JPWO2018216777A1 - Method for producing fluorine-containing ether compound and fluorine-containing ether compound - Google Patents

Abstract

Provided is 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 as a surface treatment agent in a high yield. A compound represented by the following formula (1), a compound represented by the following formula (2) and a compound represented by the following formula (3) are reacted by reacting R1OH with the compound represented by the following formula (1). A method for producing a fluorinated ether compound. HO (O) C-Rf2O- (Rf1O) m-Rf2-C (O) OH ... (1) HO (O) C-Rf2O- (Rf1O) m-Rf2-C (O) OR1 ... ( 2) R1O (O) C-Rf2O- (Rf1O) m-Rf2-C (O) OR1 (3) where Rf1 and Rf2 are each independently a perfluoroalkylene group, and m is 2 to 200 (Rf1O) m may be composed of two or more kinds of Rf1O, and R1 is a monovalent organic group.

Description

  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 repellency and oil repellency can be formed on the surface of a substrate. The surface treatment agent containing a fluorinated ether compound has the property that water and oil repellency is not easily reduced even if the surface layer is repeatedly rubbed with a finger (rub resistance) and the ability to easily remove fingerprints attached to the surface layer by wiping. It is used as a surface treatment agent for a member that forms a surface of a touch panel, which is to be touched by a finger, for applications in which (fingerprint stain removability) is required to be maintained for a long time.

  As a fluorine-containing ether compound capable of forming a surface layer having excellent friction resistance and fingerprint stain removal properties on the surface of a substrate, a fluorine-containing ether compound having a hydrolyzable silyl group introduced at one end has been proposed (Patent Documents) 1). As an intermediate of a fluorinated ether compound having a hydrolyzable silyl group introduced at one end, a fluorinated ether compound having a hydroxyl group, a carbonyl group-containing group (a carboxylic acid halide group, an ester group, or the like) 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), a compound represented by the following formula (1b) and a compound represented by the following formula (1c) are obtained by fluorinating a compound represented by the following formula (1b) with fluorine gas. To obtain 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)
p and q are, for example, 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 the formula (1a). The mixture after purification is hydrogen-reduced 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)

  Further, 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 converted into a supercritical or subcritical carbon dioxide as a mobile phase. There is also proposed a method of obtaining a mixture containing a compound represented by the formula (1a) at a high concentration by purification by silica gel chromatography (Patent Document 2).

JP-A-2012-07272 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 always produced. The compound represented by the formula (1c) does not have a functional group that interacts with or chemically binds to the substrate, and thus is not suitable for a surface treatment agent. Further, the compound represented by the formula (1c) is a stable compound and cannot be reused as a raw material represented by the formula (1b) by decomposing only the terminal. Therefore, in the method described in Patent Document 1, the compound represented by the formula (1a) useful as an intermediate of a fluorine-containing ether compound suitably used as a surface treatment agent, and further the compound represented by the formula (2a) Cannot be obtained in good yield.

  INDUSTRIAL APPLICABILITY The present invention is preferably used as 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 as a surface treatment agent in a high yield, and a surface treatment agent. An object of the present invention is to provide a fluorine-containing ether compound useful as an intermediate of a 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 give a compound represented by the following formula (1), a compound represented by the following formula (2) and a compound represented by the following formula (3): A method for producing a fluorine-containing ether compound, comprising obtaining a mixture containing the compound represented by the formula (I).
HO (O) C- ^Rf2O- ( ^Rf1O ) _m- ^Rf2- 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 of 2 to 200;
(R ^f1 O) _m may be composed of two or more kinds of R ^f1 O;
R ¹ is a monovalent organic group.
[2] Unreacted compound represented by the formula (1) is recovered, and the compound represented by the formula (1) in the reaction between the compound represented by the formula (1) and the R ¹ OH The manufacturing method according to [1], wherein the method is reused.
[3] The compound represented by the formula (3) is recovered and hydrolyzed to obtain a compound represented by the formula (1), and the compound represented by the formula (1) and the R ¹ OH The method according to [1] or [2], wherein the compound is reused as the compound represented by the formula (1) in the reaction with

[4] A method for producing a fluorine-containing ether compound, comprising fluorinating a compound represented by the following formula (2) with 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)
^FR- f2O- ( ^Rf1O ) _m- ^Rf2- C (O) OR ^f3 (4)
However,
R ^f1 and R ^f2 are each independently a perfluoroalkylene group,
m is an integer of 2 to 200;
(R ^f1 O) _m may be composed of two or more kinds 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 fluorine-containing ether compound, which comprises transesterifying a compound represented by the following formula (4) with R ² OH to obtain a compound represented by the following formula (5).
^FR- f2O- ( ^Rf1O ) _m- ^Rf2- 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 of 2 to 200;
(R ^f1 O) _m may be composed of two or more kinds 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 fluorinated ether compound, comprising obtaining a compound represented by the following formula (6) by reducing a compound represented by the following formula (5) with a reducing agent using hydrogen.
_{^{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 of 2 to 200;
(R ^f1 O) _m may be composed of two or more kinds 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)
^FR- f2O- ( ^Rf1O ) _m- ^Rf2- C (O) OR ^f3 (4)
However,
R ^f1 and R ^f2 are each independently a perfluoroalkylene group,
m is an integer of 2 to 200;
(R ^f1 O) _m may be composed of two or more kinds 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 (6) is reacted with a compound represented by the following formula (1) to give a compound represented by the following formula (1) or a compound represented by the following formula (12) And obtaining a mixture containing a compound represented by the following formula (13):
HO (O) C- ^Rf2O- ( ^Rf1O ) _m- ^Rf2- 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 kinds of R ^f1 O.
[9] The unreacted compound represented by the formula (1) is recovered, and the compound represented by the formula (1) in the reaction between the compound represented by the formula (1) and the compound represented by the formula (6) is recovered. The method of [8], wherein the compound represented by the formula (2) is reused.
[10] The compound represented by the formula (13) is recovered and hydrolyzed to obtain a compound represented by the formula (1) and a compound represented by the formula (6). [8] is reused as 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) with the compound represented by the formula (6). Or the manufacturing method of [9].

[11] A method for producing a fluorine-containing ether compound, comprising fluorinating a compound represented by the following formula (12) with 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 kinds of R ^f1 O.
[12] A method for producing a fluorine-containing ether compound, which comprises transesterifying a compound represented by the following formula (14) with 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 kinds of R ^f1 O;
R ² is a monovalent organic group.

[13] A compound represented by the following formula (6) obtained by subjecting the compound represented by the following formula (5) obtained by the production method of the above [12] to hydrogen reduction using a reducing agent. A method for producing a fluorine-containing ether compound, which is characterized by the following.
_{^{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 kinds of R ^f1 O;
R ² is a monovalent organic group.
[14] A compound represented by the following formula (1) by reacting the compound represented by the formula (6) obtained by the production method of the above [13] with a compound represented by the following formula (1): And obtaining a mixture containing a compound represented by the following formula (12) and a compound represented by the following formula (13).
HO (O) C- ^Rf2O- ( ^Rf1O ) _m- ^Rf2- 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 kinds 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 kinds of R ^f1 O.

ADVANTAGE OF THE INVENTION According to the manufacturing method of the fluorine-containing ether compound of this invention, the fluorine-containing ether compound useful as an intermediate of the fluorine-containing ether compound suitably used for a surface treatment agent can be manufactured with high yield.
The fluorinated ether compound of the present invention is useful as an intermediate of a fluorinated ether compound suitably used as a surface treatment agent.

In this 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 meaning of the following terms in this specification is as follows.
The “perfluoro organic group” means a group in which all of the hydrogen atoms bonded to carbon atoms of the organic group are substituted with fluorine atoms.
In the chemical formula of the oxyperfluoroalkylene group, its oxygen atom is described and described on the right side of the perfluoroalkylene group.
The “etheric oxygen atom” means an oxygen atom that forms an ether bond (—O—) between carbon atoms.
The “hydrolyzable silyl group” means a group capable of forming a silanol group (Si—OH) by a hydrolysis reaction. For example, a ^SiR _{3 n L 3-n} in the formula (21) to (24).
“Surface layer” means a layer formed on the surface of a substrate.
The “number average molecular weight” of the fluorinated 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 the terminal groups by ¹ H-NMR and ¹⁹ F-NMR. End groups, for example, ^{F-R f2} or ^SiR _{3 n L 3-n} in the formula (21) to (24).

[First Synthesis Route of Compound (6)]
As a synthetic route of the compound (6) starting from the compound (1), the following first synthetic route can be mentioned.

(Compound (1))
Compound (1) is a starting material in the synthesis route of compound (6).
HO (O) C- ^Rf2O- ( ^Rf1O ) _m- ^Rf2- 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 kinds of R ^f1 O. Is also good.

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

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

  m is preferably an integer of 5 to 150, particularly preferably an integer of 10 to 100. When m is at least the lower limit of the above range, the surface layer composed of the finally obtained surface treatment agent will have excellent water and oil repellency. When m is equal to or less than the upper limit of the above range, the surface layer is excellent in friction resistance. That is, if the number average molecular weight of the surface treatment agent is too large, the number of hydrolyzable silyl groups existing per unit molecular weight decreases, and the friction resistance of the surface layer decreases.

In ^(R f1 _{O) m,} if two or more of ^{R f1} O are present, binding order of ^{R f1} O is not limited, random, alternating, or may be arranged 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 kinds 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 } has x1 ( CF ₂ O) and x2 (CF ₂ CF ₂ O) are randomly arranged. _{Further, (CF 2 CF 2 O-} CF 2 CF 2 CF 2 CF 2 O) structure represented by _x3 is, x3 amino _(CF 2 _CF 2 O) and x3 amino _{(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 surface treatment agent finally obtained is more excellent in friction resistance, fingerprint stain removal properties, 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 preferable. Examples of the group having 1 to 4 other (R ^f1 O) at one or both ends thereof include, for example, (CF ₂ CF ₂ O) ₂ ｛(CF ₂ O) _m1 (CF ₂ CF ₂ O) _{m2-2 },} and a _{(CF 2 CF 2 O-CF} 2 CF 2 CF 2 CF 2 O) m5-1 (CF 2 CF 2 O) and the like. As (R ^f1 O) _m , a group having {(CF ₂ O) _m1 (CF ₂ CF ₂ O) _m2 } is particularly preferable.
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 done. m3 and m4 are each an integer of 2 to 200, and m5 is an integer of 1 to 100.

<R ^f2 group>
The carbon number of 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 composed of the surface treatment agent finally obtained is further excellent in friction resistance and fingerprint stain removal properties. 1 and 2 are particularly preferred from the viewpoint of more excellent lubricity.
The carbon number of 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 , _{(CF 2 CF 2 CF 2 O} ) when it is _m4, a _{2, (CF 2 CF 2 O} -CF 2 CF 2 CF 2 CF 2 O) when it is _m5, a 3 a and linear. 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 ).
When ^Rf2 is a straight chain, the surface layer is excellent in friction resistance and lubricity.

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

(Method for producing compound (2))
Compound (2) is useful as an intermediate of a fluorine-containing ether compound suitably used as a surface treatment agent.
The first aspect of the method for producing a fluorinated ether compound of the present invention is a method of reacting compound (1) with R ¹ OH to obtain a mixture containing compound (1), compound (2) and compound (3). It is.
HO (O) C- ^Rf2O- ( ^Rf1O ) _m- ^Rf2- 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 which may have a substituent. Examples of the monovalent hydrocarbon group include an alkyl group, an aryl group, and a cycloalkyl group. The carbon number of R ¹ is preferably 1 to 20, and particularly preferably 1 to 10.
R ¹ is simultaneously fluorinated when the carboxyl group reacts with fluorine gas, but it is desirable that no reaction other than the replacement of a hydrogen atom by a fluorine atom occurs. From this viewpoint, R ¹ may contain an etheric oxygen atom, and is preferably a monovalent hydrocarbon group in which a part of hydrogen atoms may be replaced by fluorine atoms. R ¹ OH is preferably a primary alcohol in that the reaction easily proceeds in the esterification reaction after fluorination.
As R ¹ , an alkyl group is preferable, and 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 preferable. Is particularly preferred.

The reaction conditions for the compound (1) and R ¹ OH may be any ordinary esterification reaction conditions, and are not particularly limited.

As a method for recovering each compound from the mixture, a known purification method (eg, column chromatography using silica gel or an ion exchange resin) can be used.
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.
It is preferable that the recovered compound (3) is hydrolyzed to obtain a compound (1) and reused as the compound (1) in the reaction between the 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, compound (2), compound (4), compound (5) and compound (6) can be produced in good yield.

(Method for producing compound (4))
Compound (4) is useful as an intermediate of a fluorine-containing ether compound suitably used as a surface treatment agent.
The second aspect of the method for producing a fluorinated ether compound of the present invention is a method of fluorinating compound (2) with fluorine gas to obtain compound (4).
^FR- f2O- ( ^Rf1O ) _m- ^Rf2- 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 compound (2), examples of R ^f3 include those obtained by fluorinating R ^1, and those obtained by fluorinating a preferable form of R ¹ are preferable.

  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))
Compound (5) is useful as an intermediate of a fluorinated ether compound suitably used for a surface treatment agent.
The third embodiment of the method for producing a fluorinated ether compound of the present invention is a method for obtaining a compound (5) by transesterification of the compound (4) 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 a monovalent organic group.

Examples of R ² include 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. The carbon number of R ¹ is preferably 1 to 20, and particularly preferably 1 to 10.
As R ² , an alkyl group is preferable, and an alkyl group having 1 to 10 carbon atoms is particularly preferable, since R ² OH does not have a high boiling point and can easily remove R ² OH in a subsequent step.

The reaction conditions for the compound (4) and R ² OH may be any ordinary transesterification reaction conditions, and are not particularly limited.

(Method for producing compound (6))
Compound (6) is useful as an intermediate of a fluorine-containing ether compound suitably used as a surface treatment agent.
In the method for producing a fluorinated ether compound of the present invention, compound (6) may be obtained by hydrogenating 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.), and hydrogen gas in the presence of a metal catalyst (palladium catalyst, platinum catalyst, etc.).

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

[Second synthetic route of compound (6)]
As another synthetic route of compound (6) starting from compound (1), the following second synthetic route can be mentioned.

(Method for producing compound (12))
Compound (12) is useful as an intermediate of a fluorine-containing ether compound suitably used as a surface treatment agent.
In a fourth aspect of the method for producing a fluorine-containing ether compound of the present invention, a compound (1) is reacted with a compound (6) to obtain a mixture containing the compound (1), the compound (12) and the compound (13). Is the way.
HO (O) C- ^Rf2O- ( ^Rf1O ) _m- ^Rf2- 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. (R ^f1 O) _m of the compound (1) and the compound ( It is preferable that (R ^f1 O) _{m in} 6) is the same.

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

As a method for recovering each compound from the mixture, a known purification method (eg, column chromatography using silica gel or an ion exchange resin) can be used.
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 a compound (1) and a compound (6). It is preferable to use it.
By reusing compound (1) and compound (13) as raw materials, compound (12), compound (14), compound (5) and compound (6) can be produced in good yield.

(Method for producing compound (14))
Compound (14) is useful as an intermediate of a fluorine-containing ether compound suitably used for a surface treatment agent.
The fifth aspect of the method for producing a fluorinated ether compound of the present invention is a method of fluorinating compound (12) with fluorine gas to obtain compound (14).
_{^{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))
Compound (5) is useful as an intermediate of a fluorinated ether compound suitably used for a surface treatment agent.
The sixth embodiment 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 the compound (14) with R ² OH is shown in the following formula. Two moles of R ² OH react with one mole of compound (14) to produce two moles of compound (5).

The reaction condition of compound (14) with R ² OH may be any ordinary transesterification reaction condition, and is not particularly limited.

(Method for producing compound (6))
In the method for producing a fluorinated ether compound of the present invention, the compound (6) may be obtained by subjecting the compound (5) obtained from the compound (14) to hydrogen reduction 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.

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

[Surface treatment agent]
Examples of the fluorine-containing ether compound which can be produced from compound (6) as a raw material and which is preferably used as a surface treatment agent include, for example, compound (21), compound (22), compound (23) and compound (24). Can be

_{^{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 to 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 carbon atom between carbon atoms of an alkylene group having 2 or more carbon atoms. A group having —NH—, r is 0 or 1 (however, when Q ² is a single bond, it is 0), and Q ³ is an alkylene group or an alkylene group having 2 or more carbon atoms. carbon - etheric oxygen atom between carbon atoms, a group having an -NH- or a divalent organopolysiloxane residues, the two _{^{[-Q 3 -SiR 3 n L 3}} -n] is the same May also be different.
In the formula (23), Q ⁴ is a single bond, an alkylene group, or a group having an etheric oxygen atom between the carbon atoms of the alkylene group having 2 or more carbon atoms, and Q ⁵ is an alkylene group or a carbon atom. A group having an etheric oxygen atom or a divalent organopolysiloxane residue between the carbon-carbon atoms of the alkylene group of several or more, and s is 0 or 1 (however, when Q ⁴ is a single bond, . a a a), t is 0 or 1, of the three ^{_{[- (O) t -Q 5}} -SiR 3 n L 3-n] may be 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 the 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 fluorinated ether compound which can be produced using compound (5) as a raw material and which is preferably used as a surface treatment agent include compound (25), compound (26), compound (27) and compound (28). Can be

_{^{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 [-O-Q 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 for 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 organopolycarbon between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms. This is a group having a siloxane residue.
In Formula (26), R ⁶ is a hydrogen atom or an alkyl group, and Q ⁹ 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. 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 the formula (27), Q ¹¹ represents an alkylene group, a group having an etheric oxygen atom or a silphenylene skeleton between carbon-carbon atoms of the alkylene group having 2 or more carbon atoms, or a carbon atom of an alkylene group having 2 or more carbon atoms. a group having a divalent organopolysiloxane residue or dialkyl silylene group at the end on the side bonded to the carbon atom or between O, Q ¹² is the carbon of the alkylene group or an alkylene group having 2 or more carbon - carbon atoms A group having an etheric oxygen atom or a silphenylene skeleton between them, two Q ^{12 s} may be the same or different, and three -SiR ³ _n L _3-n may be the same It 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 the alkylene group having 2 or more carbon atoms. _{^{-Q 13 -SiR n L 3-n}} ] it may not be the same group.

( ^{FR f2} group)
Since the terminal has F—R ^f2 , one terminal of the surface treatment agent is CF ₃ — and the other terminal is a hydrolyzable silyl group. According to the surface treating agent having such a structure, a surface layer having low surface energy can be formed, so that the surface layer is excellent in lubricity and friction resistance. On the other hand, conventional fluorinated ether compounds having hydrolyzable silyl groups at both terminals have insufficient lubricity and friction resistance of the surface layer.

( ¹ Q to ¹³ Q)
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 the alkylene group having 2 to 10 carbon atoms, and 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. In terms of the compound (21) the ease of manufacture _of, -CH 2 _CH 2 CH ₂ - or _{-CH 2 CH 2 OCH 2 CH 2} CH 2 - (. However, the right side is attached to the Si) are preferred.

As Q ² , 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 the alkylene group having 2 to 10 carbon atoms is preferable. An alkylene group having 1 to 7 carbon atoms, or a group having an etheric oxygen atom or -NH- between carbon-carbon atoms of the alkylene group having 2 to 7 carbon atoms is particularly preferable. The _(X) r ^{Q 2,} in terms of ease of preparation of the compound (22) is a single bond, -OCH ₂ CH ₂ - or -NHCH ₂ CH ₂ - (where the right side is attached to the N. 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 the 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. In terms of the compound (22) the ease of manufacture _of, -CH 2 _CH 2 CH ₂ - or _{-CH 2 CH 2 OCH 2 CH 2} CH 2 - (. However, the right side is attached to the Si) are 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 the carbon-carbon atoms of the alkylene group having 2 to 10 carbon atoms. Particularly preferred is an alkylene group having 7 or an alkylene group having 2 to 7 carbon atoms having an etheric oxygen atom between carbon and carbon atoms. 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 the alkylene group having 2 to 10 carbon atoms, and 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) The t -Q ^5, from the viewpoint of ease of preparation of the compound _{(23), -CH 2 CH 2 CH 2 -} , - CH 2 OCH 2 CH 2 CH 2 - or _-CH 2 OCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ — (however, the right side is bonded to Si) is preferable.

As Q ⁶ , an alkylene group having 1 to 10 carbon atoms or a group having an etheric oxygen atom between carbon-carbon atoms of the alkylene group having 2 to 10 carbon atoms is preferable, and a single bond, an alkylene group having 1 to 7 carbon atoms is preferable. A group 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. As Q ⁶ , from the viewpoint of easy production of the compound (24), —CH ₂ CH ₂ CH ₂ — or —CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ — (however, the right side is bonded to Si 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 the alkylene group having 2 to 10 carbon atoms, and 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. The Q ^7, from the viewpoint of ease of preparation of the compound _(24), -CH 2 _CH 2 CH ₂ - or _{-CH 2 CH 2 OCH 2 CH 2} CH 2 - ( provided that the right ^SiR ₃ n L _3-n ).

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 the alkylene group having 2 to 10 carbon atoms. As Q ⁸ , an alkylene group having 2 to 6 carbon atoms is preferable 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 the carbon-carbon atoms of the 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 the 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 - it is preferred.

Silphenylene skeleton in Q ^{11 _{is, -Si (R a) 2 PhSi}} (R a) 2 - (. However, Ph is a phenylene group, the ^{R a} is a monovalent organic group), a group represented by by is there. R ^a is preferably an alkyl group having 1 to 10 carbon atoms, a methyl group is particularly preferred.
Dialkylsilylene group in Q ¹¹ is, -Si ^(R _{b) 2} - (provided that the ^{R b} is an alkyl group.) A group represented by. 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 the alkylene group having 2 to 10 carbon atoms, or an alkylene group having 2 to 10 carbon atoms. Is preferably a group having a divalent organopolysiloxane residue or a dialkylsilylene group at the carbon-carbon atom or at the terminal bonded to O. The Q ^11, from the viewpoint of ease of preparation of the compound _{(27), -CH 2 CH 2} CH 2 -, - Si (CH 3) 2 CH 2 CH 2 CH 2 -, - Si (CH 3) 2 _{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 - is preferred (but the right side is attached to the 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 the 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 preferable (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 the 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 preferable (however, the right side is bonded to Si).

(R ^{5 to} R ⁶ )
As R ⁵ and R ⁶ , a hydrogen atom is preferable. When R ⁵ or R ⁶ is an alkyl group, it preferably has 1 to 4 carbon atoms.

^(SiR _{3 n L 3-n} group)
SiR _{³ n} L _^3-n is a hydrolyzable silyl group.
The surface treating agent has a hydrolyzable silyl group at a terminal. Since the surface treatment agent having the structure has a strong chemical bond with the base material, the surface layer has excellent friction resistance.
The surface treating agent has a hydrolyzable silyl group only at one end. Since the surface treatment agent having this structure is less likely to aggregate, 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, the terminal Si-L of the surface treatment agent is converted into a silanol group (Si-OH) by a hydrolysis reaction. The silanol groups further react between molecules to form Si-O-Si bonds. 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, an isocyanate group (—NCO), and the like. 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 easy production of the surface treatment agent. L is preferably an alkoxy group having 1 to 4 carbon atoms in terms of low outgassing at the time of application and excellent storage stability of the surface treatment agent. In the case where long-term storage stability of the surface treatment agent is required, ethoxy is used. Groups are particularly preferred, and methoxy groups are 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.
As R ³ , a monovalent hydrocarbon group is preferable, and a monovalent saturated hydrocarbon group is particularly preferable.
When R ³ is a monovalent hydrocarbon group, the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, more preferably 1 to 6, particularly preferably 1 to 3, and most preferably 1 or 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, and particularly preferably 0. The presence of a plurality of L in one hydrolyzable silyl group enhances the adhesion to the substrate.

The ^{_{SiR 3 n L 3-n,}} 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. Si (OCH ₃ ) ₃ is particularly preferred from the viewpoint of easy handling in industrial production.
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 easy production of the surface treatment agent. .

(Specific examples of surface treatment agents)
Specific examples of the compound (21) include, for example, compounds of the following formula.

  Specific examples of compound (22) include, for example, compounds of the following formula.

  Specific examples of compound (23) include, for example, compounds of the following formula.

  Specific examples of compound (24) include, for example, compounds of the following formula.

  Specific examples of compound (25) include, for example, compounds of the following formula.

  Specific examples of compound (26) include, for example, compounds of the following formula.

  Specific examples of compound (27) include, for example, compounds of the following formula.

  Specific examples of the compound (28) include, for example, compounds of the following formula.

However, PFPE is the polyfluoropolyether chain, i.e. _{^{F-R f2 O- (R f1}} O) m -R f2 - a. A preferred form of PFPE is a combination of the preferred (R ^f1 O) _m and R ^f2 described above.

(Production method of surface treatment agent)
Compound (21) can be produced by a known method described in Patent Literature 1, Patent Literature 2, WO 2013/121984 and the like.
Compound (22) can be produced by a known method described in WO2017 / 038832.
Compound (23) can be produced by a known method described in WO 2017/038830.
Compound (24) can be produced by a known method described in JP-A-2006-037541, WO 2016/121211, and the like.
Compound (25) can be produced by a known method described in WO 2013/121984.
Compound (26) can be produced by a known method described in WO 2017/038830.
Compound (27) can be produced by a known method described in JP-A-2006-204656.
Compound (28) can be produced by a known method described in JP-A-2006-037541.

Hereinafter, the present invention will be described in more detail with reference to 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)
In a 200 mL three-necked flask, 11.8 g of ethanol and 100.0 g of compound (1-1) (FOMBLIN (registered trademark) ZDIAC4000, manufactured by Solvay Solexis) were added, and the mixture was stirred at 50 ° C for 4 hours. The reaction mixture was concentrated by an evaporator to obtain 100.4 g of a crude product. The crude product was separated by developing on silica gel column chromatography. The compound (3-1) was eluted using CF ₃ CH ₂ OCF ₂ CF ₂ H (manufactured by Asahi Glass Co., Ltd., AE-3000) as a developing solvent. The 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-trifluoroethanol = 2/8 (mass ratio) as a developing solvent. With respect to each of the obtained components, the average value of the structure of the terminal group and the number of units (x1, x2) of the structural unit 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 25.4 g 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)
The average value of the number of units x1, 19, the average value of the number of units x2, 21, the number average molecular weight of the 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).
The average value of the number of units x1, 19, the average value of the number of units x2, 21, the number average molecular weight of the 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).
The average value of the number of units x1, 19, the average value of the number of units x2, 21, the number average molecular weight of the 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 packed bed of NaF pellets, and a cooler maintained at 0 ° C were installed in series. A liquid return line was provided for returning the condensed liquid from the cooler maintained at 0 ° C. to the autoclave.
The autoclave was charged with 350g of _{ClCF 2 CFClCF 2 OCF 2 CF 2} Cl (CFE-419), it was stirred while maintaining to 25 ° C.. After nitrogen gas was blown into the autoclave at 25 ° C. for 1 hour, 20% fluorine gas was blown at 25 ° C. at a flow rate of 1.0 L / hour for 1 hour. A solution in which 40.0 g of the compound (2-1) obtained in Example 1-1 was dissolved 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) while blowing 20% fluorine gas at the same flow rate. 6 mL of a benzene solution containing 0.05 g / mL of 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 injected again while maintaining the temperature at 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. The stirring was continued for 1 hour while blowing 20% fluorine gas at the same flow rate. The pressure in the autoclave was adjusted to the atmospheric pressure, and nitrogen gas was blown for one hour. The contents of the autoclave were 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 , standard: 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).
The average value of the number of units x1, 19, the average value of the number of units x2, 21, the number average molecular weight of the compound (4-1): 3,980.

(Example 1-3)
A round bottom flask made of tetrafluoroethylene-perfluoro (alkoxyvinyl ether) copolymer (PFA) was charged with 39.0 g of the compound (4-1) obtained in Example 1-2 and 50 g of AE-3000. The mixture was stirred while being cooled in an ice bath, and 3.2 g of methanol was slowly dropped from a dropping funnel under a nitrogen atmosphere. The mixture was stirred for 12 hours while bubbling with nitrogen. The reaction mixture was concentrated with 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 , standard: 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).
The average value of the number of units x1, 19, the average value of the number of units x2, 21, the number average molecular weight of the compound (5-1): 3,880.

(Example 1-4)
In a 200 mL three-neck eggplant flask, 1.80 g of sodium borohydride was dissolved in 10 g of ethanol and 20 g of AE-3000, and the compound obtained in Example 1-3 (5- A solution obtained by mixing 37.0 g of 1) with 37.0 g of AE-3000 was slowly dropped. The ice bath was removed, and stirring was continued while slowly raising the temperature to room temperature. After stirring at room temperature for 12 hours, an aqueous hydrochloric acid solution was added dropwise until the solution became acidic. The organic phase was collected, washed once with water and once with saturated saline, and the organic phase was recovered. The collected organic phase was concentrated with 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 , standard: 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).
The average value of the number of units x1, 19, the average value of the number of units x2, 21, and the number average molecular weight of the 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 the mixture was stirred at 80 ° C for 2 hours. This was transferred to a separating funnel, 30 mL of diluted hydrochloric acid was added, and the mixture was extracted five 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).

A compound was prepared in the same manner as in Example 1 except that 22.6 g of the compound (1-1) regenerated from the compound (3-1) was used, and the amounts of the respective raw materials were changed in accordance with the amount of the 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)
20.0 g of the compound (1-1) and 20.0 g of the compound (6-1) obtained in Example 1-4 were placed in a 100 mL three-necked flask, and the mixture was heated to 80 ° C and stirred. The by-produced water was distilled off under reduced pressure, and NMR analysis confirmed that the 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: 12%) of compound (12-1) were obtained. Rate: 48.0%) and 14.5 g of compound (13-1) (yield: 24.2%).
_{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).
The average value of the number of units x1, 19, the average value of the number of units x2, 21, the number average molecular weight of the 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).
The average value of the number of units x1, 19, the average value of the number of units x2, 21, the number average molecular weight of the 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 , standard: CFCl ₃ ) δ (ppm): -52.2 to -55.5 (114F), -56.3 to -58.3 (6F), -77.5 to -80.3 (8F), -89.3 to -90.9 (252F).
The average value of the number of units x1, 19, the average value of the number of units x2, 21, the number average molecular weight of the compound (13-1): 11,570.

(Example 3-2)
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), in the same manner as in Example 1-2. 18.8 g (yield 98.8%) of the 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).
The average value of the number of units x1, 19, the average value of the number of units x2, 21, the number average molecular weight of the compound (14-1): 7,740.

(Example 3-3)
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), in the same manner as in 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 , standard: 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).
The average value of the number of units x1, 19, the average value of the number of units x2, 21, the number average molecular weight of the 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-shaped flask, 14.0 g of the compound (13-1) obtained in Example 3-1 and 1.0 g of a 48% aqueous sodium hydroxide solution were added, and the mixture was stirred at 80 ° C for 2 hours. This was transferred to a separating funnel, diluted with 20 mL of hydrochloric acid, and extracted five times with 20 mL of AE-3000. The collected solution was concentrated by an evaporator, and the obtained 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 (197% yield) was obtained.
The compound (13-1) can be reused as the compound (1-1) and the compound (6-1). By recycling the compound (13-1), almost no waste of the fluorine-containing ether compound is generated. I can't say that.

[Example 5]
(Production Example of Surface Treatment Agent Using Compound (5-1))
A surface treating agent was produced according to the method described in Example 1-6 of WO 2013/121984. 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 , standard: 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).
The average value of the number of units x1, 19, the average value of the number of units x2, 21, the number average molecular weight of the 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 WO2017 / 0388830.
_{F-CF 2 O - {(} CF 2 O) x1 (CF 2 CF 2 O) x2} -CF 2 -CH 2 OCH 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 , standard: 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).
The average value of the number of units x1, 19, the average value of the number of units x2, 21, the number average molecular weight of the compound (23-1): 4,370.

The fluorinated ether compound obtained by the production method of the present invention can be used for various applications that are required to impart lubricity and water / oil repellency. For example, display input devices such as touch panels; surface protection coats made of transparent glass or transparent plastic members, antifouling coats for kitchens; water repellent and moistureproof coats and antifouling coats for electronic equipment, heat exchangers, batteries, etc., and toiletries Antifouling coat; Coating for members requiring liquid repellency while conducting; Water-repellent, waterproof, water-sliding coat for heat exchanger; Vibration sieve, low friction surface coat for cylinder interior, etc. More specific examples of use include a front protective plate of a display, an anti-reflection plate, a polarizing plate, an anti-glare plate, or a surface having an anti-reflection film treated thereon, and a touch panel of a device such as a mobile phone or a portable information terminal. Various devices having display input devices such as sheets and touch panel displays that perform operations on the screen with human fingers or palms, decorative building materials around water such as toilets, baths, washrooms, kitchens, etc. Water / water repellent coat, water repellent coat for solar cells, waterproof / water repellent coat for printed wiring boards, waterproof / water repellent coat for electronic equipment housing and electronic parts, insulation improving coat for power transmission lines, waterproof for various filters Water repellent coat, waterproof coat of radio wave absorbing material and sound absorbing material, bath, kitchen equipment, antifouling coat for toiletry, water repellent / waterproof / water sliding 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 by reference as the disclosure of the specification of the present invention. It is.

Claims (15)

A compound represented by the following formula (1) is reacted with R ¹ OH to give a compound represented by the following formula (1), a compound represented by the following formula (2), and a compound represented by the following formula (3) A method for producing a fluorine-containing ether compound, comprising obtaining a mixture containing the compound.
HO (O) C- ^Rf2O- ( ^Rf1O ) _m- ^Rf2- 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 of 2 to 200;
(R ^f1 O) _m may be composed of two or more kinds 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 between the compound represented by the formula (1) and the R ¹ OH. The manufacturing method according to claim 1, wherein The compound represented by the formula (3) is recovered and hydrolyzed to obtain a compound represented by the formula (1), and the reaction between the compound represented by the formula (1) and the R ¹ OH The method according to claim 1, wherein the compound is reused as the compound represented by the formula (1). A method for producing a fluorine-containing ether compound, comprising fluorinating a compound represented by the following formula (2) with 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)
^FR- f2O- ( ^Rf1O ) _m- ^Rf2- C (O) OR ^f3 (4)
However,
R ^f1 and R ^f2 are each independently a perfluoroalkylene group,
m is an integer of 2 to 200;
(R ^f1 O) _m may be composed of two or more kinds of R ^f1 O;
R ¹ is a monovalent organic group,
R ^f3 is a monovalent perfluoro organic group derived from R ¹ . A process for producing a fluorine-containing ether compound, comprising subjecting a compound represented by the following formula (4) to transesterification with R ² OH to obtain a compound represented by the following formula (5).
^FR- f2O- ( ^Rf1O ) _m- ^Rf2- 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 of 2 to 200;
(R ^f1 O) _m may be composed of two or more kinds of R ^f1 O;
R ^f3 is a monovalent perfluoro organic group,
R ² is a monovalent organic group. A method for producing a fluorine-containing ether compound, comprising obtaining a compound represented by the following formula (6) by hydrogen-reducing 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 of 2 to 200;
(R ^f1 O) _m may be composed of two or more kinds 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)
^FR- f2O- ( ^Rf1O ) _m- ^Rf2- C (O) OR ^f3 (4)
However,
R ^f1 and R ^f2 are each independently a perfluoroalkylene group,
m is an integer of 2 to 200;
(R ^f1 O) _m may be composed of two or more kinds 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 a compound represented by the following formula: (13) A method for producing a fluorine-containing ether compound, which comprises obtaining a mixture containing the compound represented by (13).
HO (O) C- ^Rf2O- ( ^Rf1O ) _m- ^Rf2- 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 kinds of R ^f1 O.   The unreacted compound represented by the formula (1) is recovered, and the compound represented by the formula (1) is reacted with 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 to be used is reused.   The compound represented by the formula (13) is recovered and hydrolyzed to obtain a compound represented by the formula (1) and a compound represented by the formula (6). The compound represented by the formula (1) or the compound represented by the formula (6) in the reaction of the compound represented by the formula (6) with the compound represented by the formula (6). The manufacturing method as described. A method for producing a fluorine-containing ether compound, comprising fluorinating a compound represented by the following formula (12) with 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 kinds of R ^f1 O. A method for producing a fluorine-containing ether compound, comprising subjecting a compound represented by the following formula (14) to transesterification with 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 kinds of R ^f1 O;
R ² is a monovalent organic group. A compound represented by the following formula (6) is obtained by subjecting a compound represented by the following formula (5) obtained by the production method according to claim 12 to hydrogen reduction using a reducing agent. For producing a fluorinated 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 kinds 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 fluorine-containing ether compound, comprising obtaining a mixture containing a compound represented by the formula (12) and a compound represented by the following formula (13).
HO (O) C- ^Rf2O- ( ^Rf1O ) _m- ^Rf2- 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 kinds 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 kinds of R ^f1 O.