WO2018216777A1

WO2018216777A1 - Method for producing fluorine-containing ether compounds and fluorine-containing ether compounds

Info

Publication number: WO2018216777A1
Application number: PCT/JP2018/020030
Authority: WO
Inventors: 星野　泰輝; 清貴高尾
Original assignee: Ａｇｃ株式会社
Priority date: 2017-05-26
Filing date: 2018-05-24
Publication date: 2018-11-29
Also published as: JP2020117733A; CN110650991A; CN110650991B; JPWO2018216777A1; JP6705557B2; CN116041689A

Abstract

Provided is a method for producing fluorine-containing ether compositions with which can be produced, in good yields, fluorine-containing ether compounds that are suitably used for surface treatment agents and which are useful as intermediates for fluorine-containing ether compounds. The method for producing fluorine-containing ether compounds according to the present invention involves carrying out the reaction of R1OH with a compound represented by formula (1) to obtain the compound represented by formula (1), a compound represented by formula (2), and a compound represented by formula (3). (1): HO(O)C-Rf2O-(Rf1O)m-Rf2-C(O)OH (2): HO(O)C-Rf2O-(Rf1O)m-Rf2-C(O)OR1 (3): R1O(O)C-Rf2O-(Rf1O)m-Rf2-C(O)OR1 Rf1 and Rf2 are each independently a perfluoroalkylene group; m is an integer from 2 to 200; (Rf1O)m may comprise two or more species of Rf1O; and R1 is a monovalent organic group.

Description

Method for producing fluorine-containing ether compound and fluorine-containing ether compound

The present invention relates to a method for producing a fluorinated ether compound and a fluorinated ether compound.

A fluorine-containing ether compound having a poly (oxyperfluoroalkylene) chain can be suitably used as a surface treatment agent because a surface layer exhibiting high lubricity, water / oil repellency, and the like can be formed on the surface of the substrate. Surface treatment agent containing a fluorinated ether compound has a performance that prevents water and oil repellency from decreasing even when the surface layer is repeatedly rubbed with a finger (rubbing resistance) and a capability to easily remove fingerprints attached to the surface layer by wiping. It is used as a surface treatment agent for a member that constitutes a surface touched by a finger of a touch panel, for example, in applications where (fingerprint stain removability) is required to be maintained for a long period of time.

As a fluorine-containing ether compound capable of forming a surface layer excellent in friction resistance and fingerprint stain removability on the surface of a substrate, a fluorine-containing ether compound having a hydrolyzable silyl group introduced at one end has been proposed (Patent Document) 1). As an intermediate of a fluorine-containing ether compound having a hydrolyzable silyl group introduced at one end, a fluorine-containing ether compound having a hydroxyl group, a carbonyl group-containing group (such as a carboxylic acid halide group or an ester group) at one end is useful. is there. A fluorine-containing ether compound having a hydroxyl group at one end is produced, for example, as follows (Patent Document 1).

A compound represented by the following formula (1b) is fluorinated with fluorine gas, a compound represented by the following formula (1a), a compound represented by the following formula (1b), and a compound represented by the following formula (1c) A mixture consisting of
CF ₃ (OC ₂ F ₄ ) _p (OCF ₂ ) _q OCF ₂ C (O) OH (1a)
_{_{_{_{HO (O) CCF 2 (OC}}}} 2 F 4) p (OCF 2) q OCF 2 C (O) OH ··· (1b)
CF ₃ (OC ₂ F ₄ ) _p (OCF ₂ ) _q OCF ₃ (1c)
For example, p and q are p / q = 0.9 and p + q≈45.

The mixture is purified using an ion exchange resin to increase the proportion of the compound represented by formula (1a). The mixture after purification is reduced with hydrogen using a reducing agent to obtain a mixture containing a compound represented by the following formula (2a) at a high concentration.
CF ₃ (OC ₂ F ₄ ) _p (OCF ₂ ) _q OCF ₂ CH ₂ OH (2a)

In addition, a mixture of the compound represented by the formula (1a), the compound represented by the formula (1b), and the compound represented by the formula (1c) is mixed with supercritical or subcritical carbon dioxide as a mobile phase. There is also proposed a method of obtaining a mixture containing the compound represented by the formula (1a) at a high concentration by purification by silica gel chromatography (Patent Document 2).

JP 2012-072272 A JP 2015-164906 A

However, in the method described in Patent Document 1 in which the compound represented by the formula (1b) is fluorinated with fluorine gas, the compound represented by the formula (1c) is necessarily generated. Since the compound represented by the formula (1c) does not have a functional group that interacts or chemically bonds with the base material, it is not suitable as a surface treatment agent. Further, the compound represented by the formula (1c) is a stable compound and cannot be reused as a compound represented by the formula (1b) which is a raw material by decomposing only the terminal. Therefore, in the method described in Patent Document 1, a compound represented by the formula (1a) useful as an intermediate of a fluorine-containing ether compound suitably used for a surface treating agent, and further a compound represented by the formula (2a) Cannot be obtained in good yield.

INDUSTRIAL APPLICABILITY The present invention is suitably used for a method for producing a fluorinated ether composition capable of producing a fluorinated ether compound useful as an intermediate of a fluorinated ether compound suitably used for a surface treatment agent, and a surface treatment agent. The object is to provide a fluorine-containing ether compound useful as an intermediate of the fluorine-containing ether compound.

The present invention provides a method for producing a fluorinated ether compound having the following constitutions [1] to [15] and a fluorinated ether compound.
[1] A compound represented by the following formula (1) is reacted with R ¹ OH to obtain a compound represented by the following formula (1), a compound represented by the following formula (2), and the following formula (3): A method for producing a fluorine-containing ether compound, comprising obtaining a mixture containing the compound represented by the formula:
HO (O) C—R ^f2 O— (R ^f1 O) _m —R ^f2 —C (O) OH (1)
HO (O) C—R ^f2 O— (R ^f1 O) _m —R ^f2 —C (O) OR ¹ (2)
R ¹ O (O) C—R ^f2 O— (R ^f1 O) _m —R ^f2 —C (O) OR ¹ (3)
However,
R ^f1 and R ^f2 are each independently a perfluoroalkylene group,
m is an integer from 2 to 200;
(R ^f1 O) _m may be composed of two or more types of R ^f1 O,
R ¹ is a monovalent organic group.
[2] A compound represented by the formula (1) in the reaction of the compound represented by the formula (1) and the R ¹ OH by recovering the unreacted compound represented by the formula (1). The manufacturing method of [1], which is reused as
[3] The compound represented by the formula (3) is recovered, hydrolyzed to obtain the compound represented by the formula (1), and the compound represented by the formula (1) and the R ¹ OH. The production method of [1] or [2], which is reused as the compound represented by the formula (1) in the reaction with.

[4] A method for producing a fluorinated ether compound, characterized in that a compound represented by the following formula (4) is obtained by fluorinating a compound represented by the following formula (2) with a fluorine gas.
HO (O) C—R ^f2 O— (R ^f1 O) _m —R ^f2 —C (O) OR ¹ (2)
F—R ^f2 O— (R ^f1 O) _m —R ^f2 —C (O) OR ^f3 (4)
However,
R ^f1 and R ^f2 are each independently a perfluoroalkylene group,
m is an integer from 2 to 200;
(R ^f1 O) _m may be composed of two or more types of R ^f1 O,
R ¹ is a monovalent organic group,
R ^f3 is a monovalent perfluoro organic group derived from R ¹ .
[5] A method for producing a fluorinated ether compound, comprising transesterifying a compound represented by the following formula (4) and R ² OH to obtain a compound represented by the following formula (5):
F—R ^f2 O— (R ^f1 O) _m —R ^f2 —C (O) OR ^f3 (4)
F—R ^f2 O— (R ^f1 O) _m —R ^f2 —C (O) OR ² (5)
However,
R ^f1 and R ^f2 are each independently a perfluoroalkylene group,
m is an integer from 2 to 200;
(R ^f1 O) _m may be composed of two or more types of R ^f1 O,
R ^f3 is a monovalent perfluoro organic group,
R ² is a monovalent organic group.

[6] A method for producing a fluorine-containing ether compound, wherein the compound represented by the following formula (6) is obtained by hydrogen reduction of the compound represented by the following formula (5) using a reducing agent.
F—R ^f2 O— (R ^f1 O) _m —R ^f2 —C (O) OR ² (5)
F—R ^f2 O— (R ^f1 O) _m —R ^f2 —CH ₂ OH (6)
However,
R ^f1 and R ^f2 are each independently a perfluoroalkylene group,
m is an integer from 2 to 200;
(R ^f1 O) _m may be composed of two or more types of R ^f1 O,
R ² is a monovalent organic group.
[7] A fluorine-containing ether compound represented by the following formula (2) or a fluorine-containing ether compound represented by the following formula (4).
HO (O) C—R ^f2 O— (R ^f1 O) _m —R ^f2 —C (O) OR ¹ (2)
F—R ^f2 O— (R ^f1 O) _m —R ^f2 —C (O) OR ^f3 (4)
However,
R ^f1 and R ^f2 are each independently a perfluoroalkylene group,
m is an integer from 2 to 200;
(R ^f1 O) _m may be composed of two or more types of R ^f1 O,
R ¹ is a monovalent organic group,
R ^f3 is a monovalent perfluoro organic group.

[8] A compound represented by the following formula (1) and a compound represented by the following formula (12) by reacting the compound represented by the following formula (1) with the compound represented by the following formula (6): And a method for producing a fluorine-containing ether compound, comprising obtaining a mixture comprising a compound represented by the following formula (13):
HO (O) C—R ^f2 O— (R ^f1 O) _m —R ^f2 —C (O) OH (1)
F—R ^f2 O— (R ^f1 O) _m —R ^f2 —CH ₂ OH (6)
HO (O) C—R ^f2 O— (R ^f1 O) _m —R ^f2 —C (O) OCH ₂ —R ^f2 — (OR ^f1 ) _m —OR ^f2 —F (12)
F—R ^f2 O— (R ^f1 O) _m —R ^f2 —CH ₂ O (O) C—R ^f2 O— (R ^f1 O) _m —R ^f2 —C (O) OCH ₂ —R ^f2 — (OR ^f1 ) _m- OR ^f2- F (13)
However,
R ^f1 and R ^f2 are each independently a perfluoroalkylene group,
m is each independently an integer of 2 to 200;
(R ^f1 O) _m may be composed of two or more types of R ^f1 O.
[9] The unreacted compound represented by the formula (1) is recovered and the formula (1) in the reaction between the compound represented by the formula (1) and the compound represented by the formula (6). The production method according to [8], wherein the compound represented by (2) is reused.
[10] The compound represented by the formula (13) is recovered and hydrolyzed to obtain the compound represented by the formula (1) and the compound represented by the formula (6). The compound represented by formula (6) and the compound represented by formula (6) are reused in the reaction of the compound represented by formula (6) and the compound represented by formula (6). [8] Or the manufacturing method of [9].

[11] A method for producing a fluorinated ether compound, wherein a compound represented by the following formula (14) is obtained by fluorinating a compound represented by the following formula (12) with a fluorine gas.
HO (O) C—R ^f2 O— (R ^f1 O) _m —R ^f2 —C (O) OCH ₂ —R ^f2 — (OR ^f1 ) _m —OR ^f2 —F (12)
F—R ^f2 O— (R ^f1 O) _m —R ^f2 —C (O) OCF ₂ —R ^f2 — (OR ^f1 ) _m —OR ^f2 —F (14)
However,
R ^f1 and R ^f2 are each independently a perfluoroalkylene group,
m is each independently an integer of 2 to 200;
(R ^f1 O) _m may be composed of two or more types of R ^f1 O.
[12] A process for producing a fluorinated ether compound, wherein the compound represented by the following formula (5) is obtained by transesterifying the compound represented by the following formula (14) with R ² OH.
F—R ^f2 O— (R ^f1 O) _m —R ^f2 —C (O) OCF ₂ —R ^f2 — (OR ^f1 ) _m —OR ^f2 —F (14)
F—R ^f2 O— (R ^f1 O) _m —R ^f2 —C (O) OR ² (5)
However,
R ^f1 and R ^f2 are each independently a perfluoroalkylene group,
m is each independently an integer of 2 to 200;
(R ^f1 O) _m may be composed of two or more types of R ^f1 O,
R ² is a monovalent organic group.

[13] Obtaining a compound represented by the following formula (6) by hydrogen reduction of the compound represented by the following formula (5) obtained by the production method of the above [12] using a reducing agent. A method for producing a featured fluorine-containing ether compound.
F—R ^f2 O— (R ^f1 O) _m —R ^f2 —C (O) OR ² (5)
F—R ^f2 O— (R ^f1 O) _m —R ^f2 —CH ₂ OH (6)
However,
R ^f1 and R ^f2 are each independently a perfluoroalkylene group,
m is each independently an integer of 2 to 200;
(R ^f1 O) _m may be composed of two or more types of R ^f1 O,
R ² is a monovalent organic group.
[14] A compound represented by the following formula (1) obtained by reacting the compound represented by the above formula (6) obtained by the production method of [13] with a compound represented by the following formula (1): A method for producing a fluorinated ether compound, comprising: obtaining a mixture comprising a compound represented by the following formula (12) and a compound represented by the following formula (13):
HO (O) C—R ^f2 O— (R ^f1 O) _m —R ^f2 —C (O) OH (1)
HO (O) C—R ^f2 O— (R ^f1 O) _m —R ^f2 —C (O) OCH ₂ —R ^f2 — (OR ^f1 ) _m —OR ^f2 —F (12)
F—R ^f2 O— (R ^f1 O) _m —R ^f2 —CH ₂ O (O) C—R ^f2 O— (R ^f1 O) _m —R ^f2 —C (O) OCH ₂ —R ^f2 — (OR ^f1 ) _m- OR ^f2- F (13)
However,
R ^f1 and R ^f2 are each independently a perfluoroalkylene group,
m is each independently an integer of 2 to 200;
(R ^f1 O) _m may be composed of two or more types of R ^f1 O.
A fluorine-containing ether compound represented by the following formula (12) or a fluorine-containing ether compound represented by the following formula (14).
HO (O) C—R ^f2 O— (R ^f1 O) _m —R ^f2 —C (O) OCH ₂ —R ^f2 — (OR ^f1 ) _m —OR ^f2 —F (12)
F—R ^f2 O— (R ^f1 O) _m —R ^f2 —C (O) OCF ₂ —R ^f2 — (OR ^f1 ) _m —OR ^f2 —F (14)
However,
R ^f1 and R ^f2 are each independently a perfluoroalkylene group,
m is each independently an integer of 2 to 200;
(R ^f1 O) _m may be composed of two or more types of R ^f1 O.

According to the method for producing a fluorine-containing ether compound of the present invention, a fluorine-containing ether compound useful as an intermediate of a fluorine-containing ether compound suitably used for a surface treating agent can be produced with high yield.
The fluorinated ether compound of the present invention is useful as an intermediate of a fluorinated ether compound that is suitably used for a surface treatment agent.

In the present specification, a compound represented by the formula (1) is referred to as a compound (1). The same applies to compounds represented by other formulas.
The meanings of the following terms in this specification are as follows.
“Perfluoro organic group” means a group in which all of hydrogen atoms bonded to carbon atoms of an organic group are substituted with fluorine atoms.
The chemical formula of the oxyperfluoroalkylene group is expressed by describing the oxygen atom on the right side of the perfluoroalkylene group.
The “etheric oxygen atom” means an oxygen atom that forms an ether bond (—O—) between carbon-carbon atoms.
The “hydrolyzable silyl group” means a group that can form a silanol group (Si—OH) by a hydrolysis reaction. For example, SiR ³ _n L _3-n in the formulas (21) to (24).
“Surface layer” means a layer formed on the surface of a substrate.
The “number average molecular weight” of the fluorine-containing ether compound is calculated by the following method using NMR analysis.
It is calculated by determining the number (average value) of oxyperfluoroalkylene groups based on terminal groups by ¹ H-NMR and ¹⁹ F-NMR. The terminal group is, for example, F—R ^f2 or SiR ³ _n L _3-n in formulas (21) to (24).

[First Synthesis Route of Compound (6)]
Examples of the synthesis route of the compound (6) starting from the compound (1) include the following first synthesis route.

(Compound (1))
Compound (1) is the starting material in the synthetic route of compound (6).
HO (O) C—R ^f2 O— (R ^f1 O) _m —R ^f2 —C (O) OH (1)
However, R ^f1 and R ^f2 are each independently a perfluoroalkylene group, m is an integer of 2 to 200, and (R ^f1 O) _m is composed of two or more types of R ^f1 O. Also good.

<(R ^f1 O) _m >
The number of carbon atoms of R ^f1 is preferably 1 to 6, more preferably 1 to 4, and more preferably 1 to 4, from the viewpoint that the surface layer comprising the finally obtained surface treatment agent is further excellent in friction resistance and fingerprint stain removal. From the viewpoint of further excellent lubricity, 1 to 2 is particularly preferable.
R ^f1 may be a straight chain structure or a branched structure, but a straight chain structure is preferable from the viewpoint that the friction resistance and lubricity of the surface layer are further improved.

Since compound (1) has (R ^f1 O) _m , the content of fluorine atoms is large. Therefore, the finally obtained surface treatment agent can form a surface layer excellent in water / oil repellency, friction resistance and fingerprint stain removability.

M is preferably an integer of 5 to 150, particularly preferably an integer of 10 to 100. When m is not less than the lower limit of the above range, the water and oil repellency of the surface layer comprising the finally obtained surface treatment agent is excellent. If m is less than or equal to the upper limit of the above range, the surface layer has excellent friction resistance. That is, if the number average molecular weight of the surface treatment agent is too large, the number of hydrolyzable silyl groups present per unit molecular weight decreases, and the friction resistance of the surface layer decreases.

In (R ^f1 O) _m , when two or more types of R ^f1 O are present, the bonding order of each R ^f1 O is not limited and may be arranged randomly, alternately, or in blocks.
The two or more R ^{f1 O} is present, that there are two or more R ^{f1 O} having different numbers of carbon atoms, and, whether or side chain type of side chains may be the same number of carbon atoms (the side chain refers to R ^{f1 O} is present the number and number of carbon atoms in the side chain, etc.) two or more different of.
Regarding the arrangement of two or more types of R ^f1 O, for example, in the case of the fluorine-containing ether compound of the example, the structure represented by {(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 } is x1 ( CF ₂ O) and x2 amino and _(CF 2 _CF 2 O) represents that it is randomly arranged. In addition, the structure represented by (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _{x 3} has x 3 (CF ₂ CF ₂ O) and x 3 (CF ₂ CF ₂ CF ₂ CF _2). O) are alternately arranged.

(R ^f1 O) _m is {(CF ₂ O) _m1 (CF ₂ CF) from the viewpoint that the surface layer composed of the finally obtained surface treatment agent is further excellent in friction resistance, fingerprint stain removability, and lubricity. _{_{_{_{2 O) m2}, (CF}}}} 2 CF 2 O) m3, (CF 2 CF 2 CF 2 O) m4, (CF 2 CF 2 O-CF 2 CF 2 CF 2 CF 2 O) m5, and these one or A group having 1 to 4 other (R ^f1 O) at both ends is preferred. Examples of the group having 1 to 4 other (R ^f1 O) at one or both ends thereof include (CF ₂ CF ₂ O) ₂ {(CF ₂ O) _m1 (CF ₂ CF ₂ O) _{m 2-2.} }, (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _m5-1 (CF ₂ CF ₂ O), and the like. (R ^f1 O) _m is particularly preferably a group having {(CF ₂ O) _m1 (CF ₂ CF ₂ O) _m2 }.
However, m1 is an integer of 1 or more, m2 is an integer of 1 or more, m1 + m2 is an integer of 2 to 200, and the bonding order of m1 CF ₂ O and m2 CF ₂ CF ₂ O is limited Not. m3 and m4 are each an integer of 2 to 200, and m5 is an integer of 1 to 100.

<R ^f2 group>
The number of carbon atoms in R ^f2 is preferably 1 to 6, more preferably 1 to 4, and more preferably 1 to 4, from the viewpoint that the surface layer comprising the finally obtained surface treatment agent is further excellent in friction resistance and fingerprint stain removal. From the viewpoint of further excellent lubricity, 1 to 2 is particularly preferable.
The number of carbon atoms in R ^f2 is 1, for example, when (R ^f1 O) _m is {(CF ₂ O) _m1 (CF ₂ CF ₂ O) _m2 } and (CF ₂ CF ₂ O) _m3 , When (CF ₂ CF ₂ CF ₂ O) _m4, it is 2, and when it is (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _m5, it is 3 and linear. Further, when R ^f1 is a branched perfluoroalkylene group, R ^f2 may be a branched perfluoroalkylene group. For example, when R ^f1 is (CF (CF ₃ ) CF ₂ O), R ^f2 is CF (CF ₃ ).
If R ^f2 is a straight chain, the surface layer is excellent in friction resistance and lubricity.

Examples of commercially available compounds (1) include FOMBLIN (registered trademark) ZDIAC4000 manufactured by Solvay Solexis.

(Method for producing compound (2))
The compound (2) is useful as an intermediate of a fluorine-containing ether compound that is suitably used for a surface treatment agent.
In the first aspect of the method for producing a fluorinated ether compound of the present invention, a compound (1) is reacted with R ¹ OH to obtain a mixture containing the compound (1), the compound (2) and the compound (3). It is.
HO (O) C—R ^f2 O— (R ^f1 O) _m —R ^f2 —C (O) OH (1)
HO (O) C—R ^f2 O— (R ^f1 O) _m —R ^f2 —C (O) OR ¹ (2)
R ¹ O (O) C—R ^f2 O— (R ^f1 O) _m —R ^f2 —C (O) OR ¹ (3)
^{However, (R} f1 _{O) m} and ^{R f2} are described in Compound ^₍₁₎ (R f1 O) is the same as _m and ^{R f2,} which is the preferred form as well. R ¹ is a monovalent organic group.

Examples of R ¹ include a monovalent hydrocarbon group that may have a substituent. Examples of the monovalent hydrocarbon group include an alkyl group, an aryl group, and a cycloalkyl group. R ¹ preferably has 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms.
R ¹ is simultaneously fluorinated when the carboxyl group reacts with the fluorine gas, but it is desirable that no reaction occurs except that the hydrogen atom is replaced with a fluorine atom. From this point, R ¹ may contain an etheric oxygen atom, and is preferably a monovalent hydrocarbon group in which a part of the hydrogen atoms may be substituted with fluorine atoms. In addition, R ¹ OH is preferably a primary alcohol because the reaction proceeds easily in the esterification reaction after fluorination.
R ¹ is preferably an alkyl group. From the viewpoint that a compound derived from R ¹ OH by-produced in the esterification reaction after fluorination can be easily removed (the boiling point is not high), an alkyl group having 1 to 10 carbon atoms Is particularly preferred.

The reaction conditions for the compound (1) and R ¹ OH are not particularly limited as long as they are ordinary esterification reaction conditions.

Examples of a method for recovering each compound from the mixture include known purification methods (such as column chromatography using silica gel or an ion exchange resin).
The recovered compound (2) is used for the production of the next compound (4).
The recovered compound (1) is preferably reused as the compound (1) in the reaction between the compound (1) and R ¹ OH.
The recovered compound (3) is preferably hydrolyzed to obtain compound (1), which is preferably reused as compound (1) in the reaction between compound (1) and R ¹ OH.
Since compound (1) and compound (3) can be reused as raw materials, compound (1) and compound (3) are not wasted. Therefore, the compound (2), further the compound (4), the compound (5) and the compound (6) can be produced with high yield.

(Method for producing compound (4))
The compound (4) is useful as an intermediate of a fluorine-containing ether compound that is suitably used for a surface treatment agent.
The second aspect of the method for producing a fluorinated ether compound of the present invention is a method for obtaining a compound (4) by fluorinating the compound (2) with a fluorine gas.
F—R ^f2 O— (R ^f1 O) _m —R ^f2 —C (O) OR ^f3 (4)
^{However, (R} f1 _{O) m} and ^{R f2} are described in Compound ^₍₁₎ (R f1 O) is the same as _m and ^{R f2,} which is the preferred form as well. R ^f3 is a monovalent perfluoro organic group derived from R ¹ .

Since R ^f3 is a group obtained by fluorinating R ¹ of the compound (2), examples of R ^f3 include those in which R ¹ is fluorinated, and those in which a preferred form of R ¹ is fluorinated are preferred.

The reaction conditions for fluorinating the compound (2) with fluorine gas are not particularly limited as long as they are ordinary fluorination reaction conditions.

(Production method of compound (5))
The compound (5) is useful as an intermediate of a fluorinated ether compound suitably used for a surface treatment agent.
The third aspect of the method for producing a fluorinated ether compound of the present invention is a method for obtaining a compound (5) by transesterification between the compound (4) and R ² OH.
F—R ^f2 O— (R ^f1 O) _m —R ^f2 —C (O) OR ² (5)
^{However, (R} f1 _{O) m} and ^{R f2} are described in Compound ^₍₁₎ (R f1 O) is the same as _m and ^{R f2,} which is the preferred form as well. R ² is a monovalent organic group.

R ² includes a monovalent hydrocarbon group which may have a substituent. Examples of the monovalent hydrocarbon group include an alkyl group, an aryl group, and a cycloalkyl group. R ¹ preferably has 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms.
As R ² , an alkyl group is preferable, and as R ² OH, a boiling point is not high, and an alkyl group having 1 to 10 carbon atoms is particularly preferable because R ² OH can be easily removed in a later step.

The reaction conditions for the compound (4) and R ² OH are not particularly limited as long as they are ordinary transesterification reaction conditions.

(Production method of compound (6))
The compound (6) is useful as an intermediate of a fluorine-containing ether compound that is suitably used for a surface treatment agent.
In the method for producing a fluorinated ether compound of the present invention, compound (6) may be obtained by hydrogen reduction of compound (5) using a reducing agent.
F—R ^f2 O— (R ^f1 O) _m —R ^f2 —CH ₂ OH (6)
^{However, (R} f1 _{O) m} and ^{R f2} are described in Compound ^₍₁₎ (R f1 O) is the same as _m and ^{R f2,} which is the preferred form as well.

Examples of the reducing agent include sodium borohydride, lithium aluminum hydride, borane (monoborane, diborane, etc.), hydrogen gas in the presence of a metal catalyst (palladium catalyst, platinum catalyst, etc.), and the like.

The reaction conditions for the compound (5) and the reducing agent are not particularly limited as long as they are normal hydrogen reduction reaction conditions.

[Second Synthesis Route of Compound (6)]
Another synthetic route for compound (6) starting from compound (1) includes the following second synthetic route.

(Method for producing compound (12))
The compound (12) is useful as an intermediate of a fluorinated ether compound suitably used for a surface treatment agent.
In the fourth aspect of the method for producing a fluorinated ether compound of the present invention, compound (1) is reacted with compound (6) to obtain a mixture containing compound (1), compound (12) and compound (13). Is the method.
HO (O) C—R ^f2 O— (R ^f1 O) _m —R ^f2 —C (O) OH (1)
F—R ^f2 O— (R ^f1 O) _m —R ^f2 —CH ₂ OH (6)
HO (O) C—R ^f2 O— (R ^f1 O) _m —R ^f2 —C (O) OCH ₂ —R ^f2 — (OR ^f1 ) _m —OR ^f2 —F (12)
F—R ^f2 O— (R ^f1 O) _m —R ^f2 —CH ₂ O (O) C—R ^f2 O— (R ^f1 O) _m —R ^f2 —C (O) OCH ₂ —R ^f2 — (OR ^f1 ) _m- OR ^f2- F (13)
^{However, (R} f1 _{O) m} and ^{R f2} are described in Compound ^₍₁₎ (R f1 O) is the same as _m and ^{R f2,} which is the preferred form as well.

And ^(R f1 _{O) m} of the compound of (1) ^(R f1 _{O) m} and the compound (6) may be the same or may be different. From the point that a uniform compound is obtained as the compound (5) obtained from the compound (14) described later and the compound (6) obtained from the compound (5), (R ^f1 O) _m of the compound (1) and the compound ( 6) (R ^f1 O) _m is preferably the same.

The reaction conditions for the compound (1) and the compound (6) are not particularly limited as long as they are ordinary esterification reaction conditions.

Examples of a method for recovering each compound from the mixture include known purification methods (such as column chromatography using silica gel or an ion exchange resin).
The recovered compound (12) is used for the production of the next compound (14).
The recovered compound (1) is preferably reused as the compound (1) in the reaction between the compound (1) and the compound (6).
The recovered compound (13) is hydrolyzed to obtain compound (1) and compound (6), which are re-generated as compound (1) and compound (6) in the reaction of compound (1) and compound (6). It is preferable to use it.
By reusing the compound (1) and the compound (13) as raw materials, the compound (12), further the compound (14), the compound (5) and the compound (6) can be produced with high yield.

(Production method of compound (14))
The compound (14) is useful as an intermediate of a fluorine-containing ether compound that is suitably used for a surface treatment agent.
A fifth aspect of the method for producing a fluorinated ether compound of the present invention is a method for obtaining a compound (14) by fluorinating the compound (12) with a fluorine gas.
F—R ^f2 O— (R ^f1 O) _m —R ^f2 —C (O) OCF ₂ —R ^f2 — (OR ^f1 ) _m —OR ^f2 —F (14)
^{However, (R} f1 _{O) m} and ^{R f2} are described in Compound ^₍₁₎ (R f1 O) is the same as _m and ^{R f2,} which is the preferred form as well.

The reaction conditions for fluorinating the compound (12) with fluorine gas are not particularly limited as long as they are ordinary fluorination reaction conditions.

(Production method of compound (5))
The compound (5) is useful as an intermediate of a fluorinated ether compound suitably used for a surface treatment agent.
The sixth aspect of the method for producing a fluorinated ether compound of the present invention is a method for obtaining compound (5) by reacting compound (14) with R ² OH.
F—R ^f2 O— (R ^f1 O) _m —R ^f2 —C (O) OR ² (5)
^{However, (R} f1 _{O) m} and ^{R f2} are described in Compound ^₍₁₎ (R f1 O) is the same as _m and ^{R f2,} which is the preferred form as well. R ² is also the same as ^{R 2} in ^R 2 OH as described above, the preferred form as well.

The reaction mechanism of compound (14) and R ² OH is shown in the following formula. 2 mol of R ² OH reacts with 1 mol of compound (14) to produce 2 mol of compound (5).

The reaction conditions for the compound (14) and R ² OH are not particularly limited as long as they are ordinary transesterification reaction conditions.

(Production method of compound (6))
In the method for producing a fluorinated ether compound of the present invention, compound (6) may be obtained by hydrogen reduction of compound (5) obtained from compound (14) in the same manner as described above.
F—R ^f2 O— (R ^f1 O) _m —R ^f2 —CH ₂ OH (6)
^{However, (R} f1 _{O) m} and ^{R f2} are described in Compound ^₍₁₎ (R f1 O) is the same as _m and ^{R f2,} which is the preferred form as well.

Part of the obtained compound (6) is preferably reused as an alcohol to be reacted with the starting compound (1).
When R ¹ OH other than compound (6) is used as the alcohol to be reacted with compound (1), R ^f3 OH produced by transesterification of compound (4) and R ² OH when producing compound (5) (Alcohol derived from R ¹ OH) is wasted. On the other hand, when compound (6) is used as the alcohol to be reacted with compound (1), 2 mol of compound (5) is produced from 1 mol of compound (14) when producing compound (5). The alcohol used (compound (6)) is not wasted.

[Surface treatment agent]
Examples of the fluorine-containing ether compound that can be produced using the compound (6) as a raw material and are suitably used for the surface treatment agent include the compound (21), the compound (22), the compound (23), and the compound (24). It is done.

^{^{_{^{F-R f2 O- (R f1}}}} O) m -R f2 -CH 2 O-Q 1 -SiR 3 n L 3-n ··· (21)
F—R ^f2 O— (R ^f1 O) _m —R ^f2 —CH ₂ — (X) _r —Q ² —N [—Q ³ —SiR ³ _n L _3-n ] ₂ (22)
^{^{_{^{F-R f2 O- (R f1}}}} O) m -R f2 -CH 2 O-Q 4 - (O) s -C [- (O) t -Q 5 -SiR 3 n L 3-n] 3 ··・ (23)
F—R ^f2 O— (R ^f1 O) _m —R ^f2 —CH ₂ O—Q ⁶ —Si [—Q ⁷ —SiR ³ _n L _3-n ] ₃ (24)

^{However, (R} f1 _{O) m} and ^{R f2} are described in Compound ^₍₁₎ (R f1 O) is the same as _m and ^{R f2,} which is the preferred form as well. R ³ is a hydrogen atom or a monovalent hydrocarbon group, L is a hydrolyzable group, and n is an integer of 0-2.
In the formula (21), Q ¹ is an alkylene group or a group having an etheric oxygen atom or a divalent organopolysiloxane residue between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms.
In the formula (22), X is an etheric oxygen atom or —NH—, and Q ² is a single bond, an alkylene group, or an etheric oxygen atom or a carbon atom between carbon atoms of an alkylene group having 2 or more carbon atoms. A group having —NH—, r is 0 or 1 (provided that 0 when Q ² is a single bond), and Q ³ is an alkylene group or an alkylene group having 2 or more carbon atoms. A group having an etheric oxygen atom, —NH— or a divalent organopolysiloxane residue between carbon-carbon atoms, and two [—Q ³ —SiR ³ _n L _3-n ] are the same, May be different.
In Formula (23), Q ⁴ is a single bond, an alkylene group, or a group having an etheric oxygen atom between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, and Q ⁵ is an alkylene group or carbon A group having an etheric oxygen atom or a divalent organopolysiloxane residue between carbon-carbon atoms of an alkylene group of 2 or more, and s is 0 or 1 (provided that 0 when Q ⁴ is a single bond). And t is 0 or 1, and the three [— (O) _t —Q ⁵ —SiR ³ _n L _3-n ] may be the same or different.
In the formula (24), Q ⁶ is an alkylene group or a group having an etheric oxygen atom or a divalent organopolysiloxane residue between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, and Q ⁷ is , An alkylene group, or a group having an etheric oxygen atom or a divalent organopolysiloxane residue between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, and three [—Q ⁷ —SiR ³ _n L _{3 -N} ] may be the same or different.

Examples of the fluorine-containing ether compound that can be produced using the compound (5) as a raw material and that are suitably used for the surface treatment agent include the compound (25), the compound (26), the compound (27), and the compound (28). It is done.

F—R ^f2 O— (R ^f1 O) _m —R ^f2 —C (O) N (R ⁵ ) —Q ⁸ —SiR ³ _n L _3-n (25)
F—R ^f2 O— (R ^f1 O) _m —R ^f2 —C (O) N (R ⁶ ) —Q ⁹ — (O) _u —C [— (O) _v —Q ¹⁰ —SiR ³ _n L _{3 −n} ] ₃ (26)
F—R ^f2 O— (R ^f1 O) _m —R ^f2 —C [—OQ ¹¹ —SiR ³ _n L _3-n ] [— Q ¹² —SiR ³ _n L _3-n ] _2. 27)
F—R ^f2 O— (R ^f1 O) _m —R ^f2 —C (OH) [—Q ¹³ —SiR ³ _n L _3-n ] ₂ (28)

^{However, (R} f1 _{O) m} and ^{R f2} are described in Compound ^₍₁₎ (R f1 O) is the same as _m and ^{R f2,} which is the preferred form as well. R ³ , L and n are the same as R ³ , L and n described in the compound (21) and the like.
In the formula (25), R ⁵ is a hydrogen atom or an alkyl group, and Q ⁸ is an alkylene group or an etheric oxygen atom or a divalent organopolyoxy group between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms. A group having a siloxane residue.
In the formula (26), R ⁶ represents a hydrogen atom or an alkyl group, and Q ⁹ represents a single bond, an alkylene group, or a group having an etheric oxygen atom between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms. Q ¹⁰ is an alkylene group or a group having an etheric oxygen atom or a divalent organopolysiloxane residue between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, and u is 0 or 1 (However, when Q ⁹ is a single bond, it is 0.), v is 0 or 1, and three [— (O) _v -Q ¹⁰ -SiR ³ _n L _3-n ] are They may be the same or different.
In Formula (27), Q ¹¹ represents an alkylene group, a group having an etheric oxygen atom or a silphenylene skeleton between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, or a carbon atom of an alkylene group having 2 or more carbon atoms— Q ¹² is a group having a divalent organopolysiloxane residue or a dialkylsilylene group at the terminal between carbon atoms or on the side bonded to O, and Q ¹² is an alkylene group or a carbon-carbon atom of an alkylene group having 2 or more carbon atoms A group having an etheric oxygen atom or a silphenylene skeleton in between, two Q ¹² may be the same or different, and three —SiR ³ _n L _3-n may be the same May be different.
In the formula (28), Q ¹³ is an alkylene group or a group having an etheric oxygen atom or a divalent organopolysiloxane residue between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, -Q ¹³ -SiR _n L _3-n ] may not be the same group.

(F—R ^f2 group)
Since the terminal has F—R ^f2 , one end of the surface treatment agent becomes CF ₃ — and the other end becomes a hydrolyzable silyl group. According to the surface treatment agent having this structure, a surface layer having a low surface energy can be formed, so that the surface layer is excellent in lubricity and friction resistance. On the other hand, conventional fluorine-containing ether compounds having hydrolyzable silyl groups at both ends have insufficient surface layer lubricity and friction resistance.

(Q ¹ group-Q ¹³ group)
Q ¹ is preferably an alkylene group having 1 to 10 carbon atoms, or a group having an etheric oxygen atom between carbon-carbon atoms of an alkylene group having 2 to 10 carbon atoms, or an alkylene group having 1 to 7 carbon atoms, or A group having an etheric oxygen atom between carbon-carbon atoms of an alkylene group having 2 to 7 carbon atoms is particularly preferred. From the viewpoint of ease of production of the compound (21), —CH ₂ CH ₂ CH ₂ — or —CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ — (wherein the right side is bonded to Si) is preferable.

Q ² is preferably a single bond, an alkylene group having 1 to 10 carbon atoms, or a group having an etheric oxygen atom or —NH— between carbon-carbon atoms of an alkylene group having 2 to 10 carbon atoms, Particularly preferred is an alkylene group having 1 to 7 carbon atoms or a group having an etheric oxygen atom or —NH— between the carbon-carbon atoms of the alkylene group having 2 to 7 carbon atoms. (X) _r Q ² is a single bond, —OCH ₂ CH ₂ — or —NHCH ₂ CH ₂ — (wherein the right side is bonded to N from the viewpoint of easy production of the compound (22)). ) Is preferred.

Q ³ is preferably an alkylene group having 1 to 10 carbon atoms, or a group having an etheric oxygen atom or —NH— between carbon-carbon atoms of an alkylene group having 2 to 10 carbon atoms, and having 1 to 7 carbon atoms. An alkylene group or a group having an etheric oxygen atom or —NH— between carbon-carbon atoms of an alkylene group having 2 to 7 carbon atoms is particularly preferred. From the viewpoint of ease of production of the compound (22), —CH ₂ CH ₂ CH ₂ — or —CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ — (where the right side is bonded to Si) is preferred.

Q ⁴ is preferably a single bond, an alkylene group having 1 to 10 carbon atoms, or a group having an etheric oxygen atom between carbon-carbon atoms of an alkylene group having 2 to 10 carbon atoms. A group having an etheric oxygen atom between carbon-carbon atoms of an alkylene group of 7 or an alkylene group of 2 to 7 carbon atoms is particularly preferred. Q ⁴ - The _{(O) s,} in terms of ease of preparation of the compound (23), a single _{_{bond, -CH 2 -, - CH 2}} CH 2 O- or _-CH 2 _CH 2 _OCH 2 - ( However, the right side is bonded to C.).

Q ⁵ is preferably an alkylene group having 1 to 10 carbon atoms, or a group having an etheric oxygen atom between carbon-carbon atoms of an alkylene group having 2 to 10 carbon atoms, or an alkylene group having 1 to 7 carbon atoms, or A group having an etheric oxygen atom between carbon-carbon atoms of an alkylene group having 1 to 7 carbon atoms is particularly preferred. (O) _t -Q ⁵ is preferably —CH ₂ CH ₂ CH ₂ —, —CH ₂ OCH ₂ CH ₂ CH ₂ — or —CH ₂ OCH _{2 in} terms of ease of production of the compound (23). CH ₂ CH ₂ CH ₂ CH ₂ — (where the right side is bonded to Si) is preferred.

Q ⁶ is preferably an alkylene group having 1 to 10 carbon atoms or a group having an etheric oxygen atom between carbon-carbon atoms of an alkylene group having 2 to 10 carbon atoms, a single bond, an alkylene having 1 to 7 carbon atoms And a group having an etheric oxygen atom between carbon-carbon atoms of an alkylene group having 2 to 7 carbon atoms is particularly preferred. Q ⁶ is —CH ₂ CH ₂ CH ₂ — or —CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ — (where the right side is bonded to Si from the viewpoint of ease of production of the compound (24)) .) Is preferred.

Q ⁷ is preferably an alkylene group having 1 to 10 carbon atoms, or a group having an etheric oxygen atom between carbon-carbon atoms of an alkylene group having 2 to 10 carbon atoms, or an alkylene group having 1 to 7 carbon atoms, or A group having an etheric oxygen atom between carbon-carbon atoms of an alkylene group having 2 to 7 carbon atoms is particularly preferred. Q ⁷ is —CH ₂ CH ₂ CH ₂ — or —CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ — (wherein the right side is SiR ³ _n L from the viewpoint of ease of production of the compound (24)) _3-n is preferred).

Q ⁸ is preferably an alkylene group having 1 to 10 carbon atoms or a group having an etheric oxygen atom between carbon-carbon atoms of an alkylene group having 2 to 10 carbon atoms. Q ⁸ is preferably an alkylene group having 2 to 6 carbon atoms from the viewpoint of easy production of the compound (25).

Q ⁹ is preferably a single bond, an alkylene group having 1 to 10 carbon atoms, or a group having an etheric oxygen atom between carbon-carbon atoms of an alkylene group having 2 to 10 carbon atoms. Q ⁹ is preferably a single bond, —CH ₂ — or —CH ₂ CH ₂ — from the viewpoint of easy production of the compound (26).

Q ¹⁰ is preferably an alkylene group having 1 to 10 carbon atoms or a group having an etheric oxygen atom between carbon-carbon atoms of an alkylene group having 2 to 10 carbon atoms. The Q ^10, from the viewpoint of ease of preparation of the compound _{_{_{_{(26), -CH 2 CH 2 -, -}}}} CH 2 CH 2 CH 2 -, - CH 2 OCH 2 CH 2 CH 2 -, - CH 2 OCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ — is preferred.

The silphenylene skeleton in Q ¹¹ is a group represented by —Si (R ^a ) ₂ PhSi (R ^a ) ₂ — (where Ph is a phenylene group and R ^a is a monovalent organic group). is there. R ^a is preferably an alkyl group having 1 to 10 carbon atoms, and particularly preferably a methyl group.
The dialkylsilylene group in Q ¹¹ is a group represented by —Si (R ^b ) ₂ — (wherein R ^b is an alkyl group). R ^b is preferably an alkyl group having 1 to 10 carbon atoms, and particularly preferably a methyl group.
Q ¹¹ is an alkylene group having 1 to 10 carbon atoms, a group having an etheric oxygen atom or a silphenylene skeleton between carbon-carbon atoms of an alkylene group having 2 to 10 carbon atoms, or an alkylene group having 2 to 10 carbon atoms. A group having a divalent organopolysiloxane residue or a dialkylsilylene group at the terminal between carbon and carbon atoms or at the side bonded to O is preferred. Q ¹¹ represents —CH ₂ CH ₂ CH ₂ —, —Si (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ —, —Si (CH ₃ ) ₂ from the viewpoint of ease of production of the compound (27). OSi (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ PhSi (CH ₃ ) ₂ CH ₂ CH ₂ — are preferred (where the right side is bonded to Si. ).

Q ¹² is preferably an alkylene group having 1 to 10 carbon atoms or a group having an etheric oxygen atom between carbon-carbon atoms of an alkylene group having 2 to 10 carbon atoms. The Q ^12, from the viewpoint of ease of preparation of the compound _{_{_{_{(27), -CH 2 CH 2 -, -}}}} CH 2 CH 2 CH 2 -, - CH 2 OCH 2 CH 2 CH 2 -, - CH 2 OCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ — is preferred (however, the right side is bonded to Si).

Q ¹³ is preferably an alkylene group having 1 to 10 carbon atoms or a group having an etheric oxygen atom between carbon-carbon atoms of an alkylene group having 2 to 10 carbon atoms. The Q ^13, from the viewpoint of ease of preparation of the compound _{_{_{_{(28), -CH 2 CH 2 -, -}}}} CH 2 CH 2 CH 2 -, - CH 2 OCH 2 CH 2 CH 2 -, - CH 2 OCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ — is preferred (however, the right side is bonded to Si).

^{(R 5} groups ~ ^{R 6} groups)
R ⁵ and R ⁶ are preferably a hydrogen atom. When R ⁵ or R ⁶ is an alkyl group, the number of carbon atoms is preferably 1 to 4.

(SiR ³ _n L _3-n group)
SiR ³ _n L _3-n is a hydrolyzable silyl group.
The surface treatment agent has a hydrolyzable silyl group at the terminal. Since the surface treatment agent having this structure is strongly chemically bonded to the base material, the surface layer is excellent in friction resistance.
The surface treatment agent has a hydrolyzable silyl group only at one end. Since the surface treatment agent having such a structure hardly aggregates, the surface layer is excellent in appearance.

L is a hydrolyzable group. The hydrolyzable group is a group that becomes a hydroxyl group by a hydrolysis reaction. That is, Si—L at the end of the surface treatment agent becomes a silanol group (Si—OH) by hydrolysis reaction. The silanol group further reacts between molecules to form a Si—O—Si bond. Further, the silanol group undergoes a dehydration condensation reaction with a hydroxyl group (base material-OH) on the surface of the base material to form a chemical bond (base material-O-Si).

Examples of L include an alkoxy group, a halogen atom, an acyl group, and an isocyanate group (—NCO). As the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferable. As the halogen atom, a chlorine atom is preferable.
L is preferably an alkoxy group or a halogen atom from the viewpoint of ease of production of the surface treatment agent. L is preferably an alkoxy group having 1 to 4 carbon atoms from the viewpoint of less outgassing at the time of coating and excellent storage stability of the surface treatment agent, and ethoxy when long-term storage stability of the surface treatment agent is required. A group is particularly preferred, and a methoxy group is particularly preferred when the reaction time after coating is short.

R ³ is a hydrogen atom or a monovalent hydrocarbon group. Examples of the monovalent hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, and an aryl group.
R ³ is preferably a monovalent hydrocarbon group, particularly preferably a monovalent saturated hydrocarbon group.
When R ³ is a monovalent hydrocarbon group, the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 6, particularly preferably 1 to 3, and most preferably 1 to 2. When the carbon number of R ³ is within this range, the compound (5) can be easily produced.

N is preferably 0 or 1, particularly preferably 0. By the presence of a plurality of L in one hydrolyzable silyl group, the adhesion to the substrate becomes stronger.

SiR ³ _n L _3-n includes Si (OCH ₃ ) ₃ , SiCH ₃ (OCH ₃ ) ₂ , Si (OCH ₂ CH ₃ ) ₃ , SiCl ₃ , Si (O (O) CCH ₃ ) ₃ , Si ( NCO) ₃ is preferred. From the viewpoint of ease of handling in industrial production, Si (OCH ₃ ) ₃ is particularly preferable.
The plurality of SiR ³ _n L _3-n in the compounds (22) to (24) and (26) to (28) are preferably the same group from the viewpoint of ease of production of the surface treatment agent. .

(Specific examples of surface treatment agents)
Specific examples of the compound (21) include compounds represented by the following formula.

Specific examples of the compound (22) include compounds represented by the following formula.

Specific examples of the compound (23) include compounds represented by the following formula.

Specific examples of the compound (24) include compounds represented by the following formula.

Specific examples of the compound (25) include compounds represented by the following formula.

Specific examples of the compound (26) include compounds represented by the following formula.

Specific examples of the compound (27) include compounds represented by the following formula.

Specific examples of the compound (28) include compounds represented by the following formula.

However, PFPE is a polyfluoropolyether chain, that is, F—R ^f2 O— (R ^f1 O) _m —R ^f2 —. A preferred form of PFPE is a combination of the preferred (R ^f1 O) _m and R ^f2 described above.

(Method for producing surface treatment agent)
Compound (21) can be produced by a known method described in Patent Document 1, Patent Document 2, International Publication No. 2013/121984, and the like.
Compound (22) can be produced by a known method described in International Publication No. 2017/038832.
Compound (23) can be produced by a known method described in International Publication No. 2017/038830.
Compound (24) can be produced by a known method described in JP-A-2016-037541 and International Publication No. 2016/1212111.
Compound (25) can be produced by a known method described in International Publication No. 2013/121984.
Compound (26) can be produced by a known method described in International Publication No. 2017/038830.
Compound (27) can be produced by a known method described in JP-A-2016-204656.
Compound (28) can be produced by a known method described in JP-A-2016-037541.

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples.
Hereinafter, “%” is “% by mass” unless otherwise specified.
Examples 1 to 4 are examples, and examples 5 to 6 are production examples.

[Example 1]
(Example 1-1)
A 200 mL three-necked flask was charged with 11.8 g of ethanol and 100.0 g of compound (1-1) (manufactured by Solvay Solexis, FOMBLIN (registered trademark) ZDIAC4000), and stirred at 50 ° C. for 4 hours. The reaction mixture was concentrated with an evaporator to obtain 100.4 g of a crude product. The crude product was separated by development on silica gel column chromatography. Compound (3-1) was eluted using CF ₃ CH ₂ OCF ₂ CF ₂ H (Asahi Glass Co., Ltd., AE-3000) as a developing solvent. Compound (2-1) was eluted using AE-3000 / acetone = 7/3 (mass ratio) as a developing solvent. Compound (1-1) was eluted using AE-3000 / 2,2,2,2-trifluoroethanol = 2/8 (mass ratio) as a developing solvent. For each component obtained, the average value of the structure of the terminal group and the number of structural units (x1, x2) was determined from the integrated values of ¹ H-NMR and ¹⁹ F-NMR. 24.1 g (yield: 24.1%) of compound (1-1), 48.4 g (yield: 48.1%) of compound (2-1), and 25. of compound (3-1). 9 g (yield: 25.6%) was obtained.
HO (O) C—CF ₂ O — {(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 } —CF ₂ —C (O) OH (1-1)
HO (O) C—CF ₂ O — {(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 } —CF ₂ —C (O) OCH ₂ CH ₃ (2-1)
CH ₃ CH ₂ O (O) C—CF ₂ O — {(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 } —CF ₂ —C (O) OCH ₂ CH ₃ (3-1)

NMR spectrum of compound (1-1);
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −52.1 to −55.4 (38F), −77.8 (2F), −79.8 ( 2F), -89.2 to -90.8 (84F)
Average value of unit number x1: 19; average value of unit number x2: 21; number average molecular weight of compound (1-1): 3,900.

NMR spectrum of compound (2-1);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: tetramethylsilane (TMS)) δ (ppm): 4.3 (2H), 1.3 (3H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −52.2 to −55.5 (38F), −77.8 (1F), −78.3 ( 1F), -79.9 (2F), -89.3 to -90.9 (84F).
Average value of unit number x1: 19; average value of unit number x2: 21; number average molecular weight of compound (2-1): 3,920.

NMR spectrum of compound (3-1);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 4.3 (4H), 1.3 (6H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −52.2 to −55.5 (38F), −78.3 (2F), −80.0 ( 2F), -89.3 to -90.9 (84F).
Average value of unit number x1: 19; average value of unit number x2: 21; number average molecular weight of compound (3-1): 3,940.

(Example 1-2)
At the gas outlet of a 500 mL nickel autoclave, a cooler maintained at 20 ° C., a NaF pellet packed bed, and a cooler maintained at 0 ° C. were installed in series. A liquid return line for returning the liquid aggregated from the cooler maintained at 0 ° C. to the autoclave was installed.
350 g of ClCF ₂ CFClCF ₂ OCF ₂ CF ₂ Cl (CFE-419) was placed in the autoclave and stirred while maintaining at 25 ° C. After nitrogen gas was blown into the autoclave at 25 ° C. for 1 hour, 20% fluorine gas was blown in at 25 ° C. and a flow rate of 1.0 L / hour for 1 hour. While blowing 20% fluorine gas at the same flow rate, a solution of 40.0 g of the compound (2-1) obtained in Example 1-1 in 120 g of CFE-419 was injected into the autoclave over 4 hours. While blowing 20% fluorine gas at the same flow rate, the internal pressure of the autoclave was increased to 0.15 MPa (gauge pressure). 6 mL of a benzene solution containing 0.05 g / mL benzene in CFE-419 was injected into the autoclave while heating from 25 ° C. to 40 ° C., and the benzene solution inlet of the autoclave was closed. After stirring for 15 minutes, 6 mL of the benzene solution was again injected while maintaining 40 ° C., and the injection port was closed. The same operation was repeated three more times. The total amount of benzene injected was 1.5 g. Stirring was continued for 1 hour while blowing 20% fluorine gas at the same flow rate. The pressure in the autoclave was set to atmospheric pressure, and nitrogen gas was blown for 1 hour. The content of the autoclave was concentrated with an evaporator to obtain 39.8 g (yield 97.9%) of compound (4-1).
F—CF ₂ O — {(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 } —CF ₂ —C (O) OCF ₂ CF ₃ (4-1)

NMR spectrum of compound (4-1);
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): −52.3 to −55.6 (38F), −56.3 to −58.3 (3F), -77.8 (1F), -78.3 (1F), -87.5 (3F), -89.0 to -90.9 (86F).
Average value of unit number x1: 19; average value of unit number x2: 21; number average molecular weight of compound (4-1): 3,980.

(Example 1-3)
In a round bottom flask made of tetrafluoroethylene-perfluoro (alkoxy vinyl ether) copolymer (PFA), 39.0 g of the compound (4-1) obtained in Example 1-2 and 50 g of AE-3000 were placed. The mixture was stirred while being cooled in an ice bath, and 3.2 g of methanol was slowly dropped from the dropping funnel under a nitrogen atmosphere. The mixture was stirred for 12 hours while bubbling with nitrogen. The reaction mixture was concentrated by an evaporator to obtain 37.7 g (yield 99.4%) of compound (5-1).
F—CF ₂ O — {(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 } —CF ₂ —C (O) OCH ₃ (5-1)

NMR spectrum of compound (5-1);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 3.9 (3H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): −52.3 to −55.6 (38F), −56.3 to −58.3 (3F), -78.2 (1F), -79.9 (1F), -89.0 to -90.9 (84F).
Average value of unit number x1: 19; average value of unit number x2: 21; number average molecular weight of compound (5-1): 3,880.

(Example 1-4)
In a 200 mL three-necked eggplant flask, 1.80 g of sodium borohydride was dissolved in 10 g of ethanol and 20 g of AE-3000, and cooled in an ice bath, the compound (5- A solution prepared by mixing 37.0 g of 1) with 37.0 g of AE-3000 was slowly added dropwise. The ice bath was removed and stirring was continued while slowly warming to room temperature. After stirring at room temperature for 12 hours, an aqueous hydrochloric acid solution was added dropwise until the liquid became acidic. The organic phase was collected, washed once with water and once with saturated brine, and the organic phase was recovered. The collected organic phase was concentrated by an evaporator to obtain 36.5 g (yield 98.2%) of compound (6-1).
F—CF ₂ O — {(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 } —CF ₂ —CH ₂ OH (6-1)

NMR spectrum of compound (6-1);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 3.9 (2H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): −52.3 to −55.6 (38F), −56.3 to −58.3 (3F), -80.7 (1F), -82.8 (1F), -89.0 to -90.9 (84F).
Average value of unit number x1: 19; average value of unit number x2: 21; number average molecular weight of compound (6-1): 3,900.

[Example 2]
In a 100 mL eggplant flask, 25.0 g of the compound (3-1) obtained in Example 1-1 and 2.0 g of a 48% aqueous sodium hydroxide solution were added and stirred at 80 ° C. for 2 hours. This was transferred to a separatory funnel, 30 mL of diluted hydrochloric acid was added, and the mixture was extracted 5 times with 30 mL of AE-3000. The collected solution was concentrated by an evaporator to obtain 22.6 g (yield 97.1%) of compound (1-1).

Compound 2 was prepared in the same manner as in Example 1 except that 22.6 g of compound (1-1) regenerated from compound (3-1) was used and the amount of each raw material was changed according to the amount of compound (1-1). (6-1) was obtained.
The compound (3-1) can be reused as the compound (1-1), and it can be said that there is almost no waste of the fluorine-containing ether compound by reusing the compound (3-1).

[Example 3]
(Example 3-1)
In a 100 mL three-necked flask, 20.0 g of the compound (1-1) and 20.0 g of the compound (6-1) obtained in Example 1-4 were placed, heated to 80 ° C. and stirred. By-produced water was distilled off under reduced pressure, and it was confirmed by NMR analysis that compound (6-1) had disappeared. The obtained crude product was purified in the same manner as in Example 1-1, and 5.2 g (yield: 25.8%) of compound (1-1) and 19.1 g (yield) of compound (12-1) were obtained. Rate: 48.0%), and 14.5 g (yield: 24.2%) of compound (13-1).
HO (O) C—CF ₂ —O {(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 } —CF ₂ —C (O) OH (1-1)
HO (O) C—CF ₂ —O {(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 } —CF ₂ —C (O) OCH ₂ —CF ₂ — {(OCF ₂ CF ₂ ) _x2 (OCF ₂ ) _x1 } -OCF ₂ -F (12-1)
F—CF ₂ O — {(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 } —CF ₂ —CH ₂ O (O) C—CF ₂ O — {(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 } —CF ₂ —C (O) OCH ₂ —CF ₂ — {(OCF ₂ CF ₂ ) _x2 (OCF ₂ ) _x1 } —OCF ₂ —F (13-1)

NMR spectrum of compound (1-1);
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −52.1 to −55.4 (38F), −77.8 (2F), −79.8 ( 2F), -89.2 to -90.8 (84F).
Average value of unit number x1: 19; average value of unit number x2: 21; number average molecular weight of compound (1-1): 3,900.

NMR spectrum of compound (12-1);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 4.8 (2H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −52.2 to −55.5 (76F), −56.3 to −58.3 (3F), -77.0 to -80.3 (6F), -89.3 to -90.9 (168F).
Average value of unit number x1: 19; average value of unit number x2: 21; number average molecular weight of compound (12-1): 7,730.

NMR spectrum of compound (13-1);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 4.8 (4H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): −52.2 to −55.5 (114 F), −56.3 to −58.3 (6 F), -77.5 to -80.3 (8F), -89.3 to -90.9 (252F).
Average value of unit number x1: 19; average value of unit number x2: 21; number average molecular weight of compound (13-1): 11,570.

(Example 3-2)
Except that Compound (2-1) was changed to 19.0 g of Compound (12-1) and the amount of each raw material was changed according to the amount of Compound (12-1), it was the same as Example 1-2. 18.8 g (yield 98.8%) of compound (14-1) was obtained.
F—CF ₂ O — {(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 } —CF ₂ —C (O) OCF ₂ —CF ₂ — {(OCF ₂ CF ₂ ) _x2 (OCF ₂ ) _x1 } -OCF ₂ -F (14-1)

NMR spectrum of compound (14-1);
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −52.3 to −55.6 (76F), −56.3 to −58.3 (6F), -77.8 (1F), -78.3 (1F), -89.0 to -90.9 (172F).
Average value of unit number x1: 19; average value of unit number x2: 21; number average molecular weight of compound (14-1): 7,740.

(Example 3-3)
Except that Compound (4-1) was changed to 18.5 g of Compound (14-1) and the amount of each raw material was changed according to the amount of Compound (14-1), it was the same as Example 1-3. 18.2 g (yield 96%) of compound (5-1) was obtained.
F—CF ₂ O — {(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 } —CF ₂ —C (O) OCH ₃ (5-1)

NMR spectrum of compound (5-1);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 3.9 (3H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): −52.3 to −55.6 (38F), −56.3 to −58.3 (3F), -78.2 (1F), -79.9 (1F), -89.0 to -90.9 (84F).
Average value of unit number x1: 19; average value of unit number x2: 21; number average molecular weight of compound (5-1): 3,880.
Compound (5-1) is the same as compound (5-1) obtained in Example 1, and can be derived into compound (6-1) in the same manner as in Example 1-4.

[Example 4]
In a 50 mL eggplant flask, 14.0 g of the compound (13-1) obtained in Example 3-1 and 1.0 g of 48% aqueous sodium hydroxide solution were added and stirred at 80 ° C. for 2 hours. This was transferred to a separatory funnel, 20 mL of diluted hydrochloric acid was added, and the mixture was extracted 5 times with 20 mL of AE-3000. The collected solution was concentrated with an evaporator, and the resulting crude liquid was purified by silica gel column chromatography to obtain 4.4 g (yield: 93.3%) of compound (1-1) and compound (6-1). 9.2 g (yield 197%) was obtained.
The compound (13-1) can be reused as the compound (1-1) and the compound (6-1). By reusing the compound (13-1), almost no waste of fluorine-containing ether compound is produced. I can say no.

[Example 5]
(Production Example of Surface Treatment Agent Using Compound (5-1))
A surface treatment agent was produced according to the method described in Example 1-6 of WO2013 / 121984. From NMR, it was confirmed that 99% of the compound (5-1) was converted to the compound (25-1).
F—CF ₂ O — {(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 } —CF ₂ —C (O) NH—CH ₂ CH ₂ CH ₂ —Si (OCH ₃ ) ₃ (25) -1)

NMR spectrum of compound (25-1);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.6 (2H), 1.6 (2H), 2.8 (1H), 3.2 (2H) 3.5 (9H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): −52.3 to −55.6 (38F), −56.3 to −58.3 (3F), -81.3 (1F), -84.1 (1F), -89.0 to -90.9 (84F).
Average value of unit number x1: 19; average value of unit number x2: 21; number average molecular weight of compound (25-1): 4,050.

[Example 6]
(Production Example of Surface Treatment Agent Using Compound (6-1))
Compound (23-1) was obtained according to the method described in Example 4 of International Publication No. 2017/038830.
F—CF ₂ O — {(CF ₂ O) _x1 (CF ₂ CF ₂ O) _x2 } —CF ₂ —CH ₂ O—CH ₂ —C [—CH ₂ CH ₂ CH ₂ —Si (OCH ₃ ) ₃ ] ₃ ... (23-1)

NMR spectrum of compound (23-1);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.7 (6H), 1.7 (6H), 3.4 to 3.8 (37H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): −52.3 to −55.6 (38F), −56.3 to −58.3 (3F), -77.3 (1F), -79.3 (1F), -89.0 to -90.9 (84F).
Average value of unit number x1: 19; average value of unit number x2: 21; number average molecular weight of compound (23-1): 4,370.

