Method for producing fluorovinyl ether compounds

Abstract

Provided is a method for producing a fluorovinyl ether compound capable of suppressing the generation of by-products.　The method for producing a fluorovinyl ether compound of the present invention is a method for producing a fluorovinyl ether compound that heat treats a compound having a group represented by formula (1): F-C(=O)-CF-(X)-(CF2)n-O- in the presence of an oxide including at least one element selected from the group consisting of alkali metal elements and alkaline earth metal elements to obtain a fluorovinyl ether compound having a group represented by formula (2): CF2=CF-O-, the specific surface area of the oxide before heat treatment being 1.0 m2 / g or more. In formula (1), n is 0 or 1. When n is 0, X is CF3; when n is 1, X is F.

Description

[Technical Field]

[0001] The present invention relates to a method for producing a fluorovinyl ether compound. [Background technology]

[0002] Fluorovinyl ether compounds are used, for example, as monomers for producing fluorine-containing polymers. As a method for producing such fluorovinyl ether compounds, Patent Document 1 discloses a method in which glass beads (sodium silicate glass) are brought into contact with perfluoro-2-methoxypropionyl fluoride and heated. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] U.S. Patent No. 3,291,843 Summary of the Invention [Problem to be solved by the invention]

[0004] The present inventors produced a fluorovinyl ether compound by referring to the production method described in Patent Document 1, but found that the generation of by-products could not be sufficiently suppressed and that there was room for improvement.

[0005] The present invention has been made in view of the above problems, and an object of the present invention is to provide a method for producing a fluorovinyl ether compound that can suppress the generation of by-products. [Means for solving the problem]

[0006] As a result of intensive research into the above-mentioned problems, the present inventors have discovered that when a compound having a group represented by formula (1) described below is heat-treated to obtain a compound having a group represented by formula (2) described below, it is possible to obtain an oxide containing at least one element selected from the group consisting of alkali metal elements and alkaline earth metal elements, and having a specific surface area of ​​1.0 m before the heat treatment. 2 / g or more, the generation of by-products can be suppressed, and this finding led to the present invention.

[0007] That is, the inventors have found that the above problems can be solved by the following configuration. [1] A method for producing a fluorovinyl ether compound, comprising heat-treating a compound having a group represented by the following formula (1) in the presence of an oxide containing at least one element selected from the group consisting of alkali metal elements and alkaline earth metal elements, to obtain a fluorovinyl ether compound having a group represented by the following formula (2): The specific surface area of ​​the oxide before the heat treatment is 1.0 m 2 / g or more. FC(=O)-CF(X)-(CF2) n -O- Formula (1) CF2=CF-O- Equation (2) In formula (1), n ​​is 0 or 1, and when n is 0, X is CF3, and when n is 1, X is F. [2] The method for producing a fluorovinyl ether compound according to [1], wherein the oxide contains an alkali metal element. [3] The method for producing a fluorovinyl ether compound according to any one of [1] to [2], wherein the oxide is an oxide containing at least one element selected from the group consisting of alkali metal elements and alkaline earth metal elements and other metal elements. [4] The method for producing a fluorovinyl ether compound according to any one of [1] to [3], wherein the oxide is a silicate, aluminate, aluminosilicate, borosilicate, or aluminoborosilicate containing at least one element selected from the group consisting of alkali metal elements and alkaline earth metal elements. [5] The method for producing a fluorovinyl ether compound according to any one of [1] to [4], wherein the oxide is an amorphous oxide selected from glass, amorphous silica, amorphous alumina, and amorphous silica-alumina, or a crystalline oxide selected from crystalline silica, crystalline alumina, and crystalline silica-alumina. [6] The specific surface area of ​​the oxide before the heat treatment is 1.0 to 700 m 2 The method for producing a fluorovinyl ether compound according to any one of [1] to [5], wherein the fluorovinyl ether compound is fluorovinyl ether hydroxybenzoate. [7] The heat treatment is carried out in the presence of the oxide and another oxide different from the oxide, The method for producing a fluorovinyl ether compound according to any one of [1] to [6], wherein the amount of the oxide used is 0.1 to 99 mass % based on the total amount of the oxide and the other oxide used. [8] The method for producing a fluorovinyl ether compound according to any one of [1] to [7], wherein the compound having a group represented by formula (1) is a perfluoro compound. [9] The method for producing a fluorovinyl ether compound according to any one of [1] to [8], wherein the compound represented by formula (1) is a compound represented by formula (1A): FC(=O)-CF(CF3)-OR f Formula (1A) In formula (1A), R f represents a perfluoroalkyl group which may have a monovalent substituent selected from the group consisting of -C(=O)F, a sulfonyl fluoride group, a nitrile group, and a methyl ester group, or a monovalent group in which -CF2- of the above-mentioned perfluoroalkyl group which may have a monovalent substituent is substituted with an ethereal oxygen atom.

[10] The method for producing a fluorovinyl ether compound according to [9], wherein the compound represented by formula (1A) is a compound represented by the following formula (1A-1), a compound represented by the following formula (1A-2), or a compound represented by the following formula (1A-3): FC(=O)-CF(CF3)-OZ a1 Formula (1A-1) (Za1 is a perfluoroalkyl group or a monovalent group in which —CF2— in a perfluoroalkyl group is substituted with an etheric oxygen atom. FC(=O)-CF(CF3)-OQ a2 -C(=O)-F formula (1A-2) (Q a2 is a perfluoroalkylene group or a divalent group in which —CF2— in a perfluoroalkylene group is substituted with an etheric oxygen atom. FC(=O)-CF(CF3)-OQ a3 (-SO2F) q Formula (1A-3) (Q a3 is a (q+1)-valent perfluorohydrocarbon group or a (q+1)-valent group in which —CF2— in a perfluorohydrocarbon group is substituted with an etheric oxygen atom.

[11] The method for producing a fluorovinyl ether compound according to any one of [1] to

[10] , wherein the compound represented by formula (2) is a compound represented by formula (2A): CF2=CF-OR f Formula (2A) (R f is R in formula (1A) f is equivalent to

[12] The method for producing a fluorovinyl ether compound according to

[11] , wherein the compound represented by formula (2A) is a compound represented by the following formula (2A-1), a compound represented by the following formula (2A-2-1), a compound represented by the following formula (2A-2-2), or a compound represented by the following formula (2A-3). CF2=CF-OZ a1 Formula (2A-1) (Z in formula (2A-1) a1 is Z in formula (1A-1) a1 is equivalent to CF2=CF-OQ a2 -C(=O)-F formula (2A-2-1) CF2=CF-OQ a21 -CF=CF2 formula (2A-2-2) (Q in formula (2A-2-1) a2is Q in formula (1A-2) a3 Q in formula (2A-2-2) a21 is a perfluoroalkylene group or a divalent group in which —CF2— in a perfluoroalkylene group is substituted with an etheric oxygen atom. CF2=CF-OQ a3 (-SO2F) q Formula (2A-3) (Q in formula (2A-3) a3 and q are the Q in formula (1A-3), a3 and q.)

[13] The method for producing a fluorovinyl ether compound according to any one of [1] to

[12] , wherein the oxide is dried before the heat treatment. [Effects of the Invention]

[0008] According to the present invention, a method for producing a fluorovinyl ether compound capable of suppressing the generation of by-products can be provided. Furthermore, according to the present invention, a method for producing a fluorovinyl ether compound capable of suppressing the generation of by-products can be provided even when the conversion rate of the raw materials is improved. DETAILED DESCRIPTION OF THE INVENTION

[0009] The terms used in the present invention have the following meanings. A numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits.

[0010] [Method of producing fluorovinyl ether compounds] The method for producing a fluorovinyl ether compound of the present invention comprises heat-treating a compound having a group represented by the formula (1) described below (hereinafter also referred to as compound 1) in the presence of an oxide containing at least one element selected from the group consisting of alkali metal elements and alkaline earth metal elements, to obtain a fluorovinyl ether compound having a group represented by the formula (2) described below (hereinafter also referred to as compound 2). Furthermore, the specific surface area of ​​the oxide before the heat-treatment is 1.0 m 2 / g or more. The following describes a method for producing a carbon black containing at least one element selected from the group consisting of alkali metal elements and alkaline earth metal elements, and having a specific surface area of ​​1.0 m before the heat treatment: 2 Oxides with a concentration of 1 / g or more are also called "specific oxides." According to the method for producing a fluorovinyl ether compound of the present invention, the generation of by-products can be suppressed. Generally, when the conversion rate of raw materials is improved, the amount of by-products generated also tends to increase. However, surprisingly, the present inventors have found that the generation of by-products can be suppressed by using the specific oxide.

[0011] <Compound 1> Compound 1 is a compound having a group represented by the following formula (1), and is a raw material used in producing Compound 2. FC(=O)-CF(X)-(CF2) n -O- Formula (1)

[0012] In formula (1), n ​​is 0 or 1, and when n is 0, X is CF3, and when n is 1, X is F.

[0013] From the viewpoint of the stability of Compound 1 for producing Compound 2, Compound 1 is preferably a perfluoro compound. Here, the perfluoro compound refers to a compound that does not substantially contain hydrogen atoms bonded to carbon atoms, and in which all of the hydrogen atoms bonded to carbon atoms have been replaced with fluorine atoms.

[0014] From the viewpoint of the stability of compound 1 for producing compound 2, the compound represented by formula (1) is preferably a compound represented by the following formula (1A) (hereinafter also referred to as "compound 1A"). FC(=O)-CF(CF3)-OR f Formula (1A)

[0015] R f represents a perfluoroalkyl group which may have a monovalent substituent selected from the group consisting of -C(=O)F, a sulfonyl fluoride group (-SO2F), a nitrile group (-CN) and a methyl ester group (-C(O)OCH3), or a monovalent group in which -CF2- of the above-mentioned perfluoroalkyl group which may have a monovalent substituent is substituted with an ethereal oxygen atom. R f The number of carbon atoms in the perfluoroalkyl group in the formula is preferably 1 to 20, more preferably 1 to 15, and particularly preferably 1 to 10, since an increase in the boiling point due to an increase in the carbon number can be suppressed and the production of compound 2 becomes easy. R f The perfluoroalkyl group in the formula (I) may be linear or branched. R f When the perfluoroalkyl group in the formula (I) has a monovalent substituent, the number of the monovalent substituents may be 1 or 2 or more. The monovalent substituent may be bonded to any carbon atom. Among the monovalent substituents, -C(=O)F and a sulfonyl fluoride group (-SO2F) are preferred. R f The number of etheric oxygen atoms in the monovalent group may be 1 or 2 or more. The etheric oxygen atom is preferably located between the carbon-carbon bond of the perfluoroalkyl group.

