CN116635359A

CN116635359A - Method for producing fluorine-containing polyether compound, method for producing fluorine-containing divinyl polyether compound, and fluorine-containing divinyl polyether compound

Info

Publication number: CN116635359A
Application number: CN202180086980.XA
Authority: CN
Inventors: 松浦启吾; 宇野诚人; 青山元志
Original assignee: Asahi Glass Co Ltd
Current assignee: AGC Inc
Priority date: 2020-12-25
Filing date: 2021-12-17
Publication date: 2023-08-22
Also published as: WO2022138510A1; JPWO2022138510A1

Abstract

A process for producing a fluoropolyether compound represented by (4) wherein a compound represented by (1) is reacted with a compound represented by (2) in a ratio of more than 1mol per 1mol of the compound represented by (2) to produce a compound represented by (3) and then fluorinated. CF (compact flash) ₂ ＝CR ¹ ‑O‑R ² ‑O‑CR ¹ ＝CF ₂ (1)HO‑R ³ ‑OH(2)CF ₂ ＝CR ¹ ‑O‑R ² ‑O‑(CHR ¹ ‑CF ₂ ‑O‑R ³ ‑O‑CF ₂ ‑CHR ¹ ‑O‑R ² ‑O) _a ‑CR ¹ ＝CF ₂ (3)CF ₃ ‑CFR ^F1 ‑O‑R ^F2 ‑O‑(CFR ^F1 ‑CF ₂ ‑O‑R ^F3 ‑O‑CF ₂ ‑CFR ^F1 ‑O‑R ^F2 ‑O) _a ‑CFR ^F1 ‑CF ₃ (4)。

Description

Method for producing fluorine-containing polyether compound, method for producing fluorine-containing divinyl polyether compound, and fluorine-containing divinyl polyether compound

Technical Field

The present disclosure relates to a method for producing a fluorine-containing polyether compound, a method for producing a fluorine-containing divinyl polyether compound, and a fluorine-containing divinyl polyether compound.

Background

Fluorine-containing compounds are used as surface treatment agents, lubricants, and the like because they exhibit high lubricity, water repellency, oil repellency, and the like. Among the fluorine-containing compounds, a fluorine-containing polyether compound having an ether bond is excellent in lubricity and is used for forming a coating film for the purpose of protecting a read/write head of a magnetic disk or the like.

Heretofore, a fluoropolyether compound has been produced by various methods. For example, U.S. patent No. 5258110 discloses: the fluoropolyether compound is produced by reacting tetrafluoroethylene with oxygen in the presence of a compound having a fluoroxy group or the like.

Further, U.S. Pat. No. 4845268 discloses a method for producing a fluorine-containing polyether compound by ring-opening polymerization of 2, 3-tetrafluorooxetane, and a method for producing a halogen-containing polyether compound by chlorinating and fluorinating the fluorine-containing polyether compound.

In addition, international publication No. 2013/121984 discloses that CF is caused to occur ₂ ＝CFO-CF ₂ CF ₂ CF ₂ CH ₂ OH-represented Compound with A ¹ -OH(A ¹ Methyl, and the like. ) The primary alcohols shown are reacted to produce A ¹ -O-(CF ₂ CFHO-CF ₂ CF ₂ CF ₂ CH ₂ O) _n+1 Halogen-containing polyether compounds indicated by H.

Disclosure of Invention

Problems to be solved by the invention

From the viewpoint of lubricity, fluorine-containingThe polyether compound preferably has a trifluoromethyl group (-CF) at the terminal ₃ ) However, in the production method disclosed in U.S. Pat. No. 5258110, it is difficult to produce a fluoropolyether compound having trifluoromethyl groups at both ends in high yield.

In addition, the fluoropolyether compound obtained by the production method disclosed in U.S. Pat. No. 4845268 and international publication No. 2013/121984 has a functional group at least one end, and the reaction of replacing the functional group with a trifluoromethyl group is not easy to proceed, and it is difficult to produce a fluoropolyether compound having a trifluoromethyl group at both ends.

In addition, since the coating film is required to have chemical resistance, heat resistance, and the like, the fluoropolyether compound used for forming the coating film is required to have a high molecular weight.

The present disclosure has been made in view of the above-described requirements, and an object thereof is to provide a method for producing a fluoropolyether compound, which is capable of producing a high-molecular-weight fluoropolyether compound having trifluoromethyl groups at both ends thereof in high yield.

Further, the object to be solved is to provide a method for producing a fluorinated divinyl polyether compound, which can easily produce a fluorinated divinyl polyether compound having vinyl groups at both ends and having a high molecular weight, in high yield, and a novel fluorinated divinyl polyether compound.

Solution for solving the problem

Specific means for achieving the above object are as follows.

<1> a method for producing a fluorinated polyether compound, wherein a fluorinated divinyl ether compound represented by the following general formula (1) and a diol compound represented by the following general formula (2) are reacted at a ratio of more than 1mol of the fluorinated divinyl ether compound represented by the following general formula (1) to 1mol of the diol compound represented by the following general formula (2), and then a fluorinated divinyl polyether compound represented by the following general formula (3) is fluorinated to produce a fluorinated polyether compound represented by the following general formula (4).

CF ₂ ＝CR ¹ -O-R ² -O-CR ¹ ＝CF ₂ (1)

HO-R ³ -OH(2)

CF ₂ ＝CR ¹ -O-R ² -O-(CHR ¹ -CF ₂ -O-R ³ -O-CF ₂ -CHR ¹ -O-R ² -O) _a -CR ¹ ＝CF ₂ (3)

CF ₃ -CFR ^F1 -O-R ^F2 -O-(CFR ^F1 -CF ₂ -O-R ^F3 -O-CF ₂ -CFR ^F1 -O-R ^F2 -O) _a -CFR ^F1 -CF ₃ (4)

(in the general formulae (1) to (4),

R ¹ each independently represents a fluorine atom, a hydrogen atom or a C1-3 hydrocarbon group having a hydrogen atom optionally substituted with a fluorine atom,

R ² r is R ³ Each independently represents a C1-20 2-valent hydrocarbon group, the C1-20 2-valent hydrocarbon group optionally containing a ring structure, a branched structure, optionally containing an ether bond, and a hydrogen atom optionally being substituted with a fluorine atom,

at R ¹ R being fluorine atom ^F1 Each independently represents a fluorine atom, at R ¹ R being a hydrogen atom ^F1 Each independently represents a fluorine atom, at R ¹ R is a C1-3 1-valent hydrocarbon group ^F1 Each independently represents a 1-valent perfluoroalkyl group having 1 to 3 carbon atoms,

R ^F2 each independently represents R ² The 2-valent hydrocarbon group is a 2-valent perfluorinated hydrocarbon group having 1 to 20 carbon atoms which is perfluorinated,

R ^F3 each independently represents R ³ The 2-valent hydrocarbon group is a 2-valent perfluorinated hydrocarbon group having 1 to 20 carbon atoms which is perfluorinated,

a represents an integer of 1 or more. )

<2> the process for producing a fluorinated polyether compound according to <1>, wherein the reaction of the fluorinated divinyl ether compound represented by the general formula (1) with the diol compound represented by the general formula (2) is carried out in the presence of a base catalyst.

<3> the process for producing a fluorinated polyether compound according to <1> or <2>, wherein the fluorinated divinyl polyether compound represented by the general formula (3) is carried out by introducing fluorine gas and the fluorinated divinyl polyether compound represented by the general formula (3) into a solvent,

When the introduction rate of the fluorinated divinyl polyether compound represented by the general formula (3) to the molar basis in the solvent is 1, the introduction rate of the fluorinated gas to the molar basis is in the range of 1 to 10 times the rate obtained by multiplying the introduction rate of the fluorinated divinyl polyether compound represented by the general formula (3) to the number of hydrogen atoms contained in the fluorinated divinyl polyether compound that can be substituted with the fluorinated gas to a fluorine atom.

<4> the process for producing a fluorinated polyether compound according to any one of <1> to <3>, wherein the fluorinated divinyl ether compound represented by the general formula (1) and the diol compound represented by the general formula (2) are reacted at a ratio of 3mol or less relative to 1mol of the fluorinated divinyl ether compound represented by the general formula (1) to 1mol of the diol compound represented by the general formula (2).

<5> a method for producing a fluorinated polyether compound, wherein a fluorinated divinyl ether compound represented by the following general formula (1) and a fluorinated vinyl alcohol compound represented by the following general formula (5) are reacted at a ratio of more than 1mol of the fluorinated divinyl ether compound represented by the following general formula (1) to 1mol of the fluorinated divinyl ether compound represented by the following general formula (1), and then a fluorinated divinyl polyether compound represented by the following general formula (6-1) or the following general formula (6-2) is fluorinated to produce a fluorinated polyether compound represented by the following general formula (7-1) or the following general formula (7-2).