The fluorine-containing ether compound obtained by the production method of the present invention can be used for various applications that require lubrication and water / oil repellency. For example, display input devices such as touch panels; surface protective coats made of transparent glass or transparent plastic parts, antifouling coats for kitchens; water and water repellent and antifouling coats for electronic devices, heat exchangers, batteries, etc. Antifouling coating; coating on a member that requires liquid repellency while conducting; water-repellent / waterproof / sliding coat of heat exchanger; surface sieve such as vibrating screen or inside cylinder, etc. More specific examples of use include a front protective plate of a display, an antireflection plate, a polarizing plate, an antiglare plate, or an antireflection coating on the surface thereof, a touch panel of a device such as a mobile phone or a portable information terminal. Various devices with display input devices that operate on the screen with human fingers or palms such as sheets and touch panel displays, decorative building materials around water such as toilets, baths, washrooms, and kitchens, waterproof coating heat exchangers for wiring boards Water / water-proof coating, water-repellent coating for solar cells, waterproof / water-repellent coating for printed wiring boards, waterproof / water-repellent coating for electronic equipment casings and electronic parts, insulation improvement coating for power transmission lines, various filters Water repellent coat, waterproof coat of radio wave absorber and sound absorbing material, bath, kitchen equipment, antifouling coat for toiletries, water repellent / waterproof / slidable coat of heat exchanger, vibration Low surface friction coating Rui and the cylinder interior and the like, mechanical parts, vacuum equipment parts, bearing parts, automobile parts, surface protection coating such as a tool and the like.
The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2017-104614 filed on May 26, 2017 are incorporated herein as the disclosure of the specification of the present invention. It is.

Claims

The compound represented by the following formula (1) is reacted with R 1 OH to represent the compound represented by the following formula (1), the compound represented by the following formula (2), and the following formula (3). A method for producing a fluorine-containing ether compound, comprising obtaining a mixture containing a compound.
HO (O) C—R f2 O— (R f1 O) m —R f2 —C (O) OH (1)
HO (O) C—R f2 O— (R f1 O) m —R f2 —C (O) OR 1 (2)
R 1 O (O) C—R f2 O— (R f1 O) m —R f2 —C (O) OR 1 (3)
However,
R f1 and R f2 are each independently a perfluoroalkylene group,
m is an integer from 2 to 200;
(R f1 O) m may be composed of two or more types of R f1 O,
R 1 is a monovalent organic group.
The unreacted compound represented by the formula (1) is recovered and reused as the compound represented by the formula (1) in the reaction of the compound represented by the formula (1) and the R 1 OH. The manufacturing method according to claim 1.
The compound represented by the formula (3) is recovered, hydrolyzed to obtain the compound represented by the formula (1), and the reaction between the compound represented by the formula (1) and the R 1 OH. The production method according to claim 1 or 2, wherein the compound is reused as a compound represented by the formula (1).
A method for producing a fluorinated ether compound, comprising fluorinating a compound represented by the following formula (2) with a fluorine gas to obtain a compound represented by the following formula (4):
HO (O) C—R f2 O— (R f1 O) m —R f2 —C (O) OR 1 (2)
F—R f2 O— (R f1 O) m —R f2 —C (O) OR f3 (4)
However,
R f1 and R f2 are each independently a perfluoroalkylene group,
m is an integer from 2 to 200;
(R f1 O) m may be composed of two or more types of R f1 O,
R 1 is a monovalent organic group,
R f3 is a monovalent perfluoro organic group derived from R 1 .
A method for producing a fluorinated ether compound, comprising transesterifying a compound represented by the following formula (4) and R 2 OH to obtain a compound represented by the following formula (5):
F—R f2 O— (R f1 O) m —R f2 —C (O) OR f3 (4)
F—R f2 O— (R f1 O) m —R f2 —C (O) OR 2 (5)
However,
R f1 and R f2 are each independently a perfluoroalkylene group,
m is an integer from 2 to 200;
(R f1 O) m may be composed of two or more types of R f1 O,
R f3 is a monovalent perfluoro organic group,
R 2 is a monovalent organic group.
A method for producing a fluorinated ether compound, wherein a compound represented by the following formula (6) is obtained by hydrogen reduction of a compound represented by the following formula (5) using a reducing agent.
F—R f2 O— (R f1 O) m —R f2 —C (O) OR 2 (5)
F—R f2 O— (R f1 O) m —R f2 —CH 2 OH (6)
However,
R f1 and R f2 are each independently a perfluoroalkylene group,
m is an integer from 2 to 200;
(R f1 O) m may be composed of two or more types of R f1 O,
R 2 is a monovalent organic group.
A fluorine-containing ether compound represented by the following formula (2) or a fluorine-containing ether compound represented by the following formula (4).
HO (O) C—R f2 O— (R f1 O) m —R f2 —C (O) OR 1 (2)
F—R f2 O— (R f1 O) m —R f2 —C (O) OR f3 (4)
However,
R f1 and R f2 are each independently a perfluoroalkylene group,
m is an integer from 2 to 200;
(R f1 O) m may be composed of two or more types of R f1 O,
R 1 is a monovalent organic group,
R f3 is a monovalent perfluoro organic group.
A compound represented by the following formula (6) is reacted with a compound represented by the following formula (1) to give a compound represented by the following formula (1), a compound represented by the following formula (12), and the following formula: A method for producing a fluorine-containing ether compound, comprising obtaining a mixture containing the compound represented by (13).
HO (O) C—R f2 O— (R f1 O) m —R f2 —C (O) OH (1)
F—R f2 O— (R f1 O) m —R f2 —CH 2 OH (6)
HO (O) C—R f2 O— (R f1 O) m —R f2 —C (O) OCH 2 —R f2 — (OR f1 ) m —OR f2 —F (12)
F—R f2 O— (R f1 O) m —R f2 —CH 2 O (O) C—R f2 O— (R f1 O) m —R f2 —C (O) OCH 2 —R f2 — (OR f1 ) m- OR f2- F (13)
However,
R f1 and R f2 are each independently a perfluoroalkylene group,
m is each independently an integer of 2 to 200;
(R f1 O) m may be composed of two or more types of R f1 O.
The unreacted compound represented by the formula (1) is recovered and represented by the formula (1) in the reaction between the compound represented by the formula (1) and the compound represented by the formula (6). The production method according to claim 8, wherein the compound is reused as a compound.
The compound represented by the formula (13) is recovered and hydrolyzed to obtain the compound represented by the formula (1) and the compound represented by the formula (6), and represented by the formula (1). The compound represented by the formula (1) and the compound represented by the formula (6) in the reaction of the compound represented by the formula (6) and the compound represented by the formula (6) are reused. The manufacturing method as described.
A method for producing a fluorinated ether compound, comprising fluorinating a compound represented by the following formula (12) with a fluorine gas to obtain a compound represented by the following formula (14):
HO (O) C—R f2 O— (R f1 O) m —R f2 —C (O) OCH 2 —R f2 — (OR f1 ) m —OR f2 —F (12)
F—R f2 O— (R f1 O) m —R f2 —C (O) OCF 2 —R f2 — (OR f1 ) m —OR f2 —F (14)
However,
R f1 and R f2 are each independently a perfluoroalkylene group,
m is each independently an integer of 2 to 200;
(R f1 O) m may be composed of two or more types of R f1 O.
A method for producing a fluorinated ether compound, comprising transesterifying a compound represented by the following formula (14) and R 2 OH to obtain a compound represented by the following formula (5):
F—R f2 O— (R f1 O) m —R f2 —C (O) OCF 2 —R f2 — (OR f1 ) m —OR f2 —F (14)
F—R f2 O— (R f1 O) m —R f2 —C (O) OR 2 (5)
However,
R f1 and R f2 are each independently a perfluoroalkylene group,
m is each independently an integer of 2 to 200;
(R f1 O) m may be composed of two or more types of R f1 O,
R 2 is a monovalent organic group.
A compound represented by the following formula (6) is obtained by subjecting the compound represented by the following formula (5) obtained by the production method according to claim 12 to hydrogen reduction using a reducing agent. A method for producing a fluorine-containing ether compound.
F—R f2 O— (R f1 O) m —R f2 —C (O) OR 2 (5)
F—R f2 O— (R f1 O) m —R f2 —CH 2 OH (6)
However,
R f1 and R f2 are each independently a perfluoroalkylene group,
m is each independently an integer of 2 to 200;
(R f1 O) m may be composed of two or more types of R f1 O,
R 2 is a monovalent organic group.
A compound represented by the following formula (1) obtained by reacting the compound represented by the formula (6) obtained by the production method according to claim 13 with a compound represented by the following formula (1): A method for producing a fluorinated ether compound, comprising obtaining a mixture comprising a compound represented by the formula (12) and a compound represented by the following formula (13):
HO (O) C—R f2 O— (R f1 O) m —R f2 —C (O) OH (1)
HO (O) C—R f2 O— (R f1 O) m —R f2 —C (O) OCH 2 —R f2 — (OR f1 ) m —OR f2 —F (12)
F—R f2 O— (R f1 O) m —R f2 —CH 2 O (O) C—R f2 O— (R f1 O) m —R f2 —C (O) OCH 2 —R f2 — (OR f1 ) m- OR f2- F (13)
However,
R f1 and R f2 are each independently a perfluoroalkylene group,
m is each independently an integer of 2 to 200;
(R f1 O) m may be composed of two or more types of R f1 O.
A fluorine-containing ether compound represented by the following formula (12) or a fluorine-containing ether compound represented by the following formula (14).
HO (O) C—R f2 O— (R f1 O) m —R f2 —C (O) OCH 2 —R f2 — (OR f1 ) m —OR f2 —F (12)
F—R f2 O— (R f1 O) m —R f2 —C (O) OCF 2 —R f2 — (OR f1 ) m —OR f2 —F (14)
However,
R f1 and R f2 are each independently a perfluoroalkylene group,
m is each independently an integer of 2 to 200;
(R f1 O) m may be composed of two or more types of R f1 O.