JPH0798814B2 - Para- (perfluoroalkenyloxy) benzoic acid glycidyl ester and process for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel epoxide group-containing fluorine-containing compound useful in a wide range of fine chemical fields such as surfactants, lubricants, cosmetics and polymer modifiers, and the like. It relates to a manufacturing method.

BACKGROUND ART Fluorine-containing compounds are generally known to have properties such as water / oil repellency, non-adhesiveness, chemical resistance, and low friction and abrasion resistance. Attempts have been made to impart new properties to obtain new functional compounds.

However, most of the conventional functional compounds of this type have a linear perfluoroalkyl group as a fluorine-containing group, and therefore, by imparting another characteristic, the original characteristics of the fluorine-containing compound can be obtained. , For example, there is a problem that sliding properties such as low friction wear resistance and surfactants are impaired, and the intended purpose cannot be sufficiently achieved depending on the application field (for example, foam of a foam type fire extinguisher). When used as a shape retention agent, sufficient shape retention is not obtained).

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present invention has high versatility by imparting various reaction characteristics to the compound without impairing the original characteristics of the fluorine-containing compound including sliding characteristics and surfactant characteristics. It was made to provide a functional fluorine-containing compound.

Means for Solving the Problems That is, the present invention has the general formula (I): {In the formula, Rf is the general formula (II): [Wherein, R _{1 to} R ₃ are each independently CnF ₂ n + ₁ (n is 1 to 3)
The perfluoroalkyl group represented by the formula (1) is shown]], and the para- (perfluoroalkenyloxy) benzoic acid glycidyl ester is represented by the formula (1).

The structural characteristic of the fluorine-containing compound represented by the formula (I) according to the present invention is that the perfluoroalkenyl group represented by the formula (II) is bonded to a benzene ring through an ether bond, and the benzene ring has glycidyl. That is, the ester group is bonded.

Suitable perfluoroalkenyl groups Rf include the following formula (a)
Examples of residues represented by ~ (d) are: These residues are derived from oligomers of hexafluoropropene, for example as described below. That is, the residue represented by the formula (a) is 2 of hexafluoropropene.
Derived from the trimer, the residues of formulas (b) to (d) are derived from the hexafluoropropene trimer.

Since the perfluoroalkenyl group limits the freedom of molecular motion due to the presence of an unsaturated bond, it imparts resistance to external force at the interface to the compound having the group. When the group has a structure in which the group is bonded to the benzene ring through an ether bond, as in the compound represented by the formula (I), the compound is more effectively exhibited.

The structure containing such a perfluoroalkenyl group also contributes to the thermal and chemical stability of the compound represented by formula (I).

On the other hand, the glycidyl ester group has various reactivity, particularly high reactivity with active hydrogen such as alcohols, phenols, amines, carboxylic acids, etc. Therefore, the above-mentioned perfluoroalkenyl group can be used in a wide variety of fields. The compound represented by the formula (I) according to the present invention becomes a highly versatile functional compound.

The production method of compound (I) according to the present invention is not particularly limited, but the following production method is exemplified.

The first method is the general formula (III): (In the formula, X represents a halogen atom) A para- (perfluoroalkenyloxy) benzoic acid halide represented by the formula is reacted with glycidol in the presence of a basic compound.

The para- (perfluoroalkenyloxy) benzoic acid halide represented by the formula (III) is obtained by reacting para-hydroxybenzoic acid with a perfluoroalkene in the presence of a polar catalyst such as trimethylamine or triethylamine. It can be easily prepared by halogenating (perfluoroalkenyloxy) benzoic acid with SOCl ₂ , PBr ₃ , PCl ₅ or the like.

Suitable perfluoroalkenes are represented by the following formula (a ′)
An example is the hexafluoropropene oligomer represented by (d '): Examples of the basic compound used in the reaction of the above benzoic acid halide and glycidol include organic bases such as tertiary amines such as triethylamine and aniline, potassium carbonate and NaOH.
Inorganic bases such as The basic compound is added to neutralize the hydrogen halide produced as a by-product during the reaction so that it does not add to the epoxy group of the target product.

The reaction solvent and the reaction temperature may be appropriately selected depending on the type of the basic compound used, etc., in addition to the reactivity and solubility of the reaction components.

For example, when a tertiary amine such as triethylamine or aniline is used, any solvent that does not undergo a nucleophilic substitution reaction may be used, such as acetone, DMF, chloroform, hexane, etc., regardless of the polarity of the solvent. Aqueous acetone, which promotes rate, is preferred. In this case, the reaction is usually
Perform at 50 ° C or below.

On the other hand, when using an inorganic base such as potassium carbonate or NaOH, it is preferable to use a solvent such as DMF or DMSO having a large solubility, but even if these inorganic bases are dissolved in a small amount of water and used. Good. In this case, the reaction temperature is 5 ° C. or lower so that hydrolysis of the epoxy group does not occur.

In the above reaction, glycidol is preferably used in an excess amount with respect to the compound represented by the general formula (III), whereby the compound (III) hardly remains in the reaction product and the by-product. Since the epoxy polymer to be used can be removed by washing with water, a high-purity compound (I) can be easily obtained.

The second method for producing the compound represented by the formula (I) is the general formula
(IV):(In the formula, n represents a number of 1 to 2, and Mⁿ Is 1 or 2
Represents a valent cation) is represented by para- (perfluoroalkenylene)
Si) Method of reacting benzoic acid with epihalogenhydrin
Is.

Para- (perfluoroalkenyloxy) benzoic acid represented by the formula (IV) is, for example, para- (perfluoroalkenyloxy) benzoic acid prepared as described above is dissolved in a solvent such as acetone, It is prepared by adding an alkali hydroxide, an alkaline earth hydroxide compound and a tertiary amine compound. In this case, a small amount of water may be added for smooth neutralization.

In the general formula (IV), Mⁿ Is a monovalent or divalent tick
ON, but preferably an alkali metal cation or
It is an ammonium cation.

The reaction of the benzoate with epihalogenhydrin is usually
It is carried out in a polar solvent such as DMF, DMSO or N-methylpyrrolidone at a temperature of about 50 ° C or lower. Also in this case, as in the case of the above-mentioned first production method, it is preferable to use the epihalogenhydrin in an excessive amount with respect to the benzoate, whereby a compound (I) of high purity can be easily obtained.

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

EXAMPLES Example 1 40.7 g (0.55 mol) of glycidol and 500 ml of acetone were placed in a 2000 ml flask, the temperature of the system was maintained at about 20 ° C., and 293 g (0.50 mol) of para- (perfluorononenyloxy) benzoic acid chloride was added. Then the temperature of the system was kept below 40 ° C. and 55.7 g (0.55 mol) of triethylamine was added.

After continuing stirring at 40 ° C. for 4 hours, the reaction mixture was put into water, and the precipitated crystals were collected by filtration, washed with water and recrystallized from alcohol to give para- (perfluorononenyloxy) benzoic acid glycidyl ester. 228g was obtained (yield
73%).

The physical properties of this product are shown in Table 1 below.

Example 2 303 g (0.50 mol) potassium para- (perfluorononenyloxy) benzoate and 500 ml DMSO in a 2000 ml flask.
, Keep the system temperature at about 40 ° C, and
After adding 75.3g (0.55mol) and continuing stirring for 4 hours,
The reaction mixture was poured into ice water and then extracted with dichloromethane. The extract was washed with water to remove excess epibromohydrin and by-products, and then dried with sodium sulfate. After the solvent was distilled off, alcohol was added and the precipitated crystals were collected by filtration to obtain the same para- (perfluorononenyloxy) benzoic acid glycidyl ester as in Example 1.

Example 3 Para- (perfluorohexenyl) according to the procedure of Example 2 except that para- (perfluorohexenyloxy) benzoic acid chloride was used instead of para- (perfluorononenyloxy) benzoic acid chloride. Oxy)
A glycidyl benzoate ester was prepared.

The physical properties of the obtained product are shown in Table 2 below.

Example 4 Similar to Example 3, according to the procedure of Example 2 except that potassium para- (perfluorohexenyloxy) benzoate is used instead of potassium para- (perfluorononenyloxy) benzoate. Para- (perfluorohexenyloxy) benzoic acid glycidyl ester of was prepared.

EFFECTS OF THE INVENTION Para- (perfluoroalkenyloxy) benzoic acid glycidyl ester represented by the general formula (I) according to the present invention is water / oil repellency, non-adhesiveness (release property), antifouling property, chemical resistance. Properties, low friction and abrasion resistance, and optical specificity (sharpening, darkening, etc.), high-performance surfactants, lubricants, release agents, cosmetics, textiles and paper finishing agents. It can be used as various processing agents and processing agents such as film processing finishing agents and polymer modifiers.

Further, since the glycidyl ester (I) has various reactive epoxy groups, it can react with a wide range of functional groups of an object to be treated to effectively impart a desired function to the object. .

In addition, the compound (I) according to the present invention can be easily produced at low cost and has excellent storage stability.

Claims (4)

[Claims] 1. General formula (I): {In the formula, Rf is the general formula (II): [Wherein, R _{1 to} R ₃ are each independently CnF ₂ n + ₁ (n is 1 to 3)
Represents a perfluoroalkyl group represented by the following formula]] represents a perfluoroalkenyl group represented by the following formula] represents a para- (perfluoroalkenyloxy) benzoic acid glycidyl ester. 2. Rf is expressed by the following equations (a) to (d): Paragraph according to item 1, which is any residue represented by
(Perfluoroalkenyloxy) benzoic acid glycidyl ester. 3. General formula (III): (In the formula, X represents a halogen atom) Para- (perfluoroalkenyloxy) benzoic acid halide is reacted with glycidol in the presence of a basic compound. Roxy) A method for producing a glycidyl benzoate ester. 4. General formula (IV):(In the formula, n represents a number of 1 to 2, and Mⁿ Is 1 or 2
Represents a valent cation) is represented by para- (perfluoroalkenylene)
D) reacting benzoic acid with epihalogenhydrin
Para- (perfluoroalkenyloxy) an which is characterized by
Process for producing glycidyl benzoate ester.