JP3297093B2 - Novel diamines and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel diamine having an amide bond and a method for producing the same. This compound is a useful compound as a starting material such as polyimide, polyamide, polyamideimide, bismaleimide, diisocyanate, or epoxy resin.

[0002]

2. Description of the Related Art In recent years, research and development of high-functional polymer materials have become more and more active, and accordingly, a reactive polymer having highly reactive functional groups arranged in a fixed manner has been demanded. In particular,
Among functional polymer materials, polyimide and polyamide are expected to be widely used in a wide range of fields because of their excellent heat resistance and dimensional stability.

[0003] However, there are many polyimides and polyamides which have been developed so far, which have excellent mechanical properties and heat resistance. However, when these resins are molded, their workability is insufficient and water absorption. There was a problem in workability such as a high rate. For example, as an aromatic diamine, p
-A polyamide obtained from phenylenediamine as a raw material, for example, the following formula (6)

Embedded image A wholly aromatic polyamide (manufactured by DuPont; trade name Kevlar) having a basic skeleton represented by the formula (1) does not have a clear glass transition temperature, and has a difficulty in workability when used as a moldable material. . Therefore, an improvement is attempted by adding an aliphatic diamine or an aliphatic dicarboxylic acid.

On the other hand, as a means for improving the moldability, it is also known that it is effective to make the position of the aromatic amino group meta-position to the bonding group (DuPont) Manufactured by Nomex). Further, a polyamide comprising m-xylylenediamine and an aliphatic dicarboxylic acid, for example, the following formula (7)

Embedded image It has been reported that a polyamide (manufactured by Mitsubishi Gas Chemical Company; trade name: RENY) having a repeating structure having a basic skeleton represented by is excellent in oxygen gas barrier properties.

[0005] As described above, changing the starting material (aromatic) diamine as one of the starting materials greatly changes the glass transition temperature, the melting point, the thermal decomposition temperature, and the processability of the polyamide resin. Many new diamines having performance have been developed.

[0006]

An object of the present invention is to provide a novel diamine useful as a raw material for a novel polyamide, polyimide, epoxy resin curing agent and the like, and a method for producing the same.

[0007]

Means for Solving the Problems In order to solve the above problems, the present inventors have intensively studied the synthesis of various novel diamine compounds. As a result, the general formula (8)

Embedded image (Wherein, R ₁ represents an alkyl group, and the NH ₂ group is located at the meta or para position). When the diamine is reacted with a dibasic acid or a derivative thereof, an amino group directly substituted on an aromatic nucleus is obtained. As compared with the above, the reactivity of the amino group bonded to the aliphatic carbon is higher, and it is possible to obtain a novel diamine compound of the present invention by reacting with a dibasic acid. In addition, the general formula (9)

Embedded image (Wherein, R ₁ represents an alkyl group, and the NO ₂ group is located at the meta or para position), which is obtained by reacting an α- (nitrophenyl) alkylamine with a dibasic acid or a derivative thereof. The inventors have found that the novel diamine compound of the present invention can be obtained by catalytically reducing a dinitro compound in the presence of an alkali, and have completed the present invention.

That is, the present invention relates to a compound of the formula (1)

Embedded image (Wherein, R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, X represents a phenylene group, a cyclohexylene group, or an alkylene group having 2 to 10 carbon atoms, and the NH ₂ group is located at the meta or para position. A diamine represented by formula (2):

Embedded image (In the formula, R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the NH ₂ group is located at the meta or para position.)
And a diamine represented by the general formula (3):

Embedded image (X represents a phenylene group, a cyclohexylene group or an alkylene group having 2 to 10 carbon atoms, and M represents a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms) or a dibasic acid or a derivative thereof. And a method for producing a diamine, and a general formula (4)

Embedded image (Wherein, R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the NO ₂ group is located at the meta or para position)
Α- (nitrophenyl) alkylamine represented by the general formula (3 ′)

Embedded image (X represents a phenylene group, a cyclohexylene group or an alkylene group having 2 to 10 carbon atoms, and M represents a hydroxyl group, a halogen atom or an alkoxy group having 1 to 4 carbon atoms) or a dibasic acid or a derivative thereof. After the reaction, general formula (5)

Embedded image (Wherein, R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, X represents a phenylene group, a cyclohexylene group or an alkylene group having 2 to 10 carbon atoms, and the NO ₂ group is located at the meta or para position. The present invention relates to a method for producing diamines by catalytically reducing a dinitro compound represented by the formula (1) in the presence of an alkali.

The diamines of the present invention are novel compounds which have not been known so far, and the amino group substituted on the aromatic nucleus is meta-position, para-position or a mixture thereof with respect to the amide bond. The diamine of the present invention, for example, when the amino group is at the meta position, it can be expected that the moldability is improved due to the bent structure of the polymer molecule, and when it is at the para position, the heat resistance is improved. Is a compound that can be expected.

The diamine used in the reaction with the dibasic acid in the present invention, which specifically explains the process for producing the diamine of the present invention, is represented by the general formula (2). Aminobenzylamine, α- (4-aminophenyl) methylamine, α- (3-aminophenyl) ethylamine,
α- (4-aminophenyl) ethylamine, α- (3-
Aminophenyl) propylamine, α- (4-aminophenyl) propylamine, α- (3-aminophenyl)
Butylamine, α- (4-aminophenyl) butylamine, α- (3-aminophenyl) pentylamine, α-
(4-aminophenyl) pentylamine, α- (3-aminophenyl) hexylamine, α- (4-aminophenyl) hexylamine, α- (3-aminophenyl) heptylamine, α- (4-aminophenyl) heptylamine , Α- (3-aminophenyl) octylamine, α-
(4-aminophenyl) octylamine, α- (3-aminophenyl) nonylamine, α- (4-aminophenyl) nonylamine, α- (3-aminophenyl) decylamine, and α- (4-aminophenyl) decylamine And preferably m-aminobenzylamine, α-
(4-aminophenyl) methylamine, α- (3-aminophenyl) ethylamine, and α- (3-aminophenyl) propylamine. The α- (nitrophenyl) alkylamine used in the reaction with the dibasic acid in the present invention is represented by the general formula (4), and specifically, α- (3-nitrophenyl) methylamine, α- ( 4-nitrophenyl) methylamine, α- (3-nitrophenyl) ethylamine, α- (4-nitrophenyl) ethylamine, α
-(3-nitrophenyl) propylamine, α- (4-
Nitrophenyl) propylamine, α- (3-nitrophenyl) butylamine, α- (4-nitrophenyl) butylamine, α- (3-nitrophenyl) pentylamine, α- (4-nitrophenyl) pentylamine, α-
(3-nitrophenyl) hexylamine, α- (4-nitrophenyl) hexylamine, α- (3-nitrophenyl) heptylamine, α- (4-nitrophenyl) heptylamine, α- (3-nitrophenyl) Octylamine, α- (4-nitrophenyl) octylamine, α
-(3-nitrophenyl) nonylamine, α- (4-nitrophenyl) nonylamine, α- (3-nitrophenyl) decylamine, α- (4-nitrophenyl) decylamine, and preferably α- (nitrophenyl) ) Α- selected from m- or p-nitro forms of methylamine, α- (nitrophenyl) ethylamine, α- (nitrophenyl) propylamine and mixtures thereof
— (Nitrophenyl) alkylamine.

On the other hand, the dibasic acid or its derivative used in the reaction with the diamine in the present invention is represented by the general formula (3), and specifically includes phthalic acid, terephthalic acid, isophthalic acid, succinic acid, Glutaric acid, adipic acid, pimelic acid,
Derivatives such as suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, hexahydrophthalic acid or esters can be used.
The dibasic acid or its derivative used in the reaction with the (nitrophenyl) alkylamine is represented by the general formula (3 ′):
Specifically, phthalic acid, terephthalic acid, isophthalic acid,
Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid,
A derivative such as dodecane diacid, hexahydrophthalic acid, or an ester or acid halide thereof can be used. The halogens constituting the halide include F, Cl,
Br and I are used, preferably Cl. Specifically, terephthalic acid dichloride, isophthalic acid dichloride, o-phthalic acid dichloride, succinic acid dichloride, glutaric acid dichloride, adipic acid dichloride, pimelic acid dichloride, suberic acid dichloride, azelaic acid dichloride, sebacic acid dichloride, dodecane diacid Dichloride and the like.

The method of the present invention comprises the step of reacting the above diamine or α- (nitrophenyl) alkylamine with a dibasic acid or a derivative thereof with respect to 2 equivalents of diamine or α- (nitrophenyl) alkylamine. This is a method for producing a diamine of the present invention by using one equivalent of the derivative to react, and the reaction method is not particularly limited. The reaction method is, for example, a method in which a diamine or α- (nitrophenyl) alkylamine is heated to near the melting point of the dibasic acid to be used and melted, and then the dibasic acid is added to carry out the reaction. A method in which a dibasic acid is heated and melted to a temperature equal to or higher than the melting point, and a reaction is performed by adding a diamine or an α- (nitrophenyl) alkylamine. There is a method in which a diamine or α- (nitrophenyl) alkylamine is dispersed or dissolved in an organic solvent, and then a dibasic acid is added and reacted.

