JPH01246247A - Novel fluorine-containing aromatic diamine and production thereof - Google Patents

Abstract

NEW MATERIAL:A fluorine-containing aromatic diamine shown by formula I (Rl and R2 are 1-10C perfluoroalkyl or H and a case wherein R1=R2=H is omitted). EXAMPLE:2,2-Bis[(4-amino-2 trifluoromethylphenoxy)phenyl]hexafluoropropane. USE:Useful as a basic component of polyimide, polyamide, etc. A polymer obtained from the diamine has excellent heat resistance, can improve water vapor resistance and reduce permittivity and is extremely useful. PREPARATION:2,2-Bis(4-hydroxyphenyl)hexafluoropropane is condensed with a nitrobenzene shown by formula II (X is halogen) in an aprotic solvent in the presence of a base to give a dinitro compound shown by formula III. Then the compound shown by formula III is reduced to give a compound shown by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel fluorine-containing aromatic diamine.

Diamine is an important compound as a hexamer in polycondensation polymer materials, and is used as a base component of polyimide, polyamide, polyamideimide, and the like. In particular, wholly aromatic condensation polymer materials are used as structural materials and materials that require heat resistance.
It is attracting attention as an electronic material, and because it contains perfluoroalkyl, it is expected that it will impart favorable physical properties, especially for electronic material applications. The present invention was made from the above viewpoint, and provides a novel aromatic diamine having a perfluoroalkyl group as a substituent.

[Prior Art] Hitherto, no fluorine-containing aromatic diamine having a perfluoroalkyl group as a substituent has been known.

[Means for Solving the Problems] As a result of studies on compounds useful as base components for polyimides, polyamides, etc., the present invention obtained a novel fluorine-containing aromatic diamine having a perfluoroalkyl group as a substituent. This led to the invention.

That is, the present invention is based on the general formula (wherein R, R, are perfluorocarbon atoms having 1 to 10 carbon atoms!
2,2-bis(4-hydroxyphenyl)hexafluoropropane In the presence of a base, the general formula (wherein R,, R. is a perfluoroalkyl group having 1 to 10 carbon atoms or hydrogen, not R, = R, = H, and X is a halogen atom) Reducing a dinitro compound represented by the general formula (wherein R,, R, is the same as in the case of -maximum (II)) obtained by condensation with a nitrobenzene represented by in an aprotic solvent. It can be obtained by

The nitrobenzenes (■) used here are 4-halogeno-2-perfluoroalkylnitrobenzene, 4-
halogeno-3-perfluoroalkylnitrobenzene,
4-halogeno-2,5-bisperfluoroalkylnitrobenzene, specifically 4-chloro-3-trifluoromethylnitrobenzene, 4-chloro-3-nonafluorobutylnitrobenzene, and 4-chloro-2-trifluorobutylnitrobenzene. Fluoromethylnitrobenzene, 4-chloro-2-nonafluorobutylnitrobenzene, 4-chloro-2.5-
Examples include bistrifluoromethylnitrobenzene. The amount used is 2,2-bis(4-hydroxyphenyl)
The amount is preferably 1.05 to 1.2 times mole relative to hexafluorobroban.

The bases used include alkali metal hydroxides, carbonates, hydrogen carbonates, hydrides, etc., specifically sodium hydroxide, potassium hydroxide, lithium hydroxide,
Examples include potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, and sodium hydride. The amount of base is 2,2-bis(4-hydroxyphenyl)
The amount is 1 to 5 times equivalent, preferably 1 to 31 sonic equivalents, relative to hexafluorobroban.

The aprotic polar solvents used include amides, sulfoxides, sulfones, nitriles, and specifically N-methylformamide, N-methylformamide, and N-methylformamide.

Examples include N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, dimethylsulfone, sulfolane, l-methyl-2-pyrrolidinone, and benzonitrile. The amount of solvent is 1-10 to the raw material.
Weight times are used.

As for the reaction method, when using hydroxide as a base, water is produced, so 2,2-bis(4-hydroxyphenyl)hexafluorobrobane and a solvent such as benzene, toluene, xylene, or chlorobenzene are prepared. ,2
．． After preparing the alkali metal salt of 2-bis(4-hydroxyphenyl)hexafluorobroban and removing the resulting water as an azeotrope with the solvent, the solvent is converted to an aprotic polar solvent and condensed with nitrobenzenes. method and when using a base other than hydroxide, 2.2
There are two methods in which -bis(4-hydroxyphenyl)hexafluorobrobane, nitrobenzenes, a base, and an aprotic polar solvent are all charged and condensation is carried out in one stage.

The reaction temperature is 100-150°C, preferably 120-1
40'C.

Further, a reaction time of 1 to 2 hours is sufficient.

After the reaction is completed, the base and the generated alkali halide are removed and water is added to the reaction solution to obtain a dinitro compound.

The desired new diamine is synthesized by catalytic reduction of this dinitro compound.

The dinitro compound is soluble as a solvent for the reduction reaction, and the raw material,
The material is not limited as long as it is inert to the product, and examples include alcohols, ethers, and esters, such as methanol, ethanol, ether, tetrahydrofuran, ethyl acetate, butyl acetate, and the like.

As a catalyst, a metal catalyst used for catalytic reduction may be used for -a, and it is preferable to use a palladium catalyst industrially.
It is 5%.

The reaction temperature is preferably in the range of 40 to 100°C, and the reaction pressure is preferably in the range of 4 to 10 kg/-.

The reaction is carried out by charging raw materials, a catalyst, and a solvent, and introducing hydrogen at a predetermined temperature with stirring.9 The end point of the reaction can be determined by the amount of hydrogen absorbed.

After the reaction is completed, the catalyst is removed and the solvent is distilled off to obtain the desired new diamine.

Hereinafter, the present invention will be explained in detail with reference to Examples.

Example 1 67.2 g (0.2 mol) of 2,2-bis(4-hydroxyphenyl)hexafluorobroban, 4
-chloro-5-trifluoromethylnitrobenzene 10
8, g (0,48 mol), potassium carbonate 67.2 g
,N.

Pour 300 ml of N dimethylacetamide and raise the temperature to 130'C in about 1 hour.
Allowed time to react. After cooling to room temperature, KCI, K2CO3
etc. were separated by 0. While stirring the four liquids, 200ml of water was added to precipitate the dinitro compound, which was separated, washed with methanol, and dried to give 2,2-bis[(4-nitro-2-trifluoromethylphenoxy)phenyl]hexane. Yellow crystals of fluorobroban were obtained.

