Process for producing fluoro vinyl ether compounds

Abstract

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

Description

TECHNICAL FIELD

[0001] The present application relates to a production method of fluoro vinyl ether compound. BACKGROUND

[0002] Fluoro vinyl ether compounds are used as, for example, monomers for producing fluorine-containing polymers. As a production method of such fluoro vinyl ether compounds, a method of bringing glass beads (sodium silicate glass) into contact with perfluoro-2-methoxypropionyl fluoride and heating is disclosed in Patent Literature 1.

[0003] PRIOR ART DOCUMENTS

[0004] PATENT LITERATURE

[0005] Patent Literature 1: U.S. Patent No. 3291843 SUMMARY

[0006] PROBLEMS TO BE SOLVED BY THE INVENTION

[0007] The present inventors found that, when a fluoro vinyl ether compound was produced by the production method described in Patent Literature 1, generation of a by-product could not be sufficiently suppressed, and there was room for improvement.

[0008] The present application was made in view of the above problem, and has an object to provide a production method of fluoro vinyl ether compound capable of suppressing generation of a by-product.

[0009] MEANS FOR SOLVING THE PROBLEM

[0010] The present inventors made intensive studies on the above problem, and as a result, found that, when a compound having a group represented by the following formula (1) is subjected to a heating treatment to obtain a compound having a group represented by the following formula (2), if an oxide containing at least one element selected from the group consisting of alkali metal elements and alkaline earth metal elements is used, and the specific surface area of the oxide before the above heating treatment is 1.0 m 2 / g or more, generation of a by-product can be suppressed, thereby completing the present application.

[0011] That is, the present inventors found that the above problem can be solved by the following configuration.

[0012] [1] A production method of fluoro vinyl ether compound, characterized by subjecting a compound having a group represented by the following formula (1) to a heating treatment 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 fluoro vinyl ether compound having a group represented by the following formula (2),

[0013] the specific surface area of the above oxide before the above heating treatment is 1.0 m 2 / g or more.

[0014] F-C(=O)-CF(X)-(CF2) n -O- Formula (1)

[0015] CF2=CF-O- Formula (2)

[0016] In Formula (1), n is 0 or 1, X is CF3 when n is 0, and X is F when n is 1.

[0017] [2] The method for producing a fluoro vinyl ether compound according to [1], wherein the oxide contains an alkali metal element.

[0018] [3] The method for producing a fluoro vinyl 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 an alkali metal element and an alkaline earth metal element and other metal elements.

[0019] [4] The method for producing a fluoro vinyl ether compound according to any one of [1] to [3], wherein the oxide is a silicate, an aluminate, an aluminosilicate, a borosilicate or an aluminoborosilicate containing at least one element selected from the group consisting of an alkali metal element and an alkaline earth metal element.

[0020] [5] The method for producing a fluoro vinyl ether compound according to any one of [1] to [4], wherein the oxide is an amorphous oxide selected from a glass, an amorphous silicon dioxide, an amorphous aluminum oxide and an amorphous silicon dioxide aluminum oxide; or a crystalline oxide selected from a crystalline silicon dioxide, a crystalline aluminum oxide and a crystalline silicon dioxide aluminum oxide.

[0021] [6] The method for producing a fluoro vinyl ether compound according to any one of [1] to [5], wherein the specific surface area of the oxide before the heat treatment is 1.0 to 700 m 2 / g.

[0022] [7] The method for producing a fluoro vinyl ether compound according to any one of [1] to [6], wherein the heat treatment is performed in the presence of the oxide and another oxide different from the oxide,

[0023] the amount of the oxide is 0.1 to 99 mass% relative to the total amount of the oxide and the other oxide.

[0024] [8] The method for producing a fluoro vinyl ether compound according to any one of [1] to [7], wherein the compound having a group represented by Formula (1) is a perfluorinated compound.

[0025] [9] The method for producing a fluoro vinyl ether compound according to any one of [1] to [8], wherein the compound represented by the aforementioned formula (1) is a compound represented by the following formula (1A).

[0026] F-C(=O)-CF(CF3)-O-R f Formula (1A)

[0027] In formula (1A), R f represents a perfluoroalkyl group optionally having a monovalent substituent selected from the group consisting of -C(=O)F, a fluorosulfonyl group, a nitrile group and a methyl ester group; or R f represents a monovalent group in which -CF2- of the perfluoroalkyl group optionally having a monovalent substituent is replaced with an etheric oxygen atom.

[0028]

[10] The method for producing a fluoro vinyl ether compound according to [9], wherein the compound represented by the aforementioned 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).

[0029] F-C(=O)-CF(CF3)-O-Z a1 Formula (1A-1)

[0030] Z a1 is a perfluoroalkyl group or a monovalent group in which -CF2- of the perfluoroalkyl group is replaced with an etheric oxygen atom,

[0031] F-C(=O)-CF(CF3)-O-Q a2 -C(=O)-F Formula (1A-2)

[0032] Q a2 is a perfluoroalkylene group or a divalent group in which -CF2- of the perfluoroalkylene group is replaced with an etheric oxygen atom;

[0033] F-C(=O)-CF(CF3)-O-Q a3 (-SO2F) q Formula (1A-3)

[0034] Q a3 is a (q+1) valent perfluoroalkyl group or a (q+1) valent group in which -CF2- of the perfluoroalkyl group is replaced with an etheric oxygen atom.

[0035]

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

[10] , wherein the compound represented by the aforementioned formula (2) is a compound represented by the following formula (2A).

[0036] CF2=CF-O-R f Formula (2A)

[0037] R f the same meaning as R f in formula (1A).

[0038]

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

[11] , wherein the compound represented by the aforementioned 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).

[0039] CF2=CF-O-Z a1 formula (2A-1)

[0040] Z in formula (2A-1) a1 the same meaning as Z a1 in formula (1A-1).

[0041] CF2=CF-O-Q a2 -C(=O)-F formula (2A-2-1)

[0042] CF2=CF-O-Q a21 -CF=CF2 formula (2A-2-2)

[0043] Q in formula (2A-2-1) a2 the same meaning as Q a3 in formula (1A-2). Q in formula (2A-2-2) a21 is a perfluoroalkylene group or a divalent group in which -CF2- of a perfluoroalkylene group is replaced with an etheric oxygen atom.

[0044] CF2=CF-O-Q a3 (-SO2F) q formula (2A-3)

[0045] Q in formula (2A-3) a3 and q have the same meaning as Q a3 and q in formula (1A-3).

[0046]

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

[12] , wherein, before the aforementioned heat treatment, the aforementioned oxide is subjected to a drying treatment.

[0047] Effects of the Invention

[0048] According to the present application, it is possible to provide a method for producing a fluoro vinyl ether compound capable of suppressing generation of a by-product. In addition, according to the present application, it is possible to provide a method for producing a fluoro vinyl ether compound capable of suppressing generation of a by-product even when the conversion rate of a raw material is improved. DETAILED DESCRIPTION

[0049] The meanings of the terms in the present application are as shown below.

[0050] The numerical range indicated using "~" means a range including the numerical values recited before and after "~" as lower limit values and upper limit values.

[0051] [Method for producing fluoro vinyl ether compound]

[0052] In the method for producing a fluoro vinyl ether compound of the present application, a compound having a group represented by the following formula (1) (hereinafter also referred to as compound 1) is subjected to a heat treatment 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 fluoro vinyl ether compound having a group represented by the following formula (2) (hereinafter also referred to as compound 2). In addition, the specific surface area of the above-mentioned oxide before the above-mentioned heat treatment is 1.0 m 2 / g or more.

[0053] Hereinafter, the 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 2 / g or more before the above-mentioned heat treatment is referred to as "specific oxide".

[0054] According to the method for producing a fluoro vinyl ether compound of the present application, the generation of a by-product can be suppressed. Generally, in the case where the conversion rate of a raw material is increased, there is a tendency that the amount of generation of a by-product also increases, but surprisingly, the present inventors et al. found that by using the above-mentioned specific oxide, the generation of a by-product can be suppressed.

[0055] [Compound 1]

[0056] Compound 1 is a compound having a group represented by the following formula (1), and is a raw material for producing compound 2.

[0057] F-C(=O)-CF(X)-(CF2) n -O- Formula (1)

[0058] In formula (1), n is 0 or 1, X is CF3 when n is 0, and X is F when n is 1.

[0059] From the viewpoint of the stability of compound 1 which is used for producing compound 2, compound 1 is preferably a perfluorinated compound.

[0060] Here, the perfluorinated compound means a compound substantially containing no hydrogen atom bonded to a carbon atom, in which all the hydrogen atoms bonded to carbon atoms are replaced with fluorine atoms.

[0061] From the viewpoint of stability of compound 1 used 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").

[0062] F-C(=O)-CF(CF3)-O-R f Formula (1A)

[0063] R f represents a perfluoroalkyl group optionally having a monovalent substituent selected from the group consisting of -C(=O)F, fluorosulfonyl (-SO2F), nitrile (-CN) and methyl ester (-C(O)OCH3); or R f represents a monovalent group in which -CF2- of the above perfluoroalkyl group optionally having a monovalent substituent is replaced with an etheric oxygen atom.

[0064] From the viewpoint of being able to suppress the rise in boiling point due to an increase in the number of carbon atoms, and of easily producing compound 2, the number of carbon atoms in the perfluoroalkyl group of R f is preferably 1 to 20, more preferably 1 to 15, and particularly preferably 1 to 10.

[0065] R f The perfluoroalkyl group of R

[0066] In the case where the perfluoroalkyl group of R f has a monovalent substituent, the number of monovalent substituents can be one or more. The monovalent substituent can be bonded to any carbon atom.

[0067] Among the monovalent substituents, -C(=O)F and fluorosulfonyl (-SO2F) are preferable.

[0068] R f The number of etheric oxygen atoms possessed by the monovalent group in R

[0069] From the viewpoint of easily producing compound 2, 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").

[0070] F-C(=O)-CF(CF3)-O-Z a1 Formula (1A-1)

[0071] Z a1 is a perfluoroalkyl group or a monovalent group in which -CF2- of the perfluoroalkyl group is replaced with an etheric oxygen atom.

[0072] The number of carbon atoms of the perfluoroalkyl group is preferably from 1 to 10, and particularly preferably from 1 to 6. The perfluoroalkyl group can be linear or branched.

[0073] Z a1 The number of etheric oxygen atoms possessed by the monovalent group in the formula (1A-1) can be one or two or more. The etheric oxygen atom is preferably located between carbon-carbon bonds of the perfluoroalkyl group.

[0074] The 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 the following formula 1A-1-2 (hereinafter also referred to as "compound 1A-1-2").

[0075] F-C(=O)-CF(CF3)-O-R f11 Formula (1A-1-1)

[0076] R f11 is a perfluoroalkyl group. The number of carbon atoms of the perfluoroalkyl group is preferably from 1 to 10, and particularly preferably from 1 to 6. The perfluoroalkyl group can be linear or branched.

[0077] F-C(=O)-CF(CF3)-O-(R f12 O) m1 -R f13 Formula (1A-1-2)

[0078] R f12 is a perfluoroalkylene group. The number of carbon atoms of the perfluoroalkylene group is preferably from 1 to 10, and particularly preferably from 1 to 6. The perfluoroalkylene group can be linear or branched.

[0079] R f13 is a perfluoroalkyl group. The number of carbon atoms of the perfluoroalkyl group is preferably from 1 to 10, and particularly preferably from 1 to 6. The perfluoroalkyl group can be linear or branched.

[0080] m1 is an integer of 1 or more, and is preferably from 1 to 6, and particularly preferably from 1 to 3. In the case where m1 is 2 or more, the plurality of (R f12 O) are optionally the same or different from each other.

[0081] F-C(=O)-CF(CF3)-O-Q a2 -C(=O)-F Formula (1A-2)

[0082] The definitions of the groups in the formula (1A-2) are shown below.

[0083] Q a2 is a perfluoroalkylene group or a divalent group in which -CF2- of the perfluoroalkylene group is replaced with an etheric oxygen atom.

[0084] The number of carbon atoms of the perfluoroalkylene group is preferably from 1 to 10, and particularly preferably from 1 to 6. The perfluoroalkylene group can be linear or branched.

[0085] Q a2 The number of etheric oxygen atoms possessed by the divalent group in the formula (1A-2) can be one or more than two. The etheric oxygen atom is preferably located between the carbon-carbon bonds of the perfluoroalkylene group.

[0086] The 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 the following formula 1A-2-2 (hereinafter also referred to as "compound 1A-2-2").

[0087] F-C(=O)-CF(CF3)-O-R f21 -C(=O)-F formula (1A-2-1)

[0088] R f21 is a perfluoroalkylene group. The number of carbon atoms of the perfluoroalkylene group is preferably from 1 to 10, and particularly preferably from 1 to 6. The perfluoroalkylene group can be linear or branched.

[0089] F-C(=O)-CF(CF3)-O-(R f22 O) m2 -R f23 -C(=O)-F formula (1A-2-2)

[0090] R f22 is a perfluoroalkylene group. The number of carbon atoms of the perfluoroalkylene group is preferably from 1 to 10, and particularly preferably from 1 to 6. The perfluoroalkylene group can be linear or branched.

[0091] R f23 is a perfluoroalkylene group. The number of carbon atoms of the perfluoroalkylene group is preferably from 1 to 8, and particularly preferably from 1 to 5. The perfluoroalkylene group can be linear or branched.

[0092] m2 is an integer of 1 or more, and is preferably from 1 to 6, and particularly preferably from 1 to 3. In the case where m2 is 2 or more, the plurality of (R f22 O) are optionally the same or different from each other.

[0093] F-C(=O)-CF(CF3)-O-Q a3 (-SO2F) q formula (1A-3)

[0094] The definitions of the groups in the formula (1A-3) are shown below.

[0095] Q a3a (q+1)-valent group of a perfluorohydrocarbon group or a (q+1)-valent group in which a -CF2- of a perfluorohydrocarbon group is replaced with an etheric oxygen atom.

[0096] The number of carbon atoms of the perfluorohydrocarbon group is preferably from 1 to 10. The perfluorohydrocarbon group can be linear or branched.

[0097] Q a3 The number of etheric oxygen atoms possessed by the (q+1)-valent group in the above formula (1A-3-1) or (1A-3-2) can be one or two or more. The etheric oxygen atom is preferably located between carbon atoms of the perfluorohydrocarbon group.

[0098] q is an integer of from 1 to 3.

[0099] The 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 the following formula 1A-3-2 (hereinafter also referred to as "compound 1A-3-2").

[0100] F-C(=O)-CF(CF3)-(OCF2CFZ a1 ) m3 -(O) p3 -(CF2) n3 -SO2F formula

[0101] (1A-3-1)

[0102] The definitions of the groups in the formula (1A-3-1) are as follows.

[0103] Z a1 is a fluorine atom or a trifluoromethyl group.

[0104] m3 is an integer of from 0 to 3.

[0105] p3 is 0 or 1.

[0106] n3 is an integer of from 1 to 12.

[0107] wherein m3 + p3 is one or more.

[0108] F-C(=O)-CF(CF3)-O-(CF2) n4 -(O) p4 -C(Z a2 )(-Q a31 -SO2F)(-Q a32 -SO2F)

[0109] Formula (1A-3-2)

[0110] The definitions of the groups in the formula (1A-3-2) are as follows.

[0111] Za2 It is a perfluoroalkyl group, a monovalent group of perfluoroalkyl group whose -CF2- is replaced by an ether-oxygen atom, or a fluorine atom.

[0112] The perfluoroalkyl group preferably has 1 to 6 carbon atoms. The perfluoroalkyl group can be linear or branched, but is preferably linear.

[0113] Z a2 The monovalent group in the alkyl group can have one or more ether oxygen atoms. Furthermore, the ether oxygen atom can be located between carbon-carbon bonds in the perfluoroalkyl group, or it can be located at the end of a carbon bond and adjacent to a -C(Z) group. a2 The side where the C (carbon atom) is directly bonded.

[0114] n4 is an integer from 1 to 3.

[0115] p4 is either 0 or 1.

[0116] Q a31 It is a perfluoroalkyl group or a divalent group of perfluoroalkyl group whose -CF2- is replaced by an ether-oxygen atom.

[0117] Q a32 It is a single bond, a perfluoroalkyl group, or a divalent group of a perfluoroalkyl group whose -CF2- is replaced by an ether-like oxygen atom.

[0118] The perfluoroalkyl group preferably has 1 to 6 carbon atoms, and more preferably 1 to 4. The perfluoroalkyl group can be linear or branched, but is preferably linear.

[0119] Q a31 and Q a32 The number of ether-containing oxygen atoms in the divalent group can be one or more. Furthermore, the ether-containing oxygen atom is preferably located between carbon-carbon bonds of the perfluoroalkyl group, or at the end of a carbon bond and adjacent to -C(Z). a2 The side where the C (carbon atom) is directly bonded.

[0120] <Specific Oxides>

[0121] The specific oxide contains at least one element selected from the group consisting of alkali metals and alkaline earth metals (hereinafter also referred to as the "specific element"), and preferably contains an alkali metal from the viewpoint of further suppressing the generation of byproducts.

[0122] Specific examples of alkali metal elements include lithium, sodium, potassium, rubidium, cesium, and francium. From the viewpoint of further suppressing the generation of byproducts, sodium and potassium are preferred. The alkali metal element may be one or more.

[0123] As specific examples of the alkaline earth metal element, beryllium, magnesium, calcium, strontium, barium can be given, and from the viewpoint of further suppressing the generation of by-products, magnesium, calcium, barium are preferable. The alkaline earth metal element can include only one kind, or two or more kinds.

[0124] In addition, as the component that can be included in the specific oxide, known metal elements, compounds that can be converted from F-C(=0)- into a fluoro-vinyl ether compound, and that derive a carboxylate, an alkyl ether, such as silver, ammonium, hydroxide, alkoxide, as shown in the known literature (J. Am. Chem. Soc, 1953, 75, 18, 4525-4528) or the like, can be included.

[0125] From the viewpoint of manufacturing the compound 2, the specific element can exist in the form of an oxide, or in the form of an ionic species.

[0126] In the specific oxide, as the element that assumes the role of supporting the specific element as an oxide or an ionic species, other elements than the specific element are preferably included. As specific examples of the other elements, silicon, aluminum, manganese, lead, boron, zinc, zirconium, phosphorus, magnesium can be given, and from the viewpoint of further suppressing the generation of by-products, silicon, aluminum are preferable, and these elements exist in the form of an oxide.

[0127] The valence number of the other element varies depending on the ratio of the specific element and the other element, and from the viewpoint of the role of supporting the specific element as an oxide or an ionic species, and the manufacturing of the compound 2, the valence number is not limited.

[0128] The specific oxide can be a single oxide of the specific element, or an oxide including the specific metal element and other metal elements, and is preferably an oxide including the specific metal element and other metal elements. The oxide including the specific metal element and other metal elements can be a composite oxide of an oxide of the specific element and an oxide of the other element.

[0129] The specific oxide is preferably a silicate, an aluminate, an aluminosilicate, a borosilicate, or an aluminoborosilicate including the specific element.

[0130] The structure of the specific oxide can be amorphous, or crystalline, and can be non-porous, or porous.

[0131] As specific examples of the specific oxide which is amorphous, various glasses, amorphous silica (also referred to as non-crystalline silica. For example, silica gel), amorphous alumina (for example, alumina gel), amorphous silica alumina can be given. In addition, as specific examples of the specific oxide which is crystalline, crystalline silica (for example, cristobalite, mesoporous silica, silica analogues), crystalline alumina (for example, γ-alumina, η-alumina, θ-alumina, α-alumina, etc.), crystalline silica alumina (a substance which does not have a regular structure: silica alumina, etc.; a substance which has a regular structure: mesoporous silica alumina, zeolite, etc.) can be given.

[0132] As the glass, a known composition in which SiO2 is the main component can be used, and as the specific element, it is preferable to contain at least one component selected from Li2O, Na2O, K2O, MgO, CaO, BaO at 0.01 to 20 mass%.

[0133] From the viewpoint of being able to further suppress the generation of by-products, the glass preferably contains at least one of sodium and potassium.

[0134] As examples of specific compositions, sodium calcium glass in which SiO2, Na2O, CaO are the main components; potassium calcium sodium glass in which SiO2, Na2O, K2O, CaO are the main components; aluminosilicate glass in which SiO2, Al2O3, Na2O, K2O are the main components; lead glass in which SiO2, K2O, PbO are the main components; borosilicate glass in which SiO2, B2O3, Na2O, K2O are the main components; aluminoborosilicate glass in which SiO2, Na2O, K2O, Al2O3, B2O3 are the main components, etc. can be given, as long as they are oxide compositions containing the specific metal element and other metal elements, and are not limited thereto.

[0135] From the viewpoint of increasing the alkali content, the Si / Al (molar ratio of silicon oxide element to aluminum element) in the glass is preferably 100 or less, and from the viewpoint of acid resistance, the Si / Al (molar ratio of silicon oxide element to aluminum element) in the glass is preferably 0.9 or more.

[0136] In the case where roughening treatment is performed using an acidic gas or the like, from the viewpoint of being able to further suppress the generation of by-products, the average pore diameter of the concave-convex structure formed on the surface of the glass is preferably 30 nm or less, and from the viewpoint of being able to improve reactivity, the average pore diameter of the concave-convex structure formed on the surface of the glass is preferably 5 nm or more.

[0137] As the amorphous silicon dioxide, silica gel using sodium metasilicate (Na2SiO3) as a raw material, precipitated silica obtained by neutralization reaction of sodium silicate (Na2O-nSiO2-mH2O) with an acid, and gel silica can be used, and as a specific element, it is preferable to contain at least one oxide selected from Li2O, Na2O, K2O, MgO, CaO, BaO in an amount of 0.01 to 20 mass%.

