1 H-NMR method and 19 F-NMR analysis confirmed that the crude product A-1 contained a diacyloxy polyether compound a represented by the following chemical formula (6-1), an acyloxy polyether compound a represented by the chemical formula (6-2), and a polyether compound b represented by the above chemical formula (3-2), and that the average value of n in the chemical formulas (6-1), (6-2), and (3-2) was 8. Also, 1 H-NMR method and 19 The proportions of terminal groups possessed by the compounds contained in the crude product A-1 were determined by F-NMR. The proportion of -OC(=O)CF(CF3)-OC3F7 was 94 mol % and the proportion of -OCF=CF2 was 6 mol %, relative to a total of 100 mol % of -OC(=O)CF(CF3)-OC3F7 and -OCF=CF2. The Mw / Mn of the compound contained in the crude product A-1 was 1.52.

[0165] The diacyloxy polyether compound a represented by the chemical formula (6-1) is shown below. [ka]

[0166] The acyloxy polyether compound a represented by the chemical formula (6-2) is shown below. [ka]

[0167] (Synthesis Example 1-3) 2800 g of CFE-419 was introduced into a 3000 mL nickel autoclave, stirred, and cooled until the internal temperature of the flask reached 20° C. A condenser maintained at 20° C., the same internal temperature as the flask, was installed at the gas outlet of the autoclave.

[0168] Next, nitrogen gas was bubbled into the CFE-419 at a rate of 155 L / hour for 1 hour. After bubbling with nitrogen gas, 20% by volume fluorine gas diluted with nitrogen gas (hereinafter referred to as 20% by volume fluorine gas) was bubbled into CFE-419 at a rate of 155 L / hour, and simultaneously, a solution prepared by diluting 315 g of crude product A-1 obtained in Synthesis Example 1-2 with CFE-419 was introduced thereinto over 6 hours.

[0169] After the introduction of the solution, a solution of benzene diluted with CFE-419 (hereinafter referred to as CFE-419 solution) was intermittently introduced. The benzene concentration in the CFE-419 solution was 0.1 mass %, and the amount of benzene was 0.3 g. After the introduction of the CFE-419 solution in benzene, 20% by volume fluorine gas was bubbled in for 1 hour, and then nitrogen gas was blown in for 1 hour to thoroughly replace the atmosphere inside the autoclave.

[0170] The material recovered from the autoclave was concentrated to obtain 378 g of an oily crude product A-2 (fluorine-containing polyether composition). 1 H-NMR method and 19It was confirmed by F-NMR that the crude product A-2 contains a fluorinated polyether compound a represented by the following chemical formula (7-1), a fluorinated polyether compound b represented by the chemical formula (7-2), and a fluorinated polyether compound c represented by the chemical formula (7-3), and that the average value of n in the chemical formulas (7-1) to (7-3) is 8. Also, 1 H-NMR method and 19 The proportions of the terminal groups of the compounds contained in the crude product A-2 were determined by F-NMR. The proportion of -OC(=O)CF(CF3)-OC3F7 was 94 mol % and the proportion of -OCF2CF3 was 6 mol %, relative to a total of 100 mol % of -OC(=O)CF(CF3)-OC3F7 and -OCF2CF3. The Mw / Mn of the compound contained in the crude product A-2 was 1.62.

[0171] The fluorine-containing polyether compound a represented by the chemical formula (7-1) is described below. [ka]

[0172] The fluorine-containing polyether compound b represented by the chemical formula (7-2) is shown below. [ka]

[0173] The fluorine-containing polyether compound c represented by the chemical formula (7-3) is shown below. [ka]

[0174] (Synthesis Example 1-4) Into a 500 mL flask, 370 g of the crude product A-2 obtained in Synthesis Example 1-3, 32 g of sodium fluoride (HF scavenger), and 24 g of methanol were placed, and the flask was cooled until the internal temperature reached 0°C, followed by stirring and mixing for 2 hours. After stirring and mixing, the flask was heated until the internal temperature reached 25°C, and the contents were filtered using a PTFE membrane filter.

[0175] Low boiling components were distilled off from the filtered content at 60° C. under vacuum to obtain 321 g of an oily crude product A-3. 1 H-NMR method and 19 It was confirmed by F-NMR that the crude product A-3 contains a fluorine-containing diacylalkoxycarbonyl polyether compound a represented by the following chemical formula (8-1), a fluorine-containing acylalkoxycarbonyl polyether compound a represented by the chemical formula (8-2), and a fluorine-containing polyether compound b represented by the above chemical formula (7-2), and that the average value of n in the chemical formulas (8-1), (8-2), and (7-2) is 8. Also, 1 H-NMR method and 19 The proportion of terminal groups possessed by the compounds contained in the crude product A-3 was determined by F-NMR. The proportion of -C(=O)OCH3 was 94 mol% and the proportion of -O-CF2CF3 was 6 mol%, relative to a total of 100 mol% of -C(=O)OCH3 and -OCF2CF3. The Mw / Mn of the compound contained in the crude product A-3 was 1.56.

[0176] The fluorine-containing diacylalkoxycarbonyl polyether compound a represented by the chemical formula (8-1) is shown below. [ka]

[0177] The fluorine-containing acylalkoxycarbonyl polyether compound a represented by the chemical formula (8-2) is shown below. [ka]

[0178] (Synthesis Example 1-5) 5.7 g of NaBH powder (reducing agent) was placed in a 1000 mL three-neck flask, followed by 640 g of AC-2000 and 70 g of ethanol. The flask was cooled to an internal temperature of 0°C and then mixed with stirring. 320 g of the crude product A-3 obtained in Synthesis Example 1-4 was introduced into a three-necked flask, and the contents were mixed with stirring for 2 hours while maintaining the internal temperature of the three-necked flask at 0°C. After stirring and mixing, hydrochloric acid was introduced into the three-necked flask until the contents of the three-necked flask became acidic, and a reaction crude liquid separated into an organic phase and an aqueous phase was obtained. The reaction crude liquid obtained was separated, and the organic phase was recovered. The organic phase was concentrated, and low boiling components were distilled off, to obtain an oily crude product A-4 (fluorine-containing polyether composition). 1 H-NMR method and 19 It was confirmed by F-NMR that the crude product A-4 contains a fluorinated polyether compound d represented by the following chemical formula (9-1), a fluorinated divinyl polyether compound e represented by the chemical formula (9-2), and a fluorinated polyether compound b represented by the chemical formula (7-2), and that the average value of n in the chemical formulas (9-1), (9-2), and (7-2) is 8. Also, 1 H-NMR method and 19 The proportions of the terminal groups of the compounds contained in the crude product A-4 were determined by F-NMR. The proportion of -OH was 94 mol % and the proportion of -O-CFCF was 6 mol %, relative to a total of 100 mol % of -OH and -OCFCF. The Mw / Mn of the compound contained in the crude product A-4 was 1.50.

[0179] NMR spectrum of crude product A-4 1 H-NMR δ(ppm): 4.0 ppm (3.76H) 19F-NMR δ(ppm):-76ppm(3.76F),-86ppm(32F),-89ppm(0.18F),-92ppm(95.76F),-93ppm(0.12F),-128ppm(16F)

[0180] The fluorine-containing polyether compound d represented by the chemical formula (9-1) is shown below. [ka]

[0181] The fluorine-containing polyether compound e represented by the chemical formula (9-2) is shown below. [ka]

[0182] The crude product A-4 was purified by column chromatography to obtain a fluorinated polyether compound d. The Mw / Mn of the fluorinated polyether compound d was 1.48. 1 H-NMR method and 19 The NMR spectrum of fluorine-containing polyether compound d was obtained by F-NMR, and it was confirmed that it was a compound represented by the above chemical formula (9-1) in which the average value of n is 8.

[0183] NMR spectrum of fluorine-containing polyether compound d 1 H-NMR δ(ppm): 4.0 ppm (4H) 19 F-NMR δ(ppm): -76ppm(4F), -86ppm(32F), -92ppm(96F), -128ppm(16F)

[0184] (Synthesis Example 2-1) Into 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 (alkali catalyst) were placed, heated until the temperature inside the three-necked flask reached 40°C, and mixed by stirring for 10 minutes. Next, 172 g of the divinyl ether (0.5 mol) represented by the above chemical formula (2-1) was introduced into the three-neck flask at a rate of 0.25 mol / hour per 1 mol of ethylene glycol. After the introduction of the divinyl ether, the flask was heated to an internal temperature of 70°C, and the contents were stirred and mixed to carry out a first polymerization reaction, thereby obtaining a first polymer composition.

