JPH08157411A - Organic fluorine compound and its production - Google Patents

Abstract

PURPOSE: To provide a new organic fluorine compound useful as an intermediate for the synthesis of a fluorine-containing polymer or a reagent for introducing a fluorine-group. CONSTITUTION: This organic fluorine compound is expressed by formula I (Rf is a perfluoroalkyl, a perfluoroalkylene or a uni- or bivalent perfluoropolyether group; n is 1 or 2), e.g. the perfluoroacid fluoride of formula II. The compound of formula I can be produced by reacting an organic fluorine compound of formula III with a vinyl Grignard reagent of formula IV (X<1> is a halogen). This new organic fluorine compound is easily producible by the reaction with a Grignard reagent. Since the fluorine-content in the molecule can be selected over a wide range, the compound is extremely useful as a modification reagent for polymers, etc., as well as a monomer for the synthesis of a fluorine- containing polymer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel organic fluorine compound, and more particularly to an organic fluorine compound useful as an intermediate or a fluorine group-introducing reagent when synthesizing a fluorine-containing polymer, and a method for producing the same.

[0002]

2. Description of the Related Art Fluorine atom-containing polymers are not only improved in heat resistance, chemical resistance and weather resistance with the introduction amount of fluorine atoms, but are also excellent in electrical characteristics, have a non-adhesive surface, and have a friction coefficient. While exhibiting various properties such as low, there is a drawback that the formability and creep resistance deteriorate. Therefore, in recent years, polysynthetic monomers such as fluorinated allyl compounds have been favored for the purpose of modifying a polymer by appropriately introducing a fluorine atom or synthesizing a polymer having an appropriate fluorine atom. Therefore, there has been a demand for the development of new fluoropolymers and novel monomers useful for increasing the possibility of modification for various applications.

[0003]

SUMMARY OF THE INVENTION Accordingly, the present inventors
From the viewpoint of containing a large number of fluorine atoms, as a result of diligent studies on a fluorine-containing monomer having an unsaturated carbon-carbon double bond in the molecule, as a result of reacting an organic fluorine compound with a vinyl Grignard reagent, the objective can be easily achieved. The inventors have found that the compound having

Therefore, the first object of the present invention is to provide a monomer for synthesizing a fluoropolymer containing a large amount of fluorine atoms. The second object of the present invention is to
An object of the present invention is to provide an organic fluorine compound having a large amount of fluorine atoms, which is suitable for imparting specificity to a polymer by fluorine atoms. A third object of the present invention is to provide an organic fluorine compound which has a large amount of fluorine atoms in the molecule and also has a carbon-carbon double bond.

[0005]

The above objects of the present invention have been achieved by an organic fluorine compound represented by Rf (COCH ₂ CH ₂ CH = CH ₂ ) _n and a method for producing the same. Rf in the above general formula is, for example, a perfluoroalkyl group having 1 to 50 carbon atoms, preferably 2 to 30 carbon atoms, a perfluoroalkyl group having 1 to 20 carbon atoms, preferably 2 to 10 carbon atoms, And monovalent perfluoro (poly) having 3 to 200 carbon atoms, preferably 5 to 120 carbon atoms
A monovalent group which may contain an ether-bonded oxygen atom selected from an ether group or a divalent perfluoro (poly) ether group having 3 to 400 carbon atoms, preferably 6 to 200 carbon atoms. Alternatively, it is a divalent fluorocarbon group, and n is 1 or 2.

The organic fluorine compound of the present invention has the general formula Rf
It can be easily produced by reacting an organic fluorine compound such as perfluorocarboxylic acid halide or perfluorocarboxylic acid ester represented by (COX) _n with a vinyl Grignard reagent. However, Rf and n in the above formula are the same as Rf and n described above, X is a halogen atom such as chlorine, bromine, iodine, or OR (R is a methyl group, an ethyl group, a propyl group, an isopropyl group) , Butyl group, isobutyl group, ter-butyl group, hexyl group, cyclohexyl group and other alkyl groups, phenyl group, tolyl group, xylyl group and other aryl groups, vinyl group, allyl group,
An organic fluorine compound represented by a monovalent hydrocarbon group having usually 1 to 8 carbon atoms, which is exemplified by an alkenyl group such as a propenyl group, an isopropenyl group, a butenyl group, an aralkyl group such as a benzyl group, and the like. .

The reaction of Rf (COX) _n with a vinyl Grignard reagent is represented by the following chemical formula 1.

Embedded image The above reaction is performed at 0 to 100 ° C., preferably 20 to 50 ° C.
And proceed quantitatively. In this reaction, an organic fluorine compound represented by Rf (COX) _n and vinyl Grignard reagent CH ₂
= CHMgX ¹ is charged with CH ₂ == CO ₂ groups in the reaction system
The molar ratio of CHMgX ¹ is 1.8 to 4 times, especially 2.2 to 3.
It is preferable to set it to be about 0 times the mole.

Specific examples of the organic fluorine compound of the present invention thus obtained are shown in the following chemical formula 2. However, <n> and <a + b> in the formula are n and (a + b), respectively.
Represents the average value of.

Embedded image The organic fluorine compound of the present invention can be made into a fluorine-containing polymer by polymerizing its vinyl bond, and is also useful as a fluorine group-introducing reagent for a compound or polymer having a group that reacts with a vinyl group.

[0009]

INDUSTRIAL APPLICABILITY The organofluorine compound of the present invention can be easily obtained by reaction with a Grignard reagent, and the fluorine content in the molecule can be widely selected. It is extremely useful not only as a monomer but also as a modifying reagent for polymers and the like.

[0010]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. Example 1. 25 g of magnesium (1.03 mol) was charged into a 1-liter four-necked flask equipped with a stirrer, a thermometer, a dry ice cooler, a dropping funnel and a nitrogen introducing tube,
After heating with a dryer to dry magnesium while ventilating nitrogen, the flask was cooled while ventilating nitrogen, and 300 g of THF (tetrahydrofuran) was charged.

Vinyl bromide was introduced into the flask through a drying tube. As the vinyl bromide was introduced, magnesium began to react and exothermic. Vinyl bromide 119.3g
(1.12 mol) was introduced over 2 hours, followed by aging for 1 hour. After the aging, 186.8 g (0.375 mol) of perfluoro acid fluoride represented by the following chemical formula 3 was dropped.

Embedded image

Since heat was generated at the same time as perfluorofluoride was dropped, 186.
8g was dripped over 1 hour. When the reaction mixture was filtered and then distilled under reduced pressure, the boiling point was 68 to 69 ° C./8 mmHg.
And the fraction of which the refractive index is 1.3115 (25 ° C) is 81.0 g.
(0.152 mol) (yield 40.4%) was obtained. It was confirmed by ¹ H-NMR, ¹⁹ F-NMR, IR and elemental analysis that this fraction was a compound represented by the following chemical formula 4.

[Chemical 4]

¹ H-NMR (TMS standard) δ 2.44 ppm (t, C (= O) -CH ₂ , 2H) δ 2.7-3.0 ppm (m, C-CH ₂ -C =, 2H) δ 4. _{8~5.2ppm (m, C = CH 2} , 2H) δ5.4~6.1ppm (m, C-CH = C, 1H) 19 F-NMR (CF 3 COOH standard) φ: -3.6~ -5.1ppm (a, 13F) φ: -52.68ppm (b, 2F) φ: -58.49pp (c, 1F) φ: -67.83ppm (d, 1F) The above a to d are It represents the position of a fluorine atom represented by the following chemical formula 5.

Embedded image

IR (see FIG. 1) νc = o: 1760 cm ⁻¹ νc = c: 1645 cm ⁻¹

Example 2. 25 g (1.03 mol) of magnesium was charged into a 1-liter four-necked flask equipped with a stirrer, a thermometer, a dry ice cooler, a dropping funnel, and a nitrogen introducing tube, and was heated with a drier while aeration of nitrogen to magnesium After drying, the flask was cooled while nitrogen was aerated, and 300 g of THF was charged.

Vinyl bromide was introduced into the flask through a drying tube. As the vinyl bromide was introduced, magnesium began to react and exothermic. Vinyl bromide 119.7 g
(1.12 mol) was introduced over 2 hours, followed by aging for 1 hour. After the aging, 173.0 g (0.187 mol) of perfluoro acid fluoride represented by the following chemical formula 6 was dropped.

[Chemical 6]

Since heat was generated at the same time as the addition of perfluorofluoride, 186.
8g was dripped over 1 hour. When the reaction mixture was filtered and distilled under reduced pressure, the boiling point was 136 to 138 ° C / 2 mm.
Fraction 79.Hg, refractive index 1.3197 (25 ° C.) 79.
4 g (0.0797 mol) (yield 42.6%) was obtained. This fraction was confirmed by ¹ H-NMR, ¹⁹ F-NMR, 1R and elemental analysis to be a compound represented by the following chemical formula 7.

[Chemical 7]

[0018] ¹ H-NMR (TMS standard) δ2.43ppm (t, C (= O) -CH 2, 2H) δ2.7~3.0ppm (m, C-CH 2 -C =, 2H) δ4. 8-5.2 ppm (m, C = CH ₂ , 2H) δ 5.4-6.1 ppm (m, C-CH = C, 1H)

¹⁹ F-NMR (CF ₃ COOH standard) φ: −3.4 to −6.4 ppm (a, 25 F) φ: −58.38 ppm (b, 2F) φ: −67.77 ppm (c, 3F) ) In addition, the above a to c represent the position of the fluorine atom represented by the following chemical formula 8.

Embedded image

[0020] IR (see Figure ^{2) νc = o: 1765cm -1} νc = c: 1650cm -1

[Brief description of drawings]

FIG. 1 is an infrared spectrum diagram of an organic fluorine compound synthesized in Example 1.

FIG. 2 is an infrared spectrum diagram of an organic fluorine compound synthesized in Example 2.

Claims (2)

[Claims] 1. An organic fluorine compound represented by the general formula, Rf (COCH ₂ CH ₂ CH═CH ₂ ) _n , wherein Rf in the above formula is a perfluoroalkyl group, a perfluoroalkylene group, and a monovalent group. Alternatively, it is a group selected from divalent perfluoropolyether groups, and n is 1 or 2. 2. A method for producing an organic fluorine compound according to claim 1, which comprises reacting an organic fluorine compound represented by the general formula Rf (COX) _n with a vinyl Grignard reagent; Rf in the formula is a group selected from a perfluoroalkyl group, a perfluoroalkylene group, and a monovalent or divalent perfluoro (poly) ether group, and X is a halogen atom or an —OR group (provided that R is a monovalent hydrocarbon group) and n is 1 or 2.