JPH08165272A - Organic fluorine compound - Google Patents

Abstract

PURPOSE: To provide a novel organic fluorine compound which is excellent in resistance to solvents and chemicals and useful as a starting substance for rubber materials, water-repellent and oil-repellent agents and release agents. CONSTITUTION: This organic fluorine compound is expressed by formula I (R<1> f is a divalent perfluoroalkylene, a divalent perfluoropolyether; R<2> f is a monovalent perfluoroalkyl, perfluoroalkyl ether; n is an integer of 1-5), for example, a polymer of an organic fluorine compound of formula II (m+n=35). The compound of formula I is obtained, for example, by reaction of a compound bearing acid fluoride groups on both chain terminals of formula III with a fluorine- containing allylamine of formula IV in the presence of an acid acceptor.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a novel organic material which can be effectively used as a raw material for a rubber material having solvent resistance and chemical resistance, a water / oil repellent agent, a release agent material and the like. It relates to a fluorine compound.

[0002]

2. Description of the Related Art Conventionally, organic fluorine compounds have been used in various fields,
For example, an elastomer is obtained by crosslinking a polymer of an organic fluorine compound with a crosslinking agent, and this is used as a rubber material and a release agent.

However, the elastomer obtained from the conventional organic fluorine compound may not have sufficient solvent resistance and chemical resistance, and an elastomer having more excellent solvent resistance and chemical resistance is desired.

Further, it is more desirable that the elastomer used as a sealant, a molded part or the like has excellent releasability and water / oil repellency.

The present invention has been made in view of the above circumstances.
It is an object of the present invention to provide a novel organic fluorine compound which is excellent in solvent resistance and chemical resistance, and also provides an elastomer having excellent releasability and water / oil repellency.

[0006]

Means for Solving the Problems and Actions The inventors of the present invention have conducted extensive studies to achieve the above-mentioned object, and as a result, for example, a compound represented by the following general formula (2) having an acid fluoride group at both ends and the following general formula: By reacting the fluorine-containing allylamine compound represented by the formula (3) in the presence of an acid acceptor, a novel organic fluorine compound represented by the following general formula (1) can be obtained, and further, this organic fluorine compound However, they have found that an elastomer having a high fluorine content and a low surface energy can be obtained, and thus the present invention has been accomplished.

[0007]

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Therefore, the present invention provides an organic fluorine compound represented by the above formula (1).

The present invention will be described in more detail below. The organic fluorine compound of the present invention is represented by the following general formula (1).

[0010]

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In the above formula (1), R ¹ f is a divalent perfluoroalkylene group or a divalent perfluoropolyether group, and particularly as a divalent perfluoroalkylene group, —C _m F _2m — (where m = 1 to 10, preferably 2 to 6) is preferred, and the divalent perfluoropolyether group is preferably one represented by the following formula.

[0012]

[Chemical 4]

Specific examples of R ¹ f include the following.

[0014]

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As the monovalent perfluoroalkyl group for R ² f, --C _p F _{2p + 1} (provided that p = 1 to 20, preferably 4 to 12).
The linear or branched one represented by is preferable, and the monovalent perfluoroalkyl ether group is preferably the one represented by the following formula.

[0016]

[Chemical 6]

Specific examples of R ² f include the following.

[0018]

[Chemical 7]

In the above formula, n is an integer of 1 to 5, and is preferably 1, 2 or 3 in view of easiness of synthesis, stability and the like.

In the present invention, the above-mentioned organic fluorine compound includes a low viscosity polymer having a viscosity (25 ° C., hereinafter the same) of several tens cs to a solid raw rubber-like polymer.
From the viewpoint of ease of handling, for example, a raw rubber-like polymer is preferably used for a heat-vulcanized rubber, and a polymer having a viscosity of about 100 to 100,000 cs is preferably used for a liquid rubber. If the viscosity is too low, the resulting cured product will have a small elongation as an elastomer, and it may not be possible to obtain balanced physical properties.

The organic fluorine compound of the above formula (1) can be obtained by the following method. That is, for example, a compound represented by the following general formula (2) having an acid fluoride group at both ends and a fluorine-containing allylamine compound represented by the following general formula (3) are reacted in the presence of an acid acceptor such as trimethylamine. Can be synthesized by.

[0022]

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In this case, the ratio of the charged amounts of the compound having an acid fluoride group at both ends of the formula (2) and the fluorine-containing allylamine compound of the formula (3) is not particularly limited, but in terms of mol. Ratio (a) / (b) of the charged amount (a) of the compound of the formula (2) and the charged amount (b) of the compound of the formula (3).
Is preferably 0.5 to 0.2 mol / mol.

The conditions of the above reaction are not particularly limited,
20 to 100 ° C for 1 to 8 hours, preferably 20 to 50 ° C
It is preferable to react for 2 to 4 hours.

Since the organic fluorine compound of the present invention can be an elastomer having a high fluorine content and a low surface energy, it is a material for rubber materials having chemical resistance and solvent resistance, a mold release agent, a water / oil repellent agent, etc. It can be used for various purposes as a raw material for the coating material. For example, an elastomer can be obtained by reacting an organic fluorine compound having both ends blocked with alkenyl groups with a compound having three or more hydroxylyl groups in one molecule in the presence of an addition reaction catalyst. Since this elastomer has a high fluorine content, it is excellent in solvent resistance and chemical resistance, and also has low surface energy and is therefore excellent in releasability, water repellency, and oil repellency. It can be effectively used as a coating material, a release agent, a water / oil repellent, and the like.

[0026]

Industrial Applicability The organic fluorine compound of the present invention can be an elastomer having a high fluorine content and a low surface energy, and is a solvent-resistant and chemical-resistant rubber material material, a release agent, a water-repellent / repellent agent. It is effective as a material for coating materials such as oils.

[0027]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited to the following examples.

Example 1 118.1 g (viscosity: 410 cs; 25 ° C.) of a compound represented by the following formula (4) having an acid fluoride group at both ends was attached to a stir bar, thermometer, Dimroth, and dropping funnel. The mixture was placed in a 200 ml four-necked flask, and a mixture of 25.7 g of fluorine-containing allylamine represented by the following formula (5) and 4.1 g of triethylamine was added dropwise at 20 ° C. with stirring from a dropping funnel.

[0029]

[Chemical 9]

After the dropping, the reaction is carried out at 60 ° C. for 2 hours,
The filtrate obtained by filtering the reaction mixture under pressure is 120 ° C./1
After vacuum stripping with mmHg, 135.9 g of a pale yellow transparent liquid compound was obtained. The obtained compound is
Viscosity 1714 cs (25 ° C), specific gravity 1.848 (25
C.) and the refractive index was 1.3106 (25.degree. C.). The result of IR measurement of this compound is shown in FIG. From FIG. 1, the following absorption was recognized.

[0031] ^{_{1100~1300cm -1 ν CF 1695cm -1 ν C}} = O also was quantified allyl group content of the compound, 0.
It was 029 mol / 100 g, and it was confirmed that the obtained compound was a polymer of an organic fluorine compound represented by the following structural formula (6).

[0032]

[Chemical 10]

Example 2 100.5 g of a compound represented by the following formula (7) having an acid fluoride group at both ends (viscosity: 3120 cs; 25 ° C.) was charged in the same apparatus as in Example 1 and stirred. A mixture of 8.2 g of the fluorine-containing allylamine represented by the above formula (5) and 1.3 g of triethylamine was added dropwise from the dropping funnel at 20 ° C., and the reaction and post-treatment were carried out in the same manner as in Example 1. As a result, 103.8 g of a liquid compound was obtained.

[0034]

[Chemical 11]

The obtained compound has a viscosity of 7083 cs (2
5 ° C), specific gravity 1.890 (25 ° C), refractive index 1.306
4 (25 ° C). The result of IR measurement of this compound is shown in FIG. From FIG. 2, the following absorption was recognized.

1100 to 1300 cm ⁻¹ ν _CF 1695 cm ⁻¹ ν _{C═O Further} , when the amount of allyl group of this compound was quantified, it was found to be 0.
It was 012 mol / 100 g, and it was confirmed that the obtained compound was an organic fluorine compound represented by the following structural formula (8).

[0037]

[Chemical 12]

Example 3 A device similar to that of Example 1 was charged with 118.1 g of a compound represented by the above formula (4) and having an acid fluoride group at both ends, and the mixture was mixed with the following formula (9) from a dropping funnel while stirring. The mixture of 14.5 g of the fluorine-containing allylamine compound represented by
When the mixture was added dropwise at 0 ° C. and reacted and post-treated in the same manner as in Example 1, 128.1 g of a pale yellow transparent liquid compound was obtained.

[0039]

[Chemical 13]

The obtained compound has a viscosity of 1361 cs (2
5 ° C), specific gravity 1.855 (25 ° C), refractive index 1.311
It was 8 (25 degreeC). The result of IR measurement of this compound is shown in FIG. From FIG. 3, the following absorption was recognized.

1100 to 1300 cm ⁻¹ ν _CF 1685 cm ⁻¹ ν _{C═O Further} , when the amount of allyl group of this compound was quantified, it was found to be 0.
It was 031 mol / 100 g, and it was confirmed that the obtained compound was an organic fluorine compound represented by the following structural formula (10).

[0042]

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[Brief description of drawings]

FIG. 1 is a chart showing an IR spectrum of an organic fluorine compound of Example 1.

2 is a chart showing an IR spectrum of the organic fluorine compound of Example 2. FIG.

FIG. 3 is a chart showing an IR spectrum of the organic fluorine compound of Example 3.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical display location C09K 3/18 103 (72) Inventor Koichi Ishida 1 Hitomi, Daiji, Matsuida-cho, Usui-gun, Gunma 10 Shinetsu Chemical Industry Co., Ltd. Silicone Electronic Materials Research Laboratory

Claims (1)

[Claims] 1. An organic fluorine compound represented by the following general formula (1): Embedded image