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

文档序号：1651939 发布日期：2019-12-24 浏览：23次中文

阅读说明：本技术 含氟醚化合物的制造方法和含氟醚化合物 (Method for producing fluorine-containing ether compound, and fluorine-containing ether compound ) 是由富依勇佑高尾清贵于 2018-04-23 设计创作，主要内容包括：本发明提供含氟醚化合物的制造方法,其能够以低成本且生产性良好地制造适合用于表面处理剂的含氟醚化合物或可用作该含氟醚化合物的中间体的含氟醚化合物。含氟醚化合物的制造方法是使NH3与A-O-Q-(Rf1O)m-Rf2-R1-CO-Z反应,得到A-O-Q-(Rf1O)m-Rf2-R1-CO-NH2。其中,A是碳数1～20的全氟烷基,Q是单键、含有1个以上的氢原子的氟代亚烷基等,Rf1和Rf2分别独立地为全氟亚烷基,m是2～200的整数,(Rf1O)m可以由2种以上的Rf1O构成,R1是单键、亚烷基等,Z是-OR4等,R4是1价的烃基。(Disclosed is a method for producing a fluorine-containing ether compound, which enables to produce a fluorine-containing ether compound suitable for a surface treatment agent or a fluorine-containing ether compound useful as an intermediate for the fluorine-containing ether compound at low cost with good productivity. The process for producing the fluorine-containing ether compound comprises reacting NH 3 With A-O-Q- (R) f1 O) m ‑R f2 ‑R 1 -CO-Z reaction to obtain A-O-Q- (R) f1 O) m ‑R f2 ‑R 1 ‑CO‑NH 2 . Wherein A is a C1-20 perfluoroalkyl group, Q is a single bond, a fluoroalkylene group containing 1 or more hydrogen atoms, or the like, and R is f1 And R f2 Are each independentlyPerfluoroalkylene, m is an integer of 2 to 200, (R) f1 O) m Can be composed of more than 2 kinds of R f1 O is formed of R 1 Is a single bond, alkylene, OR the like, Z is-OR 4 Etc. R 4 Is a hydrocarbyl radical having a valence of 1.)

1. A process for producing a fluorine-containing ether compound, characterized by reacting NH with₃Reacting with a compound represented by the following formula (1) to obtain a compound represented by the following formula (2),

A-O-Q-(R^f1O)_m-R^f2-R¹-CO-Z…(1)

A-O-Q-(R^f1O)_m-R^f2-R¹-CO-NH₂…(2)

wherein the content of the first and second substances,

a is a C1-20 perfluoroalkyl group,

q is a single bond, a fluoroalkylene group containing 1 or more hydrogen atoms, or a fluoroalkylene group containing 1 or more hydrogen atoms^f1O)_mA group having an etheric oxygen atom at the end of the side to which the compound is bonded, a group having an etheric oxygen atom between carbon-carbon atoms of a C2 or more fluoroalkylene group containing 1 or more hydrogen atoms, or a compound of (R) and (C2 or more fluoroalkylene group containing 1 or more hydrogen atoms^f1O)_mA group having an etheric oxygen atom between the terminal of the bonded side and the carbon-carbon atom,

R^f1and R^f2Each of which is independently a perfluoroalkylene group,

m is an integer of 2 to 200,

(R^f1O)_mcan be composed of more than 2 kinds of R^f1O, and the mixture is mixed to form the alloy,

R¹is a single bond, alkylene, in alkylene only with R^f2A group having an etheric oxygen atom or-NH-at the terminal of the side to which the bond is made, a group having an etheric oxygen atom or-NH-between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, or an alkylene group having 2 or more carbon atomsOf radicals only with R^f2A group having an etheric oxygen atom or-NH-between the terminal of the bonded side and the carbon-carbon atom,

z is-OH, -OR⁴、-R⁵A halogen atom or a hydrogen atom, R⁴And R⁵Each being a 1-valent hydrocarbon group.

2. The method of claim 1, wherein Z is-OR⁴To make NH₃Reacting with a compound shown as a formula (1) in an alcohol solvent or a fluorine-containing solvent.

3. A process for producing a fluorine-containing ether compound, characterized by reacting a reducing agent with a compound represented by the following formula (2) to obtain a compound represented by the following formula (3),

A-O-Q-(R^f1O)_m-R^f2-R¹-CO-NH₂…(2)

A-O-Q-(R^f1O)_m-R^f2-R¹-CH₂-NH₂…(3)

wherein the content of the first and second substances,

a is a C1-20 perfluoroalkyl group,

R^f1and R^f2Each of which is independently a perfluoroalkylene group,

m is an integer of 2 to 200,

(R^f1O)_mcan be composed of more than 2 kinds of R^f1O, and the mixture is mixed to form the alloy,

R¹is a single bond, alkylene, in alkylene only with R^f2In combination with oneA group having an etheric oxygen atom or-NH-at a side terminal thereof, a group having an etheric oxygen atom or-NH-between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, or an alkylene group having 2 or more carbon atoms only with R^f2An etheric oxygen atom or-NH-group is present between the terminal of the bonded side and the carbon-carbon atom.

4. A process for producing a fluorine-containing ether compound, characterized in that YR is reacted with a fluorine-containing ether compound²¹Reacting with a compound represented by the following formula (3) to obtain a compound represented by the following formula (4),

A-O-Q-(R^f1O)_m-R^f2-R¹-CH₂-NH₂…(3)

A-O-Q-(R^f1O)_m-R^f2-R¹-CH₂-NR²¹ ₂…(4)

wherein the content of the first and second substances,

a is a C1-20 perfluoroalkyl group,

R^f1and R^f2Each of which is independently a perfluoroalkylene group,

m is an integer of 2 to 200,

(R^f1O)_mcan be composed of more than 2 kinds of R^f1O, and the mixture is mixed to form the alloy,

R¹is a single bond, alkylene, in alkylene only with R^f2A group having an etheric oxygen atom or-NH-at the end of the side to which the bond is made, a group having an etheric oxygen atom or-NH-between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, or an alkylene group having 2 or more carbon atoms only bonded with R^f2End of one side of the combinationAnd a group having an etheric oxygen atom or-NH-between carbon-carbon atoms,

y is HO-, R⁶O-or halogen atoms, R⁶Is a hydrocarbyl radical having a valence of 1,

R²¹is a 1-valent organic group having a vinyl group at the terminal or a 1-valent hydrocarbon group other than the group having a vinyl group at the terminal.

5. The method according to claim 4, wherein Y is a halogen atom, and R is a halogen atom²¹Is allyl or allyloxyalkyl.

6. A process for producing a fluorine-containing ether compound, characterized by reacting a compound represented by the following formula (4a) with HSiR³ _nX_3-nCarrying out hydrosilylation reaction to obtain a compound shown as the following formula (5),

A-O-Q-(R^f1O)_m-R^f2-R¹-CH₂-NR²² ₂…(4a)

A-O-Q-(R^f1O)_m-R^f2-R¹-CH₂-N[-R²-SiR³ _nX_3-n]₂…(5)

wherein the content of the first and second substances,

a is a C1-20 perfluoroalkyl group,

R^f1and R^f2Each of which is independently a perfluoroalkylene group,

m is an integer of 2 to 200,

(R^f1O)_mcan be composed of more than 2 kinds of R^f1O, and the mixture is mixed to form the alloy,

R¹is a single bond, alkylene, in alkylene only with R^f2A group having an etheric oxygen atom or-NH-at the end of the side to which the bond is made, a group having an etheric oxygen atom or-NH-between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, or an alkylene group having 2 or more carbon atoms only bonded with R^f2A group having an etheric oxygen atom or-NH-between the terminal of the bonded side and the carbon-carbon atom,

R²²is a 1-valent organic group having a vinyl group at the terminal, 2R²²Which may be the same or different from each other,

R²is derived from R²²The 2-valent organic group of (a),

R³is a hydrogen atom or a 1-valent hydrocarbon group,

x is a hydrolyzable group which is a hydroxyl group,

n is an integer of 0 to 2.

