WO2023189217A1

WO2023189217A1 - Method for producing fluorine-containing cyclic olefin composition, and fluorine-containing cyclic olefin composition

Info

Publication number: WO2023189217A1
Application number: PCT/JP2023/008150
Authority: WO
Inventors: 啓介川島; 慎吾山本; 謙一藤井; 隆志中野
Original assignee: 三井化学株式会社
Priority date: 2022-03-29
Filing date: 2023-03-03
Publication date: 2023-10-05
Also published as: TW202340125A

Abstract

This method for producing a fluorine-containing cyclic olefin composition includes: a mixing step for mixing an acid catalyst and one or more types of hydroxyl group-containing compounds (C) which are selected from the group consisting of water and alkyl alcohol into a composition (X) which contains a fluorine-containing cyclic olefin compound (A) represented by formula (1) and a cyclic diolefin compound (B1) which does not contain fluorine; and a reaction step for obtaining one or more types of compound selected from the group consisting of a hydrate compound (B2) which does not contain fluorine and an ether compound (B3) which does not contain fluorine, by reacting the cyclic diolefin compound (B1) which does not contain fluorine and the hydroxyl group-containing compounds (C) with one another.

Description

Method for producing fluorine-containing cyclic olefin composition and fluorine-containing cyclic olefin composition

The present invention relates to a method for producing a fluorine-containing cyclic olefin composition and a fluorine-containing cyclic olefin composition.

A fluorine-containing cyclic olefin compound that is a raw material for a fluorine-containing cyclic olefin polymer can be produced, for example, by subjecting a fluorine-containing olefin and a cyclic polyene to a Diels-Alder reaction.
Examples of techniques related to the method for producing such fluorine-containing cyclic olefin compounds include those described in Patent Document 1.

Patent Document 1 describes a process for producing a fluorine-containing cyclic olefin monomer, which includes a step (A) of continuously producing a fluorine-containing cyclic olefin monomer by continuously reacting a fluorine-containing olefin and a cyclic polyene in a reaction vessel. In the step (A), the cyclic polyene is continuously or intermittently supplied into the reaction vessel, and the fluorine-containing olefin is continuously or intermittently supplied into the reaction vessel, or By charging the fluorine-containing olefin and the cyclic polyene into the reaction vessel, the fluorine-containing olefin and the cyclic polyene can be continuously reacted, and the content of the fluorine-containing olefin relative to the content of the cyclic polyene in the reaction vessel X ₁ . A method for producing a fluorine-containing cyclic olefin monomer is described in which _{the molar ratio X 2} _/ X ₁ of X 2 is adjusted within a range of 1.01 or more. Patent Document 1 describes that according to the production method, the target fluorine-containing cyclic olefin monomer can be obtained with high selectivity.

JP2019-89714A

According to the studies of the present inventors, when producing a fluorine-containing cyclic olefin compound using a fluorine-containing olefin and a cyclic polyene, the cyclic polyenes undergo a Diels-Alder reaction with each other, and a fluorine-free cyclic diolefin compound is produced as a by-product. It became clear that it would occur as a thing. Since fluorine-free cyclic diolefin compounds are highly reactive, undesired side reactions may occur when using fluorine-containing cyclic olefin compounds containing fluorine-free cyclic diolefin compounds as by-products. there were.
On the other hand, the boiling point difference between the target product, the fluorine-containing cyclic olefin compound, and the by-product, the fluorine-free cyclic diolefin compound, may be small. It was sometimes difficult to separate compounds.

The present invention has been made in view of the above circumstances, and provides a manufacturing method capable of obtaining a fluorine-containing cyclic olefin composition with a reduced content of a fluorine-free cyclic diolefin compound.

The present inventors have made extensive studies to solve the above problems. As a result, by hydrating and/or etherifying the by-product fluorine-free cyclic diolefin compound with the hydroxyl group-containing compound, the target fluorine-containing cyclic olefin compound and the fluorine-free by-product It has been discovered that it is possible to obtain a fluorine-containing cyclic olefin composition that can be easily separated from a fluorine-containing cyclic diolefin compound and has a reduced content of a fluorine-free cyclic diolefin compound as a by-product, and has developed the present invention. Completed.
According to the present invention, a method for producing a fluorine-containing cyclic olefin composition and a fluorine-containing cyclic olefin composition shown below are provided.

[1]
For a composition (X) containing a fluorine-containing cyclic olefin compound (A) and a fluorine-free cyclic diolefin compound (B1) represented by the following formula (1), an acid catalyst and a compound selected from the group consisting of water and an alkyl alcohol. a mixing step of mixing at least one selected hydroxyl group-containing compound (C);
By reacting the fluorine-free cyclic diolefin compound (B1) with the hydroxyl group-containing compound (C), a compound selected from the group consisting of a fluorine-free hydrated compound (B2) and a fluorine-free ether compound (B3) is produced. a reaction step for obtaining at least one type of
A method for producing a fluorine-containing cyclic olefin composition.

(In the above formula (1), at least one of R ¹ to R ⁴ is fluorine, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a fluorine-containing alkoxy group having 1 to 10 carbon atoms, or It is an alkoxyalkyl group having 2 to 10 carbon atoms containing fluorine, and when R ¹ to R ⁴ are groups not containing fluorine, R ¹ to R ⁴ are hydrogen, an alkyl group having 1 to 10 carbon atoms, or selected from alkoxy groups having 1 to 10 carbon atoms or alkoxyalkyl groups having 2 to 10 carbon atoms, R ¹ to R ⁴ may be bonded to each other to form a ring structure, and X is -CH ₂ - or O -, n indicates 0 or 1)
[2]
The fluorine-containing cyclic olefin according to [1] above, wherein the absolute value of the difference between the boiling point of the fluorine-containing cyclic olefin compound (A) and the boiling point of the non-fluorine-containing cyclic diolefin compound (B1) is 10°C or less Method for manufacturing the composition.
[3]
The method for producing a fluorine-containing cyclic olefin composition according to [1] or [2] above, wherein the alkyl alcohol has 3 or more and 10 or less carbon atoms.
[4]
The method for producing a fluorine-containing cyclic olefin composition according to any one of [1] to [3] above, wherein the acid catalyst contains at least one selected from the group consisting of inorganic acids, organic acids, and solid acids.
[5]
The absolute value of the difference between the HOMO energy (E ₁ ) of the fluorine-containing cyclic olefin compound (A) and the HOMO energy (E ₂ ) of the fluorine-free cyclic diolefin compound (B1) |E ₂ −E ₁ | The method for producing a fluorine-containing cyclic olefin composition according to any one of [1] to [4] above, which has a voltage of 0.3 eV or more.
[6]
The fluorine-containing cyclic olefin compound (A) is a fluorine-containing cyclic olefin compound (A1) in which n is 0 in the formula (1) and a fluorine-containing cyclic olefin compound (A2) in which n is 1 in the formula (1). The method for producing a fluorine-containing cyclic olefin composition according to any one of [1] to [5] above, comprising both of the above.
[7]
The fluorine-containing cyclic olefin composition according to [6], further comprising a separation step of separating the fluorine-containing cyclic olefin compound (A1) and the fluorine-containing cyclic olefin compound (A2) by distillation after the reaction step. How things are manufactured.
[8]
After the reaction step, separation of the fluorine-containing cyclic olefin compound (A), at least one selected from the group consisting of the fluorine-free hydrated compound (B2) and the fluorine-free ether compound (B3) is performed by distillation. The method for producing a fluorine-containing cyclic olefin composition according to any one of [1] to [7] above, further comprising a separation step of separating.
[9]
The content of the fluorine-free cyclic diolefin compound (B1) in the fluorine-containing cyclic olefin composition is 5.0% by mass or less when the entire fluorine-containing cyclic olefin composition is 100% by mass. , the method for producing a fluorine-containing cyclic olefin composition according to any one of [1] to [8] above.
[10]
When the content of the fluorine-containing cyclic olefin compound (A1) in which n is 0 in the formula (1) in the fluorine-containing cyclic olefin composition is 100% by mass of the entire fluorine-containing cyclic olefin composition. , 99.0% by mass or more, the method for producing a fluorine-containing cyclic olefin composition according to [8] above.
[11]
When the content of the fluorine-containing cyclic olefin compound (A2) in which n is 1 in the formula (1) in the fluorine-containing cyclic olefin composition is 100% by mass of the entire fluorine-containing cyclic olefin composition. , 99.0% by mass or more, the method for producing a fluorine-containing cyclic olefin composition according to [8] above.
[12]
A fluorine-containing cyclic olefin composition comprising a fluorine-containing cyclic olefin compound (A) and a fluorine-free cyclic diolefin compound (B1) represented by the following formula (1),
The content of the fluorine-free cyclic diolefin compound (B1) in the fluorine-containing cyclic olefin composition is more than 0% by mass and 1.0% by mass when the entire fluorine-containing cyclic olefin composition is 100% by mass. % or less.

(In the above formula (1), at least one of R ¹ to R ⁴ is fluorine, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a fluorine-containing alkoxy group having 1 to 10 carbon atoms, or It is an alkoxyalkyl group having 2 to 10 carbon atoms containing fluorine, and when R ¹ to R ⁴ are groups not containing fluorine, R ¹ to R ⁴ are hydrogen, an alkyl group having 1 to 10 carbon atoms, or selected from alkoxy groups having 1 to 10 carbon atoms or alkoxyalkyl groups having 2 to 10 carbon atoms, R ¹ to R ⁴ may be bonded to each other to form a ring structure, and X is -CH ₂ - or O -, n indicates 0 or 1)

According to the present invention, it is possible to provide a manufacturing method capable of obtaining a fluorine-containing cyclic olefin composition with a reduced content of a fluorine-free cyclic diolefin compound.

Hereinafter, the present invention will be described based on embodiments. In this embodiment, unless otherwise specified, "A to B" indicating a numerical range represents A or more and B or less. Moreover, when numerical ranges are described in stages, the upper and lower limits of each numerical range can be arbitrarily combined.

1. Method for producing a fluorine-containing cyclic olefin composition The method for producing a fluorine-containing cyclic olefin composition of the present invention comprises a fluorine-containing cyclic olefin compound (A) represented by the following formula (1) and a fluorine-free cyclic diolefin compound (B1). a mixing step of mixing an acid catalyst and at least one hydroxyl group-containing compound (C) selected from the group consisting of water and an alkyl alcohol; By reacting the olefin compound (B1) with the hydroxyl group-containing compound (C), at least one selected from the group consisting of a fluorine-free hydrated compound (B2) and a fluorine-free ether compound (B3) is obtained. A reaction step.
Here, in this specification, the reaction product of the fluorine-free cyclic diolefin compound (B1) and water is referred to as the fluorine-free hydrated compound (B2), and the fluorine-free cyclic diolefin compound (B1) and the alkyl The reaction product with alcohol is called a fluorine-free ether compound (B3). That is, in the method for producing a fluorine-containing cyclic olefin composition of the present invention, when the hydroxyl group-containing compound (C) contains water, the fluorine-free cyclic diolefin compound (B1) and the hydroxyl group-containing compound (C) are reacted. When the hydroxyl group-containing compound (C) contains an alkyl alcohol, the fluorine-free cyclic diolefin compound (B1) and the hydroxyl group-containing compound (C) are combined. The method includes a reaction step of obtaining a fluorine-free ether compound (B3) by reacting the following.

In the formula (1), at least one of R ¹ to R ⁴ is fluorine, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a fluorine-containing alkoxy group having 1 to 10 carbon atoms, or fluorine. is an alkoxyalkyl group having 2 to 10 carbon atoms, and when R ¹ to R ⁴ are groups not containing fluorine, R ¹ to R ⁴ are hydrogen, an alkyl group having 1 to 10 carbon atoms, or an alkoxyalkyl group having 1 to 10 carbon atoms. selected from an alkoxy group having 1 to 10 carbon atoms or an alkoxyalkyl group having 2 to 10 carbon atoms, R ¹ to R ⁴ may be bonded to each other to form a ring structure, and X is -CH ₂ - or O- , and n represents 0 or 1.

According to the method for producing a fluorine-containing cyclic olefin composition according to the present invention, it is possible to obtain a fluorine-containing cyclic olefin composition in which the content of a fluorine-free cyclic diolefin compound is reduced.
The reason why such an effect is obtained is presumed to be as follows.
By reacting the fluorine-free cyclic diolefin compound (B1) and the hydroxyl group-containing compound (C) in the presence of an acid catalyst, the hydroxyl group-containing compound (C) is added to the fluorine-free cyclic diolefin compound (B1). The addition produces a fluorine-free hydrated compound (B2) or a fluorine-free ether compound (B3). Thereby, the content of the fluorine-free cyclic diolefin compound (B1) in the fluorine-containing cyclic olefin composition can be reduced.
Furthermore, the boiling point difference between the fluorine-free hydrated compound (B2) or the fluorine-free ether compound (B3) and the fluorine-containing cyclic olefin compound (A) is the same as that between the fluorine-free cyclic diolefin compound (B1) and the fluorine-containing cyclic olefin compound. Since the boiling point difference is larger than that of compound (A), the fluorine-free hydrated compound (B2) or the fluorine-free ether compound (B3) can be easily separated from the fluorine-containing cyclic olefin composition by distillation. Therefore, according to the method for producing a fluorine-containing cyclic olefin composition according to the present invention, by-products can be easily separated, so it is possible to obtain a fluorine-containing cyclic olefin composition with improved purity.
Each step will be explained below.

[Mixing process]
The method for producing a fluorine-containing cyclic olefin composition according to the present invention includes a composition (X) containing a fluorine-containing cyclic olefin compound (A) represented by the above formula (1) and a fluorine-free cyclic diolefin compound (B1). On the other hand, it includes a mixing step of mixing an acid catalyst and at least one hydroxyl group-containing compound (C) selected from the group consisting of water and alkyl alcohol.

(Composition (X))
Composition (X) contains a fluorine-containing cyclic olefin compound (A) and a fluorine-free cyclic diolefin compound (B1).
Composition (X) is, for example, a composition obtained by subjecting a fluorine-containing olefin and a cyclic polyene to a Diels-Alder reaction.

In the formula (1), at least one of R ¹ to R ⁴ is fluorine, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a fluorine-containing alkoxy group having 1 to 10 carbon atoms, or fluorine. is an alkoxyalkyl group having 2 to 10 carbon atoms, and when R ¹ to R ⁴ are groups not containing fluorine, R ¹ to R ⁴ are hydrogen, an alkyl group having 1 to 10 carbon atoms, or an alkoxyalkyl group having 1 to 10 carbon atoms. It is selected from an alkoxy group having 1 to 10 carbon atoms or an alkoxyalkyl group having 2 to 10 carbon atoms, and R ¹ to R ⁴ may be bonded to each other to form a ring structure. Among these, R ¹ to R ⁴ are preferably fluorine or a fluorine-containing alkyl group having 1 to 4 carbon atoms, more preferably fluorine or a trifluoromethyl group, and one of R ¹ to R ⁴ is trifluoromethyl. It is more preferable that the remainder be fluorine.
X represents -CH ₂ - or O-, preferably -CH ₂ -.
n represents 0 or 1, preferably 1.

In the formula (1), R ¹ to R ⁴ more specifically include fluorine; fluoromethyl group, difluoromethyl group, trifluoromethyl group, trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group. , hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro-2-methylisopropyl group, perfluoro-2-methylisopropyl group, n-perfluorobutyl group, n-perfluoropentyl group, perfluorocyclopentyl group, etc. An alkyl group containing 1 to 10 carbon atoms containing fluorine, such as an alkyl group partially or completely substituted with fluorine; a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, a trifluoroethoxy group, a pentafluoroethoxy group, Heptafluoropropoxy group, hexafluoroisopropoxy group, heptafluoroisopropoxy group, hexafluoro-2-methylisopropoxy group, perfluoro-2-methylisopropoxy group, n-perfluorobutoxy group, n-perfluoropentoxy group, perfluoro A fluorine-containing alkoxy group having 1 to 10 carbon atoms, such as an alkoxy group in which some or all of the hydrogen atoms of an alkoxy group such as a cyclopentoxy group are substituted with fluorine; fluoromethoxymethyl group, difluoromethoxymethyl group, trifluoro Methoxymethyl group, trifluoroethoxymethyl group, pentafluoroethoxymethyl group, heptafluoropropoxymethyl group, hexafluoroisopropoxymethyl group, heptafluoroisopropoxymethyl group, hexafluoro-2-methylisopropoxymethyl group, perfluoro-2 - Alkoxyalkyl groups in which some or all of the hydrogen atoms of an alkoxy group are substituted with fluorine, such as methylisopropoxymethyl group, n-perfluorobutoxymethyl group, n-perfluoropentoxymethyl group, perfluorocyclopentoxymethyl group, etc. Examples include fluorine-containing alkoxyalkyl groups having 2 to 10 carbon atoms.

Further, R ¹ to R ⁴ may be bonded to each other to form a ring structure, or may form a ring such as a perfluorocycloalkyl group or a perfluorocycloether group via oxygen.
Furthermore, other R ¹ to R ⁴ that do not contain fluorine include hydrogen; methyl group, ethyl group, propyl group, isopropyl group, 2-methylisopropyl group, n-butyl group, n-pentyl group, cyclopentyl group, etc. Alkyl group having 1 to 10 carbon atoms; alkoxy group having 1 to 10 carbon atoms such as methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group, methoxymethyl group, ethoxymethyl group, propoxymethyl group, butoxymethyl group, Examples include alkoxyalkyl groups having 2 to 10 carbon atoms such as pentoxymethyl group.

The fluorine-containing cyclic olefin compound (A) is, for example, a composition obtained by subjecting a fluorine-containing olefin and a cyclic polyene to a Diels-Alder reaction, and is a fluorine-containing cyclic olefin compound in which n is 0 in the formula (1) above. There may be a mixture containing both (A1) and the fluorine-containing cyclic olefin compound (A2) in which n is 1 in the formula (1).
In the case of a mixture containing both the fluorine-containing cyclic olefin compound (A1) in which n is 0 in the formula (1) and the fluorine-containing cyclic olefin compound (A2) in which n is 1 in the formula (1), the fluorine-containing In the cyclic olefin compound (A1) and the fluorine-containing cyclic olefin compound (A2), in the formula (1), X is -CH ₂ -, and R ¹ to R ⁴ are fluorine or a trifluoromethyl group. Preferably, one of R ¹ to R ⁴ is a trifluoromethyl group, and the remaining ones are more preferably fluorine.

The fluorine-containing cyclic olefin compound (A) preferably contains at least one selected from fluorine-containing tetracyclododecene, fluorine-containing norbornene, fluorine-containing oxotetracyclododecene, and fluorine-containing oxonorbornene, and more preferably fluorine-containing It contains at least one selected from tetracyclododecene and fluorine-containing norbornene, and more preferably contains fluorine-containing tetracyclododecene.
Here, tetracyclododecene means tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene. Norbornene refers to bicyclo[2.2.1]hept-2-ene. Further, oxonorbornene refers to oxabicyclo[2.2.1]hept-2-ene.
The fluorine-containing tetracyclododecene is a fluorine-containing cyclic olefin in which X is -CH ₂ - and n is 1 in the formula (1).
The fluorine-containing norbornene is a fluorine-containing cyclic olefin in which, in the formula (1), X is -CH ₂ - and n is 0.
The fluorine-containing oxotetracyclododecene is a fluorine-containing cyclic olefin in which X is -O- and n is 1 in the formula (1).
The fluorine-containing oxonorbornene is a fluorine-containing cyclic olefin in which X is -O- and n is 0 in the formula (1).

(Fluorine-containing olefin)
As the fluorine-containing olefin, for example, a fluorine-containing olefin represented by the following formula (2) can be used.

In the formula (2), at least one of R ¹ to R ⁴ is fluorine, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a fluorine-containing alkoxy group having 1 to 10 carbon atoms, or fluorine. is an alkoxyalkyl group having 2 to 10 carbon atoms, and when R ¹ to R ⁴ are groups not containing fluorine, R ¹ to R ⁴ are hydrogen, an alkyl group having 1 to 10 carbon atoms, or an alkoxyalkyl group having 1 to 10 carbon atoms. It is selected from an alkoxy group having 1 to 10 carbon atoms or an alkoxyalkyl group having 2 to 10 carbon atoms, and R ¹ to R ⁴ may be bonded to each other to form a ring structure. Among these, R ¹ to R ⁴ are preferably fluorine or a fluorine-containing alkyl group having 1 to 4 carbon atoms, more preferably fluorine or a trifluoromethyl group, and one of R ¹ to R ⁴ is trifluoromethyl. It is more preferable that the remainder be fluorine.

In the formula (2), R ¹ to R ⁴ more specifically include fluorine; fluoromethyl group, difluoromethyl group, trifluoromethyl group, trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group. , hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro-2-methylisopropyl group, perfluoro-2-methylisopropyl group, n-perfluorobutyl group, n-perfluoropentyl group, perfluorocyclopentyl group, etc. An alkyl group containing 1 to 10 carbon atoms containing fluorine, such as an alkyl group partially or completely substituted with fluorine; a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, a trifluoroethoxy group, a pentafluoroethoxy group, Heptafluoropropoxy group, hexafluoroisopropoxy group, heptafluoroisopropoxy group, hexafluoro-2-methylisopropoxy group, perfluoro-2-methylisopropoxy group, n-perfluorobutoxy group, n-perfluoropentoxy group, perfluoro A fluorine-containing alkoxy group having 1 to 10 carbon atoms, such as an alkoxy group in which some or all of the hydrogen atoms of an alkoxy group such as a cyclopentoxy group are substituted with fluorine; fluoromethoxymethyl group, difluoromethoxymethyl group, trifluoro Methoxymethyl group, trifluoroethoxymethyl group, pentafluoroethoxymethyl group, heptafluoropropoxymethyl group, hexafluoroisopropoxymethyl group, heptafluoroisopropoxymethyl group, hexafluoro-2-methylisopropoxymethyl group, perfluoro-2 - Alkoxyalkyl groups in which some or all of the hydrogen atoms of an alkoxy group are substituted with fluorine, such as methylisopropoxymethyl group, n-perfluorobutoxymethyl group, n-perfluoropentoxymethyl group, perfluorocyclopentoxymethyl group, etc. Examples include fluorine-containing alkoxyalkyl groups having 2 to 10 carbon atoms.

(cyclic polyene)
Examples of the cyclic polyene include cyclopentadiene, cyclohexadiene, ethylcyclohexadiene, cycloheptadiene, dicyclopentadiene, dicyclohexadiene, 1-oxa-2,4-cyclopentadiene, 1-oxa-2-ethyl-2, 4-cyclopentadiene, 1-oxa-2-vinyl-2,4-cyclopentadiene, ethylidenenorbornene, vinylnorbornene, isopropylidenenorbornene, methylhydroindene, diisopropylidenenorbornene, propenylisonorbornadiene, and the like can be used.
These cyclic polyenes may be used singly or in combination of two or more.
Among these, as the cyclic polyene, cyclopentadiene, dicyclopentadiene, and 1-oxa-2,4-cyclopentadiene (commonly referred to as furan) are preferred, dicyclopentadiene and furan are more preferred, and dicyclopentadiene is preferred. is even more preferable.

(Fluorine-free cyclic diolefin compound (B1))
The fluorine-free cyclic diolefin compound (B1) is, for example, a compound obtained by a Diels-Alder reaction between the cyclic polyenes, and examples thereof include dicyclopentadiene, tricyclopentadiene, and the like. The fluorine-free cyclic diolefin compound (B1) may contain at least one selected from dicyclopentadiene and tricyclopentadiene.

In the composition (X), when the absolute value of the difference between the boiling point of the fluorine-containing cyclic olefin compound (A) and the boiling point of the fluorine-free cyclic diolefin compound (B1) is 10°C or less, the fluorine-containing cyclic olefin compound is removed by distillation. Since it is difficult to separate the olefin compound (A) and the fluorine-free cyclic diolefin compound (B1), from the viewpoint of obtaining a fluorine-containing cyclic olefin composition with improved purity, the fluorine-containing cyclic olefin composition according to the present invention is The manufacturing method is effective.
In this specification, the boiling point refers to the boiling point at 1 atmosphere.

(acid catalyst)
The acid catalyst is not particularly limited as long as it is a Brønsted acid, and includes at least one selected from the group consisting of inorganic acids, organic acids, and solid acids.
Examples of the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid.
Examples of the organic acid include methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, 10-camphorsulfonic acid, and trifluoroacetic acid.
Examples of the solid acid include strong acidic cation exchange resins having sulfonic acid groups.
Among these, strongly acidic cation exchange resins are preferred from the viewpoint that the acid catalyst can be separated by filtration without performing a step of neutralizing and extracting the used acid with an alkaline solution such as an aqueous sodium hydroxide solution after the reaction. Furthermore, from the viewpoint of increasing the contact area with the reaction substrate, a strongly acidic cation exchange resin having a macroporous structure with a large surface area is preferred.
The acid dissociation constant (pKa) of the acid catalyst is preferably 2 or less from the viewpoint of further improving the reactivity between the fluorine-free cyclic diolefin compound (B1) and the hydroxyl group-containing compound (C).