CF ₂ ＝CR ¹ -O-R ² -O-CR ¹ ＝CF ₂ (1)

CF ₂ ＝CR ¹ -O-R ⁴ -OH (5)

CF ₂ ＝CR ¹ -O-(R ⁴ -O-CF ² -CHR ¹ -O) _b -R ⁴ -O-CF ₂ -CHR ¹ -O-R ² -O-CHR ¹ -CF ₂ -O-R ⁴ -(O-CHR ¹ -CF ₂ -O-R ⁴ ) _c -O-CR ¹ ＝CF ₂ (6-1)

CF ₂ ＝CR ¹ -O-(R ⁴ -O-CF ² -CHR ¹ -O) _d -R ⁴ -O-CF ₂ -CHR ¹ -O-R ² -O-CR ¹ ＝CF ₂ (6-2)

CF ₃ -CFR ^F1 -O-(R ^F4 -O-CF ² -CFR ^F1 -O) _b -R ^F4 -O-CF ₂ -CFR ^F1 -O-R ^F2 -O-CFR ^F1 -CF ₂ -O-R ^F4 -(O-CFR ^F1 -CF ₂ -O-R ^F4 ) _c -O-CFR ^F1 -CF ₃ (7-1)

CF ₃ -CFR ^F1 -O-(R ^F4 -O-CF ² -CFR ^F1 -O) _d -R ^F4 -O-CF ₂ -CFR ^F1 -O-R ^F2 -O-CFR ^F1 -CF ₃ (7-2)

(general formula (1), general formula (5), general formula (6-1), general formula (6-2), general formula (7-1) and general formula (7-2),

R ² r is R ⁴ Each independently represents a C1-20 2-valent hydrocarbon group, the C1-20 2-valent hydrocarbon group optionally containing a ring structure, a branched structure, optionally containing an ether bond, and a hydrogen atom optionally being substituted with a fluorine atom,

R ^F4 each independently represents R ⁴ The 2-valent hydrocarbon group is a 2-valent perfluorinated hydrocarbon group having 1 to 20 carbon atoms which is perfluorinated,

b. c and d each independently represent an integer of 0 or 1 or more. )

<6> the process for producing a fluorine-containing polyether compound according to <5>, wherein the reaction of the fluorine-containing divinyl ether compound represented by the general formula (1) with the fluorine-containing vinyl alcohol compound represented by the general formula (5) is carried out in the presence of a base catalyst.

<7> the process for producing a fluorinated polyether compound according to <5> or <6>, wherein the fluorinated compound of the general formula (6-1) or the fluorinated divinyl polyether compound of the general formula (6-2) is produced by introducing a fluorine gas and the fluorinated divinyl polyether compound of the general formula (6-1) or the general formula (6-2) into a solvent,

when the introduction rate of the fluorodivinyl polyether compound represented by the general formula (6-1) or the general formula (6-2) to the molar basis in the solvent is 1, the introduction rate of the fluorine gas to the molar basis is in the range of 1 to 10 times the rate obtained by multiplying the introduction rate of the fluorodivinyl polyether compound represented by the general formula (6-1) or the general formula (6-2) to the molar basis of the fluorodivinyl polyether compound represented by the general formula (6-1) or the general formula (6-2) by the number of hydrogen atoms that can be substituted with the fluorine gas to fluorine atoms.

<8> the process for producing a fluorinated polyether compound according to any one of <5> to <7>, wherein the reaction between the fluorinated divinyl ether compound represented by the general formula (1) and the fluorinated vinyl alcohol compound represented by the general formula (5) is carried out at a ratio of 20mol or less relative to 1mol of the fluorinated divinyl ether compound represented by the general formula (1).

<9> a process for producing a fluorodivinyl polyether compound, wherein a fluorodivinyl ether compound represented by the following general formula (1) and a diol compound represented by the following general formula (2) are reacted at a ratio of more than 1mol per 1mol of the diol compound represented by the following general formula (2), to produce a fluorodivinyl polyether compound represented by the following general formula (3).

CF ₂ ＝CR ¹ -O-R ² -O-CR ¹ ＝CF ₂ (1)

HO-R ³ -OH(2)

(in the general formulae (1) to (3),

a represents an integer of 1 or more. )

<9> a process for producing a fluorodivinyl polyether compound, wherein a fluorodivinyl ether compound represented by the following general formula (1) and a fluorovinyl alcohol compound represented by the following general formula (5) are reacted at a ratio of more than 1mol of the fluorovinyl alcohol compound represented by the following general formula (5) to 1mol of the fluorodivinyl ether compound represented by the following general formula (1), to produce a fluorodivinyl polyether compound represented by the following general formula (6-1) or the following general formula (6-2).

CF ₂ ＝CR ¹ -O-R ² -O-CR ¹ ＝CF ₂ (1)

CF ₂ ＝CR ¹ -O-R ⁴ -OH (5)

(in the general formula (1), the general formula (5), the general formula (6-1) and the general formula (6-2),

b. c and d each independently represent an integer of 0 or 1 or more. )

<10> a method for producing a fluorinated polyether compound, wherein a fluorinated divinyl polyether compound represented by the following general formula (3) is fluorinated to produce a fluorinated polyether compound represented by the following general formula (4).

(in the general formulae (1) to (4),

R ² r is R ³ Each independently represents a C1-20 hydrocarbon group having 2-valency, wherein the C1-20 hydrocarbon group optionally contains a ring structure, a branched structure, optionally contains an ether bond,and the hydrogen atom is optionally substituted with a fluorine atom,

a represents an integer of 1 or more. )

<11> a method for producing a fluorinated polyether compound, wherein a fluorinated divinyl polyether compound represented by the following general formula (6-1) or the following general formula (6-2) is fluorinated to produce a fluorinated polyether compound represented by the following general formula (7-1) or the following general formula (7-2).

CF ₂ ＝CR ¹ -O-R ² -O-CR ¹ ＝CF ₂ (1)

CF ₂ ＝CR ¹ -O-R ⁴ -OH (5)

b. c and d each independently represent an integer of 0 or 1 or more. )

<12> a fluorine-containing divinyl polyether compound represented by the following general formula (3).

(in the general formula (3),

R ¹ each independently represents a fluorine atom,A hydrogen atom or a C1-3 hydrocarbon group in which a hydrogen atom is optionally substituted with a fluorine atom,

a represents an integer of 1 or more. )

<13> a fluorine-containing divinyl polyether compound represented by the following general formula (6-1).

(in the general formula (6-1),

b and c each independently represent an integer of 0 or 1 or more. )

<14> a fluorine-containing divinyl polyether compound represented by the following general formula (6-2).

(in the general formula (6-2),

R ² r is R ⁴ Each independently representsA C1-20 hydrocarbon group having 2-valency, wherein the C1-20 hydrocarbon group optionally contains a ring structure, a branched structure, optionally contains an ether bond, and a hydrogen atom is optionally substituted with a fluorine atom,

d represents an integer of 0 or 1 or more. )

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present disclosure, a high molecular weight fluoropolyether compound having trifluoromethyl groups at both ends and a method for producing a fluoropolyether compound are provided.

Further, according to the present disclosure, a method for producing a fluorinated divinyl polyether compound capable of producing a fluorinated divinyl polyether compound having a high molecular weight and a vinyl group at both ends thereof in high yield, and a novel fluorinated divinyl polyether compound are provided.

Detailed Description

The following describes in detail the manner in which the present disclosure is implemented. However, the present disclosure is not limited to the following embodiments. In the following embodiments, the constituent elements (including the element steps) are not necessarily required unless otherwise specified. As such, the numerical values and ranges thereof are not limiting of the present disclosure.

In the present disclosure, the numerical ranges indicated by the terms "to" include the numerical values before and after the term "to" as the minimum value and the maximum value, respectively.

In the numerical ranges described in stages in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of the other numerical range described in stages. In the numerical ranges described in the present disclosure, the upper limit or the lower limit of the numerical range may be replaced with the values shown in the synthesis examples.

In the present disclosure, "fluoroalkylene group" includes a perfluoroalkylene group in which all hydrogen atoms are replaced with fluorine atoms and a fluoroalkylene group in which a part of hydrogen atoms is replaced with fluorine atoms. In the present disclosure, "fluorocycloalkane" and the like are described to include not only perfluorocyclobutene in which all hydrogen atoms of cyclobutene are substituted with fluorine atoms, but also cyclobutene in which a part of hydrogen atoms are substituted with fluorine atoms.

The ingredients in the present disclosure may comprise a variety of conforming compounds. For example, the molar ratio in the reaction of the fluorodivinyl ether compound represented by the general formula (1) and the diol compound represented by the general formula (2) is calculated based on the total of the compounds corresponding to the respective components.

The expression of the group (radical) in the present disclosure includes those having no substituent and those having a substituent, as well as those having no substituent, in which the expressions of substitution and unsubstituted are not described.

In the present disclosure, the carbon number refers to the total number of carbon atoms contained in the whole of a certain group, and in the case where the group has no substituent, the number of carbon atoms forming the skeleton of the group, and in the case where the group has a substituent, the total number of carbon atoms forming the skeleton of the group plus the number of carbon atoms in the substituent, are represented.

In the present disclosure, a 1-valent or 2-valent hydrocarbon group "perfluorinated" means that the hydrocarbon group is fluorinated to the following state.

In the case where the 1-valent or 2-valent hydrocarbon group is a saturated hydrocarbon group, the state where all of the fluorinated hydrogen atoms bonded to carbon atoms constituting the 1-valent or 2-valent hydrocarbon group are fluorinated is referred to as "perfluorinated" hydrocarbon group.

In the case where the 1-valent or 2-valent hydrocarbon group is an unsaturated hydrocarbon group, a state in which all of the fluorinatable hydrogen atoms bonded to carbon atoms constituting the 1-valent or 2-valent hydrocarbon group are fluorinated, and 2 carbon atoms forming an unsaturated bond between carbon and carbon such as a carbon-carbon double bond or a carbon-carbon triple bond are each added with a fluorine atom to thereby eliminate the unsaturated bond between carbon and carbon is referred to as "perfluorinated" hydrocarbon group. For example, the number of the cells to be processed, >C＝C<If perfluorinated, becomes>CF-CF<(C.ident.C-if perfluorinated, becomes-CF) ₂ -CF ₂ -. In addition, perfluorinated hydrogen atoms may be bonded to the fluorinated radicals, e.g., -CH=CH-if perfluorinated, becoming-CF ₂ -CF ₂ -。

In the present disclosure, the number average molecular weight (Mn) and the mass average molecular weight (Mw) are measured by gel permeation chromatography (hereinafter also referred to as "GPC"). GPC-based measurement was performed under the following conditions according to the method described in Japanese patent application laid-open No. 2001-208736.

Mobile phase: mixed solvent of R-225 (trade name: ASAHIKLIN (registered trademark) AK-225SEC grade 1, manufactured by AGC Co., ltd.) and hexafluoroisopropyl alcohol (HFIP) (R-225: HFIP=99:1 (volume ratio))

Analytical column: 2 PLgel MIXED-E columns (manufactured by Polymer Laboratories Co.) were connected in series

Molecular weight measurement standard sample: 4 perfluoropolyethers having a molecular weight distribution (Mw/Mn) of less than 1.1 and a Mn of 2,000 to 10,000, and 1 perfluoropolyether having a Mw/Mn of 1.1 or more and a Mn of 1,300

Mobile phase flow rate: 1.0 mL/min

Column temperature: 37 DEG C

Detector: evaporative light scattering detector

(Process for producing the fluoropolyether Compound of embodiment 1)

First, a method for producing a fluoropolyether compound represented by the general formula (4) will be described. The fluorinated divinyl polyether compound represented by the general formula (3) and the method for producing the same are also described.

In the method for producing a fluorinated polyether compound according to embodiment 1, a fluorinated divinyl ether compound represented by the following general formula (1) (hereinafter, also referred to as a compound of formula (1)) and a diol compound represented by the following general formula (2) (hereinafter, also referred to as a compound of formula (2)) are reacted at a ratio of more than 1mol of the compound of formula (1) to 1mol of the compound of formula (2), whereby a fluorinated divinyl polyether compound represented by the following general formula (3) (hereinafter, also referred to as a compound of formula (3)) is produced, and thereafter, the compound of formula (3) is fluorinated to produce a fluorinated polyether compound represented by the following general formula (4) (hereinafter, also referred to as a compound of formula (4)).

CF ₂ ＝CR ¹ -O-R ² -O-CR ¹ ＝CF ₂ (1)

HO-R ³ -OH(2)

In the general formula (1) and the general formula (3), R ¹ Each independently represents a fluorine atom, a hydrogen atom or a C1-3 hydrocarbon group in which a hydrogen atom is optionally substituted with a fluorine atom.

In the general formulae (1) to (3), R ² R is R ³ Each independently represents a 2-valent hydrocarbon group of 1 to 20 carbon atoms, the 2-valent hydrocarbon group of 1 to 20 carbon atoms optionally containing a ring structure, a branched structure, optionally containing an ether bond, and a hydrogen atom optionally being substituted with a fluorine atom.

In the general formula (4), R is ¹ R being fluorine atom ^F1 Each independently represents a fluorine atom, at R ¹ R being a hydrogen atom ^F1 Each independently represents a fluorine atom, at R ¹ R is a C1-3 1-valent hydrocarbon group ^F1 Each independently represents a 1-valent perfluoroalkyl group having 1 to 3 carbon atoms.

In the general formula (4), R ^F2 Each independently represents R ² The 2-valent hydrocarbon group is a 2-valent perfluorinated hydrocarbon group having 1 to 20 carbon atoms which is perfluorinated.

In the general formula (4), R ^F3 Each independently represents R ³ The 2-valent hydrocarbon group is a 2-valent perfluorinated hydrocarbon group having 1 to 20 carbon atoms which is perfluorinated.

In the general formulae (3) and (4), a represents an integer of 1 or more, preferably an integer of 3 or more, and more preferably an integer of 5 or more. In addition, a is preferably an integer of 15 or less.

The method for producing a fluoropolyether compound according to claim 1 enables production of a high-molecular-weight fluoropolyether compound having trifluoromethyl groups at both ends thereof in high yield.

The reason why the above-described effects are exerted is presumed to be as follows, but is not limited thereto.

In the reaction of the compound of formula (1) and the compound of formula (2), the polymerization reaction proceeds smoothly by performing the reaction at a ratio of more than 1mol with respect to 1mol of the compound of formula (2), and therefore the compound of formula (3) having a high molecular weight can be produced in a high yield.

Further, the compound of formula (3) obtained by the above reaction has vinyl groups (CF) at both ends ₂ ＝CR ¹ By contacting the vinyl group with fluorine gas, fluorination is easy, and thus a compound of formula (4) having a high molecular weight and trifluoromethyl groups at both ends can be produced in high yield.

Hereinafter, the production of the fluorinated divinyl polyether compound included in the method for producing a fluorinated polyether compound according to the first embodiment will be described.

Production of fluorine-containing divinyl polyether compounds

The vinyl groups at both ends of the compound of formula (3) produced by the reaction of the compound of formula (1) and the compound of formula (2) are easily fluorinated by contact with fluorine gas or the like, and therefore the compound of formula (4) having trifluoromethyl groups at both ends can be produced.

In the reaction of the compound of formula (1) with the compound of formula (2), the reaction is preferably carried out at a rate of 1.01mol or more, more preferably at a rate of 1.1mol or more, relative to 1mol of the compound of formula (2).

By reacting the compound of formula (1) with the compound of formula (2) in the above-described molar ratio, the polymerization reaction proceeds smoothly, and therefore the compound of formula (3) having a high molecular weight can be produced in a high yield.

In the reaction of the compound of formula (1) and the compound of formula (2), the reaction is preferably carried out at a rate of 3mol or less, more preferably at a rate of 2mol or less, relative to 1mol of the compound of formula (2).

The reaction of the compound of formula (1) with the compound of formula (2) is preferably carried out in the presence of a base catalyst. By reacting the compound of formula (1) with the compound of formula (2) in the presence of a base catalyst, the molecular weight and yield of the produced compound of formula (3) can be further improved.

Examples of the base catalyst include sodium hydroxide, potassium hydroxide, sodium carbonate, cesium fluoride, and potassium carbonate is preferable from the viewpoints of the molecular weight and yield of the fluorine-containing divinyl polyether compound and the fluorine-containing polyether compound.

The reaction of the compound of formula (1) with the compound of formula (2) may be carried out in a solvent or may be carried out without using a solvent. The solvent is not particularly limited, and when the compound of formula (3) is fluorinated, a solvent which does not undergo fluorination is preferable, and specifically, a fluorine-based solvent is preferable. Examples of the fluorine-based solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, and fluoroalcohols.

The reaction temperature of the compound of formula (1) and the compound of formula (2) is preferably 80 to 160 ℃, more preferably 90 to 140 ℃, from the viewpoints of the molecular weight and yield of the compound of formula (3).

The reaction of the compound of formula (1) with the compound of formula (2) may be carried out in a batch manner or in a continuous manner, and a known manner may be suitably employed.

In the case where the reaction of the compound of formula (1) and the compound of formula (2) is carried out in a batch manner, for example, the compound of formula (2) is stored in a reactor in advance, the compound of formula (1) may be added to the reactor, or a diluent of the compound of formula (1) may be added.

In the case of adding the compound of formula (1) or a dilution thereof to the compound of formula (2) previously stored in the reactor, it is preferable to add the compound of formula (2) after heating the compound to the reaction temperature to bring the compound into an alkylene oxide state from the viewpoint of reactivity.

From the viewpoints of the molecular weight and yield of the compound of formula (3), the addition of the compound of formula (1) to the compound of formula (2) is preferably carried out at a rate of 0.01 to 10 mol/hr, more preferably at a rate of 0.1 to 0.5 mol/hr, relative to 1mol of the compound of formula (2) in the reaction of the compound of formula (1) with the compound of formula (2).

After the compound of formula (1) and the compound of formula (2) are reacted, at least 1 selected from the group consisting of a solvent, water and an aqueous solution for adjusting to an appropriate acidity may be added and separated, and then the organic phase may be concentrated. The reaction crude liquid obtained by concentrating the organic phase may be purified. The solvent is not particularly limited, and the above-mentioned fluorine-based solvent is preferable.

The compound of formula (1), the compound of formula (2) and the compound of formula (3) will be described below.

Compounds of formula (1)

In the following general formula (1), R is from the viewpoint of lubricity ¹ Preferably, at least one is a fluorine atom, more preferably both are fluorine atoms.

CF ₂ ＝CR ¹ -O-R ² -O-CR ¹ ＝CF ₂ (1)

In the general formula (1), R ² Represents a C1-20 hydrocarbon group having 2-atoms, wherein the C1-20 hydrocarbon group optionally contains a ring structure, a branched structure, optionally contains an ether bond, and a hydrogen atom is optionally substituted with a fluorine atom.

The carbon number of the 2-valent hydrocarbon group is preferably 15 or less, more preferably 10 or less. Since the polymerization reaction proceeds more smoothly by setting the carbon number of the 2-valent hydrocarbon group to 15 or less, a high-molecular-weight fluoropolyether compound can be produced in a high yield.

From the viewpoint of suppressing the production of cyclized products in the polymerization reaction, the carbon number of the 2-valent hydrocarbon group is preferably 2 or more, more preferably 3 or more.

As R ² Examples of the 2-valent hydrocarbon group include an alkylene group such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group, a fluoromethylene group, a fluoroethylene group, a fluorotrimethylene group, a fluorotetramethylene group, a fluoropentamethylene group, and a fluorohexamethylene group.

R ² The 2-valent hydrocarbon group shown may be a group shown by the following general formula (X).

*-R ^x -(O-R ^x ) _n -*(X)

In the general formula (X), R ^x Represents ethylene, trimethylene, propylene, fluoroethylene, fluorotrimethylene or fluoropropylene, and n represents an integer of 1 or more.

In the general formula (X), the X represents a bonding moiety to an oxygen atom.

R ² The 2-valent hydrocarbon group may be a group represented by the following general formula (A).

*-R ^b -O-R ^a -O-R ^b -*(A)

In the general formula (A), R ^a Represents cycloalkanediyl, fluorocyclocycloalkanediyl or arylene.

Examples of the cycloalkanediyl group and fluorocycloalkane-ediyl group include cyclobutanediyl group, fluorocyclobutane-diyl group, cyclopentanediyl group, fluorocyclopentane-diyl group, cyclohexanediyl group, fluorocyclohexane-diyl group, adamantanediyl group, and norbornanediyl group. The cycloalkanediyl group, fluorocycloalkane diyl group and arylene group may have, as a substituent, an alkyl group having 1 to 3 carbon atoms, a hydrogen atom of which is optionally substituted with a fluorine atom.

In the general formula (A), R ^b Each independently represents a 2-valent hydrocarbon group having 1 to 10 carbon atoms, the 2-valent hydrocarbon group having 1 to 10 carbon atoms optionally containing a ring structure, a branched structure, and a hydrogen atom optionally being substituted with a fluorine atom.

In the general formula (a), the bonding moiety to an oxygen atom is represented.

Examples of the hydrocarbon group satisfying the general formula (a) include, but are not limited to, the following groups.

In addition, R ² The 2-valent hydrocarbon group shown may be a group shown by the following general formulae (B) to (D).

*-R ^c -R ^a -R ^c -* (B)

*-R ^a -R ^c -R ^a -* (C)

*-R ^b -R ^d -R ^b -* (D)

In the general formulae (B) to (D), the "bond" to the oxygen atom is represented.

R in the above general formulae (B) to (D) ^a The groups represented by the general formula (A) are the same as those described above.

In additionIn the general formulae (B) and (C), R ^c Each independently represents a single bond, or a 2-valent hydrocarbon group of 1 to 10 carbon atoms, the 2-valent hydrocarbon group of 1 to 10 carbon atoms optionally containing a ring structure, a branched structure, and a hydrogen atom optionally being substituted with a fluorine atom.

In the general formula (D), R is ^d Represents a cycloalkane-1, 1-diyl group having 3 to 6 carbon atoms.

Examples of the group satisfying any one of the general formulae (B) to (D) include, but are not limited to, the following groups.

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The molecular weight of the compound of formula (1) is preferably 150 to 1000, more preferably 200 to 600. The reaction with the compound of formula (2) proceeds smoothly by bringing the molecular weight of the compound of formula (1) into the above-mentioned numerical range.

As described above, the compounds of formula (1) are exemplified by, but not limited to, the following.

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From the viewpoint of lubricity, R may be contained in the compound of formula (1) ¹ Are all fluorine, and R ² Is a perfluorinated 2-valent hydrocarbon group.

Compounds of formula (2)

In the following general formula (2), R ³ Represents a C1-20 hydrocarbon group having 2-atoms, wherein the C1-20 hydrocarbon group optionally contains a ring structure, a branched structure, optionally contains an ether bond, and a hydrogen atom is optionally substituted with a fluorine atom. The 2-valent hydrocarbon group can be selected from R ² The same groups as those of the 2-valent hydrocarbon group are omitted here. In addition, R ² R is R ³ May be the same group or may be different groups.

HO-R ³ -OH(2)

The molecular weight of the compound of formula (2) is preferably 50 to 400, more preferably 60 to 300. The reaction with the compound of formula (1) proceeds smoothly by bringing the molecular weight of the compound of formula (2) into the above-mentioned numerical range.

The acidity (pKa) of the compound of formula (2) is preferably 8 to 18, more preferably 9 to 15. The reaction with the compound of formula (1) proceeds smoothly by bringing the pKa of the compound of formula (2) into the above-mentioned numerical range.

In the present disclosure, pKa is a value in water at 25℃and is calculated by the method described in the redacted 5 edition II-331 to II-343 (Japanese chemical society, wan Co., ltd.).

The compound of formula (2) is exemplified by, but not limited to, the following.

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From the standpoint of reactivity, the compound of formula (1) and the compound of formula (2) are preferably a combination of 1 or more compounds of formula (1) selected from group a below and a compound of formula (2) selected from group B below, more preferably a combination of 1 or more compounds of formula (1) selected from group a' below and a compound of formula (2) selected from group B below, but are not limited thereto.

Group a is as follows.

Group A' is as follows.

Group B is as follows.

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Compounds of formula (3)

A fluorodivinyl polyether compound represented by the following general formula (3) is produced by reacting a compound of formula (1) with a compound of formula (2). In the general formula (3), R ¹ 、R ² R is R ³ Since the description is given above, the description is omitted here.

The compound of formula (3) is exemplified by, but not limited to, the following. Since the divinyl groups at both ends of the compound of formula (3) are easily fluorinated, a compound of formula (4) having a high molecular weight and trifluoromethyl groups at both ends can be produced in high yield.

Fluorination of fluorine-containing divinyl polyether compounds

In the method for producing a fluoropolyether compound according to embodiment 1, a compound of formula (3) is fluorinated to produce a fluoropolyether compound represented by the following general formula (4).

The method for fluorinating the compound of formula (3) is not particularly limited, and can be carried out by a conventionally known method. For example, the fluorination may be carried out by contacting fluorine gas with the compound of formula (3).

The fluorination process of the compound of formula (3) may be carried out in a batch mode or in a continuous mode. The fluorination reaction is preferably carried out by the following < method 1> or < method 2>, and from the viewpoint of the yield of the compound of formula (4), the following < method 2> is more preferable. In the case of batch-wise operation and in the case of continuous operation, the fluorine gas may be diluted with an inert gas such as nitrogen gas.

< method 1>

The method 1 comprises the following steps: the compound of formula (3) and the solvent are charged into the reactor and stirring is started. A method of continuously supplying fluorine gas diluted with an inert gas to a solvent at a predetermined reaction temperature and reaction pressure to perform a reaction.

< method 2>

The method 2 comprises the following steps: the solvent was charged into the reactor and stirred. Then, a method of continuously supplying fluorine gas diluted with an inert gas, a compound of formula (3) and a solvent to a fluorination reaction solvent at a predetermined molar ratio at a predetermined reaction temperature and reaction pressure.

< method 3>

The method 3 comprises the following steps: and a method in which a solvent is continuously introduced into a tubular reactor and flowed through the tubular reactor, then fluorine gas diluted with an inert gas and a solution in which a compound of formula (3) is dissolved are continuously supplied to and mixed with the solvent flow in the tubular reactor in a ratio such that the fluorine gas and the compound of formula (3) are in a predetermined molar ratio, the fluorine gas and the compound of formula (3) are brought into contact with each other in the tubular reactor to react, and a solvent containing a reaction product is taken out of the tubular reactor. In this method, the solvent is circulated, and the reaction product is taken out from the circulated solvent, whereby the fluorination reaction can be performed in a continuous manner.

In the method 2, as in the case of the embodiment 3, it is preferable to supply the compound of the formula (3) diluted with the solvent at the time of supplying the compound of the formula (3) in order to increase the selectivity of the compound of the formula (4) and to suppress the amount of by-products. In addition, when the compound of formula (3) is diluted with a solvent, the amount of the solvent relative to the compound of formula (3) is preferably 5 times or more, more preferably 7 times or more, based on mass.

Examples of the inert gas include rare gases such as helium, neon, and argon, and nitrogen, preferably nitrogen and helium, and more preferably nitrogen from the viewpoint of economic advantage. The ratio of fluorine gas (hereinafter also referred to as "fluorine amount") is preferably 15 to 60% by volume based on 100% by volume of the total of fluorine gas and inactive gas.

In the case of carrying out the fluorination of the compound of formula (3) in a solvent, the solvent may be subjected to nitrogen substitution in advance in order to reduce the oxygen content in the solvent.

In addition, in the case of introducing the compound of formula (3) into the solvent, the solvent may be replaced with nitrogen in advance, and then the solvent may be replaced with fluorine.

In the fluorination reaction, it is preferable that either in a batch mode or in a continuous mode: the amount of fluorine gas which fluorinates all of the fluorinatable hydrogen atoms in the compound of formula (3) is always set to an excess amount. The amount of fluorine gas is preferably 1.1 times or more equivalent, more preferably 1.3 times or more equivalent of the theoretical amount required for completely fluorinating the hydrogen atoms which can be fluorinated.

When the compound of formula (3) is fluorinated by introducing fluorine gas and the compound of formula (3) into the solvent, the molar reference introduction rate of the compound of formula (3) into the solvent may be 1 to 10 times or 2 to 7 times the molar reference introduction rate of the compound of formula (3) multiplied by the number of hydrogen atoms contained in the compound of formula (3) that may be substituted with fluorine atoms, assuming that the molar reference introduction rate of the compound of formula (3) into the solvent is 1. By setting the relation of the introduction rates to the above numerical ranges, the yield of the compound of formula (4) can be improved.

In order to effectively perform the fluorination reaction of the compound of formula (3), it is preferable to add a compound containing a c—h bond other than the compound of formula (3) to the solvent or to irradiate ultraviolet rays to the solvent. These are preferably carried out later in the fluorination reaction. This effectively fluorinates the compound of formula (3) in the solvent, and can increase the yield of the compound of formula (4).

The C-H bond-containing compound is preferably an aromatic hydrocarbon, and examples thereof include benzene and toluene. The amount of the C-H bond-containing compound to be added is preferably 0.1 to 10 mol%, more preferably 0.1 to 5 mol%, based on the hydrogen atom in the compound of formula (3).

The C-H bond-containing compound is preferably added to a solvent in which fluorine gas is present. Furthermore, when the C-H bond-containing compound is added, the reaction system is preferably pressurized. The reaction pressure at the time of pressurization is preferably 0.01MPa to 5MPa (gauge pressure).

When ultraviolet rays are irradiated to the reaction system, the irradiation time is preferably 0.1 to 3 hours.

After the fluorination reaction, at least 1 selected from the group consisting of a solvent, water and an aqueous solution for adjusting to an appropriate acidity may be added to the reaction solution and separated, and then the organic phase may be concentrated to obtain the compound of formula (4). Alternatively, the compound of formula (4) may be obtained by purifying a crude reaction solution obtained by concentrating an organic phase.

The compound of formula (4) will be described below.

Compounds of formula (4)

R is as follows ² R is R ³ In the case where the 2-valent hydrocarbon group has an aromatic ring, the aromatic ring is perfluorinated, and a perfluorocycloalkyl ring is formed.

The number average molecular weight (Mn) of the compound of formula (4) obtained by the production method according to embodiment 1 is preferably 1000 to 30000, more preferably 2000 to 20000, still more preferably 2000 to 10000. By setting Mn of the compound of formula (4) to the above numerical range, it is possible to suppress the viscosity of the compound of formula (4) from becoming too high, and to facilitate handling in production and use.

The molecular weight distribution (Mw/Mn) of the compound of formula (4) is preferably 1 to 3, more preferably 1 to 2.5, and still more preferably 1 to 1.5. By setting the Mw/Mn of the compound of formula (4) to the above-described numerical range, volatilization of the compound of formula (4) when used in a high-temperature environment can be suppressed.

In the method for producing a fluoropolyether compound according to embodiment 1, the compound of formula (4) obtained by fluorination of the compound of formula (3) is exemplified by, but not limited to, the following.

(method for producing fluoropolyether Compound of embodiment 2)

Next, a method for producing the fluoropolyether compound represented by the general formula (7-1) or the general formula (7-2) will be described. The fluorinated divinyl polyether compounds represented by the general formula (6-1) or the general formula (6-2) and the method for producing the same are also described together.

In the method for producing a fluorinated polyether compound according to embodiment 2, a fluorinated divinyl ether compound represented by the following general formula (1) (hereinafter, also referred to as a compound of formula (1)) and a fluorinated vinyl alcohol compound represented by the following general formula (5) (hereinafter, also referred to as a compound of formula (5)) are reacted at a ratio of more than 1mol of the compound of formula (5) to 1mol of the compound of formula (1), whereby a fluorinated divinyl polyether compound represented by the following general formula (6-1) or the following general formula (6-2) (hereinafter, also referred to as a compound of formula (6-1) and a compound of formula (6-2)), respectively, is produced, and then the compound of formula (6-1) or the compound of formula (6-2) is fluorinated, whereby a fluorinated polyether compound represented by the following general formula (7-1) or the following general formula (7-2) (hereinafter, also referred to as a compound of formula (7-1) and a compound of formula (7-2)) is produced.

CF ₂ ＝CR ¹ -O-R ² -O-CR ¹ ＝CF ₂ (1)

CF ₂ ＝CR ¹ -O-R ⁴ -OH (5)

In the general formula (1), the general formula (5), the general formula (6-1) and the general formula (6-2), R ¹ Each independently represents a fluorine atom, a hydrogen atom or a C1-3 hydrocarbon group in which a hydrogen atom is optionally substituted with a fluorine atom.

In the general formula (1), the general formula (5), the general formula (6-1) and the general formula (6-2), R ² R is R ⁴ Each independently represents a 2-valent hydrocarbon group of 1 to 20 carbon atoms, the 2-valent hydrocarbon group of 1 to 20 carbon atoms optionally containing a ring structure, a branched structure, optionally containing an ether bond, and a hydrogen atom optionally being substituted with a fluorine atom.

In the general formula (7-1) and the general formula (7-2), R is ¹ R being fluorine atom ^F1 Each independently represents a fluorine atom, at R ¹ R being a hydrogen atom ^F1 Each independently represents a fluorine atom, at R ¹ R is a C1-3 1-valent hydrocarbon group ^F1 Each independently represents a 1-valent perfluoroalkyl group having 1 to 3 carbon atoms.

In the general formula (7-1) and the general formula (7-2), R ^F2 Each independently represents R ² The 2-valent hydrocarbon group is a 2-valent perfluorinated hydrocarbon group having 1 to 20 carbon atoms which is perfluorinated.

In the general formula (7-1) and the general formula (7-2), R ^F4 Each independently represents R ⁴ The 2-valent hydrocarbon group is a 2-valent perfluorinated hydrocarbon group having 1 to 20 carbon atoms which is perfluorinated.

In the general formulae (6-1), (6-2), (7-1) and (7-2), b, c and d each independently represent an integer of 0 or 1 or more, preferably an integer of 3 or more, and more preferably an integer of 5 or more.

The method for producing a fluoropolyether compound according to claim 2 enables production of a high-molecular-weight fluoropolyether compound having trifluoromethyl groups at both ends thereof in high yield.

The reason for the above effect is presumed to be as follows, but is not limited thereto.

In the reaction of the compound of formula (1) and the compound of formula (5), the polymerization reaction proceeds smoothly by performing the reaction at a ratio of more than 1mol with respect to 1mol of the compound of formula (1), and therefore the compound of formula (6-1) or the compound of formula (6-2) having a high molecular weight can be produced in a high yield.

Further, the compound of formula (6-1) or the compound of formula (6-2) obtained by the above reaction has vinyl groups (CF) at both ends ₂ ＝CR ¹ By contacting the vinyl group with fluorine gas, fluorination is easily performed, and thus a compound of formula (7-1) or a compound of formula (7-2) having a high molecular weight and a trifluoromethyl group at both ends can be produced in high yield.

Hereinafter, the production of the fluorinated divinyl polyether compound included in the method for producing a fluorinated polyether compound according to claim 2 will be described.

Production of fluorine-containing divinyl polyether compounds

The compound of formula (7-1) or the compound of formula (7-2) having trifluoromethyl groups at both ends can be produced by bringing vinyl groups at both ends of the compound of formula (6-1) or the compound of formula (6-2) produced by reacting the compound of formula (1) with the compound of formula (5) into contact with fluorine gas or the like, and thus can be easily fluorinated.

In the reaction of the compound of formula (1) with the compound of formula (5), the reaction is preferably carried out at a rate of 2mol or more, more preferably at a rate of 5mol or more, relative to 1mol of the compound of formula (1).

The polymerization reaction proceeds smoothly by reacting the compound of formula (1) with the compound of formula (5) in the above-mentioned molar ratio, and therefore the compound of formula (6-1) or the compound of formula (6-2) can be produced in high yield.

In the reaction of the compound of formula (1) and the compound of formula (5), the reaction is preferably carried out at a rate of 20mol or less, more preferably 15mol or less, relative to 1mol of the compound of formula (1).

By reacting the compound of formula (1) with the compound of formula (5) in the above-described relation of the molar ratio, homopolymerization of the compound of formula (5) can be prevented, and the compound of formula (6-1) or the compound of formula (6-2) can be produced in high yield.

As in embodiment 1, the reaction of the compound of formula (1) with the compound of formula (5) is preferably carried out in the presence of a base catalyst.

The reaction may be carried out in a solvent or without using a solvent. The solvent is not particularly limited, and the above-mentioned fluorine-based solvent is preferable.

The reaction of the compound of formula (1) with the compound of formula (5) can be carried out by adding a mixture of the compound of formula (1) and the compound of formula (5) to the above-mentioned solvent heated to the reaction temperature described below. From the viewpoint of reactivity, the rate of addition of the mixture is preferably 0.5% by mass/hr to 70% by mass/hr, more preferably 1% by mass/hr to 50% by mass/hr, relative to the total mass of the mixture.

The reaction temperature of the compound of formula (1) and the compound of formula (5) is preferably 80 to 160 ℃, more preferably 90 to 140 ℃ from the viewpoints of the molecular weights and yields of the compound of formula (6-1) and the compound of formula (6-2).

The reaction of the compound of formula (1) with the compound of formula (5) may be carried out in a batch manner or in a continuous manner, and a known manner may be suitably employed.

After the compound of formula (1) and the compound of formula (5) are reacted, at least 1 selected from the above-mentioned solvents, water and aqueous solutions for adjusting to proper acidity may be added and separated, and then the organic phase may be concentrated. The reaction crude liquid obtained by concentrating the organic phase may be purified.

The compound of formula (1), the compound of formula (5), the compound of formula (6-1) and the compound of formula (6-2) will be described below.

Compounds of formula (5)

In the following general formula (5), R ⁴ Represents a C1-20 hydrocarbon group having 2-atoms, wherein the C1-20 hydrocarbon group optionally contains a ring structure, a branched structure, optionally contains an ether bond, and a hydrogen atom is optionally substituted with a fluorine atom. The 2-valent hydrocarbon group can be selected from R ² R is R ³ The same groups as those of the 2-valent hydrocarbon group are omitted here.

CF ₂ ＝CR ¹ -O-R ⁴ -OH (5)

The molecular weight of the compound of formula (5) is preferably 90 to 800, more preferably 100 to 600. The reaction with the compound of formula (1) proceeds smoothly by bringing the molecular weight of the compound of formula (5) into the above-mentioned numerical range.

The pKa of the compound of formula (5) is preferably 8 to 16, more preferably 9 to 14. The reaction with the compound of formula (1) proceeds smoothly by bringing the pKa of the compound of formula (5) into the above-mentioned numerical range.

The compound of formula (5) is exemplified by, but not limited to, the following. The compound of formula (1) is exemplified in embodiment 1.

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From the standpoint of reactivity, the compound of formula (1) and the compound of formula (5) are preferably a combination of 1 or more compounds of formula (1) selected from group a and compounds of formula (5) selected from group C.

Group C is as follows.

Compounds of formula (6-1) and compounds of formula (6-2)

A fluorinated divinyl polyether compound represented by the following general formula (6-1) or the following general formula (6-2) is produced by reacting a compound of the formula (1) with a compound of the formula (5). In the general formula (3), R ¹ 、R ² R is R ⁴ Since the description is given above, the description is omitted here.

The compounds of the formula (6-1) and the formula (6-2) are exemplified by, but not limited to, the following. Since the compound of formula (6-1) and the compound of formula (6-2) have both terminal divinyl groups which are easily fluorinated, a high-molecular-weight fluoropolyether compound having trifluoromethyl groups at both terminals can be produced in high yield.

Fluorination of fluorine-containing divinyl polyether compounds

In the method for producing a fluoropolyether compound according to the mode 2, a compound of the formula (6-1) or a compound of the formula (6-2) is fluorinated to produce a fluoropolyether compound represented by the following general formula (7-1) or the following general formula (7-2).

The method for fluorinating the compound of formula (6-1) or the compound of formula (6-2) is not particularly limited, and can be carried out by a conventionally known method. For example, the fluorination may be carried out by contacting fluorine gas with the compound of the formula (6-1) or the compound of the formula (6-2). The specific fluorination method is the same as in embodiment 1, and therefore description thereof is omitted here.

When the compound of formula (6-1) or the compound of formula (6-2) is fluorinated by introducing fluorine gas and the compound of formula (6-1) or the compound of formula (6-2) into a solvent, the introduction rate of the fluorine gas may be in the range of 1 to 10 times or 2 to 7 times the rate obtained by multiplying the introduction rate of the fluorine gas by the number of hydrogen atoms contained in the compound of formula (6-1) or the compound of formula (6-2) that may be substituted with fluorine gas, when the introduction rate of the compound of formula (6-1) or the compound of formula (6-2) to the molar basis of the fluorination of the compound of formula (6-2) into the solvent is 1. By setting the relation of the introduction rates to the above numerical ranges, the yield of fluorination of the compound of formula (7-1) or the compound of formula (7-2) can be improved.

The compound of formula (7-1) and the compound of formula (7-2) are described below.

Compounds of formula (7-1) and compounds of formula (7-2)

In the general formula (7-1) and the general formula (7-2), R ^F4 Each independently represents R ⁴ The 2-valent hydrocarbon group is a 2-valent perfluorinated hydrocarbon group having 1 to 20 carbon atoms which is perfluorinated. R is R ⁴ In the case where the above-mentioned 2-valent hydrocarbon group has an aromatic ring, the aromatic ring is shownThe ring is perfluorinated to become a perfluorocycloalkyl ring.

With respect to R ^F1 R is R ^F2 The groups shown are the same as those in embodiment 1, and therefore description thereof is omitted here.

In the method for producing a fluoropolyether compound according to embodiment 2, the compound of formula (7-1) or the compound of formula (7-2) obtained by fluorinating the compound of formula (6-1) or the compound of formula (6-2) is exemplified by, but not limited to, the following.

Examples

The above-described embodiments are described more specifically below with reference to synthesis examples, but the above-described embodiments are not limited to these synthesis examples.

[ evaluation method ]

(NMR analysis)

NMR analysis was performed under the following conditions.

¹ The H-NMR (300.4 MHz) standard substance used 7.5ppm nitrobenzene.

· ¹⁹ As a reference material for F-NMR (282.7 MHz), perfluoro benzene was used at-162.5 ppm.

As the solvent for NMR, a mixed solvent of deuterated chloroform and hexafluorobenzene or a mixed solvent of deuterated chloroform and 1, 4-bistrifluoromethyl benzene was used.

(GPC analysis)

The number average molecular weight (Mn) and the mass average molecular weight (Mw) were measured by GPC. GPC-based measurements were performed as described above.

Synthesis example 1-1

Into a 200mL eggplant-type flask, 3.3g of ethylene glycol (pKa: 14.22) satisfying the above general formula (2) and 4g of potassium carbonate were placed, and the flask was stirred at an internal temperature of 120 ℃.

Next, 20g of the following fluorodivinyl ether compound (1A) satisfying the above general formula (1) was added at a rate of 0.37 times mol/hr relative to 1mol of ethylene glycol, and the flask was stirred at an internal temperature of 120℃for 2 hours.

The reaction was carried out at a ratio of 1.11mol of the fluorodivinyl ether compound (1A) to 1mol of ethylene glycol.

CF ₂ ＝CF-O-CF ₂ CF ₂ CF ₂ -O-CF＝CF ₂ (1A)

Thereafter, 20g of each of a fluorine-based solvent (AC2000, ASAHIKLIN (registered trademark), 1H-tridecane, hereinafter referred to as "AC-2000") and hydrochloric acid was placed in the flask at an internal temperature of 25℃to obtain a reaction crude liquid separated into an organic phase and an aqueous phase. The obtained reaction crude liquid was separated, and then, the organic phase was concentrated.

The crude reaction solution obtained by concentrating the organic phase was purified by column chromatography to obtain 15g (yield 65%) of the following fluorodivinyl polyether compound (3A) satisfying the general formula (3). The average value of the number of repeating units a was 9.

Hereinafter, the fluorinated divinyl polyether compound (3A) is described.

250mL of CFE-419 were placed in a 500mL nickel reactor, followed by bubbling nitrogen gas.

It was confirmed that the dissolved oxygen concentration was sufficiently reduced, and 20% by volume of fluorine gas diluted with nitrogen gas was blown in for 1 hour (bubbling).

Next, a CFE-419 solution of the fluorodivinyl polyether compound (3A) was added to the CFE-419 in the reactor over 3 hours. The concentration of the fluorodivinyl polyether compound (3A) in the CFE-419 solution was 10% by mass, and the amount of the fluorodivinyl polyether compound (3A) was 15g. The CFE-419 solution was added while bubbling fluorine gas into the CFE-419.

When the introduction rate of the fluorodivinyl polyether compound (3A) into the solvent based on the mole thereof is 1, the introduction rate of the fluorine gas based on the mole thereof is 2 times the rate obtained by multiplying the introduction rate of the fluorodivinyl polyether compound (3A) based on the mole thereof by the number of hydrogen atoms contained in the fluorodivinyl polyether compound (3A) that can be substituted with fluorine atoms.

After the addition of the CFE-419 solution of the fluorodivinyl polyether compound and the blowing of fluorine gas, the CFE-419 solution of benzene was intermittently added. The benzene concentration in the CFE-419 solution was 0.1 mass% and the benzene amount was 0.1g.

After the addition of the CFE-419 benzene solution, fluorine gas was blown in for 1 hour, and finally the inside of the reactor was fully replaced with nitrogen gas. The solvent was distilled off to obtain 17g (yield 90%) of the following fluoropolyether compound (4A) satisfying the above general formula (4).

The structure of the fluoropolyether compound (4A) is obtained by ¹ H-NMR method ¹⁹ F-NMR method. The fluorine-containing polyether compound (4A) had Mn of 5000 and Mw/Mn of 1.8.

The fluoropolyether compound (4A) is described below.

Synthesis examples 1 to 2

Into a 200mL eggplant-type flask, 5.9g of 1, 4-benzenediol (pKa: 9.8) satisfying the above general formula (2) and 4g of potassium carbonate were placed, and the flask was stirred at an internal temperature of 120 ℃.

Next, 20g of the following fluorodivinyl ether compound (1A) satisfying the general formula (1) was added at a rate of 0.27 times mol/hr relative to 1mol of 1, 4-benzenediol, and the flask was stirred at an internal temperature of 120℃for 2 hours.

The reaction was carried out at a ratio of 1.08mol of the fluorodivinyl ether compound (1A) to 1mol of 1, 4-benzenediol.

Next, the internal temperature of the flask was set to 25℃and 20g of each of the above-mentioned AC-2000 and hydrochloric acid was placed therein to obtain a crude reaction solution separated into an organic phase and an aqueous phase. The obtained reaction crude liquid was separated, and then, the organic phase was concentrated.

The crude reaction solution obtained by concentrating the organic phase was purified by column chromatography to obtain 20g (yield 79%) of the following fluorodivinyl polyether compound (3B) satisfying the general formula (3). The average value of the number of repeating units a was 12.

The fluorinated divinyl polyether compound (3B) is described below.

250mL of CFE-419 were placed in a 500mL nickel reactor, and then nitrogen was bubbled.

It was confirmed that the dissolved oxygen concentration was sufficiently reduced, and 20% by volume of fluorine gas diluted with nitrogen gas was bubbled for 1 hour.

In addition, a CFE-419 solution of the fluorodivinyl polyether compound (3B) was added to the CFE-419 in the reactor over 3 hours. The concentration of the fluorodivinyl polyether compound (3B) in the CFE-419 solution was 10% by mass, and the amount of the fluorodivinyl polyether compound (3B) was 20g. The CFE-419 solution was added while bubbling fluorine gas into the CFE-419.

When the introduction rate of the fluorodivinyl polyether compound (3B) into the solvent based on the mole is 1, the introduction rate of the fluorine gas based on the mole is 3 times the rate obtained by multiplying the introduction rate of the fluorodivinyl polyether compound (3B) based on the mole by the number of hydrogen atoms contained in the fluorodivinyl polyether compound (3B) that can be substituted with fluorine gas as fluorine atoms.

After the addition of the CFE-419 solution of the fluorodivinyl polyether compound, the CFE-419 solution of benzene as described above was intermittently added.

After the addition of the CFE-419 benzene solution, fluorine gas was blown in over 1 hour, and finally the inside of the reactor was fully replaced with nitrogen gas. The solvent was distilled off to obtain 24g (yield: 81%) of the following fluoropolyether compound (4B) satisfying the above general formula (4).

The structure of the fluoropolyether compound (4B) is obtained by ¹ H-NMR method ¹⁹ F-NMR method. The fluorine-containing polyether compound (4B) had Mn of about 8000 and Mw/Mn of 1.8.

The fluoropolyether compound (4B) is described below.

Synthesis examples 1 to 3

9.7g of tetraethylene glycol (pKa: 14.1) satisfying the above general formula (2) and 4g of potassium carbonate were placed in a 200mL eggplant-type flask, and the flask was stirred at an internal temperature of 120 ℃.

Next, 20g of the following fluorodivinyl ether compound (1A) satisfying the above general formula (1) was added at a rate of 0.29 times mol/hr relative to 1mol of tetraethylene glycol, and the flask was stirred at an internal temperature of 120℃for 2 hours.

The reaction was carried out at a ratio of 1.16mol of the fluorodivinyl ether compound (1A) to 1mol of tetraethylene glycol.

The crude reaction solution obtained by concentrating the organic phase was purified by column chromatography to obtain 21g (yield: 72%) of the following fluorodivinyl polyether compound (3C) satisfying the general formula (3). The average value of the number of repeating units a was 6.

The fluorinated divinyl polyether compound (3C) is described below.

Next, a CFE-419 solution of the fluorodivinyl polyether compound (3C) was added to the CFE-419 in the reactor over 3 hours. The concentration of the fluorodivinyl polyether compound (3C) in the CFE-419 solution was 10% by mass, and the amount of the fluorodivinyl polyether compound (3C) was 21g. The CFE-419 solution was added while bubbling fluorine gas into the CFE-419.

When the introduction rate of the fluorodivinyl polyether compound (3C) into the solvent based on the mole is 1, the introduction rate of the fluorine gas based on the mole is 2 times the rate obtained by multiplying the introduction rate of the fluorodivinyl polyether compound (3C) based on the mole by the number of hydrogen atoms contained in the fluorodivinyl polyether compound (3C) that can be substituted with fluorine gas as fluorine atoms.

After the addition of the CFE-419 solution of benzene, the CFE-419 solution of benzene was added, fluorine gas was blown in for 1 hour, and finally the inside of the reactor was sufficiently replaced with nitrogen gas. The solvent was distilled off to obtain 33g (yield 98%) of the following fluoropolyether compound (4C) satisfying the above general formula (4).

The structure of the fluoropolyether compound (4C) is obtained by ¹ H-NMR method ¹⁹ F-NMR method. The fluorine-containing polyether compound (4C) had Mn of 5000 and Mw/Mn of 1.6.

The fluoropolyether compound (4C) is described below.

Synthesis example 2-1

Into a 200mL eggplant-type flask, 2g of a fluorine-based solvent (manufactured by AGC Co., ltd., ASAHIKLIN (registered trademark) AC-6000, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane) and 2g of potassium carbonate were placed, and the flask was stirred at an internal temperature of 120 ℃.

Next, a mixture of 5g of the above-mentioned fluorodivinyl ether compound (1A) and 40g of the following fluorovinyl alcohol compound (5A) (pKa: 12.5) satisfying the above-mentioned general formula (5) was added over 8 hours, and the flask was allowed to warm to 120℃for 2 hours with stirring.

The reaction was carried out at a ratio of 9.92mol of the fluorovinyl alcohol compound (5A) to 1mol of the fluorodivinyl ether compound (1A).

CF ₂ ＝CF-O-CF ₂ CF ₂ CF ₂ CH ₂ -OH(5A)

The internal temperature of the flask was set to 25℃and 20g of each of the above-mentioned AC-2000 and hydrochloric acid was placed therein to obtain a crude reaction solution separated into an organic phase and an aqueous phase. The obtained reaction crude liquid was separated, and then, the organic phase was concentrated.

The crude reaction solution obtained by concentrating the organic phase was purified by column chromatography to obtain 25g (yield: 56%) of the following fluorodivinyl polyether compound (6-1A) satisfying the general formula (6-1). The average value of the number of repeating units b+c was 7.

The fluorodivinyl polyether compound (6-1A) is described below.

In addition, a CFE-419 solution of the fluorodivinyl polyether compound (6-1A) was added to the CFE-419 in the reactor over 3 hours. The concentration of the fluorodivinyl polyether compound (6-1A) in the CFE-419 solution was 10% by mass, and the amount of the fluorodivinyl polyether compound (6-1A) was 25g. The CFE-419 solution was added while bubbling fluorine gas into the CFE-419.

When the introduction rate of the fluorodivinyl polyether compound (6-1A) to the molar basis in the solvent is 1, the introduction rate of the fluorine gas to the molar basis is 2 times the rate obtained by multiplying the introduction rate of the fluorodivinyl polyether compound (6-1A) to the molar basis by the number of hydrogen atoms contained in the fluorodivinyl polyether compound (6-1A) that can be substituted with fluorine atoms.

After the addition of the CFE-419 solution of benzene, the CFE-419 solution of benzene was added, fluorine gas was blown in for 1 hour, and finally the inside of the reactor was sufficiently replaced with nitrogen gas. The solvent was distilled off to obtain 30g (yield: 98%) of the following fluoropolyether compound (7-1A) satisfying the above general formula (7-1).

The structure of the fluoropolyether compound (7-1A) is obtained by ¹ H-NMR method ¹⁹ F-NMR method. The fluorine-containing polyether compound (7-1A) had Mn of 3500 and Mw/Mn of 1.6.

The fluoropolyether compound (7-1A) is described below.

Synthesis example 3-1

The same procedure as in Synthesis example 1-1 was repeated except that the reaction was carried out in a ratio of 1mol or less of the fluorodivinyl ether compound (1-1) to 1mol of ethylene glycol, to thereby produce a fluoropolyether compound (4A), and a fluoropolyether compound having trifluoromethyl groups at both ends could not be produced.

Synthesis example 3-2

The same procedure as in Synthesis example 2-1 was repeated except that the reaction was carried out in such a manner that the amount of the fluorovinyl alcohol compound (5A) was 1mol or less relative to 1mol of the fluorodivinyl ether compound (1A), thereby producing a fluoropolyether compound (6-1A), and a fluoropolyether compound (6-1A) having a sufficient molecular weight could not be produced.

The above synthesis examples show that the process for producing a fluoropolyether compound of the present disclosure can produce a fluorinated alkyl group (-CF) having both ends in high yield ₃ ) A high molecular fluorine-containing polyether compound.

The disclosure of japanese patent application 2020-217442, filed on even 25 months in 2020, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described in this specification are incorporated by reference into this specification to the same extent as if each document, patent application, and technical standard were specifically and individually indicated to be incorporated by reference.

Claims

1. A process for producing a fluorinated polyether compound, wherein a fluorinated divinyl ether compound represented by the following general formula (3) is produced by reacting a fluorinated divinyl ether compound represented by the following general formula (1) with a diol compound represented by the following general formula (2) in a ratio of more than 1mol of the fluorinated divinyl ether compound represented by the following general formula (1) to 1mol of the diol compound represented by the following general formula (2), and then a fluorinated divinyl polyether compound represented by the following general formula (3) is produced,

CF ₂ ＝CR ¹ -O-R ² -O-CR ¹ ＝CF ₂ (1)

HO-R ³ -OH(2)

in the general formulae (1) to (4),

R ^F2 each independently represents R ² 2 as shownA 2-valent perfluorinated hydrocarbon group having 1 to 20 carbon atoms in which the valent hydrocarbon group is perfluorinated,

a represents an integer of 1 or more.

2. The method for producing a fluorine-containing polyether compound according to claim 1, wherein the reaction of the fluorine-containing divinyl ether compound represented by the general formula (1) and the diol compound represented by the general formula (2) is carried out in the presence of a base catalyst.

3. The method for producing a fluorinated polyether compound according to claim 1 or 2, wherein the fluorinated divinyl polyether compound represented by the general formula (3) is carried out by introducing fluorine gas and the fluorinated divinyl polyether compound represented by the general formula (3) into a solvent,

When the introduction rate of the fluorinated divinyl polyether compound represented by the general formula (3) to the molar basis in the solvent is 1, the introduction rate of the fluorinated gas is in the range of 1 to 10 times the rate obtained by multiplying the introduction rate of the fluorinated divinyl polyether compound represented by the general formula (3) to the number of hydrogen atoms contained in the fluorinated divinyl polyether compound that can be substituted with the fluorinated gas by the number of fluorine atoms.

4. The method for producing a fluorine-containing polyether compound according to any one of claims 1 to 3, wherein the fluorine-containing divinyl ether compound represented by the general formula (1) and the diol compound represented by the general formula (2) are reacted at a ratio of 3mol or less relative to 1mol of the fluorine-containing divinyl ether compound represented by the general formula (1) and the diol compound represented by the general formula (2).

5. A process for producing a fluorinated polyether compound, wherein a fluorinated divinyl ether compound represented by the following general formula (1) is reacted with a fluorinated vinyl alcohol compound represented by the following general formula (5) in such a ratio that the fluorinated vinyl alcohol compound represented by the following general formula (5) exceeds 1mol per 1mol of the fluorinated divinyl ether compound represented by the following general formula (1), to produce a fluorinated divinyl polyether compound represented by the following general formula (6-1) or the following general formula (6-2), and then the fluorinated divinyl polyether compound represented by the following general formula (6-1) or the following general formula (6-2) is fluorinated to produce a fluorinated polyether compound represented by the following general formula (7-1) or the following general formula (7-2),

CF ₂ ＝CR ¹ -O-R ² -O-CR ¹ ＝CF ₂ (1)

CF ₂ ＝CR ¹ -O-R ⁴ -OH (5)

CF ₂ ＝CR ¹ -O-(R ⁴ -O-CF ² -CHR ¹ -O) _b -R ⁴ -O-CF ₂ -CHR ¹ -O-R ² -O-CHR ¹ -CF ₂ -

O-R ⁴ -(O-CHR ¹ -CF ₂ -O-R ⁴ ) _c -O-CR ¹ ＝CF ₂ (6-1)

In the general formula (1), the general formula (5), the general formula (6-1), the general formula (6-2), the general formula (7-1) and the general formula (7-2),

R ¹ each independently represents fluorine atom, hydrogenA 1-valent hydrocarbon group of 1 to 3 carbon atoms in which an atom or a hydrogen atom is optionally substituted with a fluorine atom,

b. c and d each independently represent an integer of 0 or 1 or more.

6. The method for producing a fluorine-containing polyether compound according to claim 5, wherein the reaction of the fluorine-containing divinyl ether compound represented by the general formula (1) and the fluorine-containing vinyl alcohol compound represented by the general formula (5) is carried out in the presence of a base catalyst.

7. The method for producing a fluorinated polyether compound according to claim 5 or 6, wherein the fluorinated divinyl polyether compound represented by the general formula (6-1) or the general formula (6-2) is produced by introducing fluorine gas and the fluorinated divinyl polyether compound represented by the general formula (6-1) or the general formula (6-2) into a solvent,

when the introduction rate of the fluorinated divinyl polyether compound represented by the general formula (6-1) or the general formula (6-2) to the molar basis in the solvent is 1, the introduction rate of the fluorinated gas is in the range of 1 to 10 times the rate obtained by multiplying the introduction rate of the fluorinated divinyl polyether compound represented by the general formula (6-1) or the general formula (6-2) by the number of hydrogen atoms contained in the fluorinated divinyl polyether compound that can be substituted with the fluorinated gas to a fluorine atom.

8. The method for producing a fluorine-containing polyether compound according to any one of claims 5 to 7, wherein the reaction of the fluorine-containing divinyl ether compound represented by the general formula (1) and the fluorine-containing vinyl alcohol compound represented by the general formula (5) is carried out at a ratio of 20mol or less relative to 1mol of the fluorine-containing divinyl ether compound represented by the general formula (1).

9. A process for producing a fluorodivinyl polyether compound, wherein a fluorodivinyl ether compound represented by the following general formula (1) and a diol compound represented by the following general formula (2) are reacted at a ratio of more than 1mol of the fluorodivinyl ether compound represented by the following general formula (1) to 1mol of the diol compound represented by the following general formula (2) to produce a fluorodivinyl polyether compound represented by the following general formula (3),

CF ₂ ＝CR ¹ -O-R ² -O-CR ¹ ＝CF ₂ (1)

HO-R ³ -OH(2)

in the general formulae (1) to (3),

a represents an integer of 1 or more.

10. A process for producing a fluorodivinyl polyether compound, wherein a fluorodivinyl ether compound represented by the following general formula (1) and a fluorovinyl alcohol compound represented by the following general formula (5) are reacted at a ratio of more than 1mol of the fluorovinyl alcohol compound represented by the following general formula (5) to 1mol of the fluorodivinyl ether compound represented by the following general formula (1) to produce a fluorodivinyl polyether compound represented by the following general formula (6-1) or the following general formula (6-2),

CF ₂ ＝CR ¹ -O-R ² -O-CR ¹ ＝CF ₂ (1)

CF ₂ ＝CR ¹ -O-R ⁴ -OH (5)

O-R ⁴ -(O-CHR ¹ -CF ₂ -O-R ⁴ ) _c -O-CR ¹ ＝CF ₂ (6-1)

In the general formula (1), the general formula (5), the general formula (6-1) and the general formula (6-2),

b. c and d each independently represent an integer of 0 or 1 or more.

11. A process for producing a fluorinated polyether compound, wherein a fluorinated divinyl polyether compound represented by the following general formula (3) is fluorinated to produce a fluorinated polyether compound represented by the following general formula (4),

in the general formulae (1) to (4),

a represents an integer of 1 or more.

12. A process for producing a fluorinated polyether compound, wherein a fluorinated divinyl polyether compound represented by the following general formula (6-1) or the following general formula (6-2) is fluorinated to produce a fluorinated polyether compound represented by the following general formula (7-1) or the following general formula (7-2),

CF ₂ ＝CR ¹ -O-R ² -O-CR ¹ ＝CF ₂ (1)

CF ₂ ＝CR ¹ -O-R ⁴ -OH (5)

O-R ⁴ -(O-CHR ¹ -CF ₂ -O-R ⁴ ) _c -O-CR ¹ ＝CF ₂ (6-1)

at R ¹ R being fluorine atom ^F1 Each independently represents a fluorine atom,at R ¹ R being a hydrogen atom ^F1 Each independently represents a fluorine atom, at R ¹ R is a C1-3 1-valent hydrocarbon group ^F1 Each independently represents a 1-valent perfluoroalkyl group having 1 to 3 carbon atoms,

b. c and d each independently represent an integer of 0 or 1 or more.

13. A fluorine-containing divinyl polyether compound represented by the following general formula (3),

in the general formula (3),

a represents an integer of 1 or more.

14. A fluorine-containing divinyl polyether compound represented by the following general formula (6-1),

O-R ⁴ -(O-CHR ¹ -CF ₂ -O-R ⁴ ) _c -O-CR ¹ ＝CF ₂ (6-1)

in the general formula (6-1),

b and c each independently represent an integer of 0 or 1 or more.

15. A fluorine-containing divinyl polyether compound represented by the following general formula (6-2),

in the general formula (6-2),

d represents an integer of 0 or 1 or more.