7. A method for producing a fluorine-containing ether compound, characterized by comprising steps 1 to 4 of obtaining a compound represented by the following formula (5) from a compound represented by the following formula (1),

step 1: by reaction of NH₃A step of reacting the compound with a compound represented by the following formula (1) to obtain a compound represented by the following formula (2);

and a step 2: a step of reacting a reducing agent with a compound represented by the following formula (2) to obtain a compound represented by the following formula (3);

step 3: make YR²²A step of reacting the compound with a compound represented by the following formula (3) to obtain a compound represented by the following formula (4 a);

and step 4: reacting a compound represented by the following formula (4a) with HSiR³ _nX_3-nA step of obtaining a compound represented by the following formula (5) by performing a hydrosilylation reaction;

A-O-Q-(R^f1O)_m-R^f2-R¹-CO-Z…(1)

A-O-Q-(R^f1O)_m-R^f2-R¹-CO-NH₂…(2)

A-O-Q-(R^f1O)_m-R^f2-R¹-CH₂-NH₂…(3)

A-O-Q-(R^f1O)_m-R^f2-R¹-CH₂-NR²² ₂…(4a)

A-O-Q-(R^f1O)_m-R^f2-R¹-CH₂-N[-R²-SiR³ _nX_3-n]₂…(5)

wherein the content of the first and second substances,

a is a C1-20 perfluoroalkyl group,

R^f1and R^f2Each of which is independently a perfluoroalkylene group,

m is an integer of 2 to 200,

(R^f1O)_mcan be composed of more than 2 kinds of R^f1O, and the mixture is mixed to form the alloy,

R¹is a single bond, alkylene, in alkylene only with R^f2A group having an etheric oxygen atom or-NH-at the end of the side to which the bond is made, a group having an etheric oxygen atom or-NH-between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, or an alkylene group having 2 or more carbon atoms only bonded with R^f2A group having an etheric oxygen atom or-NH-between the terminal of the bonded side and the carbon-carbon atom,

z is-OH, -OR⁴、-R⁵A halogen atom or a hydrogen atom, R⁴And R⁵Respectively, a hydrocarbon group having a valence of 1,

y is HO-, R⁶O-or halogen atoms, R⁶Is a hydrocarbyl radical having a valence of 1,

R²²having ethylene at the endAn organic group having a valence of 1 of the group,

R²is derived from R²²The 2-valent organic group of (a),

R³is a hydrogen atom or a 1-valent hydrocarbon group,

x is a hydrolyzable group which is a hydroxyl group,

n is an integer of 0 to 2.

8. The method of claim 7, wherein Z is-OR⁴To make NH₃Reacting with a compound shown as a formula (1) in an alcohol solvent or a fluorine-containing solvent.

9. The production process according to claim 7 or 8, wherein Y is a halogen atom, and R is²²Is allyl or allyloxyalkyl.

10. The production method according to any one of claims 7 to 9, wherein Q and R are¹Are all single bonds.

11. A fluorine-containing ether compound represented by the following formula (2),

A-O-Q-(R^f1O)_m-R^f2-R¹-CO-NH₂…(2)

wherein the content of the first and second substances,

a is a C1-20 perfluoroalkyl group,

R^f1and R^f2Each of which is independently a perfluoroalkylene group,

m is an integer of 2 to 200,

(R^f1O)_mcan be composed of more than 2 kinds of R^f1O, and the mixture is mixed to form the alloy,

R¹is a single bond, alkylene, in alkylene only with R^f2A group having an etheric oxygen atom or-NH-at the end of the side to which the bond is made, a group having an etheric oxygen atom or-NH-between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, or an alkylene group having 2 or more carbon atoms only bonded with R^f2An etheric oxygen atom or-NH-group is present between the terminal of the bonded side and the carbon-carbon atom.

12. A compound of claim 11, wherein Q and R are¹Are all single bonds.

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

A-O-Q-(R^f1O)_m-R^f2-R¹-CH₂-NH₂…(3)

wherein the content of the first and second substances,

a is a C1-20 perfluoroalkyl group,

R^f1and R^f2Each of which is independently a perfluoroalkylene group,

m is an integer of 2 to 200,

(R^f1O)_mcan be composed of more than 2 kinds of R^f1O, and the mixture is mixed to form the alloy,

R¹is a single bond, alkylene, in alkylene only with R^f2A group having an etheric oxygen atom or-NH-at the end of one side to which the bond is bondedA group having an etheric oxygen atom or-NH-between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, or an alkylene group having 2 or more carbon atoms only with R^f2An etheric oxygen atom or-NH-group is present between the terminal of the bonded side and the carbon-carbon atom.

14. A compound of claim 13, wherein Q and R are¹Are all single bonds.

Technical Field

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

Background

The fluorine-containing ether compound having a poly (oxyperfluoroalkylene) chain is suitably used as a surface treatment agent because it can form a surface layer exhibiting high lubricity, water and oil repellency, and the like on the surface of a substrate. A surface treatment agent containing a fluorine-containing ether compound is used, for example, as a surface treatment agent for a member constituting a finger contact surface of a touch panel in applications requiring the performance (rubbing resistance) of maintaining the water/oil repellency of a surface layer not to be lowered even when the surface layer is repeatedly rubbed with a finger and the performance (fingerprint stain removal performance) of easily removing a fingerprint adhering to the surface layer by wiping.

As a fluorine-containing ether compound capable of forming a surface layer excellent in water-and oil-repellency, abrasion resistance, fingerprint stain removability, lubricity, chemical resistance and light resistance on the surface of a substrate, a fluorine-containing ether compound in which 2 hydrolyzable silyl groups are introduced into one end of a fluorine-containing ether compound through a branched structure based on a nitrogen atom has been proposed (patent document 1).

The fluorine-containing ether compound described in patent document 1 (compound represented by the following formula (1A)) is produced as follows.

The compound represented by the following formula (14) is hydrogen-reduced by using a reducing agent to obtain a compound represented by the following formula (15).

A¹-O-(CF₂CF₂O)(CF₂CF₂O)(R^f11O)_x-CF₂-COOR…(14)

A¹-O-(CF₂CF₂O)(CF₂CF₂O)(R^f11O)_x-CF₂-CH₂OH…(15)

Wherein A is¹Is a C1-20 perfluoroalkyl group, R^f11Is a perfluoroalkylene group, and x is an integer of 1 to 198And R is an alkyl group.

In a fluorine-containing solvent in the presence of a basic compound₃SO₂Cl is reacted with the compound represented by the above formula (15) to obtain a compound represented by the following formula (16).

A¹-O-(CF₂CF₂O)(CF₂CF₂O)(R^f11O)_x-CF₂-CH₂OSO₂CF₃…(16)

Reacting HN (CH) in the presence of a basic compound₂CH＝CH₂)₂And (3) reacting with the compound represented by the above formula (16) to obtain a compound represented by the following formula (17).

A¹-O-(CF₂CF₂O)(CF₂CF₂O)(R^f11O)_x-CF₂-CH₂-N(CH₂CH＝CH₂)₂…(17)

Reacting a compound represented by the above formula (17) with HSiR¹³ _n1X¹ _3-n1Hydrosilylation reaction was carried out to obtain a compound represented by the following formula (1A).

A¹-O-(CF₂CF₂O)(CF₂CF₂O)(R^f11O)_x-CF₂-CH₂-N[CH₂CH₂CH₂-SiR¹³ _n1X¹ _3-n1]₂…(1A)

Wherein R is¹³Is a hydrogen atom or a 1-valent hydrocarbon group, X¹Is a hydrolyzable group, and n1 is an integer of 0 to 2.

Disclosure of Invention

Technical problem to be solved by the invention

However, the method described in patent document 1 has the following problems.

CF by reaction with a compound of formula (15)₃SO₂Production of fluorinated ether compound with high Cl priceThe cost is high.

In the reaction of HN (CH)₂CH＝CH₂)₂When reacting with a compound represented by the formula (16) to obtain a compound represented by the formula (17), a trifluoromethanesulfonic acid by-product which is difficult to handle is formed. The treatment of trifluoromethanesulfonic acid takes time, and therefore, the productivity of the fluorine-containing ether compound is poor.

An object of the present invention is to provide a method for producing a fluorine-containing ether compound, which can produce a fluorine-containing ether compound suitable for a surface treatment agent or a fluorine-containing ether compound useful as an intermediate of the fluorine-containing ether compound, at low cost and with good productivity, and a fluorine-containing ether compound useful as an intermediate of a fluorine-containing ether compound suitable for a surface treatment agent.

Technical scheme for solving technical problem

The present invention provides a method for producing a fluorine-containing ether compound having the following configurations [1] and [2], a method for producing a fluorine-containing ether compound having the following configuration [3], a method for producing a fluorine-containing ether compound having the following configurations [4] and [5], a method for producing a fluorine-containing ether compound having the following configuration [6], a method for producing fluorine-containing ether compounds having the following configurations [7] to [10], a fluorine-containing ether compound having the following configurations [11] and [12], and a fluorine-containing ether compound having the following configurations [13] and [14 ].

[1]A process for producing a fluorine-containing ether compound, characterized by reacting NH₃Reacting with a compound represented by the following formula (1) to obtain a compound represented by the following formula (2),

A-O-Q-(R^f1O)_m-R^f2-R¹-CO-Z…(1)

A-O-Q-(R^f1O)_m-R^f2-R¹-CO-NH₂…(2)

wherein the content of the first and second substances,

a is a C1-20 perfluoroalkyl group,

q is a single bond, a fluoroalkylene group containing 1 or more hydrogen atoms, or a fluoroalkylene group containing 1 or more hydrogen atoms^f1O)_mA group having an etheric oxygen atom at the end of one side to which the group is bonded, 1 or moreA group having an etheric oxygen atom between carbon and carbon atoms of a C2 or more fluoroalkylene group having a hydrogen atom or a group containing 1 or more hydrogen atoms and only (R) a C2 or more fluoroalkylene group^f1O)_mA group having an etheric oxygen atom between the terminal of the bonded side and the carbon-carbon atom,

R^f1and R^f2Each of which is independently a perfluoroalkylene group,

m is an integer of 2 to 200,

(R^f1O)_mcan be composed of more than 2 kinds of R^f1O, and the mixture is mixed to form the alloy,

R¹is a single bond, alkylene, in alkylene only with R^f2A group having an etheric oxygen atom or-NH-at the end of the side to which the bond is made, a group having an etheric oxygen atom or-NH-between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, or an alkylene group having 2 or more carbon atoms only bonded with R^f2A group having an etheric oxygen atom or-NH-between the terminal of the bonded side and the carbon-carbon atom,

z is-OH, -OR⁴、-R⁵A halogen atom or a hydrogen atom, R⁴And R⁵Each being a 1-valent hydrocarbon group.

[2]Such as [1]]The production method described above, wherein Z is-OR⁴To make NH₃Reacting with a compound shown as a formula (1) in an alcohol solvent or a fluorine-containing solvent.

[3] A process for producing a fluorine-containing ether compound, characterized by reacting a reducing agent with a compound represented by the following formula (2) to obtain a compound represented by the following formula (3),

A-O-Q-(R^f1O)_m-R^f2-R¹-CO-NH₂…(2)

A-O-Q-(R^f1O)_m-R^f2-R¹-CH₂-NH₂…(3)

wherein the content of the first and second substances,

a is a C1-20 perfluoroalkyl group,

q is a single bond, a fluoroalkylene group containing 1 or more hydrogen atoms, or a fluoroalkylene group containing 1 or more hydrogen atoms^f1O)_mBonding ofA group having an etheric oxygen atom at one end thereof, a group having an etheric oxygen atom between carbon-carbon atoms of a C2 or more fluoroalkylene group containing 1 or more hydrogen atoms, or a group having only a (R) and a C2 or more fluoroalkylene group containing 1 or more hydrogen atoms^f1O)_mA group having an etheric oxygen atom between the terminal of the bonded side and the carbon-carbon atom,

R^f1and R^f2Each of which is independently a perfluoroalkylene group,

m is an integer of 2 to 200,

(R^f1O)_mcan be composed of more than 2 kinds of R^f1O, and the mixture is mixed to form the alloy,

R¹is a single bond, alkylene, in alkylene only with R^f2A group having an etheric oxygen atom or-NH-at the end of the side to which the bond is made, a group having an etheric oxygen atom or-NH-between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, or an alkylene group having 2 or more carbon atoms only bonded with R^f2An etheric oxygen atom or-NH-group is present between the terminal of the bonded side and the carbon-carbon atom.

[4]A process for producing a fluorine-containing ether compound, characterized in that YR is reacted with a fluorine-containing ether compound²¹Reacting with a compound represented by the following formula (3) to obtain a compound represented by the following formula (4),

A-O-Q-(R^f1O)_m-R^f2-R¹-CH₂-NH₂…(3)

A-O-Q-(R^f1O)_m-R^f2-R¹-CH₂-NR²¹ ₂…(4)

wherein the content of the first and second substances,

a is a C1-20 perfluoroalkyl group,

R^f1and R^f2Each of which is independently a perfluoroalkylene group,

m is an integer of 2 to 200,

(R^f1O)_mcan be composed of more than 2 kinds of R^f1O, and the mixture is mixed to form the alloy,

R¹is a single bond, alkylene, in alkylene only with R^f2A group having an etheric oxygen atom or-NH-at the end of the side to which the bond is made, a group having an etheric oxygen atom or-NH-between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, or an alkylene group having 2 or more carbon atoms only bonded with R^f2A group having an etheric oxygen atom or-NH-between the terminal of the bonded side and the carbon-carbon atom,

y is HO-, R⁶O-or halogen atoms, R⁶Is a hydrocarbyl radical having a valence of 1,

R²¹is a 1-valent organic group having a vinyl group at the terminal or a 1-valent hydrocarbon group other than the group having a vinyl group at the terminal.

[5]Such as [4]]The production process described above, wherein Y is a halogen atom and R is²¹Is allyl or allyloxyalkyl.

[6]A process for producing a fluorine-containing ether compound, characterized by reacting a compound represented by the following formula (4a) with HSiR³ _nX_3-nCarrying out hydrosilylation reaction to obtain a compound shown as the following formula (5),

A-O-Q-(R^f1O)_m-R^f2-R¹-CH₂-NR²² ₂…(4a)

A-O-Q-(R^f1O)_m-R^f2-R¹-CH₂-N[-R²-SiR³ _nX_3-n]₂…(5)

wherein the content of the first and second substances,

a is a C1-20 perfluoroalkyl group,

q is a single bond, a fluoroalkylene group containing 1 or more hydrogen atoms, or a fluoroalkylene group containing 1 or more hydrogen atoms(R^f1O)_mA group having an etheric oxygen atom at the end of the side to which the compound is bonded, a group having an etheric oxygen atom between carbon-carbon atoms of a C2 or more fluoroalkylene group containing 1 or more hydrogen atoms, or a compound of (R) and (C2 or more fluoroalkylene group containing 1 or more hydrogen atoms^f1O)_mA group having an etheric oxygen atom between the terminal of the bonded side and the carbon-carbon atom,

R^f1and R^f2Each of which is independently a perfluoroalkylene group,

m is an integer of 2 to 200,

(R^f1O)_mcan be composed of more than 2 kinds of R^f1O, and the mixture is mixed to form the alloy,

R¹is a single bond, alkylene, in alkylene only with R^f2A group having an etheric oxygen atom or-NH-at the end of the side to which the bond is made, a group having an etheric oxygen atom or-NH-between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, or an alkylene group having 2 or more carbon atoms only bonded with R^f2A group having an etheric oxygen atom or-NH-between the terminal of the bonded side and the carbon-carbon atom,

R²²is a 1-valent organic group having a vinyl group at the terminal, 2R²²Which may be the same or different from each other,

R²is derived from R²²The 2-valent organic group of (a),

R³is a hydrogen atom or a 1-valent hydrocarbon group,

x is a hydrolyzable group which is a hydroxyl group,

n is an integer of 0 to 2.

[7] A process for producing a fluorine-containing ether compound, characterized by comprising the steps of 1 to 4 as follows to obtain a compound represented by the following formula (5) from a compound represented by the following formula (1),

step 1: by reaction of NH₃A step of reacting the compound with a compound represented by the following formula (1) to obtain a compound represented by the following formula (2);

and a step 2: a step of reacting a reducing agent with a compound represented by the following formula (2) to obtain a compound represented by the following formula (3);

step 3: make YR²²And the formula(3) A step for obtaining a compound represented by the following formula (4a) by reacting the compound represented by the formula (I);

A-O-Q-(R^f1O)_m-R^f2-R¹-CO-Z…(1)

A-O-Q-(R^f1O)_m-R^f2-R¹-CO-NH₂…(2)

A-O-Q-(R^f1O)_m-R^f2-R¹-CH₂-NH₂…(3)

A-O-Q-(R^f1O)_m-R^f2-R¹-CH₂-NR²² ₂…(4a)

A-O-Q-(R^f1O)_m-R^f2-R¹-CH₂-N[-R²-SiR³ _nX_3-n]₂…(5)

wherein the content of the first and second substances,

a is a C1-20 perfluoroalkyl group,

R^f1and R^f2Each of which is independently a perfluoroalkylene group,

m is an integer of 2 to 200,

(R^f1O)_mcan be composed of more than 2 kinds of R^f1O, and the mixture is mixed to form the alloy,

R¹is a single bond, alkylene, in alkylene only with R^f2End of one side of the combinationA group having an etheric oxygen atom or-NH-, a group having an etheric oxygen atom or-NH-between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, or an alkylene group having 2 or more carbon atoms only with R^f2A group having an etheric oxygen atom or-NH-between the terminal of the bonded side and the carbon-carbon atom,

z is-OH, -OR⁴、-R⁵A halogen atom or a hydrogen atom, R⁴And R⁵Respectively, a hydrocarbon group having a valence of 1,

y is HO-, R⁶O-or halogen atoms, R⁶Is a hydrocarbyl radical having a valence of 1,

R²²is a 1-valent organic group having a vinyl group at the terminal,

R²is derived from R²²The 2-valent organic group of (a),

R³is a hydrogen atom or a 1-valent hydrocarbon group,

x is a hydrolyzable group which is a hydroxyl group,

n is an integer of 0 to 2.

[8]Such as [7]]The production method described above, wherein Z is-OR⁴To make NH₃Reacting with a compound shown as a formula (1) in an alcohol solvent or a fluorine-containing solvent.

[9]Such as [7]]Or [ 8]]The production process described above, wherein Y is a halogen atom and R is²²Is allyl or allyloxyalkyl.

[10]Such as [7]]～[9]The process according to any one of the above, wherein Q and R are¹Are all single bonds.

[11] A fluorine-containing ether compound represented by the following formula (2),

A-O-Q-(R^f1O)_m-R^f2-R¹-CO-NH₂…(2)

wherein the content of the first and second substances,

a is a C1-20 perfluoroalkyl group,

q is a single bond, a fluoroalkylene group containing 1 or more hydrogen atoms, or a fluoroalkylene group containing 1 or more hydrogen atoms^f1O)_mHaving a group having an etheric oxygen atom at the end of the bonding side and a fluoroalkylene group having 2 or more carbon atoms and containing 1 or more hydrogen atomsA group having an etheric oxygen atom between carbon and carbon atoms or a fluorinated alkylene group having 1 or more hydrogen atoms and having 2 or more carbon atoms only with (R)^f1O)_mA group having an etheric oxygen atom between the terminal of the bonded side and the carbon-carbon atom,

R^f1and R^f2Each of which is independently a perfluoroalkylene group,

m is an integer of 2 to 200,

(R^f1O)_mcan be composed of more than 2 kinds of R^f1O, and the mixture is mixed to form the alloy,

R¹is a single bond, alkylene, in alkylene only with R^f2A group having an etheric oxygen atom or-NH-at the end of the side to which the bond is made, a group having an etheric oxygen atom or-NH-between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, or an alkylene group having 2 or more carbon atoms only bonded with R^f2An etheric oxygen atom or-NH-group is present between the terminal of the bonded side and the carbon-carbon atom.

[12]Such as [11]]The compound of (1), wherein Q and R are as defined above¹Are all single bonds.

[13] A fluorine-containing ether compound represented by the following formula (3),

A-O-Q-(R^f1O)_m-R^f2-R¹-CH₂-NH₂…(3)

wherein the content of the first and second substances,

a is a C1-20 perfluoroalkyl group,

R^f1and R^f2Each of which is independently a perfluoroalkylene group,

m is an integer of 2 to 200,

(R^f1O)_mcan be composed of more than 2 kinds of R^f1O, and the mixture is mixed to form the alloy,

R¹is a single bond, alkylene, in alkylene only with R^f2A group having an etheric oxygen atom or-NH-at the end of the side to which the bond is made, a group having an etheric oxygen atom or-NH-between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, or an alkylene group having 2 or more carbon atoms only bonded with R^f2An etheric oxygen atom or-NH-group is present between the terminal of the bonded side and the carbon-carbon atom.

[14]Such as [13]]The compound of (1), wherein Q and R are as defined above¹Are all single bonds.

Effects of the invention

According to the method for producing a fluorinated ether compound of the present invention, a fluorinated ether compound suitable for a surface treatment agent or a fluorinated ether compound useful as an intermediate of the fluorinated ether compound can be produced at low cost with good productivity.

The fluorine-containing ether compound of the present invention is useful as an intermediate of a fluorine-containing ether compound suitable for a surface treatment agent.

Detailed Description

In the present specification, the compound represented by formula (1) will be referred to as compound (1). The same applies to compounds represented by other formulae.

The meanings of the following terms and the description of the chemical formulae in the present specification are as follows.

The chemical formula of oxyperfluoroalkylene is shown in such a manner that the oxygen atom is located on the right side of the perfluoroalkylene group.

"etheric oxygen atom" means an oxygen atom forming an ether bond (-O-) between carbon atoms.

"hydrolyzable silyl group" refers to a group capable of forming a silanol group (Si-OH) by a hydrolysis reaction. For example, SiR in the formula (5)³ _nL_3-n。

The "surface layer" refers to a layer formed on the surface of the substrate.

The "number average molecular weight" of the fluorine-containing ether compound was calculated by the following method using NMR analysis.

By using¹H-NMR and¹⁹F-NMR was carried out by obtaining the number (average value) of oxyperfluoroalkylene groups based on the terminal groups to calculate the number average molecular weight. The terminal group being, for example, A or SiR of the formula (5)³ _nL_3-n。

[ Compound (5) ]

The compound (5) suitable for use as a surface treatment agent is a target substance finally obtained in the method for producing a fluorine-containing ether compound of the present invention.

A-O-Q-(R^f1O)_m-R^f2-R¹-CH₂-N[-R²-SiR³ _nX_3-n]₂…(5)

Wherein A is a perfluoroalkyl group having 1 to 20 carbon atoms, Q is a single bond, a fluoroalkylene group having 1 or more hydrogen atoms, or a fluoroalkylene group having 1 or more hydrogen atoms at the terminal (but not limited to R^f1O)_mThe side to which they are bonded) a group having an etheric oxygen atom, a group having an etheric oxygen atom between carbon-carbon atoms of a C2 or more fluoroalkylene group containing 1 or more hydrogen atoms, or a group having a C2 or more fluoroalkylene group containing 1 or more hydrogen atoms at the terminal thereof (but is limited to the group bonded to (R)^f1O)_mBonded side) and a carbon-carbon atom having an etheric oxygen atom, R^f1And R^f2Each independently a perfluoroalkylene group, m is an integer of 2 to 200, (R)^f1O)_mCan be composed of more than 2 kinds of R^f1O is formed of R¹Is a single bond, alkylene, at the end of alkylene (but limited to R)^f2The terminal of the side to which the bond is made) has an etheric oxygen atom or-NH-, a group having an etheric oxygen atom or-NH-between carbon atoms of an alkylene group having 2 or more carbon atoms, or the terminal of an alkylene group having 2 or more carbon atoms (but is limited to R and R only)^f2The terminal of the bonded side) and a group having an etheric oxygen atom or-NH-between carbon and carbon atoms, R²Is R derived from the compound (4) described later²²A 2-valent organic radical of (A), R³Is a hydrogen atom or a 1-valent hydrocarbon group, X is a hydrolyzable group, and n is an integer of 0 to 2.

(A group)

The component A is preferably a C1-10 perfluoroalkyl group, more preferably a C1-6 perfluoroalkyl group, and particularly preferably a C1-3 perfluoroalkyl group, from the viewpoint of further improving lubricity and abrasion resistance of the surface layer formed of the compound (5).

A has CF at the end₃-, whereby one side of the compound (5) is terminated with CF₃The other terminal is a hydrolyzable silyl group. With the compound (5) of this structure, a surface layer having a low surface energy can be formed, and therefore the surface layer is excellent in lubricity and friction resistance. On the other hand, in the case of conventional fluorine-containing ether compounds having hydrolyzable silyl groups at both ends, lubricity and abrasion resistance of the surface layer are insufficient.

(Q group)

Q is preferably a single bond, a C1-10 fluoroalkylene group containing 1 or more hydrogen atoms, or a C1-10 fluoroalkylene group containing 1 or more hydrogen atoms at the end (but not limited to R^f1O)_mThe side to which the fluorine-containing compound is bonded) a group having an etheric oxygen atom, a group having an etheric oxygen atom between carbon-carbon atoms of a C2-10 fluoroalkylene group containing 1 or more hydrogen atoms, and a group having a C2-10 fluoroalkylene group containing 1 or more hydrogen atoms at the terminal thereof (but not limited to (R) and (R)^f1O)_mThe side to which they are bonded) and a carbon-carbon atom having an etheric oxygen atom therebetween.

When Q is not a single bond, the number of hydrogen atoms in Q is 1 or more, preferably 2 or more, and particularly preferably 3 or more, from the viewpoint of excellent appearance of the surface layer. From the viewpoint of further improving the water and oil repellency of the surface layer, the number of hydrogen atoms in Q is preferably (number of carbon atoms of Q) × 2 or less, and particularly preferably (number of carbon atoms of Q) or less.

Q has a hydrogen atom, so that the solubility of the compound (5) in a liquid medium becomes high. Therefore, the compound (5) is less likely to aggregate in the coating liquid, and the compound (5) is less likely to aggregate in the drying process after being applied to the substrate surface, so that the appearance of the surface layer is more excellent.

As Q, a single bond, -R is particularly preferred^f5O-and-R^f5O-R^f6O-is formed. Wherein R is^f5、R^f6Each independently represents a C2-C6 fluoroalkylene group having a hydrogen atom. R^f5、R^f6The number of hydrogen atoms in (1) or (2) is preferred.

As R^f5O, preferably an oxyfluoroalkylene group having a hydrogen atom on the carbon atom to which A-O-is bonded, particularly preferably CHFCF₂And O. As R^f6O, preferably at R^f5Examples of the oxyfluoroalkylene group having a hydrogen atom on the carbon atom to which O is bonded may include CH₂CF₂O、CH₂CF₂CF₂O、CH₂CF₂CF₂CF₂O, and the like. as-R^f5O-R^f6O-, and may be exemplified by-CHFCF₂O-CH₂CF₂O-, etc.

Q is particularly preferably a single bond.

((R^f1O)_m)

As R^f1The perfluoroalkylene group having 1 to 6 carbon atoms is preferable, the perfluoroalkylene group having 1 to 4 carbon atoms is more preferable, and the perfluoroalkylene group having 1 to 2 carbon atoms is particularly preferable, from the viewpoint of more excellent lubricity of the surface layer, from the viewpoint of more excellent abrasion resistance and fingerprint stain removing property of the surface layer.

The compound (5) has (R)^f1O)_mTherefore, the content of fluorine atoms is large. Therefore, the compound (5) can form a surface layer excellent in water-and oil-repellency, abrasion resistance, and fingerprint stain removability.

In addition, R^f1If it is a perfluoroalkylene group having no branched structure, (R)^f1O)_mIs in a straight chain structure. According to the compound (5) of this structure, the friction resistance and lubricity of the surface layer are excellent. On the other hand, in the case where the poly (oxyperfluoroalkylene) chain has a branched structure, the friction resistance and lubricity of the surface layer are slightly inferior.

m is preferably an integer of 5 to 150, and particularly preferably an integer of 10 to 100. When m is not less than the lower limit of the above range, the surface layer is excellent in 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 compound (5) is too large, the number of hydrolyzable silyl groups present per unit molecular weight decreases, and the abrasion resistance of the surface layer decreases.

In (R)^f1O)_mIn (A), more than 2 kinds of R exist^f1In the case of O, each R^f1The order of bonding of O is not limited. For example, in the presence of CF₂O and CF₂CF₂In the case of O, CF₂O and CF₂CF₂O may be arranged randomly, alternately, or in blocks.

There are more than 2R^f1O means that 2 or more R having different carbon numbers are present^f1O and 2 or more R's having the same carbon number but different in the presence or absence of a side chain or the kind of a side chain (the number of side chains, the carbon number of side chains, etc.)^f1O。

With respect to 2 or more kinds of R^f1Configuration of O, for example, in the case of the fluorine-containing ether compound of the example, { (CF)₂O)_x1(CF₂CF₂O)_x2The structures shown represent x1 (CF)₂O) and x2 (CF)₂CF₂O) are randomly configured. Furthermore, (CF)₂CF₂O-CF₂CF₂CF₂CF₂O)_x3The structure shown represents x3 (CF)₂CF₂O) and x3 (CF)₂CF₂CF₂CF₂O) are alternately arranged.

As (R)^f1O)_mFrom the viewpoint of more excellent abrasion resistance, fingerprint stain removability and lubricity of the surface layer, { (CF) is preferred₂O)_m1(CF₂CF₂O)_m2}、(CF₂CF₂O)_m3、(CF₂CF₂CF₂O)_m4、(CF₂CF₂O-CF₂CF₂CF₂CF₂O)_m5And 1-4 other (R) s at one or both ends thereof^f1O) group. Particularly, when Q is a single bond, it is preferable that 1 to 4 other groups (R) are present on the A-O-side^f1O) group. Having 1 to 4 other (R) s at one or both ends^f1O) group, for example, can be exemplified by (CF)₂CF₂O)₂{(CF₂O)_m1(CF₂CF₂O)_m2-2}、(CF₂CF₂O-CF₂CF₂CF₂CF₂O)_m5-1(CF₂CF₂O), and the like. As (R)^f1O)_mParticularly preferably has { (CF)₂O)_m1(CF₂CF₂O)_m2The group of (a).

