JPH06279390A - Triamine, triisocyanate and production thereof - Google Patents

Abstract

PURPOSE:To obtain a novel compound useful as a curing agent for a epoxy resin, a polyurethane or a polyurea and a raw material for a polyamide, a polyimide and a polyimide-amide, producible in a high purity and high yield. CONSTITUTION:A compound of formula I (R1 is 1-5C alkyl; R2 is H or methyl) such as 1-(3'-aminophenyl)-1-(2'',4''-diamino-5''-methylphenyl)ethane. The compound is obtained by condensing an alpha-(aminophenyl)alkyl alcohol of formula II with an aromatic diamine in the presence of an acid catalyst (preferably hydrochloric acid) preferably at 120-220 deg.C. The alpha-(aminophenyl)alkyl alcohol is preferably obtained by nitrating an alpha-(phenyl)alkyl alcohol and catalytically reducing or nitrating an alkyl phenyl ketone and catalytically reducing the nitrated nitro compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to triamine, triisocyanate and a method for producing them.
These triamines and triisocyanates are useful as various raw materials in the chemical industry.

[0002]

BACKGROUND ART Triamine is expected to have a characteristic performance as a curing agent for epoxy resins, polyurethanes or polyureas, and a raw material for polyamides. Isocyanate is used as a raw material for polyurethane resins and polyurea resins, for example, as foams and elastic materials. It can be used in various fields such as body, synthetic leather, paint, adhesive, film, etc. So far,
(4-Aminophenyl)-(2 ', 4'-diaminophenyl) methane, (4-aminophenyl)-(2', 4 '
-Diamino-5-methylphenyl) methane, (4-isocyanatophenyl)-(2 ', 4'-diisocyanato-
Triamines such as 5-methylphenyl) methane and triisocyanates are known. However, in these compounds, since the bonding group of the two benzene rings is a methylene chain, for example, in the case of triisocyanate, it is difficult to recognize the difference in the reactivity of the isocyanate group, and the weather resistance is also poor. I have a problem.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned drawbacks and to provide industrially useful triamines and triisocyanates having a novel structure, and a process for producing them.

[0004]

The present inventors have completed the present invention as a result of various studies to achieve the above-mentioned object. That is, the present invention relates to a triamine represented by the formula (1) (formula 5) and a triisocyanate represented by the formula (2) (formula 6).

[0005]

[Chemical 5] (In the formula, R ₁ represents a C _{1 to} C ₅ alkyl group, and R ₂ represents a hydrogen atom or a methyl group.)

[0006]

[Chemical 6] (In the formula, R ₁ represents a C ₁ -C ₅ alkyl group, R ₂ represents a hydrogen atom or a methyl group. However, the two isocyanate groups of the benzene ring B are not adjacent to each other.) A method for producing a triamine represented by the formula (1), in which an α- (aminophenyl) alkyl alcohol represented by the formula (3) (Formula 7) and an aromatic diamine are condensed in the presence of an acid catalyst, and Formula (2) in which a triamine represented by Formula (4) (Chemical Formula 8) or a salt thereof is reacted with phosgene
The present invention relates to a method for producing triisocyanate represented by.

[0007]

[Chemical 7] (In the formula, R ₁ represents a C _{1 to} C ₅ alkyl group)

[0008]

[Chemical 8] (In the formula, R ₁ represents a C ₁ -C ₅ alkyl group, R ₂ represents a hydrogen atom or a methyl group. However, the two amino groups of the benzene ring B are not adjacent to each other.) The triamine of the present invention is It is a novel compound represented by the formula (1). The triamine of the present invention is produced by condensing an α- (aminophenyl) alkyl alcohol and an aromatic diamine in the presence of an acid catalyst.

The α- (aminophenyl) alkyl alcohol used in the present invention includes α- (2-aminophenyl) ethyl alcohol, α- (2-aminophenyl) propyl alcohol and α- (2-aminophenyl) butyl alcohol. , Α- (2-aminophenyl) pentyl alcohol, α- (2-aminophenyl) hexyl alcohol, α- (3-aminophenyl) ethyl alcohol, α
-(3-aminophenyl) propyl alcohol, α-
(3-aminophenyl) butyl alcohol, α- (3-
Aminophenyl) pentyl alcohol, α- (3-aminophenyl) hexyl alcohol, α- (4-aminophenyl) ethyl alcohol, α- (4-aminophenyl) propyl alcohol, α- (4-aminophenyl)
Butyl alcohol, α- (4-aminophenyl) pentyl alcohol, α- (4-aminophenyl) hexyl alcohol and the like can be mentioned. These α- (aminophenyl) alkyl alcohols can be obtained by nitrating α- (phenyl) alkyl alcohol and then catalytically reducing it, or by catalytically reducing a nitro compound obtained by nitration of alkylphenyl ketone. it can. For example, α
-(3-Aminophenyl) ethyl alcohol can be obtained in good yield by catalytically reducing 3-nitroacetophenone obtained by nitration of acetophenone.

The aromatic diamine used in the present invention includes o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene and 2,3-diaminotoluene. , 3,4-diaminotoluene and the like. These are commercially available and are easily available. When α- (aminophenyl) alkyl alcohol and aromatic diamine are condensed in the presence of an acid catalyst, a compound having a secondary amine bond represented by formula (5) (formula 9) is used as an intermediate. To generate. This intermediate is further subjected to a transfer reaction by any means such as (1) increasing the acid catalyst, (2) increasing the reaction temperature, (3) increasing the reaction time, or a combination thereof. Then, the triamine of the present invention represented by the formula (1) can be obtained.

[0011]

[Chemical 9] (In the formula, R ₁ represents a C _{1 to} C ₅ alkyl group, and R ₂ represents a hydrogen atom or a methyl group.)

The amount of the α- (aminophenyl) alkyl alcohol and the aromatic diamine used is in the range of 1 to 20 mol of the aromatic diamine per 1 mol of the α- (aminophenyl) alkyl alcohol. The smaller the amount of aromatic diamine used, the lower the yield of triamine, because α- (aminophenyl) alkyl alcohol is accompanied by some self-condensation reaction. The molar amount of the aromatic diamine may be determined in consideration of economic efficiency due to problems such as volumetric efficiency and the amount of catalyst used, but is preferably 1 to 10 mol. The acid catalyst used is an inorganic or organic acid,
For example, mineral acids such as hydrochloric acid, phosphoric acid, sulfuric acid or nitric acid, or Friedel-Crafts type catalysts such as zinc chloride, stannic chloride, aluminum chloride, ferric chloride, methanesulfonic acid, p-toluenesulfonic acid, etc. Examples of the organic sulfonic acid include trifluoromethanesulfonic acid, and Nafion H (trade name: manufactured by DuPont). These may be used alone or in combination. Industrially preferable is inexpensive hydrochloric acid. The amount of catalyst used is α
A range of 1 mol% to 100 mol% with respect to the total amount of-(aminophenyl) alkyl alcohol and aromatic diamine,
It is preferably 3 to 50 mol%.

The reaction temperature is in the range of 50 to 220.degree. C., but 100.degree.
Preferably a temperature of 120 ° C. or higher is required. The method for producing the triamine of the present invention may use a solvent inert to the reaction, or may be carried out without a solvent.
Examples of the solvent include aromatic hydrocarbons such as benzene, toluene and xylene, chlorinated hydrocarbons such as monochlorobenzene and orthodichlorobenzene, ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, n-butyl acetate and isoamyl acetate. The esters of are often used. After the completion of the reaction, the acid used as the catalyst is neutralized with, for example, a caustic soda aqueous solution, a potassium hydroxide aqueous solution, a dilute alkaline aqueous solution such as ammonia water, and then separated and removed. The target product can be obtained by subjecting the obtained organic layer to vacuum distillation.

The triisocyanate of the present invention has the formula (2)
The compound represented by the formula ( ₁₎ has a C ₁ -C ₅ alkyl group in the methylene chain, which is a bonding group of two benzene rings, and is a novel compound having a difference depending on the reactivity of each isocyanate. The triisocyanate of the present invention has the formula (4)
Of the triamine of formula (4) directly with phosgene, or the hydrochloride, carbonate, sulfate of triamine of formula (4),
It is produced by a method of suspending or dissolving a phosphate, acetate or the like in an inert solvent and reacting with phosgene.
For example, triamine is dissolved in an inert solvent and reacted with phosgene at low temperature to obtain a carbamoyl chloride compound, which is then thermally decomposed at 50 to 200 ° C. to give triisocyanate. When the starting material, triamine, is reacted as a salt, it is sufficiently pulverized and suspended in an inert solvent for reaction. The amount of phosgene used may be 1 equivalent to 50 times equivalent, or preferably 2 to 10 times equivalent, based on the amino group.

The reaction temperature during the phosgenation is 50 to 20.
0 ° C is preferred. If it exceeds 200 ° C., a large amount of resinous product is produced, resulting in a decrease in yield. On the other hand, when the temperature is lower than 50 ° C, the reaction becomes slow and it takes a long time to complete the reaction. Examples of the inert solvent used in the present invention include aromatic hydrocarbons such as benzene, toluene and xylene which are usually used for phosgenation, chlorinated hydrocarbons such as monochlorobenzene and orthodichlorobenzene, ethyl acetate and butyl acetate. , Esters such as amyl acetate can be used. After completion of the reaction, the solvent is removed and further distilled under reduced pressure to obtain the triisocyanate of the present invention.

The isocyanate of the present invention is binuclear and trifunctional, and is characterized by a high number of functional groups and different reactivity of the three isocyanate groups. Therefore, these characteristics can be utilized for various applications. For example, when this isocyanate is used as a polyurethane raw material, a characteristic polyurethane resin can be expected because the crosslinking density is higher than that in the case of a conventional difunctional isocyanate. In addition, when this isocyanate is used as a foam, the reactivity of the three isocyanate groups is different from that in the case of the conventional isocyanate, so that it is considered that the expansion ratio becomes high, and the characteristic foam Can be expected. Furthermore, since the vapor pressure of this isocyanate is extremely low near room temperature, it can be handled safely without contaminating the working environment.

[0017]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. Example 1 3-nitroacetophenone 3 was placed in a 3-liter closed container.
30.4 g (2 mol), 5% Pd—C catalyst (13.2 g) and methanol (2000 ml) were charged, and hydrogen was introduced with vigorous stirring. Blow-in of hydrogen was continued for 12 hours while maintaining the reaction temperature at 50 to 55 ° C., and the process was terminated when the absorption of hydrogen was no longer observed. next,
The reaction system was purged with nitrogen and then filtered to remove the catalyst.
The filtrate was concentrated and then vacuum distilled to obtain 255.2 g of α- (3-aminophenyl) ethyl alcohol. (Yield 93
%, Boiling point 135 to 136 ° C./3 mmHg, melting point 64 to 6
Next, 82.3 g (0.6 mol) of this α- (3-aminophenyl) ethyl alcohol and 293.3 g (2.4 mol) of 2,4-diaminotoluene were charged into a reactor and used as a catalyst. 90 g (0.9 mol) of 35% hydrochloric acid aqueous solution was added, and the temperature was raised while introducing nitrogen gas. While removing the distilled water to the outside of the system, the temperature was raised to 160 ° C and the temperature was raised to 5
The reaction was carried out over time. After completion of the reaction, cool to 100 ° C,
To this, 380 g of a 10% aqueous sodium hydroxide solution was added for neutralization. Since it separated into two layers when left standing, the aqueous layer was removed to obtain a reddish brown oily organic layer. This organic layer is vacuum distilled,
A pale yellow fraction was obtained. Yield 116.8 g, 81% yield,
Boiling point 223 to 226 ° C / 0.02 mmHg, melting point 140
-142 ° C The elemental analysis values of this fraction were as follows. Also, the IR spectrum of this fraction (Figure 1), ¹ H-
The NMR spectrum is shown in (FIG. 2). Furthermore, in the MS spectrum, (M ⁺ ) = 241 was observed, and
It was in agreement with the molecular weight of the compound represented by. From the above results, this fraction is the target product, 1- (3'-aminophenyl) -1- (2 ", 4" -diamino-5 "-methylphenyl).
Identified as ethane.

Example 2 800 g of butyl acetate was charged into a 2-liter reaction flask equipped with a stirrer, a thermometer, a phosgene gas introduction tube, a cooling tube, and a dropping funnel. While stirring, the reaction flask was immersed in an ice water bath, the internal temperature was kept at about 2 ° C., and phosgene gas was introduced into the flask at a rate of 50 g / hr for 1 hour. Then, 1- (3'-aminophenyl) -1-dissolved in 200 g of butyl acetate
(2 ", 4" -diamino-5 "-methylphenyl) ethane 4
8.3 g (0.2 mol) was added dropwise over 1 hour. Cold phosgenation was performed at 0 to 12 ° C. while introducing phosgene gas at a rate of 50 g / hr even when dropping the amine. After dropping the amine, the inside of the flask became a pale yellowish white slurry state. After the dropping, phosgene was further introduced at a rate of 50 g / hr for 30 minutes at 2 to 15 ° C. Next, while introducing phosgene at a rate of 50 g / hr, the liquid in the reaction flask was heated to 100 ° C. for 30 minutes. After raising the temperature, while continuing to introduce phosgene, 1
Timed thermal phosgenation was performed. During the process of thermal phosgenation, the liquid in the flask became a brown transparent solution. 2 in total in this reaction
00 g of phosgene gas was introduced. This was about 3.4 times the theoretical amount. After completion of the thermal phosgenation, nitrogen gas was introduced at 100 ° C. to remove phosgene. After cooling, the mixture was filtered, and butyl acetate as a solvent was distilled off under reduced pressure to obtain 66.7 g of a brown liquid. Further, by vacuum distillation, 54.3
A boiling point of 181 to 183 ° C./0.02 mmHg of distillate was obtained. Yield 85%, pale yellow viscous liquid, NCO content 39.
5% Elemental analysis values of this fraction were as follows. Also, the IR spectrum of this fraction (Figure 3), ¹ H-
The NMR spectrum is shown in (FIG. 4). Furthermore, in the MS spectrum, (M ⁺ ) = 319 was observed, and
It was in agreement with the molecular weight of the compound represented by. From the above results, this fraction was identified as the target product, 1- (3'-isocyanatophenyl) -1- (2 ", 4" -diisocyanato-5 "-methylphenyl) ethane.

Example 3 In a reaction flask similar to that of Example 2, 48.3 g of 1- (3'-aminophenyl) -1- (2 ", 4" -diamino-5 "-methylphenyl) ethane (0. (2 mol) was dissolved in 1000 g of butyl acetate, and hydrogen chloride was bubbled through the solution while stirring to generate a hydrochloride salt. 35
The temperature was kept below ℃. After 1 hour, the introduction of hydrogen chloride was stopped. 50 g / hr of phosgene gas was added to the produced hydrochloride slurry.
The temperature is raised while blowing at a rate of 100% for 30 minutes.
The temperature was raised to ° C. Blowing of phosgene gas was continued at 100 ° C. for another 2 hours. In this process, the reaction solution became brown and transparent. A total of 125 g of phosgene gas was introduced in this reaction. This is about 2.1 times the theoretical amount. After completion of phosgenation, nitrogen gas was introduced at 100 ° C. to remove phosgene. After cooling, the mixture was filtered and the solvent butyl acetate was distilled off under reduced pressure to obtain 67.2 g of a brown liquid. Further, it is distilled under reduced pressure to give a boiling point of 52.6 g 181-184 ° C / 0.02.
A fraction of mmHg was obtained. Yield 82.3%, pale yellow viscous liquid, NCO content 39.5% The elemental analysis values of this fraction were as follows. The IR spectrum and ¹ H-NMR spectrum of this fraction were similar to those of Example 2.

[0020]

INDUSTRIAL APPLICABILITY The triamine of the present invention has a novel structure and can be used in various fields as a raw material for epoxy resin, polyurethane or polyurea curing agent, polyamide, polyimide and polyimideamide. Isocyanate of the present invention is also a triisocyanate of a novel structure, as a raw material of polyurethane resin and polyurea resin, foams, elastic bodies, synthetic leather, paints, adhesives, films, etc. It is a very useful compound. In addition, the production method of the present invention is an industrially extremely useful method capable of obtaining highly pure triamine and triisocyanate in high yield.

[Brief description of drawings]

FIG. 1 is an IR spectrum of the compound obtained in Example 1.

FIG. 2 ¹ H-NMR spectrum of the compound obtained in Example 1.

FIG. 3 is an IR spectrum of the compound obtained in Example 2.

FIG. 4 ¹ H-NMR spectrum of the compound obtained in Example 2.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location // C07B 61/00 300 C08G 18/32 NDT 8620-4J 18/76 NFH 8620-4J 59/50 NJA 8416-4J (72) Inventor Ryuji Haseyama Mitsui Toatsu Chemical Co., Ltd. 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa

Claims (4)

[Claims] 1. A triamine represented by the formula (1) (formula 1). [Chemical 1] (In the formula, R ₁ represents a C _{1 to} C ₅ alkyl group, and R ₂ represents a hydrogen atom or a methyl group.) 2. A triisocyanate represented by formula (2) (formula 2). [Chemical 2] (In the formula, R ₁ represents a C ₁ -C ₅ alkyl group and R ₂ represents a hydrogen atom or a methyl group. However, the two isocyanate groups of the benzene ring B are not adjacent to each other.) 3. An α- (aminophenyl) alkyl alcohol represented by formula (3) (formula 3) and The method for producing a triamine according to claim 1, wherein the aromatic diamine (wherein R ₁ represents a C ₁ -C ₅ alkyl group) is condensed in the presence of an acid catalyst. 4. A triamine represented by the formula (4) (formula 4): (In the formula, R ₁ represents a C ₁ -C ₅ alkyl group, R ₂ represents a hydrogen atom or a methyl group. However, two amino groups of the benzene ring B are not adjacent to each other) or a salt thereof, The method for producing triisocyanate according to claim 2, which comprises reacting with phosgene.