[0016] Compound 1A is preferably a compound represented by the following formula 1A-1 (hereinafter also referred to as "compound 1A-1"), a compound represented by the following formula 1A-2 (hereinafter also referred to as "compound 1A-2"), or a compound represented by the following formula 1A-3 (hereinafter also referred to as "compound 1A-3"), in view of ease of production of compound 2.

[0017] FC(=O)-CF(CF3)-OZ a1 Formula (1A-1)

[0018] Z a1 is a perfluoroalkyl group or a monovalent group in which —CF2— of a perfluoroalkyl group is substituted with an etheric oxygen atom. The number of carbon atoms in the perfluoroalkyl group is preferably 1 to 10, particularly preferably 1 to 6. The perfluoroalkyl group may be linear or branched. Z a1 The number of etheric oxygen atoms in the monovalent group may be 1 or 2 or more. The etheric oxygen atom is preferably located between the carbon-carbon bond of the perfluoroalkyl group.

[0019] Compound 1A-1 is preferably a compound represented by the following formula 1A-1-1 (hereinafter also referred to as "compound 1A-1-1") or a compound represented by the following formula 1A-1-2 (hereinafter also referred to as "compound 1A-1-2").

[0020] FC(=O)-CF(CF3)-OR f11 Formula (1A-1-1)

[0021] R f11 is a perfluoroalkyl group. The number of carbon atoms in the perfluoroalkyl group is preferably 1 to 10, particularly preferably 1 to 6. The perfluoroalkyl group may be linear or branched.

[0022] FC(=O)-CF(CF3)-O-(R f12 O) m1 -R f13 Formula (1A-1-2)

[0023] R f12 is a perfluoroalkylene group. The number of carbon atoms in the perfluoroalkylene group is preferably 1 to 10, particularly preferably 1 to 6. The perfluoroalkylene group may be linear or branched. R f13 is a perfluoroalkyl group. The number of carbon atoms in the perfluoroalkyl group is preferably 1 to 10, particularly preferably 1 to 6. The perfluoroalkyl group may be linear or branched. m1 is an integer of 1 or more, preferably 1 to 6, and particularly preferably 1 to 3. When m1 is 2 or more, a plurality of (R f12 O) may be the same or different from each other.

[0024] FC(=O)-CF(CF3)-OQ a2 -C(=O)-F formula (1A-2)

[0025] The definitions of each group in formula (1A-2) are as follows. Q a2 is a perfluoroalkylene group or a divalent group in which —CF2— in a perfluoroalkylene group is substituted with an etheric oxygen atom. The number of carbon atoms in the perfluoroalkylene group is preferably from 1 to 10, particularly preferably from 1 to 6. The perfluoroalkylene group may be linear or branched. Q a2 The number of etheric oxygen atoms in the divalent group may be 1 or more. The etheric oxygen atom is preferably located between the carbon-carbon bonds of the perfluoroalkylene group.

[0026] Compound 1A-2 is preferably a compound represented by the following formula 1A-2-1 (hereinafter also referred to as "compound 1A-2-1") or a compound represented by the following formula 1A-2-2 (hereinafter also referred to as "compound 1A-2-2").

[0027] FC(=O)-CF(CF3)-OR f21 -C(=O)-F formula (1A-2-1)

[0028] R f21is a perfluoroalkylene group. The number of carbon atoms in the perfluoroalkylene group is preferably 1 to 10, particularly preferably 1 to 6. The perfluoroalkylene group may be linear or branched.

[0029] FC(=O)-CF(CF3)-O-(R f22 O) m2 -R f23 -C(=O)-F formula (1A-2-2)

[0030] R f22 is a perfluoroalkylene group. The number of carbon atoms in the perfluoroalkylene group is preferably 1 to 10, particularly preferably 1 to 6. The perfluoroalkylene group may be linear or branched. R f23 is a perfluoroalkylene group. The number of carbon atoms in the perfluoroalkylene group is preferably 1 to 8, particularly preferably 1 to 5. The perfluoroalkylene group may be linear or branched. m2 is an integer of 1 or more, preferably 1 to 6, and particularly preferably 1 to 3. When m2 is 2 or more, a plurality of (R f22 O) may be the same or different from each other.

[0031] FC(=O)-CF(CF3)-OQ a3 (-SO2F) q Formula (1A-3)

[0032] The definitions of each group in formula (1A-3) are as follows. Q a3 is a (q+1)-valent perfluorohydrocarbon group or a (q+1)-valent group in which —CF2— in a perfluorohydrocarbon group is substituted with an etheric oxygen atom. The number of carbon atoms in the perfluorohydrocarbon group is preferably 1 to 10. The perfluorohydrocarbon group may be linear or branched. Q a3The number of etheric oxygen atoms in the (q+1)-valent group in the formula (I) may be 1 or 2 or more. The etheric oxygen atom is preferably located between the carbon atom-carbon atom bond of the perfluorohydrocarbon group. q is an integer of 1 to 3.

[0033] Compound 1A-3 is preferably a compound represented by the following formula 1A-3-1 (hereinafter also referred to as "compound 1A-3-1") or a compound represented by the following formula 1A-3-2 (hereinafter also referred to as "compound 1A-3-2").

[0034] FC(=O)-CF(CF3)-(OCF2CFZ a1 ) m3 -(O) p3 -(CF2) n3 -SO2F formula (1A-3-1)

[0035] The definitions of each group in formula (1A-3-1) are as follows. Z a1 is a fluorine atom or a trifluoromethyl group. m3 is an integer from 0 to 3. p3 is 0 or 1. n3 is an integer from 1 to 12. However, m3+p3 is 1 or greater.

[0036] FC(=O)-CF(CF3)-O-(CF2) n4 -(O) p4 -C(Z a2 )(-Q a31 -SO2F)(-Q a32 -SO2F) Formula (1A-3-2)

[0037] The definitions of each group in formula (1A-3-2) are as follows. Z a2 is a perfluoroalkyl group, a monovalent group in which —CF2— of a perfluoroalkyl group is substituted with an etheric oxygen atom, or a fluorine atom. The number of carbon atoms in the perfluoroalkyl group is preferably 1 to 6. The perfluoroalkyl group may be linear or branched, but is preferably linear. Z a2 The number of etheric oxygen atoms in the monovalent group may be one or two or more. The etheric oxygen atom may be located between the carbon atom-carbon atom bond of the perfluoroalkyl group, or may be located at the carbon atom bond terminal and have the structure -C(Z a2 ) may be located on the side directly bonded to C (carbon atom). n4 is an integer of 1 to 3. p4 is 0 or 1. Q a31 is a perfluoroalkylene group or a divalent group in which —CF2— in a perfluoroalkylene group is substituted with an etheric oxygen atom. Q a32 is a single bond, a perfluoroalkylene group, or a divalent group in which —CF2— in a perfluoroalkylene group is substituted with an etheric oxygen atom. The number of carbon atoms in the perfluoroalkylene group is preferably 1 to 6, particularly preferably 1 to 4. The perfluoroalkylene group may be linear or branched, but is preferably linear. Q a31 and Q a32 The number of etheric oxygen atoms in the divalent group in the formula (I) may be one or more. The etheric oxygen atom is located between the carbon-carbon bonds of the perfluoroalkylene group or at the carbon atom bond terminal of the -C(Z a2 It is preferable that the carbon atom is directly bonded to the C in the alkyl group.

[0038] <Specific oxides> The specific oxide contains at least one element selected from the group consisting of alkali metal elements and alkaline earth metal elements (hereinafter also referred to as "specific element"), and it is preferable that the specific oxide contains an alkali metal element, as this can further suppress the generation of by-products. Specific examples of alkali metal elements include lithium, sodium, potassium, rubidium, cesium, and francium, with sodium and potassium being preferred since they can further suppress the generation of by-products. Only one type of alkali metal element may be contained, or two or more types may be contained. Specific examples of alkaline earth metal elements include beryllium, magnesium, calcium, strontium, and barium, with magnesium, calcium, and barium being preferred in terms of further suppressing the generation of by-products. Only one type of alkaline earth metal element may be contained, or two or more types may be contained. Furthermore, components that can be contained in the specific oxide may be known metal elements or compounds that can convert FC(═O)— into a fluorovinyl ether compound, such as those shown in known literature (J. Am. Chem. Soc, 1953, 75, 18, 4525-4528), and that derive carboxylates or alkyl ethers, and may include, for example, silver, ammonium, hydroxides, and alkoxides. In terms of producing compound 2, the specific element may be present as an oxide or an ion species.

[0039] The specific oxide preferably contains an element other than the specific element as an element that plays a role in supporting the specific element as an oxide or ion species. Specific examples of the other element include silicon, aluminum, manganese, lead, boron, zinc, zirconium, phosphorus, and magnesium. Silicon and aluminum are preferred because they can further suppress the generation of by-products, and these elements exist as oxides. The valence of the other elements varies depending on the ratio of the specific element to the other elements, but the valence is not limited in terms of supporting the specific element as an oxide or ion species and producing compound 2.

[0040] The specific oxide may be a single oxide of the specific element or an oxide containing the specific metal element and another metal element, but is preferably an oxide containing the specific metal element and another metal element. The oxide containing the specific metal element and another metal element may be a composite oxide containing an oxide of the specific element and an oxide of another element.

[0041] The specific oxide is preferably a silicate, aluminate, aluminosilicate, borosilicate or aluminoborosilicate containing a specific element. The structure of the specific oxide may be amorphous or crystalline, and may be non-porous or porous. Specific examples of amorphous specific oxides include various glasses, amorphous silica (also referred to as non-crystalline silica, e.g., silica gel), amorphous alumina (e.g., alumina gel), and amorphous silica-alumina. Specific examples of crystalline specific oxides include crystalline silica (e.g., cristobalite, mesoporous silica, silicalite), crystalline alumina (e.g., γ-alumina, η-alumina, θ-alumina, α-alumina, etc.), and crystalline silica-alumina (those without an ordered structure: silica-alumina, etc.; those with an ordered structure: mesoporous silica-alumina, zeolite, etc.).

[0042] The glass may have a known composition containing SiO2 as the main component, and preferably contains 0.01 to 20 mass % of at least one component selected from Li2O, Na2O, K2O, MgO, CaO, and BaO as a specific element. The glass preferably contains at least one of sodium and potassium, since this can further suppress the generation of by-products. Specific examples of compositions include soda lime glass mainly composed of SiO2, Na2O, and CaO, potassium crystal glass mainly composed of SiO2, Na2O, K2O, and CaO, aluminosilicate glass mainly composed of SiO2, Al2O3, Na2O, and K2O, lead glass mainly composed of SiO2, K2O, and PbO, borosilicate glass mainly composed of SiO2, B2O3, Na2O, and K2O, and aluminoborosilicate glass mainly composed of SiO2, Na2O, K2O, Al2O3, and B2O3, but are not limited to these as long as it is an oxide composition containing a specific metal element and other metal elements. The Si / Al (molar ratio of silica element to aluminum element) in the glass is preferably 100 or less from the viewpoint of increasing the alkali content, and is preferably 0.9 or more from the viewpoint of acid resistance. When roughening treatment is performed using an acidic gas or the like, the average pore size of the uneven structure formed on the glass surface is preferably 30 nm or less in order to further suppress the generation of by-products, and is preferably 5 nm or more in order to improve reactivity.