Wherein 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 m1 CF₂O and m2 CF₂CF₂The order of bonding of O is not limited. m3 and m4 are integers of 2 to 200, respectively, and m5 is an integer of 1 to 100.

(R^f2Radical)

As R^f2The perfluoroalkylene group having 1 to 6 carbon atoms is preferable, the perfluoroalkylene group having 1 to 4 carbon atoms is more preferable, and the perfluoroalkylene group having 1 to 2 carbon atoms is particularly preferable, from the viewpoint of more excellent lubricity of the surface layer, from the viewpoint of more excellent abrasion resistance and fingerprint stain removing property of the surface layer.

For example, in (R)^f1O)_mIs { (CF)₂O)_m1(CF₂CF₂O)_m2And (CF)₂CF₂O)_m3In the case of (1), R^f2Is C1 perfluoroalkylene, in (R)^f1O)_mIs (CF)₂CF₂CF₂O)_m4In the case of (1), R^f2Is C2 perfluoroalkylene, in (R)^f1O)_mIs (CF)₂CF₂O-CF₂CF₂CF₂CF₂O)_m5In the case of (1), R^f2Is a C3 linear perfluoroalkylene group. In addition, in R^f1In the case of perfluoroalkylene having a branch, R^f2Is perfluoroalkylene having a branch, for example as in R^f1Is (CF)₃)CF₂O) in the case of R^f2Is CF (CF)₃)。

R^f2If it is a perfluoroalkylene group having no branched structure, the following tableThe surface layer is excellent in abrasion resistance and lubricity.

(R¹Radical)

As R¹Preferably, the carbon atom-containing group is a single bond, an alkylene group having 1 to 10 carbon atoms, or a group formed at the end of an alkylene group having 1 to 10 carbon atoms (but not limited to R)^f2The terminal of the side to which the above-mentioned groups are bonded) has an etheric oxygen atom or-NH-, a group having an etheric oxygen atom or-NH-between carbon-carbon atoms of an alkylene group having 2 to 10 carbon atoms, and a terminal of an alkylene group having 2 to 10 carbon atoms (but not limited to R)^f2The terminal on the side of bonding) and a carbon-carbon atom, particularly preferably a C1-7 alkylene group, and a C2-7 alkylene group having an etheric oxygen atom or-NH-between the carbon-carbon atoms. From the viewpoint of ease of production of the compound (5), it is preferably selected from the group consisting of a single bond, -CH₂-、-CH₂CH₂-、-CH₂OCH₂-and-CH₂NHCH₂Group of (wherein, left side is R)^f2Combined).

R¹Particularly preferred is a single bond.

R¹Since the surface layer does not have an ester bond having high polarity and insufficient chemical resistance and light resistance, the initial water repellency, chemical resistance and light resistance of the surface layer are excellent.

(R²Radical)

As R²The alkylene group having 2 to 10 carbon atoms is preferably a group having an etheric oxygen atom or-NH-between carbon-carbon atoms of the alkylene group having 3 to 10 carbon atoms, and particularly preferably a group having 2 to 7 carbon atoms and an etheric oxygen atom or-NH-between carbon-carbon atoms of the alkylene group having 3 to 7 carbon atoms. From the viewpoint of ease of production of the compound (5), -CH is preferred₂CH₂CH₂-or-CH₂CH₂OCH₂CH₂CH₂- (where the right side is bonded to Si).

R²Since the surface layer does not have an ester bond having high polarity and insufficient chemical resistance and light resistance, the initial water repellency, chemical resistance and light resistance of the surface layer are excellent.

As R²Excellent in light resistance from the surface layerFrom the viewpoint of the above, a group having no etheric oxygen atom is particularly preferred.

2R in Compound (5)²May be the same or different. From the viewpoint of ease of production of the compound (5), 2R's are preferred²Are the same group.

(SiR³ _nX_3-nRadical)

SiR³ _nX_3-nIs a hydrolyzable silyl group.

The compound (5) has 2 hydrolyzable silyl groups at the terminal. Since the compound (5) having such a structure is strongly chemically bonded to the base material, the surface layer has excellent abrasion resistance.

Further, the compound (5) has a hydrolyzable silyl group at only one terminal. The compound (5) having such a structure is less likely to aggregate, and therefore the surface layer has an excellent appearance.

X is a hydrolyzable group. The hydrolyzable group is a group that forms a hydroxyl group by a hydrolysis reaction. That is, Si-X at the terminal of the compound (5) forms a silanol group (Si-OH) by hydrolysis reaction. Further reaction between silanol-based molecules forms Si-O-Si bonds. In addition, the silanol group and the hydroxyl group on the surface of the substrate (substrate-OH) undergo a dehydration condensation reaction to form a chemical bond (substrate-O-Si).

Examples of X include an alkoxy group, a halogen atom, an acyl group, and an isocyanate group (-NCO). The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms. As the halogen atom, a chlorine atom is particularly preferable.

The compound (5) is preferably an alkoxy group or a halogen atom, because X is easily produced. X is preferably an alkoxy group having 1 to 4 carbon atoms, particularly preferably an ethoxy group when long-term storage stability of the compound (5) is required, and particularly preferably a methoxy group when the reaction time after coating is shortened, from the viewpoint of reducing outgassing (Japanese: アウトガス) during coating and excellent storage stability of the compound (5).

R³Is a hydrogen atom or a 1-valent hydrocarbon group. Examples of the 1-valent hydrocarbon group include an alkyl group, an aryl group, a cycloalkyl group, an alkenyl group, and a combination of 2 or more of these groups.

As R³The hydrocarbon group having a valence of 1 is preferable, and the saturated hydrocarbon group having a valence of 1 is particularly preferable. The number of carbon atoms of the 1-valent saturated hydrocarbon group is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2. R³When the number of carbon atoms is in this range, the compound (5) can be easily produced.

n is preferably 0 or 1, particularly preferably 0. When a plurality of X groups are present in 1 hydrolyzable silyl group, adhesion to the substrate is further enhanced.

As SiR³ _nX_3-nPreferably Si (OCH)₃)₃、SiCH₃(OCH₃)₂、Si(OCH₂CH₃)₃、SiCl₃、Si(OCOCH₃)₃And Si (NCO)₃. Si (OCH) is particularly preferable from the viewpoint of ease of handling in industrial production₃)₃。

2 SiRs in Compound (5)³ _nX_3-nMay be the same or different. The same groups are preferable in terms of ease of production of the compound (5).

(preferred embodiment of Compound (5))

Examples of the compound (5) include compounds of the following formula. The compound is preferable from the viewpoint of being industrially easy to produce, easy to handle, water-and oil-repellent, abrasion-resistant, fingerprint stain-removing, lubricating, chemical-resistant and light-resistant.

[ solution 1]

Wherein G is a polyfluoropolyether chain, i.e. A-O-Q- (R)^f1O)_m-R^f2-. Preferred embodiments of G are A, Q and (R) described above^f1O)_mAnd R^f2The combination of the two components.

[ Compound (1) ]

In the method for producing a fluorinated ether compound of the present invention, the compound (1) is a starting material.

A-O-Q-(R^f1O)_m-R^f2-R¹-CO-Z…(1)

A, Q, (R) among them^f1O)_m、R^f2And R¹And A, Q (R) described in the Compound (5)^f1O)_m、R^f2And R¹Similarly, the preferred embodiments are also the same. Z is-OH, -OR⁴、-R⁵A halogen atom or a hydrogen atom, R⁴And R⁵Each being a 1-valent hydrocarbon group.

Z is preferably-OH OR-OR from the viewpoint of excellent reactivity⁴、-R⁵And a halogen atom, particularly preferably-OR from the viewpoint of reducing the number of reaction steps⁴and-R⁵。

At R⁴And R⁵In the (1) -valent hydrocarbon group, an alkyl group, an aryl group, a cycloalkyl group, an alkenyl group, a combination of 2 or more of these groups, and the like may be mentioned. Among them, an alkyl group is preferable in view of reducing the number of reaction steps. The number of carbon atoms of the 1-valent hydrocarbon group is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 6, and particularly preferably 1, from the viewpoint of ease of separation during synthesis and little influence on the reaction system.

Compound (1) can be produced by a known method such as the method described in patent document 1, the method described in international publication No. 2013/121984, and the method described in international publication No. 2015/087902.

[ Process for producing Compound (2) ]

The compound (2) is useful as an intermediate of a fluorine-containing ether compound suitable for a surface treatment agent, such as the compound (5).

In the first embodiment of the process for producing a fluorinated ether compound of the present invention, NH is used₃A method of reacting with the compound (1) to obtain the compound (2). In the case of the present invention, where the compound (5) is produced from the compound (1), the step 1 is to convert NH₃A step of reacting the compound (1) with a compound (2).

A-O-Q-(R^f1O)_m-R^f2-R¹-CO-NH₂…(2)

A, Q, (R) among them^f1O)_m、R^f2And R¹And compound (5)A, Q item (1), (R)^f1O)_m、R^f2And R¹Similarly, the preferred embodiments are also the same.

In the process for producing a fluorinated ether compound of the present invention, inexpensive NH is used₃Replacing the conventional CF₃SO₂Since Cl and other expensive acid chlorides are used, the compound (2) and the compounds (3) to (5) using the compound (2) as a raw material can be produced at low cost. Further, the compound (2) and the compounds (3) to (5) using the compound (2) as a raw material can be produced with good productivity without generating a by-product such as trifluoromethanesulfonic acid, which is difficult to handle. Further, Compound (1) and NH₃Since the reaction of (2) is carried out under mild conditions of relatively low temperature and normal pressure, the compound (2) can be easily produced without requiring a special apparatus.

(solvent)

Compound (1) and NH₃The reaction of (3) is preferably carried out in a solvent. As solvent, in the presence of Z-OR⁴In the case of (2), an alcohol (HOR) corresponding to Z is preferred⁴). As the solvent, a fluorine-containing solvent is also preferably used.

Examples of the alcohol corresponding to Z include alkyl alcohols (e.g., methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, and tert-butanol).

The fluorine-containing solvent may, for example, be a fluoroalkane, a fluoroaromatic compound, a fluoroalkyl ether, a fluoroalkyl amine or a fluoroalcohol.

The fluoroalkane is preferably a C4-C8 compound. Examples of the commercially available products may include C₆F₁₃H (ASAHIKLIN (registered trademark) AC-2000, manufactured by AGC K.K.) and C₆F₁₃C₂H₅(manufactured by AGC corporation, ASAHIKLIN (registered trademark) AC-6000), C₂F₅CHFCHFCF₃(manufactured by Keveil corporation (ケマーズ Co., Ltd.) Vertrel (registered trademark) XF).

Examples of the fluorinated aromatic compound include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis (trifluoromethyl) benzene.

The fluoroalkyl ether is preferably a compound having 4 to 12 carbon atoms. AsExamples of the commercially available products include CF₃CH₂OCF₂CF₂H (ASAHIKLIN (registered trademark) AE-3000, manufactured by AGC K.K.) and C₄F₉OCH₃(Novec (registered trademark) 7100, manufactured by 3M Co.) C₄F₉OC₂H₅(Novec (registered trademark) 7200, manufactured by 3M Co.) C₂F₅CF(OCH₃)C₃F₇(Novec (registered trademark) 7300, manufactured by 3M Co.).

Examples of the fluoroalkyl amine include perfluorotripropylamine and perfluorotributylamine.

Examples of the fluoroalcohol include 2,2,3, 3-tetrafluoropropanol, 2,2, 2-trifluoroethanol and hexafluoroisopropanol.

(reaction conditions)

The reaction temperature is preferably 0 to 400 ℃, more preferably 0 to 300 ℃, and particularly preferably 10 to 150 ℃.

The reaction pressure is preferably 0 to 30MPa [ gauge pressure ], more preferably 0 to 20MPa [ gauge pressure ], particularly preferably 0 to 10MPa [ gauge pressure ].

The reaction time is preferably more than 0 and 400 hours or less, more preferably 0.01 to 200 hours, and particularly preferably 1 to 150 hours.

High temperature and high pressure are preferable in view of good productivity, but mild conditions are preferable in view of safety, operability, and high selectivity of the target.

NH reacted with Compound (1)₃It may be a gas or a liquid, or may be dissolved in a solvent.

NH₃The amount of (c) is preferably 0.5 mol or more, particularly preferably 1 mol or more, based on 1 mol of the compound (1). The upper limit is not particularly limited, but is preferably 1000 mol.

Compound (1) and NH₃The reaction (2) may be a continuous reaction or a batch reaction (batch reaction).

[ Process for producing Compound (3) ]

The compound (3) is useful as an intermediate of a fluorine-containing ether compound suitable for a surface treatment agent, such as the compound (5).

The second embodiment of the process for producing a fluorinated ether compound of the present invention is a process for obtaining a compound (3) by reacting a reducing agent with a compound (2). In the case of the method of the present invention for producing the compound (5) from the compound (1), the step 2 is a step of reacting the compound (2) with a reducing agent to obtain the compound (3).

A-O-Q-(R^f1O)_m-R^f2-R¹-CH₂-NH₂…(3)

A, Q, (R) among them^f1O)_m、R^f2And R¹And A, Q (R) described in the Compound (5)^f1O)_m、R^f2And R¹Similarly, the preferred embodiments are also the same.

(reducing agent)

Examples of the reducing agent include sodium borohydride, lithium aluminum hydride, borane (monoborane, diborane, etc.), metallic sodium, sodium bis (2-methoxyethoxy) aluminum hydride, diisobutylaluminum hydride, lithium borohydride, lithium triethylborohydride, hydrogen gas in the presence of a metal catalyst (palladium catalyst, platinum catalyst, etc.), and the like.

2 of these may be used in combination, or a co-catalyst may be used in addition to the reducing agent.

The cocatalyst may, for example, be a Lewis acid. The lewis acid may, for example, be a metal halide or iodine. Examples of the metal halide include aluminum fluoride, aluminum chloride, boron trifluoride, chromium chloride, nickel chloride hexahydrate, titanium chloride, and lithium chloride.

(reaction conditions)

The reaction temperature is preferably-20 to 180 ℃, more preferably-10 to 150 ℃, further preferably 0 to 100 ℃, and particularly preferably 20 to 90 ℃.

The reaction time is preferably 0.1 to 48 hours, particularly preferably 3 to 24 hours.

The reaction of the compound (2) with the reducing agent may be a continuous reaction or a batch reaction (batch reaction).

[ Process for producing Compound (4) ]

The compound (4) is useful as an intermediate of a fluorine-containing ether compound suitable for a surface treatment agent, such as the compound (5).

In a third embodiment of the process for producing a fluorinated ether compound of the present invention, YR is used²¹A method of reacting with the compound (3) to obtain the compound (4). In the case of the method of the present invention for producing the compound (5) from the compound (1), the step 3 is to convert YR to YR²²A step of reacting the compound (3) with the compound (4 a). Wherein R is²²Only represents R²¹Wherein the terminal group has a 1-valent organic group of a vinyl group.

A-O-Q-(R^f1O)_m-R^f2-R¹-CH₂-NR²¹ ₂…(4)

A-O-Q-(R^f1O)_m-R^f2-R¹-CH₂-NR²² ₂…(4a)

A, Q, (R) among them^f1O)_m、R^f2And R¹And A, Q (R) described in the Compound (5)^f1O)_m、R^f2And R¹Similarly, the preferred embodiments are also the same. Y is HO-, R⁶O-or halogen atoms, R⁶Is a hydrocarbyl radical having a valence of 1, R²¹Is a 1-valent organic group or a 1-valent hydrocarbon group having a vinyl group at the terminal (except for the group having a vinyl group at the terminal), R²²Is a 1-valent organic group having a vinyl group at the terminal.

(YR²¹、YR²²)

Y is preferably HO-or a halogen atom, particularly preferably a halogen atom, from the viewpoint of excellent reactivity. Examples of the halogen atom include F, Cl, Br and I.

R⁶In the (1) -valent hydrocarbon group, an alkyl group, an aryl group, a cycloalkyl group, an alkenyl group, a combination of 2 or more of these groups, and the like may be mentioned. Among them, an alkyl group is preferable in view of reducing the number of reaction steps. The number of carbon atoms of the 1-valent hydrocarbon group is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 6, and particularly preferably 1, from the viewpoint of ease of separation during synthesis and little influence on the reaction system.

As R²¹From the viewpoint of ease of production of the compound (5), the compound is preferably at the terminalOrganic radical having a valence of 1 of the vinyl radical, R²²Is a 1-valent organic group having a vinyl group at the terminal.

R²¹、R²²Among these, the 1-valent organic group having a vinyl group at the terminal is preferably a group having an etheric oxygen atom or-NH-between carbon-carbon atoms (excluding carbon-carbon atoms of the vinyl group) of an aliphatic hydrocarbon group having a vinyl group at the terminal and aliphatic hydrocarbon groups having 3 to 10 carbon atoms at the terminal, more preferably an aliphatic hydrocarbon group having a vinyl group at the terminal and aliphatic hydrocarbon groups having 2 to 7 carbon atoms at the terminal and aliphatic hydrocarbon groups having a vinyl group at the terminal and aliphatic hydrocarbon groups having 3 to 7 carbon atoms at the terminal (excluding carbon-carbon atoms of the vinyl group).

As R²²And a 1-valent organic group R having a vinyl group at the terminal²¹Easy availability of YR²¹、YR²²From the viewpoint of (1), preferred are allyl and allyloxyalkyl, more preferred are allyloxyalkyl having 2 to 6 carbon atoms in the allyl and alkyl moiety, and particularly preferred is-CH₂CH＝CH₂and-CH₂CH₂OCH₂CH＝CH₂。

Further, 2 Rs in the compound (4)²¹And 2R in the compound (4a)²²May be different. From the viewpoint of ease of production of the compound (4) and the compound (4a), 2R's are preferred²¹2R²²Are the same group.

R²¹In the above formula, the hydrocarbyl group having a valence of 1 (excluding the group having a vinyl group at the terminal) may, for example, be an alkyl group, an aryl group, a cycloalkyl group, an alkenyl group (excluding the group having a vinyl group at the terminal), or a combination of 2 or more of these. The number of carbon atoms of the 1-valent hydrocarbon group (excluding the group having a vinyl group at the terminal) is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 6, and particularly preferably 1.

As YR²¹、YR²²Specific preferred examples of (3) include FCH₂CH＝CH₂、ClCH₂CH＝CH₂、BrCH₂CH＝CH₂、ICH₂CH＝CH₂、FCH₂CH₂OCH₂CH＝CH₂、ClCH₂CH₂OCH₂CH＝CH₂、BrCH₂CH₂OCH₂CH＝CH₂、ICH₂CH₂OCH₂CH＝CH₂、FCH₂CH₂OCH＝CH₂、ClCH₂CH₂OCH＝CH₂、BrCH₂CH₂OCH＝CH₂、ICH₂CH₂OCH＝CH₂。

(basic Compound)

Compound (3) and YR from the viewpoint of promoting the reaction²¹、YR²²The reaction of (3) is preferably carried out in the presence of a basic compound.

Examples of the basic compound include basic organic compounds and basic inorganic compounds.

The basic organic compound may, for example, be an alkylamine compound, an arylamine compound, an alkenylamine compound or a heterocyclic amine compound, and in view of excellent versatility, an alkylamine compound or a heterocyclic amine compound is preferable.

The alkylamine compound may, for example, be triethylamine.

Examples of the heterocyclic amine compound include pyridine, lutidine, collidine, pyrrole, pyrimidine, N-dimethyl-4-aminopyridine, 2, 6-lutidine, and 2, 6-di-t-butylpyridine.

Examples of the basic inorganic compound include alkali metal hydrides (e.g., sodium hydride), carbonates (e.g., sodium carbonate, potassium carbonate, and cesium carbonate), bicarbonates (e.g., sodium bicarbonate and potassium bicarbonate), alkali metal hydroxides (e.g., sodium hydroxide and potassium hydroxide), and alkali metal alkoxides (e.g., potassium tert-butoxide).

The basic compound may be used alone in 1 kind, or 2 or more kinds may be used in combination.

(phase transfer catalyst)

Compound (3) and YR²¹、YR²²The reaction of (a) may be carried out in the presence of a phase transfer catalyst.

The phase transfer catalyst may, for example, be a quaternary ammonium salt such as tetrabutylammonium bromide or benzyltriethylammonium chloride.

(solvent)

Compound (3) and YR from the viewpoint of excellent solubility²¹、YR²²The reaction of (3) is preferably carried out in a fluorine-containing solvent.

The fluorine-containing solvent may, for example, be the same fluorine-containing solvent as can be used for producing the compound (2), and the preferred embodiment is also the same.

The solvent can be used alone in 1, also can be used in 2 or more combination.

(reaction conditions)

The reaction temperature is preferably 0 to 200 ℃, more preferably 20 to 150 ℃, and particularly preferably 50 to 100 ℃.

The reaction time is preferably 0.01 to 24 hours, more preferably 0.3 to 20 hours, and particularly preferably 0.3 to 15 hours.

YR²¹、YR²²The amount of (c) is preferably 0.5 to 20 mol, more preferably 1 to 15 mol, particularly preferably 2 to 8 mol, based on 1 mol of the compound (3).

Compound (3) and YR²¹、YR²²The reaction (2) may be a continuous reaction or a batch reaction (batch reaction).

[ Process for producing Compound (5) ]

In a fourth embodiment of the process for producing a fluorinated ether compound of the present invention, HSiR is used³ _nX_3-nA method of obtaining the compound (5) by subjecting the compound (4a) to a hydrosilylation reaction. In the case of the process for producing the compound (5) from the compound (1) of the present invention, the step 4 is to cause HSiR³ _nX_3-nAnd (3) a step of obtaining a compound (5) by subjecting the compound (4a) to a hydrosilylation reaction.

(HSiR³ _nX_3-n)

HSiR³ _nX_3-nR in (1)³X and n with R specified in the Compound (5)³X and n are the same, and the preferred forms are the same.

As HSiR³ _nX_3-nPreferably HSi (OCH)₃)₃、HSiCH₃(OCH₃)₂、HSi(OCH₂CH₃)₃、HSiCl₃、Si(OCOCH₃)₃And HSi (NCO)₃. HSi (OCH) is particularly preferable from the viewpoint of ease of handling in industrial production₃)₃。

(hydrosilylation reaction)

The hydrosilylation reaction is preferably performed using a transition metal catalyst such as platinum, palladium, silver, gold, or rhodium, or a radical initiator such as an organic peroxide.

The reaction temperature is preferably 0 to 150 ℃, more preferably 10 to 100 ℃, and particularly preferably 20 to 60 ℃.

The reaction time is preferably 0.01 to 24 hours, more preferably 1 to 15 hours, and particularly preferably 3 to 10 hours.

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

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