JPH029848A - Novel diamine - Google Patents

Abstract

NEW MATERIAL:A diamine shown by the formula (X is >C=0 or >SO2). EXAMPLE:4,4'-Bis[3-(4-imino-alpha-alpha'-dimethylbenzyl)phenoxy]diphenyl ketone. USE:Useful as a raw material for heat-resistant resins and a curing agent for epoxy resins. Polyimides obtained by using the diamine are soluble in organic solvents and show a low-softening point. PREPARATION:A 4,4'-dihalogenobenzophenone or a 4,4'- dihalogenodiphenylsulfone is reacted with 2-(3-hydroxyphenyl)-2-(4'-aminophenyl) propane in the presence of a base in an aprotic solvent (e.g., N-methyl-2- pyrrolidone is used and amount of solvent used is 1-10 times as much as raw material) at 100-250 deg.C, preferably 120-200 deg.C to give a compound shown by the formula.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel diamine that can be used as a raw material for heat-resistant resins or as a curing agent.

[Conventional technology]

For example, as raw materials for heat-resistant resins such as polyimide, the following formula (n)...
II) in which X is co or SO2.

In addition, the above-mentioned publication discloses a diamine represented by the general formula (n) and an acid dianhydride (for example, pyromellitic dianhydride).
It has been shown that the polyimide obtained from and has excellent moldability and thermal stability, and there are examples of using this polyimide as a molding material, that is, examples of producing a molded article by compressing the polyimide at high temperature, and cases where the polyimide is used as a molding material. An example of using the polyimide as an adhesive, that is, sandwiching the polyimide film between steel plates and compressing them at high temperatures to connect the steel plates is shown.

[Problem to be solved by the invention]

The polyimide obtained using the diamine represented by the above general formula (■) has the advantage of being excellent in thermal stability as described above.In other words, this means that the polyimide has a high glass transition point and a high It has a softening point. Therefore, high-temperature heating is required when using the polyimide as a molding material or as an adhesive.

Therefore, the polyimide is not a practical material when heating at a relatively low temperature is required. Moreover, the polyimide has poor solubility in organic solvents.

In this way, the properties of polyimide depend on its raw material (diamine)
Therefore, in order to solve the above problems, it is desired to develop a new raw material (diamine).

[Means to solve the problem]

The present invention relates to general formula (I) % formula %(I) ).

The diamine represented by the above general formula (I) is 4゜4'-
Dihalogenobenzophenone or 4,4' dihalogenodiphenyl sulfone and 2-(3-hydroxyphenyl)-
It can be produced by reacting 2-(4'-aminophenyl)propane in an aprotic polar solvent in the presence of a base. This manufacturing method will be described in detail below.

The above 4,4'-dihalogenobenzophenone is 4,
4'-dichlorobenzophenone, 4゜4'-difluorobenzophenone, 4,4'-dibromobenzophenone, etc. 4,4'-difluorobenzophenone is preferred from the viewpoint of yield, and 4,4'- Dichlorobenzophenone is preferred. Examples of 4,4'-dihalogenodiphenylsulfone include 4,4'-dichlorodiphenylsulfone and 4,4'-difluorodiphenylsulfone.

4,4'-dibromodiphenyl sulfone and the like can be used, and 4,4'-dichlorodiphenyl sulfone is industrially preferred.

2-(, which is the reaction partner of 4.4'-dihalogenobenzophenone or 4゜4'-dihalogenodiphenylsulfone)
The amount of hydroxyphenyl)-2-(4-aminophenyl)propane used is at least twice the molar amount of dihalogenobenzophenone or dihalogenodiphenylsulfone,
2 to 3 times the molar amount is preferred.

Bases that can be used in the above reaction include alkali hydroxides such as potassium hydroxide and sodium hydroxide, alkali metal carbonates such as potassium carbonate and sodium carbonate, and alkali metal carbonates such as potassium hydrogen carbonate and sodium hydrogen carbonate. Bicarbonate.

Alkali metal alkoxides such as potassium ethoxide and sodium methoxide. The amount of '42N used is approximately equivalent mole to 2-(hydroxyphenyl)-2-(4-aminophenyl)propane, which is 0.9
A molar amount of ~1.2 times is preferred, and a molar amount of 0.9 to 1.0 times is particularly preferred.

Examples of aprotic polar solvents that can be used in the reaction include N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, sulfolane, hexamethylphosphoric triamide, 1, 3-dimethyl-2-imidazolitone, etc., and the amount used is usually 1 to 10 times the amount of the raw material. It is also possible to use a mixture of these solvents with a solvent that is azeotropic with water, such as toluene, benzene, xylene, or chlorobenzene.

The reaction is usually carried out at a temperature of 100 to 250°C, and a temperature of 120 to 2
Preferably, it is carried out at 00°C. The reaction time depends on the raw materials used,
Although it varies depending on the solvent, the product is confirmed by liquid chromatography, etc.

It is sufficient to carry out the reaction until the end of the reaction. Further, as a catalyst, crown ether, cryptand, polyethylene glycol, polyethylene glycol alkyl ether, quaternary ammonium salt, quaternary phosphonium salt, etc. may be used.

General operations in the above reaction include 2-(hydroxyphenyl)-2-(aminophenoxy)propane,
Either a base and a solvent may be placed in a reaction vessel and heated to form a phenol salt, and then dihalogenobenzophenone or dihalogenodiphenylsulfone is added and reacted, or all raw materials are added simultaneously from the beginning and reacted. In addition, if water is generated in the system due to the reaction,
It is preferable to remove water by a method such as blowing nitrogen gas or the like, adding a solvent that is azeotropic with water to cause azeotropic distillation, or the like.

After the reaction is completed, the desired compound can be obtained by pouring the reaction solution into water to precipitate the product, filtering out the salt and then concentrating it, or reprecipitating it with water, etc. .

The diamine represented by the general formula (I) according to the present invention can be used not only as a raw material for heat-resistant resins such as polyimide, polyamide, and polymaleimide, but also as a curing agent for epoxy resins and the like.

〔Example〕

Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these scopes.

Example 1 2-(3-Hydroxyfunyuni/L/) was placed in a four-bottle flask equipped with a cooling tube, thermometer, stirrer, and nitrogen gas introduction tube.
-2-(4'-aminophenyl)propane 45.4g,
Dimethyl sulfoxide 10omQ.

An aqueous solution prepared by dissolving 13 g of water-brewed potassium in the same amount of water to which 120 mu of chlorobenzene was added and dissolved at room temperature was added. Water was produced by heating and stirring while flowing nitrogen gas.

After the water production has stopped, lower the temperature to 100℃ and heat 4,4
21.8 g of '-difluorobenzophenone was added and reacted at 165°C for 4 hours. After cooling to room temperature and removing the precipitate by filtration, the mixture was poured into water to obtain a crude product. The crude product was recrystallized from a toluene-hexane mixed solvent to obtain the target compound 4.41-bis(3-(4-amino-α).

α'-dimethylbenzyl)phenoxy]diphenylketone was obtained. Yield 45.5g, melting point 107-111℃ Liquid chromatography (column: Tosoh Corporation TSK)
Connecting Gel G2000H and G3000H, purity 99.0% (area ratio) using eluent tetrahydrofuran
Met.

The analysis results of this diamine are as follows.

(I) Elemental analysis value (%) C43H*. N20゜CHN Calculated value 81.65 6.33 4.43 Actual value
81,57 6,41 4.32 (2) Absorption position of infrared absorption spectrum (IR) (KBr tablet method, C11-'
) 3460.3390 (amino group) 2970.2870 (methyl group) 1600 (carbonyl group) 1250
(ether group) (3) Nuclear magnetic resonance absorption (NMR) spectral position (D
M SC-ds+ppm) 157 (I2H-multiplet) 4.86 (4H-multiplet) 6.4-7.8 (24H-multiplet) Note) DMS○ means dimethyl sulfoxide.

Example 2 2-(3-hydroxyphenyl)-2- was placed in a four-bottle flask equipped with a cooling tube, thermometer, stirrer, and nitrogen gas introduction tube.
(4'-aminophenyl)propane 68.1g, dimethyl sulfoxide 150mΩ, chlorobenzene 180mA
, 40.75 g of 4,4'-dichlorodiphenylsulfone
, 20.5 g of anhydrous potassium carbonate were charged, and the mixture was heated and stirred under nitrogen gas to produce water. 4 at 165℃
After reacting for an hour, the mixture was cooled to room temperature. The reaction solution was poured into water to obtain a crude product. Recrystallization from a benzene-hexane mixed solvent gave 71.1 g of the target compound 4,4'-bis[3-(4-amino-α,α'-dimethylbenzyl)phenoxyfudiphenylsulfone. Melting point 67-7
Purity by liquid chromatography at 0°C is 99.4%
Met.

The analysis results of this diamine are as follows.

(I) Elemental analysis value (%) C42H4°N20. SCHN
S Calculated value 75,45 5,99 4.19 4.79
Actual value 75,18 6.03 4.02 4.66
(2) IR absorption position (KBrBr method, (n-') 34
50.3390 (amino group) 2970.2870 (methyl group) 1290.1110 (sulfonyl group) 1250
(ether group) (3) NMR spectral position (DMS○-dc+ppm) 1.55 (I2H
- double line) 4.87 (4H-multiple line) 6.4 to 8.0 (24H multiple line) Application example 1 Implemented in a four-loop flask equipped with a stirrer, thermometer, nitrogen gas inlet tube, and downward cooling tube. 3.16 g of 4,4'-bis(3-(4-amino-α,αdimethylbenzyl)phenoxy)benzophenone obtained in Example 1, 2.88 g of bisphenol A bistrimelitate dianhydride, and N-methylpyrrolidone. (NMP) 15mQ and 0.2g of triphenyl phosphite were added and heated to 200°C while flowing nitrogen gas.
A polyimide varnish was obtained by reacting for a period of time. This varnish was poured into water and reprecipitated, ground and dried to obtain polyimide powder. This polyimide has a reduced viscosity (in DMF, concentration 0.
1g/dR1 temperature 30℃) is 0.47d 27g, softening point (load 10kg/cd, Koka type flow tester) is 16
Lydimethylformamide (DMF) N-methylpyrrolidone (NMP) at 5°C and 5% weight loss temperature of 437°C;
It was soluble in dioxane, tetrahydrofuran and methylene chloride at room temperature (at a polyimide concentration of 5% by weight).
).

Application Example 2 The 4,4'- obtained in Example 2 was placed in a four-loaf flask equipped with a stirrer, a thermometer, a calcium chloride tube, and a nitrogen gas introduction tube.
Bis(3-(4-amino-α.

3.34 g of α'-dimethylbenzyl)phenoxy]diphenylsulfone and N,N-dimethylformamide (
Add 20 mQ of DMF and dissolve. Bisphenol A bistrimelitate dianhydride while cooling to below 5°C2.
After adding 88 g little by little.

A polyamic acid varnish was obtained by reacting at 5° C. or lower for 3 hours and at room temperature for 1 hour. To this varnish, 1.3 g of acetic anhydride and 1.0 g of pyridine were added and reacted at room temperature for 3 hours to obtain a polyimide varnish. This varnish was poured into water and reprecipitated, ground and dried to obtain polyimide powder. This polyimide is
Reduced viscosity (in DMF, a degree 0.1 g/d Q, temperature 3
0°C) force 0.33d 27g, softening point (load 10kg
/- and Koka type flow tester) was 162°C.

This polyimide powder was soluble at room temperature in each of DMF, dioxane, tetrahydrofuran, and methylene chloride (polyimide concentration 5% by weight). Further, the 5% weight loss temperature was 432°C.

〔Effect of the invention〕

The diamine according to the present invention is a new compound, and the diamine is useful as a raw material for heat-resistant resins, a curing agent for epoxy resins, etc., and the polyimide obtained using the diamine is soluble in organic solvents and has a low Softening-4:

Claims (1)

[Claims] 1. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (However, in the formula, X is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲Mathematical formula , chemical formula, table, etc.) Diamine represented by ▼).