[0185] To the first polymer composition, 172 g of divinyl ether (0.5 mol) represented by the above chemical formula (2-1) was introduced at a rate of 20 mol / hour relative to 1 mol of ethylene glycol used in the first polymerization reaction, and the internal temperature of the flask was maintained at 70°C, followed by stirring and mixing to carry out a second polymerization reaction.The internal temperature of the flask was then cooled to 25°C, thereby obtaining a second polymer composition. The first polymerization reaction time was 3 hours, and the second polymerization reaction time was 5 hours.

[0186] After the second polymerization reaction, hydrochloric acid was added to the second polymerization composition and stirred and mixed to obtain a reaction crude liquid separated into an organic phase and an aqueous phase. The obtained reaction crude liquid was separated, and 333 g of the organic phase (polyether composition B) was recovered. 1 H-NMR method and 19 By F-NMR, it was confirmed that polyether composition B contains polyether compound a represented by the above chemical formula (3-1), polyether compound b represented by the above chemical formula (3-2), and polyether compound c represented by the above chemical formula (3-3), and that the average value of n in chemical formulas (3-1) to (3-3) is 8. The yield of the polyether compound was 82%. Also, 1 H-NMR method and 19The proportions of the terminal groups of the polyether compound contained in polyether composition B were determined by F-NMR. The proportion of -OH was 2 mol % and the proportion of -OCH=CH 2 was 98 mol %, with the total of -OH and -OCH=CH 2 being 100 mol %. The compound contained in Polyether Composition B had an Mw / Mn of 1.55.

[0187] NMR spectrum of polyether composition B 1 H-NMR δ(ppm): 2.8ppm(0.02H), 3.7ppm(0.04H), 3.87ppm(32H), 3.9ppm(0.04H), 6.0ppm(16.02H) 19 F-NMR δ(ppm): -84ppm(36F), -87ppm(32.04F), -114ppm(1.96F), -122ppm(1.96F), -128ppm(17.96F), -135ppm(1.96F), -145ppm(8.16F)

[0188] (Synthesis Example 2-2) 2800 g of CFE-419 was introduced into a 3000 mL nickel autoclave, stirred, and cooled until the internal temperature of the flask reached 20° C. A condenser maintained at 20° C. was installed at the gas outlet of the autoclave.

[0189] Next, nitrogen gas was bubbled into the CFE-419 at a rate of 178 L / hour for 1 hour. After bubbling with nitrogen gas, 20% by volume fluorine gas was bubbled into the CFE-419 at a rate of 178 L / hour, and simultaneously, a solution prepared by diluting 330 g of the polyether composition B obtained in Synthesis Example 1-2 with CFE-419 was introduced over 6 hours.

[0190] After the introduction of the solution, the CFE-419 solution was intermittently introduced. After the introduction of the CFE-419 solution in benzene, 20% by volume fluorine gas was bubbled in at a rate of 178 L / hour for 1 hour, and finally nitrogen gas was blown in for 1 hour to thoroughly replace the atmosphere inside the reactor.

[0191] The product recovered from the autoclave was concentrated to obtain 404 g of an oily crude product B-1 (fluorine-containing polyether composition). 1 H-NMR method and 19 It was confirmed by F-NMR that the fluorine-containing polyether composition contains a fluorine-containing polyether compound f represented by the following chemical formula (4-1), a fluorine-containing polyether compound g represented by the following chemical formula (4-2), and a fluorine-containing polyether compound h represented by the following chemical formula (4-3), and that the average value of n in the chemical formulas (4-1) to (4-3) is 8. The Mw / Mn of the compound contained in the fluorinated polyether composition was 1.52.

