JP2550367B2 - Fluorine-containing aromatic carboxylic acid ester - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel fluorine-containing aromatic carboxylic acid ester useful as a surfactant, a lubricant, a release agent, a cosmetic agent, a polymer surface modifier, and the like. .

2. Description of the Related Art Conventionally, various types of fluorine-containing organic compounds have been developed and used in various fields. Among them, fluorine-containing compounds having a polyalkylene oxide group such as polyethylene oxide group are widely used as a surfactant, a lubricant, a cosmetic agent, a polymer surface modifier and the like.

However, since the conventional fluorine-containing compound of this type contains a linear perfluoroalkyl group as the fluorine-containing group and contains only one perfluoroalkyl group in the molecule, other types of fluorine-containing compounds can be used. Not only is it inferior in terms of low friction wear resistance and surface activity, etc.
There is a problem that the intended purpose cannot be sufficiently achieved depending on the application field because of low viscosity and poor compatibility with a base or the like.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present invention provides a fluorine-containing compound which does not have such drawbacks of the conventional fluorine-containing compound of this kind, and is a high-performance surfactant, lubricant, cosmetic agent and It was made in order to provide a novel fluorine-containing organic compound useful as a polymer surface modifier and the like.

Means for Solving the Problems That is, the present invention has the general formula (I): (In the formula, R _f is a perfluoroalkenyl group C ₆ F ₁₁ or C
₉ F ₁₇ , X represents a hydrogen atom or a methyl group, and n
Represents a number from 1 to 140) and represents a fluorine-containing aromatic carboxylic acid ester.

The perfluoroalkenyl group C ₆ F ₁₁ or C ₉ F ₁₇ represented by R _f in the general formula (I) is generally a monovalent residue derived from a dimer or trimer of hexafluoropropene.

Further, in the general formula (I), X represents a hydrogen atom or a methyl group.

That is, CH ₂ CH (X) O _n represents a polyethylene oxide group or a polypropylene oxide group. In this case, n represents a number of 1-40.

Among the fluorine-containing aromatic carboxylic acid esters represented by the general formula (I), particularly preferred are the following formula (Ia): (In the formula, Rf, X and n have the same meanings as described above).

As the compound represented by the formula (Ia), the following formulas (1) to
The one represented by (5) is exemplified: The method for producing the fluorine-containing aromatic carboxylic acid ester represented by the general formula (I) is not particularly limited, but as a simple method, the following production methods 1 to 3 are exemplified.

Process 1 General formula (II): (In the formula, R _f has the same meaning as described above) A perfluoroalkenyloxy aromatic carboxylic acid chloride such as p- (perfluorononenyloxy) benzoic acid chloride is represented by a basic compound such as pyridine. The general formula (III) in the presence of an organic base such as triethylamine, dimethylaniline or an inorganic base such as potassium carbonate or sodium hydroxide. (In the formula, X and n have the same meanings as described above) and are reacted with polyethylene glycol or polypropylene glycol.

Usually, the reaction molar ratio is (II) :( III) = 2: 1 and the reaction temperature is about 0 to 50 ° C.

Process 2 General formula (IV): (In the formula, R _f has the same meaning as described above) A perfluoroalkenyloxy aromatic carboxylic acid represented by, for example, p- (perfluorononenyloxy) benzoic acid is used as an acid catalyst such as p-toluenesulfonic acid, concentrated. The reaction is carried out with the polyethylene glycol or polypropylene glycol represented by the above general formula (III) in the presence of sulfuric acid, concentrated hydrochloric acid, a strongly acidic ion exchange resin or the like.

Usually, the reaction molar ratio is (IV) :( III) = 2: 1 to 2.2: 1,
The reaction temperature is about 100-150 ° C.

Manufacturing method 3 General formula (V): (In the formula, R _f has the same meaning as described above and R represents a methyl group or an ethyl group.) A perfluoroalkenyloxy aromatic carboxylic acid ester, for example, methyl p- (perfluorononenyloxy) benzoate Are reacted with the polyethylene glycol or polypropylene glycol represented by the general formula (III) in the presence of the above-mentioned acid catalyst.

Usually, the reaction molar ratio is (V) :( III) = 2: 1 to 2.2: 1,
The reaction temperature is about 100-150 ° C.

The reaction in the above Production Methods 1 to 3 may be carried out without using a solvent, but a solvent such as carbon tetrachloride, chloroform, benzene, toluene or acetone may be appropriately used.

 Hereinafter, the present invention will be described with reference to examples.

Example 1 In a reaction vessel (200 ml) equipped with a dropping funnel and a stirrer, 2.0 g of ethylene glycol, 8.0 g of pyridine and carbon tetrachloride.
20 ml was added, and a solution of 45.0 g of p- (perfluorononenyloxy) benzoic acid chloride in 80 ml of carbon tetrachloride was added dropwise to the mixture at room temperature with stirring, and the reaction was carried out for 4 hours with stirring. Konatsuta

The reaction mixture was filtered, the filtrate was transferred to a separatory funnel, washed with 100 ml of water three times, and the organic layer was dried with a mixture of magnesium hydroxide and anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 34.7 g of the compound (1) (yield 93
%).

 The physical properties of compound (1) are shown in Table 1.

Example 2 The above compound (2) was prepared according to the procedure of Example 1 (yield 83%).

 Physical properties of compound (2) are shown in Table 1.

Example 3 40 g of polyethylene glycol (average molecular weight: 1000), 10.0 g of pyridine and 50 ml of carbon tetrachloride were placed in a reaction vessel (500 ml) equipped with a dropping funnel and a stirrer, and p was added to the mixture.
-(Perfluorononenyloxy) benzoic acid chloride 58.6
A solution prepared by dissolving g in 250 ml of carbon tetrachloride was added dropwise at room temperature with stirring, and the reaction was carried out for 4.5 hours with stirring.

The reaction mixture was filtered, 1 ml of water was added to the filtrate, the solvent was distilled off under reduced pressure while heating, and the residue was added to a silica gel column [60 mm (diameter) x 30 mm with carbon tetrachloride (500 ml) as an eluent. (Height)] After subjecting to the above chromatographic treatment, the solvent was distilled off under reduced pressure to obtain 70.3 g of the compound (3) (yield 83%).

 Table 1 shows the physical properties of the compound (3).

Example 4 The compound (4) was prepared according to the procedure of Example 3 (yield 76%).

 Table 1 shows the physical properties of the compound (4).

Example 5 The compound (5) was prepared according to the procedure of Example 3 (yield 85%).

Physical properties of compound (5) are shown in Table 1. Perfluorononenyl group C ₉ F _{17 in the} above chemical formulas (1) to (5)
The structure of − is as follows: EFFECTS OF THE INVENTION The fluorine-containing aromatic carboxylic acid ester according to the present invention not only has excellent water and oil repellency, low friction and abrasion resistance, surface activity, etc., but also has good compatibility with various bases and the like. In addition to exhibiting high thermal and chemical stability, high-performance surfactants, lubricants, release agents, cosmetics, finishing agents for fibers and films, polymer surface modifiers ( For example, it is useful for imparting lubricity and water / oil repellency to the film surface, imparting slidability to the surface of the magnetic recording material, etc.).

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C10M 107/38 C10M 107/38 147/04 147/04 C10N 40:36 (72) Inventor Nemoto Fuji People 1-1, Oike-cho, Kosai-cho, Koga-gun, Shiga Prefecture Within Neos Co., Ltd.

Claims (1)

(57) [Claims] 1. General formula (I): (In the formula, R _f is a perfluoroalkenyl group C ₆ F ₁₁ or C
₉ F ₁₇ , X represents a hydrogen atom or a methyl group, and n
Represents a number from 1 to 140) and a fluorine-containing aromatic carboxylic acid ester represented by