[0138] From the viewpoint of further suppressing generation of by-products, the amorphous silicon dioxide preferably contains at least one of sodium and potassium.

[0139] From the viewpoint of further suppressing generation of by-products, the average fine pore diameter of the amorphous silicon dioxide is preferably 30 nm or less, and from the viewpoint of improving reactivity, the average fine pore diameter is preferably 5 nm or more.

[0140] As the amorphous aluminum oxide, alumina gel (Al2O3-nH2O), aluminate obtained by dissolving aluminum and aluminum hydroxide in a solution of an alkali hydroxide can be used, and as a specific element, it is preferable to contain at least one component selected from Li2O, Na2O, K2O, MgO, CaO, BaO in an amount of 0.01 to 20 mass%.

[0141] From the viewpoint of further suppressing generation of by-products, the amorphous aluminum oxide preferably contains at least one of sodium and potassium.

[0142] As examples of specific compositions, there can be mentioned: alkali metal salts using a structural formula of MAlO2 (M is a monovalent metal) such as NaAlO2 and KAlO2; compounds using a structural formula of MAlO2-nH2O such as NaAlO2-5 / 4H2O, NaAlO2-3H2O, and KAlO2-3 / 2H2O; and compounds using a structural formula of general formula xM2O-yAl2O2-zH2O (including z = 0).

[0143] From the viewpoint of further suppressing generation of by-products, the average fine pore diameter of the amorphous aluminum oxide is preferably 30 nm or less, and from the viewpoint of improving reactivity, it is preferably 5 nm or more.

[0144] As the amorphous silica alumina, for example, silica alumina gel prepared by a sol-gel method or the like can be calcined to obtain silica alumina, and as a specific element, it is preferable to contain at least one component selected from Li2O, Na2O, K2O, MgO, CaO, BaO in an amount of 0.01 to 20 mass%.

[0145] From the viewpoint of further suppressing generation of by-products, the amorphous silica alumina preferably contains at least one of sodium and potassium.

[0146] From the viewpoint of increasing the alkali content, the Si / Al in the amorphous silica alumina is preferably 100 or less, and from the viewpoint of acid resistance, the Si / Al in the amorphous silica alumina is preferably 0.9 or more.

[0147] From the viewpoint of further suppressing the generation of by-products, the average pore diameter of the amorphous silica alumina is preferably 30 nm or less, and from the viewpoint of improving reactivity, the average pore diameter of the amorphous silica alumina is preferably 5 nm or more.

[0148] As the crystalline silica, quartz, cristobalite, hydrothermal quartz, super quartz, and the like can be used, and as the specific element, it is preferable to contain at least one component selected from Li20, Na20, K20, MgO, CaO, BaO at 0.01 to 20 mass%.

[0149] From the viewpoint of further suppressing the generation of by-products, the crystalline silica preferably contains at least one of sodium and potassium.

[0150] From the viewpoint of further suppressing the generation of by-products, the average pore diameter of the amorphous silica alumina is preferably 30 nm or less, and from the viewpoint of improving reactivity, the average pore diameter of the amorphous silica alumina is preferably 5 nm or more.

[0151] As the crystalline alumina, γ-Al203, η-Al203, θ-Al203, α-Al203, and the like can be used, and as the specific element, it is preferable to contain at least one component selected from Li20, Na20, K20, MgO, CaO, BaO at 0.01 to 20 mass%.

[0152] In addition, as the crystalline alumina, spinel structure, incomplete spinel structure, and the like formed in the form of a sintered product between monovalent basic oxide (Na20, K20), divalent weak basic oxide (MgO, CoO, NiO, CuO, ZnO, MnO) and Al203 can be exemplified.

[0153] From the viewpoint of further suppressing the generation of by-products, the crystalline alumina preferably contains at least one of sodium and potassium.

[0154] From the viewpoint of further suppressing the generation of by-products, the average pore diameter of the crystalline alumina is preferably 30 nm or less, and from the viewpoint of improving reactivity, the average pore diameter of the crystalline alumina is preferably 5 nm or more.

[0155] As the crystalline silica alumina having no regular structure, an aluminian mullite, a kaolinite, or the like having a single chain structure can be used, and as the specific element, it is preferable to contain at least one component selected from Li20, Na20, K20, MgO, CaO, BaO in an amount of 0.01 to 20 mass%.

[0156] The crystalline silica alumina having no regular structure preferably contains at least one of sodium and potassium.

[0157] From the viewpoint of increasing the amount of alkali, the Si / Al in the crystalline silica alumina having no regular structure is preferably 100 or less, and from the viewpoint of acid resistance, the Si / Al in the crystalline silica alumina having no regular structure is preferably 0.9 or more.

[0158] From the viewpoint of further suppressing the generation of by-products, the average fine pore diameter of the crystalline silica alumina having no regular structure is preferably 30 nm or less, and from the viewpoint of improving reactivity, the average fine pore diameter of the crystalline silica alumina having no regular structure is preferably 5 nm or more.

[0159] As the crystalline silica alumina having a regular structure, a mesoporous silica alumina, a zeolite, or the like can be used, and as the specific element, it is preferable to contain at least one component selected from Li20, Na20, K20, MgO, CaO, BaO in an amount of 0.01 to 20 mass%.

[0160] From the viewpoint of further suppressing the generation of by-products, the crystalline silica alumina having a regular structure preferably contains at least one of sodium and potassium.

[0161] From the viewpoint of increasing the amount of alkali, the Si / Al in the crystalline silica alumina having a regular structure is preferably 100 or less, and from the viewpoint of acid resistance, the Si / Al in the crystalline silica alumina having a regular structure is preferably 0.9 or more, more preferably 3.0 or more, and further preferably 5.0 or more.

[0162] From the viewpoint of further suppressing the generation of by-products, the average fine pore diameter of the crystalline silica alumina having a regular structure is preferably 30 nm or less, and from the viewpoint of improving reactivity, the average fine pore diameter of the crystalline silica alumina having a regular structure is preferably 5 nm or more.

[0163] The crystal structure of the zeolite can use a known structure, the list of which is disclosed by the International Zeolite Association (http: / / www.iza-structure.org / ). As specific examples of structures that can be industrially used, there can be mentioned A type, offretite type, mordenite type, L type, X type, Y type, CHA type, TON type, AFI type, BEA type, CON type, MTW type, CFI type, MEL type, and the like.

[0164] From the viewpoint of being able to further suppress the generation of by-products, the zeolite preferably contains at least one of sodium and potassium.

[0165] From the viewpoint of increasing the amount of the cation species (alkali metal or the like) present in order to compensate for the negative charge of the four-coordinated Al site, the Si / Al in the zeolite is preferably 100 or less, from the viewpoint of acid resistance, preferably 0.9 or more, more preferably 3.0 or more, and further preferably 5.0 or more.

[0166] From the viewpoint of being able to further suppress the generation of by-products, the ring structure possessed by the zeolite structure is preferably LTA type, UFI type, AEI type, CHA type, AFX type, LEV type, DDR type, RHO type having an eight-membered ring with a small pore diameter, and more preferably LTA type, CHA type, DDR type, from the viewpoint of being able to improve reactivity, preferably BEA type, CFI type, AFI type, FAU type, LTL type, MTW type, MOR type, FER type having a 12-membered ring, a 14-membered ring with a large pore diameter, and more preferably BEA type, FAU type, LTL type, MOR type, FER type.

[0167] The zeolite containing the specific element can be natural or synthetic. The zeolite containing the specific element can be a commercially available product, and can be a powder or a molded body.

[0168] The specific oxide has a specific surface area of 1.0 m 2 / g or more, from the viewpoint of being able to further suppress the generation of by-products, preferably 2 m 2 / g or more, more preferably 10 m 2 / g or more, particularly preferably 20 m 2 / g or more.

[0169] From the viewpoint of the structural stability of the specific oxide at the time of the heating treatment described later, the specific surface area before the heating treatment described later is preferably 1000 m 2 / g or less, more preferably 800 m 2 / g or less, particularly preferably 700 m 2 / g or less.

[0170] The specific oxide has a specific surface area of 1.0 m2 / g or more. The specific surface area of the specific oxide is a value obtained by analyzing the results measured using a device (for example, "3 Flex" manufactured by MICRO-METRIC Corporation) using a gas adsorption method using nitrogen gas as the measuring principle by the BET method. In the case where the specific oxide is a porous body or a particle aggregate, the specific surface area includes not only the total surface area of the structure including the inside of the fine pores and the gaps between the particles but also the outer surface area excluding the inside of the fine pores and the gaps between the particles. The outer surface area can be calculated using a known analysis method, and can be obtained by analyzing, for example, by the t-plot method. Furthermore, if the obtained data is analyzed by the BJH method, the pore diameter distribution and the average pore diameter of the specific oxide can also be obtained.

[0171] Here, among the oxides containing the specific element, the oxides that do not satisfy the above specific surface area in the untreated state can be made to satisfy the above specific surface area by performing a heat treatment, a roughening treatment, or the like.

[0172] The heat treatment can be performed by, for example, heating in an electric furnace, a reaction tube, or the like in an atmosphere of an oxygen-containing gas such as air, a non-active gas such as nitrogen gas, or the like. The heat treatment temperature varies depending on the crystal structure and the heat resistance of the oxide, and from the viewpoint of increasing the specific surface area, it is preferably 1000°C or lower, more preferably 800°C or lower, and particularly preferably 600°C or lower.

[0173] The roughening treatment is performed by, for example, contact or immersion in an acid or an alkaline solution, or contact with an acidic gas.

[0174] From the viewpoint of controlling the structure and the reproducibility at the time of production, the specific oxide is preferably crystalline.

[0175] In the present application, in the diffraction pattern measured using an XRD (X-ray diffraction device, for example, "Smart Lab" manufactured by Rigaku Corporation), the case where the diffraction peak in accordance with the crystal structure is included as the main component is regarded as crystalline, and the case where the diffraction peak in accordance with the crystal structure is not included as the main component is regarded as amorphous.

[0176] The specific oxide can be a powder or a granular substance, and the reaction form of a fluidized bed or a fixed bed can be used depending on the particle diameter.

[0177] <Other Oxide>

[0178] The heat treatment described later can be performed in the presence of the specific oxide and an oxide other than the specific oxide.

[0179] As the oxide other than the specific oxide, an oxide not containing the specific element and an oxide having a specific surface area of less than 1.0 m 2 / g can be given.

[0180] As specific examples of the oxide not containing a specific element, zinc oxide, silicon dioxide, aluminum oxide, zirconium oxide, and titanium oxide can be given.

[0181] As specific examples of the oxide having a specific surface area of less than 1.0 m 2 / g, a silicate glass in which SiO2not subjected to roughening treatment is the main component can be given.

[0182] <Manufacturing Process>

[0183] In the manufacturing method of the fluoro vinyl ether compound of the present application, there is a heating step of subjecting the compound 1 to a heating treatment in the presence of a specific oxide. By this, a thermal decomposition reaction of the compound 1 occurs, and the compound 2 is obtained. Specifically, after an intermediate is generated by the reaction of the compound 1 with the specific oxide, thermal decomposition and decarboxylation of the intermediate occur, and the compound 2 is obtained.

[0184] From the viewpoint of the reactivity of the 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.

[0185] From the viewpoint of further suppressing the generation of a by-product, 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 reducing the heating energy, it is preferable to lower the reaction temperature.

[0186] The reaction time is not particularly limited, and is preferably 0.1 to 120 seconds, and particularly preferably 0.5 to 60 seconds.

[0187] Here, the reaction time means the contact time of the specific oxide with the compound 1. For example, in the case of using a pipe-type reactor, the contact time can be calculated from the value of the amount of the gas containing the compound 1 flowing in the pipe-type reactor and the filling volume of the specific oxide in the pipe-type reactor.

[0188] The reaction pressure is not particularly limited, and is preferably 0 to 1 MPaG, and particularly preferably 0 to 0.1 MPaG.

[0189] The reaction of the compound 1 in the heating step can be any of a gas phase reaction, a liquid phase reaction, or a solid phase reaction, and from the viewpoint of easily manufacturing the compound 2, it is preferably a gas phase reaction.

[0190] In the case where the reaction of the compound 1 is a gas phase reaction, it is preferable to dilute the compound 1 with a non-active gas or the like and reuse it. As specific examples of the non-active gas, nitrogen gas, carbon dioxide gas, helium gas, and argon gas can be given.

[0191] In the case of using the non-active gas, the amount of the non-active gas is preferably 50 to 99.9 mol%, particularly preferably 80 to 99.9 mol% relative to the total amount of Compound 1 and the non-active gas.

[0192] The specific oxide can be used in a fixed bed method or in a fluidized bed method.

[0193] The amount of the specific oxide is preferably 0.00001 to 10 kg, particularly preferably 0.005 to 5 kg relative to 1 mole of Compound 1.

[0194] In the case of using the specific oxide in combination with the other oxide, the amount of the specific oxide is preferably 0.1 to 99 mass%, more preferably 0.1 to 80 mass%, particularly preferably 0.1 to 70 mass% relative to the total amount of the specific oxide and the other oxide from the viewpoint of further suppressing the generation of by-products.

[0195] The production method of the fluoro vinyl ether compound of the present application preferably has a drying step of drying the specific oxide before the heat treatment. Thereby, the generation of by-products which are difficult to separate and which can be generated due to the presence of water can be further suppressed.

[0196] The method of drying the specific oxide is not particularly limited, and a method of heating the specific oxide can be exemplified.

[0197] The heating temperature when the drying treatment is performed by heating is preferably 100 to 450°C, particularly preferably 150 to 450°C. In addition, the heating time when the drying treatment is performed by heating is preferably 10 minutes to 1 week, particularly preferably 30 minutes to 24 hours.

[0198] <Compound 2>

[0199] The fluoro vinyl ether compound obtained by the production method in the present application is a compound (i.e., Compound 2) having a group represented by the following formula (2).

[0200] CF2=CF-O- Formula (2)

[0201] In the production method of the present application, in the case of using Compound 1A, a compound represented by the following formula (2A) is obtained.

[0202] CF2=CF-O-R f Formula (2A)

[0203] R in Formula (2A) f R in Formula (1A) f The meanings are the same.

[0204] In the production method of the present application, in the case where the compound 1A-1 is used, a compound represented by the following formula (2A-1) is obtained.

[0205] CF2=CF-O-Z a1 Formula (2A-1)

[0206] Z in formula (2A-1) a1 Z in formula (1A-1) a1 have the same meaning.

[0207] In the production method of the present application, in the case where the compound 1A-1-1 is used, a compound represented by the following formula (2A-1-1) is obtained.

[0208] CF2=CF-O-R f11 Formula (2A-1-1)

[0209] R in formula (2A-1-1) f11 R in formula (1A-1-1) f11 have the same meaning.

[0210] As specific examples of the compound represented by formula (2A-1-1), CF2=CF-O-CF3, CF2=CF-O-CF2CF3, CF2=CF-O-CF2CF2CF3 can be given.

[0211] In the production method of the present application, in the case where the compound 1A-1-2 is used, a compound represented by the following formula (2A-1-2) is obtained.

[0212] CF2=CF-O-(R f12 O) m1 -R f13 Formula (2A-1-2)

[0213] R in formula (2A-1-2) f12 , R f13 and m1 in formula (1A-1-2) f12 , R f13 and m1 have the same meaning.

[0214] As specific examples of the compound represented by formula (2A-1-2), 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, CF2=CF-O-CF2CFO-CF2CFO-CF2CF3 can be given.

[0215] In the production method of the present application, in the case where the compound 1A-2 is used, by appropriately adjusting the production conditions, a compound represented by the following formula (2A-2-1) or a compound represented by the following formula (2A-2-2) is obtained. In order to obtain the compound represented by formula (2A-2-2), Q a2 It is required to have -CF(CF3)- or -CF2-CF2- directly bonded to -C(=O)-F.

[0216] CF2=CF-O-Q a2 -C(=O)-F formula (2A-2-1)

[0217] CF2=CF-O-Q a21 -CF=CF2 formula (2A-2-2)

[0218] Q in formula (2A-2-1) a2 Q in formula (1A-2) a3 have the same meaning.

[0219] Q in formula (2A-2-2) a21 is a perfluoroalkylene group or a divalent group in which the -CF2- of the perfluoroalkylene group is replaced with an etheric oxygen atom. The number of carbon atoms of the perfluoroalkylene group is preferably from 1 to 8, and particularly preferably from 1 to 4. The perfluoroalkylene group can be linear or branched. Q a21 The number of etheric oxygen atoms possessed by the divalent group in formula (2A-2-2) can be 1 or more than 2. The etheric oxygen atom is preferably located between the carbon-carbon bonds of the perfluoroalkylene group.

[0220] In the production method of the present application, in the case where the 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. In order to obtain the compound represented by formula (2A-2-12), R f21 It is required to have -CF(CF3)- or -CF2-CF2- directly bonded to -C(=O)-F.

[0221] CF2=CF-O-R f21 -C(=O)-F formula (2A-2-11)

[0222] CF2=CF-O-R f211 -CF=CF2 formula (2A-2-12)

[0223] R in formula (2A-2-11) f21 R in formula (1A-2-1) f21 have the same meaning.

[0224] R in formula (2A-2-12) is a perfluoroalkylene group. The number of carbon atoms in the perfluoroalkylene group is preferably from 1 to 8, and particularly preferably from 1 to 4. The perfluoroalkylene group can be linear or branched. f211 is a perfluoroalkylene group. The number of carbon atoms in the perfluoroalkylene group is preferably from 1 to 8, and particularly preferably from 1 to 4. The perfluoroalkylene group can be linear or branched.

[0225] As specific examples of the compound represented by formula (2A-2-11), there can be mentioned CF2=CF-O-CF2CF2-C(=O)-F, CF2=CF-O-CF2CF2CF2-C(=O)-F, CF2=CF-O-CF2CF2CF2CF2-C(=O)-F, CF2=CF-O-CF(CF3)-CF2-CF2-C(=O)-F, CF2=CF-O-CF2CF(CF3)-CF2-C(=O)-F.

[0226] As specific examples of the compound represented by formula (2A-2-12), there can be mentioned 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, CF2=CF-O-CF2CF(CF3)-CF=CF2, and the like.

[0227] The compound represented by formula (2A-2-11) can be converted into a vinyl ether carboxylate by a publicly known method such as that disclosed in Japanese Patent Publication No. 62-51943. Specifically, there are a method in which an alcohol is reacted; a method in which hydrolysis is performed to produce a vinyl ether carboxylic acid, and further esterification is performed.

[0228] In the production method of the present application, in the case where the 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. In order to obtain the compound represented by formula (2A-2-22), R f23 It is necessary to have -CF(CF3)- or -CF2-CF2- directly bonded to -C(=O)-F.

[0229] CF2=CF-O-(R f22 O) m2 -R f23 -C(=O)-F formula (2A-2-21)

[0230] CF2=CF-O-(R f22 O) m2 -R f231-CF=CF2 formula (2A-2-22)

[0231] In formula (2A-2-21) and formula (2A-2-22), R f22 and m2have the same meanings as R f22 and m2in formula (1A-2-2).

[0232] R in formula (2A-2-21) f23 has the same meaning as R f23 in formula (1A-2-2).

[0233] R in formula (2A-2-22) f231 is a perfluoroalkylene group. The number of carbon atoms of the perfluoroalkylene group is preferably from 1 to 6, and particularly preferably from 1 to 3. The perfluoroalkylene group can be linear or branched.

[0234] As specific examples of the compound represented by formula (2A-2-22), 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 can be given.

[0235] As specific examples of the compound represented by formula (2A-2-23), CF2=CF-O-CF2CF(CF3)O-CF2-CF=CF2, CF2=CF-O-CF2CF2CF2O-CF2-CF=CF2, and CF2=CF-O-CF2CF2O-CF2-CF=CF2 can be given.

[0236] In the production method of the present application, in the case where the compound 1A-3 is used, a compound represented by the following formula (2A-3) is obtained.

[0237] CF2=CF-O-Q a3 (-SO2F) q Formula (2A-3)

[0238] Q in formula (2A-3) a3 and q have the same meanings as Q a3 and q in formula (1A-3).

[0239] In the production method of the present application, in the case where the compound 1A-3-1 is used, a compound represented by the following formula (2A-3-1) is obtained.

[0240] CF2=CF-(OCF2CFZ a1 ) m3 -O p3 -(CF2)n3 -SO2F formula (2A-3-1)

[0241] Z in formula (2A-3-1) a1 m3, p3 and n3 in formula (2A-3-1) are the same as Z a1 m3, p3 and n3 in formula (2A-3-1) are the same as Z

[0242] As specific examples of the compound represented by formula (2A-3-1), CF2=CF-OCF2CF2-SO2F, CF2=CF-OCF2CF2CF2-SO2F, CF2=CF-OCF2CF2CF2CF2-SO2F, CF2=CF-OCF2CF2-OCF2CF2-SO2F, CF2=CF-OCF2CF(CF3)-OCF2CF2-SO2F can be given.

[0243] In the production method of the present application, in the case where the compound 1A-3-2 is used, the compound represented by the following formula (2A-3-2) is obtained.

[0244] CF2=CF-O-(CF2) n4 -(O) p4 -C(Z a2 )(-Q a31 -SO2F)(-Q a32 -SO2F) formula

[0245] (2A-3-2)

[0246] n4, p4, Z a2 , Q a31 and Q a32 in formula (2A-3-2) are the same as n4, p4, Z a2 , Q a31 and Q a32 in formula (1A-3-2).

[0247] As specific examples of the compound represented by formula (2A-3-2), CF2=CF-O-CF2-CF(-OCF2CF2-SO2F)(-CF2CF2-SO2F), CF2=CF-O-CF2-CF2CF2OCF(CF2-SO2F)(CF2-SO2F), CF2=CF-O-CF2-CF(-OCF2CF2-SO2F)(-CF2-OCF2CF2-SO2F) can be given.

[0248] In the case where the compound 2 has a fluorosulfonyl group, the compound 2 can be suitably used as a monomer component for producing a fluorine-containing polymer containing a sulfonic acid group. Here, the fluorine-containing polymer containing a sulfonic acid group can be suitably used for producing an electrolyte membrane.

[0249] <By-products>

[0250] As by-products, not limited thereto, for example, a compound obtained by adding hydrogen fluoride to the vinyl ether group of Compound 2 (hereinafter also referred to as "specific by-product") can be exemplified. The specific by-product is sometimes difficult to separate from Compound 2, and sometimes the separation operation becomes complicated.

[0251] In view of such a problem, according to the production method of the present application, the generation of by-products such as the specific by-product can be suppressed, and Compound 2 of high purity can be obtained, and thus the separation operation and the like can be simplified.

[0252] For example, in the case where Compound 1A is used in the production method of the fluoro vinyl ether compound of the present application, as the specific by-product, a compound represented by the following formula (3A) is sometimes generated.

[0253] CF3-CHF-O-R f Formula (3A)

[0254] R in Formula (3A) f R in Formula (1A) f has the same meaning.

[0255] Examples

[0256] Hereinafter, the present application will be explained in detail by way of examples. Examples 1-2 to 1-7, Examples 2-2 to 2-7, Examples 3-2 to 3-4, Examples 4-2 to 4-4, Examples 5-2 to 5-5, and Examples 6-2 to 6-6 are examples, and Examples 1-1, Example 2-1, Example 3-1, Example 4-1, Example 5-1, and Example 6-1 are comparative examples. However, the present application is not limited to these examples.

[0257] Note that the examples and the comparative examples were all carried out under normal pressure.

[0258] [Specific surface area]

[0259] The specific surface area of the oxide was calculated by analyzing the results measured using "3Flex" manufactured by MICRO-METRIC Co., Ltd. using a gas adsorption method (using nitrogen) by the BET method.

[0260] [Crystallinity]

[0261] As to whether the oxide has crystallinity or not, it was determined based on the diffraction pattern measured using "Smart Lab" manufactured by RIGAKU Co., Ltd., and the case where the diffraction peak conforming to the crystal structure was included was regarded as having crystallinity, and the case where the diffraction peak conforming to the crystal structure was not included was regarded as not having crystallinity.

[0262] [Amount of by-product generated relative to the amount of fluoro vinyl ether compound generated]

[0263] The amount of by-product generated with respect to the fluoro vinyl ether compound was calculated from the peak area as an analysis result using the following equation, for the generated gas collected from the outlet of the reactor 5 hours after the start of the reaction, using gas chromatography with the following conditions. It can be said that the smaller the calculated value, the more the generation of by-products is suppressed.

[0264] Here, the by-product refers to a group of compounds that are difficult to separate from the fluoro vinyl ether compound, and the total value of the by-product peaks detected in the gas chromatography analysis value within 20 minutes after the retention time of the fluoro vinyl ether compound, other than the raw material, was set as the amount of by-product generated.

[0265] Amount of by-product generated with respect to the amount of fluoro vinyl ether compound = (ratio of area of all by-products other than the raw material in the total area of the peaks of the generated gas [%]) ÷ (ratio of area of the fluoro vinyl ether compound in the total area of the peaks of the generated gas [%])

[0266] <Analysis conditions for gas chromatography>

[0267] The gas composition analysis of the generated gas was performed using a "6850 gas chromatograph" manufactured by Agilent Corporation, with "Rtx-200" manufactured by Restek Corporation (inner diameter 0.25 mm, length 60 m, film thickness 1.00 μm) as a capillary column, under the following conditions: carrier gas: helium, injection port temperature: 240°C, gas line speed: 22.6 cm / s, column temperature: 40°C, held for 10 minutes, then increased to 240°C at 10°C / min and held for 10 minutes, using a detector: FID.

[0268] [Conversion rate]

[0269] The generated gas collected from the outlet of the reactor 5 hours after the start of the reaction was recovered into a stainless steel cylinder cooled with liquid nitrogen, and the composition of the resulting liquid was analyzed using gas chromatography, and the conversion rate of the raw material was calculated from the following operation, and the conversion rate was evaluated according to the following evaluation criteria.

[0270] Conversion rate of raw material (%) = {1 - (raw material concentration at the outlet of the reactor (g / g)) / (raw material concentration at the inlet of the reactor (g / g))} x 100

[0271] A: The conversion rate of the raw material is 70% or more

[0272] B: The conversion rate of the raw material is 50% or more and less than 70%

[0273] C: The conversion rate of the raw material is 30% or more and less than 50%

[0274] D: Conversion of the raw material is 10% or more and less than 30%

[0275] E: Conversion of the raw material is less than 10%

[0276] [Example 1-1]

[0277] In one side (length 700 mm) of a U-shaped reaction tube made of SUS316, inner diameter 21.4 mm, and total length 1550 mm, a stainless steel-made surface dish was placed at a position 5 cm from the lower portion, and 53 mL of glass beads 1 (specific surface area: 0.5 m 2 / g, crystallinity: none, aluminosilicate containing sodium) was filled thereon, nitrogen was introduced at 330°C, and drying of the packing was performed. The amount of nitrogen introduction was set to 150 NmL / min. Thereafter, a mixed gas of nitrogen / raw material = 93.4 / 6.6 (mole / mole) was circulated at 330°C with a contact time of 10.7 seconds (performed by a flow bed method), whereby a vinyl ether compound was obtained.

[0278] Note that the contact time is a value obtained by dividing the packing height of the oxide by the empty tower gas linear velocity of the mixed gas containing the raw material and nitrogen, and the empty tower gas linear velocity is obtained by dividing the flow rate of the mixed gas at the reaction temperature and the reaction pressure by the cross-sectional area of the reaction tube. The same applies to the following [Example 1-2] to [Example 6-6].

[0279] The amount of by-product generation was 0.10 [Area% / Area%] with respect to the amount of fluoro vinyl ether compound generation. In addition, the evaluation result of the conversion of the raw material was C.

[0280] Here, the raw material was a compound represented by formula (1A-1-11). In addition, the obtained fluoro vinyl ether compound was a compound represented by formula (2A-1-11).

[0281] F-C(=O)-CF(CF3)-O-CF2CF2CF3 Formula (1A-1-11)

[0282] CF2=CF-O-CF2CF2CF3 Formula (2A-1-11)

[0283] [Example 1-2]

[0284] Glass beads 2 (specific surface area: 4.1 m 2 / g, crystallinity: none) 53 mL, nitrogen was introduced at 300°C to dry the packing. The amount of nitrogen introduced was set to 150 NmL / min. Thereafter, a mixed gas of nitrogen / starting material = 90 / 10 (mole / mole) was circulated at 300°C with a contact time of 16.7 seconds (performed by a flow bed method), whereby a fluoro vinyl ether compound represented by the above formula (2A-1-11) was obtained. Note that the starting material was a compound represented by the above formula (1A-1-11).

[0285] Here, the glass beads 2 were produced by performing a roughening treatment on the glass beads 1 using an acidic gas.

[0286] The amount of by-products generated relative to the amount of fluoro vinyl ether compound generated was 0.05 [Area% / Area%], and the generation of by-products was sufficiently suppressed compared to Example 1-1, which used the same starting material. In addition, the evaluation result of the conversion rate of the starting material was A.

[0287] [Example 1-3]

[0288] A SUS316-made U-shaped reaction tube with an inner diameter of 21.4 mm was filled with Na2SiO3(specific surface area: 2.5 m 2 / g, crystallinity: none) 53 mL, nitrogen was introduced at 300°C to dry the packing. The amount of nitrogen introduced was set to 150 NmL / min. Thereafter, a mixed gas of nitrogen / starting material = 90 / 10 (mole / mole) was circulated at 300°C with a contact time of 16.7 seconds (performed by a flow bed method), whereby a fluoro vinyl ether compound represented by the above formula (2A-1-11) was obtained. Note that the starting material was a compound represented by the above formula (1A-1-11).

[0289] The amount of by-products generated relative to the amount of fluoro vinyl ether compound generated was 0.06 [Area% / Area%], and the generation of by-products was sufficiently suppressed compared to Example 1-1, which used the same starting material. In addition, the evaluation result of the conversion rate of the starting material was B.

[0290] [Example 1-3]

[0291] A SUS316-made U-shaped reaction tube with an inner diameter of 21.4 mm was filled with Na2SiO3(specific surface area: 2.5 m 2 / g, crystallinity: yes) 53 mL, nitrogen was introduced at 280°C to dry the packing. The amount of nitrogen introduced was set to 150 NmL / min. Thereafter, a mixed gas of nitrogen / starting material = 90 / 10 (mole / mole) was circulated at 280°C with a contact time of 16.7 seconds (carried out by a fixed bed), whereby a fluoro vinyl ether compound represented by the above formula (2A-1-11) was obtained. Note that the starting material was a compound represented by the above formula (1A-1-11).

[0292] The amount of by-product produced relative to the amount of fluoro vinyl ether compound produced was 0.04 [Area% / Area%], and the production of by-products was sufficiently suppressed compared to Example 1-1, which was obtained using the same starting material. In addition, the evaluation result of the conversion rate of the starting material was B.

[0293] [Example 1-5]

[0294] A SUS316-made U-shaped reaction tube with an inner diameter of 21.4 mm was filled with an alumina adsorbent 1 containing Na (a material obtained by heat-treating Axsorb AB manufactured by Japan Light Metal Co., Ltd. at 600°C for 10 hours in an air atmosphere; specific surface area: 177 m 2 / g, crystallinity: yes) 53 mL, nitrogen was introduced at 280°C to dry the packing. The amount of nitrogen introduced was set to 150 NmL / min. Thereafter, a mixed gas of nitrogen / starting material = 90 / 10 (mole / mole) was circulated at 280°C with a contact time of 16.7 seconds (carried out by a fixed bed), whereby a fluoro vinyl ether compound represented by the above formula (2A-1-11) was obtained. Note that the starting material was a compound represented by the above formula (1A-1-11).

[0295] The amount of by-product produced relative to the amount of fluoro vinyl ether compound produced was 0.05 [Area% / Area%], and the production of by-products was sufficiently suppressed compared to Example 1-1, which was obtained using the same starting material. In addition, the evaluation result of the conversion rate of the starting material was B.

[0296] [Example 1-6]

[0297] A SUS316-made U-shaped reaction tube with an inner diameter of 21.4 mm was filled with an alumina adsorbent 2 containing Na (selexsorb COS manufactured by BASF Co., Ltd., specific surface area: 150 m 2 / g, crystallinity: yes) 53 mL, nitrogen was introduced at 280°C to dry the packing. The amount of nitrogen introduced was set to 150 NmL / min. Thereafter, a mixed gas of nitrogen / starting material = 90 / 10 (mole / mole) was circulated at 280°C with a contact time of 16.7 seconds (performed by a fixed bed method), whereby a fluoro vinyl ether compound represented by the above formula (2A-1-11) was obtained. Note that the starting material was a compound represented by the above formula (1A-1-11).

[0298] The amount of by-product produced relative to the amount of fluoro vinyl ether compound produced was 0.05 [Area% / Area%], and the production of by-products was sufficiently suppressed compared to Example 1-1, which used the same starting material. In addition, the evaluation result of the conversion rate of the starting material was C.

[0299] [Example 1-7]

[0300] A SUS316-made U-shaped reaction tube with an inner diameter of 21.4 mm was filled with zeolite 1 ("ZEORAM A-3, Type 585, 20-32 mesh" manufactured by Tosoh Corporation, specific surface area: 28 m 2 / g, crystallinity: yes, potassium-containing aluminosilicate) 53 mL, nitrogen was introduced at 252°C to dry the packing. The amount of nitrogen introduced was set to 150 NmL / min. Thereafter, a mixed gas of nitrogen / starting material = 90 / 10 (mole / mole) to which water had been added to starting material = 1 / 2 (mole / mole) was circulated at 252°C with a contact time of 21.4 seconds (performed by a fluidized bed method), whereby a fluoro vinyl ether compound was obtained.

[0301] The amount of by-product produced relative to the amount of fluoro vinyl ether compound produced was 0.03 [Area% / Area%], and the production of by-products was sufficiently suppressed compared to Example 1-1, which used the same starting material. In addition, the evaluation result of the conversion rate of the starting material was A.

[0302] [Example 2-1]

[0303] A SUS316-made U-shaped reaction tube with an inner diameter of 21.4 mm was filled with glass beads 1 (specific surface area: 0.5 m 2 / g, crystallinity: no, sodium-containing aluminosilicate) 106 mL, nitrogen was introduced at 252°C to dry the packing. The amount of nitrogen introduced was set to 150 NmL / min. Thereafter, a mixed gas of nitrogen / starting material = 90 / 10 (mole / mole) to which water had been added to starting material = 1 / 2 (mole / mole) was circulated at 252°C with a contact time of 21.4 seconds (performed by a fluidized bed method), whereby a fluoro vinyl ether compound was obtained.

[0304] The amount of by-product generated relative to the amount of fluoro vinyl ether compound generated was 0.21 [Area % / Area %]. In addition, the evaluation result of the conversion rate of the raw material was D.

[0305] Here, the raw material used was a compound represented by formula (1A-2-11). In addition, the obtained fluoro vinyl ether compound was a compound represented by formula (2A-2-111).

[0306] F-C(=O)-CF(CF3)-O-CF2CF2CF2-C(=O)-F formula (1A-2-11)

[0307] CF2=CF-O-CF2CF2CF2-C(=O)-F formula (2A-2-111)

[0308] [Example 2-2]

[0309] A SUS316-made U-shaped reaction tube with an inner diameter of 21.4 mm was filled with glass beads 2 (specific surface area: 4.1 m 2 / g, crystallinity: none) 53 mL, and drying of the packing was performed at 251°C while introducing nitrogen gas. The amount of nitrogen gas introduced was set to 150 NmL / min. Thereafter, a mixed gas obtained by adding water in the form of water / raw material = 1 / 10 (mole / mole) to nitrogen gas / raw material = 90 / 10 (mole / mole) at a contact time of 10.7 seconds at 251°C (performed by a flow bed method) was circulated, whereby a fluoro vinyl ether compound represented by the above formula (2A-2-111) was obtained. Note that the raw material used was a compound represented by the above formula (1A-2-11).

[0310] The amount of by-product generated relative to the amount of fluoro vinyl ether compound generated was 0.06 [Area % / Area %], and compared to Example 2-1, which used the same raw material, generation of by-products was sufficiently suppressed. In addition, the evaluation result of the conversion rate of the raw material was C.

[0311] [Example 2-3]

[0312] A SUS316-made U-shaped reaction tube with an inner diameter of 21.4 mm was filled with glass beads 3 (specific surface area: 13.0 m 2 / g, crystallinity: none) 53 mL, nitrogen was introduced at 250°C to dry the packing. The amount of nitrogen introduced was set to 150 NmL / min. Thereafter, a mixed gas obtained by adding water in the form of water / starting material = 1 / 10 (mole / mole) to nitrogen / starting material = 90 / 10 (mole / mole) at 252°C with a contact time of 10.7 seconds was passed (carried out by the flow bed method) to thereby obtain a fluoro vinyl ether compound represented by the above formula (2A-2-111). Note that the starting material was a compound represented by the above formula (1A-2-11).

[0313] Here, the glass beads 3 are produced by performing a roughening treatment on the glass beads 1 using an acidic gas.

[0314] The amount of by-products generated relative to the amount of fluoro vinyl ether compound generated was 0.08 [Area% / Area%], and the generation of by-products was sufficiently suppressed compared to Example 2-1, which used the same starting material. In addition, the evaluation result of the conversion rate of the starting material was D.

[0315] [Example 2-4]

[0316] A SUS316-made, U-shaped reaction tube with an inner diameter of 21.4 mm was filled with Na2SiO3 (specific surface area: 2.5 m 2 / g, crystallinity: none) 53 mL, nitrogen was introduced at 250°C to dry the packing. The amount of nitrogen introduced was set to 150 NmL / min. Thereafter, a mixed gas obtained by adding water in the form of water / starting material = 1 / 10 (mole / mole) to nitrogen / starting material = 90 / 10 (mole / mole) at 252°C with a contact time of 10.7 seconds was passed (carried out by the flow bed method) to thereby obtain a fluoro vinyl ether compound represented by the above formula (2A-2-111). Note that the starting material was a compound represented by the above formula (1A-2-11).

[0317] The amount of by-products generated relative to the amount of fluoro vinyl ether compound generated was 0.10 [Area% / Area%], and the generation of by-products was sufficiently suppressed compared to Example 2-1, which used the same starting material. In addition, the evaluation result of the conversion rate of the starting material was C.

[0318] [Example 2-5]

[0319] 53 mL of alumina adsorbent 1 containing Na was packed into a U-shaped reaction tube made of SUS316 with an inner diameter of 21.4 mm. Nitrogen gas was introduced at 250 °C to dry the packing material. The nitrogen introduction rate was set to 150 N mL / min. Subsequently, a mixed gas obtained by adding water in the form of 1 / 10 (mol / mol) of nitrogen / feed = 90 / 10 (nitrogen / feed) was passed through the tube at 250 °C for a contact time of 10.7 seconds (implemented by fixed-bed method), thereby obtaining the fluorovinyl ether compound shown in formula (2A-2-111) above. It should be noted that the raw material used is the compound shown in formula (1A-2-11) above.

[0320] The amount of byproducts generated was 0.09 [Area% / Area%] relative to the amount of fluorovinyl ether compounds generated, which sufficiently suppressed the generation of byproducts compared to Example 2-1 obtained using the same raw materials. Furthermore, the conversion rate of the raw materials was rated as B.

[0321] [Example 2-6]

[0322] A U-shaped reaction tube made of SUS316 with an inner diameter of 21.4 mm was filled with zeolite 2 (ZEORAM A-4, 14-20 mesh, specific surface area: 29 m²) manufactured by Tosoh Corporation. 2 / g, Crystallinity: Contains sodium-containing aluminosilicate) 53mL, nitrogen gas was introduced at 252°C to dry the packing material. The nitrogen gas introduction rate was set to 150NmL / min. Subsequently, a mixed gas obtained by adding water in the form of nitrogen / raw material = 90 / 10 (mol / mol) with water / raw material = 1 / 10 (mol / mol) was passed through a nitrogen / raw material mixture at 251°C for a contact time of 10.7 seconds (implemented by fixed bed method), thereby obtaining the fluorovinyl ether compound shown in formula (2A-2-111) above. It should be noted that the raw material used is the compound shown in formula (1A-2-11) above.

[0323] The amount of byproducts generated was 0.10 [Area% / Area%] relative to the amount of fluorovinyl ether compounds generated, which sufficiently suppressed the generation of byproducts compared to Example 2-1 obtained using the same raw materials. Furthermore, the conversion rate of the raw materials was evaluated as C.

[0324] [Example 3-1]

[0325] A U-shaped reaction tube made of SUS316 stainless steel with an inner diameter of 21.4 mm was filled with glass beads (specific surface area: 0.5 m²). 2 / g, crystallinity: none, aluminosilicate containing sodium) 107 mL, drying of the packing was performed by introducing nitrogen at 320°C. The amount of nitrogen introduced was set to 150 NmL / min. Thereafter, a mixed gas of nitrogen / starting material = 94.5 / 5.6 (mole / mole) was circulated at 320°C with a contact time of 10.7 seconds (performed by a flow bed method), whereby a fluoro vinyl ether compound was obtained.

[0326] The amount of by-product generated relative to the amount of fluoro vinyl ether compound generated was 1.24 [Area% / Area%]. In addition, the evaluation result of the conversion rate of the starting material was B.

[0327] Here, the starting material was a compound represented by formula (1A-2-12). In addition, the obtained fluoro vinyl ether compound was a compound represented by formula (2A-2-121).

[0328] F-C(=O)-CF(CF3)-O-CF2CF2CF2CF2-C(=O)-F formula (1A-2-12)

[0329] CF2=CF-O-CF2CF2-CF=CF2 formula (2A-2-121)

[0330] [Example 3-2]

[0331] A SUS316-made, U-shaped reaction tube with an inner diameter of 21.4 mm was filled with glass beads 4 (specific surface area: 24.4 m 2 / g, crystallinity: none) 106 mL, drying of the packing was performed by introducing nitrogen at 323°C. The amount of nitrogen introduced was set to 150 NmL / min. Thereafter, a mixed gas of nitrogen / starting material = 93.4 / 6.6 (mole / mole) was circulated at 323°C with a contact time of 10.7 seconds (performed by a flow bed method), whereby a fluoro vinyl ether compound represented by the above formula (2A-2-121) was obtained. Note that the starting material was a compound represented by the above formula (1A-2-12).

[0332] Here, the glass beads 4 were manufactured by performing a roughening treatment on the glass beads 1 using an acidic gas.

[0333] The amount of by-product generated relative to the amount of fluoro vinyl ether compound generated was 0.02 [Area% / Area%], and the generation of by-products could be sufficiently suppressed compared to Example 3-1, which was performed using the same starting material. In addition, the evaluation result of the conversion rate of the starting material was A.

[0334] [Example 3-3]

[0335] A SUS316-made U-shaped reaction tube with an inner diameter of 21.4 mm was filled with 106 mL of Na2SiO3(specific surface area: 2.5 m 2 / g, crystallinity: yes) subjected to roughening treatment with an acid gas, nitrogen was introduced at 320°C, and drying of the packing was performed. The amount of nitrogen introduced was set to 150 NmL / min. Thereafter, a mixed gas of nitrogen / starting material = 93.4 / 6.6 (mole / mole) was circulated at 320°C with a contact time of 10.7 seconds (performed by a fixed bed method), whereby a fluoroallyl ether compound represented by the above formula (2A-2-121) was obtained. Note that the starting material was a compound represented by the above formula (1A-2-12).

[0336] The amount of by-product generation relative to the amount of fluoroallyl ether compound generation was 0.04 [Area% / Area%], and the generation of by-products was sufficiently suppressed compared to Example 3-1 using the same starting material. In addition, the evaluation result of the conversion rate of the starting material was B.

[0337] [Example 3-4]

[0338] A SUS316-made U-shaped reaction tube with an inner diameter of 21.4 mm was filled with 106 mL of Na2SiO3(specific surface area: 2.5 m

[0339] The amount of by-product generation relative to the amount of fluoroallyl ether compound generation was 0.04 [Area% / Area%], and the generation of by-products was sufficiently suppressed compared to Example 3-1 using the same starting material. In addition, the evaluation result of the conversion rate of the starting material was B.

[0340] [Example 4-1]

[0341] A SUS316-made U-shaped reaction tube with an inner diameter of 21.4 mm was filled with 106 mL of Na2SiO3(specific surface area: 2.5 m 2 / g, crystallinity: yes) subjected to roughening treatment with an acid gas, nitrogen was introduced at 320°C, and drying of the packing was performed. The amount of nitrogen introduced was set to 150 NmL / min. Thereafter, a mixed gas of nitrogen / starting material = 93.4 / 6.6 (mole / mole) was circulated at 320°C with a contact time of 10.7 seconds (performed by a fixed bed method), whereby a fluoroallyl ether compound represented by the above formula (2A-2-121) was obtained. Note that the starting material was a compound represented by the above formula (1A-2-12).

[0342] The amount of by-product generated relative to the amount of fluoroallyl ether compound generated was 0.15 [Area% / Area%]. In addition, the evaluation result of the conversion rate of the raw material was D.

[0343] Here, the raw material was a compound represented by formula (1A-2-21). In addition, the obtained fluoroallyl ether compound was a compound represented by formula (2A-2-221).

[0344] F-C(=O)-CF(CF3)-OCF2CF(CF3)-OCF2CF2CF2-C(=O)-F formula

[0345] (1A-2-21)

[0346] CF2=CF-OCF2CF(CF3)-OCF2CF=CF2 formula (2A-2-221)

[0347] [Example 4-2]

[0348] A SUS316-made U-shaped reaction tube having an inner diameter of 21.4 mm was filled with glass beads 5 (specific surface area: 5.1 m 2 / g, crystallinity: none) 106 mL, and drying of the packing was performed at 320°C while introducing nitrogen gas. The amount of nitrogen gas introduced was set to 150 NmL / min. Thereafter, a mixed gas of nitrogen gas / raw material = 95.0 / 5.0 (mole / mole) was circulated at a contact time of 10.5 seconds at 320°C (performed by a flow bed method), whereby a fluoroallyl ether compound represented by the above formula (2A-2-221) was obtained. Note that the raw material was a compound represented by the above formula (1A-2-21).

[0349] Here, the glass beads 5 were produced by performing a roughening treatment on the glass beads 1 using an acidic gas.

[0350] The amount of by-product generated relative to the amount of fluoroallyl ether compound generated was 0.06 [Area% / Area%], and the generation of by-products could be sufficiently suppressed compared to Example 4-1 performed using the same raw material. In addition, the evaluation result of the conversion rate of the raw material was A.

[0351] [Example 4-3]

[0352] A SUS316-made U-shaped reaction tube having an inner diameter of 21.4 mm was filled with Na2SiO3 (specific surface area: 2.5 m 2 / g, crystallinity: yes) 106 mL, drying of the packing was performed by introducing nitrogen at 320°C. The amount of nitrogen introduction was set to 150 NmL / min. Thereafter, a mixed gas of nitrogen / starting material = 95.0 / 5.0 (mole / mole) was flowed (performed by a fixed bed method) at 300°C with a contact time of 10.2 seconds, whereby a fluoroallyl ether compound represented by the above formula (2A-2-221) was obtained. Note that the starting material was a compound represented by the above formula (1A-2-21).

[0353] The amount of generation of the by-product was 0.05 [Area % / Area %] relative to the amount of generation of the fluoroallyl ether compound, and the generation of the by-product was sufficiently suppressed compared to Example 4-1 performed using the same starting material. In addition, the evaluation result of the conversion rate of the starting material was B.

[0354] [Example 4-4]

[0355] A SUS316-made U-shaped reaction tube with an inner diameter of 21.4 mm was filled with 106 mL of alumina adsorbent 1 containing Na, drying of the packing was performed by introducing nitrogen at 300°C. The amount of nitrogen introduction was set to 150 NmL / min. Thereafter, a mixed gas of nitrogen / starting material = 95.0 / 5.0 (mole / mole) was flowed (performed by a fixed bed method) at 300°C with a contact time of 10.2 seconds, whereby a fluoroallyl ether compound represented by the above formula (2A-2-221) was obtained. Note that the starting material was a compound represented by the above formula (1A-2-21).

[0356] The amount of generation of the by-product was 0.03 [Area % / Area %] relative to the amount of generation of the fluoroallyl ether compound, and the generation of the by-product was sufficiently suppressed compared to Example 4-1 performed using the same starting material. In addition, the evaluation result of the conversion rate of the starting material was B.

[0357] [Example 5-1]

[0358] A SUS316-made U-shaped reaction tube with an inner diameter of 21.4 mm was filled with 106 mL of alumina adsorbent 1 containing Na, drying of the packing was performed by introducing nitrogen at 300°C. The amount of nitrogen introduction was set to 150 NmL / min. Thereafter, a mixed gas of nitrogen / starting material = 95.0 / 5.0 (mole / mole) was flowed (performed by a fixed bed method) at 300°C with a contact time of 10.2 seconds, whereby a fluoroallyl ether compound represented by the above formula (2A-2-221) was obtained. Note that the starting material was a compound represented by the above formula (1A-2-21). 2 / g, crystallinity: yes, aluminosilicate containing Na) 53 mL, drying of the packing was performed by introducing nitrogen at 330°C. The amount of nitrogen introduction was set to 150 NmL / min. Thereafter, a mixed gas of nitrogen / starting material = 93.4 / 6.6 (mole / mole) was flowed (performed by a flow bed method) at 330°C with a contact time of 10.7 seconds, whereby a fluoroallyl ether compound was obtained.

[0359] The amount of generation of the by-product was 0.08 [Area % / Area %] relative to the amount of generation of the fluoroallyl ether compound. In addition, the evaluation result of the conversion rate of the starting material was B.

[0360] Here, the raw material used is a compound represented by formula (1A-3-11). Also, the obtained fluoro vinyl ether compound is a compound represented by formula (2A-3-11).

[0361] F-C(=O)-CF(CF3)-OCF2CF(CF3)-OCF2CF2-SO2F formula (1A-3-11)

[0362] CF2=CF-OCF2CF(CF3)-OCF2CF2-SO2F formula (2A-3-11)

[0363] [Example 5-2]

[0364] A SUS316-made U-shaped reaction tube with an inner diameter of 21.4 mm was filled with 106 mL of glass beads 5 (specific surface area: 5.1 m 2 / g, crystallinity: none), and drying of the packing was performed while introducing nitrogen at 331°C. The amount of nitrogen introduced was set to 150 NmL / min. Thereafter, a mixed gas of nitrogen / raw material = 93.4 / 6.6 (mole / mole) was circulated at a contact time of 21.4 seconds at 331°C (performed by the flow bed method), whereby a fluoro vinyl ether compound represented by the above formula (2A-3-11) was obtained. Note that the raw material used was a compound represented by the above formula (1A-3-11).

[0365] Here, the glass beads 5 were produced by performing a roughening treatment on the glass beads 1 using an acidic gas.

[0366] The amount of by-product produced relative to the amount of fluoro vinyl ether compound produced was 0.01 [Area% / Area%], and the production of by-products was sufficiently suppressed compared to Example 5-1, which was performed using the same raw material. Also, the evaluation result for the conversion rate of the raw material was A.

[0367] [Example 5-3]

[0368] A SUS316-made U-shaped reaction tube with an inner diameter of 21.4 mm was filled with 106 mL of Na2SiO3 (specific surface area: 2.5 m 2 / g, crystallinity: yes) on which a roughening treatment had been performed using an acidic gas, and drying of the packing was performed while introducing nitrogen at 310°C. The amount of nitrogen introduced was set to 150 NmL / min. Thereafter, a mixed gas of nitrogen / raw material = 93.4 / 6.6 (mole / mole) was circulated at a contact time of 21.4 seconds at 310°C (performed by the fixed bed method), whereby a fluoro vinyl ether compound represented by the above formula (2A-3-11) was obtained. Note that the raw material used was a compound represented by the above formula (1A-3-11).

[0369] The amount of byproduct generated was 0.05 [Area% / Area%] relative to the amount of fluorovinyl ether compound generated, which sufficiently suppressed the generation of byproducts compared to Example 5-1 using the same raw materials. Furthermore, the conversion rate of the raw materials was rated as B.

[0370] [Example 5-4]

[0371] 106 mL of alumina adsorbent 1 containing Na was packed into a U-shaped reaction tube made of SUS316 with an inner diameter of 21.4 mm. Nitrogen gas was introduced at 281 °C to dry the packing material. The nitrogen introduction rate was set to 150 N mL / min. Subsequently, a nitrogen / feed mixture of 93.4 / 6.6 (mol / mol) was passed through at 280 °C for a contact time of 21.4 seconds (implemented by a fixed-bed method) to obtain the fluorovinyl ether compound shown in formula (2A-3-11) above. It should be noted that the feedstock used is the compound shown in formula (1A-3-11) above.

[0372] The amount of byproducts generated was 0.04 [Area% / Area%] relative to the amount of fluorovinyl ether compounds generated, which sufficiently suppressed the generation of byproducts compared to Example 5-1 using the same raw materials. Furthermore, the conversion rate of the raw materials was rated as B.

[0373] [Example 5-5]

[0374] A U-shaped reaction tube made of SUS316 with an inner diameter of 21.4 mm was filled with zeolite 3 (Tosoh Corporation's "HSZ-300 type 320NAD1C", specific surface area: 640 m²). 2 / g, Crystallinity: Contains sodium-containing aluminosilicate) 106 mL, nitrogen gas was introduced at 252 °C to dry the packing material. The nitrogen gas introduction rate was set to 150 N mL / min. Subsequently, a nitrogen / raw material mixture of 93.4 / 6.6 (mol / mol) was passed through at 252 °C for a contact time of 21.4 seconds (implemented by fixed bed method), thereby obtaining the fluorovinyl ether compound shown in formula (2A-3-11) above. It should be noted that the raw material used is the compound shown in formula (1A-3-11) above.

[0375] The amount of byproducts generated was 0.07 [Area% / Area%] relative to the amount of fluorovinyl ether compounds generated, which sufficiently suppressed the generation of byproducts compared to Example 5-1 using the same raw materials. Furthermore, the conversion rate of the raw materials was rated as D.

[0376] [Example 6-1]

[0377] A U-shaped reaction tube made of SUS316 stainless steel with an inner diameter of 21.4 mm was filled with glass beads (specific surface area: 0.5 m²).2 / g, crystallinity: none, aluminosilicate containing sodium) 53 mL, nitrogen was introduced at 330°C to dry the packing. The amount of nitrogen introduced was set to 150 NmL / min. Thereafter, a mixed gas of nitrogen / starting material = 93.4 / 6.6 (mole / mole) was circulated at 330°C with a contact time of 7.5 seconds (performed by a flow bed method), whereby a fluoro vinyl ether compound was obtained.

[0378] The amount of by-product generated relative to the amount of fluoro vinyl ether compound generated was 0.50 [Area% / Area%]. In addition, the evaluation result of the conversion rate of the starting material was D.

[0379] Here, the starting material was a compound represented by formula (1A-3-21). In addition, the obtained fluoro vinyl ether compound was a compound represented by formula (2A-3-21).

[0380] F-C(=O)-CF(CF3)-O-CF2-CF(-OCF2CF2-SO2F)(-CF2-OCF2CF2-SO2F)

[0381] Formula (1A-3-21)

[0382] CF2=CF-O-CF2-CF(-OCF2CF2-SO2F)(-CF2-OCF2CF2-SO2F) Formula

[0383] (2A-3-21)

[0384] [Example 6-2]

[0385] A SUS316-made, U-shaped reaction tube with an inner diameter of 21.4 mm was filled with glass beads 6 (specific surface area: 12.3 m 2 / g, crystallinity: none) 53 mL, nitrogen was introduced at 331°C to dry the packing. The amount of nitrogen introduced was set to 150 NmL / min. Thereafter, a mixed gas of nitrogen / starting material = 93.4 / 6.6 (mole / mole) was circulated at 331°C with a contact time of 7.5 seconds (performed by a flow bed method), whereby a fluoro vinyl ether compound represented by the above formula (2A-3-21) was obtained. Note that the starting material was a compound represented by the above formula (1A-3-21).

[0386] Here, the glass beads 6 were manufactured by performing a roughening treatment on the glass beads 1 using an acid gas.

[0387] The amount of by-product generated relative to the amount of fluoro vinyl ether compound generated was 0.02 [Area% / Area%], and the generation of by-products could be sufficiently suppressed compared to Example 6-1, which was performed using the same starting material. In addition, the evaluation result of the conversion rate of the starting material was B.

[0388] [Example 6-3]

[0389] A SUS316-made U-shaped reaction tube having an inner diameter of 21.4 mm was filled with 53 mL of glass beads 3 (specific surface area: 13.0 m 2 / g, crystallinity: none), and drying of the packing was performed by introducing nitrogen at 333°C. The amount of nitrogen introduced was set to 150 NmL / min. Thereafter, a mixed gas of nitrogen / starting material = 93.4 / 6.6 (mole / mole) was circulated at 333°C for a contact time of 7.5 seconds (performed by a flow bed method), whereby a fluoro vinyl ether compound represented by the above formula (2A-3-21) was obtained. Note that the starting material was a compound represented by the above formula (1A-3-21).

[0390] The amount of by-product produced relative to the amount of fluoro vinyl ether compound produced was 0.03 [Area% / Area%], and production of by-products was sufficiently suppressed compared to Example 6-1, which was performed using the same starting material. In addition, the evaluation result for the conversion rate of the starting material was B.

[0391] [Example 6-4]

[0392] A SUS316-made U-shaped reaction tube having an inner diameter of 21.4 mm was filled with 53 mL of Na2SiO3(2.5 m 2 / g, crystallinity: none), and drying of the packing was performed by introducing nitrogen at 333°C. The amount of nitrogen introduced was set to 150 NmL / min. Thereafter, a mixed gas of nitrogen / starting material = 93.4 / 6.6 (mole / mole) was circulated at 333°C for a contact time of 7.5 seconds (performed by a flow bed method), whereby a fluoro vinyl ether compound represented by the above formula (2A-3-21) was obtained. Note that the starting material was a compound represented by the above formula (1A-3-21).

[0393] The amount of by-product produced relative to the amount of fluoro vinyl ether compound produced was 0.03 [Area% / Area%], and production of by-products was sufficiently suppressed compared to Example 6-1, which was performed using the same starting material. In addition, the evaluation result for the conversion rate of the starting material was B.

[0394] [Example 6-5]

[0395] A SUS316-made U-shaped reaction tube with an inner diameter of 21.4 mm was filled with 53 mL of the Na-containing alumina adsorbent 1, and drying of the filler was performed by introducing nitrogen at 301°C. The amount of nitrogen introduced was set to 150 NmL / min. Thereafter, a mixed gas of nitrogen / starting material = 93.4 / 6.6 (mole / mole) was circulated at 300°C with a contact time of 7.5 seconds (performed by a flow bed method), whereby a fluoro vinyl ether compound represented by the above formula (2A-3-21) was obtained. Note that the starting material was a compound represented by the above formula (1A-3-21).

[0396] The amount of by-product generated relative to the amount of fluoro vinyl ether compound generated was 0.05 [Area% / Area%], and the generation of by-products was sufficiently suppressed compared to Example 6-1 performed using the same starting material. In addition, the evaluation result of the conversion rate of the starting material was C.

[0397] [Example 6-6]

[0398] A SUS316-made U-shaped reaction tube with an inner diameter of 21.4 mm was filled with 53 mL of zeolite 4 (“HSZ-500 Type 500KODAC” manufactured by Toho Chemical Industry Co., Ltd., specific surface area: 257 m2 / g, crystallinity: yes, aluminosilicate containing potassium), and drying of the filler was performed by introducing nitrogen at 301°C. The amount of nitrogen introduced was set to 150 NmL / min. Thereafter, a mixed gas of nitrogen / starting material = 93.4 / 6.6 (mole / mole) was circulated at 301°C with a contact time of 7.5 seconds (performed by a fixed bed method), whereby a fluoro vinyl ether compound represented by the above formula (2A-3-21) was obtained. Note that the starting material was a compound represented by the above formula (1A-3-21).

[0399] The amount of by-product generated relative to the amount of fluoro vinyl ether compound generated was less than 0.01 [Area% / Area%], and the generation of by-products was sufficiently suppressed compared to Example 6-1 performed using the same starting material.

[0400] Note that the specification, claims, drawings, and abstract of Japanese Patent Application No. 2020-217715 filed on December 25, 2020 are hereby incorporated by reference in their entirety as the disclosure of the present application.

Claims

1. A method for producing a fluoro vinyl ether compound, characterized by comprising the steps of, A fluorovinyl ether compound having a group represented by the following formula (2) is obtained by subjecting a compound having a group represented by the following formula (1) to a heat treatment 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, The specific surface area of the oxide before the heat treatment is 1.0 m 2 / g or more, F-C(=O)-CF(X)-(CF2) n -O- Formula (1) CF2=CF-O- Formula (2) In formula (1), n is 0 or 1, X is CF3 when n is 0, and X is F when n is 1.

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

3. The method for producing a fluoro vinyl ether compound according to any one of claims 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 fluoro vinyl ether compound according to claim 1 or 2, 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 fluoro vinyl ether compound according to claim 1 or 2, wherein, The oxide is an amorphous oxide selected from a 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 method for producing a fluoro vinyl ether compound according to claim 1 or 2, wherein, The specific surface area of the oxide before the heat treatment is 1.0 to 700 m 2 / g.

7. The method for producing a fluoro vinyl ether compound according to claim 1 or 2, wherein, The heat treatment is performed in the presence of the oxide and another oxide different from the oxide, The amount of the oxide is 0.1 to 99 mass% relative to the total amount of the oxide and the other oxide.

8. The method for producing a fluoro vinyl ether compound according to claim 1 or 2, wherein, The compound having a group represented by formula (1) is a perfluorinated compound.

9. The method for producing a fluoro vinyl ether compound according to claim 1 or 2, wherein, The compound having a group represented by formula (1) is a compound represented by the following formula (1A), F-C(=O)-CF(CF3)-O-R f formula (1A) In formula (1A), R f represents a perfluoroalkyl group optionally having a monovalent substituent selected from the group consisting of -C(=O)F, a fluorosulfonyl group, a nitrile group, and a methyl ester group; or R f represents a monovalent group in which -CF2- of said perfluoroalkyl group optionally having a monovalent substituent is replaced by an etheric oxygen atom.

10. The method for producing a fluoro vinyl ether compound according to claim 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), F-C(=O)-CF(CF3)-O-Z a1 formula (1A-1) Z a1 a monovalent group which is perfluoroalkyl or perfluoroalkyl in which the -CF2- groups are replaced by etheric oxygen atoms, F-C(=O)-CF(CF3)-O-Q a2 -C(=O)-F Formula (1A-2) Q a2 a perfluoroalkylene group or a divalent group in which a -CF2- of a perfluoroalkylene group is replaced by an etheric oxygen atom; F-C(=O)-CF(CF3)-O-Q a3 (-SO2F) q formula (1A-3) Q a3 a (q+1) valent perfluorohydrocarbyl group or a (q+1) valent group in which the -CF2- of the perfluorohydrocarbyl group is replaced by an etheric oxygen atom, q being an integer of from 1 to 3.

11. The method for producing a fluoro vinyl ether compound according to claim 1 or 2, wherein, The compound having a group represented by formula (2) is a compound represented by the following formula (2A), CF2=CF-O-R f formula (2A) R f R f have the same meaning as in formula (1A).

12. The method for producing a fluoro vinyl ether compound according to claim 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-O-Z a1 formula (2A-1) Z in formula (2A-1) a1 Z in formula (1A-1) a1 have the same meaning, CF2=CF-O-Q a2 -C(=O)-F Formula (2A-2-1) CF2=CF-O-Q a21 -CF=CF2formula (2A-2-2) Q in formula (2A-2-1) a2 Q in formula (1A-2) a2 have the same meaning, Q in formula (2A-2-2) a21 a perfluoroalkylene group or a divalent group in which the -CF2- of a perfluoroalkylene group is replaced by an etheric oxygen atom, CF2=CF-O-Q a3 (-SO2F) q formula (2A-3) Q in formula (2A-3) a3 and q have the same meaning as Q a3 and q in formula (1A-3).

13. The method for producing a fluoro vinyl ether compound according to claim 1 or 2, wherein, The oxide is subjected to a drying treatment before the heat treatment.