[0043] Examples of amorphous silica that can be used include silica gel made from sodium metasilicate (Na2SiO3), and precipitated silica or gel-process silica obtained by neutralizing sodium silicate (Na2O·nSiO2·mH2O) with an acid. Preferably, the amorphous silica contains 0.01 to 20 mass% of at least one oxide selected from Li2O, Na2O, KO, MgO, CaO, and BaO as a specific element. The amorphous silica preferably contains at least one of sodium and potassium, since this can further suppress the generation of by-products. The average pore size of the amorphous silica is preferably 30 nm or less in terms of further suppressing the generation of by-products, and is preferably 5 nm or more in terms of improving reactivity.

[0044] As the amorphous alumina, alumina gel (Al2O3·nH2O) or an aluminate obtained by dissolving aluminum or aluminum hydroxide in an alkali hydroxide solution can be used, and it is preferable that the amorphous alumina contains 0.01 to 20 mass% of at least one component selected from Li2O, Na2O, KO, MgO, CaO, and BaO as a specific element. The amorphous alumina preferably contains at least one of sodium and potassium, since this can further suppress the generation of by-products. Specific examples of compositions include alkali metal salts with the structural formula MAlO2 (M is a monovalent metal), such as NaAlO2 and KAlO2, compounds with the structural formula MAlO2 nH2O, such as NaAlO2·5 / 4H2O, NaAlO2·3H2O, and KAlO2·3 / 2H2O, and compounds with the general structural formula xM2O·yAl2O2·zH2O (including z=0). The average pore size of the amorphous alumina is preferably 30 nm or less in terms of further suppressing the generation of by-products, and is preferably 5 nm or more in terms of improving reactivity.

[0045] As the amorphous silica-alumina, for example, silica-alumina obtained by firing silica-alumina gel prepared by a sol-gel method or the like can be used, and it is preferable that the amorphous silica-alumina contains 0.01 to 20 mass % of at least one component selected from Li2O, Na2O, KO, MgO, CaO, and BaO as a specific element. The amorphous silica-alumina preferably contains at least one of sodium and potassium, since this can further suppress the generation of by-products. From the viewpoint of increasing the alkali content, the Si / Al ratio in the amorphous silica-alumina is preferably 100 or less, and from the viewpoint of acid resistance, the Si / Al ratio in the amorphous silica-alumina is preferably 0.9 or more. The average pore size of the amorphous silica alumina is preferably 30 nm or less in terms of further suppressing the generation of by-products, and is preferably 5 nm or more in terms of improving reactivity.

[0046] As the crystalline silica, quartz, cristobalite, keatite, stishovite, etc. can be used, and it is preferable that at least one component selected from Li2O, Na2O, K2O, MgO, CaO, and BaO is contained in an amount of 0.01 to 20 mass % as a specific element. The crystalline silica preferably contains at least one of sodium and potassium, since this can further suppress the generation of by-products. The average pore size of the amorphous silica alumina is preferably 30 nm or less in terms of further suppressing the generation of by-products, and is preferably 5 nm or more in terms of improving reactivity.

[0047] As the crystalline alumina, γ-Al2O3, η-Al2O3, θ-Al2O3, α-Al2O3, etc. can be used, and it is preferable that at least one component selected from Li2O, Na2O, K2O, MgO, CaO, and BaO is contained in an amount of 0.01 to 20 mass% as a specific element. Examples of crystalline alumina include spinel structures and incomplete spinel structures that are formed as sintering products between monovalent basic oxides (NaO, KO) or divalent weakly basic oxides (MgO, CoO, NiO, CuO, ZnO, MnO) and AlO. The crystalline alumina preferably contains at least one of sodium and potassium, since this can further suppress the generation of by-products. The average pore size of the crystalline alumina is preferably 30 nm or less in terms of further suppressing the generation of by-products, and is preferably 5 nm or more in terms of improving reactivity.

[0048] As the crystalline silica-alumina having no ordered structure, mullite, kaolinite, or the like, which is an aluminosilicate having a single chain structure, can be used, and it is preferable that the specific element contains 0.01 to 20 mass% of at least one component selected from Li2O, Na2O, KO, MgO, CaO, and BaO. The crystalline silica-alumina having no ordered structure preferably contains at least one of sodium and potassium. The Si / Al ratio in the crystalline silica-alumina not having an ordered structure is preferably 100 or less from the viewpoint of increasing the amount of alkali, and is preferably 0.9 or more from the viewpoint of acid resistance. The average pore size of the crystalline silica alumina not having an ordered structure is preferably 30 nm or less in terms of being able to further suppress the generation of by-products, and is preferably 5 nm or more in terms of being able to improve reactivity.

[0049] As the crystalline silica-alumina having an ordered structure, mesoporous silica-alumina and zeolite can be used, and it is preferable that the specific element contains 0.01 to 20 mass % of at least one component selected from Li2O, Na2O, K2O, MgO, CaO, and BaO. The crystalline silica-alumina having an ordered structure preferably contains at least one of sodium and potassium, since this can further suppress the generation of by-products. The Si / Al ratio in the crystalline silica-alumina having an ordered structure is preferably 100 or less from the viewpoint of increasing the amount of alkali, and is preferably 0.9 or more from the viewpoint of acid resistance, more preferably 3.0 or more, and even more preferably 5.0 or more. The average pore size of the crystalline silica alumina having an ordered structure is preferably 30 nm or less in terms of being able to further suppress the generation of by-products, and is preferably 5 nm or more in terms of being able to improve reactivity.

[0050] Known crystalline structures can be used for zeolite, and a list of these structures is published by the International Zeolite Association (http: / / www.iza-structure.org / ). Specific examples of industrially applicable structures include A-type, ferrierite-type, mordenite-type, L-type, X-type, Y-type, CHA-type, TON-type, AFI-type, BEA-type, CON-type, MTW-type, CFI-type, and MEL-type. The zeolite preferably contains at least one of sodium and potassium, since this can further suppress the generation of by-products. The Si / Al ratio in the zeolite is preferably 100 or less from the viewpoint of increasing the amount of cationic species (alkali metals, etc.) present to compensate for the negative charge of the tetrahedral Al site, and is preferably 0.9 or more from the viewpoint of acid resistance, more preferably 3.0 or more, and even more preferably 5.0 or more. The cyclic structure of the zeolite structure is preferably the LTA, UFI, AEI, CHA, AFX, LEV, DDR, or RHO type, which has 8-membered rings with small pore diameters, from the viewpoint of further suppressing the generation of by-products, with the LTA, CHA, and DDR types being more preferred, and is preferably the BEA, CFI, AFI, FAU, LTL, MTW, MOR, or FER type, which has 12- or 14-membered rings with large pore diameters, with the BEA, FAU, LTL, MOR, or FER types being more preferred, from the viewpoint of improving reactivity. The zeolite containing the specific element may be natural or synthetic. The zeolite containing the specific element may be a commercially available product, and may be in the form of a powder or a molded body.

[0051] The specific oxide has a specific surface area of ​​1.0 m before the heat treatment described below. 2 / g or more, and the generation of by-products can be further suppressed. 2 / g or more is preferable, and 10m 2 / g or more is more preferable, and 20m 2 / g or more is particularly preferred. The specific oxide has a specific surface area of ​​1000 m before the heat treatment described below, from the viewpoint of structural stability during the heat treatment described below. 2 / g or less is preferable, and 800m 2 / g or less is more preferable, and 700m 2 / g or less is particularly preferred. The specific surface area of ​​a specific oxide is a value determined by analyzing the results of measurements using a gas adsorption method with nitrogen gas (e.g., Micrometric's "3Flex") using the BET method. When the specific oxide is a porous body or particle aggregate, the specific surface area includes not only the total surface area of ​​the structure, including the interior of the pores and the interparticle gaps, but also the external surface area excluding the interior of the pores and the interparticle gaps. The external surface area can be calculated using known analytical methods, such as the t-plot method. Furthermore, the pore size distribution and average pore size of the specific oxide can also be determined by analyzing the obtained data using the BJH method. Here, among oxides containing specific elements, oxides that do not satisfy the above-mentioned specific surface area in an untreated state can be made to have the above-mentioned specific surface area by subjecting them to heat treatment, surface roughening treatment, or the like. The heat treatment is carried out, for example, in an electric furnace or a reaction tube by heating in an atmosphere of an oxygen-containing gas such as air or an inert gas such as nitrogen. The heat treatment temperature varies depending on the crystal structure and heat resistance of the oxide, but from the viewpoint of improving the specific surface area, it is preferably 1000°C or less, more preferably 800°C or less, and particularly preferably 600°C or less. The surface roughening treatment is carried out, for example, by contacting or immersing the surface in an acid or alkaline solution, or by contacting the surface with an acidic gas.

[0052] The specific oxide is preferably crystalline from the viewpoint of structural control and reproducibility during production. In the present invention, a material is defined as crystalline if it contains a diffraction peak corresponding to a crystalline structure as the main component in a diffraction pattern measured with an XRD (X-ray diffraction device, for example, "Smart Lab" manufactured by Rigaku Corporation), and a material is defined as amorphous if it does not contain a diffraction peak corresponding to a crystalline structure as the main component.

[0053] The specific oxide may be in the form of a powder or particles, and the reaction may be carried out in a fluidized bed or a fixed bed depending on the particle size.

[0054] <Other oxides> The heat treatment described below may be carried out in the presence of the specific oxide and another oxide different from the specific oxide. Other oxides include oxides that do not contain specific elements, oxides with a specific surface area of ​​1.0 m 2 / g or less. Specific examples of oxides that do not contain specific elements include zinc oxide, silica, alumina, zirconia, and titania. Specific surface area is 1.0m 2 A specific example of an oxide having a SiO2 content of less than 1 / g is a silicate glass containing SiO2 as a main component that has not been subjected to a surface roughening treatment.

[0055] <Manufacturing process> The method for producing a fluorovinyl ether compound of the present invention includes a heating step of heat-treating compound 1 in the presence of a specific oxide. This causes a thermal decomposition reaction of compound 1 to yield compound 2. Specifically, an intermediate is produced by the reaction of compound 1 with the specific oxide, and then the intermediate is thermally decomposed and decarboxylated to yield compound 2.

[0056] From the viewpoint of the reactivity of Compound 1, the lower limit of the reaction temperature is preferably 150°C or higher, more preferably 180°C or higher, and particularly preferably 200°C or higher. The upper limit of the reaction temperature is preferably 380° C. or lower, more preferably 360° C. or lower, particularly preferably 350° C. or lower, and most preferably 310° C. or lower, from the viewpoint of further suppressing the generation of by-products. Lowering the reaction temperature is preferred from the viewpoint of reducing heating energy.

[0057] The reaction time is not particularly limited, but is preferably 0.1 to 120 seconds, and particularly preferably 0.5 to 60 seconds. Here, the reaction time means the contact time between the specific oxide and compound 1. For example, when a tubular reactor is used, the contact time can be calculated from the amount of gas containing compound 1 flowing through the tubular reactor and the packed volume of the specific oxide in the tubular reactor.

[0058] The reaction pressure is not particularly limited, but is preferably 0 to 1 MPaG, and particularly preferably 0 to 0.1 MPaG.

[0059] The reaction of compound 1 in the heating step may be any of a gas phase reaction, a liquid phase reaction, and a solid phase reaction, but a gas phase reaction is preferred in terms of facilitating the production of compound 2. When the reaction of Compound 1 is a gas phase reaction, it is preferable to use Compound 1 after diluting it with an inert gas, etc. Specific examples of the inert gas include nitrogen gas, carbon dioxide gas, helium gas, and argon gas. When an inert gas is used, the amount of the inert gas used is preferably 50 to 99.9 mol %, particularly preferably 80 to 99.9 mol %, based on the total amount of Compound 1 and the inert gas used.

[0060] The specific oxide may be used in a fixed bed method or a fluidized bed method.

[0061] The amount of the specific oxide used is preferably 0.00001 to 10 kg, particularly preferably 0.005 to 5 kg, per mole of Compound 1.

[0062] When the specific oxide is used in combination with other oxides, the amount of the specific oxide used is preferably 0.1 to 99 mass%, more preferably 0.1 to 80 mass%, and particularly preferably 0.1 to 70 mass%, based on the total amount of the specific oxide and other oxides used, in order to further suppress the generation of by-products.

[0063] The method for producing a fluorovinyl ether compound of the present invention preferably includes a drying step of drying the specific oxide before the heat treatment, which can further suppress the generation of by-products that are difficult to separate due to the presence of water. The method for drying the specific oxide is not particularly limited, but may include, for example, a method in which the specific oxide is heated. When the drying treatment is carried out by heating, the heating temperature is preferably 100 to 450° C., and particularly preferably 150 to 450° C. When the drying treatment is carried out by heating, the heating time is preferably 10 minutes to 1 week, and particularly preferably 30 minutes to 24 hours.

[0064] <Compound 2> The fluorovinyl ether compound obtained by the production method of the present invention is a compound having a group represented by the following formula (2) (ie, compound 2). CF2=CF-O- Equation (2)

[0065] When compound 1A is used in the production method of the present invention, a compound represented by the following formula (2A) is obtained. CF2=CF-OR f Formula (2A) R in formula (2A) f is R in formula (1A) f is synonymous with.

[0066] When compound 1A-1 is used in the production method of the present invention, a compound represented by the following formula (2A-1) is obtained. CF2=CF-OZ a1 Formula (2A-1) Z in formula (2A-1) a1 is Z in formula (1A-1) a1 is synonymous with.

[0067] When compound 1A-1-1 is used in the production method of the present invention, a compound represented by the following formula (2A-1-1) is obtained. CF2=CF-OR f11 Formula (2A-1-1) R in formula (2A-1-1) f11 is R in formula (1A-1-1). f11 is synonymous with. Specific examples of the compound represented by formula (2A-1-1) include CF2=CF-O-CF3, CF2=CF-O-CF2CF3, and CF2=CF-O-CF2CF2CF3.

[0068] When compound 1A-1-2 is used in the production method of the present invention, a compound represented by the following formula (2A-1-2) is obtained. CF2=CF-O-(R f12 O) m1 -R f13 Formula (2A-1-2) R in formula (2A-1-2) f12 , R f13 and m1 are R in formula (1A-1-2), f12 , R f13 and m1. Specific examples of the compound represented by formula (2A-1-2) include CF2=CF-O-CF2-OCF2CF3, CF2=CF-O-CF2O-CF3, CF2=CF-O-CF2O-CF2CF2O-CF3, CF2=CF-O-CF2CF2CF2O-CF3, CF2=CF-O-CF2CF(CF3)O-CF2CF2CF3, and CF2=CF-O-CF2CFO-CF2CFO-CF2CF3.

[0069] In the production method of the present invention, when compound 1A-2 is used, a compound represented by the following formula (2A-2-1) or a compound represented by the following formula (2A-2-2) can be obtained by appropriately adjusting the production conditions. However, in order to obtain the compound represented by formula (2A-2-2), Q in the above formula (1A-2) a2 must have -CF(CF3)- or -CF2-CF2- directly bonded to -C(=O)-F. CF2=CF-OQ a2 -C(=O)-F formula (2A-2-1) CF2=CF-OQ a21 -CF=CF2 formula (2A-2-2) Q in formula (2A-2-1) a2 is Q in formula (1A-2) a3 is synonymous with. Q in formula (2A-2-2) a21 is a perfluoroalkylene group or a divalent group in which -CF2- in a perfluoroalkylene group is substituted with an etheric oxygen atom. The number of carbon atoms in the perfluoroalkylene group is preferably 1 to 8, and particularly preferably 1 to 4. The perfluoroalkylene group may be linear or branched. Q a21 The number of etheric oxygen atoms in the divalent group may be 1 or more. The etheric oxygen atom is preferably located between the carbon-carbon bonds of the perfluoroalkylene group.

[0070] In the production method of the present invention, when compound 1A-2-1 is used, a compound represented by the following formula (2A-2-11) or a compound represented by the following formula (2A-2-12) is obtained. However, in order to obtain the compound represented by formula (2A-2-12), R f21 must have -CF(CF3)- or -CF2-CF2- directly bonded to -C(=O)-F. CF2=CF-OR f21 -C(=O)-F formula (2A-2-11) CF2=CF-OR f211 -CF=CF2 formula (2A-2-12) R in formula (2A-2-11) f21 is R in formula (1A-2-1) f21 is synonymous with. R in formula (2A-2-12) f211 is a perfluoroalkylene group. The number of carbon atoms in the perfluoroalkylene group is preferably 1 to 8, particularly preferably 1 to 4. The perfluoroalkylene group may be linear or branched. Specific examples of the compound represented by formula (2A-2-11) include CF2=CF-O-CF2CF2-C(=O)-F, CF2=CF-O-CF2CF2CF2-C(=O)-F, CF2=CF-O-CF2CF2CF2CF2-C(=O)-F, CF2=CF-O-CF2CF2CF2CF2CF2-C(=O)-F, CF2=CF-O-CF(CF3)-CF2-CF2-C(=O)-F, and CF2=CF-O-CF2CF(CF3)-CF2-C(=O)-F. Specific examples of the compound represented by formula (2A-2-12) include CF2=CF-O-CF2CF=CF2, CF2=CF-O-CF2CF2-CF=CF2, CF2=CF-O-CF2CF2CF2-CF=CF2, CF2=CF-O-CF2CF2CF2CF2-CF=CF2, CF2=CF-O-CF(CF3)-CF2-CF=CF2, and CF2=CF-O-CF2CF(CF3)-CF=CF2. The compound represented by formula (2A-2-11) can be converted into a vinyl ether carboxylic acid ester by a known method such as that disclosed in JP-B-62-51943, etc. Specifically, there is a method of reacting with an alcohol, or a method of hydrolyzing the compound to a vinyl ether carboxylic acid and then subjecting it to an esterification reaction.

[0071] In the production method of the present invention, when compound 1A-2-2 is used, a compound represented by the following formula (2A-2-21) or a compound represented by the following formula (2A-2-22) is obtained. However, in order to obtain the compound represented by formula (2A-2-22), R f23 must have -CF(CF3)- or -CF2-CF2- directly bonded to -C(=O)-F. CF2=CF-O-(R f22 O) m2 -R f23 -C(=O)-F formula (2A-2-21) CF2=CF-O-(R f22 O) m2 -R f231 -CF=CF2 formula (2A-2-22) In formula (2A-2-21) and formula (2A-2-22), R f22 and m2 are R in formula (1A-2-2), f22 and m2. R in formula (2A-2-21) f23 is R in formula (1A-2-2) f23 is synonymous with. R in formula (2A-2-22) f231 is a perfluoroalkylene group. The number of carbon atoms in the perfluoroalkylene group is preferably 1 to 6, and particularly preferably 1 to 3. The perfluoroalkylene group may be linear or branched. Specific examples of the compound represented by formula (2A-2-22) include CF2=CF-O-CF2CF(CF3)O-CF2CF2-C(=O)-F, CF2=CF-O-CF2CF2CF2O-CF2CF2-C(=O)-F, and CF2=CF-O-CF2CF2O-CF2CF2-C(=O)-F. Specific examples of the compound represented by formula (2A-2-23) include CF2=CF-O-CF2CF(CF3)O-CF2-CF=CF2, CF2=CF-O-CF2CF2CF2O-CF2-CF=CF2, and CF2=CF-O-CF2CF2O-CF2-CF=CF2.

[0072] When compound 1A-3 is used in the production method of the present invention, a compound represented by the following formula (2A-3) is obtained. CF2=CF-OQ a3 (-SO2F) q Formula (2A-3) Q in formula (2A-3) a3 and q are the Q in formula (1A-3), a3 and q.

[0073] When compound 1A-3-1 is used in the production method of the present invention, a compound represented by the following formula (2A-3-1) is obtained. CF2=CF-(OCF2CFZ a1 ) m3 -O p3 -(CF2) n3 -SO2F type (2A-3-1) Z in formula (2A-3-1) a1 , m3, p3 and n3 are Z in formula (1A-3-1), a1 , m3, p3 and n3. Specific examples of the compound represented by formula (2A-3-1) include CF2=CF-OCF2CF2-SO2F, CF2=CF-OCF2CF2CF2-SO2F, CF2=CF-OCF2CF2CF2CF2-SO2F, CF2=CF-OCF2CF2-OCF2CF2-SO2F, and CF2=CF-OCF2CF(CF3)-OCF2CF2-SO2F.

[0074] When compound 1A-3-2 is used in the production method of the present invention, a compound represented by the following formula (2A-3-2) is obtained. CF2=CF-O-(CF2) n4 -(O)p4 -C(Z a2 )(-Q a31 -SO2F)(-Q a32 -SO2F) Formula (2A-3-2) n4, p4, and Z in formula (2A-3-2) a2 , Q a31 and Q a32 are n4, p4, and Z in formula (1A-3-2), respectively. a2 , Q a31 and Q a32 is synonymous with. Specific examples of the compound represented by formula (2A-3-2) include CF2=CF-O-CF2-CF(-OCF2CF2-SO2F)(-CF2CF2-SO2F), CF2=CF-O-CF2-CF2CF2OCF(CF2-SO2F)(CF2-SO2F), and CF2=CF-O-CF2-CF(-OCF2CF2-SO2F)(-CF2-OCF2CF2-SO2F).

[0075] When compound 2 has a sulfonyl fluoride group, compound 2 is suitably used as a monomer component used in the production of a sulfonic acid group-containing fluoropolymer. Here, the sulfonic acid group-containing fluoropolymer is suitably used in the production of an electrolyte membrane.

[0076] <By-products> Examples of the by-product include, but are not limited to, a compound in which hydrogen fluoride is added to the vinyl ether group of compound 2 (hereinafter also referred to as a "specific by-product"). It may be difficult to separate the specific by-product from compound 2, or the separation process may be complicated. To address such problems, the production method of the present invention can suppress the production of by-products such as specific by-products and can obtain highly pure compound 2, thereby simplifying separation procedures and the like.

[0077] For example, when compound 1A is used in the method for producing a fluorovinyl ether compound of the present invention, a compound represented by the following formula (3A) may be produced as a specific by-product. CF3-CHF-OR f Formula (3A) R in formula (3A) f is R in formula (1A) f is synonymous with. [Example]

[0078] The present invention will be described in detail below with reference to examples. Examples 1-2 to 1-7, 2-2 to 2-7, 3-2 to 3-4, 4-2 to 4-4, 5-2 to 5-5, and 6-2 to 6-6 are working examples, and Examples 1-1, 2-1, 3-1, 4-1, 5-1, and 6-1 are comparative examples. However, the present invention is not limited to these examples. All of the examples and comparative examples were carried out at normal pressure.

[0079] [Specific surface area] The specific surface area of ​​the oxide was determined by analyzing the results of measurements by the gas adsorption method (using nitrogen gas) using Micrometric's "3Flex" with the BET method.

[0080] [Crystalline] The presence or absence of crystallinity of the oxide was determined based on the diffraction pattern measured using Rigaku's "Smart Lab." Those containing diffraction peaks corresponding to the crystalline structure were judged to be crystalline, and those not containing diffraction peaks corresponding to the crystalline structure were judged to be non-crystalline.

[0081] [Amount of by-products produced relative to the amount of fluorovinyl ether compound produced] The product gas collected from the outlet of the reactor 5 hours after the start of the reaction was analyzed for its composition using a gas chromatograph under the conditions below, and the amount of by-products produced relative to the fluorovinyl ether compound was calculated from the peak area obtained from the analysis using the following formula. The smaller the calculated value, the more effectively the production of by-products was suppressed. Here, by-products are a group of compounds that are difficult to separate from the fluorovinyl ether compound, and the total value of by-product peaks, excluding raw materials detected within 20 minutes of the retention time of the fluorovinyl ether compound in gas chromatographic analysis values, was taken as the amount of by-products produced. Amount of by-products produced relative to the amount of fluorovinyl ether compound produced = (area ratio [%] of all by-products excluding raw materials in the total area of ​​the peaks of the produced gas) ÷ (area ratio [%] of fluorovinyl ether compounds in the total area of ​​the peaks of the produced gas)

[0082] <Gas chromatograph analysis conditions> The gas composition analysis of the produced gas was carried out using an Agilent "6850 Gas Chromatograph" equipped with a Restek "Rtx-200" capillary column (internal diameter 0.25 mm, length 60 m, film thickness 1.00 μm), carrier gas: helium, inlet temperature: 240°C, gas linear velocity: 22.6 cm / s, column temperature: held at 40°C for 10 minutes, then heated to 240°C at 10°C / min and held for 10 minutes, and detector: FID.

[0083] [Conversion rate] Five hours after the start of the reaction, the product gas was collected from the outlet of the reactor and recovered in a stainless steel cylinder cooled with liquid nitrogen. The resulting liquid was subjected to composition analysis by gas chromatography to determine the conversion rate of the raw materials as follows, and the conversion rate was evaluated according to the following evaluation criteria. Conversion rate of raw material (%) = {1 - (concentration of raw material at reactor outlet (g / g)) / (concentration of raw material at reactor inlet (g / g))} × 100 A: The conversion rate of raw materials is 70% or more B: Conversion rate of raw materials is 50% or more but less than 70% C: Conversion rate of raw materials is 30% or more but less than 50% D: Conversion rate of raw material is 10% or more but less than 30% E: Conversion rate of raw material is less than 10%

[0084] [Example 1-1] A stainless steel perforated plate was placed 5 cm from the bottom of a U-shaped reaction tube (700 mm long) made of SUS316, with an inner diameter of 21.4 mm and a total length of 1550 mm. Glass beads 1 (specific surface area: 0.5 m) were placed on top of the plate. 253 mL of aluminosilicate (containing sodium) was packed into the column, and nitrogen was introduced at 330°C to dry the packed material. The nitrogen introduction rate was 150 NmL / min. A mixed gas of nitrogen / raw material (mole / mole) at a ratio of 93.4 / 6.6 was then passed through the column at 330°C for a contact time of 10.7 seconds (fluidized bed method) to obtain a vinyl ether compound. The contact time was calculated by dividing the packed height of the oxide by the superficial gas linear velocity of the mixed gas consisting of the raw material and nitrogen, and the superficial gas linear velocity was calculated by dividing the mixed gas flow rate at the reaction temperature and reaction pressure by the cross-sectional area of ​​the reaction tube. The same applies to the following [Example 1-2] to [Example 6-6]. The ratio of the amount of by-products produced to the amount of fluorovinyl ether compound produced was 0.10 [Area% / Area%]. The evaluation result of the conversion rate of the raw materials was C. Here, the compound represented by formula (1A-1-11) was used as the raw material, and the resulting fluorovinyl ether compound was the compound represented by formula (2A-1-11). FC(=O)-CF(CF3)-O-CF2CF2CF3 formula (1A-1-11) CF2=CF-O-CF2CF2CF3 formula (2A-1-11)

[0085] [Example 1-2] A U-shaped reaction tube made of SUS316 with an inner diameter of 21.4 mm was filled with glass beads 2 (specific surface area: 4.1 m 2 53 mL of hexane (0.1% wt. / g, crystallinity: none) was packed in the flask, and nitrogen was introduced at 300 ° C. to dry the packed material. The nitrogen introduction rate was 150 NmL / min. Then, at 300 ° C., a mixed gas of nitrogen / raw material = 90 / 10 (mol / mol) was passed through with a contact time of 16.7 seconds (performed by a fluidized bed method) to obtain a fluorovinyl ether compound represented by the above formula (2A-1-11). The compound represented by the above formula (1A-1-11) was used as the raw material. Here, the glass beads 2 were produced by subjecting the glass beads 1 to a surface roughening treatment using an acid gas. The ratio of the amount of by-products produced to the amount of fluorovinyl ether compounds produced was 0.05 [Area% / Area%], and the generation of by-products was sufficiently suppressed compared with Example 1-1 using the same raw materials. In addition, the evaluation result of the conversion rate of raw materials was A.

[0086] [Example 1-3] A U-shaped reaction tube made of SUS316 with an inner diameter of 21.4 mm was placed in a Na2SiO3 (specific surface area: 2.5 m2) reactor that had been subjected to a surface roughening treatment using acid gas. 2 53 mL of hexane (0.1% wt. / g, crystalline: yes) was packed in, and nitrogen was introduced at 290 ° C. to dry the packed material. The nitrogen introduction rate was 150 NmL / min. Then, at 290 ° C., a nitrogen / raw material = 90 / 10 (mol / mol) mixed gas was passed through with a contact time of 16.7 seconds (performed in a fixed bed) to obtain a fluorovinyl ether compound represented by the above formula (2A-1-11). The compound represented by the above formula (1A-1-11) was used as the raw material. The ratio of the amount of by-products produced to the amount of fluorovinyl ether compounds produced was 0.06 [Area% / Area%], and compared with Example 1-1 using the same raw materials, the generation of by-products was sufficiently suppressed. In addition, the evaluation result of the conversion rate of raw materials was B.

[0087] [Example 1-4] A U-shaped reaction tube made of SUS316 with an inner diameter of 21.4 mm was filled with Na2ZrO3 (specific surface area: 1.8 m) that had been subjected to a surface roughening treatment using acid gas. 2 53 mL of hexane (0.1% wt. / g, crystalline: present) was packed, and nitrogen was introduced at 290 ° C. to dry the packed material. The nitrogen introduction rate was 150 NmL / min. Then, at 291 ° C., a nitrogen / raw material = 90 / 10 (mol / mol) mixed gas was passed through with a contact time of 16.7 seconds (performed in a fixed bed) to obtain a fluorovinyl ether compound represented by the above formula (2A-1-11). The compound represented by the above formula (1A-1-11) was used as the raw material. The ratio of the amount of by-products produced to the amount of fluorovinyl ether compounds produced was 0.04 [Area% / Area%], and compared with Example 1-1 using the same raw materials, the generation of by-products was sufficiently suppressed. In addition, the evaluation result of the conversion rate of raw materials was B.

[0088] [Example 1-5] A U-shaped reaction tube made of SUS316 with an inner diameter of 21.4 mm was filled with a Na-containing alumina adsorbent 1 (Axsorb AB manufactured by Nippon Light Metal Co., Ltd., heat-treated at 600°C for 10 hours in an air atmosphere, specific surface area: 177 m). 2 53 mL of hexane (0.1% wt. / g, crystalline: yes) was packed in, and nitrogen was introduced at 280 ° C. to dry the packed material. The nitrogen introduction rate was 150 NmL / min. Then, at 280 ° C., a nitrogen / raw material = 90 / 10 (mol / mol) mixed gas was passed through with a contact time of 16.7 seconds (performed in a fixed bed) to obtain a fluorovinyl ether compound represented by the above formula (2A-1-11). The compound represented by the above formula (1A-1-11) was used as the raw material. The ratio of the amount of by-products produced to the amount of fluorovinyl ether compounds produced was 0.05 [Area% / Area%], and compared with Example 1-1 using the same raw materials, the generation of by-products was sufficiently suppressed. In addition, the evaluation result of the conversion rate of raw materials was B.

[0089] [Example 1-6] A U-shaped reaction tube made of SUS316 with an inner diameter of 21.4 mm was filled with a Na-containing alumina adsorbent 2 (Selexsorb COS, manufactured by BASF, specific surface area: 150 m 2 53 mL of hexane (0.1% wt. / g, crystalline: yes) was packed in, and nitrogen was introduced at 280 ° C. to dry the packed material. The nitrogen introduction rate was 150 NmL / min. Then, at 280 ° C., a nitrogen / raw material = 90 / 10 (mol / mol) mixed gas was passed through with a contact time of 16.7 seconds (performed by a fixed bed method) to obtain a fluorovinyl ether compound represented by the above formula (2A-1-11). The compound represented by the above formula (1A-1-11) was used as the raw material. The ratio of the amount of by-products produced to the amount of fluorovinyl ether compound produced was 0.05 [Area% / Area%], and the generation of by-products was sufficiently suppressed compared with Example 1-1 using the same raw materials. In addition, the evaluation result of the conversion rate of the raw materials was C.

[0090] [Example 1-7] A U-shaped reactor tube made of SUS316 with an inner diameter of 21.4 mm was charged with zeolite 1 (Tosoh Corporation, "Zeolum A-3, Type 585, 20-32 mesh", specific surface area: 28 m 2 53 mL of a fluorovinyl ether (aluminosilicate containing potassium) was packed in the column, and nitrogen was introduced at 252 ° C. to dry the packed material. The nitrogen introduction rate was 150 NmL / min. Then, at 252 ° C., a nitrogen / raw material = 90 / 10 (mol / mol) mixed gas was passed through with a contact time of 16.7 seconds (performed by a fixed bed method), to obtain a fluorovinyl ether compound represented by the above formula (2A-1-11). The compound represented by the above formula (1A-1-11) was used as the raw material. The ratio of the amount of by-products produced to the amount of fluorovinyl ether compounds produced was 0.03 [Area% / Area%], and compared with Example 1-1 using the same raw materials, the generation of by-products was sufficiently suppressed. In addition, the evaluation result of the conversion rate of raw materials was A.

[0091] [Example 2-1] A U-shaped reaction tube made of SUS316 with an inner diameter of 21.4 mm was filled with glass beads 1 (specific surface area: 0.5 m 2 106 mL of aluminosilicate (containing sodium) was packed in the reactor, and nitrogen was introduced at 252 ° C. to dry the packed material. The nitrogen introduction rate was 150 NmL / min. Then, at 252 ° C., a mixed gas of nitrogen / raw material = 90 / 10 (mol / mol) and water at a water / raw material = 1 / 2 (mol / mol) was passed through the reactor for a contact time of 21.4 seconds (performed by a fluidized bed method), to obtain a fluorovinyl ether compound. The ratio of the amount of by-products produced to the amount of fluorovinyl ether compound produced was 0.21 [Area% / Area%]. The evaluation result of the conversion rate of the raw materials was D. Here, the compound represented by formula (1A-2-11) was used as the raw material, and the resulting fluorovinyl ether compound was the compound represented by formula (2A-2-111). FC(=O)-CF(CF3)-O-CF2CF2CF2-C(=O)-F Formula (1A-2-11) CF2=CF-O-CF2CF2CF2-C(=O)-F Formula (2A-2-111)

[0092] [Example 2-2] A U-shaped reaction tube made of SUS316 with an inner diameter of 21.4 mm was filled with glass beads 2 (specific surface area: 4.1 m 2 53 mL of ammonium hydroxide (0.01g / g, crystallinity: none) was packed in the flask, and nitrogen was introduced at 251 ° C. to dry the packed material. The nitrogen introduction rate was 150 NmL / min. Then, at 251 ° C., a mixed gas of nitrogen / raw material = 90 / 10 (mol / mol) and water / raw material = 1 / 10 (mol / mol) was passed through the flask for a contact time of 10.7 seconds (performed by a fluidized bed method), to obtain a fluorovinyl ether compound represented by the above formula (2A-2-111). The compound represented by the above formula (1A-2-11) was used as the raw material. The ratio of the amount of by-products produced to the amount of fluorovinyl ether compound produced was 0.06 [Area% / Area%], and the generation of by-products was sufficiently suppressed compared with Example 2-1 using the same raw materials. In addition, the evaluation result of the conversion rate of the raw materials was C.

[0093] [Example 2-3] A U-shaped reaction tube made of SUS316 with an inner diameter of 21.4 mm was filled with glass beads 3 (specific surface area: 13.0 m 2 53 mL of ammonium hydroxide (0.01g / g, crystallinity: none) was packed in the flask, and nitrogen was introduced at 250 ° C. to dry the packed material. The nitrogen introduction rate was 150 NmL / min. Then, at 252 ° C., a mixed gas of nitrogen / raw material = 90 / 10 (mol / mol) and water / raw material = 1 / 10 (mol / mol) was passed through the flask for a contact time of 10.7 seconds (performed by a fluidized bed method), to obtain a fluorovinyl ether compound represented by the above formula (2A-2-111). The compound represented by the above formula (1A-2-11) was used as the raw material. Here, the glass beads 3 were produced by subjecting the glass beads 1 to a surface roughening treatment using an acid gas. The ratio of the amount of by-products produced to the amount of fluorovinyl ether compounds produced was 0.08 [Area% / Area%], and the generation of by-products was sufficiently suppressed compared with Example 2-1 using the same raw materials. In addition, the evaluation result of the conversion rate of raw materials was D.

[0094] [Example 2-4] A U-shaped reaction tube made of SUS316 with an inner diameter of 21.4 mm was placed in a Na2SiO3 (specific surface area: 2.5 m2) reactor that had been subjected to a surface roughening treatment using acid gas. 2 53 mL of ammonium hydroxide (0.01g / g, crystalline: present) was packed in the flask, and nitrogen was introduced at 250 ° C. to dry the packed material. The nitrogen introduction rate was 150 NmL / min. Then, at 252 ° C., a mixed gas of nitrogen / raw material = 90 / 10 (mol / mol) and water / raw material = 1 / 10 (mol / mol) was passed through the flask for a contact time of 10.7 seconds (performed by a fixed bed method), to obtain a fluorovinyl ether compound represented by the above formula (2A-2-111). The compound represented by the above formula (1A-2-11) was used as the raw material. The ratio of the amount of by-products produced to the amount of fluorovinyl ether compound produced was 0.10 [Area% / Area%], and the generation of by-products was sufficiently suppressed compared with Example 2-1 using the same raw materials. In addition, the evaluation result of the conversion rate of the raw materials was C.

[0095] [Example 2-5] A U-shaped reaction tube made of SUS316 and having an inner diameter of 21.4 mm was filled with 53 mL of alumina adsorbent 1 containing Na, and nitrogen was introduced at 250 ° C to dry the packed material. The nitrogen introduction rate was 150 NmL / min. Then, at 250 ° C, a mixed gas of nitrogen / raw material = 90 / 10 (mol / mol) and water at a ratio of water / raw material 1 / 10 (mol / mol) was passed through for a contact time of 10.7 seconds (performed by a fixed bed method), to obtain a fluorovinyl ether compound represented by the above formula (2A-2-111). The compound represented by the above formula (1A-2-11) was used as the raw material. The ratio of the amount of by-products produced to the amount of fluorovinyl ether compound produced was 0.09 [Area% / Area%], and the generation of by-products was sufficiently suppressed compared with Example 2-1 using the same raw materials. In addition, the evaluation result of the conversion rate of raw materials was B.

[0096] [Example 2-6] A U-shaped reaction tube made of SUS316 with an inner diameter of 21.4 mm was filled with zeolite 2 (Tosoh Corporation, "Zeolum A-4, 14-20 mesh", specific surface area: 29 m 2 / g, crystallinity: yes, sodium-containing aluminosilicate) was packed in 53 mL, and nitrogen was introduced at 252 ° C. to dry the packed material. The nitrogen introduction rate was 150 NmL / min. Then, at 251 ° C., a mixed gas of nitrogen / raw material = 90 / 10 (mol / mol) and water / raw material = 1 / 10 (mol / mol) was passed through for a contact time of 10.7 seconds (performed by a fixed bed method), to obtain a fluorovinyl ether compound represented by the above formula (2A-2-111). The compound represented by the above formula (1A-2-11) was used as the raw material. The ratio of the amount of by-products produced to the amount of fluorovinyl ether compound produced was 0.10 [Area% / Area%], and the generation of by-products was sufficiently suppressed compared with Example 2-1 using the same raw materials. In addition, the evaluation result of the conversion rate of the raw materials was C.

[0097] [Example 3-1] A U-shaped reaction tube made of SUS316 with an inner diameter of 21.4 mm was filled with glass beads 1 (specific surface area: 0.5 m 2 107 mL of aluminosilicate (containing sodium) was packed into the column, and nitrogen was introduced at 320 ° C to dry the packed material. The nitrogen introduction rate was 150 NmL / min. Then, a mixed gas of nitrogen / raw material = 94.5 / 5.6 (mol / mol) was passed through the column at 320 ° C for a contact time of 10.7 seconds (performed by a fluidized bed method), to obtain a fluorovinyl ether compound. The ratio of the amount of by-products produced to the amount of fluorovinyl ether compound produced was 1.24 [Area% / Area%]. The evaluation result of the conversion rate of the raw materials was B. Here, the compound represented by formula (1A-2-12) was used as the raw material, and the resulting fluorovinyl ether compound was the compound represented by formula (2A-2-121). FC(=O)-CF(CF3)-O-CF2CF2CF2CF2-C(=O)-F Formula (1A-2-12) CF2=CF-O-CF2CF2-CF=CF2 formula (2A-2-121)

[0098] [Example 3-2] A U-shaped reaction tube made of SUS316 with an inner diameter of 21.4 mm was filled with glass beads 4 (specific surface area: 24.4 m 2 106 mL of hexane (106 mL / g, crystallinity: none) was packed in the flask, and nitrogen was introduced at 323 ° C. to dry the packed material. The nitrogen introduction rate was 150 NmL / min. Then, at 323 ° C., a mixed gas of nitrogen / raw material = 93.4 / 6.6 (mol / mol) was passed through with a contact time of 10.7 seconds (performed by a fluidized bed method), to obtain a fluorovinyl ether compound represented by the above formula (2A-2-121). The compound represented by the above formula (1A-2-12) was used as the raw material. Here, the glass beads 4 were produced by subjecting the glass beads 1 to a surface roughening treatment using an acid gas. The ratio of the amount of by-products produced to the amount of fluorovinyl ether compound produced was 0.02 [Area% / Area%], and compared with Example 3-1 using the same raw materials, the generation of by-products was sufficiently suppressed. In addition, the evaluation result of the conversion rate of raw materials was A.

[0099] [Example 3-3] A U-shaped reaction tube made of SUS316 with an inner diameter of 21.4 mm was placed in a Na2SiO3 (specific surface area: 2.5 m2) reactor that had been subjected to a surface roughening treatment using acid gas. 2 106 mL of HCl (106 mL / g, crystalline: present) was packed, and nitrogen was introduced at 320 ° C. to dry the packed material. The nitrogen introduction rate was 150 NmL / min. Then, at 320 ° C., a nitrogen / raw material = 93.4 / 6.6 (mol / mol) mixed gas was passed through with a contact time of 10.7 seconds (performed by a fixed bed method) to obtain a fluorovinyl ether compound represented by the above formula (2A-2-121). The compound represented by the above formula (1A-2-12) was used as the raw material. The ratio of the amount of by-products produced to the amount of fluorovinyl ether compounds produced was 0.04 [Area% / Area%], and compared with Example 3-1 using the same raw materials, the generation of by-products was sufficiently suppressed. In addition, the evaluation result of the conversion rate of raw materials was B.

[0100] [Example 3-4] A U-shaped reaction tube made of SUS316 and having an inner diameter of 21.4 mm was filled with 106 mL of alumina adsorbent 1 containing Na, and nitrogen was introduced at 290 ° C to dry the packed material. The nitrogen introduction rate was 150 NmL / min. Then, at 291 ° C, a mixed gas of nitrogen / raw material = 93.4 / 6.6 (mol / mol) was passed through for a contact time of 21.4 seconds (performed by a fixed bed method) to obtain a fluorovinyl ether compound represented by the above formula (2A-2-121). The compound represented by the above formula (1A-2-12) was used as the raw material. The ratio of the amount of by-products produced to the amount of fluorovinyl ether compounds produced was 0.06 [Area% / Area%], and compared with Example 3-1 using the same raw materials, the generation of by-products was sufficiently suppressed. In addition, the evaluation result of the conversion rate of raw materials was B.

[0101] [Example 4-1] A U-shaped reaction tube made of SUS316 with an inner diameter of 21.4 mm was filled with glass beads 1 (specific surface area: 0.5 m 2 53 mL of a fluoroallyl ether (aluminosilicate containing sodium) was packed into the column, and nitrogen was introduced at 320°C to dry the packed material. The nitrogen introduction rate was 150 NmL / min. A 95.0 / 5.0 (mol / mol) mixed gas of nitrogen and raw material was then passed through the column at 320°C for a contact time of 10.1 seconds (fluidized bed method), yielding a fluoroallyl ether compound. The ratio of the amount of by-products produced to the amount of fluoroallyl ether compounds produced was 0.15 [Area% / Area%]. The evaluation result of the conversion rate of the raw materials was D. Here, the compound represented by formula (1A-2-21) was used as the raw material, and the resulting fluoroallyl ether compound was the compound represented by formula (2A-2-221). FC(=O)-CF(CF3)-OCF2CF(CF3)-OCF2CF2CF2-C(=O)-F Formula (1A-2-21) CF2=CF-OCF2CF(CF3)-OCF2CF=CF2 formula(2A-2-221)

[0102] [Example 4-2] A U-shaped reaction tube made of SUS316 with an inner diameter of 21.4 mm was filled with glass beads 5 (specific surface area: 5.1 m 2 106 mL of HCl (0.01g / g, crystallinity: none) was packed in the flask, and nitrogen was introduced at 320°C to dry the packed material. The nitrogen introduction rate was 150 NmL / min. Then, at 320°C, a mixed gas of nitrogen / raw material = 95.0 / 5.0 (mol / mol) was passed through for a contact time of 10.5 seconds (performed by a fluidized bed method) to obtain a fluoroallyl ether compound represented by the above formula (2A-2-221). The compound represented by the above formula (1A-2-21) was used as the raw material. Here, the glass beads 5 were produced by subjecting the glass beads 1 to a surface roughening treatment using an acid gas. The ratio of the amount of by-products produced to the amount of fluoroallyl ether compounds produced was 0.06 [Area% / Area%], and the generation of by-products was sufficiently suppressed compared to Example 4-1 using the same raw materials. In addition, the evaluation result of the conversion rate of the raw materials was A.

[0103] [Example 4-3] A U-shaped reaction tube made of SUS316 with an inner diameter of 21.4 mm was placed in a Na2SiO3 (specific surface area: 2.5 m2) reactor that had been subjected to a surface roughening treatment using acid gas. 2 106 mL of HCl (106 mL / g, crystalline: present) was packed in the column, and nitrogen was introduced at 320 ° C to dry the packed material. The nitrogen introduction rate was 150 NmL / min. Then, at 300 ° C, a mixed gas of nitrogen / raw material = 95.0 / 5.0 (mol / mol) was passed through for a contact time of 10.2 seconds (performed by a fixed bed method), to obtain a fluoroallyl ether compound represented by the above formula (2A-2-221). The compound represented by the above formula (1A-2-21) was used as the raw material. The ratio of the amount of by-products produced to the amount of fluoroallyl ether compounds produced was 0.05 [Area% / Area%], and the generation of by-products was sufficiently suppressed compared to Example 4-1 using the same raw materials. In addition, the evaluation result of the conversion rate of the raw materials was B.

[0104] [Example 4-4] A U-shaped reaction tube made of SUS316 and having an inner diameter of 21.4 mm was filled with 106 mL of Na-containing alumina adsorbent 1, and nitrogen was introduced at 300 ° C to dry the packed material. The nitrogen introduction rate was 150 NmL / min. Then, at 280 ° C, a nitrogen / raw material = 95.05.0 (mol / mol) mixed gas was passed through for a contact time of 10.3 seconds (performed by a fixed bed method) to obtain a fluoroallyl ether compound represented by the above formula (2A-2-221). The compound represented by the above formula (1A-2-21) was used as the raw material. The ratio of the amount of by-products produced to the amount of fluoroallyl ether compounds produced was 0.03 [Area% / Area%], and the generation of by-products was sufficiently suppressed compared to Example 4-1 using the same raw materials. In addition, the evaluation result of the conversion rate of the raw materials was B.

[0105] [Example 5-1] A U-shaped reaction tube made of SUS316 with an inner diameter of 21.4 mm was filled with glass beads 1 (specific surface area: 0.5 m 2 53 mL of aluminosilicate (containing sodium) was packed into the column, and nitrogen was introduced at 330 ° C to dry the packed material. The nitrogen introduction rate was 150 NmL / min. Then, a mixed gas of nitrogen / raw material = 93.4 / 6.6 (mol / mol) was passed through the column at 330 ° C for a contact time of 10.7 seconds (performed by a fluidized bed method), to obtain a fluorovinyl ether compound. The ratio of the amount of by-products produced to the amount of fluorovinyl ether compound produced was 0.08 [Area% / Area%]. The evaluation result of the conversion rate of the raw materials was B. Here, the compound represented by formula (1A-3-11) was used as the raw material, and the resulting fluorovinyl ether compound was the compound represented by formula (2A-3-11). FC(=O)-CF(CF3)-OCF2CF(CF3)-OCF2CF2-SO2F Formula (1A-3-11) CF2=CF-OCF2CF(CF3)-OCF2CF2-SO2F Formula (2A-3-11)

[0106] [Example 5-2] A U-shaped reaction tube made of SUS316 with an inner diameter of 21.4 mm was filled with glass beads 5 (specific surface area: 5.1 m 2 106 mL of hexane (0.1% wt. / g, crystallinity: none) was packed in, and nitrogen was introduced at 331 ° C. to dry the packed material. The nitrogen introduction rate was 150 NmL / min. Then, at 331 ° C., a nitrogen / raw material = 93.4 / 6.6 (mol / mol) mixed gas was passed through with a contact time of 21.4 seconds (performed by a fluidized bed method) to obtain a fluorovinyl ether compound represented by the above formula (2A-3-11). The compound represented by the above formula (1A-3-11) was used as the raw material. Here, the glass beads 5 were produced by subjecting the glass beads 1 to a surface roughening treatment using an acid gas. The ratio of the amount of by-products produced to the amount of fluorovinyl ether compounds produced was 0.01 [Area% / Area%], and compared with Example 5-1 using the same raw materials, the generation of by-products was sufficiently suppressed. In addition, the evaluation result of the conversion rate of raw materials was A.

[0107] [Example 5-3] A U-shaped reaction tube made of SUS316 with an inner diameter of 21.4 mm was placed in a Na2SiO3 (specific surface area: 2.5 m2) reactor that had been subjected to a surface roughening treatment using acid gas. 2 106 mL of HCl (0.1% wt. / g, crystalline: yes) was packed in, and nitrogen was introduced at 310 ° C. to dry the packed material. The nitrogen introduction rate was 150 NmL / min. Then, at 310 ° C., a nitrogen / raw material = 93.4 / 6.6 (mol / mol) mixed gas was passed through with a contact time of 21.4 seconds (performed by a fixed bed method) to obtain a fluorovinyl ether compound represented by the above formula (2A-3-11). The compound represented by the above formula (1A-3-11) was used as the raw material. The ratio of the amount of by-products produced to the amount of fluorovinyl ether compounds produced was 0.05 [Area% / Area%], and compared with Example 5-1 using the same raw materials, the generation of by-products was sufficiently suppressed. In addition, the evaluation result of the conversion rate of raw materials was B.

[0108] [Example 5-4] A U-shaped reaction tube made of SUS316 and having an inner diameter of 21.4 mm was filled with 106 mL of alumina adsorbent 1 containing Na, and nitrogen was introduced at 281 ° C. to dry the packed material. The nitrogen introduction rate was 150 NmL / min. Then, at 280 ° C., a nitrogen / raw material = 93.4 / 6.6 (mol / mol) mixed gas was passed through with a contact time of 21.4 seconds (performed by a fixed bed method) to obtain a fluorovinyl ether compound represented by the above formula (2A-3-11). The compound represented by the above formula (1A-3-11) was used as the raw material. The ratio of the amount of by-products produced to the amount of fluorovinyl ether compounds produced was 0.04 [Area% / Area%], and compared with Example 5-1 using the same raw materials, the generation of by-products was sufficiently suppressed. In addition, the evaluation result of the conversion rate of raw materials was B.

[0109] [Example 5-5] A U-shaped reactor tube made of SUS316 with an inner diameter of 21.4 mm was filled with zeolite 3 (Tosoh Corporation "HSZ-300 Type 320NAD1C", specific surface area: 640 m 2 / g, crystallinity: yes, sodium-containing aluminosilicate) was packed in 106 mL, and nitrogen was introduced at 252 ° C. to dry the packed material. The nitrogen introduction rate was 150 NmL / min. Then, at 252 ° C., a nitrogen / raw material = 93.4 / 6.6 (mol / mol) mixed gas was passed through for a contact time of 21.4 seconds (performed by a fixed bed method), to obtain a fluorovinyl ether compound represented by the above formula (2A-3-11). The compound represented by the above formula (1A-3-11) was used as the raw material. The ratio of the amount of by-products produced to the amount of fluorovinyl ether compounds produced was 0.07 [Area% / Area%], and compared with Example 5-1 using the same raw materials, the generation of by-products was sufficiently suppressed. In addition, the evaluation result of the conversion rate of raw materials was D.

[0110] [Example 6-1] A U-shaped reaction tube made of SUS316 with an inner diameter of 21.4 mm was filled with glass beads 1 (specific surface area: 0.5 m 253 mL of aluminosilicate (containing sodium) was packed into the column, and nitrogen was introduced at 330 ° C to dry the packed material. The nitrogen introduction rate was 150 NmL / min. Then, a mixed gas of nitrogen / raw material = 93.4 / 6.6 (mol / mol) was passed through the column at 330 ° C for a contact time of 7.5 seconds (performed by a fluidized bed method), to obtain a fluorovinyl ether compound. The ratio of the amount of by-products produced to the amount of fluorovinyl ether compound produced was 0.50 [Area% / Area%]. The evaluation result of the conversion rate of the raw materials was D. Here, the compound represented by formula (1A-3-21) was used as the raw material, and the resulting fluorovinyl ether compound was the compound represented by formula (2A-3-21). FC(=O)-CF(CF3)-O-CF2-CF(-OCF2CF2-SO2F)(-CF2-OCF2CF2-SO2F) Formula (1A-3-21) CF2=CF-O-CF2-CF(-OCF2CF2-SO2F)(-CF2-OCF2CF2-SO2F) Formula (2A-3-21)

[0111] [Example 6-2] A U-shaped reaction tube made of SUS316 with an inner diameter of 21.4 mm was filled with glass beads 6 (specific surface area: 12.3 m 2 53 mL of a fluorovinyl ether (2A-3-21) was packed in the flask, and nitrogen was introduced at 331 ° C. to dry the packed material. The nitrogen introduction rate was 150 NmL / min. Then, at 331 ° C., a nitrogen / raw material = 93.4 / 6.6 (mol / mol) mixed gas was passed through the flask with a contact time of 7.5 seconds (performed by a fluidized bed method), to obtain a fluorovinyl ether compound represented by the above formula (2A-3-21). The compound represented by the above formula (1A-3-21) was used as the raw material. Here, the glass beads 6 were produced by subjecting the glass beads 1 to a surface roughening treatment using an acid gas. The amount of by-products produced relative to the amount of fluorovinyl ether compound produced was 0.02 [Area% / Area%], and compared with Example 6-1 using the same raw materials, the generation of by-products was sufficiently suppressed. In addition, the evaluation result of the conversion rate of raw materials was B.

[0112] [Example 6-3] A U-shaped reaction tube made of SUS316 with an inner diameter of 21.4 mm was filled with glass beads 3 (specific surface area: 13.0 m 2 53 mL of a fluorovinyl ether (2A-3-21) was packed in the flask, and nitrogen was introduced at 333 ° C. to dry the packed material. The nitrogen introduction rate was 150 NmL / min. Then, at 333 ° C., a mixed gas of nitrogen / raw material = 93.4 / 6.6 (mol / mol) was passed through for a contact time of 7.5 seconds (performed by a fluidized bed method), to obtain a fluorovinyl ether compound represented by the above formula (2A-3-21). The compound represented by the above formula (1A-3-21) was used as the raw material. The ratio of the amount of by-products produced to the amount of fluorovinyl ether compounds produced was 0.03 [Area% / Area%], and compared with Example 6-1 using the same raw materials, the generation of by-products was sufficiently suppressed. In addition, the evaluation result of the conversion rate of raw materials was B.

[0113] [Example 6-4] A U-shaped reaction tube made of SUS316 with an inner diameter of 21.4 mm was placed in a Na2SiO3 (specific surface area: 2.5 m2) reactor that had been subjected to a surface roughening treatment using acid gas. 2 53 mL of hexane (0.1% wt. / g, crystalline: yes) was packed in, and nitrogen was introduced at 320 ° C. to dry the packed material. The nitrogen introduction rate was 150 NmL / min. Then, at 320 ° C., a nitrogen / raw material = 93.4 / 6.6 (mol / mol) mixed gas was passed through for a contact time of 7.5 seconds (performed by a fluidized bed method) to obtain a fluorovinyl ether compound represented by the above formula (2A-3-21). The compound represented by the above formula (1A-3-21) was used as the raw material. The ratio of the amount of by-products produced to the amount of fluorovinyl ether compounds produced was 0.10 [Area% / Area%], and compared with Example 6-1 using the same raw materials, the generation of by-products was sufficiently suppressed. In addition, the evaluation result of the conversion rate of raw materials was B.

[0114] [Example 6-5] A U-shaped reaction tube made of SUS316 and having an inner diameter of 21.4 mm was filled with 53 mL of alumina adsorbent 1 containing Na, and nitrogen was introduced at 301 ° C to dry the packed material. The nitrogen introduction rate was 150 NmL / min. Then, at 300 ° C, a mixed gas of nitrogen / raw material = 93.4 / 6.6 (mol / mol) was passed through for a contact time of 7.5 seconds (performed by a fluidized bed method) to obtain a fluorovinyl ether compound represented by the above formula (2A-3-21). The compound represented by the above formula (1A-3-21) was used as the raw material. The ratio of the amount of by-products produced to the amount of fluorovinyl ether compounds produced was 0.05 [Area% / Area%], and compared with Example 6-1 using the same raw materials, the generation of by-products was sufficiently suppressed. In addition, the evaluation result of the conversion rate of raw materials was C.

[0115] [Example 6-6] A U-shaped reaction tube made of SUS316 and having an inner diameter of 21.4 mm was filled with 53 mL of zeolite 4 (Tosoh Corporation's "HSZ-500 Type 500KODAC", specific surface area: 257 m2 / g, crystallinity: yes, potassium-containing aluminosilicate), and nitrogen was introduced at 301 ° C to dry the packed material. The nitrogen introduction rate was 150 NmL / min. Then, at 301 ° C, a nitrogen / raw material = 93.4 / 6.6 (mol / mol) mixed gas was passed through with a contact time of 7.5 seconds (performed by a fixed bed method) to obtain the fluorovinyl ether compound represented by the above formula (2A-3-21). The compound represented by the above formula (1A-3-21) was used as the raw material. The ratio of the amount of by-products produced to the amount of fluorovinyl ether compound produced was less than 0.01 [Area% / Area%], and the generation of by-products was sufficiently suppressed compared to Example 6-1, which used the same raw materials.

[0116] The entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2020-217715, filed on December 25, 2020, are hereby incorporated by reference as the disclosure of the specification of the present invention.

Claims

1. A method for producing a fluorovinyl ether compound, comprising heat-treating a compound having a group represented by the following formula (1A) in the presence of a specific oxide to obtain a fluorovinyl ether compound having a group represented by the following formula (2): the reaction of the compound having a group represented by formula (1A) in the heat treatment is a gas phase reaction, the specific oxide is a silicate, aluminate, aluminosilicate, borosilicate, aluminoborosilicate, or zirconate containing at least one specific element selected from the group consisting of alkali metal elements and alkaline earth metal elements, and at least one other element selected from the group consisting of silicon, aluminum, manganese, lead, boron, zinc, zirconium, phosphorus, and magnesium; The specific oxide has a specific surface area of ​​1.0 m before the heat treatment. ２ / g or more. FC(=O)-CF(CF 3 )-O-R f Formula (1A) CF ２ = CF - O - formula (2) In formula (1A), R f represents a perfluoroalkyl group which may have a monovalent substituent selected from the group consisting of —C(═O)F, a sulfonyl fluoride group, a nitrile group, and a methyl ester group, or a monovalent group in which —CF 2 — of the perfluoroalkyl group which may have a monovalent substituent is substituted with an etheric oxygen atom.

2. The method for producing a fluorovinyl ether compound according to claim 1 , wherein the specific oxide contains an alkali metal element.

3. The method for producing a fluorovinyl ether compound according to claim 1 or 2, wherein the specific oxide is an amorphous oxide selected from glass, amorphous silica, amorphous alumina, and amorphous silica-alumina, or a crystalline oxide selected from crystalline silica, crystalline alumina, and crystalline silica-alumina.

4. The specific surface area of ​​the specific oxide before the heat treatment is 1.0 to 700 m ２ The method for producing a fluorovinyl ether compound according to any one of claims 1 to 3, wherein the fluorovinyl ether compound is hydroxybenzoate.

5. the heat treatment is carried out in the presence of the specific oxide and another oxide different from the specific oxide, The method for producing a fluorovinyl ether compound according to any one of claims 1 to 4, wherein the amount of the specific oxide used is 0.1 to 99 mass% based on the total amount of the specific oxide and the other oxide used.

6. The method for producing a fluorovinyl ether compound according to any one of claims 1 to 5, wherein the compound having a group represented by formula (1A) is a perfluoro compound.

7. The compound represented by formula (1A) is a compound represented by the following formula (1A-1), a compound represented by the following formula (1A-2), or a compound represented by the following formula (1A-3): The method for producing a fluorovinyl ether compound according to any one of claims 1 to 6. F−C(=O)−CF(CF ３ )−O−Z ａ１ Formula (1A-1) (Z ａ１ is a perfluoroalkyl group or a —CF of a perfluoroalkyl group ２ - is a monovalent group substituted with an etheric oxygen atom. FC(=O)-CF(CF ３ )-O-Q ａ２ -C(=O)-F Formula (1A-2) (Q ａ２ is a perfluoroalkylene group or a perfluoroalkylene group -CF ２ - is a divalent group substituted with an etheric oxygen atom. FC(=O)-CF(CF ３ )-O-Q ａ３ (-SO ２ F) ｑ Formula (1A-3) (Q ａ３ is a (q+1)-valent perfluorohydrocarbon group or a perfluorohydrocarbon group -CF ２ - is a (q+1)-valent group substituted with an etheric oxygen atom, and q is an integer of 1 to 3.

8. The method for producing a fluorovinyl ether compound according to any one of claims 1 to 7, wherein the compound represented by formula (2) is a compound represented by the following formula (2A): CF ２ = CF - O - R ｆ Formula (2A) (R ｆ is R in formula (1A). ｆ is synonymous with

9. The compound represented by formula (2A) is a compound represented by the following formula (2A-1), a compound represented by the following formula (2A-2-1), a compound represented by the following formula (2A-2-2), or a compound represented by the following formula (2A-3): The method for producing a fluorovinyl ether compound according to claim 8. CF ２ = CF - O - Z ａ１ Formula (2A - 1) (Z in formula (2A-1) ａ１ represents Z in formula (1A-1). ａ１ is synonymous with CF ２ = CF - O - Q ａ２ -C(=O)-F Formula (2A-2-1) CF ２ = CF - O - Q ａ２１ -CF=CF ２ Formula (2A - 2 - 2) (Q in formula (2A-2-1) ａ２ is Q in formula (1A-2) ａ３ Q in formula (2A-2-2) ａ２１ is a perfluoroalkylene group or a perfluoroalkylene group -CF ２ - is a divalent group substituted with an etheric oxygen atom. CF ２ = CF - O - Q ａ３ (-SO ２ F) ｑ Formula (2A - 3) (Q in formula (2A-3) ａ３ and q are Q in formula (1A-3), ａ３ and q.)

10. The method for producing a fluorovinyl ether compound according to any one of claims 1 to 9, wherein the specific oxide is dried before the heat treatment.