JP2883925B2 - Fluorine-containing glycerin derivative - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel fluorine-containing glycerin derivative useful as a surface modifier or the like that exerts a sustained effect.

2. Description of the Related Art Conventionally, surface modifiers having a fluorine-containing group have been used in various paints, inks, leveling agents, anti-fog and anti-fog agents for the purpose of dispersing polymers, especially fluorine-based polymers.

However, the conventional fluorine-based surface modifier has a problem that the sustainability of the effect is inferior due to the low functionality of the surface-active group, and its improvement has been demanded.

Problems to be Solved by the Invention The present invention has been made to provide a fluorine-containing compound useful as a surface modifier or the like that exhibits a sustained effect.

Means for Solving the Problems That is, the present invention provides a compound represented by the following general formula (I): (In the formula, AO represents an oxyethynylene group and / or an oxypropylene group, and at least one of R _{1 to} R ₃ + n is a fluorinated group C ₆ F ₁₁ −, C ₉ F ₁₇ − or C ₉ F _17. O ・ C ₆ H ₄・ CO
-Represents the rest of the hydrogen atoms, m ₁ , m ₂ ,... M ₃ + n represents a number of 0 to 30, and n represents a number of 0 or 1 to 9). .

In the general formula (I), AO represents an oxyethylene group and / or an oxypropylene group, at least one of R _{1 to} R ₃ + n represents the following fluorine-containing group, and the rest represents a hydrogen atom: C _{6 F 11 -, C 9 F 17} O or _{C 9 F 17 O · C 6} H 4 · CO- in this case, C ₆ F ₁₁ - are derived from a dimer or trimer of hexafluoropropene as - or C ₉ F ₁₇ Exemplary residues are those having the following structure: In the general formula _{(I), m 1, m} 2 ..., m 3 + n is 0
30, preferably 5 to 20, and n is 0 or 1 to
9, preferably a number from 0 to 5.

The fluorine-containing glycerin derivative represented by the general formula (I) is obtained, for example, by adding an alkylene oxide to a glycerin represented by the following general formula (I ′), and converting the active hydrogen at the terminal of the adduct to the above-mentioned fluorine-containing group. Manufactured by substituting: (In the formula, n has the same meaning as described above.) In this case, the properties of the fluorinated glycerin derivative can be adjusted by appropriately selecting the substitution ratio of the terminal active hydrogen of the adduct by the fluorinated group. .

The production method of the fluorine-containing glycerin derivative represented by the general formula (I) is not particularly limited, but a preferable production method is to add ethylene oxide and / or propylene oxide to glycerin, diglycerin, triglycerin or the like or any mixture thereof. And reacting the adduct with a dimer or trimer of hexafluoropropene or p-perfluorononenyloxybenzoic acid or its acid chloride.

The general formula is that the reaction of the adduct with the dimer or trimer of hexafluoropropene is carried out in a non-aqueous polar solvent in the presence of a basic catalyst at a temperature of 0 to 50 ° C.

Non-aqueous polar solvents include acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N-
Examples thereof include methylpyrrolidone, dimethylsulfoxide, diethyl ether, dioxane, and tetrahydrofuran, and acetonitrile, N, N-dimethylformamide and N, N-dimethylacetamide are preferred.

As the basic catalyst, potassium carbonate, sodium carbonate, triethylamine, trimethylamine and N, N-
Dimethylaniline and the like are exemplified, but potassium carbonate and triethylamine are preferred.

The reaction between the above adduct and p-perfluorononenyloxybenzoic acid is carried out, for example, by using an acid catalyst (hydrochloric acid, nitric acid, p-
The general formula is that the reaction is carried out at a temperature of 50 to 150 ° C. in the presence of toluenesulfonic acid or the like.

Further, the reaction of the above adduct with p-perfluorononenyloxybenzoic acid acid chloride is carried out, for example, in the presence of a basic reaction accelerator (triethylamine, pyridine and the like).
The reaction may be performed at a temperature of 50 ° C., or at a temperature of 50 to 150 ° C. using a reaction accelerator.

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

Example 1 The following compound (Ia) was prepared by the following procedure according to the formulation shown in Table 1 below.

Compound (1) 104.7 g (0.1 mol), potassium carbonate 55.2 g (0.4 mol) and acetonitrile 400 m in a four-necked flask (1000 ml) equipped with a thermometer, a condenser and a dropping funnel.
l, add hexafluoropropene trimer C ₉ F ₁₈ 180 g
(0.4 mol) was gradually added dropwise over about 30 minutes, and after completion of the addition, stirring was continued at room temperature for about 12 hours.

The potassium carbonate was filtered off from the reaction mixture, and the solvent was distilled off using an evaporator.
226 g of a) were obtained (yield: 82%).

 The physical properties of compound (Ia) are shown in Table 2 below.

(However, ₅ of CH ₂ CH ₂ O ₅ indicates an average value.) Examples 2 to 5 The following compound (Ib) according to the procedure shown in Table 1 below and according to the procedure of Example 1. ~ (Ie) was prepared.

Table 2 below shows the physical properties of the compounds (Ib) to (Ie).

Example 6 In a four-necked flask (500 ml) equipped with a thermometer, a condenser and a dropping funnel, 19.28 g (0.01 mol) of compound (2), 4.04 g (0.04 mol) of triethylamine and chloroform 2
Then, a solution prepared by dissolving 21.86 g (0.04 mol) of C ₉ F ₁₇ O.C ₆ H ₄ .COCl in 50 ml of chloroform was gradually added dropwise over a period of about 30 minutes. Time continued.

Triethylamine hydrochloride precipitated from the reaction mixture was separated by filtration, and the filtrate was washed twice with about 200 ml of water, and then the organic phase was separated. The organic phase was dried over anhydrous magnesium sulfate and filtered, and the filtrate was concentrated using an evaporator to obtain 39 g of the following compound (If) (yield: 98%).

 Table 2 below shows the physical properties of the compound (If).

Effect of the Invention Since the fluorine-containing glycerin derivative according to the present invention has a multifunctional high-functional fluorine-containing group, it has various properties such as antifouling property, weather resistance, anti-fog anti-fog property, chemical resistance, and flame retardancy. And so on. Therefore, the glycerin derivative is a polymer, particularly a fluorine-based polymer surface modifier, anti-fog and anti-fog agent,
Particularly useful as a leveling agent and the like.

Continuation of front page (72) Inventor Masaaki Yamamoto 1-1, Oikecho, Kosai-cho, Koga-gun, Shiga Prefecture Neos Co., Ltd. (56) References JP-A-1-125338 (JP, A) (58) Fields investigated (Int) .Cl. ⁶ , DB name) C07C 43/12 C08G 65/32 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. A compound of the general formula (I): (In the formula, AO represents an oxyethynylene group and / or an oxypropylene group, and at least one of R _{1 to} R ₃ + n is a fluorinated group C ₆ F ₁₁ −, C ₉ F ₁₇ − or C ₉ F _17. O ・ C ₆ H ₄・ CO
, M represents a hydrogen atom, m ₁ , m ₂ ,... M ₃ + n represents a number of 0 to 30, and n represents a number of 0 or 1 to 9).