JPH05320110A - New diamines and their productions - Google Patents

Abstract

PURPOSE:To obtain a new diamine containing an amide bond useful as a starting raw material for polyimide, polyamide, polyamideimide, bismaleimide, epoxy resin, etc., requiring heat resistance and processability and diisocyanate. CONSTITUTION:A diamine of formula I (R is H or 1-10C alkyl; X is phenylene, cyclohexyl or 2-10C alkylene; NH2 is located at meta- or para-position) such as a compound of formula II. The compound is produced by (a) reacting a compound of formula III (NH2 is located at meta- or para-position) such as alpha-(3-aminophenyl)methylamine with a compound of formula IV (M is OH or 1-4C alkoxy) or (b) reacting a compound of formula V (NO2 is located at meta- or para-position) such as alpha-(nitrophenyl)methylamine with a compound of formula VI (M' is OH, halogen or 1-4C alkoxy) and catalytically reducing a compound of formula VII in the presence of an alkali.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel diamine having an amide bond and a method for producing the same. This compound is a compound useful as a starting material for polyimide, polyamide, polyamideimide, bismaleimide, diisocyanate, epoxy resin or the like.

[0002]

2. Description of the Related Art In recent years, research and development of highly functional polymer materials have become more active, and accordingly, reactive polymers in which highly reactive functional groups are uniformly arranged are required. In particular,
Among the functional polymer materials, polyimide and polyamide are expected to be widely used in a wide range of fields because they have excellent heat resistance and dimensional stability.

However, although many polyimides, polyamides, etc. which have been developed so far have excellent mechanical properties and heat resistance, they lack processability when molding these resins and absorb water. There was a problem in workability such as high rate. For example, as an aromatic diamine, p
A polyamide obtained by using phenylenediamine as a raw material, for example, the following formula (6)

[Chemical 7] The wholly aromatic polyamide having a basic skeleton represented by (DuPont; trade name: Kevlar) does not have a clear glass transition temperature, and has a problem in processability when used as a moldable material. .. Therefore, improvements are attempted by adding an aliphatic diamine or an aliphatic dicarboxylic acid.

On the other hand, as a means for improving moldability, it is also known that it is effective to position the aromatic amino group at the meta position with respect to the bonding group (Dupont Company). Made; trade name Nomex). Further, a polyamide composed of m-xylylenediamine and an aliphatic dicarboxylic acid, for example, the following formula (7)

[Chemical 8] It has been reported that a polyamide (trade name: RENY, manufactured by Mitsubishi Gas Chemical Co., Inc.) having a repeating structure having a basic skeleton represented by the following has an excellent oxygen gas barrier property.

As described above, by changing one of the starting materials (aromatic) diamines, a large difference occurs in the glass transition temperature, the melting point, the thermal decomposition temperature and the processability of the polyamide resin. There have been many developments of various new diamines having performance.

[0006]

An object of the present invention is to provide a novel diamine useful as a raw material for novel polyamides, polyimides, epoxy resin curing agents 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 made extensive studies on the synthesis of various novel diamine compounds. As a result, the general formula (8) (formula 9)

[Chemical 9] (Wherein R ₁ represents an alkyl group and the NH ₂ group is located at the meta or para position) is reacted with a dibasic acid or a derivative thereof, and an amino group directly substituted on an aromatic nucleus is obtained. The amino group bonded to the aliphatic carbon has higher reactivity than that of, and the novel diamine compound of the present invention can be obtained by reacting with a dibasic acid. In addition, the general formula (9) (Chemical formula 10)

[Chemical 10] (Wherein R ₁ represents an alkyl group and the NO ₂ group is located at the meta or para position) and 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 is based on the formula (1)

[Chemical 11] (In the formula, 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. ) And diamines represented by the formula (2)

[Chemical formula 12] (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)

[Chemical 13] (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) and a dibasic acid or a derivative thereof. And a method for producing a diamine, characterized by the general formula (4)

[Chemical 14] (In the formula, 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 ′)

[Chemical 15] (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 derivative thereof. After reacting, the compound represented by the general formula (5)

[Chemical 16] (In the formula, 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. And a dinitro compound represented by the formula (1) is catalytically reduced 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 in the aromatic nucleus is in the 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 in 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 in the para position, the heat resistance is improved. Is a compound that can be expected.

The diamine used in the reaction of the present invention with a dibasic acid will be specifically described below with reference to the general formula (2). Specifically, m- 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-
Examples include (4-aminophenyl) octylamine, α- (3-aminophenyl) nonylamine, α- (4-aminophenyl) nonylamine, α- (3-aminophenyl) decylamine, and α- (4-aminophenyl) decylamine. 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 and 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
Examples include-(3-nitrophenyl) nonylamine, α- (4-nitrophenyl) nonylamine, α- (3-nitrophenyl) decylamine, and α- (4-nitrophenyl) decylamine, and α- (nitrophenyl) is preferable. ) Methylamine, α- (nitrophenyl) ethylamine, α- (nitrophenyl) propylamine α-m- or p-nitro compounds and mixtures thereof
-(Nitrophenyl) alkylamine.

On the other hand, the dibasic acid or its derivative used for the reaction with the diamine in the present invention is represented by the general formula (3), and specifically, phthalic acid, terephthalic acid, isophthalic acid, succinic acid, Glutaric acid, adipic acid, pimelic acid,
Derivatives of suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, hexahydrophthalic acid or esters can be used, and α-
The dibasic acid or its derivative used for the reaction with (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, undecanedioic acid,
Dodecanedioic acid, hexahydrophthalic acid, or their derivatives such as esters or acid halides can be used. The halogens forming 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, dodecanedioic acid. Examples thereof include dichloride.

In the method of the present invention, the above-mentioned diamine or α- (nitrophenyl) alkylamine and dibasic acid or a derivative thereof are added to diamine or α- (nitrophenyl) alkylamine to 2 equivalents of dibasic acid or This is a method for producing a diamine of the present invention by reacting one equivalent of the derivative, 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 at a temperature equal to or higher than the melting point, and then a diamine or α- (nitrophenyl) alkylamine is added to carry out a reaction. 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 in the parenthesis of the solvent),
Isoquinoline (243 ° C), quinoline (237 ° C), N
-Methyl-2-pyrrolidone (202 ° C), m-cresol (203 ° C), dimethylsulfoxide (189 ° C) are used. When an organic solvent having a boiling point of 180 ° C. or lower is used, the reaction can be carried out while distilling off the organic solvent, or under pressure. For example, N, N
-Dimethylformamide (153 ° C), N, N-dimethylacetamide (166 ° C), 2,4-lutidine (15
7 ° C), cyclohexanone (156 ° C), toluene (1
10 ° C), xylene (144 ° C), triethylamine (90 ° C), methanol (65 ° C), acetone (56
℃) and the like. These solvents may be used alone or in 2
You may use it in mixture of 2 or more types. Although the amount of the solvent used does not cause a problem in the reaction when used in excess, it is economically disadvantageous. Usually, it is preferable to use it in a range of 10 to 20 times the weight ratio of the raw material amine.

The reaction temperature of the diamine or α- (nitrophenyl) alkylamine and the dibasic acid or its ester in the present invention varies depending on the type of reaction raw material monomer, the reaction method and the type of solvent, but is usually 150 to 250. ℃
It is implemented within a range of degrees. When a dibasic acid is used as a reaction raw material for the reaction, 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), undecanedioic acid (melting point 111 ° C), hexahydroterephthalic acid (cis,
Trans melting point 165 to 250 ° C.) and the like, and then the diamine is inserted under a nitrogen stream while maintaining fluidity. The diamine dropping time is sufficient if it is 1 to 8 hours, preferably about 2 to 5 hours. At this time, it is preferable that the dropping temperature is dropped within a range not exceeding 35 ° C. from the melting point of the dibasic acid. It is not preferable to carry out the reaction at a temperature significantly above the melting point because of the thermal stability of the dibasic acid.

The reaction time varies depending on the type of reaction raw material monomer, the reaction method, and the type of solvent, but usually the reaction is performed for a time sufficient to complete the production 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 time is until the distilling of water is stopped, but the reaction time is generally 2-8.
It is carried out 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,
Charge a dibasic acid halide under a nitrogen stream, and
The reaction is carried out in the range of -80 ° C. In this case, since heat is generated when charging the raw materials, the first half with 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 carry out accurately at the above temperature, in some cases, the temperature is previously set to -30 to -10 ° C.
It is preferable to cool to a certain degree.

When using a dibasic acid halide,
Usually, a dehalogenating agent is used together. As the dehalogenating agent used, a base or an oxirane compound is used. Examples of the base include triethylamine, tributylamine, tripentylamine, N, N-dimethylaniline,
N, N-diethylaniline, pyridine, α-picoline,
β-picoline, γ-picoline, 2,4-lutidine, 2,
Examples of 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 dehalogenating agent may be used in a stoichiometric amount with respect to the functional group. For example, when triethylamine is used as the dehalogenating agent, it may be used in an amount of 2 times the mole of the dibasic acid halide, which is a reaction raw material, in 1 mole.

As the organic solvent used in the above method,
For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,
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, Examples include isophorone. These solvents may be used alone or in combination of two or more.

The amount of the organic solvent used is in the range of 3 to 8 parts by weight with respect to 1 part by weight of α- (nitrophenyl) alkylamines. If the amount used is 3 parts by weight or less, the system will become viscous because the triethylamine hydrochloride will precipitate after the reaction. Further, when the salt is filtered off, the filtration becomes slow. When the amount used is 8 parts by weight or more, the amount of water, alcohol, etc. used when discharging is increased. It is preferably used in the range of 4 to 6 parts by weight.

After the reaction as described above, since the reaction solution is usually a viscous solution, it is discharged and crystallized after the reaction. When the reaction is performed using an organic solvent, if the solvent is a mixture with water, the solvent is discharged into water to precipitate crystals, which is then filtered. If the solvent is immiscible with water,
By distilling off the solvent and then discharging it, a diamine and a dinitro compound having an amide bond can be obtained.

The method of reducing the dinitro compound obtained as described above is not particularly limited, and a method of reducing a nitro group to an amino group can be applied, but 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, etc. can be used. It is industrially preferable to use a palladium catalyst. These catalysts are also used in the metallic state, but usually carbon, barium sulfate, silica gel, alumina,
It is used by supporting it on the surface of a simple substance such as Celite, or as a Raney catalyst for nickel, cobalt, copper or the like.

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 with respect to the raw material dinitro compound, and is usually used in the state of metal. In the case of 2 to 8% by weight, when loaded 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. , Ethers such as tetrahydrofuran, methyl cellosolve, and aliphatic hydrocarbons such as hexane and 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, 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, but usually 4.0 to 4.0 with respect to the raw materials.
It is carried out at 15 times the weight.

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

The diamine thus obtained contains a small amount of diamine other than the target substance and must be removed. There are various methods for removing these by-produced diamines. For example, after disperse the crude crystals of the obtained diamine in water, add an acid to form a salt to completely dissolve in water, neutralize with an alkali to precipitate a by-product diamine that is hardly soluble in water, After separating by filtration, salting out is performed from the filtrate. After forming a salt, water-insoluble impurities are filtered off and then neutralized with an alkali. The diamines of the present invention can be isolated by any method.

As a general embodiment of the process according to the invention, in the case of the reaction of a diamine and a dibasic acid, the dibasic acid 1
An equivalent amount is heated to a melting point under a nitrogen stream and dissolved, and then 2 equivalent amounts of a diamine are charged and reacted. After the theoretical amount of water is distilled off, it is discharged into a porcelain flat plate for crystallization while keeping the fluidity. On the other hand, in the case of the reaction of α- (nitrophenyl) alkylamine with dibasic acid dichloride, 2 equivalents of α- (nitrophenyl) alkylamine and triethylamine 2 were added to a N-methyl-2-pyrrolidone solvent under a nitrogen stream.
After charging an equivalent amount, the reaction is carried out at 0 ° C. or below by charging 1 equivalent amount of dibasic acid dichloride. After the reaction, the precipitated triethylamine hydrochloride is filtered off, and the filtrate is discharged into water or alcohol to precipitate crystals, whereby the dinitro compound can be isolated. After catalytic reduction of the obtained dinitro compound in an organic solvent, the catalyst was filtered off,
By recovering the organic solvent, the target product can be easily obtained.

Since the diamine in the present invention has an amide bond, it is necessary to have heat resistance and processability, such as polyimide, polyamide, polyamideimide, bismaleimide,
It is a very useful diamine that can be expected to be used for various purposes as a starting material for diisocyanates or epoxy resins.

[0030]

EXAMPLES The present invention will now be described in more detail with reference to examples. The structural analysis of these was confirmed by comparing the NH protons of the amide bond and the methylene protons of the dibasic acid skeleton from the ¹ H-NMR measurement results. ^{The 1} H-NMR measurement results are shown based on TMS.

Example 1 7.3 g (0.05 mol) of adipic acid was charged in 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 it. .. Then, 13.6 g (0.1 mol) of m-aminophenylethylamine was charged for 1 hour. Then, the reaction was carried out at the same temperature for 4 hours (distilled water 1.51 g, 83.9% theoretical distillate%).
After the reaction, the crystals were discharged into a flat plate made of porcelain. Yield 18.2 g Yield 95.0% ¹ H-NMR of the crude crystal obtained here was measured and the result was
It was as follows. That is, the NH protons of the amide bond are 8.2 ppm (1H) and 9.8 ppm (1H),
In addition, 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 of water (10 times amount), 2
At 0 to 25 ° C., 11.1 g (0.10 mol) of 35% hydrochloric acid was added dropwise and dissolved. Next, 45% sodium hydroxide 8.
It was neutralized to pH 6.5 with 7 g (0.098 mol). After filtering off the precipitated brown component, the filtrate was salted out with sodium chloride,
A white crystal was obtained by filtration, washing and drying. Yield 16.4 g Yield 85.7% Melting point 100.8
~ 123 ° C The ¹ H-NMR measurement results of the purified product obtained here are as follows. That is, the NH protons of the amide crystals are 8.2 ppm (1H) and the methylene protons are 1.
46 ppm (2H) was observed.

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

Reference Example-2 In a container equipped with a stirrer and a nitrogen introducing tube, 9.3 g (0.1 mol) of aniline and N-methyl-in a nitrogen atmosphere.
2-Pyrrolidone 93.0 g (10 times amount / aniline) and triethylamine 10.1 g (0.1 mol) were charged. After cooling to 0 ° C., adipic acid dichloride 9.2
g (0.05 mol) was charged. After reacting at 0 to 5 ° C for 1 hour, it was further reacted at 20 to 25 ° C for 3 hours. After the reaction, the resulting crystals were 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,
Amido bond NH protons were observed at 9.8 ppm (1H) and methylene protons at 1.60 ppm (2H).

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

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

[Chemical 17]

[Chemical 18]

[Chemical 19]

[Chemical 20]

As is clear from the compounds shown above and the proton signals, 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. Shows the same proton signal as. Compounds obtained by reacting adipic acid chloride of Reference Examples 2 and 3 with an amino group directly substituted on an aromatic nucleus and diamines having adipic acid directly substituted on an aliphatic carbon-bonded amino group and an aromatic nucleus are obtained. It's obvious.

Example 2 9.4 g (0.05 mol) of azelaic acid was charged in a container equipped with a stirrer and a nitrogen introducing tube under a nitrogen atmosphere and then heated to 105 to 110 ° C. to dissolve it. .. Then m-
Aminophenylethylamine 13.6 g (0.1 mol)
It took 1 hour to charge. Raise the 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 crystals were discharged into a flat plate made of porcelain. Yield 20.5 g Yield 96.6% This crystal was treated in the same manner as in Example 1 to give a white crystal 17.
4 g (yield 82.1%) was obtained. This crystal is ¹ H-NM
It was confirmed from R analysis that it was a single component. That is, NH protons of the amide bond were observed at 8.2 ppm (1H) and methylene protons at 1.46 ppm (2H).

Example 3 13.2 g (0.1 mol) of glutaric acid was charged in a container equipped with a stirrer and a nitrogen introducing tube under a nitrogen atmosphere, and then heated to 90 to 95 ° C. to dissolve it. .. Next, 27.2 g (0.2 mol) of m-aminophenylethylamine was charged in 1 hour. It took 2 hours to raise the temperature to 170 to 180 ° C., and reacted at the same temperature for 4 hours (distilled water 3.42 g,
95.0% theoretical distillation amount%). After the reaction, the crystals were discharged into a flat plate made of porcelain. Yield 36.1 g Yield 98.1% Melting point 59.8-
67.8 ° C. This crystal was treated in the same manner as in Example 1 to give a white crystal 17.
4 g (yield 82.1%) was obtained. This crystal is ¹ H-NM
It was confirmed from R analysis that it was a single component. That is, NH protons of the amide bond were observed at 8.2 ppm (1H) and methylene protons at 1.46 ppm (2H).

EXAMPLE 4 70.8 g of water and 35.4 g (0.3 mol) of succinic acid were charged in a container equipped with a stirrer and a nitrogen introducing tube under a nitrogen atmosphere, and then the temperature was raised to 80 to 95 ° C. Warmed and dissolved.
Next, 81.7 g of m-aminophenylethylamine (0.
(6 mol) was charged in 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 product was discharged into a porcelain flat plate to obtain a salt of white crystals of succinic acid and diamine. 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 container equipped with a stirrer and a nitrogen introducing tube,
The temperature was raised to ° C and the reaction was carried out at the same temperature for 5 hours to distill 1.5 g of water. After the reaction, the white crystals were discharged onto a flat plate made of porcelain. Yield 17.0 g Yield 96.0%

Example 5 N-methyl-2 was placed in a container equipped with a stirrer and a nitrogen introducing tube.
-Pyrrolidone 99.6g 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.
Cooled to. 18.7 g of adipic acid dichloride at the same temperature
After inserting (0.1 mol), the mixture was stirred at 10 to 15 ° C for 2 hours. Furthermore, it stirred at 25-30 degreeC 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 filter cake was washed with water and dried. Yield 43.2 g Yield 98.0% Melting point 198.0
201.5 ° C. The elemental analysis result of the dinitro compound obtained here is as follows. In a catalytic hydrogenation margen for 100 ml, 22.1 g (0.05 mol) of the above dinitro compound and 132.
After inserting 6 g (7 times amount / dinitro body), 0.442 g (3 wt) of 5% Pd-C (50% hydrous product) under a nitrogen stream.
% / Dinitro form) is charged and the system is replaced with hydrogen.
It took 3 hours at 45 to 50 ° C. to absorb 7.34 l of hydrogen (dispersion state to complete dissolution). After the reaction, the system was replaced with nitrogen, and the catalyst was filtered off. The reaction solution was concentrated under reduced pressure to give white crystals. Yield 18.7 g Yield 97.8% Melting point 180.8-1
84.4 ° C. The ¹ H-NMR measurement result of this crystal is as follows. That is, the NH proton of the amide bond is 8.2 p
1.46 ppm of pm (1H) and methylene protons
(2H) was observed. The elemental analysis results of the diamine obtained here are as follows.

Example 6 A container equipped with a stirrer and a nitrogen inlet tube was charged with N-methyl-2.
-Pyrrolidone 99.6g 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.
Cooled to. Isophthalic dichloride 20.3 at the same temperature
After inserting g (0.1 mol), the mixture was stirred at 10 to 15 ° C for 2 hours and further 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 filter cake was washed with water and dried. Yield 45.3 g Yield 98.1% Melting point 184.8-
193.1 ° C. A catalytic hydrogenation margen for 100 ml contained 23.1 g (0.05 mol) of the above dinitro compound and 161.
After inserting 7 g (7 times amount / dinitro body), 1.326 g (3 wt) of 5% Pd-C (50% hydrous product) under a nitrogen stream.
% / Dinitro form) is charged and the system is replaced with hydrogen.
It took 3 hours at 45 to 50 ° C. to absorb 7.34 l of hydrogen (dispersion state to complete dissolution). After the reaction, the system was replaced with nitrogen, and the catalyst was filtered off. The reaction solution was concentrated under reduced pressure to give pale yellow crystals. Yield 19.6 g Yield 98.0%

Example 7 Toluene 332 was placed in a container equipped with a stirrer and a nitrogen introducing tube.
g and α- (p-nitrophenyl) ethylamine 33.2
g (0.2 mol) and triethylamine 20.2 g
(0.2 mol) was charged. After inserting 18.7 g (0.1 mol) of adipic acid dichloride at 20 to 25 ° C., 2
It stirred at 5-30 degreeC 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, cool to 25 to 30 ° C,
The precipitated crystals were filtered, and the filter cake contained 33.2 g of methanol.
Washed with. Yield 42.2 g Yield 95.7% Melting point 199.8-
At 201.1 ° C or lower, catalytic reduction of the dinitro compound was carried out in the same manner as in Example 1 to obtain a diamine. Yield 18.7 g Yield 97.8% Melting point 180.8-
184.4 ° C

Example 8 Toluene 332 was placed in a container equipped with a stirrer and a nitrogen introducing tube.
g and α- (m-nitrophenyl) ethylamine 33.2
g (0.2 mol) and triethylamine 20.2 g
(0.2 mol) was charged. After inserting 18.7 g (0.1 mol) of adipic acid dichloride at 20 to 25 ° C., 2
It stirred at 5-30 degreeC 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, cool to 25 to 30 ° C,
The precipitated crystals were filtered, and the filter cake contained 33.2 g of methanol.
Washed with. Yield 42.3 g Yield 95.9% Melting point 196-
Catalytic hydrogenation margen for 199 ° C. 100 ml, 22.1 g (0.05 mol) of the above dinitro compound and 44.2 methanol.
After inserting g (2 times amount / dinitro body), 0.442 g (1 wt% of 5% Pd-C (50% hydrous product) under a nitrogen stream.
(/ Dinitro form) and replace the inside of the system with hydrogen. Four
It took 7 hours at 5-55 ° C to absorb 7.34 l of hydrogen. After the reaction, the system was replaced with nitrogen, and the catalyst was filtered off. The reaction liquid was concentrated under reduced pressure to obtain 18.7 g of crude crystals. Yield 18.2 g Yield 95.0% Melting point 101-122
℃

Example 9 A container equipped with a stirrer and a nitrogen inlet tube was charged with N-methyl-2.
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 acid dichloride at the same temperature 18.
After inserting 7 g (0.1 mol), the mixture was stirred at 10 to 15 ° C for 2 hours and further 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 filter 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, catalytic reduction of the dinitro compound was performed in the same manner as in Example 1 to obtain a diamine as an m / p-mixture. 18.6 g Yield 97.4%

Example 10 23.9 g (0.1 mol) g (0.0 mol) of sebacic acid was placed in a container equipped with a stirrer and a nitrogen introducing tube under a nitrogen atmosphere.
(5 mol), and the temperature was raised to 105 to 110 ° C. to dissolve it. Next, m-nitrophenylethylamine 13.6
g (0.1 mol) was charged in 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 distillate amount%). After the reaction, it was discharged to obtain crystals. Yield 20.5 g Yield 96.6% This crystal was catalytically reduced under the same conditions as in Example 1 to obtain 17.4 g of white crystal (yield 82.1%).

[0046]

INDUSTRIAL APPLICABILITY Since the novel diamine in the present invention has an amide bond, it can be used as a starting material for polyimide, polyamide, polyamideimide, bismaleimide, diisocyanate, epoxy resin or the like which requires heat resistance and processability. An extremely useful aromatic diamine that can be expected to be used for various purposes.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Ryuji Haseyama 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd.

Claims (6)

[Claims] 1. General formula (1) (Chemical formula 1) (In the formula, 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 the general formula (1) is a hydrogen atom or a methyl group. 3. General formula (2) (Chemical 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) (Chemical 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) and a dibasic acid or a derivative thereof. The method for producing a diamine according to claim 1, wherein 4. The general formula (4) (chemical formula 4): (In the formula, 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 ′) (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 derivative thereof. After the reaction, the compound represented by the general formula (5) (chemical formula 6): (In the formula, 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 method for producing diamines according to claim 1, wherein the dinitro compound represented by the formula (1) is catalytically reduced in the presence of an alkali. 5. The general formula (2) is α- (3-aminophenyl) methylamine, α- (3-aminophenyl) ethylamine, α- (3-aminophenyl) propylamine,
The production method according to claim 3, which is an α- (3-aminophenyl) alkylamine selected from α- (3-aminophenyl) butylamine. 6. The general formula (4) is α- (nitrophenyl).
Methylamine, α- (nitrophenyl) ethylamine,
The production method according to claim 4, which is an α- (nitrophenyl) alkylamine selected from α- (nitrophenyl) propylamine and α- (nitrophenyl) butylamines.