Our company 121.3g (yield 84.9%), purity 97.8
% (HPLC), 1. PL72.0~173.7°C
1'/Fnmr, δCFCI 3-62.19 ppm
(S, 6F, -CF3) LF Iko 2,2-bis[(4-nitro-2-trifluoromethylphenoxy)phenyl]hexafluorobroban 1
04g (0.14 mol), 1g of 5% Pd/C, and 200g of ethyl acetate were placed in a 1ρ SUS pressurized reactor, and the reaction was carried out for 2 hours until a predetermined amount of hydrogen was consumed. After cooling to room temperature, the catalyst was removed and the solvent was distilled off to give 2,2-bis[(4-amino-2-trifluoromethylphenoxy)].
A yellow waxy substance of phenyl]hexafluoropropane was obtained. Yield 98.7g (yield 96.5%), purity 9
9.5% (HPLC), a portion was treated with n-hexane and crystallized. m, p 58.0-60.5" 3.36 g of 2,2-bis(4-hydroxyphenyl)hexafluorobroban in a 50 m (l) four-eye flask equipped with a C1 thermometer, stirrer, and condenser (0 ,01 mol), 4-chloro-2-trifluoromethylnitrobenzene 5°4g
(0,024 mol), potassium carbonate 3.36 g, N
, 15 ml of N-dimethylacetamide was added, and the mixture was allowed to react for about 1 hour. After cooling to room temperature, KCL K2
When 50 mA of water was added to the 9-mouth solution from which C03 and the like had been removed while stirring, the dinitro compound became an oily substance. The water was removed by decantation, the dinitro compound was dissolved in diethyl ether, magnesium sulfate was added, and the mixture was dried overnight. After distilling off the ether, a yellow oily crude product 6 was obtained.
9g was obtained. A waxy substance of 2,2-bis[(4-nitro-3-trifluoromethylphenoxy)phenyl]hexafluorobroban was obtained by column chromatography with methylene chloride/n-hexane-171 (purity 79.4% (IPLC)). Ta. Yield 5, Og (Yield 70.2%) Purity 94.2% (HPLC) The infrared absorption spectrum of this compound is shown in FIG. Above, 2.2-bis[(4-nitro-3-trifluoromethylphenoxy)phenyl]
Hexafluoropropane 5.0g (0,007 mol)
5% Pd/CO, 01g, ethyl acetate lOg 50m
The mixture was charged into a pressure-resistant reactor, and the reaction was carried out for about 3 hours until a predetermined amount of hydrogen was consumed. After cooling to room temperature, the catalyst was separated and the solvent was distilled off to give 2,2-bis[(4-amino-3-trifluoromethylphenoxy)phenyl].
A yellow wax of hexafluoropropane was obtained.

Yield 4.35g (yield 95.0%), purity 94.6
% (HPLC), /lFnmr, δCFCI:s 62.
64 PPII (S, 6F, -CF3) -63,
53 ppm (S, 6F, '-CF3) The infrared absorption spectrum of this product is shown in FIG.

[Effects of the Invention] The novel fluorine-containing aromatic diamine of the present invention is composed of polyimide,
It is excellent as a base component for polyamides and the like, and the resulting polymer has excellent heat resistance, and is extremely useful as it can improve moisture resistance and lower dielectric constant.

Patent Applicant: Central Glass Co., Ltd. Procedural Manual (Method): 1989, 5th, 10th, 1989) Commissioner of the Patent Office: Yoshi 1) Written by Tsuyoshi Tsuyoshi\ 2. Name of the Invention: Novel fluorine-containing aromatic diamine and Its manufacturing method 3,
Relationship with the case of the person making the amendment Patent applicant address 5253 Okiube, Ube City, Yamaguchi Prefecture Name (2)
20) Central Glass Co., Ltd. Representative Kakuhei Wada 4, Agent address 8-3-607 Horinouchi-chome, Suginami-ku, Tokyo Date of dispatch: April 25, 1999 6. Subject to amendment + 1) " In Item 7 of Brief Explanation of Drawings J and Its Contents, change the line after "-111" in the 8th line of the 12th line of the Statement of Contents of the Amendment and insert the following sentence.

[Brief explanation of the drawing]

FIG. 1 shows an infrared absorption spectrum of a nitrate which is an intermediate for producing the compound of the present invention. Moreover, FIG. 2 shows the infrared absorption spectrum of the compound of the present invention. ”

Claims (2)

[Claims] (1) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1 and R_2 are perfluoroalkyl groups having 1 to 10 carbon atoms or hydrogen, and R_1=R_2=H
A novel fluorine-containing aromatic diamine represented by (2) 2,2-bis(4-hydroxyphenyl)hexafluoroblobane and the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, R_1 and R_2 are the same as in the general formula (I) (X is a halogen atom) is condensed in an aprotic solvent in the presence of a base to form the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) (In the formula, R_1 and R_2 have the same meanings as in the general formula (I)), and then reduce it. There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) (Formula where R_1 and R_2 are perfluoroalkyl groups having 1 to 10 carbon atoms or hydrogen, and R_1=R_2=H
A method for producing a novel fluorine-containing aromatic diamine represented by