The mixing amount of the acid catalyst in the mixing step is preferably from the viewpoint of further improving the reactivity between the fluorine-free cyclic diolefin compound (B1) and the hydroxyl group-containing compound (C) based on 100 parts by mass of the composition (X). is 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.1 parts by mass or more, even more preferably 0.5 parts by mass or more, still more preferably 1.0 parts by mass or more, and even more preferably is 1.5 parts by mass or more, and preferably 50 parts by mass or less, more preferably 30 parts by mass or less, still more preferably 25 parts by mass or less, still more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less. , more preferably 10 parts by mass or less.

(Hydroxy group-containing compound (C))
The hydroxyl group-containing compound (C) is at least one selected from the group consisting of water and alkyl alcohol. Alkyl alcohol is preferred because it increases the difference between the boiling point of the fluorine-containing cyclic olefin compound (A) and the boiling point of the fluorine-free ether compound (B3) to facilitate separation in the separation step.
The number of carbon atoms in the alkyl alcohol is determined from the viewpoints of increasing the reaction temperature by increasing the boiling point of the alkyl alcohol to further improve the reactivity between the fluorine-free cyclic diolefin compound (B1) and the hydroxyl group-containing compound (C), and From the viewpoint of increasing the difference in boiling point from the containing cyclic olefin compound (A) to facilitate separation in the separation step, it is preferably 3 or more, and preferably 10 or less, more preferably 8 or less, and even more preferably 6 It is as follows. From these viewpoints, the number of carbon atoms in the alkyl alcohol is preferably 3 or more and 10 or less, more preferably 3 or more and 8 or less, and still more preferably 3 or more and 6 or less.
From the viewpoint of further improving the reactivity between the fluorine-free cyclic diolefin compound (B1) and the hydroxyl group-containing compound (C), the alkyl alcohol is preferably 1-propanol, 2-propanol, 1-butanol, or 2-butanol. , 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 1-hexanol, 2-hexanol, 1-heptanol, 2-heptanol, 1-octanol, 1-nonanol and 1-decanol, more preferably at least one selected from the group consisting of 1-propanol, 1-butanol, 1-pentanol, and 1-hexanol.

The amount of the hydroxyl group-containing compound (C) mixed in the mixing step is such that the reactivity between the fluorine-free cyclic diolefin compound (B1) and the hydroxyl group-containing compound (C) is further improved based on 100 parts by mass of the composition (X). From this point of view, it is preferably 1 part by mass or more, more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, still more preferably 20 parts by mass or more, even more preferably 30 parts by mass or more, and preferably 1000 parts by mass. parts by weight or less, more preferably 500 parts by weight or less, still more preferably 250 parts by weight or less, still more preferably 150 parts by weight or less, still more preferably 100 parts by weight or less, still more preferably 60 parts by weight or less.

In the mixing step, any method may be used to mix each component. There is no restriction on the order of mixing the components, and the mixing may be carried out in any manner such as all at once or divided. There is no restriction on the device for mixing each component, and any device capable of stirring and mixing, batch type or continuous type, may be used. The temperature at which each component is mixed can be arbitrarily selected within the range from room temperature to the boiling point of the solvent.
Further, the mixing step may be performed simultaneously with the reaction step described below, or may be performed before the reaction step.

[Reaction process]
The method for producing a fluorine-containing cyclic olefin composition according to the present invention includes reacting a fluorine-free cyclic diolefin compound (B1) with a hydroxyl group-containing compound (C) to produce a fluorine-free hydrated compound (B2) and It includes a reaction step for obtaining at least one selected from the group consisting of fluorine-free ether compounds (B3).
Here, the fluorine-containing cyclic olefin compound (A) and the fluorine-free cyclic diolefin compound (B1) usually have different electron densities at the double bond part, and the fluorine-free cyclic diolefin compound (B1) is better than the fluorine-containing cyclic diolefin compound (B1). expensive. Therefore, when the composition (X) containing the fluorine-containing cyclic olefin compound (A) and the fluorine-free cyclic diolefin compound (B1) is reacted with the hydroxyl group-containing compound (C) in the presence of an acid catalyst, fluorine The addition reaction of the hydroxyl group-containing compound (C) proceeds more selectively in the non-containing cyclic diolefin compound (B1), so that it can be hydrated or etherified.

Here, in the composition (X), the absolute difference between the HOMO energy (E ₁ ) of the fluorine-containing cyclic olefin compound (A) and the HOMO energy (E ₂ ) of the fluorine-free cyclic diolefin compound (B1) The value |E ₂ −E ₁ | is preferably 0.3 eV or more, from the viewpoint of further improving the selective reactivity between the hydroxyl group-containing compound (C) and the fluorine-free cyclic diolefin compound (B1) in the reaction step, More preferably, it is 0.5 eV or more.
Here, HOMO is the highest occupied molecular orbital, and the HOMO energy of each compound can be calculated using long-range corrected density functional theory. Using Gaussian16 Rev.B.01, ωB97X-D is selected as the functional, 6-31G(d) is used as the basis function, and the structure is optimized for calculation.

The reaction between the fluorine-free cyclic diolefin compound (B1) and the hydroxyl group-containing compound (C) can be carried out, for example, by the reaction between the composition (X), the acid catalyst, and the hydroxyl group-containing compound (C) obtained in the mixing step. This can be done by heating the mixture.
The heating temperature in the reaction step is not particularly limited as it is set appropriately depending on the type and amount of each component to be treated, but from the viewpoint of further promoting the reaction between the fluorine-free cyclic diolefin compound (B1) and the hydroxyl group-containing compound (C). , preferably 60°C or higher, more preferably 80°C or higher, even more preferably 90°C or higher, and from the viewpoint of further suppressing volatilization of the acid catalyst and decomposition of each component, preferably 150°C or lower, more preferably 130°C or higher. The temperature is preferably 120°C or lower, more preferably 120°C or lower. From these viewpoints, the heating temperature in the reaction step is preferably 60°C or more and 150°C or less, more preferably 80°C or more and 130°C or less, and even more preferably 90°C or more and 120°C or less.

In addition, the heating time (reaction time) in the reaction step is not particularly limited as it is appropriately set depending on the type and amount of each component to be treated, but the reaction between the fluorine-free cyclic diolefin compound (B1) and the hydroxyl group-containing compound (C) From the viewpoint of further promoting the process, the time period is preferably 1 hour or more, more preferably 2 hours or more, still more preferably 4 hours or more, even more preferably 8 hours or more, and from the viewpoint of improving productivity, preferably 48 hours or less, More preferably 24 hours or less, still more preferably 20 hours or less. From these viewpoints, the heating time (reaction time) in the reaction step is preferably 1 hour or more and 48 hours or less, more preferably 2 hours or more and 24 hours or less, even more preferably 4 hours or more and 20 hours or less, and even more preferably 8 hours. The duration is 20 hours or less.
Further, the reaction step can be carried out, for example, in an inert gas atmosphere such as nitrogen gas, and under normal pressure (atmospheric pressure).

[Separation process]
The method for producing a fluorine-containing cyclic olefin composition according to the present invention is aimed at controlling the purity of the obtained fluorine-containing cyclic olefin composition, that is, the content of the fluorine-containing cyclic olefin compound (A), which is the target substance in the fluorine-containing cyclic olefin composition. From the viewpoint of further improvement, after the reaction step, at least one selected from the group consisting of the fluorine-containing cyclic olefin compound (A), the fluorine-free hydrated compound (B2), and the fluorine-free ether compound (B3) is removed by distillation. It is preferable to further include a separation step of separating one type.
The distillation method is not particularly limited as long as it is a distillation method that can separate the fluorine-containing cyclic olefin compound (A) and the fluorine-free hydrated compound (B2) or the fluorine-free ether compound (B3), but for example, atmospheric pressure. For example, distillation under normal pressure may be carried out under reduced pressure, vacuum distillation may be carried out under reduced pressure in the system, and the like.

Further, the fluorine-containing cyclic olefin compound (A) is a fluorine-containing cyclic olefin compound (A1) in which n is 0 in the formula (1) and a fluorine-containing cyclic olefin compound (A2) in which n is 1 in the formula (1). ), the method for producing a fluorine-containing cyclic olefin composition according to the present invention improves the purity of the obtained fluorine-containing cyclic olefin composition, that is, the fluorine-containing cyclic olefin compound that is the target substance in the fluorine-containing cyclic olefin composition. From the viewpoint of further increasing the content of (A), it is possible to further include a separation step of separating the fluorine-containing cyclic olefin compound (A1) and the fluorine-containing cyclic olefin compound (A2) by distillation after the reaction step. preferable.
The distillation method is not particularly limited as long as it is a distillation method that can separate the fluorine-containing cyclic olefin compound (A1) and the fluorine-containing cyclic olefin compound (A2), but examples include atmospheric distillation conducted under atmospheric pressure, Examples include vacuum distillation performed under reduced pressure.

In the method for producing a fluorine-containing cyclic olefin composition according to the present invention, the content of the fluorine-free cyclic diolefin compound (B1) in the obtained fluorine-containing cyclic olefin composition is determined based on the entire fluorine-containing cyclic olefin composition. When taken as 100% by mass, preferably 5.0% by mass or less, more preferably 3.0% by mass or less, even more preferably 2.0% by mass or less, even more preferably 1.0% by mass or less, even more preferably 0 .8% by mass or less, more preferably 0.3% by mass or less.
Further, since the content of the fluorine-free cyclic diolefin compound (B1) in the obtained fluorine-containing cyclic olefin composition is preferably as small as possible, the lower limit of the content is not particularly limited, but for example, it is more than 0% by mass. The content may be 0.01% by mass or more, 0.05% by mass or more, or 0.1% by mass or more.

In addition, in the method for producing a fluorine-containing cyclic olefin composition according to the present invention, the content of the fluorine-containing cyclic olefin compound (A), which is the target substance in the obtained fluorine-containing cyclic olefin composition, is Preferably 75.0% by mass or more, more preferably 80.0% by mass or more, even more preferably 85.0% by mass or more, still more preferably 90.0% by mass or more, when the whole product is 100% by mass. be.
In the method for producing a fluorine-containing cyclic olefin composition according to the present invention, after the separation step of separating at least one selected from the group consisting of a fluorine-free hydrated compound (B2) and a fluorine-free ether compound (B3), The content of the target fluorine-containing cyclic olefin compound (A) in the obtained fluorine-containing cyclic olefin composition is preferably 99.0% by mass or more, more preferably 99.2% by mass or more, even more preferably It is 99.5% by mass or more, more preferably 99.7% by mass or more.
In addition, in the method for producing a fluorine-containing cyclic olefin composition according to the present invention, a fluorine-containing cyclic olefin compound (A1 ) is preferably 99.0% by mass or more, more preferably 99.2% by mass or more, even more preferably 99.5% by mass or more, when the entire fluorine-containing cyclic olefin composition is 100% by mass. , more preferably 99.7% by mass or more.
In addition, in the method for producing a fluorine-containing cyclic olefin composition according to the present invention, a fluorine-containing cyclic olefin compound (A2 ) is preferably 99.0% by mass or more, more preferably 99.2% by mass or more, even more preferably 99.5% by mass or more, when the entire fluorine-containing cyclic olefin composition is 100% by mass. , more preferably 99.7% by mass or more.
Here, the content of each component in the fluorine-containing cyclic olefin composition can be measured, for example, by gas chromatography. The measurement method is to use "GC-2010Plus" manufactured by Shimadzu Corporation, and "DB-5" (length 30 m x diameter 0.25 mm x film thickness 0.5 μm, manufactured by Agilent Technologies) as a capillary column. I can do it. The concentration of each component can be measured under conditions of holding the temperature at 40°C for 2 minutes and then increasing the temperature to 250°C at a rate of 10°C/min. The concentration of each component can be determined by the peak area ratio (mass %) of each component to the total peak area in the obtained chromatogram.

According to the fluorine-containing cyclic olefin composition of the present invention, for example, coordination polymerization in which a polymer is synthesized using a transition metal catalyst in the coexistence of an alkali metal as a promoter; Radical polymerization, which synthesizes polymers by generating A fluorine-containing cyclic olefin polymer can be synthesized by a method such as metathesis polymerization, in which a polymer is synthesized using a method such as metathesis polymerization. In each polymerization method, two or more types of fluorine-containing cyclic olefin compositions according to the present invention may be used together.
Furthermore, in various polymerization methods, non-fluorine-based cyclic or chain olefins may be present and copolymerized with the fluorine-containing cyclic olefin composition of the present invention. It may also be used as a transfer agent.
In addition to the properties of the obtained polymer as a cyclic olefin polymer, due to the effect of the fluorine atom and/or the fluorine-containing substituent, the molded product exhibits low refractive and highly transparent resin properties, such as lenses. It can be widely used in the fields of optical and electronic materials in the form of films, optical waveguides, fibers, etc.

Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than those described above may also be adopted.
Further, the present invention is not limited to the above-described embodiments, and modifications, improvements, etc. are included within the scope of the present invention without impairing the effects of the present invention.

Hereinafter, this embodiment will be described in detail with reference to examples and the like. Note that this embodiment is in no way limited to the description of these examples.

[Measurement of the content of each composition in the fluorine-containing cyclic olefin composition before and after distillation purification]
The content (% by mass) of each composition in the fluorine-containing cyclic olefin composition before and after distillation purification was measured by gas chromatography.
As the gas chromatography device, "GC-2010Plus" manufactured by Shimadzu Corporation was used, and as the capillary column, "DB-5" manufactured by Agilent Technologies (length 30 m x diameter 0.25 mm x film thickness 0.5 μm) was used. used. The measurement was carried out under conditions of holding the temperature at 40°C for 2 minutes and then increasing the temperature to 250°C at a rate of 10°C/min. The concentration of each component was determined by the peak area ratio (mass %) of each component to the total peak area in the obtained chromatogram.

[Example 1]
Under a nitrogen atmosphere, 5.8 kg of dicyclopentadiene (manufactured by Tokyo Kasei Kogyo Co., Ltd., hereinafter also referred to as "DCp") and 16.8 kg of hexafluoropropene (manufactured by Takachiho Kagaku Kogyo Co., Ltd.) were placed in a 25 L autoclave equipped with a magnetic stirring device. 6 kg was added thereto, heated and stirred at 160°C for 24 hours, and then heated and stirred at 180°C for 15 hours. After cooling, 3.9 kg of unreacted hexafluoropropene was collected, and 17.9 kg of the reaction solution was taken out.
Next, the obtained reaction solution is distilled to obtain 5,5,6-trifluoro-6-trifluoromethyl-bicyclo[2.2.1]hept-2-ene (hereinafter also referred to as "NBF ₆ "). ) and DCp were obtained, and 8,8,9-trifluoro-9-trifluoromethyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene (hereinafter also referred to as "TDF ₆ "), NBF ₆ , DCp, and tricyclopentadiene (hereinafter also referred to as "TCPD") 2.2 kg of composition (X1) was obtained. did. Here, the boiling point of TDF ₆ is 240°C, the boiling point of NBF ₆ is 165°C, the boiling point of DCp is 170°C, and the boiling point of TCPD is 248°C.
Further, the HOMO energy of TDF ₆ is -8.7 eV, the HOMO energy of NBF ₆ is -9.3 eV, the HOMO energy of DCp is -8.4 eV, and the HOMO energy of TCPD is -8.2 eV.
Here, HOMO is the highest occupied molecular orbital, and the HOMO energy of each compound can be calculated using long-range corrected density functional theory. Using Gaussian16 Rev.B.01, ωB97X-D was selected as the functional, 6-31G(d) was used as the basis function, and structure optimization was performed.

Next, 250 g of composition (X1), 100 g of water as a hydroxyl group-containing compound (C), and 5 g of sulfuric acid as an acid catalyst were placed in a 1000 mL glass reactor equipped with a stirrer and a condenser, and under a nitrogen atmosphere, The mixture was heated and stirred at 100°C for 18 hours to carry out a hydration reaction of DCp and TCPD in composition (X1) (hereinafter also referred to as "reaction step"). Next, the obtained reaction solution was cooled to room temperature, and then neutralized and extracted with a 5% NaOH aqueous solution to obtain a fluorine-containing cyclic olefin composition before purification by distillation. This fluorine-containing cyclic olefin composition before distillation purification was analyzed by gas chromatography.
In addition, a Sneader fractionator tube and a Liebig condenser tube were attached to a round bottom flask containing the fluorine-containing cyclic olefin composition before distillation purification, and a NBF _6- containing composition and a TDF _6- containing composition were obtained by fractional distillation by vacuum distillation. and gas chromatography.
Here, DCp-OH and TCPD-OH in Table 1 mean hydrated compounds of DCp and TCPD, respectively.

[Examples 2 to 6]
Example except that the types of acid catalyst and hydroxyl group-containing compound (C) were changed to those listed in Table 1, the amount of acid catalyst input was 13 g, and the heating conditions in the reaction step were changed to those listed in Table 1. In the same manner as in Example 1, a TDF _6- containing composition and a NBF _6- containing composition were manufactured and evaluated, respectively. Here, Examples 4 and 5 used composition (X2) instead of composition (X1), and Example 6 used composition (X3) instead of composition (X1). When a solid acid was used as the acid catalyst, the solid acid catalyst was removed by vacuum filtration and used as a measurement sample for gas chromatography analysis.
Details of solid acids A and B in Table 1 are as follows.
Solid acid A: cation exchange resin having sulfonic acid groups (AmberLite ^TM HPR2900 H Cation Exchange Resin, manufactured by Sigma-Aldrich, acid dissociation constant pKa = 2 or less)
Solid acid B: Cation exchange resin with sulfonic acid group (AMBERLYST 15JS-HG・DRY, manufactured by Organo, acid dissociation constant pKa = 2 or less)
Here, DCp-OPr or -OHx and TCPD-OPr in Table 1 mean alkyl etherified products of DCp and TCPD, respectively.

(Preparation of composition (X2))
Under a nitrogen atmosphere, 3.8 kg of DCp (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 11.5 kg of hexafluoropropene (manufactured by Takachiho Kagaku Kogyo Co., Ltd.) were placed in a 25 L autoclave equipped with a magnetic stirring device, and heated at 160°C for 24 hours. The mixture was stirred and then heated and stirred at 180° C. for 15 hours. After cooling, 2.5 kg of unreacted hexafluoropropene was collected, and 12.4 kg of the reaction solution was taken out.
Next, 11.0 kg of a composition containing NBF ₆ and DCp was obtained by distilling the obtained reaction solution, and a composition containing TDF ₆ , NBF ₆ , and TCPD (X2) was obtained from the residual liquid in the distillation apparatus. 1.0 kg of was obtained.

(Preparation of composition (X3))
Under a nitrogen atmosphere, 5.2 kg of DCp (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 14.2 kg of hexafluoropropene (manufactured by Takachiho Kagaku Kogyo Co., Ltd.) were placed in a 25 L autoclave equipped with a magnetic stirring device, and heated at 160°C for 24 hours. The mixture was stirred and then heated and stirred at 180° C. for 15 hours. After cooling, 1.9 kg of unreacted hexafluoropropene was collected, and 16.3 kg of the reaction solution was taken out.
Next, 14.7 kg of a composition containing NBF ₆ and DCp was obtained by distilling the obtained reaction solution, and a composition containing TDF ₆ , NBF ₆ , and TCPD (X3) was obtained from the residual liquid in the distillation apparatus. 1.3 kg of was obtained.

[Comparative example 1]
An NBF _6- containing composition and a TDF ₆ -containing composition were manufactured and evaluated in the same manner as in Example 1, except that the etherification reaction was not performed.

The above results are shown in Table 1.

This application claims priority based on Japanese Patent Application No. 2022-054139 filed on March 29, 2022, and the entire disclosure thereof is incorporated herein.

Claims

For a composition (X) containing a fluorine-containing cyclic olefin compound (A) and a fluorine-free cyclic diolefin compound (B1) represented by the following formula (1), an acid catalyst and a compound selected from the group consisting of water and an alkyl alcohol. a mixing step of mixing at least one selected hydroxyl group-containing compound (C);
By reacting the fluorine-free cyclic diolefin compound (B1) with the hydroxyl group-containing compound (C), a compound selected from the group consisting of a fluorine-free hydrated compound (B2) and a fluorine-free ether compound (B3) is produced. a reaction step for obtaining at least one type of
A method for producing a fluorine-containing cyclic olefin composition.

(In the above formula (1), at least one of R 1 to R 4 is fluorine, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a fluorine-containing alkoxy group having 1 to 10 carbon atoms, or It is an alkoxyalkyl group having 2 to 10 carbon atoms containing fluorine, and when R 1 to R 4 are groups not containing fluorine, R 1 to R 4 are hydrogen, an alkyl group having 1 to 10 carbon atoms, or selected from alkoxy groups having 1 to 10 carbon atoms or alkoxyalkyl groups having 2 to 10 carbon atoms, R 1 to R 4 may be bonded to each other to form a ring structure, and X is -CH 2 - or O -, n indicates 0 or 1)
The fluorine-containing cyclic olefin composition according to claim 1, wherein the absolute value of the difference between the boiling point of the fluorine-containing cyclic olefin compound (A) and the boiling point of the fluorine-free cyclic diolefin compound (B1) is 10° C. or less. How things are manufactured.
The method for producing a fluorine-containing cyclic olefin composition according to claim 1 or 2, wherein the alkyl alcohol has 3 or more and 10 or less carbon atoms.
The method for producing a fluorine-containing cyclic olefin composition according to any one of claims 1 to 3, wherein the acid catalyst contains at least one selected from the group consisting of inorganic acids, organic acids, and solid acids.
The absolute value of the difference between the HOMO energy (E 1 ) of the fluorine-containing cyclic olefin compound (A) and the HOMO energy (E 2 ) of the fluorine-free cyclic diolefin compound (B1) |E 2 −E 1 | The method for producing a fluorine-containing cyclic olefin composition according to any one of claims 1 to 4, wherein the fluorine-containing cyclic olefin composition is 0.3 eV or more.
The fluorine-containing cyclic olefin compound (A) is a fluorine-containing cyclic olefin compound (A1) in which n is 0 in the formula (1) and a fluorine-containing cyclic olefin compound (A2) in which n is 1 in the formula (1). The method for producing a fluorine-containing cyclic olefin composition according to any one of claims 1 to 5, comprising both of the above.
The fluorine-containing cyclic olefin composition according to claim 6, further comprising a separation step of separating the fluorine-containing cyclic olefin compound (A1) and the fluorine-containing cyclic olefin compound (A2) by distillation after the reaction step. manufacturing method.
After the reaction step, separation of the fluorine-containing cyclic olefin compound (A), at least one selected from the group consisting of the fluorine-free hydrated compound (B2) and the fluorine-free ether compound (B3) is performed by distillation. The method for producing a fluorine-containing cyclic olefin composition according to any one of claims 1 to 7, further comprising a separation step of.
The content of the fluorine-free cyclic diolefin compound (B1) in the fluorine-containing cyclic olefin composition is 5.0% by mass or less when the entire fluorine-containing cyclic olefin composition is 100% by mass. A method for producing a fluorine-containing cyclic olefin composition according to any one of claims 1 to 8.
When the content of the fluorine-containing cyclic olefin compound (A1) in which n is 0 in the formula (1) in the fluorine-containing cyclic olefin composition is 100% by mass of the entire fluorine-containing cyclic olefin composition. The method for producing a fluorine-containing cyclic olefin composition according to claim 8, wherein the fluorine-containing cyclic olefin composition is 99.0% by mass or more.
When the content of the fluorine-containing cyclic olefin compound (A2) in which n is 1 in the formula (1) in the fluorine-containing cyclic olefin composition is 100% by mass of the entire fluorine-containing cyclic olefin composition. The method for producing a fluorine-containing cyclic olefin composition according to claim 8, wherein the fluorine-containing cyclic olefin composition is 99.0% by mass or more.
A fluorine-containing cyclic olefin composition comprising a fluorine-containing cyclic olefin compound (A) and a fluorine-free cyclic diolefin compound (B1) represented by the following formula (1),
The content of the fluorine-free cyclic diolefin compound (B1) in the fluorine-containing cyclic olefin composition is more than 0% by mass and 1.0% by mass when the entire fluorine-containing cyclic olefin composition is 100% by mass. % or less.

(In the above formula (1), at least one of R 1 to R 4 is fluorine, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a fluorine-containing alkoxy group having 1 to 10 carbon atoms, or It is an alkoxyalkyl group having 2 to 10 carbon atoms containing fluorine, and when R 1 to R 4 are groups not containing fluorine, R 1 to R 4 are hydrogen, an alkyl group having 1 to 10 carbon atoms, or selected from alkoxy groups having 1 to 10 carbon atoms or alkoxyalkyl groups having 2 to 10 carbon atoms, R 1 to R 4 may be bonded to each other to form a ring structure, and X is -CH 2 - or O -, n indicates 0 or 1)