WO2002026682A1 - Process for producing fluorinated vinyl ethers - Google Patents

Abstract

A process is provided by which fluorinated vinyl ethers can be efficiently produced from more inexpensive raw materials without separating operation in the production process. Specifically, a process for producing fluorinated vinyl ethers (8), characterized by subjecting a mixture of a compound (2F) and a compound (3F) to thermal decomposition: (2F) (3F) (8) wherein RAF is a monovalent organic group stable to thermal decomposition.

Description

 Specification

 Technical field of producing fluorine-containing pinyl ether compounds>

 The present invention relates to a method for producing a fluorinated biether compound useful as a raw material monomer of a fluororesin. More specifically, the present invention relates to a method for efficiently producing a fluorine-containing vinyl ether compound in a short process and at a high yield. Background technology>

Conventionally, as a method of fluorinating all C--H portions in C--H-containing compounds such as hydrocarbon compounds to C--F, a method using cobalt trifluoride or a direct method using fluorine gas has been used. There is known a method of fluorination, or a method of performing a fluorination reaction by electrolyzing hydrogen fluoride in an electrolytic cell (hereinafter, referred to as a “p-method” (hereinafter, referred to as “6 to 1 ch0 chemicalfluorination”)). the _c are, in the case of a method of direct fluorination with fluorine gas, a method of performing in a manner and the liquid phase carried out in the gas phase are known.

 A method has also been reported in which fluorine gas is allowed to act on non-fluorinated compounds to fluorinate in the liquid phase (US Pat. No. 5,093,432). A method is also known in which a perfluorinated ester compound is subjected to a thermal decomposition reaction to obtain an acid fluoride compound, and the compound is prepared by converting a hydrocarbon ester compound having a corresponding structure into fluorine gas. (J. Am. Chem. Soc., 120, 7117 (1998)).

Perfluoro (alkyl vinyl ether) is useful as a raw material monomer for fluororesins with excellent heat and chemical resistance. The compound is perfluoro Perfluoro (2-alkoxyalkanoic acid) fluoride by dimerization of epoxides or by reacting perfluoroalkanoic acid fluoride with perfluoroepoxides in the presence of metal fluoride It is industrially manufactured by pyrolysis (US Pat. No. 3,291,843).

 However, the conventional method of producing perfluoro (alkyl vinyl ether) has a problem that it is difficult to control the dimerization reaction, the raw material is expensive, and it is economically disadvantageous.

 An object of the present invention is to solve the above problems and to provide a method capable of efficiently producing a fluorine-containing vinyl ether compound in a short process and in a high yield.

<Disclosure of Invention>

 The present inventors have found that a target fluorine-containing vinyl ether compound can be suitably produced by subjecting a mixture of specific raw material compounds to a pyrolysis reaction as it is. Further, they have found that the use of the mixture as a raw material is economically advantageous as an industrial process and can be an efficient continuous process. The present invention has been completed based on these findings.

That is, the present invention provides a method for producing the following fluorinated vinyl ether compound, and a novel compound useful as an intermediate in the production method. 1. A process for producing the following fluorine-containing vinyl ether compound (8), which comprises subjecting a mixture of the following compound (2F) and the following compound (3F) to a thermal decomposition reaction. However, in the formula, R ^AF represents a monovalent organic group which is not changed by the thermal decomposition reaction.

A ^F OCF (CF 3) COF (2 F) R ^AF 〇 (CF ₂ ) ₂ COF (3 F)

R ^AF OC F = CF ₂ (8)

2. In the following compound (6) or a mixture of the following compound (6) and the following compound (7), an ester bond is decomposed to give the following compound (2F) and the following compound (3F). A method for producing the following fluorinated vinyl ether compound (8), characterized in that a mixture is obtained and then subjected to a thermal decomposition reaction in the mixture _c, wherein R ^AF is a monovalent organic group which is not changed by the thermal decomposition reaction. Is shown.

R ^AF 0 (CF ₂ ) 3 OCOC F (CF ₃ ) OR ^AF (6)

R ^AF O (CF ₂ ) 3 OCOC F ₂ CF ₂ OR ^AF (7)

R ^AF OC F (CF ₃ ) COF (2 F)

A ^F 0 (CF ₂ ) ₂ COF (3 F)

 3. The compound (6) undergoes an esterification reaction between the following compound (1) and the following compound (2) to produce the following compound (4), and then the compound (4) is fluorinated in a liquid phase. A mixture of compound (6) and compound (7) reacts with a mixture of compound (1), compound (2), and compound (3) to form compound (3) A mixture of the compound (4) and the following compound (5) is produced, and the mixture of the compound (4) and the compound (5) is reacted with fluorine in a liquid phase to produce a reaction product. The manufacturing method as described.

However, in the formula, R ^A , R ^B , and R ^C are each independently the same monovalent organic group as R ^AF or a monovalent organic group that becomes R ^AF when reacted with fluorine in a liquid phase. And R ^AF are monovalent organic groups that are not changed by a thermal decomposition reaction, and X represents a halogen atom.

R ^A 0 (CH ₂ ) 3 OH (1)

XCOC F (CF ₃ ) OR ^B (2) XCO (CF ₂ ) 2 _? OR ^C (3)

R ^A O (CH ₂ ) 3 OCOC F (CF 3,) OR ¹³ (4)

R ^A O (CH ₂ ) 3 OCO (CF ₂ ) ₂ OR ^C (5)

 4. The production method according to claim 3, wherein the fluorine content in the compound (4) is 30% by mass or more, and the fluorine content in the compound (5) is 30% by mass or more.

5. The mixture of compound (6) and compound (7) undergoes esterification reaction of the following compound (1) with the mixture of compound (2F) and compound (3F) shown below to give compound (4) 3. The production method according to claim 2, wherein the reaction product is a reaction product obtained by producing a mixture of F) and the following compound (5F), and then reacting the mixture with fluorine in a liquid phase. However. Wherein, R ^A represents a 1 Ataiyu machine group consisting R ^AF by reacting with fluorine in R ^AF same 1 Ataiyu machine group or in the liquid phase,, R ^AF is changed by pyrolysis reaction Indicates a monovalent organic group.

R ^A 0 (CH ₂ ) 3 OH (1)

R ^AF OC F (CF 3) COF (2 F)

R ^AF O (CF ₂ ) ₂ COF (3 F)

R ^A O (CH ₂ ) 3 OCOC F (CF ₃ ) OR ^AF (4 F)

R ^A O (CH ₂ ) 3 OCOCF ₂ CF ₂ OR ^AF (5 F)

6. A mixture of the compound (2F) and the compound (3F) is a part or a part of a reaction product obtained by subjecting a mixture of the following compound (6) and the following compound (7) to an ester bond decomposition reaction. The production method according to claim 5, which is all. However, in the formula, R ^AF represents a monovalent organic group which is not changed by a thermal decomposition reaction.

R ^AF 0 (CF ₂ ) 3 OCOC F (CF ₃ ) OR ^AF (6)

R ^AF 0 (CF ₂ ) 3 OCOC F ₂ CF ₂ OR ^AF (7)

7. When reacting with fluorine in the liquid phase, at least one selected from compound (2F), compound (3F), compound (6), and compound (7) is used as the liquid phase. The production method according to claim 3, 4, 5, or 6, wherein a kind of compound is used.

8. R ^AF is a perfluoro (monovalent saturated hydrocarbon) group, a perfluoro (partially halogenated monovalent saturated hydrocarbon) group, a perfluoro (monovalent saturated hydrocarbon containing hetero atom) group, or a perfluoro (partially halogenated heteroatom) The production method according to any one of claims 1 to 7, which is an atom-containing monovalent saturated hydrocarbon) group.

 9. The following compound (la) is subjected to an esterification reaction with a mixture of the following compound (2a) and the following compound (3a) to obtain a mixture of the following compound (4a) and the following compound (5a), Next, the mixture of the compounds (4a) and (5a) is reacted with fluorine in a liquid phase to obtain the following compound (6a) and the following compound

The mixture of (7a) is obtained, and then the ester bond is decomposed in the mixture of the compounds (6a) and (7a) to give the compound (2a) and the compound (3a) Obtaining a mixture of the compound (2a) and the compound (3a) in an amount larger than that of the mixture of the compound (a), and then performing a thermal decomposition reaction of the mixture of the compound (2a) and the compound (3a). A process for producing the following compound (8a):

CH ₂ = CHCH ₂ OCH ₂ CH ₂ CH ₂ OH (1 a)

CF ₃ CF ₂ CF ₂ OCF (CF3) COF (2 a)

CF ₃ CF ₂ CF ₂ OCF ₂ CF ₂ COF (3 a)

CH ₂ = CHCH ₂ OCH ₂ CH ₂ CH ₂ OCOCF (CF ₃ ) OCF ₂ CF ₂ CF ₃ (4a)

CH ₂ = CHCH ₂ OCH ₂ CH ₂ CH ₂ OCOCF ₂ CF ₂ OCF ₂ CF ₂ CF ₃ (5a)

CF ₃ CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ OCOCF (CF ₃ ) OCF ₂ CF ₂ CF ₃ (6 a)

CF ₃ CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ OCOCF ₂ CF ₂ OCF ₂ CF ₂ CF ₃ (7a)

CF ₃ CF ₂ CF ₂ OCF = CF ₂ (8 a)

10. The following compound (7A). Here, n in the formula represents an integer of 1 to 10. F (CF ₂ ) _n O (CF ₂ ) 3 OCOCF ₂ CF ₂ O (CF ₂ ) _n F (7 A)

In the present invention, R ^AF represents a monovalent organic group that is not changed by a thermal decomposition reaction. In the present specification, the monovalent organic group refers to a monovalent group essentially having a carbon atom, and may be a saturated organic group or an unsaturated organic group.

The monovalent organic group (R ^AF ) which does not change by the thermal decomposition reaction in the present invention is a group which does not contain a functional group or atomic group which changes by the thermal decomposition in the group, and

A monovalent organic group whose chemical structure does not change before and after a thermal decomposition reaction in a mixture of (2F) and compound (3F). Examples of the monovalent organic group include groups having no partial structure such as COO CF ₂ C—CX ^a — (where ^a is a halogen atom), —CF 2 CF ₂ COF, and _CF (CF ₃ ) COF. And a group that does not have a structure that is chemically unstable under the reaction conditions of thermal decomposition. For example, a monovalent hydrocarbon group or a halogenated monovalent hydrocarbon group is a group that is not usually changed by a thermal decomposition reaction. Heteroatom-containing monovalent hydrocarbon group or halogenated

The (heteroatom-containing monovalent hydrocarbon) group is a group which usually does not change by thermal decomposition when the heteroatom or heteroatom in the group does not change by the thermal decomposition reaction.

The R ^AF in the present invention, the raw material availability ease, usefulness of the object compound, in terms of implementation ease of efficient continuous process to be described later, Perufuruoro (monovalent saturated hydrocarbon) group, Perufuruoro (partially halogenated Monovalent saturated hydrocarbon) group, perfluoro (heteroatom-containing monovalent saturated hydrocarbon) group, or perfluoro

(Partially halogenated heteroatom-containing monovalent saturated hydrocarbon) group, particularly perfluoro monovalent saturated hydrocarbon group, perfluoro (etheric oxygen atom) Preferred is a perfluoro (partial chroma monovalent saturated hydrocarbon) group, or a perfluoro (partial chroma (monovalent saturated hydrocarbon containing an etheric oxygen atom)) group.

 The hydrocarbon group in the present specification may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group. In addition, a single bond, a double bond, or a triple bond may be present as a carbon-carbon bond in the aliphatic hydrocarbon group. The aliphatic hydrocarbon group may have any of a linear structure, a branched structure, a ring structure, and a structure partially having a ring structure.

The saturated hydrocarbon group means a group in which a carbon-carbon bond in the group is composed of only a single bond. An unsaturated bond other than a carbon-carbon unsaturated bond (for example, C = o or so ₂ ) may be present in the group.

 As the monovalent saturated hydrocarbon group in the present specification, an alkyl group may be mentioned, and the structure may be any of a linear structure, a branched structure, a ring structure (that is, a cycloalkyl group), or a partially ring-shaped structure. It may be.

 The alkyl group preferably has 1 to 10 carbon atoms. Examples of the alkyl group having a linear structure include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the alkyl group having a branched structure include an isopropyl group, an isobutyl group, a sec-butyl group, a t-tert-butyl group, and the like. Examples of the alkyl group having a ring structure include a cycloalkyl group, a bicycloalkyl group, and a group having an alicyclic spiro structure, and a 3- to 6-membered cycloalkyl group is preferable, and a cyclopentyl group and a cycloalkyl group are preferred. Hexyl group and the like.

As the alkyl group having a ring portion, an alkyl group (having a linear or branched structure) substituted with the above-described alkyl group having a ring structure or a ring group portion of the alkyl group further having a (a linear structure or a branched structure) A group substituted with an alkyl group, a cycloalkyl group, or a group having an alicyclic spiro structure; A group in which one or more of the elemental atoms are substituted with a 3- to 6-membered cyclic alkyl group is preferable, and a cyclopentylmethyl group, a cyclohexylethyl group, an ethylcyclohexylmethyl group, and the like are particularly preferable. Examples of other groups include an alkyl group having an aromatic ring (eg, an aralkyl group such as a benzyl group and a phenethyl group), and an alkyl group having a heterocycle (eg, a pyridylmethyl group, a furfuryl group, and the like).

 The halogen atom in the halogenated group is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and is preferably a fluorine atom, a chlorine atom, or a bromine atom. Or a fluorine atom and a chlorine atom are preferred.

 In the present specification, “halogenation” means that one or more hydrogen atoms have been replaced with halogen atoms. The term "partially halogenated" means that a part of a hydrogen atom has been replaced with a halogen atom '. Perhalogenation means that all of the hydrogen atoms have been halogenated, and there are no hydrogen atoms in the group. The meanings of the terms halogenation, partial halogenation, and perhalogenation have the same meaning when a halogen atom is specified. The halogen atom present in the halogenated group and the perhalogenated group may be one kind or two or more kinds.

 In the present specification, a halogenated monovalent saturated hydrocarbon group refers to a group in which one or more hydrogen atoms present in a monovalent saturated hydrocarbon group are substituted with a halogen atom. A halogen atom may or may not be present in the halogenated monovalent saturated hydrocarbon group. The halogen atom in the halogenated monovalent saturated hydrocarbon group is preferably a fluorine atom, or a fluorine atom and a chlorine atom.

In the present specification, a partially halogenated monovalent saturated hydrocarbon group means that a part of the hydrogen atoms present in the above monovalent saturated hydrocarbon group is replaced by a halogen atom. Group. Partially halogenated monovalent saturated hydrocarbon groups contain hydrogen atoms.

 In the present specification, a perhalogenated monovalent saturated hydrocarbon group refers to a group in which substantially all of the hydrogen atoms present in the monovalent saturated hydrocarbon group have been replaced by halogen atoms. Belha genogenation There is no hydrogen atom in the monovalent saturated hydrocarbon group.

 In the present specification, the halogenated monovalent saturated hydrocarbon group may have a linear structure or a branched structure, a ring structure, or a structure having a ring structure portion. Examples of the halogenated monovalent saturated hydrocarbon group include a fluoroalkyl group and a fluoro (partial cycloalkyl) group. The carbon number of the halogenated monovalent saturated hydrocarbon group is preferably 1 to 20.

 In the present specification, the perhalogenated monovalent saturated hydrocarbon group includes a perfluoroalkyl group or a perfluoro (partial alkyl) group (that is, a group in which all hydrogen atoms in the partial alkyl group are fluorinated) Is preferred. The perfluoro (partially fluoroalkyl) group is the same as the perfluoroalkyl group.

In the present specification, the heteroatom-containing monovalent saturated hydrocarbon group refers to a saturated group consisting of a heteroatom such as an oxygen atom, a nitrogen atom or a sulfur atom, a carbon atom and a hydrogen atom. The heteroatom may be the heteroatom itself or a heteroatom formed by bonding heteroatoms to each other or a heteroatom and another atom. It is preferable that neither the hetero atom nor the heteroatom group be changed by the thermal decomposition reaction. Examples of the hetero atom include an etheric oxygen atom (C—O—C O), = 0, and the like, and an etheric oxygen atom is particularly preferred. The heteroatom-containing monovalent saturated hydrocarbon group preferably has 1 to 20 carbon atoms. Examples of the heteroatom-containing monovalent saturated hydrocarbon group include carbons of the aforementioned saturated hydrocarbon groups. A group in which a divalent heteroatom or a divalent heteroatom group is introduced between an element and a carbon atom, or a group in which a heteroatom is bonded to a carbon atom in the saturated hydrocarbon group, or A group in which a divalent heteroatom or a divalent heteroatom group is bonded to the carbon atom at the bond terminal is preferable.

 In the present specification, as the hetero atom-containing group, an etheric oxygen atom-containing group is particularly preferable from the viewpoint of the usefulness of the compound. In particular, an alkyl group containing an etheric oxygen atom (for example, an alkoxyalkyl group, etc.) is preferred from the viewpoints of availability, production, and usefulness of the product. Examples of the monovalent aliphatic hydrocarbon group having a ring portion in which an etheric oxygen atom is inserted between carbon-carbon atoms include an alkyl group having a dioxolane skeleton.

 In the present specification, the alkoxyalkyl group is preferably a group in which one of the hydrogen atoms present in the alkyl group mentioned in the above monovalent aliphatic hydrocarbon group has been substituted with an alkoxy group. The alkoxy group preferably has 1 to 10 carbon atoms. Examples of the alkoxyalkyl group include an ethoxymethyl group, an 11-propoxyl group, a 2-propoxyl group and the like.

In the present specification, the halogenated (hetero atom-containing monovalent saturated hydrocarbon) group may be a fluoro (hetero atom-containing monovalent saturated hydrocarbon) group or a fluoro (partial port (hetero atom-containing monovalent saturated hydrocarbon) group. )) Groups are preferred. The halogenated (heteroatom-containing monovalent saturated hydrocarbon) group preferably has 1 to 20 carbon atoms. In the present specification, the perhalogenated (heteroatom-containing monovalent saturated hydrocarbon) group may have a linear or branched structure, and may be a perfluoro (heteroatom-containing monovalent saturated hydrocarbon) group or A perfluoro (partial chroma (heteroatom-containing monovalent saturated hydrocarbon)) group is preferred, and a perfluoro (hetero atom-containing alkyl) group or perfluoro (partial chroma (hetero atom-containing alkyl) is preferred. Particularly preferred are the perfluoro (alkoxyl) and perfluoro (partial cyclo (alkoxyl)) groups.

Specific examples of these groups include the groups described in the following examples. In the present invention, a mixture of the compound (2F) and the compound (3F) is subjected to a thermal decomposition reaction to be converted to a fluorine-containing vinyl ether compound (8). Compound (2F) and compound (3F) are both converted to the same fluorine-containing vinyl ether compound (8) by a thermal decomposition reaction. That is, in this method, the compound (2F) and one target compound (8) having a structure corresponding to the compound (3F) are produced. R ^AF in the fluorine-containing vinyl ether compound (8) is the same as R ^AF in the compound (2 F) and Compound (3 F). Examples of the fluorine-containing vinyl ether compound (8) include the following compounds, and the compound (8a) is preferable.

CF 3 CF ₂ CF ₂ OCF = CF ₂ (8 a)

CF 3 OCF CF ₂ (8 b)

CF 3 CF ₂ OC F = CF ₂ (8 c)

CF ₃ (CF ₂ ) ₅ OCF = CF ₂ (8 d)

CF 3 (CF ₂ ) g OCF = CF ₂ (8 e)

 Examples of the compound (2F) include the following compounds, and the compound (2a) is preferable from the viewpoint of the usefulness of the target compound.

CF 3 CF ₂ CF ₂ OCF (CF ₃ ) COF (2 a)

CF ₃ OCF (CF ₃ ) COF (2 b)

CF ₃ CF ₂ OCF (CF ₃ ) COF (2 c)

CF 3 (CF ₂ ) ₅ OCF (CF 3) COF (2 d)

CF ₃ (CF ₂ ) ₉ OCF (CF ₃ ) COF (2 e)

Compound (3F) Examples include the following compounds. Compound (3a) is preferred.

CF 3 CF ₂ CF ₂ OCF ₂ CF ₂ CO F (3 a)

CF ₃ OCF ₂ CF ₂ C〇F (3 b)

CF ₃ CF ₂ OCF ₂ CF ₂ CO F (3 c)

CF ₃ (CF ₂ ) ₅ OCF ₂ CF ₂ COF (3 d)

CF 3 (CF,) ₉ OCF ₂ CF ₂ CO F (3 e)

 Further, in the mixture of the compound (2F) and the compound (3F) in the present invention (hereinafter, referred to as a mixture (2F-3F)), the compound (2F) and the compound (2F)

The quantitative ratio of each of (3F) is not particularly limited, and the production method of the present invention can be carried out with any quantitative ratio. When the production method of the present invention is carried out by a continuous method described below, at the start of the method, the compound (2F-3F) is added to the mixture (2F-3F).

Preferably, (2F) is 40 to 60% by mass and compound (3F) is 40 to 60% by mass. The ratio of each compound in the mixture (2F-3F) is not particularly limited. When the continuous production method described later is repeated, the content of the compound (2F) gradually decreases, and the compound (3F) Content gradually increases.

 The thermal decomposition reaction of the mixture (2F-3F) can be carried out by a gas phase reaction or a liquid phase reaction, and is preferably carried out by a gas phase reaction because it is efficient. The method and reaction temperature of the thermal decomposition reaction are preferably selected according to the boiling point and stability of the mixture (2F-3F). The mixture (2F-3F) preferably has a boiling point at normal pressure of 350 ° C. or lower so that a pyrolysis reaction can be performed in a gas phase reaction. Further, the boiling point of the mixture (2F-3F) is preferably 50 ° C or more. The gas phase reaction is preferably performed by a continuous reaction. In the continuous reaction, the vaporized mixture (2F-3F) is passed through a heated reaction tube, and the resulting fluorine-containing vinyl ether compound is formed.

(8) is obtained as an outlet gas, which is preferably condensed and continuously recovered. The reaction temperature when performing pyrolysis in the gas phase reaction depends on the compound Although it can be appropriately changed depending on the structures of (2F) and the compound (3F), it is generally preferably 150 ° C or higher, particularly preferably 200 to 500 ° C, and particularly preferably 250 ° (: to 450 ° C. If the reaction temperature is too high, the decomposition reaction of the product may occur and the yield may decrease, and if the reaction temperature is too low, each reaction of the compound (2F) and the compound (3F) may occur. Conversion rate may decrease.

 When a pyrolysis reaction is performed in a gas phase reaction, it is preferable to use a tubular reactor. When a tubular reactor is used, the residence time is preferably about 0.1 second to 10 minutes on an empty tower basis. The reaction pressure is not particularly limited. When the mixture (2F-3F) has a high boiling point, the reaction is preferably performed under reduced pressure. When the mixture (2F-3F) has a low boiling point, decomposition of the product is suppressed and the reaction rate is increased. Therefore, the reaction is preferably performed under pressure. If the mixture (2F-3F) has a high boiling point, thermal decomposition should be performed by liquid phase reaction.

When a gas phase reaction is carried out using a tubular reactor, it is preferable to fill the reaction tube with a glass, an alkali metal salt, or an alkaline earth metal salt in order to promote the reaction. As the alkali metal salt or the alkaline earth metal salt, a carbonate or a fluoride is preferable. Examples of the glass include common soda glass, and glass beads in which the fluidity is improved by forming beads are particularly preferable. Alkali metal salts include sodium carbonate, sodium fluoride, potassium carbonate, or lithium carbonate. Examples of the alkaline earth metal salt include calcium carbonate, calcium fluoride, barium carbonate, and magnesium carbonate. Furthermore, when the reaction tube is filled with a glass, an alkali metal salt, or an alkaline earth metal salt, the reaction tube is made of glass beads, light ash of sodium carbonate, or the like, and has a particle size of about 100 to 250 m. If you use It is particularly preferable because a fluidized bed type reaction system can be adopted.

 In the gas phase reaction, it is preferable to use an inert gas which is not directly involved in the thermal decomposition reaction in order to promote the vaporization of the mixture (2F-3F). Gas, carbon dioxide gas, helium gas, argon gas and the like. The amount of the inert gas is preferably about 0.01 to 50% by volume based on the mixture (2F-3F). If the amount of the inert gas is too large, the amount of the recovered product may decrease, which is not preferable.

 In the production method of the present invention, the product of the thermal decomposition reaction is substantially only the fluorine-containing vinyl ether compound (8). The product is preferably separated and purified by a usual method according to the purpose. Examples of the separation and purification method include a distillation method and silica gel column chromatography. In addition, the fluorine-containing vinyl ether compound (8) has a lower molecular weight than the compound (2F) and the compound (3F), and usually has a lower boiling point. Therefore, the unreacted compound (2F) And the mixture of compound (3F) is preferably removed efficiently by distillation.

 The method for obtaining the mixture (2F-3F) is not particularly limited, but in the present invention, the compound (6) or a mixture of the compounds (6) and (7) is subjected to the ester bond decomposition reaction. Preferably, the reaction product obtained by the reaction is In the decomposition reaction of the ester bond of the compound (6), the compound (2F) is stoichiometrically twice as much as the compound (6). In addition, in the decomposition reaction of the ester bond of compound (7), stoichiometrically equimolar amount of compound (2F) and compound (3F) are stoichiometrically equimolar to compound (7). ) Is generated.

 Examples of the compound (6) include the following compounds, and the compound (6a) is preferable.

CF ₃ CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ OCOC F (CF ₃ ) OCF ₂ CF ₂ CF ₃ (6 a), _{CF 3 OC F 2 CF 2 CF} 2 OCOCF (CF 3) OCF 3 (6 b), CF 3 CF 2 OC F 2 CF 2 CF 2 OCOCF (CF 3) OCF 2 CF 3 (6 c),

CF ₃ (CF ₂ ) ₅ OC F ₂ CF ₂ CF ₂ OCOCF (CF ₃ ) O (CF ₂ ) 5 CF ₃ (6 d),

_{CF 3 (CF 2) 9 OCF} 2 CF 2 CF 2 OCOCF (CF 3) O (CF 2) 9 CF 3 (6 e).

 Further, examples of the compound (7) include the following compounds. Among the compounds (7), the following compound (7A) is a novel compound. The following compound (7A) is a useful compound that can be converted to perfluoro (alkyl vinyl ether), which is useful as a raw material monomer of a fluororesin, by a process described below. As the compound (7A), the compound (7a) is preferable. Here, in the formula, n represents an integer of 1 to L 0.

F (CF ₂ ) _n O (CF ₂ ) 3 〇COCF ₂ CF ₂ O (CF ₂ ) _n F (7 A),

CF 3 CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ OCOC F ₂ CF ₂ OC F ₂ CF ₂ CF ₃ (7a),

CF ₃ OC F ₂ CF ₂ CF ₂ OCOCF ₂ CF ₂ OC F ₃ (7 b)

CF ₃ CF ₂ OCF ₂ CF ₂ CF ₂ OCOCF ₂ CF ₂ OC F ₂ CF ₃ (7 c),

CF ₃ (CF ₂ ) ₅ 〇CF ₂ CF ₂ CF ₂ OCOCF, CF ₂ O (CF ₂ ) 5 CF ₃ (7 d),

CF a (CF ₂ ) ₉ OC F ₂ CF ₂ CF ₂ OCOCF ₂ CF ₂ O (CF 2) 9 CF ₃ (7 e),

When compound (6) or mixture (6-7) is subjected to ester bond decomposition reaction In this case, the reaction is preferably carried out by a thermal decomposition reaction or a decomposition reaction carried out in the liquid phase in the presence of a nucleophile or an electrophile.

 When the decomposition reaction of the ester bond is performed by a thermal decomposition reaction, it can be carried out by heating the compound (6) or the mixture (6-7). The reaction type of the thermal decomposition reaction is preferably selected depending on the boiling point of the compound (6) or the mixture (6-7) and its stability. For example, when a mixture (6-7) that is easily vaporized is subjected to an ester pyrolysis reaction, it is continuously decomposed in the gas phase to condense the outlet gas containing the resulting mixture (2F-3F). A vapor phase pyrolysis method for recovery may be employed. The reaction temperature of the gas phase pyrolysis method is preferably from 50 to 350 ° C, particularly preferably from 50 to 300 ° C, particularly preferably from 150 to 250 ° C. In addition, an inert gas that is not directly involved in the reaction may coexist in the reaction system. Examples of the inert gas include nitrogen gas and carbon dioxide gas. It is preferable to add about 0.01 to 50% by volume of the inert gas to the compound (6) or the mixture (6-7). Large amounts of inert gas may reduce the amount of product recovered.

 On the other hand, when the boiling point of the compound (6) or the mixture (6-7) is high, the thermal decomposition reaction of the ester bond is preferably performed by a liquid phase pyrolysis method in which the mixture is heated in a liquid state in a reactor. The reaction pressure in this case is not limited. Usually, the product containing the mixture (2F-3F) has a lower boiling point, so that the liquid phase pyrolysis reaction is carried out while performing distillation in a reactor having a distillation column, and the product It is preferable to carry out a method of vaporizing and continuously extracting. Further, after performing the thermal decomposition reaction without performing distillation, the product may be collectively extracted from the product. The reaction temperature of this liquid phase pyrolysis method is preferably from 50 to 300 ° C, more preferably from 100 to 250 ° C.

When performing the ester bond decomposition reaction by the liquid phase pyrolysis method, perform the reaction without solvent. May be carried out in the presence of a solvent. The solvent is one that does not react with both compound (6) and compound (7) and is compatible with these compounds, and does not react with compound (2F) and compound (3F) that are formed. There is no particular limitation. As the solvent, it is preferable to select a solvent that can be easily separated during purification of the mixture of the compound (2F) and the compound (3F). Specific examples of the solvent include an inert solvent such as perfluorotrialkylamine and perfluorodylamine, a chlorotrifluoroethylene oligomer having a high boiling point among black fluorocarbons (eg, trade name: CFC), Compound (2F), compound (3F) and the like are preferred. Also, the amount of solvent

10 to 10% with respect to (6-7); L 000% by mass is preferred.

When the compound (6) or the mixture (6-7) is reacted with a nucleophile or an electrophile in a liquid phase to decompose an ester bond, the reaction may be performed without a solvent. Alternatively, the reaction may be performed in the presence of a solvent. This solvent is preferably the same as the solvent used in the above-mentioned liquid phase pyrolysis method. As the nucleophile, F_ is preferable, and F— derived from an alkali metal fluoride is particularly preferable. As the alkali metal fluoride, NaF, NaHF ₂ , KF and CsF are preferred, and NaF is particularly preferred from the viewpoint of economy. The amount of the nucleophile such as F_ is preferably 1 to 500 mol%, particularly preferably 10 to 100 mol%, particularly preferably 5 to 50 mol%, based on the compound (6) or the mixture (6-7). % Is preferred. The lower limit of the reaction temperature is preferably -30 ° C or higher, and the upper limit is the boiling point of the solvent and the compound.

The lowest temperature of the boiling point of (6) and the boiling point of compound (7) is preferred, and particularly preferred is −20 ° C. to 10250.

Even in the case of performing the ester bond decomposition reaction by the liquid phase method, it is preferable that the reaction is performed while performing distillation using a reactor having a distillation column, and the product is vaporized and continuously taken out. Compound (6) can be obtained by subjecting compound (1) to an esterification reaction with compound (2) to give compound (4), and then reacting compound (4) in a liquid phase. Is preferred. Also, a mixture of compound (6) and compound (7)

(Hereinafter, referred to as a mixture (6-7).) Is an esterification reaction of the compound (1) with a mixture of the compound (2) and the compound (3) (hereinafter, referred to as a mixture (2-3)). To form a mixture of the compound (4) and the compound (5) (hereinafter, referred to as a mixture (415)), and then reacting the mixture (415) with fluorine in a liquid phase. Available from When the mixture (2-3) is used, the compound

The quantitative ratio of (2) to compound (3) is not particularly limited.

The compound (1) in the method is a compound that can be obtained at a lower cost than R ^A OCH ₂ CH (CH ₃ ) OH [hereinafter, referred to as compound (1 ′)]. Therefore, a mixture (2F-3F) is obtained by esterifying the compound (1) using an inexpensive compound (1), fluorinating it, and decomposing the ester bond, and subjecting the mixture to thermal decomposition. To obtain a single useful fluorine-containing vinyl ether compound (8). The method of the present invention is an efficient and excellent method as an industrial production method. Whether the compound to be used for the esterification reaction with compound (1) is compound (2) or a mixture (2F-3F) is determined in consideration of the availability and economics. The effect of the present invention can be exerted by using any of them.

 Alternatively, the mixture (6-7) may be obtained by a fluorination reaction of the mixture (4F-5F) described below. The method using a mixture (4F-5F) is an advantageous method when it is carried out as a continuous production method.

The concept of the production process of the present invention, including the route of obtaining the mixture (2F-3F) and the continuous production method described below, is shown below. However, the compounds in [] are compounds that are formed when the mixture (2-3) is used, and are not formed when the compound (2) is used.

R ^AF OCF = CF ₂ (8)

Here, R ^A , R ^B, or R ^c are each independently the same group as R ^AF , or a monovalent group that becomes R ^AF by reacting with fluorine in a liquid phase <X is a halogen atom It is. R ^A is a group having a carbon skeleton corresponding to R ^AF , and it is preferable that one or more, and preferably all, of the fluorine atoms in R ^AF are monovalent groups substituted with hydrogen atoms. Further, R ^B and R ^c are preferably the same groups as R ^AF .

Preferably, R ^A , R ^B , and R ^c are each independently a monovalent saturated hydrocarbon group, a halogenated monovalent saturated hydrocarbon group, or a heteroatom-containing monovalent saturated hydrocarbon group. In addition, one or more carbon-carbon single bonds in these groups may be an unsaturated group in which a carbon-carbon unsaturated bond such as a double bond or a triple bond is formed. Examples of the unsaturated group include a monovalent unsaturated hydrocarbon group, a halogenated monovalent unsaturated hydrocarbon group, and a heteroatom-containing monovalent unsaturated hydrocarbon group. Specific examples of the unsaturated group include an alkenyl group, a cycloalkenyl group, a partially alkenyl group, a partially chloroalkenyloxyalkyl group and the like. The unsaturated group can be converted to a carbon-carbon single bond by adding fluorine to the carbon-carbon double bond by fluorination in a liquid phase. When a carbon-carbon double bond is present in an organic group, fluorine is added to the carbon-carbon triple bond by fluorination in a liquid phase to form a carbon-carbon single bond or a carbon-carbon single bond. A carbon double bond is formed.

 Examples of the compound (1) include the following compounds, and the compound (la) is preferable. Compound (1) is a compound that is easily and inexpensively available or can be easily and inexpensively synthesized by a known method.

CH ₂ = CHCH ₂ OCH ₂ CH ₂ CH ₂ OH (1a),

CH ₃ OCH ₂ CH ₂ CH ₂ OH (lb),

CH CH OCH ₂ CH ₂ CH ₂ OH (1 c), CH ₃ (CH ₂ ) ₅ OCH ₂ CH ₂ CH ₂ OH (1 d), CH ₃ (CH ₂ ) ₉ OCH ₂ CH ₂ CH ₂ OH (1 e).

 Examples of the compound (2) include the same compound as the compound (2F), a compound in which one COF in the compound (2F) has become -COC1, and C-F in the compound (2F) has C- The compound having become H is mentioned, and the following compound (2a) is preferable.

FCOCF (CF ₃ ) OCF ₂ CF ₂ CF ₃ (2 a) ₀

 Examples of the compound (3) include the same compound as the compound (3F), the compound in which the COF is changed to COC 1 in the compound (3F), and the C-1 in the compound (3F).

Compounds in which F is C-H are mentioned, and the following compound (3a) is preferable.

FCOCF ₂ CF ₂ OCF ₂ CF ₂ CF ₃ (3a).

 Examples of the compound (4) include the following compounds, and the compound (4a) is preferable.

CH ₂ = CHCH ₂ OCH ₂ CH ₂ CH ₂ OCOCF (CF ₃ ) 〇CF ₂ CF ₂ CF ₃ (4 a),

CH ₃ OCH ₂ CH ₂ CH ₂ OCOCF (CF ₃ ) OCF ₃ (4 b), CH ₃ CH ₂ OCH ₂ CH ₂ CH ₂ OCOCF (CF ₃ ) OCF ₂ CF ₃ (4 c),

CH ₃ (CH ₂ ) ₅ OCH ₂ CH ₂ CH ₂ OCOCF (CF ₃ ) 〇 (CF 2) 5 CF ₃ (4 d),

CH ₃ (CH ₂ ) ₉ OCH ₂ CH ₂ CH ₂ OCOCF (CF ₃ ) O (CF ₂ ) ₉ CF ₃ (4 e),

 Examples of the compound (5) include the following compounds, and the compound (5a) is preferable.

CH ₂ = CHCH ₂ O CH ₂ CH ₂ CH ₂ OCOC F ₂ CF ₂ OCF ₂ CF ₂ CF ₃ (5 a), CH ₃ OCH ₂ CH ₂ CH ₂ OCOCF ₂ CF ₂ OC F ₃ (5 b), CH ₃ CH ₂ OCH ₂ CH ₂ CH ₂ OCOC F ₂ CF ₂ OC F ₂ CF ₃ (5 c),

CH ₃ (CH ₂ ) ₅ O CH ₂ CH ₂ CH ₂ 〇COCF ₂ CF ₂ O (CF

2) 5 CF ₃ (5 d),

CH ₃ (CI-I ₂ ) ₉ OCH ₂ CH ₂ CH ₂ OCOCF ₂ CF ₂ O (CF ₂ ) ₉ CF ₃ (5 e),

 The esterification reaction between the compound (1) and the compound (2) or the mixture (2-3) can be carried out by applying a known esterification reaction method and conditions. The esterification reaction may be carried out in the presence of a solvent, but is preferably carried out in the absence of a solvent from the viewpoint of volumetric efficiency. When a solvent is used, dichloromethane, chloroform, triethylamine, or a mixed solvent of triethylamine and tetrahydrofuran is preferable. The amount of solvent used depends on the compound

 The content is preferably 50 to 500% by mass based on the total amount of (1), compound (2) and compound (3).

 Since an acid such as HF is generated in this esterification reaction, an alkali metal fluoride (preferably NaF or KF) or a trialkylamine as an HF scavenger may be present in the reaction system. HF scavenger is compound (1), compound

If (2) and (3) are both acid-labile compounds, they should be used. When no HF scavenger is used, it is preferable to discharge HF out of the reaction system by accompanying HF with a nitrogen stream. When the alkali metal fluoride is used, the amount is preferably 1 to 10 times the molar amount of the mixture (2-3).

In addition, the reaction temperature of the esterification reaction of the compound (1) is usually preferably −50 ° C. or higher, and + 100 ° C. or lower or the boiling point of the solvent or lower. preferable. Further, the reaction time of the reaction can be appropriately changed according to the supply rate of the raw materials and the amount of the compound used in the reaction. The reaction pressure (gauge pressure, hereinafter the same) is preferably from 0 (atmospheric pressure) to 2 MPa.

 The reaction crude product containing the compound (4) or the mixture (4-1-5) produced in the above reaction may be purified according to the purpose or used as it is in the next reaction, etc. From the viewpoint of safely performing the fluorination reaction in the above, it is desirable that compound (4) and compound (5) in the crude product be separated and purified from other compounds. The crude product can be purified by distilling the crude product as it is, by treating the crude product with dilute alkaline water or the like, and separating the crude product, extracting the crude product with an appropriate organic solvent, and then distilling the crude product. And silica gel column chromatography.

Next, the compound (4) or the mixture (4-15) is reacted with fluorine in a liquid phase to form a mixture (6-7). This reaction can be carried out by an ECF method or a cobalt fluorination method, but in the present invention, the reaction is carried out by a liquid phase fluorination method of reacting with fluorine (F ₂ ) in a liquid phase.

 That is, when the fluorination is performed by the cobalt fluorination method or the ECF method, the compound (4) or the compound (5) isomerized, the compound (4) or the compound

The cleavage reaction of the carbon-carbon bond and the carbon-oxygen bond in (5) and the recombination reaction of these broken bonds occur, and the yield of the target mixture (6-7) is reduced. It may decrease. In addition, in the case of performing fluorination by a gas-phase fluorination reaction, it is difficult to control the reaction, and a cleavage reaction of carbon-carbon bond in compound (4) or compound (5) occurs. The yield of the mixture (6-7) may be reduced. On the other hand, according to the liquid phase fluorination method, the mixture (6-7) can be obtained in good yield while preventing undesired reactions. When using liquid phase fluorination, compound (4) or mixture (4-5) A method in which fluorine gas is introduced into the liquid phase to cause a reaction is preferable. The fluorine gas may be used as it is or may be a fluorine gas diluted with an inert gas. As the inert gas, nitrogen gas and helium gas are preferable, and nitrogen gas is particularly preferable for economic reasons. The amount of fluorine gas in the inert gas is not particularly limited, and is preferably at least 10% from the viewpoint of efficiency, and particularly preferably at least 20%.

 As the liquid phase in the liquid phase fluorination method, a solvent which is inert to the fluorination reaction and contains no H bond and indispensably has a C—F bond is preferable. In addition, perfluoroalkanes and known organic solvents are Organic solvents are preferred. Further, as this solvent, a solvent having high solubility for the compound (4) and the compound (5) is preferably used, and particularly a solvent capable of dissolving the compound (4) and the compound (5) in an amount of 1% by mass or more, respectively. It is particularly preferable to use a solvent that can dissolve 5% by mass or more.

The liquid phase preferably dissolves the fluorine and dissolves the mixture (2-3). Therefore, the compound (4) is used to improve the solubility of the mixture (2-3) in the liquid phase. The content of fluorine in the compound (5) and the content of fluorine in the compound (5) are each preferably at least 30% by mass, more preferably 30 to 76% by mass. Examples of solvents used for the liquid phase fluorination method include perfluoroalkanes (FC-72, etc.), perfluoroethers (FC-75, FC-77, etc.), perfluoropolyethers (Product names: Krytox, Fomblin, Galden, Demnum, etc.), Fluorocarbons (Black), Fluoropolyethers, Fluoroalkyl ethers (for example, Perfluoroalkyl) Killamine, etc.), inert fluids (trade name: Florinert) and the like. Of these, perfluorolotrialkylamine is preferred. The liquid phase may be a compound (2F), a compound (3F), a compound (6), or a compound (7) that is involved in the reaction of the present invention and has a function as a solvent. When at least one of the above is used, there is an advantage that post-treatment after the reaction is facilitated.

 The amount of the liquid phase for performing the fluorination by the liquid phase fluorination method is preferably at least 5 times, more preferably 10 to 100 times the mass of the total amount of the compound (4) and the compound (5). Is preferred.

 The reaction type of the liquid phase fluorination reaction may be either a patch system or a continuous system. The reaction is preferably performed by the following fluorination method 1 or fluorination method 2, and particularly preferably by the following fluorination method 2 from the viewpoint of reaction yield and selectivity. The fluorine gas may be diluted with an inert gas such as nitrogen gas, regardless of whether the method is performed in a batch mode or in a continuous mode.

 [Fluorination method 1] Compound (4) or mixture (4-1-5) and a solvent are charged into a reactor, and stirring is started. A method of reacting while continuously supplying fluorine gas at a predetermined reaction temperature and reaction pressure.

 [Fluorination method 2] A solvent is charged into a reactor, and stirring is started. A method of continuously and simultaneously supplying a solvent, fluorine gas, and a compound (4) or a mixture (415) at a predetermined reaction temperature and reaction pressure at a predetermined molar ratio.

In the fluorination method 2, when the compound (4) or the mixture (4-1-5) is supplied, the mixture (4-15) diluted with a solvent is used because the selectivity is improved and the amount of by-products is suppressed. May be supplied. In the fluorination method 2, when diluting the mixture (4-1-5) with a solvent, the amount of the solvent relative to the mixture is preferably at least 5 times, more preferably at least 10 times the mass. Is preferred. In the liquid phase fluorination reaction, it is continuous even when the reaction is carried out in batch mode. Even when the reaction is carried out by the method, it is preferable to carry out the reaction in a state where fluorine is present so that the amount of fluorine is always excessively equivalent to the total number of hydrogen atoms of compound (4) and compound (5). In particular, the presence of fluorine gas is preferably 1.5 times equivalent or more (that is, 1.5 times or more) from the viewpoint of selectivity _(the amount of fluorine gas varies from the start to the end of the reaction). It is preferable to always maintain the excess amount.

 The reaction temperature of the liquid phase fluorination reaction is usually not lower than 160 ° C and not higher than the boiling point of the mixture of the compound (4) and the compound (5) or not higher than the boiling point of the compound (4). The reaction pressure of the fluorination reaction is particularly preferably from 150 ° C to 110 ° C, particularly preferably from 120 ° C to 150 ° C, from the viewpoints of selectivity and ease of industrial implementation. In particular, 0 to 2 MPa is particularly preferable from the viewpoints of reaction yield, selectivity, and industrial easiness.

 Further, in order to efficiently advance the liquid phase fluorination method, it is preferable to add a C—H bond-containing compound to the reaction system or to perform ultraviolet irradiation. Thereby, the compound (4) and the compound (5) existing in the reaction system can be efficiently fluorinated, and the reaction rate can be drastically improved. The ultraviolet irradiation time is preferably from 0.1 to 3 hours.

The C—H bond-containing compound is an organic compound other than the compound (4) and the compound (5), particularly preferably an aromatic hydrocarbon, particularly preferably benzene, toluene and the like. The amount of the C—H bond-containing compound to be added is preferably 0.1 to 10 mol%, particularly 0.1 to 5 mol%, based on the total number of hydrogen atoms of compound (4) and compound (5). Preferably it is mol%. The C-H bond-containing compound is preferably added in a state where fluorine gas is present in the reaction system. Further, when a C—H bond-containing compound is added, it is preferable to pressurize the reaction system. The pressure at the time of pressurization is preferably 0.01 to 5 MPa. In the fluorination reaction, when a reaction occurs in which a hydrogen atom is replaced with a fluorine atom, HF is by-produced. In order to remove by-product HF, it is preferable that an HF scavenger coexist in the reaction system or that the HF scavenger and the outlet gas be brought into contact at the reactor gas outlet. As the HF scavenger, the same HF scavenger as that used in the reaction between the compound (1) and the mixture (2-3) is used, and NaF is preferred.

 When the HF scavenger is present in the reaction system, the amount is preferably 1 to 20 times, and more preferably 1 to 5 times the total amount of all hydrogen atoms present in compound (4) and compound (5). Is preferred. When placing an HF scavenger at the reactor gas outlet: (a) cooler (preferably maintained at 10 ° C to room temperature (25 ° C), particularly preferably at about 20 ° C (B) packed bed of NaF pellets, and (c) cooler (preferably maintained at −78 ° C. to + 10 ° C., particularly preferably maintained at 130 ° C. to 0 ° C.) (Preferably) are preferably arranged in the order of (a)-(b)-(c). (C) A liquid return line for returning the aggregated liquid from the cooler to the reactor may be provided.

 By the fluorination reaction, compound (4) is fluorinated to compound (6), and compound (5) is fluorinated to compound (7). The crude product containing the compound (6) or the mixture (6-7) obtained by the fluorination reaction may be used as it is in the subsequent ester bond decomposition step, or may be purified to a high purity. No. Examples of the purification method include a method of distilling the crude product as it is under normal pressure or reduced pressure. The compound (6) or the mixture (6-7) can form a mixture (2F-3F) by a decomposition reaction of an ester bond.

In addition, the mixture (6-7) is also obtained by a decomposition reaction of an ester bond of a mixture of the compound (2F) and the compound (3F) (hereinafter, referred to as a mixture (2F-3F)). Available. That is, the mixture (6-7) is obtained by mixing the compound (1) with the mixture (2 F-3F) to give a corresponding mixture (4F-5F), which is then obtained by reacting the mixture (4F-5F) with fluorine in the liquid phase. In this method, the esterification reaction of the compound (1) with the mixture (2F-3F) and the fluorination reaction of the mixture (4F-5F) obtained in the reaction in the liquid phase are as described above. This can be done in the same way as the method.

 Here, specific examples of the compound (4F) include the compounds described in the examples of the compound (4), and specific examples of the compound (5F) include the compounds described in the examples of the compound (5). Is mentioned. The method for obtaining the mixture (2F-3F) is not particularly limited. In the present invention, the mixture (2F-3F) is obtained by a decomposition reaction of the ester bond of the compound (6) or the mixture (6-7). It is preferred to use part of the mixture (2F-3F). The method of circulating a part of the mixture (2F-3F) for the esterification reaction with the compound (1) is only possible by supplying the compound (1) from the outside of the reaction system. It can be a continuous process to produce vinyl ether compound (8).

The continuous process is as follows. That is, using the compound (1) as a starting material, an esterification reaction is carried out with the compound (2) or the mixture (2-3) to obtain a compound (4) or a mixture (4-1-5). 4) Alternatively, the compound (6) or the mixture (6-7) is obtained by performing a fluorination reaction of the mixture (4-1-5), and then the ester of the compound (6) or the mixture (6-7) is obtained. Break the bonds to get the first mixture (2F-3F). In the first mixture (2F-3F), the compound (1) is then esterified to obtain a mixture (4F-5F), and the mixture (4F-5F) is fluorinated. To obtain a mixture (6-7), and then to carry out a decomposition reaction of the ester bond of the mixture (6-7) to thereby obtain a larger amount of the mixture (2F- 3F) than the initial mixture (2F-3F). 3 F) is obtained. Pyrolysis reaction of this mixture (2F-3F) However, by repeating the process of reacting with the compound (1) again, a larger amount of the mixture (2F-3F) can be obtained continuously. The method of this uses a simple and inexpensive compound obtained (1), and by reducing the inter-hand product separation, the fluorine-containing bi vinyl ether compound having R ^AF group corresponding to R ^A of the compound (1) (8) is an extremely efficient process. Compound (1) is commercially available or can be easily synthesized from commercially available compounds having various structures, and can be easily obtained.

 Since the fluorine-containing vinyl ether compound (8), which is the target compound of the method of the present invention, has a polymerizable vinyl fluoride group, the fluorine-containing vinyl ether compound

A useful fluorine-containing polymer can be produced by polymerizing one or more kinds of (8), or a polymerizable monomer capable of polymerizing with the fluorine-containing vinyl ether compound (8) and the fluorine-containing pinyl ether compound (8). .

The polymerizable monomer capable of polymerizing with the fluorinated vinyl ether compound (8) is not particularly limited, and may be selected from known polymerizable monomers. Known polymerization techniques can be applied as they are to the polymerization reaction. For example, fluoroethylenes such as CF ₂ = CF ₂ , CF ₂ = CFC 1, CF ₂ = CH ₂ , fluoropropylenes such as CF ₂ = CF CF ₃ , CF ₃ CF ₂ CF ₂ CF ₂ CH-CH ₂ and _{CF 3 CF 2 CF 2 CF 2} CF = CH 2 , etc. pel full O of Russia alkyl group carbon number is 4-12 (per full O b alkyl) ethylenes, include ethylene, propylene Ren, Orefin such as Isobuchiren is Can be

The fluoropolymer obtained by the polymerization reaction is useful as a fluororesin. Fluororesin is used in a wide range of fields because of its excellent properties of heat resistance and chemical resistance. Examples> Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. In the following, gas chromatography is referred to as GC, and gas chromatography mass spectrometry is referred to as GC-MS. The purity determined from the peak area ratio of GC is referred to as GC purity, the yield is referred to as GC yield, and the yield determined from the peak area ratio of the NMR spectrum is referred to as NMR yield. Also referred to tetramethyl Sila down TMS, and CC 1 ₂ FCC 1 F ₂ the R- 1 1 3. Further, the NMR spectrum is shown as an apparent chemical shift range. Reference value of ^{1 3} reference material CDC 1 ₃ of definitive to C one NMR was set to 76. 9 p pm. C ₆ F ₆ was used as an internal standard for quantification by ¹⁹ F—N MR.

[Example 1] CH ₂ = CHCH ₂ OCH ₂ CH ₂ CH ₂ OCOCF (CF ₃ ) OCF ₂ CF ₂ CF ₃ Production Example

CH ₂ = CHCH ₂ OCH ₂ CH ₂ CH ₂ OH (13.9 g) and triethylamine (25.4 g) having a GC purity of 99% were put in a flask, and the mixture was stirred in an ice bath. FCOCF (CF ₃ ) OCF ₂ CF ₂ CF ₃ (41.7 g) was added dropwise over 2 hours while maintaining the internal temperature at 1 or less. After completion of the dropwise addition, the mixture was brought to room temperature, stirred for 1 hour, and added to 50 mL of ice water.

The obtained crude liquid was separated, and the lower layer was washed twice with 5 OmL of water, dried over magnesium sulfate, and then filtered to obtain a crude liquid. CH ₂ = CHCH ₂ 〇CH _¾ CH ₂ CH ₂ OCOCF (CF ₃ ) OCF ₂ CF ₂ CF ₃ (30.3 g) was obtained as a fraction of 89 to 90 ^ / 1.2 kPa by vacuum distillation . GC purity was 99%. The NMR spectrum data was as follows.

^{1 H-NMR (300. 4MH z} , solvent: CDC 1 _3, reference: TMS) δ (p pm) :. 1. 95~2 03 (m, 2 H), 3. 48 (t, J = 6. 0 Hz, 2H), 3.94 (dt, J = 1.5, 6.0 Hz, 2H), 4.4 2 to 4.5 5 (m, 2H), 5.16 (d, J = 1 0.5 Hz, 1 H), 5

24 (d, J = 17.1 Hz, 1 H), 5.80 to 5.93 (m, 1 H).

^{1 9 F-NMR (2 8} 2. 7MHz, solvent · · CDC 1 _3, reference · · CFC 1

3) δ (p pm):-79.9 (IF), 1 81.3 (3 F), 1 82.2 (3 F),-86.6 (IF),-1 29. 5 (2 F), 1 1 3 1.5 (1

F).

[Example 2] Production example of CF 3 CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ OCOCF (CF ₃ ) OCF ₂ CF ₂ CF ₃

 R-113 (312 g) was added to 50 OmL of a nickel autoclave, stirred, and kept at 25 ° C. At the autoclave gas outlet, a cooler kept at 20 ° C, a packed bed of NaF pellets, and a cooler kept at 110 ° C were installed in series. In addition, a liquid return line for returning the aggregated liquid from the cooler held at 110 to the autoclave was installed. After blowing nitrogen gas for 1.0 hour, fluorine gas diluted to 20% with nitrogen gas was blown at a flow rate of 6.47 LX h for 1 hour.

Next, while blowing the fluorine gas at the same flow rate, the CH ₂ = CH CH ₂ OCH ₂ CH ₂ CH ₂ OCOCF (CF ₃ ) OCF ₂ CF ₂ CF ₃ (4.99) obtained in Example 1 was −1 1 The solution dissolved in 3 (100 g) was injected over 8.0 hours.

Next, while injecting fluorine gas at the same flow rate, 9 mL of R-113 solution with a benzene concentration of 0.01 gZmL was injected while heating from 25 ° C to 40 ° C, and autoclaving. The benzene inlet of the autoclave was closed, the outlet valve of the autoclave was closed, and when the pressure reached 0.20 MPa, the fluorine gas inlet valve of the autoclave was closed, and stirring was continued for 0.6 hours. Then press the pressure While maintaining the reactor pressure at normal pressure and maintaining the temperature inside the reactor at 40 ° C, inject 6 mL of the above benzene solution, close the autoclave benzene inlet, close the autoclave outlet valve, and reduce the pressure to 0.2 OMP. At the point a, the fluorine gas inlet valve of the autoclave was closed, and stirring was continued for 0.8 hours. Further, the same operation was repeated once.

The total amount of benzene injected was 0.219 g, and the total amount of R-113 injected was 2 lmL. In addition, nitrogen gas was blown for 1.5 hours. The yield of the standard compound was 85.8% when the target compound was quantified with ¹⁹ F-NMR. The NMR spectrum data was as follows.

^{1 9 F-NMR (37 6.} 0MHz, solvent: CDC 1 _3, reference: CF C 1 3) δ ( p pm): - 7 9. 9 (IF), - 82. 1 (6 F), one 82 . 3

(3 F), — 83.9 (2 F), 1 84.7 (2 F), 1 86.9 (IF),-87.4 (2 F),-1 29.6 (2 F), -1 30.2 (2 F), 1 13.5 (2 F),-1 32.2 (1 F).

[Example 3] Production example of CF ₃ CF ₂ CF ₂ OCF ₂ CF ₂ COF

Charge CF ₃ CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ OCOCF (CF 3) OCF ₂ CF ₂ CF ₃ (8 g) obtained in Example 2 together with NaF powder (0.1 lg) in a flask, and vigorously stir. While heating in the oil pass at 120 for 10 hours. At the top of the flask, a reflux condenser adjusted to 20 ° C was installed. After cooling, a liquid sample (7 g) was collected. GC-MS confirmed that CF ₃ CF (OCF 2 CF ₂ CF ₃ ) COF and the title compound were the major products and were a 1: 1 mixture. The NMR spectrum data of the title compound were as follows.

¹⁹ F-NMR (376.0 MHz, solvent: CDC 1, standard: CFC 1 3) δ (p pm) 24.4 (IF), 1 81.9 (3 F), 1 84.7 (2 F),-859 (2 F),-1 2 1.7 (2 F) , One 130.4 (2F).

[Example 4] CH ₂ = CHCH ₂ OCH ₂ CH ₂ CH ₂ OCOCF (CF ₃ ) OCF ₂ CF ₂ CF 3 and CH ₂ = CHCH ₂ O CH ₂ CH ₂ CH ₂ OC OCF ₂ CF ₂ OCF ₂ CF ₂ CF ₃ Example of manufacturing a mixture of

CF ₃ CF ₂ CF ₂ OCF obtained in Example 3 (CF ₃₎ C_〇_F Oyobi CF ₃ CF

₂ CF ₂ OC F ₂ CF ₂ COF

A similar reaction was performed using 3 CF ₂ CF ₂ OCF (CF ₃ ) instead of COF. The title mixture was obtained by distillation under reduced pressure.

[Example 5] CF 3 CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ OCOCF (CF ₃ ) OCF ₂ CF ₂ CF 3 and CF 3 CF ₂ CF ₂ OC F ₂ CF ₂ CF ₂ OC OC F ₂ CF ₂ OCF ₂ CF ₂ Production example of CF ₃ mixture

The mixture obtained in Example 4 was reacted in the same manner as in Example 2 except that CH ₂ = CHCH ₂ OCH ₂ CH ₂ CH ₂ OCOCF (CF ₃ ) OCF ₂ CF ₂ CF ₃ to obtain the title mixture. .

The presence of _{CF 3 CF 2 CF 2 OCF 2} CF 2 CF 2 OCO CF 2 CF 2 OCF 2 CF 2 CF 3 in the mixture was confirmed by GC-MS. GC-MS: 645 (M ⁺ 1 F).

[Example 6] Production example of a mixture of CF ₃ CF ₂ CF ₂ OCF ₂ CF ₂ (30 ??? ₃ CF ₂ CF ₂ OCF (CF ₃ ) COF)

The mixture obtained in Example 5 was mixed with CF ₃ CF ₂ CF ₂ OCF ₂ CF ₂ CF in Example 3. ₂ OCOCF (CF 3) The title mixture was obtained by performing the same reaction using OCF ₂ CF ₂ CF ₃ instead of CF ₃ .

[Example 7] Production example of CF ₃ CF ₂ CF ₂ OCF = CF ₂

Connect internal diameter 20 mm, and S US column made of 1 m long average particle size 160 im of N a ₂ C0 ₃ and 2 80 g packed with an inner diameter of 45 mm, an S US-made fluidized bed reactor of height 400mm in series The reactor was placed in a salt bath, and the temperature in the salt bath was adjusted to 270 ° C. Nitrogen gas was flowed at 152 OmL / min, and the CF ₃ CF obtained in Example 6 (〇CF ₂ CF ₂ CF ₃ ) 0? The mixture of ₃ CF ₂ CF ₂ OCF ₂ CF ₂ COF was fed by a metering pump for 60.2 g / 1.8 hours. A dry ice / ethanol trap was installed at the reactor outlet to collect the product. CF 3 CF ₂ CF ₂ OCF = CF ₂ was produced at a yield of 80%. ^{1 9} F -NMR product (564. 6MHz, solvent: CDC 1 _3, reference: CFC 1 ₃₎ the peak of were consistent with those of the authentic sample.

<Possibility of industrial use>

 According to the method of the present invention, a fluorine-containing vinyl ether compound useful as a fluororesin raw material can be obtained in a short process and at a high yield from a raw material compound (1) and a mixture (2F-3F) which are inexpensive and easily available. It can be manufactured efficiently. The method of the present invention is an advantageous method that can be performed without separating the products in each step. It is an industrially useful method that can achieve a continuous production process without separating the products in each step. Further, a novel compound useful as a raw material for producing a fluorine-containing vinyl ether compound is provided.

Claims

The scope of the claims

1. A process for producing the following fluorine-containing vinyl ether compound (8), which comprises subjecting a mixture of the following compound (2F) and the following compound (3F) to a thermal decomposition reaction. However, in the formula, R ^AF represents a monovalent organic group which is not changed by the thermal decomposition reaction.

R ^AF OC F (CF ₃ ) COF (2 F)

R ^AF O (CF ₂ ) ₂ COF (3 F)

R ^AF OC F = CF ₂ (8)

2. In the following compound (6) or a mixture of the following compound (6) and the following compound (7), an ester bond is decomposed to give the following compound (2F) and the following compound (3F). the mixture obtained, the production method _c However Shikichu the next following fluorinated vinyl ether compound, characterized by performing the thermal decomposition reaction in the mixture (8), R ^AF is' monovalent organic unchanged by pyrolysis reaction Represents a group.

R ^AF O (CF ₂ ) 3 OCOC F (CF 3) OR ^AF (6)

R ^AF O (CF ₂ ) 3 OCOC F ₂ CF ₂ OR ^AF (7)

R ^AF OC F (CF ₃ ) COF (2 F)

R ^AF O (CF ₂ ) ₂ COF (3 F)

R ^AF OC F = CF ₂ (8)

3. The compound (6) undergoes an esterification reaction between the following compound (1) and the following compound (2) to produce the following compound (4), and then the compound (4) is fluorinated in a liquid phase. A mixture of the compound (6) and the compound (7), and a mixture of the following compound (1), the following compound (2), and the following compound (3). The mixture is reacted to form a mixture of the following compound (4) and the following compound (5), and the mixture of the compound (4) and the compound (5) is reacted with fluorine in a liquid phase to obtain a reaction product. The production method according to claim 2, wherein

In the ^{formula, R A, R B, R} c are each independently a R ^AF same monovalent organic group or a monovalent organic group comprising the R ^AF by reacting with fluorine in a liquid phase, And R ^AF are monovalent organic groups that are not changed by a thermal decomposition reaction, and X represents a halogen atom.

R ^A O (CH ₂ ) 3 OH (1)

XCOCF (CF ₃ ) OR ^B (2)

XCO (CF ₂ ) ₂ OR ^c (3)

AO (CH ₂ ) 3 OCOCF (CF 3) 〇R ^B (4)

R ^A O (CH ₂ ) a OCO (CF ₂ ) ₂ OR ^c (5)

4. The production method according to claim 3, wherein the fluorine content in the compound (4) is 30% by mass or more, and the fluorine content in the compound (5) is 30% by mass or more.

5. The mixture of compound (6) and compound (7) undergoes esterification reaction of the following compound (1) with the following compound (2F) and a mixture of compound (3F) to give the following compound (4F 3. The process according to claim 2, wherein the reaction product is obtained by producing a mixture of the following compound (5F) and then reacting the mixture with fluorine in a liquid phase. However. Wherein, RA represents one Ataiyu machine group consisting R ^AF by reacting with fluorine in R ^AF same 1 Ataiyu machine group or in the liquid phase,, R ^AF is not changed by the thermal decomposition reaction Shows a monovalent organic group.

R ^A O (CH ₂ ) 3 OH (1)

R ^AF OC F (CF 3) COF (2 F). R ^AF 0 (CF ₂ ) ₂ COF (3 F)

R ^A O (CH ₂ ) 3 OCOC F (CF ₃ ) OR ^AF (4 F)

R ^A O (CH ₂ ) 3 OCOCF ₂ CF ₂ OR ^AF (5 F)

6. A mixture of the compound (2F) and the compound (3F) is a part or a part of a reaction product obtained by subjecting a mixture of the following compound (6) and the following compound (7) to an ester bond decomposition reaction. The production method according to claim 5, which is all. However, in the formula, R ^AF represents a monovalent organic group which is not changed by a thermal decomposition reaction.

R ^AF 0 (CF ₂ ) 3 OCOC F (CF 3) OR ^AF (6)

R ^AF O (CF ₂ ) 3 OCOC F ₂ CF ₂ OR ^AF (7)

7. When reacting with fluorine in the liquid phase, at least one compound selected from compound (2F), compound (3F), compound (6), and compound (7) is used as the liquid phase The production method according to claim 3, 4, 5, or 6.

8. R ^AF is Perufuruoro (monovalent saturated hydrocarbon) group, Perufuruoro (partially halogenated monovalent saturated hydrocarbon) group, Perufuruoro (hetero atom-containing monovalent saturated hydrocarbon) group or Perufuruoro (hetero the partially halogenated, The production method according to any one of claims 1 to 7, which is an atom-containing monovalent saturated hydrocarbon) group.

9. The following compound (la) is subjected to an esterification reaction with a mixture of the following compound (2a) and the following compound (3a) to obtain a mixture of the following compound (4a) and the following compound (5a), Next, a mixture of the compounds (4a) and (5a) is reacted with fluorine in a liquid phase to obtain the following compound (6a) and the following compound

A mixture of (7a) is obtained, and then a mixture of the compounds (6a) and (7a) is obtained. >