JPH03291282A - Diamine compound - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R1 and R2 are H, halogen, 1-4C alkyl or alkoxy). EXAMPLE:3,9-Bis[4-(4-aminophenoxy)phenyl]-2,4,8,10-tetraoxaspiro[5.5]u ndecane. USE:A raw material for producing resins such as polyamides or polyimides and a curing agent for epoxy resins or maleimide resins. PREPARATION:Pentaerythritol and a hydroxyl group-containing aromatic aldehyde expressed by formula II are subjected to dehydrating condensation to provide a bisphenolic compound expressed by formula III, which is then subjected to condensing reaction with p-chloronitrobenzene. The resultant compound is subsequently reduced.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a novel diamine compound.

More specifically, the present invention relates to novel diamine compounds useful as monomers for polymeric materials, such as raw materials for resins such as polyamides and polyimides, or as curing agents for epoxy resins and maleimide resins.

[Conventional technology and issues]

Conventionally, polyimide resins have excellent properties such as high heat resistance, chemical resistance, electrical properties and mechanical properties.
For example, polyimides obtained from 4,4'-diaminodiphenyl ether and pyromellitic dianhydride are widely used.

However, in recent years, there has been an increasing demand for polyimide resins with low water absorption and excellent mechanical properties such as elongation, and various studies have been conducted (Japanese Patent Laid-Open No. 61-1508
No. 25, No. 61-264028).

However, in any case, a material that maintains the excellent heat resistance of polyimide and also satisfies mechanical properties such as elongation has not yet been obtained.

Therefore, the object of the present invention is to improve the elongation of conventional polyimide. ! 1. It is an object of the present invention to provide a novel diamine that is a preferable Mfl for resins due to its mechanical properties.

[Means to solve the problem]

That is, the present invention provides a diamine compound represented by the following format (1).

[In the formula, R3 and R2 are a hydrogen atom, a halogen atom, or an alkyl group or an alkoxy group having 1 to 4 carbon atoms.] The diamine represented by the general formula (1) of the present invention can be obtained, for example, as follows. It will be done. That is, by dehydrating and condensing pentaerythritol with a hydroxyl group-containing aromatic aldehyde represented by the following form (I[) υn [wherein R1 and R2 are the same as above], a bisphenol compound represented by the following form (III) is obtained. get. The diamine of the present invention can be obtained by subjecting this bisphenol compound and parachloronitrobenzene to a condensation reaction and then reducing the condensation reaction.

This will be explained in more detail below.

The hydroxyl group-containing aromatic aldehyde represented by the general formula (II) used in the present invention is, for example, salicylaldehyde,
Examples include so-hydroxybenzaldehyde, p-hydroxybenzaldehyde, vanillin, syringaldehyde, 3-chloro-4-hydroxybenzaldehyde, and the like.

The condensation reaction between pentaerythritol and hydroxyl group-containing aromatic dialdehyde is carried out using a range of 1.8 to 2.6 moles of hydroxyl group-containing aromatic dialdehyde per 1 mole of pentaerythritol, and a temperature of 80 to 200 ml. The reaction is carried out in a suitable organic solvent in the presence of an acidic catalyst at a temperature in the range of 1 to 20 hours.

Preferred organic solvents include aromatic hydrocarbons such as benzene, toluene and xylene, and halogenated hydrocarbons such as 1,2-dichloroethane and chlorobenzene.

Examples of acidic catalysts include mineral acids such as hydrochloric acid and sulfuric acid, silicic acid,
Organic acids such as para-toluenesulfonic acid are used.

In the condensation reaction between bisphenol and parachloronitrobenzene, the amount of parachlornitrobenzene is 2 to 4 mol, preferably 2 to 2.5 mol, per 1 mol of the bisphenol compound, and the temperature is 50 to 150°C. The reaction is carried out in a suitable organic solvent in the presence of a base for a time ranging from 1 to 10 hours.

Examples of organic solvents include aromatic hydrocarbons such as benzene, toluene, and xylene; ketones such as acetone and MEK;
Halogenated hydrocarbons such as 2-dichloroethane and chlorobenzene, aprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and N-methyl-2-pyrrolidone can be used. These solvents are usually used in an amount of 1 to 10 times the weight of the reaction raw materials.

As the base, for example, alkali metal oxides, hydroxides, carbonates, hydrogen carbonates, hydroxides and alkoxides are used. Although there is no particular strict limitation on the amount of the base used, it is generally 2 to 4 mol, preferably 2 to 2.5 mol, per 1 mol of the bisphenol compound. These bases react with bisphenol to produce phenolate in the reaction system, and are in a dissolved state.

After the reaction is completed, a crude product is obtained by washing the by-product salts with water. Although this crude product can be purified by recrystallization or the like, it is usually directly subjected to a reduction reaction.

Haji Tentan
A reduction catalyst such as a metal catalyst such as palladium or platinum, a supported catalyst, or a Raney catalyst such as nickel or copper is used in a solvent inert to the reaction at a temperature of 20 to 200℃ and a pressure of normal pressure to 50K.
The reaction is carried out at about g/c1.

As the reaction solvent, methanol, ethanol, ituburobanol, methyl cellosolve, ethyl cellosolve, etc. are used.

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

The compound of this invention has an infrared absorption spectrum of 34
It exhibits a characteristic absorption derived from the amino group around 50 cm-', so it can be identified based on this.

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

Trap 111 Into a 114 Tulo flask equipped with a stirrer, thermometer, reflux condenser and Dean-Stark tube, 122 g (1 mol) of rose hydroxybenzaldehyde, 68y (0.5 mol) of pentaerythritol, 500 cc of toluene, 25 cc of dimethylacetamide and para Toluenesulfone M3
y was charged and heated to reflux at 112°C. After confirming that a predetermined amount of water had been produced in 6 hours, the reaction mixture was cooled. Separate the precipitated solid, wash with hot toluene and dry.
-bis(4-hydroxyphenyl)-2,4,8,10
-Tetraoxaspiro[5,5]undecane was obtained. The yield was 103 g (0.3 mol), 60%.

The thus obtained 39-bis(4-hydroxyphenyl)-2,4,8,10-tetraoxaspiro[5
, 5] undecane (68.8 g (0.2 mol)) was charged into a 500 cc 4-turoh flask equipped with a stirrer and a thermometer, and 4-nitrochlorobenzene (94.5° (0.6
mol), 39.5 g (0,6-1 nil) of 85% KOH, and 300 cc of dimethyl sulfoxide were added, and the mixture was heated and stirred at 90° C. for 4 hours. After cooling the reaction mixture, it was added to water 21, and the precipitated solid was separated from F, washed with toluene, and dried.

The obtained 3,9-bis[4-(4'-nitrophenoxy)phenyl)-2,4,8,10tetraoxaspiro[
The yield of 5,5]undecane is 85 g (0,145 mol)
The yield was 73%.

Next, 3,9-bisC4-<
4-nitrophenoxy)phenyl]-2,4,8,10
- Citraoxasbiro C5,5] Unde Rinun 30g (0
, 05 mol), 5% Pd/C3y, toluene 120cc
and 30ee of ethyl alcohol were charged into a 300cc Hastelloy C autoclave, hydrogen gas was introduced, the reaction pressure was 3~5kg/am'', and the reaction temperature was 50~60℃.
When heated and stirred until no absorption was observed, 5
The reaction was completed in time. After cooling, the reaction mixture was filtered and
After removing %Pd/C, the r liquid was concentrated under reduced pressure to obtain a pale brown solid of 3.9-bisC4-(4-aminophenoxy)phenyl]-2,4,8,10-tetraoxaspiro[5 , 5] was obtained. The yield was 86%. The melting point of this compound is 21
The temperature was 3.5-215.5°C. The infrared absorption spectrum of this compound is shown in Figure 1, and the nuclear magnetic resonance spectrum is shown in Figure 2.
As shown in the figure.

In Figure 1, 3.450 cm-': -NH
4I, 235cz-': aromatic ether, 1.07
0 cm-: indicates aliphatic ether, and in FIG. 2, 3,3 ppm Ni CL-15,4P
ppm: = C, 6.5 to 7.4 ppm: each represents a benzene ring.

122g of L-gold Yupara hydroxybenzaldehyde and 1 part of vanillin
After obtaining bisphenol in the same manner as in Example 1 except that the amount was changed to 52 g (1 mol), this was converted into a dinitro compound, and by further reduction, a brown 3,9-bis[4
-(4-aminophenoxy)-3methoxyphenyl)-
2,4,8,10-tetraoxaspiro[5,5]undecane was obtained. The melting point of this compound is 132-136°C
Met.

Moreover, the yield at each stage was as follows.

Bisphenol 86% Dinitro compound 71% Diamine 83% [Effects of the Invention] Since the present invention is configured as described above, a novel diamine can be obtained in high yield. Furthermore, this novel diamine is a compound useful as a monomer for polymeric materials, such as a raw material for polyamide, polyimide, and polyamideimide resin, or as a curing agent for urethane compounds, epoxy compounds, and the like.

[Brief explanation of drawings]

FIG. 1 is an infrared absorption spectrum of the diamine synthesized in Example 1, and FIG. 2 is a nuclear magnetic resonance spectrum.

Claims (1)

[Claims] A diamine compound represented by ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 and R_2 are a hydrogen atom, a halogen atom, or an alkyl group or an alkoxy group having 1 to 4 carbon atoms].