[0192] The fluorine-containing polyether compound f represented by the chemical formula (4-1) is described below. [ka]

[0193] The fluorine-containing polyether compound g represented by the chemical formula (4-2) is shown below. [ka]

[0194] The fluorine-containing polyether compound h represented by the chemical formula (4-3) is shown below. [ka]

[0195] NMR spectra of fluorine-containing polyether compositions 19 F-NMR δ(ppm): -86ppm(36F), -90ppm(6F), -92ppm(96F), -93ppm(4F), -128ppm(18F)

[0196] (Synthesis Example 3-1) 83 g of cesium fluoride (alkali catalyst) was introduced into a 500 mL Hastelloy autoclave. Next, 100 g of a difluorinated acyloxy compound (0.55 mol) represented by the following chemical formula (2-2) was introduced into the autoclave, and the autoclave was filled with N2 atmosphere at an internal temperature of -196°C, followed by vacuum degassing. FC(=O)OCH2CH2CH2CH2OC(=O)F...(2-2)

[0197] After degassing, 81 g of a difluorinated acyl compound (0.27 mol) represented by the following chemical formula (1-2) was introduced into the autoclave at a rate of 0.17 mol / hour per 1 mol of the difluorinated acyloxy compound. After the introduction of the difluorinated acyl compound, the autoclave was heated until the internal temperature reached 80°C, and the mixture was stirred and mixed to carry out a first polymerization reaction. FC(=O)CF2CF2CF2CF2C(=O)F...(1-2)

[0198] Next, 81 g of the difluorinated acyl compound (0.27 mol) represented by the above chemical formula (1-2) was introduced into the autoclave at a rate of 5 mol / hour relative to 1 mol of the difluorinated acyloxy compound used in the first polymerization reaction, and the autoclave was heated to an internal temperature of 120°C, stirred and mixed, and a second polymerization was carried out. The flask was then cooled to an internal temperature of 25°C, and crude product C-1 was obtained. The first polymerization reaction time was 3 hours, and the second polymerization reaction time was 8 hours.

[0199] After the second polymerization, the alkali catalyst was filtered off from the crude product C-1 using a PTFE membrane filter. 160 g of cesium fluoride was added to the crude product C-1 from which cesium fluoride had been filtered, and the autoclave was heated to an internal temperature of 180° C., followed by stirring and mixing for 30 hours.

[0200] After stirring and mixing, nitrogen gas was blown into the autoclave to purge by-products such as HF, and the by-products such as HF in the autoclave were thoroughly replaced with nitrogen gas (nitrogen purging).

[0201] The material recovered from the autoclave was filtered using a PTFE membrane filter to obtain 160 g of a viscous polyether composition C. 1 H-NMR method and 19 By F-NMR, it was confirmed that polyether composition C contains polyether compound d represented by the following chemical formula (3-4), polyether compound e represented by chemical formula (3-5), and polyether compound f represented by chemical formula (3-6), and that the average value of n in chemical formulas (3-4) to (3-6) is 8. The yield of the polyether compound was 83%. Also, 1 H-NMR method and 19 The proportions of the terminal groups of the polyether compound contained in polyether composition C were determined by F-NMR. The proportion of -OC(=O)F was 4 mol % and the proportion of -C(=O)F was 96 mol %, relative to a total of 100 mol % of -OC(=O)F and -C(=O)F. The Mw / Mn of the polyether compound contained in Polyether Composition C was 1.58.

[0202] NMR spectrum of polyether composition C 1 H-NMR δ(ppm): 1.6ppm(0.08H), 1.8ppm(32.08H), 3.4ppm(32.08H), 4.2ppm(0.08H) 19 F-NMR δ(ppm): 14ppm(0.96F), -11ppm(0.04F), -86ppm(16.32F), -118ppm(3.84F), -121ppm(31.92F), -122ppm(33.92F), -126ppm(33.92F)

[0203] The polyether compound d represented by the chemical formula (3-4) is shown below. [ka]

[0204] The polyether compound e represented by chemical formula (3-5) is shown below. [ka]

[0205] The polyether compound f represented by the chemical formula (3-6) is shown below. [ka]

[0206] (Synthesis Example 3-2) 300 g of CFE-419 was introduced into a 500 mL nickel autoclave, stirred, and cooled until the internal temperature of the autoclave reached 20° C. A condenser maintained at 20° C. was installed at the gas outlet of the autoclave.

[0207] Next, nitrogen gas was bubbled into the CFE-419 at a rate of 63 L / hour for 1 hour. After bubbling with nitrogen gas, 20% by volume fluorine gas was bubbled into the CFE-419 at a rate of 63 L / hour. After bubbling with fluorine gas, a solution obtained by diluting 120 g of polyether composition C obtained in Synthesis Example 3-1 with CFE-419 was introduced into CFE-419 over 1 hour, and 20% by volume of fluorine gas was bubbled into CFE-419 at a rate of 63 L / hour.

[0208] After the introduction of the solution, the CFE-419 solution was introduced intermittently. After the introduction of the CFE-419 solution in benzene, 20% by volume fluorine gas was bubbled in at a rate of 63 L / hour for 1 hour, and finally nitrogen gas was blown in for 1 hour to thoroughly replace the atmosphere inside the autoclave.

[0209] The material recovered from the autoclave was concentrated to obtain 151 g of a crude product C-2 (fluorine-containing polyether composition). 1 H-NMR method and 19 It was confirmed by F-NMR that the crude product C-2 contains a fluorinated polyether compound j represented by the following chemical formula (10-1), a fluorinated polyether compound k represented by the chemical formula (10-2), and a fluorinated polyether compound l represented by the chemical formula (10-3), and that the average value of n in the chemical formulas (10-1) to (10-3) is 8. Also, 1 H-NMR method and 19 The proportions of the terminal groups of the fluorinated polyether compound contained in the crude product C-2 were determined by F-NMR. The proportion of -OC(=O)F was 4 mol % and the proportion of -C(=O)F was 96 mol %, relative to 100 mol % in total of -OC(=O)F and -C(=O)F. The Mw / Mn of the fluorine-containing polyether compound contained in crude product C-2 was 1.60.

[0210] The fluorine-containing polyether compound j represented by the chemical formula (10-1) is described below. [ka]

[0211] The fluorine-containing polyether compound k represented by the chemical formula (10-2) is shown below. [ka]

[0212] The fluorine-containing polyether compound l represented by the chemical formula (10-3) is shown below. [ka]

[0213] (Synthesis Example 3-3) Into a 500 mL flask, 150 g of the crude product C-2, 14 g of sodium fluoride (HF scavenger), 11 g of methanol, and 150 g of AC-2000 were introduced, and the flask was cooled until the internal temperature reached 0°C, followed by stirring and mixing for 2 hours.

[0214] After stirring and mixing, the flask was heated until the internal temperature reached 25°C, and the HF scavenger was filtered off from the contents using a PTFE membrane filter.

[0215] The filtered content was concentrated under vacuum at 60° C. to obtain 144 g of crude product C-3. 1 H-NMR method and 19 By F-NMR, it was confirmed that the crude product C-3 contains a fluorine-containing diacylalkoxycarbonyl polyether compound d represented by the following chemical formula (11-1), a fluorine-containing diacylalkoxycarbonyl polyether compound e represented by the chemical formula (11-2), and a fluorine-containing diacylalkoxycarbonyl polyether compound f represented by the chemical formula (11-3), and that the average value of n in the chemical formulas (11-1) to (11-3) is 8.

[0216] The fluorine-containing diacylalkoxycarbonyl polyether compound d represented by the chemical formula (11-1) is shown below. [ka]

[0217] The fluorine-containing diacylalkoxycarbonyl polyether compound e represented by the chemical formula (11-2) is shown below. [ka]

[0218] The fluorine-containing diacylalkoxycarbonyl polyether compound f represented by the chemical formula (11-3) is shown below. [ka]

[0219] (Synthesis Example 3-4) 2.3 g of NaBH powder (reducing agent) was placed in a 1000 mL three-neck flask, followed by 280 g of AC-2000 and 28 g of ethanol. The flask was cooled to an internal temperature of 0°C and then mixed with stirring. 140 g of the crude product C-3 obtained in Synthesis Example 3-3 above was placed in a three-necked flask, and the contents were mixed with stirring for 2 hours while maintaining the internal temperature of the three-necked flask at 0°C. After stirring and mixing, hydrochloric acid was added dropwise to the three-necked flask until the contents of the three-necked flask became acidic, and a reaction crude liquid separated into an organic phase and an aqueous phase was obtained. The reaction crude liquid obtained was separated, and the organic phase was recovered. The organic phase was concentrated, and low-boiling components were distilled off, to obtain an oily crude product C-4 (fluorine-containing polyether composition). The crude product C-4 was purified by column chromatography to recover 113 g of a fluorine-containing polyether composition. 1 H-NMR method and 19 It was confirmed by F-NMR that the fluorinated polyether composition contains a fluorinated polyether compound m represented by the following chemical formula (12-1), a fluorinated polyether compound n represented by the following chemical formula (12-2), and a fluorinated polyether compound o represented by the following chemical formula (12-3), and that the average value of n is 8. The Mw / Mn of the fluorinated polyether compound contained in the fluorinated polyether composition was 1.58.

[0220] The fluorine-containing polyether compound m represented by the chemical formula (12-1) is shown below. [ka]

[0221] The fluorine-containing polyether compound n represented by the chemical formula (12-2) is shown below. [ka]

[0222] The fluorine-containing polyether compound o represented by the chemical formula (12-3) is shown below. [ka]

[0223] NMR spectra of fluorine-containing diol polyether compositions 1 H-NMR δ(ppm): 4.0 ppm (4H) 19 F-NMR δ(ppm): -86ppm(64F), -121ppm(4F), -122ppm(18F), -123ppm(18F), -125ppm(64F)

[0224] (Synthesis Example 4-1) According to the method described in paragraphs

[0104] to

[0109] of WO 2018 / 108866, a crude product D-1 containing a fluorine-containing polyether compound n represented by the following chemical formula (15-1) was obtained.

[0225] The fluorine-containing polyether compound n represented by the chemical formula (15-1) is described below. [ka]

[0226] The crude product D-1 was purified by column chromatography to obtain a fluorine-containing polyether compound n. 1 H-NMR method and 19 It was confirmed by F-NMR that the fluorine-containing diol polyether compound n had a structure represented by the above chemical formula, and that the average value of n was 2.

[0227] (Synthesis Example 5-1) According to the method described in paragraphs

[0106] to

[0109] of WO 2019 / 202079, crude product E-1 was obtained. 1 H-NMR method and 19 It was confirmed by F-NMR that the crude product E-1 contains a fluorine-containing polyether compound p represented by the following chemical formula (16-1), a compound q represented by the chemical formula (16-2), and a compound r represented by the chemical formula (16-3), and that the average value of n in the chemical formulas (16-1) to (16-3) is 4. Also, 1 H-NMR method and 19 The proportions of the terminal groups of the fluorine-containing polyether compound contained in the crude product E-1 were determined by F-NMR, and it was found that the proportion of -CF3 was 56 mol% and the proportion of -C(=O)OCH2CH3 was 44 mol%, relative to a total of 100 mol% of -CF3 and -C(=O)OCH2CH3.

[0228] The fluorine-containing polyether compound p represented by the chemical formula (16-1) is described below. [ka]

[0229] The fluorine-containing polyether compound q represented by the chemical formula (16-2) is shown below. [ka]

[0230] The fluorine-containing polyether compound r represented by the chemical formula (16-3) is shown below. [ka]

[0231] (Synthesis Example 5-2) 2.2 g of NaBH powder (reducing agent) was placed in a 300 mL three-neck flask, followed by 100 g of AC-2000 and 26.3 g of ethanol. The flask was cooled to an internal temperature of 0°C and then mixed with stirring. 50 g of the crude product E-1 obtained in Synthesis Example 6-1 was introduced into a three-necked flask, and the contents were mixed with stirring for 2 hours while maintaining the internal temperature of the three-necked flask at 0°C. After stirring and mixing, hydrochloric acid was introduced into the three-necked flask until the contents of the three-necked flask became acidic, and a crude reaction liquid was obtained that separated into an organic phase and an aqueous phase. The crude reaction liquid obtained was separated, and the organic phase was recovered. The organic phase was concentrated, and low-boiling components were distilled off, yielding an oily crude product E-2. 1 H-NMR method and 19 It was confirmed by F-NMR that the crude product E-2 contained a fluorinated polyether compound p represented by the following chemical formula (16-1), a fluorinated polyether compound s represented by the chemical formula (17-1), and a fluorinated polyether compound t represented by the chemical formula (17-3), and that the average value of n in the chemical formulas (16-1), (17-1), and (17-2) was 4. Also, 1 H-NMR method and 19 The proportions of the terminal groups of the fluorine-containing polyether compound contained in the crude product E-2 were determined by F-NMR, and it was found that the proportion of -CF3 was 56 mol% and the proportion of -CH2OH was 44 mol%, relative to a total of 100 mol% of -CF3 and -CH2OH.

[0232] The fluorine-containing polyether compound s represented by the chemical formula (17-1) is shown below. [ka]

[0233] The fluorine-containing polyether compound t represented by the chemical formula (17-2) is shown below. [ka]

[0234] The crude product F-2 was purified by column chromatography to obtain a fluorine-containing polyether compound s. 1 H-NMR method and 19 The NMR spectrum of the fluorine-containing polyether compound s was obtained by F-NMR, and it was confirmed that the compound was represented by the above chemical formula (17-1) in which the average value of n was 3.

[0235] NMR spectra of fluorine-containing polyether compounds 1 H-NMR δ(ppm): 4.0 ppm (4H) 19 F-NMR δ(ppm): -86ppm(28F), -124ppm(4F), -128ppm(12F)

[0236] <<Heat resistance evaluation>> 10 mg of each of the fluorinated polyether compound d obtained in the above Synthesis Example 1-5, the fluorinated polyether composition obtained in the above Synthesis Example 2-2, the fluorinated polyether composition obtained in the above Synthesis Example 3-4, the fluorinated polyether compound n obtained in the above Synthesis Example 4-1, and the fluorinated polyether compound s obtained in the above Synthesis Example 5-2 were prepared. The above fluorinated polyether compounds and fluorinated polyether compositions were placed in a thermogravimetric / differential thermal analyzer (model name: TG / DTA6200, manufactured by Hitachi High-Tech Science Corporation) and heated from an initial temperature of 25°C to 500°C at a heating rate of 10°C / min, and the temperature at which the weight of each fluorinated polyether compound and fluorinated polyether composition became half of the introduced weight (weight half-loss temperature) was measured. The heat resistance of the fluorinated polyether compounds and fluorinated polyether compositions was evaluated based on the following evaluation criteria, and the results are summarized in Table 1. (Evaluation criteria) A: The temperature at which the weight is reduced by half was 210°C or higher. B: The temperature at which the weight was reduced by half was 200°C or higher and lower than 210°C. C: The temperature at which the weight was reduced by half was less than 200°C.

[0237] [Table 1]

[0238] The above synthesis examples have shown that the method for producing a polyether composition according to the present disclosure can produce a polyether composition containing a polyether compound having a large number of repeating units and excellent heat resistance, and that by using the polyether compound contained in the polyether composition, a fluorinated polyether composition containing a fluorinated polyether compound having excellent heat resistance can be produced.

[0239] The disclosure of Japanese Patent Application No. 2020-217941, filed on December 25, 2020, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A polyether composition containing a polyether compound is produced by multiple polymerization reactions of a compound represented by the following general formula (1) and a compound represented by the following general formula (2), the polymerization reaction including a first polymerization reaction in which a mixture obtained by mixing 1 mol of a compound represented by the following general formula (1) with less than 1 mol of a compound represented by the following general formula (2) is heated to a reaction temperature and reacted; and a second polymerization reaction in which a compound represented by the following general formula (1) is introduced into a composition obtained by the first polymerization reaction and reacted therewith, the second polymerization reaction is carried out by reacting the compound represented by the general formula (1) with the composition obtained by the first polymerization reaction in a ratio of 0.3 mol to 0.7 mol per 1 mol of the compound represented by the general formula (2) charged in the first polymerization reaction. AX-A...(1) B-Y-B...(2) (In general formula (1) and general formula (2), X and Y each independently represent a divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain an ether bond and in which a hydrogen atom may be substituted with a fluorine atom; However, X and Y do not have an aromatic ring. Two A's contained in the compound represented by general formula (1) represent the same group, and -OCF=CF ２ , -O(CF ２ ) ｍ CF = CF ２ represents a group selected from the group comprising: -C(=O)F, -OH, -OC(=O)F, -OTs, -OTf and -OMs; A is -OCF=CF ２ , -O(CF ２ ) ｍ CF = CF ２ , -OTs, -OTf or -OMs, B both represent -OH; When A represents -C(=O)F, both B's represent -OC(=O)F; When A represents -OH, both B's represent -OCF=CF ２ , -O(CF ２ ) ｍ CF = CF ２ , -OTs, -OTf or -OMs; When A represents -OC(=O)F, both B's represent -C(=O)F. Here, Ts represents a p-toluenesulfonyl group, Tf represents a trifluoromethanesulfonyl group, Ms represents a methanesulfonyl group, and m represents an integer of 1 or more.

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

3. 3. The method for producing a polyether composition according to claim 1 or 2, wherein at least one of the multiple polymerization reactions is carried out in the presence of an alkali catalyst.

4. The method for producing a polyether composition according to any one of claims 1 to 3, wherein a ratio of a time period for the second polymerization reaction to a time period for the first polymerization reaction is 1.1 to 3.

5. The method for producing a polyether composition according to any one of claims 1 to 4, wherein the first polymerization reaction is carried out by reacting 1 mol of the compound represented by the general formula (2) with 0.1 mol to 0.9 mol of the compound represented by the general formula (1).

6. The method for producing a polyether composition according to any one of claims 1 to 5, wherein the first polymerization reaction is carried out by introducing the compound represented by the general formula (2) into the compound represented by the general formula (1) at a rate of 0.01 to 100 times mol / hour per 1 mol of the compound represented by the general formula (1), and reacting them.

7. The method for producing a polyether composition according to any one of claims 1 to 5, wherein the first polymerization reaction is carried out by introducing the compound represented by the general formula (1) into the compound represented by the general formula (2) at a rate of 0.005 to 1.2 times mol / hour per 1 mol of the compound represented by the general formula (2), and reacting them.

8. The method for producing a polyether composition according to any one of claims 1 to 7, wherein the second polymerization reaction is carried out by introducing the compound represented by general formula (1) into the composition obtained by the first polymerization reaction at a rate of 0.5 to 360 times mol / hour per 1 mol of the compound represented by general formula (2) charged in the first polymerization reaction, and reacting them.

9. The method for producing a polyether composition according to any one of claims 1 to 8, wherein at least one of X in the general formula (1) and Y in the general formula (2) is a perfluorinated divalent hydrocarbon group having 1 to 20 carbon atoms which may contain an ether bond.

10. The method for producing a polyether composition according to any one of claims 1 to 9, wherein the compound represented by the general formula (1) is reacted in a ratio of 0.6 mol to 1.4 mol per 1 mol of the compound represented by the general formula (2) in the multiple polymerization reactions.

11. The method for producing a polyether composition according to any one of claims 1 to 10, wherein a proportion of the terminal group represented by A relative to a total content of terminal groups of the polyether compounds contained in the polyether composition (100 mol %) is 90 mol % or more.

12. A method for producing a fluorinated polyether composition, comprising fluorinating a polyether compound contained in a polyether composition produced by the method for producing a polyether composition according to any one of claims 1 to 11, to produce a fluorinated polyether composition containing a fluorinated polyether compound.

13. A polyether composition comprising a polyether compound having a structure represented by the following general formula (3), wherein the proportion of terminal groups represented by A relative to a total of 100 mol % of terminal groups possessed by all polyether compounds contained in the polyether composition is 90 mol % or more: A-X-(D-Y-D-X) ｎ -A・・・(3) (In general formula (3), X's each independently represent a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain an ether bond and in which a hydrogen atom may be substituted with a fluorine atom; Y's each independently represent a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain an ether bond and in which a hydrogen atom may be substituted with a fluorine atom; However, X and Y do not have an aromatic ring. A is the same group and is -OCF=CF ２ , -O(CF ２ ) ｍ CF = CF ２ represents a group selected from the group comprising - and -OH, D represents a divalent linking group; A is -OCF=CF ２ In the above case, D is *-OCFHCF ２ represents O-**, A is -O(CF ２ ) ｍ CF = CF ２ When D represents *-O(CF ２ ) ｍ CFHCF ２ represents O-**, When A represents -OH, D is **-OCFHCF ２ O-* or *-O(CF ２ ) ｍ CFHCF ２ represents O-**, n represents an integer of 6 or more, and m represents an integer of 1 or more. Here, * represents the bond to X, and ** represents the bond to Y.

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