JPH10298150A - Aromatic diamine compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound useful as a raw material, etc., for a polymer or a thermosetting resin having excellent heat resistance and a low permittivity at the same time. SOLUTION: This aromatic diamine compound is represented by formula I R<1> to R<4> are each H, a 1-6C alkyl or a 1-6C halogenated alkyl ; R<5> and R<6> are each a 1-6C alkyl or a 1-6C halogenated alkyl; (a) and (b) are each an integer of 0-4; [(a)+(b)]>=1}, e.g. 9,9-bis[4-(4-amino-2-methylphenoxy)3- methylphenyl]fluorene. The compound represented by formula I is obtained by carrying out the condensation reaction of a compound represented by formula II with a compound represented by formula III in a molar amount within the range of >=2 times, preferably 2-3 times in the presence of a basic compound in a molar amount of >=2 times based on the compound represented by formula II at usually 1-80 wt.% raw material concentration in an organic solvent at 50-250 deg.C for 0.5-24 hr, providing an aromatic dinitro compound and then reducing the resultant compound with hydrogen gas in the presence of a hydrogenating catalyst in an inert solvent at 20-200 deg.C under atmospheric pressure to 50 kgf/cm<2> pressure.

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, and more particularly to a raw material of a high molecular compound such as polyamide, polyamide imide or polyimide, or a raw material of a thermosetting resin such as epoxy resin or bismaleimide. And aromatic diamine compounds useful as curing agents and the like.

[0002]

2. Description of the Related Art Conventionally, aromatic diamine compounds have been used as raw materials for high molecular compounds such as polyamide, polyamide imide and polyimide, or as raw materials and curing agents for thermosetting resins such as epoxy resins and bismaleimides. In recent years, improvements in heat resistance, water resistance, chemical resistance, electrical characteristics, and the like have been demanded for these polymer compounds and thermosetting resins. In particular, electronic materials such as insulating materials are strongly required to have high heat resistance and low dielectric constant. Various aromatic diamines have been developed to meet such demands, for example, Japanese Patent Publication No. 7-278.
No. 070 proposes an aromatic diamine compound synthesized from bisphenol having a ring structure at a central carbon atom connecting two aromatic rings. However,
Such aromatic diamine compounds are also inadequate in terms of the high heat resistance and low dielectric properties of the resulting polymer compound or thermosetting resin, and further improvements are strongly required for aromatic diamine compounds. ing.

[0003]

An object of the present invention is to provide a polyamide having both excellent heat resistance and low dielectric properties.
New aromatic materials useful as raw materials for high molecular compounds such as polyamideimide and polyimide, or as raw materials and curing agents for thermosetting resins such as epoxy resins and bismaleimide, which have both excellent heat resistance and low dielectric properties. It is to provide a diamine compound.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, a specific aromatic diamine compound has been found to be a polymer having excellent heat resistance and low dielectric properties. It has been found that a material can be produced, and the present invention has been completed.

The gist of the present invention is that the general formula (1)

[0006]

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[In the general formula (1), R ¹ , R ² , R
³ and R ⁴ are each independently a hydrogen atom, having 1 to 6 carbon atoms.
Or a halogenated alkyl group having 1 to 6 carbon atoms, wherein R ⁵ and R ⁶ each independently represent 1 to ⁶ carbon atoms.
6 represents an alkyl group having 6 or a halogenated alkyl group having 1 to 6 carbon atoms, a and b each independently represent an integer of 0 to 4, and satisfy (a + b) ≧ 1. An aromatic diamine compound represented by the formula:

Hereinafter, the present invention will be described in detail. In the general formula (1) representing the aromatic diamine compound of the present invention (hereinafter, referred to as “aromatic diamine compound (1)”),
R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ have 1 to 1 carbon atoms
Examples of the alkyl group 6 include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group,
i-butyl group, sec-butyl group, t-butyl group, n-
Examples include a pentyl group and an n-hexyl group. Examples of the halogenated alkyl group having 1 to 6 carbon atoms include:
Fluoromethyl group, trifluoromethyl group, 2,2,2
-Trifluoroethyl group, pentafluoroethyl group,
3,3,3-trifluoropropyl group, 2,2,3
Examples thereof include a 3,3-pentafluoropropyl group, a heptafluoropropyl group, a chloromethyl group, and a bromomethyl group. Among these groups, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a t-butyl group,
A trifluoromethyl group and the like are preferred.

A preferred specific example of the aromatic diamine compound (1) is 9,9-bis [4- (4-amino-2-
Methylphenoxy) phenyl] fluorene, 9,9-bis [4- (4-amino-2-ethylphenoxy) phenyl] fluorene, 9,9-bis [4- (4-amino-2
-N-propylphenoxy) phenyl] fluorene,
9,9-bis [4- (4-amino-2-i-propylphenoxy) phenyl] fluorene, 9,9-bis [4-
(4-amino-2-t-butylphenoxy) phenyl]
Fluorene, 9,9-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] fluorene,
9,9-bis [4- (4-amino-3-methylphenoxy) phenyl] fluorene, 9,9-bis [4- (4-
Amino-3-ethylphenoxy) phenyl] fluorene, 9,9-bis [4- (4-amino-3-n-propylphenoxy) phenyl] fluorene, 9,9-bis [4- (4-amino-3- i-propylphenoxy) phenyl] fluorene, 9,9-bis [4- (4-amino-3-t-butylphenoxy) phenyl] fluorene,
9,9-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl] fluorene, 9,9-bis [4- (2-amino-3-methylphenoxy) phenyl] fluorene, 9,9-bis Bis [4- (2-amino-4
-Methylphenoxy) phenyl] fluorene, 9,9-
Bis [4- (2-amino-5-methylphenoxy) phenyl] fluorene, 9,9-bis [4- (2-amino-
6-methylphenoxy) phenyl] fluorene, 9,9
-Bis [4- (2-amino-3-ethylphenoxy) phenyl] fluorene, 9,9-bis [4- (2-amino-4-ethylphenoxy) phenyl] fluorene,
9-bis [4- (2-amino-5-ethylphenoxy)
Phenyl] fluorene, 9,9-bis [4- (2-amino-6-ethylphenoxy) phenyl] fluorene,
9,9-bis [4- (2-amino-3-n-propylphenoxy) phenyl] fluorene, 9,9-bis [4-
(2-amino-4-n-propylphenoxy) phenyl] fluorene, 9,9-bis [4- (2-amino-5
-N-propylphenoxy) phenyl] fluorene,
9,9-bis [4- (2-amino-6-n-propylphenoxy) phenyl] fluorene, 9,9-bis [4-
(2-amino-3-i-propylphenoxy) phenyl] fluorene, 9,9-bis [4- (2-amino-4
-I-propylphenoxy) phenyl] fluorene,
9,9-bis [4- (2-amino-5-i-propylphenoxy) phenyl] fluorene, 9,9-bis [4-
(2-amino-6-i-propylphenoxy) phenyl] fluorene, 9,9-bis [4- (2-amino-3
-T-butylphenoxy) phenyl] fluorene, 9,
9-bis [4- (2-amino-4-t-butylphenoxy) phenyl] fluorene, 9,9-bis [4- (2-
Amino-5-t-butylphenoxy) phenyl] fluorene, 9,9-bis [4- (2-amino-6-t-butylphenoxy) phenyl] fluorene, 9,9-bis [4- (2-amino- 3-trifluoromethylphenoxy) phenyl] fluorene, 9,9-bis [4- (2-
Amino-4-trifluoromethylphenoxy) phenyl] fluorene, 9,9-bis [4- (2-amino-5
-Trifluoromethylphenoxy) phenyl] fluorene, 9,9-bis [4- (2-amino-6-trifluoromethylphenoxy) phenyl] fluorene, 9,9-
Bis [4- (4-amino-2-methylphenoxy) -3
-Methylphenyl] fluorene, 9,9-bis [4-
(4-amino-2-ethylphenoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (4-amino-2-n-propylphenoxy) -3-methylphenyl] fluorene, 9,9-bis Bis [4- (4-amino-2
-I-propylphenoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (4-amino-2-t-
Butylphenoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (4-amino-2-trifluoromethylphenoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (4- Amino-2-methylphenoxy) -3-ethylphenyl] fluorene, 9,9-
Bis [4- (4-amino-2-ethylphenoxy) -3
-Ethylphenyl] fluorene, 9,9-bis [4-
(4-amino-2-n-propylphenoxy) -3-ethylphenyl] fluorene, 9,9-bis [4- (4-
Amino-2-i-propylphenoxy) -3-ethylphenyl] fluorene, 9,9-bis [4- (4-amino-2-t-butylphenoxy) -3-ethylphenyl]
Fluorene, 9,9-bis [4- (4-amino-2-trifluoromethylphenoxy) -3-ethylphenyl]
Fluorene, 9,9-bis [4- (4-amino-2-methylphenoxy) -3-n-propylphenyl] fluorene, 9,9-bis [4- (4-amino-2-ethylphenoxy) -3 -N-propylphenyl] fluorene,
9,9-bis [4- (4-amino-2-n-propylphenoxy) -3-n-propylphenyl] fluorene,
9,9-bis [4- (4-amino-2-i-propylphenoxy) -3-n-propylphenyl] fluorene,
9,9-bis [4- (4-amino-2-t-butylphenoxy) -3-n-propylphenyl] fluorene,
9,9-bis [4- (4-amino-2-trifluoromethylphenoxy) -3-n-propylphenyl] fluorene, 9,9-bis [4- (4-amino-2-methylphenoxy) -3 -I-propylphenyl] fluorene,
9,9-bis [4- (4-amino-2-ethylphenoxy) -3-i-propylphenyl] fluorene, 9,9
-Bis [4- (4-amino-2-n-propylphenoxy) -3-i-propylphenyl] fluorene, 9,9
-Bis [4- (4-amino-2-i-propylphenoxy) -3-i-propylphenyl] fluorene, 9,9
-Bis [4- (4-amino-2-t-butylphenoxy) -3-i-propylphenyl] fluorene, 9,9
-Bis [4- (4-amino-2-trifluoromethylphenoxy) -3-i-propylphenyl] fluorene,
9,9-bis [4- (4-amino-2-methylphenoxy) -3-t-butylphenyl] fluorene, 9,9-
Bis [4- (4-amino-2-ethylphenoxy) -3
-T-butylphenyl] fluorene, 9,9-bis [4
-(4-amino-2-n-propylphenoxy) -3-
t-butylphenyl] fluorene, 9,9-bis [4-
(4-amino-2-i-propylphenoxy) -3-t
-Butylphenyl] fluorene, 9,9-bis [4-
(4-amino-2-t-butylphenoxy) -3-t-
Butylphenyl] fluorene, 9,9-bis [4- (4
-Amino-2-trifluoromethylphenoxy) -3-
t-butylphenyl] fluorene, 9,9-bis [4-
(4-amino-2-methylphenoxy) -3-trifluoromethylphenyl] fluorene, 9,9-bis [4-
(4-amino-2-ethylphenoxy) -3-trifluoromethylphenyl] fluorene, 9,9-bis [4-
(4-amino-2-n-propylphenoxy) -3-trifluoromethylphenyl] fluorene, 9,9-bis [4- (4-amino-2-i-propylphenoxy)-
3-trifluoromethylphenyl] fluorene, 9,9
-Bis [4- (4-amino-2-t-butylphenoxy) -3-trifluoromethylphenyl] fluorene,
9,9-bis [4- (4-amino-2-trifluoromethylphenoxy) -3-trifluoromethylphenyl]
Fluorene, 9,9-bis [4- (4-amino-2-methylphenoxy) -3,5-dimethylphenyl] fluorene, 9,9-bis [4- (4-amino-2-ethylphenoxy) -3 , 5-Dimethylphenyl] fluorene,
9,9-bis [4- (4-amino-2-n-propylphenoxy) -3,5-dimethylphenyl] fluorene,
9,9-bis [4- (4-amino-2-i-propylphenoxy) -3,5-dimethylphenyl] fluorene,
9,9-bis [4- (4-amino-2-t-butylphenoxy) -3,5-dimethylphenyl] fluorene,
9,9-bis [4- (4-amino-2-trifluoromethylphenoxy) -3,5-dimethylphenyl] fluorene, 9,9-bis [4- (4-amino-2-methylphenoxy) -3 , 5-Diethylphenyl] fluorene,
9,9-bis [4- (4-amino-2-ethylphenoxy) -3,5-diethylphenyl] fluorene, 9,9
-Bis [4- (4-amino-2-n-propylphenoxy) -3,5-diethylphenyl] fluorene, 9,9
-Bis [4- (4-amino-2-i-propylphenoxy) -3,5-diethylphenyl] fluorene, 9,9
-Bis [4- (4-amino-2-t-butylphenoxy) -3,5-diethylphenyl] fluorene, 9,9
-Bis [4- (4-amino-2-trifluoromethylphenoxy) -3,5-diethylphenyl] fluorene,
9,9-bis [4- (4-amino-2-methylphenoxy) -3,5-di-n-propylphenyl] fluorene, 9,9-bis [4- (4-amino-2-ethylphenoxy) -3,5-di-n-propylphenyl] fluorene, 9,9-bis [4- (4-amino-2-n-propylphenoxy) -3,5-di-n-propylphenyl] fluorene, 9, 9-bis [4- (4-amino-2
-I-propylphenoxy) -3,5-di-n-propylphenyl] fluorene, 9,9-bis [4- (4-amino-2-t-butylphenoxy) -3,5-di-n-
Propylphenyl] fluorene, 9,9-bis [4-
(4-amino-2-trifluoromethylphenoxy)-
3,5-di-n-propylphenyl] fluorene, 9,
9-bis [4- (4-amino-2-methylphenoxy)
-3,5-di-i-propylphenyl] fluorene,
9,9-bis [4- (4-amino-2-ethylphenoxy) -3,5-di-i-propylphenyl] fluorene, 9,9-bis [4- (4-amino-2-n-propyl) Phenoxy) -3,5-di-i-propylphenyl]
Fluorene, 9,9-bis [4- (4-amino-2-i
-Propylphenoxy) -3,5-di-i-propylphenyl] fluorene, 9,9-bis [4- (4-amino-2-t-butylphenoxy) -3,5-di-i-propylphenyl] Fluorene, 9,9-bis [4- (4-
Amino-2-trifluoromethylphenoxy) -3,5
-Di-i-propylphenyl] fluorene, 9,9-bis [4- (4-amino-2-methylphenoxy) -3,
5-di-t-butylphenyl] fluorene, 9,9-bis [4- (4-amino-2-ethylphenoxy) -3,
5-di-t-butylphenyl] fluorene, 9,9-bis [4- (4-amino-2-n-propylphenoxy)
-3,5-di-t-butylphenyl] fluorene, 9,
9-bis [4- (4-amino-2-i-propylphenoxy) -3,5-di-t-butylphenyl] fluorene, 9,9-bis [4- (4-amino-2-t-butyl) Phenoxy) -3,5-di-t-butylphenyl] fluorene, 9,9-bis [4- (4-amino-2-trifluoromethylphenoxy) -3,5-di-t-butylphenyl] fluorene, 9,9-bis [4- (4-amino-2-methylphenoxy) -3,5-di (trifluoromethyl) phenyl] fluorene, 9,9-bis [4-
(4-amino-2-ethylphenoxy) -3,5-di (trifluoromethyl) phenyl] fluorene, 9,9
-Bis [4- (4-amino-2-n-propylphenoxy) -3,5-di (trifluoromethyl) phenyl] fluorene, 9,9-bis [4- (4-amino-2-i-
Propylphenoxy) -3,5-di (trifluoromethyl) phenyl] fluorene, 9,9-bis [4- (4-
Amino-2-t-butylphenoxy) -3,5-di (trifluoromethyl) phenyl] fluorene, 9,9-bis [4- (4-amino-2-trifluoromethylphenoxy) -3,5-di (Trifluoromethyl) phenyl]
Fluorene,

9,9-bis [4- (2-amino-3-methylphenoxy) -3-methylphenyl] fluorene,
9,9-bis [4- (2-amino-4-methylphenoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-amino-5-methylphenoxy) -3-methylphenyl] Fluorene, 9,9-bis [4- (2-
Amino-6-methylphenoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-amino-3
-Trifluoromethylphenoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-amino-4
-Trifluoromethylphenoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-amino-5
-Trifluoromethylphenoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-amino-6
-Trifluoromethylphenoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (3-amino-2
-Methylphenoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (3-amino-4-methylphenoxy) -3-methylphenyl] fluorene, 9,9-
Bis [4- (3-amino-5-methylphenoxy) -3
-Methylphenyl] fluorene, 9,9-bis [4-
(3-amino-6-methylphenoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (3-amino-2-ethylphenoxy) -3-methylphenyl] fluorene, 9,9-bis [ 4- (3-amino-4-ethylphenoxy) -3-methylphenyl] fluorene, 9,
9-bis [4- (3-amino-5-ethylphenoxy)
-3-methylphenyl] fluorene, 9,9-bis [4
-(3-amino-6-ethylphenoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (3-amino-2-n-propylphenoxy) -3-methylphenyl] fluorene, 9,9 -Bis [4- (3-amino-4
-N-propylphenoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (3-amino-5-n-
Propylphenoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (3-amino-6-n-propylphenoxy) -3-methylphenyl] fluorene,
9,9-bis [4- (3-amino-2-i-propylphenoxy) -3-methylphenyl] fluorene, 9,9
-Bis [4- (3-amino-4-i-propylphenoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (3-amino-5-i-propylphenoxy)-
3-methylphenyl] fluorene, 9,9-bis [4-
(3-amino-6-i-propylphenoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (3-
Amino-2-t-butylphenoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (3-amino-
4-t-butylphenoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (3-amino-5-t-
Butylphenoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (3-amino-6-t-butylphenoxy) -3-methylphenyl] fluorene, 9,
9-bis [4- (3-amino-2-trifluoromethylphenoxy) -3-methylphenyl] fluorene, 9,
9-bis [4- (3-amino-4-trifluoromethylphenoxy) -3-methylphenyl] fluorene, 9,
9-bis [4- (3-amino-5-trifluoromethylphenoxy) -3-methylphenyl] fluorene, 9,
9-bis [4- (3-amino-6-trifluoromethylphenoxy) -3-methylphenyl] fluorene and the like can be mentioned.

Among these aromatic diamine compounds (1), 9,9-bis [4- (4-amino-2-methylphenoxy) phenyl] fluorene and 9,9-bis [4-
(4-amino-2-trifluoromethylphenoxy) phenyl] fluorene, 9,9-bis [4- (4-amino-2-methylphenoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (4-amino-2-trifluoromethylphenoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (4-amino-2-methylphenoxy) -3,5-dimethylphenyl] fluorene, 9, 9-bis [4- (4-amino-2-trifluoromethylphenoxy) -3,5-dimethylphenyl] fluorene and the like are particularly preferred.

The aromatic diamine compound (1) is, for example,
A bisphenol compound represented by the following general formula (2);
It can be produced by condensing a nitrohalobenzene compound represented by the following general formula (3) or a dinitrobenzene compound represented by the following general formula (4), and then reducing the resulting aromatic dinitro compound. it can.

[0013]

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[In the general formula (2), R ¹ , R ² , R
³ and R ⁴ are each independently R ¹ ,
It is synonymous with R ² , R ³ and R ⁴ . ]

[0015]

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[0016]

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[In the general formulas (3) and (4), R has the same meaning as R ⁵ and R ⁶ in the general formula (1), and n and m each independently represent an integer of 0 to 4. Is selected so that a and b in the general formula (1) satisfy the above conditions. The bisphenol compound represented by the general formula (2) is described in, for example, JP-A-6-228035 and Research Disclos.
378 , P647-P650 (1995). Preferred specific examples of the bisphenol compound represented by the general formula (2) include 9,9
-Bis (4-hydroxyphenyl) fluorene, 9,9
-Bis (4-hydroxy-3-methylphenyl] fluorene; 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene;

Preferred specific examples of the nitrohalobenzene compound represented by the general formula (3) include 2-chloro-3-
Nitrotoluene, 2-chloro-4-nitrotoluene, 2
-Chloro-5-nitrotoluene, 2-chloro-6-nitrotoluene, 3-chloro-2-nitrotoluene, 3-chloro-4-nitrotoluene, 3-chloro-5-nitrotoluene, 3-chloro-6-nitrotoluene, 4-chloro -2-nitrotoluene, 4-chloro-3-nitrotoluene, 5-chloro-2-nitrotoluene, 2-chloro-3
-Nitrobenzotrifluoride, 2-chloro-4-nitrobenzotrifluoride, 2-chloro-5-nitrobenzotrifluoride, 2-chloro-6-nitrobenzotrifluoride, 3-chloro-2-nitrobenzotrifluoride, 3-chloro-4-nitrobenzotrifluoride,
3-chloro-5-nitrobenzotrifluoride, 3-chloro-6-nitrobenzotrifluoride, 4-chloro-
Examples thereof include 2-nitrobenzotrifluoride, 4-chloro-3-nitrobenzotrifluoride, and 5-chloro-2-nitrobenzotrifluoride.

A preferred specific example of the dinitrobenzene compound represented by the general formula (4) is 4-methyl-
1,2-dinitrobenzene, 4-methyl-1,3-dinitrobenzene, 5-methyl-1,3-dinitrobenzene, 6-methyl-1,3-dinitrobenzene, 2-methyl-1,4-dinitrobenzene , 4-trifluoromethyl-1,2-dinitrobenzene, 4-trifluoromethyl-1,3-dinitrobenzene, 5-trifluoromethyl-1,3-dinitrobenzene, 6-trifluoromethyl-1,3- Examples thereof include dinitrobenzene and 2-trifluoromethyl-1,4-dinitrobenzene.

The condensation reaction of the bisphenol compound represented by the formula (2) with the nitrohalobenzene compound represented by the general formula (3) or the dinitrobenzene compound represented by the general formula (4) is carried out by the nitrohalobenzene compound. The benzene compound or the dinitrobenzene compound is used in an amount of 2 times or more, preferably 2 to 3 times the mole of the bisphenol compound, and the concentration of the reaction raw material in the organic solvent is usually 1 to 3.
80% by weight, preferably 30 to 60% by weight, in the presence of a basic compound, at a temperature of 50 to 250 ° C, preferably 50
The reaction is carried out at 〜180 ° C. for 0.5 to 24 hours. As preferred specific examples of the organic solvent,
Aromatic hydrocarbons such as benzene, toluene and xylene;
Ketones such as acetone and methyl ethyl ketone; 1,2-
Halogenated hydrocarbons such as dichloroethane and chlorobenzene; 1,2-dimethoxyethane, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether,
Ethers such as tetrahydrofuran, 1,3-dioxane, 1,4-dioxane; aprotic polar such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, sulfolane Solvents and the like can be mentioned. These organic solvents can be used alone or in combination of two or more. Examples of the basic compound include an alkali metal hydroxide, an alkali metal bicarbonate, an alkali metal carbonate, and an alkali metal alkoxide compound. These basic compounds can be used alone or in combination of two or more. The amount of the basic compound used is usually at least 2 moles, preferably 2 to 3 moles, based on the bisphenol compound.
The range is twice as high. After the condensation reaction, after removing by-produced salts by filtration, the reaction solution is added to a poor solvent to coagulate the product compound, and then filtered or distilled off the organic solvent to obtain a predetermined solution. An aromatic dinitro compound can be obtained. The obtained aromatic dinitro compound is purified as it is or by recrystallization,
Used for reduction reaction.

The reduction method is not particularly limited. For example, a known method for reducing a nitro group to an amino group, specifically, a metal catalyst such as nickel, palladium, platinum, or the like, In a reaction solvent inert to the reaction in the presence of a supported catalyst supported on an appropriate carrier or a hydrogenation catalyst such as a Raney catalyst such as nickel or copper, 20 to 20
It can be carried out by reducing the aromatic dinitro compound to an aromatic diamino compound at 0 ° C. and a pressure of normal pressure to 50 kgf / cm ² and using hydrogen gas. Examples of the reaction solvent include aliphatic alcohols such as methanol, ethanol, and isopropanol; ethylene glycol monoalkyl ethers such as methyl cellosolve and ethyl cellosolve; aromatic hydrocarbons such as benzene, toluene, and xylene; tetrahydrofuran, dioxane; Ethers such as di-n-propyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, and diethylene glycol diethyl ether; aprotic polar solvents such as N, N-dimethylformamide and N, N-dimethylacetamide. These reaction solvents can be used alone or in combination of two or more. After the reduction reaction, the hydrogenation catalyst is removed from the reaction mixture by filtration or the like, and then the reaction solution is added to a poor solvent to coagulate the resulting compound, followed by filtration or distillation of the reaction solvent. Thereby, an aromatic diamine compound can be obtained. The obtained aromatic diamine compound is used as it is or after being purified by recrystallization or the like.

The aromatic diamine compound of the present invention thus obtained may be a raw material of a high molecular compound such as polyamide, polyamide imide or polyimide, or a raw material of a thermosetting resin such as epoxy resin or bismaleimide or a curing agent. The cured product of the polymer compound and the thermosetting resin has excellent heat resistance and low dielectric properties.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, examples of the present invention will be described,
Embodiments of the present invention will be described more specifically. However,
The present invention is not limited to these examples.

【Example】

Example 1 In a container equipped with a stirrer and a reflux condenser, 9,9-bis (4
-Hydroxy-3-methylphenyl] fluorene37.
85 g (0.1 mol), 37.75 g (0.22 mol) of 2-chloro-5-nitrotoluene, anhydrous potassium carbonate 3
6.49 g (0.264 mol) and 150 ml of N, N-dimethylformamide were charged at 160 ° C.
For 6 hours. Thereafter, the mixture was cooled, and the obtained reaction solution was added to 300 ml of a 1: 1 (volume ratio) mixed solution of water and ethanol to precipitate crystals, followed by filtration and drying, followed by drying of 9,9-bis [4- (4-nitro-2-
Methylphenoxy) -3-methylphenyl] fluorene (64.70 g) was obtained. Then, in a container equipped with a stirrer,
9,9-bis [4- (4-nitro-2-methylphenoxy) -3-methylphenyl] fluorene 60.00 g
(0.0925 mol), 1.0 g of a palladium catalyst supported on carbon black (palladium content: 5% by weight) (manufactured by Nippon Engelhardt Co., Ltd.), and 400 ml of diethylene glycol ethyl methyl ether were charged.
After the atmosphere in the vessel was replaced with nitrogen, the reaction was carried out at 70 ° C. for 8 hours with vigorous stirring while introducing hydrogen gas into the vessel.
After cooling and filtering the reaction solution to remove the catalyst, the reaction solution was added to 4 liters of a 1: 1 (volume ratio) mixed solution of water and ethanol, and the precipitated crystals were filtered and dried to obtain crude crystals. Obtained. Next, the crude crystals were recrystallized from a mixed solution of water and methanol to obtain purified 9,9-bis [4
-(4-Amino-2-methylphenoxy) -3-methylphenyl] fluorene was obtained in an amount of 33.1 g. As shown in FIG. 1, the infrared absorption spectrum (IR) of this aromatic diamine compound has a wave number of 3440 cm ⁻¹ corresponding to the NH bond.
And it showed an absorption at a wavenumber 3373cm ^-1, and absorption at a wavenumber 1217cm ^-1 corresponding to the C-O-C bond.

Example 2 In a vessel equipped with a stirrer and a reflux condenser, 9,9-bis (4
-Hydroxy-3,5-dimethylphenyl] fluorene 28.46 g (0.07 mol), 2-chloro-5-nitrotoluene 26.42 g (0.154 mol), anhydrous potassium carbonate 22.35 g (0.162 mol) , And N,
120 ml of N-dimethylformamide was charged and refluxed at 160 ° C. for 6 hours. Thereafter, the reaction solution was cooled, and the obtained reaction solution was added to 240 ml of a 1: 1 (volume ratio) mixed solution of water and ethanol to precipitate crystals, followed by filtration and drying, followed by drying of 9,9-bis [4- (4-
43.15 g of [nitro-2-methylphenoxy) -3,5-dimethylphenyl] fluorene were obtained. Then, 9,9-bis [4- (4-nitro-) was added to a container equipped with a stirrer.
2-methylphenoxy) -3,5-dimethylphenyl]
42.00 g (0.0621 mol) of fluorene, 0.7 g of a palladium catalyst supported on carbon black (palladium content: 5% by weight) (manufactured by Nippon Engelhardt), and diethylene glycol ethyl methyl ether 280
Milliliter was charged, and the inside of the container was replaced with nitrogen. Then, while introducing hydrogen gas into the container, the mixture was vigorously stirred for 10 minutes.
The reaction was performed at 0 ° C. for 22 hours. Thereafter, 140 ml of N, N-dimethylformamide was added, and the mixture was heated to dissolve the reaction product. Next, the reaction solution was filtered to remove the catalyst, and then 1: 1 of water and ethanol was added.
(Volume ratio) 400 ml of the mixed solution was added, and the mixture was allowed to cool to precipitate crystals, and the precipitated crystals were filtered and dried to obtain crude crystals. Then, the crude crystals were recrystallized from a mixed solution of N, N-dimethylformamide, ethanol and water to give purified 9,9-bis [4- (4-amino-2-methyl-phenoxy) -3, [5-dimethylphenyl] fluorene (19.4 g) was obtained. Infrared absorption spectrum of the aromatic diamine compound (IR), as shown in FIG. 2, the absorption at a wavenumber of 3354cm ^-1, which corresponds to the N-H bond, the wave number 1215 cm ^-1 corresponding to the C-O-C bond
And showed absorption.

Example 3 A container equipped with a stirrer and a reflux condenser was charged with 9,9-bis (4
-Hydroxy-3-methylphenyl] fluorene 30.
28 g (0.08 mol), 39.70 g (0.176 mol) of 2-chloro-5-nitrobenzotrifluoride, 29.19 g (0.211 mol) of anhydrous potassium carbonate, and 150 ml of N, N-dimethylformamide Was refluxed at 160 ° C. for 6 hours. Then cool down,
The obtained reaction solution was mixed with water and ethanol at a ratio of 1: 1 (volume ratio).
After adding to 300 ml of the mixed solution to precipitate crystals, the crystals were filtered and dried to obtain crude crystals. Then, the crude crystals were recrystallized from a mixed solution of N, N-dimethylformamide, ethanol and water to give purified 9,9-bis [4- (4-nitro-2-trifluoromethylphenoxy) -3. [Methylphenyl] fluorene (37.3 g) was obtained. Then, in a container equipped with a stirrer,
9,9-bis [4- (4-nitro-2-trifluoromethylphenoxy) -3-methylphenyl] fluorene 3
6.00 g (0.0476 mol) of a palladium catalyst supported on carbon black (palladium content: 5% by weight)
After 0.6 g (manufactured by Nippon Engelhardt Co., Ltd.) and 240 ml of diethylene glycol ethyl methyl ether were charged and the inside of the container was replaced with nitrogen, the mixture was reacted at 70 ° C. for 7 hours with vigorous stirring while introducing hydrogen gas into the container. Was. After cooling, the reaction solution was filtered to remove the catalyst, and then added to 2.4 liters of a 1: 1 (volume ratio) mixed solution of water and ethanol to precipitate crystals, and the precipitated crystals were filtered. After drying, crude crystals were obtained. Then
The crude crystals were recrystallized from a mixed solution of water and methanol, and purified 9,9-bis [4- (4-amino-2-
21.9 g of trifluoromethylphenoxy) -3-methylphenyl] fluorene were obtained. Infrared absorption spectrum of the aromatic diamine compound (IR), as shown in FIG. 3, the absorption at a wavenumber of 3452cm ^-1 and a wavenumber 3386cm ^-1 corresponding to the N-H bond, corresponding to the C-O-C bond Absorption at a wavenumber of 1225 cm ^-1 .

Example 4 A container equipped with a stirrer and a reflux condenser was charged with 9,9-bis (4
-Hydroxy-3,5-dimethylphenyl] fluorene 28.46 g (0.07 mol), 2-chloro-5-nitrobenzotrifluoride 34.73 g (0.154 mol), anhydrous potassium carbonate 25.54 g (0.5%). 185 mol) and 120 ml of N, N-dimethylformamide, and refluxed at 160 ° C. for 1.5 hours.
After cooling, the resulting reaction solution was added to 240 ml of a 1: 1 (volume ratio) mixed solution of water and ethanol to precipitate crystals, which were then filtered and dried to obtain crude crystals. . Next, the crude crystals were recrystallized from a mixed solution of N, N-dimethylformamide, ethanol and water to give purified 9,9-bis [4- (4-nitro-2).
-Trifluoromethylphenoxy) -3,5-dimethylphenyl] fluorene in an amount of 55.43 g. Then, 48.00 g (0.0621) of 9,9-bis [4- (4-nitro-2-trifluoromethylphenoxy) -3,5-dimethylphenyl] fluorene was placed in a vessel equipped with a stirrer.
Mol), 0.8 g of a palladium catalyst (palladium content 5% by weight) supported on carbon black (manufactured by Nippon Engelhardt Co., Ltd.), and 320 ml of diethylene glycol ethyl methyl ether, and the inside of the container was replaced with nitrogen after the inside of the container was replaced with nitrogen. The reaction was carried out at 70 ° C. for 8 hours with vigorous stirring while introducing hydrogen gas. After cooling, the reaction solution was filtered to remove the catalyst, and then added to 1.5 liter of a 1: 1 (volume ratio) mixed solution of water and ethanol to precipitate crystals, and the precipitated crystals were filtered. After drying, crude crystals were obtained. Next, the crude crystals were recrystallized from a mixed solution of water and ethanol to obtain purified 9,9
-Bis [4- (4-amino-2-trifluoromethylphenoxy) -3,5-dimethylphenyl] fluorene 3
4.6 g were obtained. As shown in FIG. 4, the infrared absorption spectrum (IR) of this aromatic diamine compound has a wave number of 3448 cm ⁻¹ and a wave number of 3394 cm corresponding to the NH bond.
^-1 absorption and wave number 1227c corresponding to C—O—C bond
m- ¹ .

Reference Example (Production of Polyimide) Nitrogen gas was flowed into a vessel equipped with a stirrer, a reflux condenser, and a nitrogen inlet tube, and N, N-dimethylformamide was 27.43.
g, 9,9-bis [4- (4-amino-
3.533 g (6 mmol) of 2-methylphenoxy) -3-methylphenyl] fluorene was added and dissolved sufficiently. Thereafter, 1.309 g of pyromellitic dianhydride (6
(Mmol) was added thereto, and the mixture was reacted with stirring at room temperature for 5 hours to obtain a polyamic acid solution. Next, the solution of the polyamic acid was applied on a SUS304 substrate by spin coating, and then applied at 80 ° C., 140 ° C., and 200 ° C.
While sequentially increasing the temperature to 250 ° C., 300 ° C., at each temperature, heating was performed for 20 minutes to produce a polyimide film. Thereafter, a gold electrode was formed on the polyimide film by mask evaporation to obtain a sample for relative dielectric constant measurement. Using this sample, the relative dielectric constant (ε) was measured as follows. As a result, ε = 2.77, which was a sufficiently low value. <Measurement of relative dielectric constant (ε)> 1 MH of polyimide film
The capacitance at z was measured using an LCR meter 4284A manufactured by Yokokawa Hewlett-Packard Co., Ltd., and the relative dielectric constant (ε) was determined by the following equation. Here, C is the capacitance, d is the thickness of the sample, ε ₀ is the dielectric constant in vacuum, and S is the area of the upper electrode. After the solution of polyamic acid was cast on a glass plate,
While sequentially heating to 40 ° C., 200 ° C., 250 ° C., and 300 ° C., heating was performed at each temperature for 20 minutes to produce a polyimide film, and the glass transition temperature (Tg) and the 5% weight loss temperature (Td5) were determined. Was measured as follows. as a result,
Tg = 312 ° C. and Td5 = 454 ° C., indicating high heat resistance. <Measurement of glass transition temperature (Tg)> Differential scanning calorimeter (DS
According to C), the measurement was performed at a heating temperature of 20 ° C./min in a nitrogen atmosphere. <Measurement of 5% Weight Loss Temperature (Td5)> Using a thermobalance, heating was performed in nitrogen at a heating rate of 10 ° C./min, and the temperature at which 5% weight loss was observed was measured.

[0028]

The aromatic diamine compound of the present invention is useful as a raw material for a high molecular compound such as polyamide, polyamide imide or polyimide, or as a raw material or a curing agent for a thermosetting resin such as an epoxy resin or a bismaleimide. The resulting cured product of the polymer compound and the thermosetting resin has both excellent heat resistance and low dielectric properties, and can be suitably used particularly as an electronic material such as an insulating material.

[Brief description of the drawings]

FIG. 1 is a diagram showing an IR of an aromatic diamine compound obtained in Example 1.

FIG. 2 is a graph showing IR of an aromatic diamine compound obtained in Example 2.

FIG. 3 is a view showing IR of an aromatic diamine compound obtained in Example 3.

FIG. 4 is a graph showing IR of an aromatic diamine compound obtained in Example 4.

Claims (1)

[Claims] 1. A compound of the general formula (1) [In the general formula (1), R ¹ , R ² , R ³ and R ⁴
Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a halogenated alkyl group having 1 to 6 carbon atoms;
⁵ and R ⁶ each independently represent an alkyl group having 1 to 6 carbon atoms or a halogenated alkyl group having 1 to 6 carbon atoms;
a and b are each independently an integer of 0 to 4, and (a +
b) Satisfies ≧ 1. ] The aromatic diamine compound represented by these.