JPH083124A - Aromatic diamine - Google Patents

Abstract

PURPOSE:To obtain a novel aromatic diamine which is useful as a starting material for resins excellent in resistance to heat and chemicals, and in electric and mechanical characteristics, or as a hardening agent or a modifier. CONSTITUTION:This aromatic diamine is expressed by formula I [Ri (i is 1-4) and Rj (j is 1-4) are each H, an alkyl, a cycloalkyl, an alkoxy, a halogen; Rm and Rn are each H, an alkyl, a halogenated alkyl, phenyl], for example, 1,1- bis[2-(4-aminophenoxy)-5-methylphenyl]methane. The aromatic diamine of formula I is prepared by condensation reaction between a bisphenol of formula II and a p-nitrohalobenzene followed by reduction of the corresponding aromatic dinitro compound. This new compound is useful as a starting chemical for resins, for example, a diisocyanate or a bismaleimide, a starting material for thermoplastic resins such as polyamide, polyimide or polyamideimide or a starting material for thermosetting resins such as epoxy resins.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel aromatic diamine compound, more specifically, a raw material for polymer materials, for example,
Diisocyanate, a raw material for chemical products for resins such as bismaleimide, a raw material for thermoplastic resins such as polyamide, polyimide and polyamideimide, a raw material for thermosetting resins such as epoxy resin, a novel agent useful as a curing agent or a modifier, etc. It relates to an aromatic diamine compound.

[0002]

2. Description of the Related Art Diamine compounds are used as raw materials in the production of thermoplastic resins such as polyamide and polyimide, and thermosetting resins such as polybismaleimide and epoxy resins. With the expansion and development of the above, it has been strongly demanded for those resins to further improve various performances such as heat resistance, water resistance, chemical resistance, electrical characteristics, and mechanical characteristics. In order to meet such demands, a new diamine compound for forming a skeleton structure of a new resin is required.

Conventionally, as such a diamine compound,
Various things have been developed. Such diamine compounds are typically generally represented by the formula _{H 2 N-Ar-O-} Ar-R-Ar-O-Ar-NH 2, here, Ar is a substituent It is a p-phenylene group which may have, R is an alkylene group which may be halogen-substituted, or an aromatic diamine compound having a para-para type structure which is a carbonyl group or a sulfone group, for example, JP-A-57-40450, JP-A-64-6246, JP-A-64-25126, JP-A-64-25127, JP-A 1-22
No. 682, Japanese Patent Application Laid-Open No. 1-238568, Japanese Patent Application Laid-Open No. 3-90052, Japanese Patent Application Laid-Open No. 3-167163.

Such an aromatic diamine compound is said to be useful, for example, as a raw material for a polyamide, a polyimide, an epoxy resin, a bismaleimide compound, a crosslinking agent, a modifier, etc., as described above. . However, despite the development of such various aromatic diamine compounds, it cannot be said to be sufficient for expanding the application fields of polymer materials, which are required to have higher functionality and higher performance. Furthermore, there is a strong demand for the development of new aromatic diamine compounds.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in order to meet the above-mentioned demands, and it is a raw material for chemical products for resins such as diisocyanate and bismaleimide, and polyamide, polyimide and polyamideimide. It is an object of the present invention to provide a novel aromatic diamine compound which is useful as a raw material of a thermoplastic resin such as, a raw material of a thermosetting resin such as an epoxy resin, and a curing agent or a modifier.

[0006]

The novel diamine compound according to the present invention has the general formula (I)

[0007]

Embedded image

(Where Ri (i = 1 to 4) and Rj (j
= 1 to 4) each independently represent hydrogen, an alkyl group, a cycloalkyl group, an alkoxy group or a halogen atom, which may be the same as or different from each other, and Rm and Rm
n independently represents hydrogen, an alkyl group, a halogenated alkyl group or a phenyl group, and even if they are the same as each other,
It may be different. ) Is represented.

That is, the novel aromatic diamine compound according to the present invention has an ortho-ortho type structure in contrast to the above-mentioned para-para type structure.

Specific examples of the aromatic diamine according to the present invention include bis [2- (4-aminophenoxy) phenyl] methane and bis [2- (4-aminophenoxy) -5-methylphenyl]. Methane, bis [2-
(4-Aminophenoxy) -3,5-dimethylphenyl]
Methane, bis [2- (4-aminophenoxy) -3,4,5
-Trimethylphenyl] methane, bis [2- (4-aminophenoxy) -3,5,6-trimethylphenyl] methane, bis [2- (4-aminophenoxy) -5-ethylphenyl] methane, bis [2- (4-Aminophenoxy) -3,5-diethylphenyl] methane, bis [2-
(4-Aminophenoxy) -5-n-propylphenyl] methane, bis [2- (4-aminophenoxy) -5
-Isopropylphenyl] methane, bis [2- (4-aminophenoxy) -3-methyl-5-isopropylphenyl] methane, bis [2- (4-aminophenoxy)-
5-methyl-3-isopropylphenyl] methane, bis [2- (4-aminophenoxy) -5-n-butylphenyl] methane, bis [2- (4-aminophenoxy)-
5-isobutylphenyl] methane, bis [2- (4-aminophenoxy) -5-s-butylphenyl] methane,
Bis [2- (4-aminophenoxy) -3-methyl-5
-T-butylphenyl] methane, bis [2- (4-aminophenoxy) -5-methyl-3-t-butylphenyl] methane, bis [2- (4-aminophenoxy) -3
-Methyl-5-octylphenyl] methane, bis [2-
(4-aminophenoxy) -3-methyl-5-nonylphenyl] methane, bis [2- (4-aminophenoxy)
-5-fluorophenyl] methane, bis [2- (4-aminophenoxy) -5-cyclohexylphenyl] methane, bis [2- (4-aminophenoxy) -3-methyl-5-cyclohexylphenyl] methane, bis [ 2-
(4-Aminophenoxy) -5-methyl-3-cyclohexylphenyl] methane, bis [2- (4-aminophenoxy) -5-phenylphenyl] methane, bis [2-
(4-Aminophenoxy) -3-methyl-5-phenylphenyl] methane, 1,1-bis [2- (4-aminophenoxy) -5-methylphenyl] ethane, 1,1-bis [2- (4 -Aminophenoxy) -3,5-dimethylphenyl] ethane, 1,1-bis [2- (4-aminophenoxy) -5-phenylphenyl] ethane, 1,1-bis [2
-(4-aminophenoxy) -5-methylphenyl] propane, 1,1-bis [2- (4-aminophenoxy)-
3,5-Dimethylphenyl] propane, 2,2-bis [2-
(4-Aminophenoxy) phenyl] propane, 2,2-
Bis [2- (4-aminophenoxy) -3,5-dimethylphenyl] propane, 1,1-bis [2- (4-aminophenoxy) -5-methylphenyl] butane, 1,1-bis [2- (4-Aminophenoxy) -3,5-dimethylphenyl] butane, 2,2-bis [2- (4-aminophenoxy) -3,5-dimethylphenyl] butane, 1,1-bis [2- (4 -Aminophenoxy) -5-methylphenyl] -3-methylpropane, 1,1-bis [2- (4-aminophenoxy) -3,5-dimethylphenyl] -3-methylpropane, 1,1-bis [ 2- (4-aminophenoxy) -3,5-dimethylphenyl] decane, 1,1-bis [2- (4-aminophenoxy) -5-methylphenyl] cyclopentane, 1,1-bis [2- ( 4-Aminophenoxy) -3,5-dimethylphenyl ] Cyclopentane, 1,1-bis [2- (4-aminophenoxy) -5-
Methylphenyl] cyclohexane, 1,1-bis [2-
(4-Aminophenoxy) -3,5-dimethylphenyl]
Cyclohexane, 1,1-bis [2- (4-aminophenoxy) -5-methylphenyl] -3,3,5-trimethylcyclohexane, 1,1-bis [2- (4-aminophenoxy) -3,5 -Dimethylphenyl] -3,3,5-trimethylcyclohexane, 9,9-bis [2- (4-aminophenoxy) -5-methylphenyl] fluorene, 9,9-bis [2- (4-aminophenoxy) Examples thereof include, but are not limited to, -3,5-dimethylphenyl] fluorene.

Such aromatic diamine compounds according to the present invention have the general formula (II)

[0012]

Embedded image

(Where Ri (i = 1 to 4) and Rj (j
= 1 to 4) each independently represent hydrogen, an alkyl group, a cycloalkyl group, an alkoxy group or a halogen atom, which may be the same as or different from each other, and Rm and Rm
n independently represents hydrogen, an alkyl group, a halogenated alkyl group or a phenyl group, and even if they are the same as each other,
It may be different. It can be obtained by condensing a bisphenol compound represented by) and p-nitrohalobenzene to obtain a corresponding aromatic dinitro compound, and then reducing the compound according to a conventional method. Here, as the p-nitrohalobenzene, for example, p-nitrochlorobenzene or p-nitrobromobenzene is preferably used.

Examples of the bisphenol compound used for producing the aromatic diamine compound according to the present invention include bis (2-hydroxyphenyl) methane and bis (2
-Hydroxy-5-methylphenyl) methane, bis (2
-Hydroxy-3,5-dimethylphenyl) methane, bis (2-hydroxy-3,4,5-trimethylphenyl) methane, bis (2-hydroxy-3,5,6-trimethylphenyl) methane, bis (2- Hydroxy-5-ethylphenyl) methane, bis (2-hydroxy-3,5-diethylphenyl) methane, bis (2-hydroxy-5-n-propylphenyl) methane, bis (2-hydroxy-5-isopropylphenyl) Methane, bis (2-hydroxy-
3-methyl-5-isopropylphenyl) methane, bis (2-hydroxy-5-methyl-3-isopropylphenyl) methane, bis (2-hydroxy-5-n-butylphenyl) methane, bis (2-hydroxy-5) -Isobutylphenyl) methane, bis (2-hydroxy-5-s
-Butylphenyl) methane, bis (2-hydroxy-3)
-Methyl-5-t-butylphenyl) methane, bis (2
-Hydroxy-5-methyl-3-t-butylphenyl)
Methane, bis (2-hydroxy-3-methyl-5-octylphenyl) methane, bis (2-hydroxy-3-methyl-5-nonylphenyl) methane, bis (2-hydroxy-5-fluorophenyl) methane, bis (2-hydroxy-5-cyclohexylphenyl) methane, bis (2-hydroxy-3-methyl-5-cyclohexylphenyl) methane, bis (2-hydroxy-3-cyclohexyl-5-methylphenyl) methane, bis (2- Hydroxy-5-phenylphenyl) methane, bis (2-hydroxy-3-methyl-5-phenylphenyl) methane, 1,1-bis (2-hydroxy-5-methylphenyl) ethane, 1,1-bis (2 -Hydroxy-3,5-dimethylphenyl) ethane, 1,1-bis (2-hydroxy-
5-phenylphenyl) ethane, 1,1-bis (2-hydroxy-5-methylphenyl) propane, 1,1-bis (2-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (2 -Hydroxyphenyl) propane,
2,2-bis (2-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (2-hydroxy-5-methylphenyl) butane, 1,1-bis (2-hydroxy-3,
5-dimethylphenyl) butane, 2,2-bis (2-hydroxy-3,5-dimethylphenyl) butane, 1,1-bis (2-hydroxy-5-methylphenyl) -3-methylpropane, 1,1 -Bis (2-hydroxy-3,5-dimethylphenyl) -3-methylpropane, 1,1-bis (2-
Hydroxy-3,5-dimethylphenyl) decane, 1,1-
Bis (2-hydroxy-5-methylphenyl) cyclopentane, 1,1-bis (2-hydroxy-3,5-dimethylphenyl) cyclopentane, 1,1-bis (2-hydroxy-5-methylphenyl) cyclohexane , 1,1-bis (2-hydroxy-5-methylphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,3,5- Trimethylcyclohexane, 9,9-bis (2-hydroxy-5-methylphenyl) fluorene, 9,9-bis (2-hydroxy-
Examples thereof include, but are not limited to, 3,5-dimethylphenyl) fluorene.

These bisphenol compounds can be obtained by a known method in which a phenol and an aldehyde or a ketone are dehydrated and condensed in the presence of an acidic catalyst.
These bisphenol compounds may be separated from the isomers and purified by a usual means such as recrystallization, if necessary.

In the production of a bisphenol compound by such a reaction, a phenol having a substituent at the para-position (4th position) or a para-position (4th position) is used as the phenol, rather than using an unsubstituted phenol. Ortho (2
It is preferable to use phenols each having a substituent at each position) because the number of kinds of isomers produced is reduced. In particular, by using phenols each having a substituent at the para position (4th position) and one ortho position (2nd position),
Preferable results can be obtained because virtually no isomers are produced. However, bis (2-hydroxyphenyl)
This is not the case for methane, since its synthesis and separation and purification methods have already been established.

In the condensation reaction between the bisphenol compound and p-nitrohalobenzene, p-nitrohalobenzene is at least 2 times mol, preferably 2 to 3 times mol, of the bisphenol compound at a temperature of 50 to 250 ° C., preferably. 5,
The reaction is carried out at 0 to 180 ° C. for 1 to 100 hours in an organic solvent in the presence of a basic compound. If necessary, in order to accelerate the reaction, a phase transfer catalyst, a copper catalyst, or the like may be used as a catalyst.

Specific preferred examples of the above reaction solvent include aromatic hydrocarbons such as benzene, toluene and xylene, ketones such as acetone and methyl ethyl ketone, and 1,2.
-Halogenated hydrocarbons such as dichloroethane, chlorobenzene, dimethylformamide, dimethylacetamide,
Dimethyl sulfoxide, N-methyl-2-pyrrolidone,
Sulfolane, 1,3-dimethyl-2-imidazolidinone,
An aprotic polar solvent such as hexamethylphosphonium triamide may be mentioned. These organic solvents are used alone or as a mixture, and usually 1 to 1 relative to the raw materials.
It is used in the range of 0 weight times.

Examples of the basic compound include alkali metal hydroxides, hydrogen carbonates, carbonates and alkoxide compounds. These basic compounds are used alone or as a mixture, usually in a range of 2 times or more, preferably 2 to 3 times, the moles of the bisphenol compound.

As the above-mentioned catalyst, a quaternary ammonium salt, a quaternary phosphonium salt, a cyclic polyether such as crown ether, a nitrogen-containing cyclic polyether such as cryptate, a nitrogen-containing chain polyether, or polyethylene glycol. , Phase transfer catalysts such as alkyl ethers thereof, copper powder, and copper compounds such as copper salts, which may be used alone or as a mixture. These catalysts differ depending on their type, but in general,
0.01 to 200% by weight based on the raw material, preferably 0.1.
It is used in the range of 01 to 10% by weight.

After the condensation reaction, the reaction mixture obtained is washed with water to remove by-produced salts, whereby a condensation reaction product of a bisphenol compound and p-nitrohalobenzene, that is, an intermediate raw material. As a result, crude crystals of the aromatic nitro compound can be obtained. This crude crystal may be recrystallized if necessary, but it is usually subjected to a reduction reaction as it is.

As the above-mentioned reduction method, a known method of reducing a nitro group to an amino group can be used. For example, nickel, metal catalysts such as palladium and platinum, supported catalysts obtained by supporting these metals on an appropriate carrier, or Raney catalysts such as nickel and copper, in a reaction solvent inert to the reaction, at a temperature 20 to 200 ° C., normal pressure to 50
Hydrogen can be used to carry out the reduction reaction of the aromatic nitro compound at about kgf / cm ² .

In the reduction reaction, examples of the organic solvent include aliphatic lower alcohols such as methanol, ethanol and isopropanol, monoalkyl ethers of ethylene glycol such as methyl cellosolve and ethyl cellosolve, toluene, benzene and xylene. The aromatic hydrocarbons, ethers such as tetrahydrofuran and dioxane, or petroleum ethers are used alone or as a mixture.

After the reduction reaction, the catalyst is removed from the obtained reaction mixture by a means such as filtration, and then the solvent is distilled off to obtain a reaction product of an aromatic diamine compound. The aromatic diamine compound according to the present invention can be obtained as a product by separating and purifying by itself or by recrystallization.

[0025]

The novel aromatic diamine compound according to the present invention is represented by the above general formula (I), and is a raw material for polymer materials, for example, raw materials for chemical products for resins such as diisocyanate and bismaleimide, polyamide, It is useful as a raw material for a thermoplastic resin such as polyimide or polyamide-imide, or a raw material for a thermosetting resin such as an epoxy resin, as well as a curing agent or a modifier. In particular, since the novel aromatic diamine compound according to the present invention has an ortho-ortho type structure, for example, it has excellent solubility in various organic solvents, and a resin obtained by using it as a raw material has heat resistance and resistance. It has excellent chemical properties, electrical properties, and mechanical properties.

[0026]

The present invention will be described below with reference to examples.
The present invention is not limited to these examples.

Example 1 22.8 g (0.10 mol) of 1,1-bis (2-hydroxy-5-methylphenyl) methane in a 1 liter four-necked flask equipped with a stirrer, a thermometer and a reflux condenser. , P-nitrochlorobenzene 34.7 g (0.22 mol), potassium carbonate 41.4 g (0.30 mol), copper acetate 1.0 g and dimethylformamide 297 g were charged and reacted at 130 ° C. for 8 hours with stirring. Let

After the reaction was completed, the obtained reaction mixture was cooled, an aqueous methanol solution was added thereto, and the precipitated crystals were separated by filtration to obtain crude crystals. The crude crystals were purified by recrystallization from a mixed solvent of dimethylformamide and methanol to give 1,1
27.2 g of -bis [2- (4-nitrophenoxy) -5-methylphenyl] methane was obtained. Next, 20 g of this aromatic nitro compound, 2 g of Raney nickel and 200 g of dioxane were charged into an autoclave with a stirrer having a capacity of 500 ml, and after purging with nitrogen, hydrogen was injected under pressure. Stirring was continued at a reaction pressure of 5 atm and a temperature of 100 ° C. until hydrogen absorption was not observed.

After completion of the reaction, the obtained reaction mixture was cooled, taken out from the autoclave, the catalyst was filtered off, the solvent was distilled off, an aqueous methanol solution was added to the obtained residue, and the precipitated composition was filtered off. After drying, 16.7 g of the target 1,1-bis [2- (4-aminophenoxy) -5-methylphenyl) methane was obtained.

Purity (liquid chromatography): 98.5
% Mass spectrum molecular ion peak (m / e): 410 Infrared absorption spectrum (cm ^-1 ): Amino group: 3430 Ether group: 1210

Example 2 1,1-bis (2-hydroxy-3,5-) was added to a 1 liter capacity four-necked flask equipped with a stirrer, a thermometer and a reflux condenser.
Dimethylphenyl) decane 57.4 g (0.15 mol), p
-Nitrochlorobenzene (49.6 g, 0.315 mol), potassium carbonate (62.2 g, 0.45 mol), copper acetate (0.5 g) and dimethylformamide (430 g) were charged, and the mixture was stirred for 13
The reaction was carried out at 0 ° C for 30 hours.

After completion of the reaction, the obtained reaction mixture was cooled, water was added thereto, the separated aqueous layer was extracted, and the remaining oil layer was washed with an aqueous methanol solution and separated. Dimethylformamide was distilled off from this oil layer to obtain 90.5 g of resinous 1,1-bis [2- (4-nitrophenoxy) -3,5-dimethylphenyl] decane.

Then, this aromatic nitro compound was reduced in the same manner as in Example 1, the catalyst was filtered off from the obtained reaction mixture, the solvent was distilled off, and the obtained residue was subjected to silica gel column chromatography. After separating and purifying with 1, the solvent was distilled off, and 12.1 g of resinous 1,1-bis [2- (4-aminophenoxy) -3,5-dimethylphenyl] decane was obtained.
I got

Purity (liquid chromatography): 95.0
% Mass spectrum molecular ion peak (m / e): 564 Infrared absorption spectrum (cm ^-1 ): Amino group: 3440 Ether group: 1220

Example 3 Bis (2-hydroxyphenyl) methane 20.0 g (0.1 mol), 48.4% hydroxylation was carried out in a 1-liter four-necked flask equipped with a stirrer, a thermometer and a condenser for distillation. Potassium 2
4.3 g (0.21 mol) and dimethyl sulfoxide 700
After adding g, 350 g of dimethyl sulfoxide was distilled off under reduced pressure at a temperature of 100 ° C. After cooling, 33.1 g (0.21 mol) of p-nitrochlorobenzene was added, and the mixture was stirred under stirring to give 13
The reaction was carried out at 0 ° C for 38 hours.

After the reaction was completed, the obtained reaction mixture was cooled, an aqueous solution of methanol was added thereto, and the precipitated crystals were filtered out to obtain 41.0 g of bis [2- (4-nitrophenoxy) phenyl] methane. Then, the aromatic nitro compound was reduced in the same manner as in Example 1 and treated in the same manner to obtain 16.7 g of bis [2- (4-aminophenoxy) phenyl] methane.

Purity (liquid chromatography): 98.0
% Mass spectrum molecular ion peak (m / e): 382 Infrared absorption spectrum (cm ^-1 ): Amino group: 3430 Ether group: 1210

Example 4 In the same manner as in Example 3 except that 2,2-bis (2-hydroxy-5-s-butylphenyl) propane was used as a raw material, 2,2-bis [2- ( 4-aminophenoxy)
16.2 g of -5-s-butylphenyl] propane was obtained.

Purity (liquid chromatography): 99.1
% Mass spectrum molecular ion peak (m / e): 522 Infrared absorption spectrum (cm ^-1 ): Amino group: 3430 Ether group: 1220

Example 5 In the same manner as in Example 3 except that 1,1-bis (2-hydroxy-5-phenylphenyl) ethane was used as a raw material, 1,1-bis [2- (4- Aminophenoxy) -5
16.9 g of -phenylphenyl] ethane were obtained.

Purity (liquid chromatography): 98.9
% Mass spectrum molecular ion peak (m / e): 548 Infrared absorption spectrum (cm ^-1 ): Amino group: 3440 Ether group: 1230

Claims (1)

[Claims] 1. A compound represented by the general formula (I): (In the formula, Ri (i = 1 to 4) and Rj (j = 1 to 4) are each independently hydrogen, an alkyl group, a cycloalkyl group,
Alkoxy group or halogen atom, which may be the same or different from each other, Rm and Rn each independently represent hydrogen, an alkyl group, a halogenated alkyl group or a phenyl group, and are the same as each other. Alternatively, they may be different. ) An aromatic diamine compound represented by: