JP2001139509A - Method for production of unsaturated compound by thermal decomposition reaction - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce an unsaturated compound useful as a fluoroplastic(s) raw material, etc., in a high yield in a short process. SOLUTION: A compound represented by formula (B) CF(OR2)=CR3R4, e.g. CF3CF2CF2OCF=CF2, etc., is obtained by the thermal decomposition reaction of a compound represented by formula (A) R1COOCF2CF(OR2)CXR3R4, e.g. CF3(CF3CF2CF2O)CFCOOCF2CF(OCF2CF2CF3)CF3, etc. (wherein R1, R2, R3 and R4 are each fluorine atom, a perfluoroalkyl group or a perfluoro (an ethereal oxygen-containing alkyl group); and X is a halogen atom).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an unsaturated compound which can be a useful resin raw material and a method for producing a polymer using the unsaturated compound.

[0002]

BACKGROUND OF THE INVENTION Unsaturated compounds such as perfluoro (alkylalkenyl ether) are useful as starting monomers for fluororesins. Fluororesins are used in a wide range of fields because they have excellent heat resistance and chemical resistance.
Conventionally perfluoro (alkyl alkenyl ether)
Is a dimerization reaction of perfluoroepoxides, or
Perfluoroalkanoic acid fluoride is reacted with perfluoroepoxides in the presence of an alkali metal fluoride to form perfluoro (2-alkoxyalkanoic acid) fluorides, which are industrially produced by a reaction of applying heat.

[0003] Further, as a method for producing a perfluoro compound by a reaction of decomposing an ester bond by heat,
A method is known in which a perfluorinated alkyl ester compound having 16 or more carbon atoms is heated to obtain an acid fluoride compound (J. Am. Chem. Soc., 120, 7117 (1998)). Also,
A reaction to obtain perfluoro (alkenyl ether) by heating perfluoro (2-alkoxyalkanoic acid) fluoride is also known (Methods of Organic Chemistry, 4, Vo).
l.10b, Part 1, p.703 etc.).

[0004]

The conventional method for producing perfluoro (alkylalkenyl ether) has a problem that the control of the reaction is difficult, the cost of the raw material is high, and it is economically disadvantageous as an industrial production method. Was.

[0005]

DISCLOSURE OF THE INVENTION The present invention is the following invention which has been made for the purpose of providing a process for obtaining an unsaturated compound in one step by using a compound which can be obtained at a low cost as a raw material.

That is, the present invention provides a method for producing an unsaturated compound represented by the following formula B by a thermal decomposition reaction of a compound represented by the following formula A.

[0007]

Embedded image _{^{R a COOCF 2 CR b R c}} -CXR d R e ··· formula ^{A CR b R c = CR d} R e ··· formula B

However, R ^a , R ^b , R ^c , R ^d , and ^Re each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group which is not changed by a thermal decomposition reaction. Also, R ^b , R ^c , R ^d , and R ^e
Two selected from the group may be linked to each other to form a divalent organic group that does not change by thermal decomposition, and the remaining two may be linked to each other to form a divalent organic group that does not change by thermal decomposition; Alternatively, each independently may be a hydrogen atom, a halogen atom, or a monovalent organic group which is not changed by a thermal decomposition reaction.

X: halogen atom.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In the present specification, an organic group means a group having a carbon atom as an essential element, and includes those having a saturated or unsaturated structure. As the organic group, a hydrocarbon group, a hetero atom-containing hydrocarbon group, a halogeno hydrocarbon group, or a halogeno (hetero atom-containing hydrocarbon) group is preferable.

[0011] The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group. 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 term "saturated organic group" refers to a group in which the carbon-carbon bond in the group comprises only a single bond. In the group, C 中 O or S
An unsaturated bond such as O ₂ may be present.

The saturated organic group is preferably a saturated hydrocarbon group. Examples of the monovalent saturated hydrocarbon group include an alkyl group, a cycloalkyl group, and a monovalent saturated hydrocarbon group having a cycloalkyl moiety (such as a cycloalkylalkyl group). Examples of the divalent saturated hydrocarbon group include an alkylene group, a group having a cycloalkylene portion, and a divalent saturated hydrocarbon group having a cycloalkyl portion (such as a cycloalkylalkylene group).

As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and a methyl group, an ethyl group and a propyl group are particularly preferable. The cycloalkyl group is preferably a 3- to 6-membered cycloalkyl group or a group in which one or more hydrogen atoms of the cycloalkyl group have been substituted with an alkyl group. As the cycloalkylalkyl group, one having 1 to 3 carbon atoms
A group in which one hydrogen atom of the alkyl group is substituted with the cycloalkyl group is preferable, and examples thereof include a cyclohexylmethyl group.

The halogen atom is a fluorine, chlorine, bromine or iodine atom, preferably a fluorine, chlorine or bromine atom, particularly preferably a fluorine or chlorine atom.

A halogeno hydrocarbon group is a group in which one or more hydrogen atoms present in the above hydrocarbon group have been replaced by halogen atoms. A hydrogen atom may or may not be present in the halogeno hydrocarbon group. As the halogen atom in the halogeno hydrocarbon group, a fluorine atom or a chlorine atom is preferable. Further, a group in which a part of hydrogen atoms present in a hydrocarbon group is substituted by a halogen atom is referred to as a partial halogeno hydrocarbon group. Hydrogen atoms are present in the partial halogeno hydrocarbon group. Further, a perhalogenohydrocarbon group refers to a group in which all of the hydrogen atoms present in the group are substituted by halogen atoms. There is no hydrogen atom in the perhalogeno hydrocarbon group. The halogen atom present in the halogeno group and the perhalogeno group is 1
The species may be two or more.

The halogeno monovalent saturated hydrocarbon group may have a linear structure or a branched structure, may have a partial ring structure, and may have a fluoroalkyl group or a fluoro (partial chloroalkyl group). ) Groups and the like. The halogeno monovalent hydrocarbon group preferably has 1 to 20 carbon atoms. The perhalogeno monovalent saturated hydrocarbon group includes a perfluoroalkyl group or a perfluoro (partially chloroalkyl) group.
Preferred are groups (ie, groups in which all of the hydrogen atoms in the partial chloroalkyl group have been fluorinated). The halogeno monovalent hydrocarbon group preferably has 1 to 20 carbon atoms. Specific examples of these groups include the groups described in the following examples.

The halogeno divalent saturated hydrocarbon group may have a linear structure or a branched structure, may have a partial ring structure, and may be a fluoroalkylene group or a fluoro (partially chloroalkylene) group. ) Groups are preferred. Examples of the perhalogeno divalent saturated hydrocarbon group include a perfluoroalkylene group and a perfluoro (partial chloroalkylene) group (that is, a group in which all of the hydrogen atoms in the partial chloroalkylene group are fluorinated).

The hetero atom-containing hydrocarbon group is a group comprising a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom, a carbon atom and a hydrogen atom. The heteroatom may be a heteroatom itself or a heteroatom bonded to form a heteroatom group. The heteroatom and the heteroatom group are preferably those which are not changed by the thermal decomposition reaction. Examples of the heteroatom include an etheric oxygen atom (—O—), a thioetheric sulfur atom (—S—), ＯO, ΔN And the like, and an etheric oxygen atom or a thioetheric sulfur atom is particularly preferred. The heteroatom-containing hydrocarbon group preferably has 1 to 20 carbon atoms. As the hetero atom-containing hydrocarbon group, a group in which a divalent hetero atom or a divalent hetero atom group is inserted between carbon-carbon atoms of the hydrocarbon group, or a hetero atom is bonded to a carbon atom in the hydrocarbon group Or a group in which a divalent heteroatom or a divalent heteroatom group is bonded to the carbon atom at the bonding end of the hydrocarbon group. The hetero atom-containing group is particularly preferably an etheric oxygen atom-containing group from the viewpoint of the usefulness of the compound, and particularly preferably a group having an etheric oxygen atom at the bonding terminal.

As the hetero atom-containing monovalent hydrocarbon group,
From the viewpoint of availability, ease of production, and usefulness of the product, an alkyl group containing an etheric oxygen atom is preferable, and an alkoxyalkyl group or an alkoxyl group is particularly preferable. The hetero atom-containing divalent hydrocarbon group is a group in which one hydrogen atom in the hetero atom-containing monovalent hydrocarbon group is a bond, and an etheric oxygen atom-containing alkylene group is preferable.

The halogeno (hetero atom-containing hydrocarbon) group is preferably a fluoro (hetero atom-containing hydrocarbon) group or a fluoro (partial chloro (hetero atom-containing hydrocarbon)) group. The halogeno (hetero atom-containing hydrocarbon) group preferably has 1 to 20 carbon atoms. As the perhalogeno (hetero atom-containing hydrocarbon) group, a perfluoro (hetero atom-containing hydrocarbon) group or a perfluoro (partial chloro (hetero atom-containing hydrocarbon)) group is preferable.

The halogeno (heteroatom-containing monovalent saturated hydrocarbon) group may have a straight-chain structure or a branched structure. Halogeno (heteroatom-containing monovalent saturated hydrocarbon)
As the group, a fluoro (hetero atom-containing alkyl) group or a fluoro (partial chloro (hetero atom-containing alkyl)) group is preferable. Perhalogeno (heteroatom containing 1
As the (valent saturated hydrocarbon) group, a perfluoro (alkoxyl) group or a perfluoro (partial chloro (alkoxyl)) group is preferable.

The halogeno (heteroatom-containing divalent saturated hydrocarbon) group is a group in which one hydrogen atom in the halogeno (heteroatom-containing monovalent saturated hydrocarbon) group is a bond, and a fluoro (etheric Preferred are an oxygen atom-containing divalent alkylene group and a fluoro (partial chloro (etheric oxygen atom-containing divalent alkylene)) group. As the perhalogeno (hetero atom-containing divalent saturated hydrocarbon) group, a perfluoro (etheric oxygen atom-containing divalent alkylene) group and a perfluoro (partial chloro (etheric oxygen atom-containing divalent alkylene)) group are preferable.

Examples of these groups are specifically shown in the specific compounds described later.

In the present invention, the thermal decomposition of the compound (formula A)
Perform the reaction. In the thermal decomposition reaction of the present invention, the compound (formula A) is
Particularly useful when it is a fluorine-containing compound, and efficient
R in formula A^a, R^b, R^c,
R^d, R^eIs changed by a fluorine atom or thermal decomposition reaction.
A perfluoromonovalent organic group that does not become
R^b, R^c, R^d, And R^eTwo selected from
Perfluoro divalent organic that does not change by thermal decomposition
It is preferably a group. R^b, R^c, R^d, And R^eFrom
The two selected are linked to each other and do not change due to thermal decomposition.
Residual perfluoro divalent organic groups are formed.
The two are connected to each other and
Forms a fluorodivalent organic group, or
Or perfluoro that does not change due to thermal decomposition
It is preferably a monovalent organic group. Also R ^aIs the thermal decomposition reaction
Is preferably a perfluoromonovalent organic group which is not changed by
Good.

The organic group which is not changed by thermal decomposition means an organic group whose chemical structure does not change before and after the thermal decomposition reaction in the present invention. The organic group which is not changed by the thermal decomposition reaction includes “COOCF ₂ C—C
X ^a ”(where X ^a is a halogen atom), a group having no structure, and a group having no structure that is chemically unstable under the conditions of thermal decomposition. For example, a hydrocarbon or halogenohydrocarbon group is a group that does not normally change upon thermal decomposition. A heteroatom-containing hydrocarbon group or a halogeno (heteroatom-containing hydrocarbon) group is a group that usually does not change by thermal decomposition when a heteroatom or heteroatom group in the group does not change by a thermal decomposition reaction. .
The above description of the organic group whose chemical structure does not change before and after the thermal decomposition reaction applies whether the organic group is monovalent or divalent.

As the organic group which is not changed by the thermal decomposition reaction, a perfluoro saturated hydrocarbon group, a perfluoro (ether hydrocarbon saturated hydrocarbon containing an oxygen atom) group, a perfluoro (partially chloro saturated hydrocarbon) group, or a perfluoro (partially chloro (ether A) a hydrocarbon group containing a neutral oxygen atom)).

When R ^a , R ^b , R ^c , R ^d , and ^Re are monovalent organic groups which are not changed by a thermal decomposition reaction, the number of carbon atoms is 1
~ 20 is preferred. The group is preferably a perfluoroalkyl group, a perfluoro (partial chloroalkyl) group, a perfluoro (etheric oxygen atom-containing alkyl) group, or a perfluoro (partial chloro (etheric oxygen atom-containing alkyl)) group.

[0029] 2 is selected from ^{R b, R c, R d} , and R ^e
Are connected to each other and are not changed by the pyrolysis reaction.
When forming a valent organic group, the number of carbon atoms is preferably 1 to 20. The divalent organic group may be one or two, and is preferably one. The remaining two groups are respectively a perfluoroalkyl group, a perfluoro (partial chloroalkyl) group, a perfluoro (etheric oxygen atom-containing alkyl) group, or a perfluoro (partial chloro (etheric oxygen atom-containing alkyl)) group. preferable.

The divalent organic group which is not changed by the thermal decomposition reaction includes a perfluoroalkylene group, a perfluoro (partial chloroalkylene) group, a perfluoro (etheric oxygen atom-containing alkylene) group and a perfluoro (partial chloro (etheric oxygen atom-containing alkylene) )) Groups are preferred.

X is preferably a fluorine atom from the viewpoint of availability of the compound (formula A), but is preferably a chlorine atom from the viewpoint of ease of the thermal decomposition reaction.

As the compound (formula A), the following compound (formula A ^F ) is preferable.

[0033]

## STR00006 ## _{^{R af COOCF 2 CR bf R cf}} -CXR df R ef ··· type A ^F

R ^{af is a} fluorine atom, a perfluoroalkyl group, a perfluoro (ether-containing oxygen atom-containing alkyl) group, a perfluoro (partially chloroalkyl) group, or a perfluoro (partial chloro (ether-containing oxygen atom-containing alkyl))
Base.

R ^bf , R ^cf , R ^df , and R ^ef each independently represent a fluorine atom, a perfluoroalkyl group, a perfluoro (ether-containing oxygen atom-containing alkyl) group, a perfluoro (partial chloroalkyl) group, or a perfluoro (partial chloroalkyl) group. (Etheric oxygen atom containing alkyl)) groups. ^{Alternatively} , two selected from R ^bf , R ^cf , R ^df , and R ^ef are connected to each other to form a perfluoroalkylene group, a perfluoro (alkylene containing an etheric oxygen atom) group, a perfluoro (partially chloroalkylene) group, or a perfluoro ( Partial chloro (etheric oxygen atom-containing alkylene)
The other two are linked together to form a perfluoroalkylene group, a perfluoro (alkylene containing an etheric oxygen atom) group, a perfluoro (partially chloroalkylene) group, or a perfluoro (partially chloro (containing an etheric oxygen atom containing Alkylene)) group, or each independently represents a fluorine atom, a perfluoroalkyl group, a perfluoro (etheric oxygen atom-containing alkyl) group, a perfluoro (partial chloroalkyl) group.
Or a perfluoro (partial chloro (etheric oxygen atom containing alkyl)) group.

X: the same meaning as in formula A.

In the present invention, R in the compound (formula A)
^aIt is preferable to change the structure of the
Good. For example, R in the compound (formula A)^aIs -C
R^bR ^c-CXR^dR^e(However, R^b, R^c, R^d, R^e,
And X are the same as defined above. ) If it is pyrolysis
Since the product of the reaction is an unsaturated compound (Formula B),
Good. In this case, a compound (formula
C) is converted to an unsaturated compound (formula B) under the conditions of the thermal decomposition reaction
The product is substantially only the compound (formula B).
This eliminates the need for separating and purifying the product. Likewise
Compound (Formula A^F) For R^afIs -CR^bfR^cf-CXR
^dfR^ef(However, R^bf, R^cf, R^df, R ^ef, And X are
Same as above definition. ) Is preferred.

Further, for example, a compound (formula C) which can be formed
However, when ^Ra is selected such that the boiling point difference from the unsaturated compound (Formula B) is large (for example, when ^Ra is a fluorine atom), the unsaturated compound (Formula B) )
And the compound (Formula C) can be easily separated, which is preferable.

Further, as the compound (Formula A), R ^b , R ^c , R
^d, and one or more groups based on having an etheric oxygen atom at the terminal selected from R ^e (e.g., perfluoro (alkoxyl group) or a perfluoro (partially chlorinated (alkoxyl)) group is preferred.), and and the remainder When a group is present, the group is preferably a fluorine atom. Especially ^{R b, R c, R d} , one of the groups selected from R ^e is perfluoro (alkoxyl group) or a perfluoro (partially chlorinated (alkoxyl)) group, and three groups of remainder with a fluorine atom Preferably it is.
When ^Rb , ^Rc , ^Rd , and ^Re form a divalent organic group, it is preferable that both bonding terminals of the divalent organic group be etheric oxygen atoms.

Specific examples of the compound (formula A) include the following compounds. However, in the following, Cy ^F represents a perfluoro (cyclohexyl) group.

[0041]

Embedded image CF ₃ (CF ₃ CF ₂ CF ₂ O) CFCOOCF ₂ CF (OCF ₂ CF ₂ CF ₃ ) CF ₃ , CF ₃ CF ₂ COOCF ₂ CF (OCF ₂ CF ₂ CF ₃ ) CF ₃ , CF ₃ ( CF ₂ ClCFClCF ₂ CF ₂ O) CFCOOCF ₂ CF (OCF ₂ CF ₂ CFClCF ₂ Cl) C
F ₃ , CF ₃ [CF ₂ ClCFClCF ₂ CF (CF ₃ ) O] CFCOOCF ₂ CF [OCF (CF ₃ ) CF ₂ CFC
lCF ₂ Cl] CF _{3 ,} CF ₃ (CF ₃ CF ₂ CF ₂ O) CFCOOCF ₂ CF (OCF ₂ CF ₂ CFClCF ₂ Cl) CF ₃ , CF ₃ (CF ₃ CF ₂ CF ₂ O) CFCOOCF ₂ CF (OCF ₂ Cy ^F ) CF ₃ , CF ₃ (CF ₃ CF ₂ CF ₂ O) CFCOOCF ₂ CF (O (CF ₂ ) ₉ CF ₃ ) CF ₃ ,

[0042]

Embedded image

In the present invention, the compound (formula C) is obtained by a thermal decomposition reaction of the compound (formula A) together with the unsaturated compound (formula B) or the unsaturated compound (formula B). The thermal decomposition reaction in the present invention refers to a reaction in which an unsaturated compound (Formula B) is formed by heating a compound (Formula A).

The thermal decomposition reaction 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 and efficient. The method and reaction temperature of the thermal decomposition reaction are preferably selected depending on the boiling point and stability of the compound (formula A).

Further, the compound (formula A) has a boiling point of 35 at normal pressure because it can undergo a thermal decomposition reaction in a gas phase reaction.
It is preferably 0 ° C. or lower. Further, the boiling point of the compound (formula A) is preferably 50 ° C. or higher. The gas phase reaction is preferably performed by a continuous reaction. In the continuous reaction, a vaporized compound (formula A) is passed through a heated reaction tube to obtain a produced unsaturated compound (formula B) as an outlet gas, which is condensed and continuously recovered. It is preferred to carry out.

The reaction temperature in the case of performing pyrolysis in a gas phase reaction can be appropriately changed depending on the structure of the compound (formula A).
Generally, 150 ° C. or higher is preferable, and 200 ° C. to 500 ° C.
Is particularly preferred, and more preferably above 250 ° C to 450 ° C. If the reaction temperature is too high, a decomposition reaction of the product may occur and the yield may be reduced. When the reaction temperature is too low, the compound (Formula A) FCOCR ^b R ^c -CXR
the amount of ^d R ^e is increased undesirably.

When a thermal decomposition reaction is performed by 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 compound (formula A) is a high-boiling compound, the reaction is preferably performed under reduced pressure. In particular, when the compound (formula A) is a low-boiling compound, it is preferable to carry out the reaction under pressure because decomposition of the product is suppressed and the reaction rate is increased.

When a gas phase reaction is carried out using a tubular reactor, it is preferable to fill the reaction tube with 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 particularly, glass beads having a fluidity in a bead form are preferable. Alkali metal salts include sodium carbonate, sodium fluoride, potassium carbonate, or lithium carbonate. Examples of the alkaline earth metal carbonate include calcium carbonate, calcium fluoride, and magnesium carbonate. Further, when the reaction tube is filled with a glass, an alkali metal salt, or an alkaline earth metal salt, glass beads, light ash of sodium carbonate, or the like having a particle size of about 100 to 250 μm. Is particularly preferable because a fluidized bed type reaction system can be employed.

In the gas phase reaction, in order to promote the vaporization of the compound (formula A), the reaction is preferably carried out in the presence of an inert gas which does not directly participate in the thermal decomposition reaction. Examples of the inert gas include nitrogen, carbon dioxide, helium, and argon. The amount of the inert gas is preferably about 0.01 to 50% by volume based on the compound (formula A). If the amount of the inert gas is too large, the amount of the recovered product may be low, which is not preferable. On the other hand, when the boiling point of the compound (formula A) is high, the thermal decomposition may be performed by a liquid phase reaction.

In the thermal decomposition reaction of the present invention, an unsaturated compound (formula B) or a compound (formula C) is formed together with the unsaturated compound (formula B). Even if the product of the thermal decomposition reaction of the present invention is only an unsaturated compound (formula B), the unsaturated compound (formula B)
And the compound (Formula C). R ^a , R ^b , R ^c in the unsaturated compound (Formula B) and the compound (Formula C)
R ^d and R ^e are groups corresponding to the compound used (Formula A).

As the unsaturated compound (formula B), at least one selected from R ^b , R ^c , R ^d and R ^e from the viewpoint of easiness of polymerization when the compound is polymerized to form a polymer. Is a group having an etheric oxygen atom at the bonding end (for example, a perfluoro (alkoxyl group) or a perfluoro (partial chloro (alkoxyl)) group is preferable), and when there is a residual group, is preferably group is a fluorine atom, a particularly ^{R b, R c, R d} , and any one group selected from R ^e perfluoro (alkoxyl group) or a perfluoro (partially chlorinated (alkoxyl)) group, It is particularly preferred that the remaining three groups are fluorine atoms. R ^b , R ^c ,
When R ^d and R ^e form a divalent organic group,
It is preferred that both terminal ends of the divalent organic group be etheric oxygen atoms.

Specific examples of the unsaturated compound (formula B) include:
The following compounds may be mentioned.

[0053]

Embedded image _{CF 2 = CFOCF 2 CF 2 CF} 3, CF 2 = CFOCF 2 CF 2 CFClCF 2 Cl, CF 2 = CFOCF 2 Cy F, CF 2 = CFO (CF 2) 9 CF 3,

[0054]

Embedded image

Specific examples of the compound (formula C) include the following compounds.

[0056]

Embedded image CF ₃ (CF ₃ CF ₂ CF ₂ O) CFCOF, CF ₃ CF ₂ COF, CF ₃ (CF ₂ ClCFClCF ₂ CF ₂ O) CFCOF, CF ₃ [CF ₂ ClCFClCF ₂ CF (CF ₃ ) O] CFCOF _, CF ₃ (CF ₃ CF ₂ CF ₂ O) CFCOF, CF ₃ (CF ₃ CF ₂ CF ₂ O) CFCOF, CF ₃ (CF ₃ CF ₂ CF ₂ O) CFCOF.

Unless the product of the thermal decomposition reaction is substantially only an unsaturated compound (formula B), the product of the thermal decomposition reaction is preferably separated and purified by a usual method. Examples of the separation and purification method include a distillation method and silica gel column chromatography. The unsaturated compound (Formula B) and the compound (Formula C) have a lower molecular weight than the compound (Formula A),
Since the compound usually has a low boiling point, the unreacted compound (formula A) can be efficiently removed by a distillation method.

The method for obtaining the compound (Formula A) of the present invention is not particularly limited, and a commercially available compound or a compound produced by a known production method can be used. Further, when the compound (formula A) is a compound (formula A ^F ), the compound (formula a ³ ) which can be produced by reacting the compound (formula a ¹ ) with the compound (formula a ² ) is added in the liquid phase. It is preferable to produce by fluorination with. The method of producing the compound (formula A ^F ) by a liquid phase fluorination reaction in a liquid phase is preferable in that the raw material (compound (formula a ³ )) is inexpensive and various structures are available.

[0059]

^Embedded image R ^aH COX ¹ ··· Formula a ¹ HOCH ₂ CR ^bH R ^cH -CX ² R ^{dH Re e} ··· Formula a ² R ^{aH COOCH} ₂ CR ^bH R ^cH -CX ² R ^dH R ^eH. Formula a ³

Wherein R ^aH is a group corresponding to R ^AF and is a group selected from an alkyl group, an etheric oxygen atom-containing alkyl group, a partial chloroalkyl group, and a partial chloro (etheric oxygen atom-containing alkyl) group; A group in which at least one hydrogen atom in the group is substituted with a fluorine atom, a group in which at least one carbon-carbon single bond in the group is substituted with a carbon-carbon double bond or a carbon-carbon triple bond Or a hydrogen atom.

R ^bH , R ^cH , R ^dH , R ^eH : R ^bH represents R ^bf ,
R ^cH The R ^cf, R ^dH is the R ^df, R ^eH is a group corresponding to R ^ef, each independently, an alkyl group, an etheric oxygen atom-containing alkyl group, partially chlorinated alkyl group, and partially chlorinated ( A group selected from among etheric oxygen atom-containing alkyl) groups, a group in which at least one hydrogen atom in the group is substituted with a fluorine atom, and at least one carbon-carbon single bond in the group is a carbon-carbon divalent bond. A group substituted by a heavy bond or a carbon-carbon triple bond, a hydrogen atom, or a fluorine atom. Or R ^bH ,
Two selected from R ^cH , R ^dH and R ^eH are connected to each other,
Alkylene group, etheric oxygen atom-containing alkylene group,
A group selected from a partial chloroalkylene group and a partial chloro (alkylene containing an etheric oxygen atom) group, a group in which at least one hydrogen atom in the group is substituted by a fluorine atom, or a carbon-carbon single atom in the group One or more of the bonds is a group substituted with a carbon-carbon double bond or a carbon-carbon triple bond, and the remaining two are linked to each other to form an alkylene group;
A group selected from an etheric oxygen atom-containing alkylene group, a partial chloroalkylene group, and a partial chloro (etheric oxygen atom-containing alkylene) group;
A group in which one or more carbon atoms are substituted with a fluorine atom, or a group in which one or more carbon-carbon single bonds are substituted with a carbon-carbon double bond or a carbon-carbon triple bond,
Alternatively, each independently, a group selected from an alkyl group, an etheric oxygen atom-containing alkyl group, a partial chloroalkyl group, and a partial chloro (etheric oxygen atom-containing alkyl) group, wherein one or more of the hydrogen atoms in the group are A group substituted with a fluorine atom, a group in which at least one carbon-carbon single bond in the group is substituted with a carbon-carbon double bond or a carbon-carbon triple bond, a hydrogen atom, or a fluorine atom Good.

X ¹ : each independently a hydrogen atom or a halogen atom.

X ² : an atom corresponding to X, a hydrogen atom or a fluorine atom when X is a fluorine atom, and the same as the halogen atom when X is a halogen atom other than a fluorine atom Halogen atom.

To obtain a compound having a perfluorocyclohexyl group or a perfluorocyclohexylene group in R ^bF , R ^cF , R ^dF and R ^{eF of the} compound (formula A ^F ), R ^bH , R ^cH , R ^dH , R ^eH , the corresponding part of which is a phenyl group or a phenylene group (formula a ² ) may be used.

In the reaction for producing the compound (formula a ³ ) from the compound (formula a ¹ ) and the compound (formula a ² ), the usual esterification reaction conditions can be employed as they are. When the fluorination reaction of the compound (formula a ³ ) is performed by a method of reacting with fluorine (molecular fluorine) in a liquid phase, the compound (formula A ^F ) can be obtained with high yield, and the reaction can be controlled. Is preferred because of the simplicity.

In the method of reacting with fluorine in the liquid phase, it is preferable to employ a method of sequentially introducing the compound (formula a ³ ) into the liquid phase. Fluorine may be present in the liquid phase in advance, fluorine gas may be introduced into the reaction system sequentially, and the latter is preferred because the amount of the compound (formula a ³ ) relative to fluorine gas can be adjusted. As the liquid phase, a solvent which does not contain a C—H bond and essentially has a C—F bond is preferable. Further, a perfluoroalkane or one or more atoms selected from a chlorine atom, a nitrogen atom, and an oxygen atom can be used. An organic solvent obtained by perfluorinating a known organic solvent having a structure is preferable. Further, as a solvent, compound (a ³ )
It is preferable to use a solvent having high solubility for the compound (a), particularly preferably a solvent capable of dissolving 1% by mass or more of the compound (a ³ ), particularly preferably a solvent capable of dissolving 5% by mass or more.

The solvent used as the liquid phase is fluorine gas.
Solvent that is dissolved and inert to fluorine gas
It is preferable to select from perfluoroalkanes (trademarks).
Product name: FC-72, etc., perfluoroethers (products)
Name: FC-75, FC-77, etc.), perfluoropolye
-Tels (trade names: Krytox, Fomblin, Gas
Ruden, Demnum and others. ), Chlorofluorocarbons
(Product name: CFC), chlorofluoropolyether
, Perfluoroalkylamines (for example,
Fluorotrialkylamine, etc.), inert fluid (trade name:
Florinate), perhalogenoester compounds (for example,
If the compound (formula A^F)), Perfluoroethers and
Terminals of lorofluoropolyethers and the like become -COF groups.
Preferred solvents (eg, compound (Formula C)). Sa
Further, as a solvent, a compound (formula A^F),
Satisfies the above conditions, and removes the product after the fluorination reaction.
It is particularly preferred because it does not need to be separated. Used for liquid phase
The amount of solvent is ^Three) To 5 times the mass
The above is preferable, and the mass is particularly preferably 10 to 100 times.

Compound (Formula a^Three) Reacts with fluorine in the liquid phase
In this case, the compound (formula a^Three) Is fully soluble in the liquid phase
A compound having a resolvable fluorine content and a gaseous phase
Compounds having a molecular weight sufficient to suppress the reaction
Compound (a)^ThreeIs to adjust the structure
preferable. That is, fluorine gas is usually used as the liquid phase.
Uses a solvent that is easily soluble, so it is easily soluble in the solvent
Compound (formula a^Three) Is a fluorine-containing compound
preferable. Compound (Formula a^Three) Has a fluorine content of 10% by mass.
It is preferable that the content is 10% to 86% by mass.
Particularly preferred, particularly preferably 30 to 76% by mass.
Good. In addition, a compound (formula a^Three) Has sufficient molecular weight
Decomposes into the gas phase during the fluorination reaction
The compound (formula a^Three)
Has a molecular weight of preferably from 200 to 1,000. Conversion
Compound (formula a^Three) Is a compound (formula a)¹R in)^aH
Is R ^afAnd the same groups.

The amount of fluorine used in the fluorination reaction is preferably such that fluorine gas is charged so that the amount of fluorine atoms is always in excess equivalent to the amount of hydrogen atoms in the compound (formula a ³ ). ^It is particularly preferable from the viewpoint of selectivity that the fluorine gas is used in an amount equivalent to 1.5 times or more the hydrogen atom in ³ ).

In the fluorination reaction, an alkali metal fluoride (preferably NaF or KF) or a trialkylamine may be present in the reaction system as a scavenger for HF. Furthermore, the yield of the fluorination reaction product can be increased by adding a compound capable of generating a fluorine radical or irradiating the reaction system with ultraviolet rays at a later stage of the fluorination reaction. Examples of the compound capable of generating a fluorine radical include aromatic compounds such as benzene and toluene.

According to the production method of the present invention, an unsaturated compound having the desired structure (formula B) can be produced in a single-stage reaction with high yield. Since the polymerizable unsaturated group is present in the obtained unsaturated compound (Formula B), the compound (Formula B) is polymerized or the compound (Formula B) and the compound (Formula B) A useful polymer can be produced by copolymerizing a polymerizable polymerizable monomer.

The polymerizable monomer capable of polymerizing with the compound (formula B) 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, when the compound (formula B) is perfluoro (alkyl vinyl ether), the polymerizable monomer capable of polymerizing with the compound is CF ₂ ＝ CF ₂ , C ₂
Fluoroethylenes such as F ₂ ＣＦCFCl and CF ₂ ＣＨCH ₂ , fluoropropylenes such as CF ₂ ＣＨCHCF ₃ , CF
₃ CF ₂ CF ₂ CF ₂ CH = CH ₂ or CF ₃ CF ₂ CF ₂ CF ₂
When the number of carbon atoms of the perfluoroalkyl group such as CF = CH ₂ is 4
To 12 (perfluoroalkyl) ethylenes, CH ₃
OC (= O) CF ₂ CF ₂ CF ₂ OCF = CF ₂ or FSO ₂
Examples thereof include vinyl ethers having a group that can be converted into a carboxylic acid group or a sulfonic acid group such as CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF ＝ CF ₂ , and olefins such as ethylene, propylene, and isobutylene.

The polymer obtained according to the present invention can be a useful resin. When the compound (B) is a fluorine-containing compound, a fluorine-containing polymer obtained by polymerizing the compound is useful as a fluorine resin. Fluororesins are used in a wide range of fields because they have excellent heat resistance and chemical resistance.

[0074]

The reaction mechanism of the thermal decomposition reaction in the present invention is not necessarily clear, but the following two reaction mechanisms are conceivable.

[0075] (Reaction mechanism 1) compound (Formula A) by decomposition FCOCR ^b R ^c -CXR ^d R ^e is produced, from which FC
A reaction mechanism in which an unsaturated compound (formula B) is generated by elimination of OX.

[0076] (Reaction mechanism 2) Compound (Formula A) by decomposition FCOCR ^b R ^c -CXR ^d R ^e is produced, -COF group is an alkali metal salt, an alkaline earth metal salt or glass surface reaction Is converted to —COOM (M is an alkali metal atom, an alkaline earth metal atom, or a silicon atom), from which carbon dioxide and MX are released, thereby generating an unsaturated compound (formula B).

The thermal decomposition reaction is a reaction that can occur due to the structure of —COOCF ₂ C—CX— (X has the same meaning as in formula A) present in the compound (formula A). To give various unsaturated compounds (formula B)
Can be easily manufactured.

[0078]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited by these examples. In the following, liter is described as L, stainless steel as SUS, gas chromatography as GC, and gas chromatography mass spectrometer as GC-MS.

Example 1 Synthesis Example of CF ₃ CF ₂ CF ₂ OCF = CF ₂ A GC thermostat was filled with a SUS column having an inner diameter of 3 mm and a length of 6 m and Na ₂ CO ₃ (7 g) having an average particle diameter of 160 μm. A SUS column having an inner diameter of 3 mm and a length of 3 m was connected and installed in series, and the temperature of the thermostat was adjusted to 250 ° C and the temperature of the GC injection was adjusted to 150 ° C. 50 mL of He gas for GC
/ Min, and a dry ice / ethanol trap was installed at the GC outlet.

The CF obtained in Example 5 described later_Three(CF_ThreeCF_TwoCF_Two
O) CFCOOCF_TwoCF (OCF_TwoCF_TwoCF_Three) CF_Three
(Purity 99%, 50μL) from injection
After that, CF_Three(CF_ThreeCF_TwoCF_TwoO) CFCOF is
Not detected, CF_ThreeCF_TwoCF _TwoOCF = CF_TwoIs quantitative
It was confirmed that it was generated. Product¹⁹F-NMR
(564.6 MHz, solvent CDCl_Three, Standard: CFC
l_Three) Peak coincided with that of the standard.

Example 2 Synthesis Example of CF ₃ CF ₂ CF ₂ OCF = CF ₂ A SUS column having an inner diameter of 20 mm and a length of 1 m and an average particle size of 1
45 m inner diameter filled with 280 g of 60 μm Na ₂ CO ₃
A SUS fluidized bed reactor having a height of 400 mm and a height of 400 mm was connected in series and placed in a salt bath, and the temperature in the salt bath was adjusted to 270 ° C. Nitrogen gas was flowed into the reactor at 1520 mL / min, and CF ₃ (CF ₃ CF ₂ CF ₂ O) CF obtained in Example 5 described later was used.
COOCF ₂ CF (OCF ₂ CF ₂ CF ₃ ) CF ₃ (purity 9
9%) using a metering pump at 60.2 g / h at 1.8.
Feed for hours. A dry ice / ethanol trap was installed at the reactor outlet, and the product was collected. CF
₃ (CF ₃ CF ₂ CF ₂ O) CFCOF is not detected and CF
₃ CF ₂ CF ₂ OCF = CF ₂ was formed in a yield of 80%. ¹⁹ F-NMR of the product (564.6 MHz, solvent CDCl
₃ , reference: CFCl ₃ ) peak coincided with that of the standard.

Example 3 Production Example of Polymer Using the unsaturated compound obtained by the method of Example 2, JP-A-6-3
The polymerization reaction was carried out in the same manner as described in No. 40719. That is, a stainless steel reaction vessel having an inner volume of 1.2 L was degassed, and water (470 g), CF ₂ ClCF ₂ CHClF
(292 g), methanol (19 g), CF ₃ CF ₂ CF ₂ OCF obtained by the method of Example 2 = CF ₂ (35 g), CF ₂ =
CF ₂ (80 g) was charged. While maintaining the temperature at 50 ° C., a 1% by weight solution of di (perfluorobutyryl) peroxide in perfluorohexane was charged as a polymerization initiator to start the reaction.

During the reaction, CF ₂ ＣＦCF ₂ was introduced into the system, and the reaction pressure was maintained at 13.5 kg / cm ² . The polymerization initiator was intermittently charged so that the polymerization rate was almost constant, and a total of 7 cc was charged. After 3.2 hours, 125 g of a white copolymer was obtained in a slurry state. This copolymer has a melting point of 307 ° C., a thermal decomposition starting point of 480 ° C., and 340 ° C.
Good compression molded products were obtained at a molding temperature of. The molded product has a tensile strength of 392 kg / cm ² and a tensile elongation of 367.
%Met.

Example 4 CF ₃ (CF ₃ CF ₂ CF ₂ O) CF
Production Example of COOCH ₂ CH (OCH ₂ CH ₂ CH ₃ ) CH ₃ CH ₃ (CH ₃ CH ₂ CH ₂ O) CHCH ₂ OH (16.5
g) was placed in a flask and stirred while bubbling nitrogen gas through. CF ₃ (CF ₃ CF ₂ CF ₂ O) CFCOF
(46.5 g) was added dropwise over 2 hours while maintaining the internal temperature at 26 to 31 ° C. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours.
Saturated aqueous sodium hydrogen carbonate (50 mL) was added at an internal temperature of 15 ° C or lower. Water (50 mL), chloroform (135 m
L) was added and the mixture was separated to give a chloroform layer as an organic layer. Further, the organic layer was washed with water (50 mL), dried over magnesium sulfate, and then filtered to obtain a crude liquid.

The crude liquid was concentrated by an evaporator and then distilled under reduced pressure to obtain a fraction at 23 to 52 ° C./4.0 kPa (1).
(29 g), 52-61 ° C./3.6-4.0 kPa fraction (2) (19 g), 52-70 ° C./1.3-3.6 k
A fraction (3) (4 g) of Pa was obtained. The GC purity of the fraction (1) was 68%, the fraction (2) was 98%, and the fraction (3) was 9%.
7%. The NMR spectrum of fraction (2) was measured, and the main component was CF ₃ CF (OCF ₂ CF ₂ CF ₃ ) COOC.
It was confirmed to be H ₂ CH (OCH ₂ CH ₂ CH ₃ ) CH ₃ and a mixture of diastereomers.

NMR spectrum of fraction (2) ¹ H-NMR (399.8 MHz, solvent CDCl ₃ , standard: TMS) δ (ppm): 0.90 (t, J = 7.5)
Hz, 3H), 1.20 (d, J = 5.4 Hz, 3
H), 1.50-1.60 (m, 2H), 3.33-
3.50 (m, 2H), 3.64-3.74 (m, 1
H), 4.23-4.29 (m, 1H), 4.34-
4.41 (m, 1H).

¹⁹ F-NMR (376.2 MHz, solvent C
DCl _{3, reference: CFCl 3) δ (ppm)} : - 80.9
(1F), -82.3 (3F), -83.1 (3F),
-87.4 (1F), -130.7 (2F), -13
2.7 (1F).

The fraction (1) and the fraction (3) were analyzed by GC.
The main component contained therein is CF ₃ (CF ₃ CF ₂ CF ₂ O) CF
It was confirmed to be COOCH ₂ CH (OCH ₂ CH ₂ CH ₃ ) CH ₃ .

Example 5 CF ₃ (CF ₃
CF ₂ CF ₂ O) CFCOOCF ₂ CF (OCF ₂ CF ₂ C
F ₃ ) Production Example of CF ₃ The fraction (2) obtained in Example 4 and the fraction (3) were mixed, and 19.5 g of the fraction was dissolved in R-113 (250 g) to obtain a fraction solution. . Meanwhile, NaF (26.1 g) was placed in a 500 mL nickel autoclave, and 1,1,2-trichlorotrifluoroethane (R-113, 324 g) was added.
Was added, and the mixture was stirred and cooled to -10 ° C. After blowing nitrogen gas for 1 hour, fluorine gas diluted to 20% with nitrogen gas is blown for 1 hour at a flow rate of 5.66 L / h, and while blowing at the same flow rate, the fraction solution is applied for 19.4 hours. And injected.

Next, a 1,1,2-trichlorotrifluoroethane solution (0.01 g / mL) of benzene was injected while blowing fluorine gas diluted to 20% with nitrogen gas while maintaining the above flow rate. The outlet valve of the autoclave was closed, and when the pressure reached 0.12 MPa, the operation of closing the inlet valve of the autoclave and continuing stirring for 1 hour was performed.

Further, the operation was carried out from -10 ° C. to room temperature.
The procedure was repeated four times during the heating and then five times at room temperature. this
In between, benzene total 0.291 g, R-113 total
45.0 g were injected. Then, blow in nitrogen gas for 2 hours
And the reaction mixture was removed by decantation. Get
The concentrated crude liquid is concentrated using an evaporator.¹⁹Generated by F-NMR
When the product was quantified, the yield was 69%. One of the crude liquid
Part of the purified CF_Three(CF_ThreeCF
_TwoCF_TwoO) CFCOOCF_TwoCF (OCF_TwoCF _TwoCF_Three)
CF_ThreeI got The product is a mixture of diastereomers.
Was.

Boiling point: 46 to 51 ° C./5.2 kPa.

High resolution mass spectrum (CI
Method) 664.9496 (M + H. Theoretical value: C ₁₂ HF ₂₄ O
₄ = 664.9492).

¹⁹ F-NMR (564.6 MHz, solvent C
DCl ₃ / C ₆ F _{6, reference: CFCl 3) δ (ppm)} : -
80.6 (1F), -80.8 and -80.9
(3F), -81.6 to -83.1 (2F), -82.
6 (6F), -82.8 (3F), -86.7 (1
F), -87.4 (1F), -87.5 (1F), -1
30.6 (4F), -132.2 (1F), -145.
7 and -145.9 (1F).

¹³ C-NMR (150.8 MHz, solvent C
DCl ₃ / C ₆ F ₆ , standard: CDCl ₃ ) δ (ppm): 1
00.26 and 100.28, 102.8, 10
6.8, 107.0, 116.0, 116.2, 11
6.5 and 116.6, 117.4, 117.
5,117.9,117.9,152.2 and 1
52.3.

[0096]

According to the present invention, a compound (formula B) which has been difficult to synthesize or a compound (formula B) which has been synthesized by an economically disadvantageous method can be converted from a compound (formula A). It can be manufactured in a short process and in high yield. The compound (Formula A) is generally easily available, easily synthesized, and inexpensive, and compounds having various structures are available.

Further, R ^aH in the formula A, further R ^bH ,
R ^cH, R ^dH, by appropriately selecting the structures of R ^eH, easily dissolved in a solvent at fluorination, since capable Advances the fluorination reaction in a liquid phase, in high yield fluorination reaction A compound (formula A) which can be carried out and can be used as a raw material for a thermal decomposition reaction can be advantageously produced.

In particular, by appropriately selecting the structure of R ^{aH in} the formula A, the separation of the products (formula B) and (formula C) becomes unnecessary. Further, the compound (formula B) can be produced in a continuous process by recycling the produced compound (formula C) as a compound (formula B) again in the reaction with the compound (formula A). Furthermore, according to the present invention, a novel compound useful as a fluororesin raw material is provided.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 34/00 C08F 34/00 // C07B 61/00 300 C07B 61/00 300 (72) Inventor Shin Tachimatsu Asahi Glass Co., Ltd., 1150 Hazawa-machi, Kanagawa-ku, Yokohama-shi, Kanagawa-ken 1150 Asahi Glass Co., Ltd. F-term (reference) 4H006 AA01 AC26 AC30 BA02 BA06 BA33 BC10 BC13 BD70 BM10 BM71 GP01 GP20 KA31 4H039 CA21 CG90 4J100 AE38P AE39P AR32P AU28P BB01P BB17P CA01

Claims (13)

[Claims] 1. A method for producing an unsaturated compound represented by the following formula B by a thermal decomposition reaction of a compound represented by the following formula A. ## STR1 ## where _{^{R a COOCF 2 CR b R c}} -CXR d R e ··· formula ^{A CR b R c = CR d} R e ··· formula ^{B, R a, R b,} R c, R d, ^Re : each independently represents a hydrogen atom, a halogen atom, or a monovalent organic group which is not changed by a thermal decomposition reaction. Also, R ^b , R ^c , R ^d , and R ^e
Two selected from the group may be linked to each other to form a divalent organic group that does not change by thermal decomposition, and the remaining two may be linked to each other to form a divalent organic group that does not change by thermal decomposition; Alternatively, each independently may be a hydrogen atom, a halogen atom, or a monovalent organic group which is not changed by a thermal decomposition reaction. X: halogen atom. 2. The process according to claim 1, wherein a compound represented by the following formula C is obtained together with the unsaturated compound represented by the formula B. ## STR2 ## R ^a COF · · · formula C provided that, R ^a is as defined above. Wherein R ^a is ^{-CR b R c -CXR d R e} ( where
R ^b , R ^c , R ^d , R ^e , and X are the same as defined above. )
The manufacturing method according to claim 1, wherein 4. The compound represented by the formula A is a compound represented by the following formula ^AF , and the unsaturated compound represented by the formula B is represented by the following formula B:
An unsaturated compound represented by ^F, the production method according to claim 1, 2 or 3, compounds of the formula C is a compound represented by the following formula C ^F. ## STR3 ## _{^{R af COOCF 2 CR bf R cf}} -CXR df R ef ··· formula ^{A F CR bf R cf = CR} df R ef ··· formula B ^F R ^af COF ··· formula C ^F wherein, R ^af : a fluorine atom, a perfluoroalkyl group, a perfluoro (etheric oxygen atom-containing alkyl) group, a perfluoro (partial chloroalkyl) group, or a perfluoro (partial chloro (etheric oxygen atom-containing alkyl))
Base. R ^bf , R ^cf , R ^df , and R ^ef each independently represent a fluorine atom, a perfluoroalkyl group, a perfluoro (etheric oxygen atom-containing alkyl) group, a perfluoro (partial chloroalkyl) group, or a perfluoro (partial chloro (etheric An oxygen atom-containing alkyl)) group; Or R ^bf ,
Two selected from R ^cf , R ^df , and R ^ef are connected to each other,
Forming a perfluoroalkylene group, a perfluoro (etheric oxygen atom-containing alkylene) group, a perfluoro (partial chloroalkylene) group, or a perfluoro (partial chloro (etheric oxygen atom-containing alkylene)) group;
The other two are linked to each other to form a perfluoroalkylene group, a perfluoro (etheric oxygen atom-containing alkylene) group, a perfluoro (partial chloroalkylene) group, or a perfluoro (partial chloro (etheric oxygen atom-containing alkylene) group). May be formed, or
Each independently a fluorine atom, a perfluoroalkyl group, a perfluoro (etheric oxygen atom-containing alkyl)
A perfluoro (partial chloroalkyl) group or a perfluoro (partial chloro (etheric oxygen atom containing alkyl)) group. X: halogen atom. Wherein R ^af is ^{-CR bf R cf -CXR df R ef} ( provided ^{that, R bf, R cf, R} df, R ef, and X are as defined above.) Is that in claim 4 The manufacturing method as described. 6. The method according to claim 4, wherein at least one of R ^bf , R ^cf , R ^df , and R ^ef is a perfluoroalkoxyl group or a perfluoro (partial chloroalkoxyl) group. 7. A compound represented by formula A ^F is prepared according to claim 4, 5 or 6 which is a compound prepared by fluorinating a compound represented by the following formula a ³ in the liquid phase Method. Embedded image _{^{R aH COOCH 2 CR bH R cH}} -CXR dH R eH ··· formula a ³ However, R ^aH: a group corresponding to R ^af, an alkyl group, an etheric oxygen atom-containing alkyl group, partially chlorinated A group selected from an alkyl group and a partial chloro (etheric oxygen atom-containing alkyl) group, a group in which at least one hydrogen atom in the group is substituted by a fluorine atom, one of carbon-carbon single bonds in the group A group in which at least one is substituted by a carbon-carbon double bond or a carbon-carbon triple bond, or a hydrogen atom. R ^bH , R ^cH , R ^dH , R ^eH : R ^bH is R ^bf , R ^cH is R
^cf , R ^dH is a group corresponding to R ^df , R ^eH is a group corresponding to R ^ef ,
A group selected from an alkyl group, an etheric oxygen atom-containing alkyl group, a partial chloroalkyl group, and a partial chloro (etheric oxygen atom-containing alkyl) group, wherein at least one hydrogen atom in the group is a fluorine atom Wherein at least one of the carbon-carbon single bonds in the group is carbon-
A group substituted by a carbon double bond or a carbon-carbon triple bond, a hydrogen atom, or a fluorine atom. Or R ^bH ,
Two selected from R ^cH , R ^dH and R ^eH are connected to each other,
Alkylene group, etheric oxygen atom-containing alkylene group,
A group selected from a partial chloroalkylene group and a partial chloro (alkylene containing an etheric oxygen atom) group, a group in which at least one hydrogen atom in the group is substituted by a fluorine atom, or a carbon-carbon single atom in the group One or more of the bonds is a group substituted with a carbon-carbon double bond or a carbon-carbon triple bond, and the remaining two are linked to each other to form an alkylene group;
A group selected from an etheric oxygen atom-containing alkylene group, a partial chloroalkylene group, and a partial chloro (etheric oxygen atom-containing alkylene) group;
A group in which one or more carbon atoms are substituted with a fluorine atom, or a group in which one or more carbon-carbon single bonds are substituted with a carbon-carbon double bond or a carbon-carbon triple bond,
Alternatively, each independently, a group selected from an alkyl group, an etheric oxygen atom-containing alkyl group, a partial chloroalkyl group, and a partial chloro (etheric oxygen atom-containing alkyl) group, wherein one or more of the hydrogen atoms in the group are A group substituted with a fluorine atom, a group in which at least one carbon-carbon single bond in the group is substituted with a carbon-carbon double bond or a carbon-carbon triple bond, a hydrogen atom, or a fluorine atom Good. X: halogen atom. 8. The process according to claim 1, wherein the compound represented by the formula A has a boiling point of 350 ° C. or lower (normal pressure). 9. The compound represented by the formula A is used at a temperature exceeding 250.degree.
The thermal decomposition reaction is performed by heating to 0 ° C.
9. The production method according to any one of the above items 8. 10. The method according to claim 1, wherein the thermal decomposition reaction is performed by a gas phase reaction. 11. A thermal decomposition reaction in the presence of glass, an alkali metal salt or an alkaline earth metal salt.
0. The production method according to item 0. 12. An unsaturated compound represented by the formula B produced by the method according to claim 1, or a polymerizable monomer capable of polymerizing the unsaturated compound and the unsaturated compound.
And a method for producing a polymer. 13. A polymer produced by the production method according to claim 12.