JPH0571582B2 - - Google Patents

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 monomer for polycondensation polymer materials, such as polyimide, polyamide,
Alternatively, it is used as a base component for polyamideimide and the like. In particular, wholly aromatic condensation polymer materials are attracting attention as structural materials and electronic materials that require heat resistance, and the introduction of perfluoroalkyl groups into these materials improves moisture resistance and lowers the dielectric constant. Therefore, it can be expected to 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] The present invention provides a novel fluorine-containing aromatic diamine having a perfluoroalkyl group as a substituent as a result of studies on compounds useful as base components for polyimides, polyamides, etc. This led to the present invention. That is, the present invention is based on the general formula

[Formula, R ₁ and R ₂ are perfluoroalkyl groups having 1 to 10 carbon atoms or hydrogen, and R ₁ = R ₂ = H
This is a novel fluorine-containing aromatic diamine represented by

Nitrobenzene represented by [Formula, R ₁ and R ₂ are perfluoroalkyl groups having 1 to 10 carbon atoms or hydrogen, R ₁ = R ₂ = H, and X is a halogen atom] General formula obtained by condensation with

It can be obtained by reducing a dinitro compound represented by the formula (wherein R ₁ and R ₂ are the same as in the general formula ()). The nitrobenzenes () used here are:
4-halogeno-2-perfluoroalkylnitrobenzene, 4-halogeno-3-perfluoroalkylnitrobenzene, 4-halogeno-2,5-bisperfluoroalkylnitrobenzene, specifically 4-chloro-3-trifluorobenzene. Fluoromethylnitrobenzene, 4-chloro-3-nonafluorobutylnitrobenzene, 4-chloro-2-trifluoromethylnitrobenzene, 4-chloro-
Examples include 2-nonafluorobutylnitrobenzene and 4-chloro-2,5-bistrifluoromethylnitrobenzene. The amount used is preferably 1.05 to 1.2 times the mole of 2,2-bis(4-hydroxyphenyl)hexafluoropropane. The bases used include alkali metal hydroxides, carbonates, hydrogen carbonates, hydrides, etc., and specifically, sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate,
Examples include sodium hydride. The amount of the base is 1 to 5 times equivalent, preferably 1 to 3 times equivalent, relative to 2,2-bis(4-hydroxyphenyl)hexafluoropropane. The aprotic polar solvent used includes amides, sulfoxides, sulfones, nitriles, and specifically N-methylformamide,
Examples include N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, dimethylsulfone, sulfolane, 1-methyl-2-pyrrolidinone, and benzonitrile. The amount of solvent used is 1 to 10 times the weight of the raw material. As for the reaction method, when using hydroxide as a base, water is produced, so 2,2-bis(4-hydroxyphenyl)hexafluoropropane and a solvent such as benzene, toluene, xylene, or chlorobenzene are used. Preparation, 2,2-bis (4-
A method of preparing an alkali metal salt of hexafluoropropane (hydroxyphenyl), removing the resulting water as an azeotrope with the solvent, converting the solvent to an aprotic polar solvent, and condensing it with nitrobenzenes; When using something other than hydroxide, there are two methods in which 2,2-bis(4-hydroxyphenyl)hexafluoropropane, nitrobenzenes, a base, and an aprotic polar solvent are all added to carry out the condensation in one step. There is a way. Reaction temperature is 100-150℃, preferably 120-140℃
It is. 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 solvent for the reduction reaction is not limited as long as it is soluble in the dinitro compound and is inert to the raw materials and products, and includes alcohols, ethers, and esters, specifically methanol, ethanol, and ether. , tetrahydrofuran, ethyl acetate, butyl acetate, and the like. As the catalyst, a metal catalyst generally used for catalytic reduction may be used, and from an industrial perspective, it is preferable to use a palladium catalyst. The amount used is 0.1 to 5% by weight, based on the dinitro compound. 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/cm ² . The reaction is carried out by charging raw materials, a catalyst, and a solvent, and introducing hydrogen at a predetermined temperature with stirring. The end point of the reaction can be determined by the amount of hydrogen absorbed. After the reaction is completed, the finished product is separated by filtration 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)hexafluoropropane was placed in a 500 ml four-necked flask equipped with a thermometer, stirrer, and condenser.
4-chloro-5-trifluoromethylnitrobenzene 108.g (0.48 mol), potassium carbonate 67.2g,
300 ml of N,N dimethylacetamide was charged, and the temperature was raised to 130°C in about 1 hour. The reaction was continued at this temperature for 1 hour. After cooling to room temperature, KCl,
K ₂ CO ₃ etc. were separated. 200ml of liquid while stirring
water was added to precipitate the dinitro compound, filtered, washed with methanol, and dried to obtain yellow crystals of 2,2-bis[(4-nitro-2-trifluoromethylphenoxy)phenyl]hexafluoropropane. I got it. Yield 121.3g (yield 84.9%), purity 97.8
% (HPLC), m.P172.0~173.7℃, ¹⁹ Fnmr, δCFCl ₃ -62.19ppm (S, 6F, -CF ₃ ) -64.43ppm (S, 6F, CF ₃ + CF ₃ ) This 2,2- Bis[(4-nitro-2-trifluoromethylphenoxy)phenyl]hexafluoropropane 104 g (0.14 mol), 5% pd/Clg,
200 g of ethyl acetate was charged into a 1SUS pressure 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 filtered off and the solvent was distilled off to obtain a yellow wax-like substance of 2,2-bis[(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane. Ta. Yield 98.7g (yield 96.5%), purity 99.5% (HPLC),
A portion was treated with n-hexane and crystallized. m.
p58.0 to 60.5℃, ¹⁹ Fnmr, δCFCl ₃ -61.01ppm (S, 6F, -CF ₃ ) -63.57ppm (S, 6F, CF ₃ + CF ₃ ) Example 2 Thermometer, stirrer, cooling tube 3.36 g (0.01 mol) of 2,2-bis(4-hydroxyphenyl)hexafluoropropane in a 50 ml four-necked flask,
4-chloro-2-trifluoromethylnitrobenzene 5.4g (0.024mol), potassium carbonate 3.36g,
15 ml of N,N-dimethylacetamide was charged and reacted for about 1 hour. After cooling to room temperature, KCl, K ₂
CO ₃ etc. were classified. When 50 ml of water was added to the filtrate while stirring, the dinitro compound turned into an oil.
Water was removed by decantation, the dinitro compound was dissolved in diethyl ether, magnesium sulfate was added, and the mixture was dried overnight. The ether was distilled off to obtain 6.9 g of a yellow oily crude product. Purity 79.4%
(HPLC) 2,2-bis[(4
-nitro-3-trifluoromethylphenoxy)
A wax-like substance of phenylhexafluoropropane was obtained. Yield 5.0g (yield 70.2%), purity 94.2%
(HPLC) ¹⁹ Fnmr, δCFCl ₃ -59.78ppm (S, 6F, -CF ₃ ) -63.43ppm (S, 6F, CF ₃ + CF ₃ ) The infrared absorption spectrum of this compound is shown in FIG. The above, 2,2-bis[(4-nitro-3-
Trifluoromethylphenoxy)phenyl]hexafluoropropane 5.0g (0.007mol) 5% pd/
0.01 g of C and 10 g of ethyl acetate were charged into a 50 ml SUS 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 filtered off and the solvent was distilled off to obtain a yellow wax-like substance of 2,2-bis[(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane. Ta. Yield 4.35g (yield 95.0%), purity 94.6%
(HPLC), ¹⁹ Fnmr, δCFCl ₃ -62.64ppm (S, 6F, -CF ₃ ) -63.53ppm (S, 6F, CF ₃ + CF ₃ ) The infrared absorption spectrum of this product is shown in Figure 2. . [Effects of the Invention] The novel fluorine-containing aromatic diamine of the present invention is excellent as a base component for polyimide, polyamide, etc. The polymer obtained thereby has excellent heat resistance, improved moisture resistance, and dielectric properties. This is an extremely useful tool that can reduce the rate.

[Brief explanation of drawings]

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 (1)

_[ Scope _of Claims] ₁ General _formula
A novel fluorine-containing aromatic diamine represented by 2 2,2-bis( _{4 -} hydroxyphenyl)hexafluorobropane and the general formula The nitrobenzenes represented by ) are condensed in an aprotic solvent in the presence of a base to form the formula [formula] (wherein R ₁ and R ₂ have the same meanings as in the general formula ()). obtain a dinitro compound represented by
The general formula [Chemical formula] (wherein 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