JPH07112959A - Perfluorocarboxylic acid amide, water-repellent containing the same and its production - Google Patents

Abstract

PURPOSE:To obtain a perfluorocarboxylic acid amide having excellent water- repellency and high solubility of other substances, a water-repellent containing the amide and a process for producing the amide. CONSTITUTION:A perfluorocarboxylic acid amide expressed by the formula CnFmC0NR<1>R<2> (R<1> is H or CaHb; R<2> is CcHd; (n), (m), (a), (b), (c) and (d) are integers satisfying the formulas 8<=n<=20, m<=2n+1, 1<=a<=20, b<=2a+1, 1<=c<=20 and d<= 2c+1), a water-repellent containing the amide and a process for producing the perfluorocarboxylic acid amide expressed by the alove formula by reacting a lower alkyl ester of a perfluorocarboxylic acid corresponding to the above formula with an amine.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a perfluorocarboxylic acid amide, a novel water repellent containing the amide, and a method for producing the amide. More specifically, the present invention provides a perfluorocarboxylic acid amide having excellent water repellency and improved solubility and affinity for other substances, a water repellent agent containing the same and a water repellent having excellent water repellency. The present invention relates to a method for efficiently producing

[0002]

2. Description of the Related Art Conventionally, fluoropolymers and oligomers have been known as excellent water repellents, but since these compounds have poor solubility and affinity for other substances, they easily peel off or There was a problem of layer separation. Perfluorocarboxylic acid and its methyl ester have poor water repellency and solubility, and perfluorocarboxylic acid amide has been known as a component of lubricants and coating compositions.
So far, its water repellency has not been known. The JP 63-77996 discloses, as compounds showing good lubricating effect in the low temperature region, C _p F _2p + 1 CONH
An amide represented by R ′ (R ′ is an alkyl group, p ≧ 3) is disclosed. However, this publication only discloses examples of amides having p of 7 or less, and does not disclose that amides having p of 8 or more exhibit water repellency. Further, in JP-A-58-213057, a fluorine-containing surfactant and _Rf- Q-NR "R"'( _Rf is defined as a coating composition excellent in smoothness and salt water resistance). A perfluoroalkyl group, Q is —CO— and R ″ and R ′ ″ are alkyl groups.). However, there is no description of water repellency in this publication, and since the above composition uses a surfactant, it seems that the water repellency is low.

[0003]

DISCLOSURE OF THE INVENTION The present invention shows excellent water repellency, and also has excellent water repellency, which is a perfluorocarboxylic acid amide having improved solubility and affinity for other substances. Another object of the present invention is to provide a water repellent and a method for efficiently producing the perfluorocarboxylic acid amide.

[0004]

The inventors of the present invention have conducted extensive studies to achieve the above object, and as a result, perfluorocarboxylic acid amide having a specific structure exhibits excellent water repellency as well as to other substances. High solubility and affinity,
It was found that this product can be efficiently obtained by reacting the corresponding lower alkyl ester of perfluorocarboxylic acid with an amine. The present invention has been completed based on such findings. That is, the present invention relates to compounds of the general formula (I) in _{^{C n F m CONR 1 R 2}} ··· (I) ( wherein, R ¹ represents a hydrogen atom or -C _a H _b, R ² is -C _c H _d , n, m, a, b, c, and d are the following conditions: 8 ≦ n ≦ 20, m ≦ 2n + 1, 1 ≦ a ≦ 20, b ≦ 2a
+ 1,1≤c≤20, d≤2c + 1. ), And a water repellent comprising at least one selected from the perfluorocarboxylic acid amides and the perfluorocarboxylic acid amides. Further, the perfluorocarboxylic acid amide represented by the general formula (I) has the general formula (II) C _n F _m COOR (II) (wherein R represents a lower alkyl group, and m and n are respectively A perfluorocarboxylic acid ester represented by the following condition 8 ≦ n ≦ 20, m ≦ 2n + 1) and a general formula (III) R ¹ R ² NH (III) (wherein R ¹ Represents _a hydrogen atom or -C _a H _b , R ² represents -C _c H _d , and a, b, c and d are the following conditions 1 ≦ a ≦ 20, b ≦ 2a + 1, 1 ≦ c ≦ 20, respectively. , D ≦ 2c
It is an integer that satisfies +1. ) It can manufacture by reacting with the amine shown by.

The perfluorocarboxylic acid amide of the present invention has a structure represented by the general formula (I) C _n F _m CONR ¹ R ² ... (I). The above general formula (I)
In, n and m are 8 ≦ n ≦ 20 and m ≦ 2n + 1
Is an integer that satisfies. When n is less than 8, the water repellency is not sufficient, and when it exceeds 20, the solubility decreases. Also, R ¹
Represents _a hydrogen atom or -C _a H _b , and R ² represents -C _c H _d . Here, a, b, c and d are 1 ≦ a ≦ 20, b
An integer that satisfies ≦ 2a + 1, 1 ≦ c ≦ 20, and d ≦ 2c + 1. If a or c exceeds 20, there is an inconvenience that the solubility decreases. Further, m is preferably m = 2n + 1, and in this case, the perfluorocarboxylic acid moiety is derived from a saturated perfluorocarboxylic acid. m
When m <2n + 1, the perfluorocarboxylic acid moiety is derived from an unsaturated perfluorocarboxylic acid having a double bond or a triple bond, and may have both a double bond and a triple bond. The number is not particularly limited and may be any number. The perfluorocarboxylic acid moiety may be derived from a linear perfluorocarboxylic acid, or may be derived from a branched perfluorocarboxylic acid having at least one branched structure in the carbon chain. Furthermore, the above b and d are b =
It is preferred that 2a + 1 and d = 2c + 1, where the amine moiety is from a saturated amine. When b and / or d is b <2a + 1, d <2c + 1, the amine moiety is derived from an unsaturated amine having a double bond or a triple bond and has both a double bond and a triple bond. The number is not particularly limited and may be any number. The amine moiety may be derived from a linear amine or a branched amine having at least one branched structure in the carbon chain.

According to the method of the present invention, the perfluorocarboxylic acid amide represented by the general formula (I) is represented by the general formula (I
I) C _n F _m COOR (II) (wherein R represents a lower alkyl group, and n and m are the same as above), and a general formula (III) It can be produced by reacting with an amine represented by R ¹ R ² NH (III) (Formula Note, R ¹ and R ² are the same as above).

The perfluorocarbon represented by the above general formula (II)
Rubonic acid esters include methyl ester and ethyl ether.
Stell, n-propyl ester, isopropyl ester
And lower alkyl esters such as
Of these, methyl ester is preferred. Represented by the general formula (II)
Specific examples of perfluorocarboxylic acid ester
Is CF₃(CF₂)₁₂COOCH₃, CF₃(C
F₂)₁₄COOCH₃, CF ₃(CF₂)₁₆COOCH
₃And the like can be preferably mentioned. On the other hand, the above general
Specific examples of the amine represented by the formula (III) include n-dode
Sylamine, n-tetradecylamine, n-hexadecyl
Primary amines such as ruamine and n-octadecylamine,
Secondary amines such as di-n-octylamine are preferred.
You can Perfluorocal represented by the above general formula (II)
Use of a bonate ester and an amine represented by the general formula (III)
The molar ratio is usually 1: 1 to 1:10, preferably
The range is from 1: 1.1 to 1: 2. This reaction is
It is usually carried out in a suitable solvent, and examples of the solvent include
For example, aliphatic hydrocarbons such as n-heptane and n-nonane,
Aromatic hydrocarbons such as benzene, toluene, xylene,
Halogenated carbon such as chloroform, carbon tetrachloride, CFC
Hydrogen fluoride or the like is used. The reaction temperature is usually 0 to
The temperature is 180 ° C, preferably 20 to 120 ° C. The
The reaction is carried out until the raw material ester is substantially 100% consumed.
However, the reaction time is usually 1 to 12
Time, preferably about 1 to 5 hours is sufficient.

The perfluorocarboxylic acid amide represented by the general formula (I) thus obtained has excellent water repellency, and is used alone or as a mixture of two or more thereof, or other known water repellency. It can be used as a water repellent in combination with a substance. The perfluorocarboxylic acid amide can also be used as a water repellency enhancer such as wax.

[0009]

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Preparation Example 1 n-C ₁₅ F ₃₁ COOCH ₃ 6.1 mmol and n-C ₁₂ H
₂₅ NH ₂ 6.7 mmol in an n-nonane solvent at 100 ° C.
After heating at room temperature for 5 hours, the reaction product was filtered after cooling to room temperature, and the obtained solid was recrystallized to produce n-C ₁₅ F ₃₁ CO 2.
NHC ₁₂ H ₂₅ was obtained. The yield was 96%. The obtained perfluorocarboxylic acid amide was confirmed by the infrared spectroscopic analysis spectrum shown in FIG. 1 and the mass spectrum shown in FIG. That is, in the infrared spectroscopic analysis, 110
C-F bonds characteristic strong absorption over the 0~1250cm ^-1, absorption of C = O bond of the amide to 1693 cm ^-1, 28
Absorption of C—H bond and 3326 at 40-2960 cm ⁻¹
Absorption of the N—H bond of the amide is observed at cm ⁻¹ . Moreover, in the mass spectrum by mass spectrometry (CI method), 9
81 peak of molecular ion was observed, these results are all supporting the structure of the above _{n-C 15 F 31 CONHC 12} H 25.

Production Examples 2 to 7 By the same procedure as in Production Example 1, the corresponding perfluorocarboxylic acid ester was reacted with an alkylamine to obtain the perfluorocarboxylic acid amides shown in Table 1.

Production Example 8 n-C ₁₅ F ₃₁ COOCH ₃ 6.1 mmol and (n-C ₈
H ₁₇₎ 1 to ₂ NH18.6 mmol, in n- heptane solvent
After refluxing at 00 ° C. for 12 hours, the reaction product was filtered after cooling to room temperature, and the obtained solid was recrystallized to obtain n-C ₁₅
To obtain a _{F 31 CON (n-C 8} H 17) 2. The yield was 56%.

[0013]

[Table 1]

Examples 1 to 7 and Comparative Examples 1 to 2 2% by weight kerosene solution of perfluorocarboxylic acid amide obtained in Production Examples 1 to 8 (Examples 1 to 8), 2% by weight solution of perfluorocarboxylic acid kerosene (Comparative Example 1) and a 2 wt% kerosene solution of perfluorocarboxylic acid ester (Comparative Example 2) were prepared. These solutions were dropped on an automobile coating film test piece, spread and dried, and then the surface of the test piece was polished with absorbent cotton to form a film on the surface of the test piece. The contact angle between this film and water was measured by a contact angle meter [CA-D manufactured by Kyowa Interface Science Co., Ltd.]. The results are shown in Table 2.

[0015]

[Table 2]

Examples 9 to 16 and Comparative Examples 3 to 4 1% by weight ether solution of perfluorocarboxylic acid amide obtained in Production Examples 1 to 8 (Examples 9 to 16), 1% by weight ether solution of perfluorocarboxylic acid (Comparative Example 3) and a 1 wt% ether solution of perfluorocarboxylic acid ester (Comparative Example 4) were prepared. After casting these solutions on a glass substrate to form a film on the substrate, the contact angle between the film and water is measured by a contact angle meter [Kyowa Interface Science Co., Ltd., CA
-D]. The results are shown in Table 3.

[0017]

[Table 3]

Examples 17 to 24 and Comparative Examples 5 to 6 Perfluorocarboxylic acid amides obtained in Production Examples 1 to 8 (Examples 17 to 24), perfluorocarboxylic acid (Comparative Example 5) and perfluorocarboxylic acid ester (Comparative) For Example 6), the solubility in toluene and chloroform was measured. The results are shown in Table 4.

[0019]

[Table 4]

[Note] S1: solubility at 20 ° C. is 1 to 5% by weight S0: solubility at the boiling point of the solvent is 1% by weight or more I: solubility at the boiling point of the solvent is less than 1% by weight

[0021]

INDUSTRIAL APPLICABILITY The perfluorocarboxylic acid amide of the present invention exhibits excellent water repellency and has good solubility and affinity with other substances. The water-repellent agent of the present invention containing the perfluorocarboxylic acid amide exhibits a high water-repellent action, has improved solubility and affinity for other substances, and is excellent in operability and film-forming property. It is effective for waterproofing various objects and adding it as a water repellent to wax, antifouling agents, etc. Further, according to the method of the present invention,
The perfluorocarboxylic acid amide can be efficiently produced, and its industrial utility value is extremely large.

[0022]

[Brief description of drawings]

1 is an infrared spectroscopic analysis spectrum diagram of a perfluorocarboxylic acid amide obtained in Production Example 1. FIG.

FIG. 2 is a mass spectrum diagram of the perfluorocarboxylic acid amide obtained in Production Example 1.

Claims (4)

[Claims] 1. General formula (I) C _n F _m CONR ¹ R ² ... (I) (In the formula, R ¹ represents a hydrogen atom or —C _a H _b , and R ² represents —C _c H _d. Where n, m, a, b, c, and d are the following conditions 8 ≦ n ≦ 20, m ≦ 2n + 1, 1 ≦ a ≦ 20, b ≦ 2a, respectively.
+ 1,1≤c≤20, d≤2c + 1. ) A perfluorocarboxylic acid amide represented by 2. A water repellent comprising at least one selected from the perfluorocarboxylic acid amides according to claim 1. 3. A perfluorocarboxylic acid amide has m =
The water repellent according to claim 2, which is 2n + 1, b = 2a + 1, d = 2c + 1. 4. A compound represented by the general formula (II) C _n F _m COOR (II) (wherein R represents a lower alkyl group, and n and m each satisfy the following conditions: 8 ≦ n ≦ 20, m ≦ 2n + 1. And a perfluorocarboxylic acid ester represented by the general formula (III) R ¹ R ² NH ... (III) (wherein R ¹ represents a hydrogen atom or —C _a H _b , R ² represents -C _c H _d , and a, b, c, and d are the following conditions: 1 ≦ a ≦ 20, b ≦ 2a + 1, 1 ≦ c ≦ 20, d ≦ 2c
It is an integer that satisfies +1. Formula which comprises reacting an amine represented _{by) (I) C n F m} CONR 1 R 2 ··· (I) ( wherein R ^1, R ^2, m and n are as defined above The method for producing a perfluorocarboxylic acid amide represented by