As the organic solvent used in this method, for example, as a high-boiling organic solvent, biphenyl (boiling point: 255 ° C., hereinafter the boiling point is shown in parentheses of the solvent),
Isoquinoline (243 ° C), quinoline (237 ° C), N
-Methyl-2-pyrrolidone (202 ° C), m-cresol (203 ° C) and dimethylsulfoxide (189 ° C) are used. When an organic solvent having a boiling point of 180 ° C. or lower is used, the reaction can be performed while distilling off the organic solvent, or can be performed under pressure. For example, N, N
-Dimethylformamide (153 ° C), N, N-dimethylacetamide (166 ° C), 2,4-lutidine (15 ° C)
7 ° C.), cyclohexanone (156 ° C.), toluene (1
10 ° C.), xylene (144 ° C.), triethylamine (90 ° C.), methanol (65 ° C.), acetone (56 ° C.)
° C). These solvents may be used alone or
You may mix and use more than one kind. The amount of the solvent used is not economically disadvantageous, although there is no problem in the reaction even if it is used in excess. Usually, it is good to use in a range of 10 to 20 times the weight ratio to the raw material amine.

In the present invention, the reaction temperature of the diamine or α- (nitrophenyl) alkylamine with the dibasic acid or its ester varies depending on the type of the starting monomer, the reaction method, and the type of the solvent. ° C
It is carried out within a range. When the reaction is carried out using a dibasic acid as a reaction raw material, for example, succinic acid (melting point 181)
-185 ° C), glutaric acid (melting point 97.5 ° C), adipic acid (melting point 153 ° C), pimelic acid (melting point 105 ° C),
Suberic acid (melting point 144 ° C), azelaic acid (melting point 10
7 ° C), sebacic acid (melting point 134 ° C), undecandioic acid (melting point 111 ° C), hexahydroterephthalic acid (cis,
(Trans melting point: 165 to 250 ° C.) The diamine is inserted under a nitrogen stream while maintaining the fluidity by heating to the melting point of the dibasic acid used. It is sufficient that the diamine dropping time is 1 to 8 hours, and preferably about 2 to 5 hours. At this time, it is preferable that the dropping temperature is not more than 35 ° C. from the melting point of the dibasic acid. It is not preferable to carry out the reaction at a temperature far above the melting point because of the thermal stability of the dibasic acid.

Although the reaction time varies depending on the type of the monomer for the reaction, the reaction method, and the type of the solvent, the reaction is usually performed for a time sufficient to complete the formation of the diamine represented by the general formula (1). This is usually about 1 to 10 hours.
For example, when a dibasic acid is used as a reaction raw material, the reaction is carried out until water is no longer distilled,
It is performed within a time range.

On the other hand, when α- (nitrophenyl) alkylamine and a dibasic acid halide are used in the reaction method of the present invention, for example, α- (nitrophenyl) alkylamine and a dehalogenating agent are used in an organic solvent. After charging,
Under a nitrogen stream, a halide of a dibasic acid is charged, and -20
The reaction is carried out in the range of ８０80 ° C. In this case, since the heat is generated at the time of charging the raw material, the first half with the heat is performed at a relatively low temperature,
It is preferable to raise the temperature from the latter half of the reaction to complete the reaction sufficiently. That is, in order to perform the above-mentioned temperature accurately, in some cases, the temperature is previously set to -30 to -10 ° C.
It is preferable to cool to the extent.

When a dibasic acid halide is used,
Usually, a dehalogenating agent is used in combination. As the dehalogenating agent to be used, a base or an oxirane compound is used. As the base, triethylamine, tributylamine, tripentylamine, N, N-dimethylaniline,
N, N-diethylaniline, pyridine, α-picoline,
β-picoline, γ-picoline, 2,4-lutidine, 2,
6-Lutidine, quinoline, isoquinoline, sodium hydroxide, potassium hydroxide, sodium carbonate, lithium carbonate, potassium carbonate, sodium hydrogen carbonate, calcium oxide, lithium oxide, and oxirane compounds include ethylene oxide and propylene oxide.

The amount of the dehalogenating agent used may be stoichiometric with respect to the functional group. For example, when triethylamine is used as the dehalogenating agent, it may be used in an amount twice as much as 1 mol of the halide of the dibasic acid, which is a reaction raw material.

The organic solvent used in the above method includes:
For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone,
3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, hexamethylphosphoramide, isoquinoline,
2,4-lutidine, quinoline, triethylamine, dichloromethane, methyl ethyl ketone, acetone, cyclohexanone, tetrahydrofuran, toluene, phenol, m-cresol, p-chlorophenol, o-chlorophenol, sulfolane, trialkylphosphine oxide, triphenylphosphine oxide, Isophorone and the like. These solvents may be used alone or as a mixture of two or more.

The amount of the organic solvent used is in the range of 3 to 8 parts by weight based on 1 part by weight of the α- (nitrophenyl) alkylamine. If the amount used is 3 parts by weight or less, the inside of the system becomes viscous because the triethylamine hydrochloride precipitates after the reaction. In addition, when the salt is separated by filtration, the filtration becomes slow. When the used amount is 8 parts by weight or more, the used amount of water, alcohol, and the like at the time of discharging increases. Preferably, it is used in the range of 4 to 6 parts by weight.

After the reaction as described above, the reaction solution is usually a viscous solution. After the reaction, the reaction solution is discharged and crystallized. When the reaction is carried out using an organic solvent, if the solvent is a solvent that is mixed with water, it is discharged into water to precipitate crystals and filtered. Also, if the solvent does not mix with water,
After distilling off the solvent and discharging, a diamine and a dinitro compound having an amide bond can be obtained.

The method for reducing the dinitro compound obtained as described above is not particularly limited, and a method for reducing a nitro group to an amino group can be generally applied. However, catalytic reduction is industrially preferable. In the case of catalytic reduction, the reduction catalyst used is a metal catalyst generally used for catalytic reduction, for example, nickel, palladium, platinum, rhodium,
Ruthenium, cobalt, copper and the like can be used. Industrially, it is preferable to use a palladium catalyst. These catalysts are also used in the metal state, but are usually carbon, barium sulfate, silica gel, alumina,
It is used by being supported on the surface of a single substance such as celite, and also used as a Raney catalyst such as nickel, cobalt and copper.

The amount of the catalyst used in the method of the present invention is not particularly limited, but is in the range of 0.01 to 10% by weight as a metal based on the starting dinitro compound, and is usually used in a metal state. In the case, it is in the range of 2 to 8% by weight, and in the case of being carried on a carrier, it is in the range of 0.1 to 5% by weight.

The reaction solvent is not particularly limited as long as it is inert to the reaction. For example, water or alcohols such as methanol, ethanol and isopropyl alcohol, glycols such as ethylene glycol and propylene glycol dioxane , Tetrahydrofuran, ethers such as methyl cellosolve and further hexane, aliphatic hydrocarbons such as cyclohexane, benzene,
Aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl acetate, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane and tetrachloroethane, and N, N
-Dimethylformamide and the like can also be used.

The amount of these solvents used is sufficient to suspend or completely dissolve the raw materials, and is not particularly limited.
It is carried out at a weight of 15 times.

The reaction temperature is not particularly limited, but is generally in the range of 5 to 100 ° C, preferably in the range of 20 to 80 ° C.

Since the diamine thus obtained contains a small amount of a diamine other than the target substance, it must be removed. There are various methods for removing these by-product diamines. For example, after dispersing the obtained crude crystals of diamine in water, an acid is added, a salt is formed and completely dissolved in water, neutralized with alkali to precipitate a by-product diamine that is hardly soluble in water, After filtering off, the filtrate is salted out. After the salt is formed, impurities insoluble in water are filtered off and neutralized with an alkali. The diamines of the present invention can be isolated by any of the methods.

In a general embodiment of the process of the invention, the reaction of a diamine with a dibasic acid,
The equivalent is heated to the melting point under a stream of nitrogen and dissolved, and then 2 equivalents of diamine are charged and reacted. After distilling off the theoretical amount of water, the mixture is discharged into a porcelain plate while maintaining the fluidity, and crystallized. On the other hand, in the case of the reaction between α- (nitrophenyl) alkylamine and dibasic acid dichloride, 2 equivalents of α- (nitrophenyl) alkylamine and triethylamine 2 are added to an N-methyl-2-pyrrolidone solvent under a nitrogen stream.
After charging the equivalent, 1 equivalent of dibasic acid dichloride is charged at 0 ° C. or lower to carry out the reaction. After the reaction, the precipitated triethylamine hydrochloride is filtered off, and then the filtrate is discharged into water or alcohol to precipitate crystals, whereby the dinitro compound can be isolated. After catalytic reduction of the resulting dinitro compound in an organic solvent, the catalyst was filtered off,
By recovering the organic solvent, the desired product can be easily obtained.

Since the diamine in the present invention has an amide bond, polyimide, polyamide, polyamide imide, bismaleimide,
It is a very useful diamine that can be expected to be used for multipurpose applications as a starting material such as diisocyanate or epoxy resin.

[0030]

The present invention will be described in more detail with reference to the following examples. In addition, these structural analyzes were confirmed by comparing the NH proton of the amide bond and the methylene proton of the dibasic acid skeleton based on the measurement results of ¹ H-NMR. ¹ H-NMR measurement results are shown on the TMS standard.

Example 1 7.3 g (0.05 mol) of adipic acid was charged in a vessel equipped with a stirrer and a nitrogen inlet tube under a nitrogen atmosphere, and then heated to 155 to 160 ° C. to dissolve it. . Next, 13.6 g (0.1 mol) of m-aminophenylethylamine was charged for 1 hour. Thereafter, the reaction was carried out at the same temperature for 4 hours (distilled water 1.51 g, 83.9% theoretical distilling amount%).
After the reaction, the mixture was discharged into a porcelain flat plate to obtain crystals. Yield 18.2 g Yield 95.0% ¹ H-NMR of the crude crystals obtained was measured.
It was as follows. That is, the NH proton of the amide bond is 8.2 ppm (1H) and 9.8 ppm (1H),
Further, methylene protons were observed at 1.46 ppm (2H) and 1.60 ppm (2H). This crude crystal 1
After dispersing 8.2 g in 182 g (10 times the amount) of water, 2
At 0 to 25 ° C, 11.1 g (0.10 mol) of 35% hydrochloric acid was dropped and dissolved. Then, 45% sodium hydroxide8.
Neutralized to pH 6.5 with 7 g (0.098 mol). After filtering off the precipitated brown component, the filtrate was salted out with salt,
White crystals were obtained by filtration, washing and drying. Yield 16.4g Yield 85.7% Melting point 100.8
１２３123 ° C. The result of measuring ¹ H-NMR of the purified product obtained here is as follows. That is, 8.2 ppm (1H) of NH protons of the amide crystal and 1 ppm of methylene protons.
46 ppm (2H) was observed.

Reference Example 1 7.3 g (0.05 mol) of adipic acid was charged into a vessel equipped with a stirrer and a nitrogen introducing tube under a nitrogen atmosphere, and then heated to 155 to 160 ° C. to dissolve. Was. Next, α-phenylethylamine (12.1 g, 0.1 mol) was charged for 1 hour. Thereafter, the reaction was carried out at the same temperature for 4 hours (distilled water 1.76 g, 97.8% theoretical distillation%). After the reaction, the mixture was discharged into a porcelain flat plate. Yield 17.0 g The result of ¹ H-NMR measurement is as follows. That is,
The NH proton of the amide bond was observed at 8.2 ppm (1H), and the methylene proton was observed at 1.46 ppm (2H).

Reference Example 2 In a vessel equipped with a stirrer and a nitrogen inlet tube, 9.3 g (0.1 mol) of aniline and N-methyl-
93.0 g (10 volumes / aniline) of 2-pyrrolidone and 10.1 g (0.1 mol) of triethylamine were charged. After cooling to 0 ° C, adipic dichloride 9.2.
g (0.05 mol) were charged. After reacting at 0-5 ° C for 1 hour, it was further reacted at 20-25 ° C for 3 hours. After the reaction, the mixture was poured into 1 liter of water, and the precipitated crystals were filtered, washed with water, and dried. Yield 12.0 g The result of ¹ H-NMR measurement is as follows. That is,
An amide bond NH proton was observed at 9.8 ppm (1H), and a methylene proton was observed at 1.60 ppm (2H).

Reference Example 3 14.6 g (0.1 mol) of adipic acid was charged into a vessel equipped with a stirrer and a nitrogen inlet tube under a nitrogen atmosphere, and then heated to 155 to 160 ° C. to dissolve. Was. Next, 12.1 g (0.1 mol) of α-phenylethylamine and 9.3 g (0.1 mol) of aniline were charged over 1 hour. 1
The temperature is raised to 65 to 170 ° C. and the same temperature is maintained for 2 hours, and
The temperature was raised to 0 to 185 ° C., and the mixture was reacted at the same temperature for 2 hours (distilled water 2.7 g, 75.0% theoretical distillation%). After the reaction, the mixture was discharged into aluminum foil. Yield 25.0 g The result of ¹ H-NMR measurement is as follows. That is,
A methylene proton was observed at 1.54 ppm (2H).

The following can be understood from the above embodiments and reference examples. Reference Example 1 is an example in which α-phenylethylamine was used as an amine compound to be reacted with adipic acid. In the compound obtained by this reaction, adipic acid reacts with the amino group bonded to the aliphatic carbon. Reference Example 2 is an example in which aniline was used as an amine compound to be reacted with adipic acid dichloride. The compound obtained by this reaction reacts with the amino group in which adipic dichloride is directly substituted on the aromatic nucleus. Reference Example 3 is an example in which α-phenylethylamine and aniline were used as amine compounds to be reacted with adipic acid. In this example, adipic acid reacts with the amino group attached to the aliphatic carbon and the amino group directly substituted on the aromatic nucleus. The structures of the compounds obtained in these Reference Examples and Examples and the signals of the NH proton and methylene proton of the amide bond in ¹ H-NMR are shown.

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As is apparent from the above-mentioned compounds and the proton signal, the diamine of the present invention obtained in Example 1 is a compound obtained by reacting adipic acid obtained in Reference Example 1 with an amino group bonded to an aliphatic carbon. The same proton signal is shown. The compounds of Reference Examples 2 and 3 in which adipic acid chloride was reacted with an amino group directly substituted on an aromatic nucleus and diamines in which adipic acid was directly substituted on an aromatic group with an amino group bonded to an aliphatic carbon were obtained. It is obvious.

Example 2 9.4 g (0.05 mol) of azelaic acid was charged into a vessel equipped with a stirrer and a nitrogen inlet tube under a nitrogen atmosphere, and then heated to 105 to 110 ° C. and dissolved. . Then m-
13.6 g (0.1 mol) of aminophenylethylamine
Was charged for 1 hour. Temperature to 130-140 ° C,
The reaction was carried out at the same temperature for 4 hours (distilled water 1.59 g, 88.
0% theoretical distillate%). After the reaction, the mixture was discharged into a porcelain flat plate to obtain crystals. The yield was 20.5 g and the yield was 96.6%. The crystals were treated in the same manner as in Example 1 to give white crystals.
4 g (82.1% yield) was obtained. This crystal is ¹ H-NM
From R analysis, it was confirmed that it was a single component. That is, the NH proton of the amide bond was observed at 8.2 ppm (1H) and the methylene proton was observed at 1.46 ppm (2H).

Example 3 A container equipped with a stirrer and a nitrogen inlet tube was charged with 13.2 g (0.1 mol) of glutaric acid under a nitrogen atmosphere, and then heated to 90 to 95 ° C. and dissolved. . Next, 27.2 g (0.2 mol) of m-aminophenylethylamine was charged over 1 hour. It took 2 hours to raise the temperature to 170 to 180 ° C. and reacted at the same temperature for 4 hours (3.42 g of distilled water,
95.0% of theoretical distillate%). After the reaction, the mixture was discharged into a porcelain flat plate to obtain crystals. Yield 36.1 g 98.1% melting point 59.8-
The crystals were treated as in Example 1 to give white crystals.
4 g (82.1% yield) was obtained. This crystal is ¹ H-NM
From R analysis, it was confirmed that it was a single component. That is, the NH proton of the amide bond was observed at 8.2 ppm (1H) and the methylene proton was observed at 1.46 ppm (2H).

Example 4 A container equipped with a stirrer and a nitrogen inlet tube was charged with 70.8 g of water and 35.4 g (0.3 mol) of succinic acid in a nitrogen atmosphere, and then heated to 80 to 95 ° C. Dissolved by warming.
Next, 81.7 g of m-aminophenylethylamine (0.
6 mol) was charged over 1 hour. The temperature was raised to 102 to 110 ° C, and the reaction was carried out at the same temperature for 4 hours while distilling off water.
After the reaction, the mixture was discharged into a porcelain flat dish to obtain a salt of succinic acid and diamine as white crystals. Yield 114.0 g Yield 97.3% Melting point 171.6
~ 174.6 ° C 19.5 g (0.05 mol) of the salt obtained here was charged into a vessel equipped with a stirrer and a nitrogen inlet tube, and the salt was poured into a vessel having a capacity of 190 to 200.
C., and reacted at the same temperature for 5 hours to distill off 1.5 g of water. After the reaction, the mixture was discharged into a porcelain flat plate to obtain white crystals. Yield 17.0 g Yield 96.0%

Example 5 N-methyl-2 was placed in a vessel equipped with a stirrer and a nitrogen inlet tube.
-99.6 g of pyrrolidone and α- (p-nitrophenyl)
After charging 33.2 g (0.2 mol) of ethylamine and 20.2 g (0.2 mol) of triethylamine, 0 ° C.
And cooled. 18.7 g of adipic dichloride at the same temperature
(0.1 mol), and the mixture was stirred at 10 to 15 ° C for 2 hours. The mixture was further stirred at 25 to 30 ° C for 3 hours. After the reaction, the precipitated triethylamine hydrochloride was filtered off, and the filtrate was discharged into 1 liter of water at a temperature of 15 to 20 ° C. The precipitated crystals were filtered, and the cake was washed with water and dried. Yield 43.2 g Yield 98.0% Melting point 198.0-
201.5 ° C. The results of elemental analysis of the dinitro compound obtained here were as follows. 22.1 g (0.05 mol) of the above dinitro compound and methanol in a catalytic hydrogenation magen for 100 ml.
After inserting 6 g (7 times amount / dinitro compound), 0.442 g (3 wt%) of 5% Pd-C (50% water-containing product) under a nitrogen stream.
% / Dinitro compound), and the system is replaced with hydrogen.
7.34 l of hydrogen was absorbed at 45 to 50 ° C for 3 hours (dispersion state to complete dissolution). After the reaction, the inside of the system was replaced with nitrogen, and then the catalyst was separated by filtration. The reaction solution was concentrated under reduced pressure to obtain white crystals. Yield 18.7g Yield 97.8% Melting point 180.8-1
84.4 ° C. The result of ¹ H-NMR measurement of this crystal is as follows. That is, the NH proton of the amide bond is 8.2p
pm (1H) and 1.46 ppm of methylene protons
(2H) was observed. The results of elemental analysis of the diamine obtained here were as follows.

Example 6 N-methyl-2 was placed in a vessel equipped with a stirrer and a nitrogen inlet tube.
-99.6 g of pyrrolidone and α- (p-nitrophenyl)
After charging 33.2 g (0.2 mol) of ethylamine and 20.2 g (0.2 mol) of triethylamine, 0 ° C.
And cooled. At the same temperature isophthalic dichloride 20.3
After inserting g (0.1 mol), the mixture was stirred at 10 to 15 ° C for 2 hours, and further stirred at 25 to 30 ° C for 3 hours. After the reaction, the precipitated triethylamine hydrochloride was filtered off, and the filtrate was discharged into 1 liter of water at a temperature of 15 to 20 ° C. The precipitated crystals were filtered, and the cake was washed with water and dried. Yield 45.3 g Yield 98.1% Melting point 184.8-
23.1 g (0.05 mol) of the above dinitro compound and methanol 161.
After inserting 7 g (7 times amount / dinitro compound), 1.326 g (3 wt%) of 5% Pd-C (50% water-containing product) was placed under a nitrogen stream.
% / Dinitro compound), and the system is replaced with hydrogen.
7.34 l of hydrogen was absorbed at 45 to 50 ° C for 3 hours (dispersion state to complete dissolution). After the reaction, the inside of the system was replaced with nitrogen, and then the catalyst was separated by filtration. The reaction solution was concentrated under reduced pressure to obtain pale yellow crystals. Yield 19.6 g Yield 98.0%

Example 7 Toluene 332 was placed in a vessel equipped with a stirrer and a nitrogen inlet tube.
g and α- (p-nitrophenyl) ethylamine 33.2
g (0.2 mol) and 20.2 g of triethylamine
(0.2 mol). After inserting 18.7 g (0.1 mol) of adipic dichloride at 20 to 25 ° C, 2
Stirred at 5-30 ° C for 2 hours. The temperature was further raised to 60 ° C, and the mixture was stirred at 65 to 70 ° C for 3 hours. After inserting 66.4 g of methanol at the same temperature, the mixture was cooled to 25 to 30 ° C.
The precipitated crystals are filtered, and the filter cake is 33.2 g of methanol.
And washed. Yield 42.2 g Yield 95.7% Melting point 199.8-
At a temperature of 201.1 ° C. or lower, the dinitro compound was catalytically reduced in the same manner as in Example 1 to obtain a diamine. Yield 18.7g Yield 97.8% Melting point 180.8 ~
184.4 ° C

Example 8 Toluene 332 was placed in a vessel equipped with a stirrer and a nitrogen inlet tube.
g and α- (m-nitrophenyl) ethylamine 33.2
g (0.2 mol) and 20.2 g of triethylamine
(0.2 mol). After inserting 18.7 g (0.1 mol) of adipic dichloride at 20 to 25 ° C, 2
Stirred at 5-30 ° C for 2 hours. The temperature was further raised to 60 ° C, and the mixture was stirred at 65 to 70 ° C for 3 hours. After inserting 66.4 g of methanol at the same temperature, the mixture was cooled to 25 to 30 ° C.
The precipitated crystals are filtered, and the filter cake is 33.2 g of methanol.
And washed. Yield 42.3 g Yield 95.9% Melting point 196 ~
22.1 g (0.05 mol) of the above dinitro compound and 44.2 g of methanol in a catalytic hydrogenation mergen for 100 ml at 199 ° C.
g (2 times the amount / dinitro compound), and then 0.442 g (1 wt%) of 5% Pd-C (50% water-containing product) under a nitrogen stream.
/ Dinitro form) and replace the system with hydrogen. 4
It took 7 hours at 5-55 ° C to absorb 7.34 l of hydrogen. After the reaction, the inside of the system was replaced with nitrogen, and then the catalyst was separated by filtration. The reaction solution was concentrated under reduced pressure to obtain 18.7 g of crude crystals. Yield 18.2 g Yield 95.0% Melting point 101-122
° C

Example 9 N-methyl-2 was placed in a vessel equipped with a stirrer and a nitrogen inlet tube.
After charging 99.6 g of pyrrolidone, 33.2 g (0.2 mol) of α- (m / p-nitrophenyl) ethylamine and 20.2 g (0.2 mol) of triethylamine,
Cooled to 0 ° C. Adipic dichloride at the same temperature;
After inserting 7 g (0.1 mol), the mixture was stirred at 10 to 15 ° C for 2 hours, and further stirred at 25 to 30 ° C for 3 hours.
After the reaction, the precipitated triethylamine hydrochloride was filtered off, and the filtrate was discharged into 1 liter of water at a temperature of 15 to 20 ° C. The precipitated crystals were filtered, and the cake was washed with 33.2 g of methanol. Yield 41.4 g Yield 93.9% Melting point 198.0-
At 201.5 ° C. or lower, the catalytic reduction of the dinitro compound was carried out in the same manner as in Example 1 to obtain a diamine of m / p-mixture Yield 18.6 g Yield 97.4%

Example 10 In a vessel equipped with a stirrer and a nitrogen inlet tube, 23.9 g (0.1 mol) g (0.0 mol) of sebacic acid were placed under a nitrogen atmosphere.
(5 mol), and the mixture was heated to 105 to 110 ° C. and dissolved. Next, m-nitrophenylethylamine 13.6
g (0.1 mol) was charged over 1 hour. 130-1
The temperature was raised to 40 ° C., and the reaction was carried out at the same temperature for 4 hours (distilled water 1.59 g, 88.0% theoretical distilling amount%). After the reaction, the mixture was discharged to obtain crystals. Yield: 20.5 g Yield: 96.6% The crystals were catalytically reduced under the same conditions as in Example 1 to obtain 17.4 g (yield: 82.1%) of white crystals.

[0046]

The novel diamine according to the present invention has an amide bond, so that it can be used as a starting material for polyimides, polyamides, polyamideimides, bismaleimides, diisocyanates or epoxy resins which require heat resistance and processability. An object of the present invention is to provide an extremely useful aromatic diamine that can be expected to be used for multipurpose applications.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI // C08G 69/26 C08G 69/26 73/10 73/10 73/14 73/14 (72) Inventor Ryuji Haseyama Yokohama, Kanagawa 1190 Kasama-cho, Sakae-ku, Mitsui Toatsu Chemical Co., Ltd. (56) References JP-A-6-100519 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (6)

(57) [Claims] 1. A compound represented by the general formula (1): (Wherein, R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, X represents a phenylene group, a cyclohexylene group, or an alkylene group having 2 to 10 carbon atoms, and the NH ₂ group is located at the meta or para position. Diamines represented by). 2. The diamine according to claim 1, wherein R in Formula (1) is a hydrogen atom or a methyl group. 3. A compound of the general formula (2) (In the formula, R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the NH ₂ group is located at the meta or para position.)
And a diamine represented by the general formula (3): (X represents a phenylene group, a cyclohexylene group or an alkylene group having 2 to 10 carbon atoms, and M represents a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms) or a dibasic acid or a derivative thereof. The method for producing a diamine according to claim 1, wherein: 4. A compound of the general formula (4) (Wherein, R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the NO ₂ group is located at the meta or para position)
And an α- (nitrophenyl) alkylamine represented by the general formula (3 ′) (X represents a phenylene group, a cyclohexylene group or an alkylene group having 2 to 10 carbon atoms, and M represents a hydroxyl group, a halogen atom or an alkoxy group having 1 to 4 carbon atoms) or a dibasic acid or a derivative thereof. After the reaction, general formula (5) (Wherein, R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, X represents a phenylene group, a cyclohexylene group or an alkylene group having 2 to 10 carbon atoms, and the NO ₂ group is located at the meta or para position. 2. The process for producing diamines according to claim 1, wherein the dinitro compound represented by the formula) is catalytically reduced in the presence of an alkali. 5. A compound of the formula (2) wherein α- (3-aminophenyl) methylamine, α- (3-aminophenyl) ethylamine, α- (3-aminophenyl) propylamine,
The method according to claim 3, which is an α- (3-aminophenyl) alkylamine selected from α- (3-aminophenyl) butylamine. 6. A compound represented by the formula (4): α- (nitrophenyl)
Methylamine, α- (nitrophenyl) ethylamine,
The method according to claim 4, which is an α- (nitrophenyl) alkylamine selected from α- (nitrophenyl) propylamine and α- (nitrophenyl) butylamines.