WO2016088620A1 - Halogenated perfluoropolyether group-containing compound, and method for producing same - Google Patents

Abstract

　Disclosed is a method for producing a compound represented by the general formula (I') [in the formula, the symbols have the same meanings as those described in the description]. The method entails reacting a compound represented by general formula (A) [in the formula, the symbols have the same meanings as those described in the description] and a compound represented by general formula (B) [in the formula, the symbols have the same meanings are those described in the description].

Description

Halogenated perfluoropolyether group-containing compound and process for producing the same

The present invention relates to a halogenated perfluoropolyether group-containing compound and a method for producing the same.

It is known that certain fluorine-containing silane compounds can provide excellent water repellency, oil repellency, antifouling properties and the like when used for surface treatment of a substrate. A layer obtained from a surface treatment agent containing a fluorine-containing silane compound (hereinafter also referred to as “surface treatment layer”) is applied as a so-called functional thin film to various substrates such as glass, plastic, fiber, and building materials. ing.

As such a fluorine-containing silane compound, a perfluoropolyether group-containing silane compound having a perfluoropolyether group in the molecular main chain and a hydrolyzable group bonded to a Si atom at the molecular terminal or terminal part is known. It has been. For example, Patent Document 1 discloses the following general formula:

[Wherein Rf is a perfluoroalkyl group, Z is a fluorine or trifluoromethyl group, and a, b, c, d and e are each independently 0 or an integer of 1 or more. , Y is hydrogen or an alkyl group having 1 to 4 carbon atoms, X is hydrogen, bromine or iodine, R ¹ is a hydroxyl group or a hydrolyzable substituent, R ² is hydrogen or 1 Is a valent hydrocarbon group, 1 is 0, 1 or 2, m is 1, 2 or 3, and n is an integer of 2 or more. ]
The perfluoropolyether group containing silane compound represented by these is described.

The above compounds can be synthesized by an iodine transfer polymerization method (see Patent Document 2). Specifically, in Patent Document 1, iodine is introduced at the end of the fluoropolymer chain, and a silane compound having an ethylenic double bond is added to the compound having iodine at the end of the obtained fluoropolymer chain. It is synthesized by living polymerization (iodine transfer polymerization).

International Publication No. 97/07155 Japanese Patent Laid-Open No. 01-294709 JP 09-263728 A

Conventionally, in order to introduce iodine into the terminal of the fluorine-containing polymer chain, the —COF group of the fluorine-containing polymer having an acid fluoride group (—COF) at the terminal is reacted with iodine under alkaline conditions to form an —I group. Substitution methods have been used (Patent Documents 1 and 3).

However, iodination as described in Patent Documents 1 and 3 can be suitably used when the fluorine-containing polymer chain has a repeating unit represented by — (OCF ₂ CF ₂ CF ₂ ) —. When the fluoropolymer chain has a repeating unit represented by — (OCF ₂ CF ₂ ) — and — (OCF ₂ ) —, the fluorine-containing polymer chain is decomposed and a by-product is generated. It was difficult.

An object of the present invention is to provide a method for suitably producing a perfluoropolyether group-containing compound having a halogen atom at the terminal regardless of the structure of the fluorine-containing polymer (that is, perfluoropolyether group). Another object of the present invention is to provide a synthetic intermediate having a novel structure for synthesizing a perfluoropolyether group-containing silane compound.

As a result of intensive studies, the present inventors have made a perfluoropolyether by reacting an alcohol having a perfluoropolyether group with a compound having a halogen atom at one end and a double bond at the other end. Even when the group has any structure, it has been found that a perfluoropolyether group-containing compound having a halogen atom at the terminal can be preferably produced, and the present invention has been completed.

That is, according to the first aspect of the present invention, the following general formula (I):

[Where:
Rf independently represents each alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms at each occurrence;
PFPE has the general formula:
-(OC ₄ F ₈ ) _a- (OC ₃ F ₆ ) _b- (OC ₂ F ₄ ) _c- (OCF ₂ ) _d-
Wherein a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d The order of existence of each repeating unit with parentheses attached with is arbitrary in the formula.)
A group represented by:
Q is a divalent organic group containing at least one hydrogen atom and at least one fluorine atom bonded to a carbon atom;
R ¹ is a hydrogen atom or a fluorine atom;
Y is a chlorine atom, a bromine atom or an iodine atom;
m is an integer from 0 to 3;
l is 0 or 1; provided that when R ¹ is a fluorine atom, l is 1. ]
Is provided.

According to the second aspect of the present invention, the following general formula (I ′):

[Where:
Rf independently represents each alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms at each occurrence;
PFPE has the general formula:
-(OC ₄ F ₈ ) _a- (OC ₃ F ₆ ) _b- (OC ₂ F ₄ ) _c- (OCF ₂ ) _d-
Wherein a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d The order of existence of each repeating unit with parentheses attached with is arbitrary in the formula.)
A group represented by:
Q ″ is a divalent organic group containing at least one fluorine atom bonded to a carbon atom;
R ¹ is a hydrogen atom or a fluorine atom;
Y is a chlorine atom, a bromine atom or an iodine atom;
m is 0-3;
l is 0 or 1. ]
A compound represented by the following general formula (A):

[Wherein Rf, PFPE, R ¹ and m are as defined above;
n is an integer of 1 to 6. ]
And a compound represented by the following formula (B):

[Wherein Y is as defined above;
Q ′ is a divalent organic group;
Each R ² is independently a hydrogen atom or a fluorine atom;
R ³ is a hydrogen atom or a fluorine atom;
R ⁴ is a hydrogen atom or a fluorine atom. ]
A method comprising reacting with a compound represented by:

According to the method of the present invention, a novel halogenated perfluoropolyether group-containing compound can be synthesized. In addition, this halogenated perfluoropolyether group-containing compound can be used as an intermediate for the production of perfluoropolyether group-containing silane compounds, enabling the synthesis of perfluoropolyether group-containing silane compounds having various structures. To do.

Hereinafter, the compound of the present invention will be described.

The present invention relates to the following general formula (I):

[Where:
Rf independently represents each alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms at each occurrence;
PFPE has the general formula:
-(OC ₄ F ₈ ) _a- (OC ₃ F ₆ ) _b- (OC ₂ F ₄ ) _c- (OCF ₂ ) _d-
Wherein a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d The order of existence of each repeating unit with parentheses attached with is arbitrary in the formula.)
A group represented by:
Q is a divalent organic group containing at least one hydrogen atom and at least one fluorine atom bonded to a carbon atom;
R ¹ is a hydrogen atom or a fluorine atom;
Y is a chlorine atom, a bromine atom or an iodine atom;
m is an integer from 0 to 3;
l is 0 or 1; provided that when R ¹ is a fluorine atom, l is 1. ]
The compound represented by these is provided.

In the above formula (I), Rf represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms.

The “alkyl group having 1 to 16 carbon atoms” in the alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms may be linear or branched. Preferably, it is a linear or branched alkyl group having 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms, and more preferably a linear alkyl group having 1 to 3 carbon atoms.

Rf is preferably an alkyl group having 1 to 16 carbon atoms, which is substituted with one or more fluorine atoms, more preferably a CF ₂ H—C _1-15 fluoroalkylene group, still more preferably Is a perfluoroalkyl group having 1 to 16 carbon atoms.

The perfluoroalkyl group having 1 to 16 carbon atoms may be linear or branched, and preferably has 1 to 6 carbon atoms, particularly 1 to 6 carbon atoms. 3 perfluoroalkyl group, more preferably a linear perfluoroalkyl group having 1 to 3 carbon atoms, specifically —CF ₃ , —CF ₂ CF ₃ , or —CF ₂ CF ₂ CF ₃ . .

In the above formula (I), PFPE has the general formula:
-(OC ₄ F ₈ ) _a- (OC ₃ F ₆ ) _b- (OC ₂ F ₄ ) _c- (OCF ₂ ) _d-
Represents a perfluoro (poly) ether group. Here, a, b, c and d are each independently an integer of 0 or 1 and are not particularly limited as long as the sum of a, b, c and d is at least 1. Preferably, a, b, c and d are each independently an integer of 0 to 200, for example, an integer of 1 to 200, more preferably an integer of 0 to 100, for example, 1 An integer of 100 or less. More preferably, the sum of a, b, c and d is 10 or more, preferably 20 or more, and 200 or less, preferably 100 or less. Further, the order of presence of each repeating unit with a, b, c or d in parentheses is arbitrary in the formula. Among these repeating units, — (OC ₄ F ₈ ) — represents — (OCF ₂ CF ₂ CF ₂ CF ₂ ) —, — (OCF (CF ₃ ) CF ₂ CF ₂ ) —, — (OCF ₂ CF (CF ₃ ) CF ₂ )-,-(OCF ₂ CF ₂ CF (CF ₃ ))-,-(OC (CF ₃ ) ₂ CF ₂ )-,-(OCF ₂ C (CF ₃ ) ₂ )-,-(OCF (CF ₃ ) CF (CF ₃ ))-,-(OCF (C ₂ F ₅ ) CF ₂ )-and-(OCF ₂ CF (C ₂ F ₅ ))-may be used, but preferably — (OCF ₂ CF ₂ CF ₂ CF ₂ ) —. -(OC ₃ F ₆ )-is any of-(OCF ₂ CF ₂ CF ₂ )-,-(OCF (CF ₃ ) CF ₂ )-and-(OCF ₂ CF (CF ₃ ))- Preferably, it is — (OCF ₂ CF ₂ CF ₂ ) —. In addition, — (OC ₂ F ₄ ) — may be any of — (OCF ₂ CF ₂ ) — and — (OCF (CF ₃ )) —, preferably — (OCF ₂ CF ₂ ) —. is there.

In one embodiment, PFPE is — (OC ₃ F ₆ ) _b — (wherein b is an integer of 1 to 200, preferably 10 to 100), preferably — (OCF ₂ CF ₂ CF ₂ ) _b — (wherein b is as defined above).

In another embodiment, the PFPE is
-(OC ₄ F ₈ ) _a- (OC ₃ F ₆ ) _b- (OC ₂ F ₄ ) _c- (OCF ₂ ) _d-
(Wherein, a and b are each independently an integer of 0 or more or 1 or more and 30 or less, preferably 0 or more and 10 or less, and c and d are each independently 1 or more and 200 or less, preferably 10 or more. It is an integer of 100 or less, and the sum of a, b, c and d is 10 or more, preferably 20 or more, and 200 or less, preferably 100 or less. The order of presence of each repeating unit in parentheses is arbitrary in the formula), preferably — (OCF ₂ CF ₂ CF ₂ CF ₂ ) _a — (OCF ₂ CF ₂ CF ₂ ) _b — (OCF ₂ CF ₂ ) _c — (OCF ₂ ) _d — (wherein a, b, c and d are as defined above). For example, PFPE may be — (OCF ₂ CF ₂ ) _c — (OCF ₂ ) _d — (wherein c and d are as defined above).

In still another embodiment, PFPE is a group represented by — (OC ₂ F ₄ —R ⁸ ) _e —. In the formula, R ⁸ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ , or a combination of 2 or 3 groups independently selected from these groups is there. The combination of 2 or 3 groups independently selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ is not particularly limited. For example, —OC ₂ F ₄ OC ₃ F ₆ —, —OC _{2 F 4 OC 4 F 8 -} , - OC 3 F 6 OC 2 F 4 -, - OC 3 F 6 OC 3 F 6 -, - OC 3 F 6 OC 4 F 8 -, - OC 4 F 8 OC 4 F _{8 -, - OC 4 F 8} OC 3 F 6 -, - OC 4 F 8 OC 2 F 4 -, - OC 2 F 4 OC 2 F 4 OC 3 F 6 -, - OC 2 F 4 OC 2 F 4 OC _{4 F 8 -, - OC 2} F 4 OC 3 F 6 OC 2 F 4 -, - OC 2 F 4 OC 3 F 6 OC 3 F 6 -, - OC 2 F 4 OC 4 F 8 OC 2 F 4 -, _{-OC 3 F 6 OC 2 F 4} OC 2 F 4 -, - OC 3 F 6 OC 2 F ₄ OC ₃ F ₆ —, —OC ₃ F ₆ OC ₃ F ₆ OC ₂ F ₄ —, —OC ₄ F ₈ OC ₂ F ₄ OC ₂ F ₄ — and the like can be mentioned. The e is an integer of 2 to 100, preferably an integer of 2 to 50. In the above formula, OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ may be either linear or branched, preferably linear. In this embodiment, the PFPE is preferably — (OC ₂ F ₄ —OC ₃ F ₆ ) _e — or — (OC ₂ F ₄ —OC ₄ F ₈ ) _e —.

In the above formula (I), Q is a divalent organic group containing at least one hydrogen atom bonded to a carbon atom and at least one fluorine atom.

As used herein, “divalent organic group” means a divalent group containing carbon. Such a divalent organic group means a group in which two hydrogen atoms are eliminated from a hydrocarbon. Such a divalent organic group is not particularly limited, but is a divalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted with one or more substituents, for example, an aliphatic group. A hydrocarbon group, an aromatic hydrocarbon group, etc. are mentioned. The “aliphatic hydrocarbon group” may be linear, branched or cyclic, and may be either saturated or unsaturated. The hydrocarbon group may also contain one or more ring structures. Such a hydrocarbon group may have one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy and the like at its terminal or molecular chain.

As used herein, the substituent of the hydrocarbon group is not particularly limited. For example, a halogen atom; a C _1-6 alkyl group which may be substituted with one or more halogen atoms C _2-6 alkenyl group, C _2-6 alkynyl group, C _3-10 cycloalkyl group, C _3-10 unsaturated cycloalkyl group, 5-10 membered heterocyclyl group, 5-10 membered unsaturated heterocyclyl group , One or more groups selected from C _6-10 aryl groups and 5- to 10-membered heteroaryl groups.

In a preferred embodiment, Q is represented by the following formula:
— (CH ₂ ) _n —O—CR ² ₂ —CR ³ ₂ —Q′-CFR ⁴ —
[Where:
Q ′ is a divalent organic group;
Each R ² is independently a hydrogen atom or a fluorine atom;
Each R ³ is independently a hydrogen atom or a fluorine atom;
R ⁴ is a hydrogen atom or a fluorine atom;
n is an integer of 1 to 6. ]
It is group represented by these.

In Q, Q ′ is a divalent organic group. In a preferred embodiment, Q ′ is represented by the following formula:
-(R ¹¹ ) _p- (R ¹² ) _q-
It is group represented by these. In this formula, the order of presence of each repeating unit in parentheses with the suffix p or q is arbitrary in the formula.

In the above Q ′, R ¹¹ is independently at each occurrence an oxygen atom, —NR ¹³ — (wherein R ¹³ may be substituted with a hydrogen atom, or one or more fluorine atoms. Represents a good lower alkyl group) or a divalent polar group. Here, the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group. May be substituted by one or more fluorine atoms. In a preferred embodiment, R ¹¹ is an oxygen atom.

The “divalent polar group” in Q ′ is not particularly limited, but —C (O) —, —C (═NR ¹³ ) —, and —C (O) NR ¹³ — (in these formulas, R ¹³ has the same meaning as described above, and represents a hydrogen atom or a lower alkyl group which may be substituted with one or more fluorine atoms. Here, the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group. May be substituted by one or more fluorine atoms.

In Q ′, R ¹² is independently at each occurrence, —CR ¹⁴ ₂ — (wherein R ¹⁴ is independently a hydrogen atom, a fluorine atom, or one or more fluorine atoms. Represents a lower alkyl group which may be substituted. Here, the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group. May be substituted by one or more fluorine atoms. In a preferred embodiment, R ¹² is —CF ₂ — or —CF (CF ₃ ) —.

In one embodiment, Q ′ is such that R ¹¹ is an oxygen atom, and R ¹² is independently —CF ₂ — or —CF (CF ₃ ) —.

In the above Q ′, p is an integer of 1 to 6, preferably an integer of 1 to 3. Q is an integer of 0 to 20, preferably an integer of 0 to 10, and more preferably an integer of 0 to 6.

Specific examples of Q ′ are not particularly limited, but include the following groups:
-O-,
-OCF _2- ,
-OCF ₂ CF _2- ,
-OCFCF ₂ CF _2-
—OCF ₂ CF (CF ₃ ) O—
—OCF ₂ CF (CF ₃ ) OCF ₂ —
—OCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ —
-CF ₂ O-,
-CF ₂ OCF _2- ,
-CF ₂ OCF ₂ CF _2- ,
-CF ₂ OCF (CF ₃ ) CF ₂ O-,
—CF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ —, or —CF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF ₂ —,
Is mentioned.

Preferably, Q ′ is
-O-
-OCF _2- ,
—OCF ₂ CF ₂ — or —OCF ₂ CF ₂ CF ₂ —
It is.

In Q, R ² is independently a hydrogen atom or a fluorine atom, and R ³ is independently a hydrogen atom or a fluorine atom. In one embodiment, at least one of R ³ is a hydrogen atom.

In the above Q, R ⁴ is a hydrogen atom or a fluorine atom, preferably a fluorine atom.

In the above Q, n is an integer of 1 to 6, preferably an integer of 1 to 3.

Specific examples of Q include, but are not limited to, the following groups:
-CH ₂ OCF ₂ CHFOCF _2- ,
-CH ₂ OCF ₂ CHFOCF ₂ CF _2- ,
-CH ₂ OCF ₂ CHFOCF ₂ CF ₂ CF _2- ,
—CH ₂ OCF ₂ CHFOCF ₂ CF (CF ₃ ) OCF ₂ —,
—CH ₂ OCF ₂ CHFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ —,
_{-CH 2 OCF 2 CHFOCF 2 CF (} CF 3) OCF 2 CF 2 CF 2 -,
-CH ₂ OCH ₂ CHFCF ₂ OCF _2- ,
-CH ₂ OCH ₂ CHFCF ₂ OCF ₂ CF _2- ,
-CH ₂ OCH ₂ CHFCF ₂ OCF ₂ CF ₂ CF _2- ,
—CH ₂ OCH ₂ CHFCF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ —,
—CH ₂ OCH ₂ CHFCF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF ₂ —, or —CH ₂ OCH ₂ CHFCF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF ₂ CF ₂ —
Is mentioned.

In the above formula (I), R ¹ is a hydrogen atom or a fluorine atom. In one embodiment, R ¹ is a fluorine atom. In the above formula (I), when l is 0, that is, when Q is not present, R ¹ is a hydrogen atom.

In the above formula (I), Y is a chlorine atom, a bromine atom or an iodine atom, preferably an iodine atom.

In the above formula (I), m is an integer of 0 to 3, preferably an integer of 0 to 2, for example 0 or 1.

In the above formula (I), l is 0 or 1. In the above formula (I), when R ¹ is a fluorine atom, 1 is 1.

In one embodiment, the compound represented by the formula (I) is represented by the following general formula (Ia):

[Where:
Rf independently represents each alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms at each occurrence;
PFPE has the general formula:
-(OC ₄ F ₈ ) _a- (OC ₃ F ₆ ) _b- (OC ₂ F ₄ ) _c- (OCF ₂ ) _d-
Wherein a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d The order of existence of each repeating unit with parentheses attached with is arbitrary in the formula.)
A group represented by:
Q ′ is a divalent organic group;
Each R ¹ is independently a hydrogen atom or a fluorine atom;
Each R ² is independently a hydrogen atom or a fluorine atom;
R ³ is a hydrogen atom or a fluorine atom;
R ⁴ is a hydrogen atom or a fluorine atom;
Y is a chlorine atom, a bromine atom or an iodine atom;
m is an integer from 0 to 3;
n is an integer of 1 to 6. ]
The compound represented by these may be sufficient.

In one embodiment, the compound represented by the formula (I) and the formula (Ia) is a compound other than CF ₃ (OCF ₂ CF ₂ ) ₂₀ (OCF ₂ ) ₁₆ OCF ₂ CH ₂ OCF ₂ CHFOCF ₂ CF ₂ I It is. That is, the compounds represented by the above formulas (I) and (Ia) do not include CF ₃ (OCF ₂ CF ₂ ) ₂₀ (OCF ₂ ) ₁₆ OCF ₂ CH ₂ OCF ₂ CHFOCF ₂ CF ₂ I.

In another aspect, the present invention _provides a _{CF 3 (OCF 2 CF 2)} 20 (OCF 2) 16 OCF 2 CH 2 OCF 2 CHFOCF 2 CF 2 I.

The compound of the present invention is used as a synthetic intermediate for a perfluoropolyether group-containing silane compound useful as a water / oil repellent.

For example, the compound represented by the formula (I) is represented by the following formula:

[Where:
R ²¹ represents, independently at each occurrence, a hydroxyl group or a hydrolyzable group;
R ²² independently represents a hydrogen atom or an alkyl group at each occurrence;
s is an arbitrary integer, for example, an integer of 1 to 20;
t is an integer of 1 to 3. ]
Is reacted with a compound represented by the following formula:

[Wherein, Rf, PFPE, R ¹ , Q, Y, m, l, R ²¹ , R ²² , s and t are as defined above, and u is an integer of 1 to 10. ]
Can be obtained.

In one aspect, the present invention provides the following general formula (I ′):

[Where:
Rf independently represents each alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms at each occurrence;
PFPE has the general formula:
-(OC ₄ F ₈ ) _a- (OC ₃ F ₆ ) _b- (OC ₂ F ₄ ) _c- (OCF ₂ ) _d-
Wherein a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d The order of existence of each repeating unit with parentheses attached with is arbitrary in the formula.)
A group represented by:
Q ″ is a divalent organic group containing at least one fluorine atom bonded to a carbon atom;
R ¹ is a hydrogen atom or a fluorine atom;
Y is a chlorine atom, a bromine atom or an iodine atom;
m is 0-3;
l is 0 or 1. ]
A compound represented by the following general formula (A):

[Wherein Rf, PFPE, R ¹ and m are as defined above;
n is an integer of 1 to 6. ]
And a compound represented by the following formula (B):

[Wherein Y is as defined above;
Q ′ is a divalent organic group;
Each R ² is independently a hydrogen atom or a fluorine atom;
R ³ is a hydrogen atom or a fluorine atom;
R ⁴ is a hydrogen atom or a fluorine atom. ]
A method comprising reacting with a compound represented by:

The method of the present invention can be used for the synthesis of a synthesis intermediate of a perfluoropolyether group-containing silane compound useful as a water / oil repellent.

In the above formula (I ′), Rf, PFPE, R ¹ , Y, m and l correspond to the same symbols in the above formula (I) and have the same meanings. The embodiments of Rf, PFPE, R ¹ , Y, m and l in the formula (I ′) are the same as the embodiments of these groups in the above formula (I).

In the above formula (I ′), Q ″ is a divalent organic group containing at least one fluorine atom bonded to a carbon atom.

In one embodiment, Q ″ is a divalent organic group containing at least one hydrogen atom and at least one fluorine atom bonded to a carbon atom, and corresponds to Q in the above formula (I). The aspect of Q ″ in the formula (I ′) is the same as the aspect of Q in the above formula (I).

In one embodiment, the compound represented by the above formula (I ′) may be a compound represented by the above formula (I).

In one embodiment, the compound represented by the above formula (I ′) may be a compound represented by the above formula (Ia). In this embodiment, Q ″ in formula (I ′) corresponds to — (CH ₂ ) _n —O—CR ² ₂ —CR ³ ₂ —Q′—CFR ⁴ — in formula (Ia).

In the method of the present invention, the following general formula (A):

And a compound represented by the following general formula (B):

The compound represented by these is made to react.

In this reaction, the —OH group of the compound represented by the formula (A) is added to the unsaturated bond of the compound represented by the formula (B), and the following formula (Ia):

Is obtained.

Those skilled in the art can select conditions such as a suitable solvent, reaction temperature, reaction time, catalyst, and the like according to the reactant used and the target product. For example, in a fluorine-based solvent such as 1,3-bis (trifluoromethyl) benzene, by adding sodium hydroxide or potassium hydroxide, for example, under alkaline conditions and heating at 50 to 100 ° C., it is easy. The desired compound can be obtained.

In the above formulas (A) and (B), Rf, PFPE, Q ′, R ¹ , R ² , R ³ , R ⁴ , Y, m and n are the same as those in the above formulas (I) and (Ia ) Is equivalent to the description. In the formula (A) and the formula (B), Rf, PFPE, Q ′, R ¹ , R ² , R ³ , R ⁴ , Y, m, and n are represented by the above formula (I) or formula (Ia ) Are the same as those of these groups.

The compounds represented by the above formulas (A) and (B) are known compounds in the art and are commercially available or can be synthesized by those skilled in the art. For example, the compound represented by the formula (A) can be synthesized by a method of reducing a perfluoropolyether group-containing terminal acid fluoride or terminal carboxylic acid with a reducing agent such as NaBH _4. ) Can be synthesized by the method described in WO2005 / 090270.

In one embodiment, the compound represented by the formula (Ia) obtained by the reaction of the compound represented by the above formula (A) and the compound represented by the formula (B) may have another formula (I It may be converted to a compound represented by -a). In another embodiment, the compound represented by the formula (Ia) obtained by reacting the compound represented by the formula (A) with the compound represented by the formula (B) is a fluorination reaction. The compound can be converted to a compound represented by the formula (I) or the formula (I ′) by subjecting to a substitution reaction or the like.

For example, fluorination such as a method in which a reactor internal temperature is 5 to 100 ° C. and an F ₂ / N ₂ mixed gas with an F ₂ gas concentration adjusted to 1 to 20 vol% is circulated at 5 to 200 ml / min for 1 to 48 hours. According to the method, a part or all of hydrogen atoms bonded to carbon can be substituted with fluorine atoms.

In one embodiment, the compound represented by formula (B) is represented by the following formula (C):

[Wherein R ² , R ³ , R ⁴ , Q ′ and Y are as defined in the formula (B);
X is a halogen atom. ]
It can obtain from the compound represented by these.

In the above formula, X is a halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably an iodine atom.

Those skilled in the art can select conditions such as a suitable solvent, reaction temperature, reaction time, catalyst, and the like according to the reactant used and the target product.

In addition, the compound represented by the formula (C) may be separately converted into a compound represented by the formula (B) or used together with the compound represented by the formula (A). The conversion into the compound represented by the formula (B) and the reaction with the compound represented by the formula (A) may be carried out continuously.

Example 1
To a 1 L four-necked flask equipped with a reflux condenser, a thermometer and a stirrer, an average composition CF ₃ (OCF ₂ CF ₂ ) ₂₀ (OCF ₂ ) ₁₆ OCF ₂ CH ₂ OH (however, in the mixture (OCF ₂ CF ₂ CF ₂ CF ₂ ) and / or a compound containing a trace amount of a repeating unit of (OCF ₂ CF ₂ CF ₂ ) (perfluoropolyether-modified alcohol) (150 g) 1,3-bis (Trifluoromethyl) benzene (100 ml) and sodium hydroxide (5.2 g) were charged, and the mixture was stirred at 70 ° C. for 2 hours. _{Thereafter, CF 2 = CFOCF 2 CF 2} it a (26.0 g) was added and stirred for 4 hours at 85 ° C.. Then, it cooled to room temperature, the perfluorohexane (220g) was added, the insoluble matter was filtered, and washing | cleaning operation by 3N hydrochloric acid was performed with the separatory funnel. Subsequently, the following perfluoropolyether group-containing iodine compound (134 g) having iodine at the terminal was obtained by distilling off the volatile matter.
・ Perfluoropolyether group-containing iodine compounds:
CF ₃ (OCF ₂ CF ₂ ) ₂₀ (OCF ₂ ) ₁₆ OCF ₂ CH ₂ OCF ₂ CHFOCF ₂ CF ₂ I
¹ H NMR was measured using 1,3-bis (trifluoromethyl) benzene (8.00 ppm: C ₆ H ₄ (CF ₃ ) ₂ ) as an internal standard substance.
¹ H NMR: δ = 4.35 (m, -C H ₂ O-), 5.97 (d, -C H F-)

Example 2
An average composition of CF ₃ (OCF ₂ CF ₂ ) ₁₉ (OCF ₂ ) ₁₄ OCF ₂ CH ₂ OH (however, (OCF in the mixture) was added to a 1 L four-necked flask equipped with a reflux condenser, thermometer and stirrer. ₂ CF ₂ CF ₂ CF ₂ ) and / or a compound containing a trace amount of a repeating unit (OCF ₂ CF ₂ CF ₂ ) (perfluoropolyether-modified alcohol) (150 g) represented by 1,3- Bis (trifluoromethyl) benzene (100 ml) and sodium hydroxide (5.0 g) were charged and stirred at 70 ° C. for 2 hours. _{Thereafter, CF 2 = CFOCF 2 CF 2} I a (25.2 g) was added and stirred for 4 hours at 85 ° C.. Then, it cooled to room temperature, the perfluorohexane (220g) was added, the insoluble matter was filtered, and washing | cleaning operation by 3N hydrochloric acid was performed with the separatory funnel. Subsequently, the following perfluoropolyether group-containing iodine compound (135 g) having iodine at the terminal was obtained by distilling off the volatile matter.
・ Perfluoropolyether group-containing iodine compounds:
CF ₃ (OCF ₂ CF ₂ ) ₁₉ (OCF ₂ ) ₁₄ OCF ₂ CH ₂ OCF ₂ CHFOCF ₂ CF ₂ I
¹ H NMR was measured using 1,3-bis (trifluoromethyl) benzene (8.00 ppm: C ₆ H ₄ (CF ₃ ) ₂ ) as an internal standard substance.
¹ H NMR: δ = 4.35 (m, -C H ₂ O-), 5.97 (d, -C H F-)

Example 3
To a 1 L four-necked flask equipped with a reflux condenser, a thermometer and a stirrer, an average composition CF ₃ (OCF ₂ CF ₂ ) ₁₈ (OCF ₂ ) ₃₀ OCF ₂ CH ₂ OH (however, in the mixture (OCF ₂ CF ₂ CF ₂ CF ₂ ) and / or a compound containing a trace amount of a repeating unit (OCF ₂ CF ₂ CF ₂ ) (perfluoropolyether-modified alcohol) (150 g) represented by 1,3- Bis (trifluoromethyl) benzene (100 ml) and sodium hydroxide (6.2 g) were charged and stirred at 70 ° C. for 2 hours. _{Thereafter, CF 2 = CFOCF 2 CF 2} it a (31.2 g) was added and stirred for 4 hours at 85 ° C.. Then, it cooled to room temperature, the perfluorohexane (220g) was added, the insoluble matter was filtered, and washing | cleaning operation by 3N hydrochloric acid was performed with the separatory funnel. Subsequently, the following perfluoropolyether group-containing iodine compound (132 g) having iodine at the terminal was obtained by distilling off the volatile matter.
・ Perfluoropolyether group-containing iodine compounds:
CF ₃ (OCF ₂ CF ₂ ) ₁₈ (OCF ₂ ) ₃₀ OCF ₂ CH ₂ OCF ₂ CHFOCF ₂ CF ₂ I
¹ H NMR was measured using 1,3-bis (trifluoromethyl) benzene (8.00 ppm: C ₆ H ₄ (CF ₃ ) ₂ ) as an internal standard substance.
¹ H NMR: δ = 4.33 (m, -C H ₂ O-), 5.96 (d, -C H F-)

Example 4
In a 1 L four-necked flask equipped with a reflux condenser, a thermometer, and a stirrer, perfluorocarbon represented by an average composition CF ₃ CF ₂ CF ₂ (OCF ₂ CF ₂ CF ₂ ) ₂₂ OCF ₂ CF ₂ CH ₂ OH A polyether-modified alcohol (150 g), 1,3-bis (trifluoromethyl) benzene (100 ml) and sodium hydroxide (5.9 g) were charged and stirred at 70 ° C. for 2 hours. _{Thereafter, CF 2 = CFOCF 2 CF 2} I a (29.6 g) was added and stirred for 4 hours at 85 ° C.. Then, it cooled to room temperature, the perfluorohexane (220g) was added, the insoluble matter was filtered, and washing | cleaning operation by 3N hydrochloric acid was performed with the separatory funnel. Subsequently, the following perfluoropolyether group-containing iodine compound (140 g) having iodine at the terminal was obtained by distilling off the volatile matter.
・ Perfluoropolyether group-containing iodine compounds:
CF ₃ CF ₂ CF ₂ (OCF ₂ CF ₂ CF ₂ ) ₂₂ OCF ₂ CF ₂ CH ₂ OCF ₂ CHFOCF ₂ CF ₂ I
¹ H NMR was measured using 1,3-bis (trifluoromethyl) benzene (8.00 ppm: C ₆ H ₄ (CF ₃ ) ₂ ) as an internal standard substance.
¹ H NMR: δ = 4.44 (m, -C H ₂ O-), 6.00 (d, -C H F-)

The present invention can be suitably used for producing a wide variety of perfluoropolyether group-containing silane compounds.

Claims (17)

1. The following general formula (I):
   

   

   [Where:
   Rf independently represents each alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms at each occurrence;
   PFPE has the general formula:
   -(OC ₄ F ₈ ) _a- (OC ₃ F ₆ ) _b- (OC ₂ F ₄ ) _c- (OCF ₂ ) _d-
   Wherein a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d The order of existence of each repeating unit with parentheses attached with is arbitrary in the formula.)
   A group represented by:
   Q is a divalent organic group containing at least one hydrogen atom and at least one fluorine atom bonded to a carbon atom;
   R ¹ is a hydrogen atom or a fluorine atom;
   Y is a chlorine atom, a bromine atom or an iodine atom;
   m is an integer from 0 to 3;
   l is 0 or 1; provided that when R ¹ is a fluorine atom, l is 1. ]
   A compound represented by
   However, CF ₃ (OCF ₂ CF ₂ ) ₂₀ (OCF ₂ ) ₁₆ OCF ₂ CH ₂ OCF ₂ CHFOCF ₂ CF ₂ I is excluded.
2. 2. The compound according to claim 1, wherein Rf is a perfluoroalkyl group having 1 to 16 carbon atoms.
3. PFPE is one of the following formulas (i) to (iv):
   -(OCF ₂ CF ₂ CF ₂ ) _b- (i)
   [Wherein, b is an integer of 1 to 200. ]
   -(OCF (CF ₃ ) CF ₂ ) _b- (ii)
   [Wherein, b is an integer of 1 to 200. ]
   _{- (OCF 2 CF 2 CF 2} CF 2) a - (OCF 2 CF 2 CF 2) b - (OCF 2 CF 2) c - (OCF 2) d - (iii)
   [Wherein, a and b are each independently 0 or an integer of 1 to 30, c and d are each independently an integer of 1 to 200, and the subscripts a, b, c, or d] The order of presence of each repeating unit in parentheses with an is optional in the formula. ]
   Or-(OC ₂ F ₄ -R ⁸ ) _e- (iv)
   [Wherein R ⁸ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ ;
   e is an integer of 2 to 100. ]
   The compound of Claim 1 or 2 which is group represented by these.
4. l is 1;
   Q is the following formula:
   — (CH ₂ ) _n —O—CR ² ₂ —CR ³ ₂ —Q′-CFR ⁴ —
   [Where:
   Q ′ is a divalent organic group;
   Each R ² is independently a hydrogen atom or a fluorine atom;
   Each R ³ is independently a hydrogen atom or a fluorine atom;
   R ⁴ is a hydrogen atom or a fluorine atom;
   n is an integer of 1 to 6. ]
   The compound according to any one of claims 1 to 3, which is a group represented by:
5. Q ′ is the following formula:
   -(R ¹¹ ) _p- (R ¹² ) _q-
   [Wherein R ¹¹ is independently at each occurrence an oxygen atom, —NR ¹³ — (wherein R ¹³ may be substituted with a hydrogen atom, or one or more fluorine atoms. Represents a lower alkyl group) or a divalent polar group;
   R ¹² is independently at each occurrence, —CR ¹⁴ ₂ —, wherein each R ¹⁴ is independently substituted with a hydrogen atom, a fluorine atom, or one or more fluorine atoms. Represents a lower alkyl group);
   p is an integer from 1 to 6;
   q is an integer from 0 to 20;
   The order of presence of each repeating unit attached with a subscript p or q and enclosed in parentheses is arbitrary in the formula. ]
   The compound of Claim 4 which is group represented by these.
6. 6. The compound according to claim 5, wherein R ¹¹ is an oxygen atom, and R ¹² is independently at each occurrence —CF ₂ — or —CF (CF ₃ ) —.
7. Q is
   -CH ₂ OCF ₂ CHFOCF _2- ,
   -CH ₂ OCF ₂ CHFOCF ₂ CF _2- ,
   -CH ₂ OCF ₂ CHFOCF ₂ CF ₂ CF _2- ,
   —CH ₂ OCF ₂ CHFOCF ₂ CF (CF ₃ ) OCF ₂ —,
   —CH ₂ OCF ₂ CHFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ —,
   _{-CH 2 OCF 2 CHFOCF 2 CF (} CF 3) OCF 2 CF 2 CF 2 -,
   -CH ₂ OCH ₂ CHFCF ₂ OCF _2- ,
   -CH ₂ OCH ₂ CHFCF ₂ OCF ₂ CF _2- ,
   -CH ₂ OCH ₂ CHFCF ₂ OCF ₂ CF ₂ CF _2- ,
   —CH ₂ OCH ₂ CHFCF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ —,
   —CH ₂ OCH ₂ CHFCF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF ₂ —, and —CH ₂ OCH ₂ CHFCF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF ₂ CF ₂ —
   The compound according to any one of claims 1 to 4, which is a group selected from:
8. The compound according to any one of claims 1 to 7, wherein Y is iodine.
9. The following general formula (Ia):
   

   

   [Where:
   Rf independently represents each alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms at each occurrence;
   PFPE has the general formula:
   -(OC ₄ F ₈ ) _a- (OC ₃ F ₆ ) _b- (OC ₂ F ₄ ) _c- (OCF ₂ ) _d-
   Wherein a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d The order of existence of each repeating unit with parentheses attached with is arbitrary in the formula.)
   A group represented by:
   Q ′ is a divalent organic group;
   Each R ¹ is independently a hydrogen atom or a fluorine atom;
   Each R ² is independently a hydrogen atom or a fluorine atom;
   R ³ is a hydrogen atom or a fluorine atom;
   R ⁴ is a hydrogen atom or a fluorine atom;
   Y is a chlorine atom, a bromine atom or an iodine atom;
   m is an integer from 0 to 3;
   n is an integer of 1 to 6. ]
   The compound of Claim 1 represented by these.
10. The compound according to claim 4 or 9, wherein R ⁴ is a fluorine atom.
11. The following structure:
    CF ₃ (OCF ₂ CF ₂ ) ₂₀ (OCF ₂ ) ₁₆ OCF ₂ CH ₂ OCF ₂ CHFOCF ₂ CF ₂ I
    A compound having
12. The following general formula (I ′):
    

    

    [Where:
    Rf independently represents each alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms at each occurrence;
    PFPE has the general formula:
    -(OC ₄ F ₈ ) _a- (OC ₃ F ₆ ) _b- (OC ₂ F ₄ ) _c- (OCF ₂ ) _d-
    Wherein a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d The order of existence of each repeating unit with parentheses attached with is arbitrary in the formula.)
    A group represented by:
    Q ″ is a divalent organic group containing at least one fluorine atom bonded to a carbon atom;
    R ¹ is a hydrogen atom or a fluorine atom;
    Y is a chlorine atom, a bromine atom or an iodine atom;
    m is 0-3;
    l is 0 or 1. ]
    A compound represented by the following general formula (A):
    

    

    [Wherein Rf, PFPE, R ¹ and m are as defined above;
    n is an integer of 1 to 6. ]
    And a compound represented by the following formula (B):
    

    

    [Wherein Y is as defined above;
    Q ′ is a divalent organic group;
    Each R ² is independently a hydrogen atom or a fluorine atom;
    R ³ is a hydrogen atom or a fluorine atom;
    R ⁴ is a hydrogen atom or a fluorine atom. ]
    Reacting with the compound represented by these.
13. The compound represented by the formula (B) is represented by the following formula (C):
    

    

    [Wherein R ² , R ³ , R ⁴ , Q ′ and Y are as defined in the formula (B);
    X is a halogen atom. ]
    The method according to claim 12, which is obtained from a compound represented by the formula:
14. The compound represented by the general formula (I ′) is represented by the following general formula (Ia):
    

    

    [Where:
    Rf independently represents each alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms at each occurrence;
    PFPE has the general formula:
    -(OC ₄ F ₈ ) _a- (OC ₃ F ₆ ) _b- (OC ₂ F ₄ ) _c- (OCF ₂ ) _d-
    Wherein a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d The order of existence of each repeating unit with parentheses attached with is arbitrary in the formula.)
    A group represented by:
    Q ′ is a divalent organic group;
    Each R ¹ is independently a hydrogen atom or a fluorine atom;
    Each R ² is independently a hydrogen atom or a fluorine atom;
    R ³ is a hydrogen atom or a fluorine atom;
    R ⁴ is a hydrogen atom or a fluorine atom;
    Y is a chlorine atom, a bromine atom or an iodine atom;
    m is an integer from 0 to 3;
    n is an integer of 1 to 6. ]
    The method of Claim 12 or 13 which is a compound represented by these.
15. Q ′ is the following formula:
    -(R ¹¹ ) _p- (R ¹² ) _q-
    [Wherein R ¹¹ is independently at each occurrence an oxygen atom, —NR ¹³ — (wherein R ¹³ may be substituted with a hydrogen atom, or one or more fluorine atoms. Represents a lower alkyl group) or a divalent polar group;
    R ¹² is independently at each occurrence, —CR ¹⁴ ₂ —, wherein each R ¹⁴ is independently substituted with a hydrogen atom, a fluorine atom, or one or more fluorine atoms. Represents a lower alkyl group);
    p is an integer from 1 to 6;
    q is an integer from 0 to 20;
    The order of presence of each repeating unit attached with a subscript p or q and enclosed in parentheses is arbitrary in the formula. ]
    The method according to any one of claims 12 to 14, which is a group represented by:
16. The method according to any one of claims 12 to 15, wherein R ⁴ is a fluorine atom.
17. Q ”
    -CH ₂ OCF ₂ CHFOCF _2- ,
    -CH ₂ OCF ₂ CHFOCF ₂ CF _2- ,
    -CH ₂ OCF ₂ CHFOCF ₂ CF ₂ CF _2- ,
    —CH ₂ OCF ₂ CHFOCF ₂ CF (CF ₃ ) OCF ₂ —,
    —CH ₂ OCF ₂ CHFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ —,
    _{-CH 2 OCF 2 CHFOCF 2 CF (} CF 3) OCF 2 CF 2 CF 2 -,
    -CH ₂ OCH ₂ CHFCF ₂ OCF _2- ,
    -CH ₂ OCH ₂ CHFCF ₂ OCF ₂ CF _2- ,
    -CH ₂ OCH ₂ CHFCF ₂ OCF ₂ CF ₂ CF _2- ,
    —CH ₂ OCH ₂ CHFCF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ —,
    —CH ₂ OCH ₂ CHFCF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF ₂ —, and —CH ₂ OCH ₂ CHFCF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF ₂ CF ₂ —
    A group selected from
    Q '
    -O-,
    -OCF-,
    -OCF ₂ CF _2- ,
    —OCF ₂ CF (CF ₃ ) O—
    —OCF ₂ CF (CF ₃ ) OCF ₂ —
    —OCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ —
    -CF ₂ O-,
    -CF ₂ OCF _2- ,
    -CF ₂ OCF ₂ CF _2- ,
    -CF ₂ OCF (CF ₃ ) CF ₂ O-,
    —CF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ —, and —CF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF ₂ —,
    The method according to any one of claims 12 to 16, wherein the group is a group selected from: