JP2002249468A - New tris(4-aminoaryl)aromatic compound and its production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new tris(4-amino)aromatic compound and its production method. SOLUTION: The tris(4-amino)aromatic compound is represented by general formula (I) (wherein Ar is a monocyclic or fused aromatic ring; R1 to R4 which are identical to or different from each other are hydrogen atom, a halogen atom, a lower alkyl group or the like; R5 and R6 which are identical to or different from each other are a lower alkyl group), and the tris(4-amino)aromatic compound is produced by reacting an aniline derivative represented by general formula (II) (wherein R1 to R4 which are identical to or different from each other are hydrogen atom, a halogen atom, a lower alkyl or the like) with a 1,3,5-triisopropenylbenzene in the presence of an acid catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel polyvalent amine useful as a resin raw material and a resin additive, tris (4-amine).
Aminoaryl) aromatic compounds and a method for producing the same.

[0002]

2. Description of the Related Art As tris (4-aminoaryl) aromatic compounds represented by the general formula (I), 1,3,3
5-Tris (1- (4-aminophenyl) -1-methylethyl) benzene was known, but no other compounds were reported (US Pat. No. 3,267,145).

As a raw material necessary for synthesizing various tris (4-aminoaryl) aromatic compounds, a method for producing tris (1-hydroxy-1-methylethyl) benzene has been known. The yield was not high and isolation and purification from by-products was a problem, and there was no rational production method (Japanese Patent Publication No. 7-107002, US 338228).
6). Further, there is no known method for easily producing a raw material such as triisopropenylbenzene or tris (1-chloroalkyl) benzene.

In particular, trifunctional amines are expected to have characteristic physical properties as resin raw materials and additives for urethane and polyimide, but only a small number of compounds have been produced.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel trifunctional amine derivative which shows characteristic physical properties as compared with conventional amines when used as a resin raw material or a resin additive. is there. Another object of the present invention is to provide a method for industrially producing the novel compound.

[0006]

Means for Solving the Problems The present inventors have already reported 1,
A method for effectively producing 3,5-triisopropenylbenzene from 1,3,5-triisopropylbenzene by a dehydrogenation reaction has been completed (Japanese Patent Application No. Hei 11-24467).
0). Further, tri-α-chloroalkylbenzenes,
A method for effectively producing from corresponding trialkylbenzenes by photochlorination has been completed (Japanese Patent Application No. 2001-23).
1308, Japanese Patent Application No. 2001-231309).

The present inventors have conducted intensive studies on the production of trifunctional amines based on these raw materials, and as a result, it has become possible to produce novel tris (4-aminoaryl) aromatic compounds. In addition, we have determined that these tri-α-
When tris (4-aminoaryl) aromatic compounds synthesized from aromatic compounds such as alkenylbenzenes and tri-α-chloroalkylbenzenes as raw materials, when used as a resin raw material or an additive, characteristic properties are reduced. The present invention was completed by finding what can be shown.

That is, the present invention provides (1) tris (4-aminoaryl) aromatic compounds represented by the following general formula (I).

Embedded image (Wherein, Ar represents a monocyclic or condensed cyclic aromatic ring,
R ^{1 to} R ⁴ are the same or different and represent a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a lower alkenyl group, an aralkyl group, or an aryl group, and R ^{5 to} R ⁶ are the same or different and are a lower alkyl group. Represents However, this excludes the case where Ar is a 1,3,5-substituted benzene ring, R ¹ = R ² = R ³ = R ⁴ = hydrogen atom and R ⁵ = R ⁶ = methyl group. )

(2) Tris (4-aminoaryl) aromatic compounds represented by the general formula (II) (1).

Embedded image (Wherein, R ^{1 to} R ⁴ are the same or different and each represent a hydrogen atom (however, excluding the case where R ¹ = R ² = R ³ = R ⁴ = hydrogen atom), a halogen atom, a lower alkyl group, a lower alkoxy group) , Lower alkenyl group, aralkyl group, aryl group)

(3) General formula (III):

Embedded image Wherein R ^{1 to} R ⁴ are the same or different and each represent a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a lower alkenyl group, an aralkyl group, or an aryl group. 3,5-triisopropenylbenzene or 1,3,5-tris (1-hydroxy-1-methylethyl) benzene or 1,3-bis (1-hydroxy-1-methylethyl) -5-isopropenylbenzene or 1,3-diisopropenyl-5
(1-hydroxy-1-methylethyl) benzene or 1,3,5-tris (1-chloro-1-methylethyl)
Reacting a compound selected from the group consisting of benzene in the presence of an acidic catalyst;
^{1 to} R ⁴ are the same or different, and represent a hydrogen atom (R ¹ = R ² = R
³ = R ⁴ = hydrogen atom), a halogen atom, a lower alkyl group, a lower alkoxy group, a lower alkenyl group, an aralkyl group, and an aryl group. A method for producing a tris (4-aminoaryl) aromatic compound represented by the formula:

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. Ar in the formula (I) represents a monocyclic or condensed aromatic ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, and a pyrene ring. The substitution position of the substituent is not particularly limited. Formulas (I) to (II)
In R ^{1 to} R ⁴ of I), a halogen atom is a fluorine atom,
Represents a chlorine, bromine or iodine atom.

As the lower alkyl group, a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group Butyl group, pentyl group, neopentyl group, cyclopentyl group, hexyl group,
Represents a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, or the like.

As the lower alkoxy group, a linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms, for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group,
n-butoxy group, isobutoxy group, tert-butoxy group, n-
It represents a pentyloxy group, an isopentyloxy group, a neopentyloxy group, an n-hexyloxy group, a cyclohexyloxy group, or the like.

The lower alkenyl group is a straight-chain or branched alkenyl group having 2 to 6 carbon atoms, and examples thereof include a vinyl group, an allyl group, an isopropenyl group, a 4-pentenyl group and a 5-hexenyl group. .

The aralkyl group includes an aralkyl group having 7 to 15 carbon atoms, such as a benzyl group, a phenethyl group, a benzhydryl group and a phenylpropyl group.

The aryl group has 6 to 1 carbon atoms.
And 5 aryl groups, for example, a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

The lower alkyl group represented by R ⁵ or R ⁶ in the general formula (I) or (II) is a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. the same thing can be mentioned a lower alkyl group exemplified in ¹ to R ^4.

The aniline derivatives represented by the general formula (III) include aniline, 2-fluoroaniline, 2-chloroaniline, 2-bromoaniline, 2-iodoaniline, 2-chloro-6-methylaniline, and 2-chloro-aniline. 3
-Methylaniline, 2-methylaniline, 2-ethylaniline, 2-tert-butylaniline, 2,6-dimethylaniline, 2-methoxyaniline, 2-ethoxyaniline, 3-methylaniline, 3-ethylaniline, 3
-Fluoroaniline, 3-chloroaniline, 3-bromoaniline, 3-iodoaniline, 3-methoxyaniline, 3-ethoxyaniline, 2,3-dimethylaniline, 2-ethyl-6-methylaniline, 2,6-diisopropyl Aniline, 3-fluoro-2-methylaniline, 3-chloro-2-methylaniline, 2,6-difluoroaniline, 2,3-difluoroaniline, 2,6-
Dichloroaniline, 2,3-dichloroaniline, 2,6
-Dibromoaniline, 2,3-dibromoaniline, 2-
Methoxy-6-methylaniline, 3-fluoro-2-methoxyaniline, 2,6-dichloro-3-methylaniline, 2,3,5,6-tetrachloroaniline and the like can be mentioned.

The raw materials 1,3,5-triisopropenylbenzene and 1,3,5-tris (1-hydroxy-1
-Methylethyl) benzene, 1,3-bis (1-hydroxy-1-methylethyl) -5-isopropenylbenzene, 1,3-diisopropenyl-5- (1-hydroxy-1-methylethyl) benzene, 1,3,5-Tris (1-chloro-1-methylethyl) benzene (hereinafter, these compounds are referred to as “raw material triisopropylbenzene derivatives”) is obtained from 1,3,5-triisopropylbenzene by the following methods. Can be manufactured.

As described above, 1,3,5-triisopropenylbenzene can be obtained in good yield by dehydrogenation reaction.
It can be produced in one step from triisopropylbenzene (Japanese Patent Application No. 11-244670).

1,3,5-tris (1-hydroxy-1
(-Methylethyl) benzene can be produced by air oxidation of 1,3,5-triisopropylbenzene and subsequent reduction (Japanese Patent Publication No. 7-107002, US3382).
286).

1,3-bis (1-hydroxy-1-methylethyl) -5-isopropenylbenzene and 1,3-diisopropenyl-5- (1-hydroxy-1-methylethyl) benzene are 1,3 , 5-tris (1-hydroxy-1-methylethyl) benzene can be produced as a single substance or a mixture by dehydration.

1,3,5-tris (1-chloro-1-methylethyl) benzene can be produced by photochlorination of 1,3,5-triisopropylbenzene or the like (Japanese Patent Application No. 2001-231308, Japanese Patent Application 2001-231
309).

Hereinafter, the method for producing the tris (4-aminoaryl) aromatic compound of the present invention will be described.

Examples of the acid catalyst used for the reaction between the aniline derivative and the starting material triisopropylbenzene derivative include mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid, sulfonic acids such as p-toluenesulfonic acid, Amberlyst-15, and activated clay. And the like. These acids may be used alone or as a mixture of two or more. Solid acids such as activated clay or mineral acids such as hydrochloric acid are particularly preferred from the viewpoint of simplicity of operation.

The amount of the acid catalyst used is 1 to 20 times by mass, preferably 10 to 10 times by mass, and more preferably 20 to 20 times by mass relative to the raw material triisopropylbenzene derivative.
% By mass to 5 times by mass.

Examples of the solvent used in the reaction include aliphatic and alicyclic hydrocarbons such as hexane, heptane, decane and cyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, and those aliphatic or aromatic hydrocarbons. Oxygen-containing, nitrogen-containing or sulfur-containing polar solvents such as halides, dimethylformamide, N-methylpyrrolidone, acetonitrile, dimethylacetamide, dimethylsulfoxide, sulfolane, anisole, and n-butylether, and mixed solvents thereof are used. These solvents may be used alone or as a mixture. The amount of the solvent used affects the solubility of the raw material, but is 3 to 150 times by mass, preferably 5 to 100 times by mass relative to the raw material triisopropylbenzene derivative,
More preferably, it is 10 to 50 times by mass.

The reaction is carried out, for example, as follows. The raw material anilines and the acid catalyst are added to the solvent, and the reaction temperature is adjusted to 10 to 10.
The temperature is adjusted to 300 ° C, preferably 30 to 250 ° C. The reaction pressure may be normal pressure or under pressure. A solution in which the raw material triisopropylbenzene derivative is dissolved in a solvent is added dropwise to the reaction solution. The amount of the aniline used is 1 to 50 times mol, preferably 3 to 30 times mol, more preferably 5 to 2 times mol based on the raw material triisopropylbenzene derivative.
It is 5 times mol.

The dropping time of the raw material triisopropylbenzene derivative solution is 1 to 10 hours, preferably 2 to 5 hours. After completion of the dropping, stirring may be continued at a predetermined temperature. The progress of the reaction is confirmed by liquid chromatography or gas chromatography. After completion of the reaction, the acid catalyst is removed, and excess aniline is removed by distillation or the like.

The obtained target product may be used as it is or may be purified by recrystallization. As a solvent used for recrystallization, any solvent may be used as long as it is an inert solvent.For example, hydrocarbons such as pentane, hexane or heptane, aromatic hydrocarbons such as toluene, xylene or ethylbenzene, methanol, ethanol, and propanol Alternatively, alcohols such as butanol and ethers such as tetrahydrofuran and 1,4-dioxane can be mentioned.
These solvents may be used alone or as a mixture.

Next, a resin composition obtained by using the novel tris (4-aminoaryl) aromatic compound of the present invention will be described.

The novel tris (4-aminoaryl) aromatic compounds of the present invention can be used as various resin compositions or resin modifiers, crosslinking agents, curing agents and the like.

The novel tris (4-aminoaryl) aromatic compounds of the present invention can be used in the production of thermosetting resin compositions. The compositions are made from the novel tris (4-aminoaryl) aromatics and one or more liquid coreactants and optionally other additives.

The liquid co-reactant includes a compound represented by the general formula (I)
And bismaleimides represented by V).

Embedded image (Wherein, R represents a divalent group)

R in the general formula (IV) is, for example, p-phenylene group, m-phenylene group, o-phenylene group or -R-

Embedded image _{(Wherein, -B -: - CH 2 -} , - C (CH 3) 2 -, - O -, - S
-, -SO _2- , -CO-, -NHCO-, -C (CF ₃ ) _2- ) and the like, but are not limited thereto.

Further, a thermosetting resin composition comprising a bismaleimide represented by the general formula (IV) and a diamine,
The novel tris (4-aminoaryl) aromatic compounds according to the invention may be added as crosslinking agents.

The diamines used herein include p
-Phenylenediamine, m-phenylenediamine, 2-
Methyl-m-phenylenediamine, 6-methyl-m-phenylenediamine, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 4,4′-
Diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenylthioether, 3,3′-diaminodiphenylthioether,
4,4'-diaminodiphenylsulfone, 3,3'-
Diaminodiphenylsulfone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone,
4,4′-diaminobiphenyl, 3,3′-diaminobiphenyl, 2,2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) propane,
4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-dimethylbiphenyl, 1,3-bis (3-aminophenoxy) benzene, 4,4'-bis ( Examples thereof include, but are not limited to, 3-aminophenoxy) biphenyl and the like. The compound which is solid at room temperature is heated and used in a molten state.

An organic or inorganic filler may be dispersed in the thermosetting resin composition to increase the strength of the thermosetting resin composition. Further, the thermosetting resin composition may be used as a prepreg resin by impregnating an organic or inorganic fiber cloth.

The novel tris (4-aminoaryl) aromatic compounds according to the present invention can be used as curing agents for epoxy resins. It may be used alone, or may be used by adding a curing accelerator such as a phenol or a tertiary amine or an auxiliary such as a pigment, a filler, a bulking agent, a reinforcing agent, or an inert solvent.

Examples of the epoxy resin in which a novel tris (4-aminoaryl) aromatic compound can be used as a curing agent include bisphenol type epoxy resin, alicyclic epoxy resin, polyglycidyl ether of polyhydric alcohol and the like. Is mentioned.

When the epoxy resin curing agent of the present invention is used, the epoxy resin and the curing agent of the present invention may be mixed as they are, or may be mixed in the presence of a solvent.
Either method may be used. Curing may be performed at room temperature or may be performed while heating.

The epoxy resin curing agent of the present invention may be used in combination with other known curing agents such as polyamidoamine, aliphatic polyamine, polyamine having an aromatic ring, and alicyclic polyamine. The epoxy resin curing agent of the present invention is used together with an epoxy resin, for example, a paint,
It can be used for civil engineering and construction resins and adhesives, adhesives, casting resins, and laminates.

The novel tris (4-aminoaryl) aromatic compounds according to the present invention can be added to a polyimide resin composition or a urethane prepolymer as a crosslinking agent to improve the properties of the resin.

[0044]

EXAMPLES Examples are shown below, but the present invention is not limited to these examples.

Example 1 1,3,5-Tris (1-
Synthesis of (4-amino-3-chlorophenyl) -1-methylethyl) benzene 1.98 g of activated clay and 2-
127.57 g (1.00 mol) of chloroaniline, 1,
20.87 g (purity: 95% by mass, 0.10 mol) of 3,5-triisopropenylbenzene was charged and stirred at 210 ° C. for 3 hours. The mixture was cooled to 100 ° C. and the activated clay was filtered off. The filtrate is subjected to high performance liquid chromatography (HPL
As a result of the analysis in C), 1,3,5-tris (1- (4-amino-3-chlorophenyl) -1-methylethyl) benzene as a target product was produced at a reaction yield of 86.5%. . After distilling off excess 2-chloroaniline under reduced pressure,
42.8 g (purity: 95% by mass, 70 mmol, isolation yield: 70%) of the desired product was obtained. The physical properties of the target are as follows. Melting point 108.0-109.0 ° C ¹ H-NMR (CDCl ₃ ) δ: 1.46 (s, 18H), 3.90 (s, 6H), 6.
60 (d, 3H, J = 8.4 Hz), 6.75 (dd, 3H, J = 8.4, 1.9
Hz), 6.84 (s, 3H), 7.01 (d, 3H, J = 1.9 Hz) FD-mass 528 (M ⁺ )

Example 2 1,3,5-Tris (1-
Synthesis of (4-aminophenyl) -1-methylethyl) benzene An aniline 3 was placed in a 100 ml three-necked reaction vessel under a nitrogen atmosphere.
0 ml and 10.36 g (80 mmol) of aniline hydrochloride were added, and the temperature was raised to 150 ° C. While stirring the reaction solution,
5.0 g (purity 75% by mass, 12.2 mmol) of 3,5-tris (1-chloro-1-methylethyl) benzene was added to 150
After addition at 0 ° C, the mixture was stirred at 180 ° C for 5 hours. The reaction solution was cooled to 150 ° C., and added to a mixed solvent of 200 ml of hexane and 400 ml of ethyl acetate to precipitate crystals.
After cooling to 15 ° C., the crystals were filtered off. The obtained crystals were reslurried in 200 ml of water to remove aniline hydrochloride. After filtering off the crystals, 50 ml of ethyl acetate
And 50 ml of water and neutralized using a 10% aqueous sodium hydroxide solution. After separating the organic phase, the solvent was concentrated. Recrystallization was performed using hexane, and the desired product, 1,3,5-tris (1- (4-aminophenyl) -1) was obtained.
3.88 g of (-methylethyl) benzene was obtained (purity: 98% by mass, 8.1 mmol, isolation yield: 66%). The physical properties of the target product are as follows. Melting point 143.3-143.8 ° C ¹ H-NMR (CDCl ₃ ) δ: 1.52 (s, 18H), 3.53 (br, 6H),
6.55 (dd, 6H, J = 8.6,1.9 Hz), 6.89 (s, 3H), 6.91
(dd, 6H, J = 8.6, 1.9 Hz) FD-mass 477 (M ⁺ )

Example 3 2.54 g of 1,3,5-triisopropenylbenzene instead of 1,3,5-tris (1-chloro-1-methylethyl) benzene as a raw material
(Purity: 95% by mass, 12.2 mmol), except that the same reaction procedure as in Example 2 was carried out.
3.83 g of 5-tris (1- (4-aminophenyl) -1-methylethyl) benzene (98% by mass, 8.
0 mmol, isolation yield 65%).

[0048]

According to the present invention, a novel trifunctional amine derivative exhibiting characteristic physical properties as compared with conventional amines as a resin raw material and a resin additive, and an industrial production method thereof can be provided. .

Claims (3)

[Claims] 1. A method of producing tris (4-) represented by the following general formula (I):
Aminoaryl) aromatic compounds. Embedded image (Wherein, Ar represents a monocyclic or condensed cyclic aromatic ring,
R ^{1 to} R ⁴ are the same or different and represent a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a lower alkenyl group, an aralkyl group, or an aryl group, and R ^{5 to} R ⁶ are the same or different and are a lower alkyl group. Represents However, this excludes the case where Ar is a 1,3,5-substituted benzene ring, R ¹ = R ² = R ³ = R ⁴ = hydrogen atom and R ⁵ = R ⁶ = methyl group. ) 2. The tris (4-aminoaryl) aromatic compounds according to claim 1, represented by the general formula (II). Embedded image (Wherein, R ^{1 to} R ⁴ are the same or different and each represent a hydrogen atom (however, excluding the case where R ¹ = R ² = R ³ = R ⁴ = hydrogen atom), a halogen atom, a lower alkyl group, a lower alkoxy group) , Lower alkenyl group, aralkyl group, and aryl group.) 3. A compound of the general formula (III): Wherein R ^{1 to} R ⁴ are the same or different and each represent a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a lower alkenyl group, an aralkyl group, or an aryl group. 3,5-triisopropenylbenzene or 1,3,5-tris (1-hydroxy-1-methylethyl) benzene or 1,3-bis (1-hydroxy-1-methylethyl) -5-isopropenylbenzene or 1,3-diisopropenyl-5
(1-hydroxy-1-methylethyl) benzene or 1,3,5-tris (1-chloro-1-methylethyl)
Reacting a compound selected from the group consisting of benzene in the presence of an acidic catalyst;
^{1 to} R ⁴ are the same or different, and represent a hydrogen atom (R ¹ = R ² = R
³ = R ⁴ = hydrogen atom), a halogen atom, a lower alkyl group, a lower alkoxy group, a lower alkenyl group, an aralkyl group, and an aryl group. A method for producing a tris (4-aminoaryl) aromatic compound represented by the formula: