JPH09316190A - Novel aromatic diamine compound, its production, and its polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a super engineering plastic excellent in mechanical strengths and heat resistance and having a relatively good processibility and an arom. diamine compd. which is a monomer for obtaining the same by reacting specific compds. SOLUTION: This arom. diamine compd. is represented by formula I and is obtd. by reacting a halobenzoyldimethylnaphthalene represented by formula II (wherein X is a halogen) with aminophenoxide. An arom. polyamide comprising repeating units represented by formula III (wherein Z is O, S, SO2 , CO, CH2 , C(CH3 )2 , or C(CF3 )2 ; R is a 1-4C alkyl, an alkoxy, a halogen, or phenyl; a is 0-1; and b is 0-4) is obtd. by polycondensing the diamine compd. with a dicarboxylic acid. An arom. polyimide represented by formula IV is obtd. by reacting the diamine compd. with an arom. tetracarboxylic dianhydride and subjecting the resultant polyamic acid represented by formula V (wherein W is a tetravalent arom. hydrocarbon group) to cyclodehydration.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an aromatic polyamide having a dimethylnaphthalene skeleton excellent in heat resistance and easy solubility, an aromatic diamine compound which is a novel monomer for producing a so-called aramid resin, and a method for producing the same. Regarding the polymer.

[0002]

2. Description of the Related Art Aromatic polyamides obtained by reacting aromatic diamines with aromatic dicarboxylic acids or their derivatives are known as resins having excellent mechanical properties and heat resistance. Formula (VII)

[Chemical 7] (In the above formula, a resin or the like comprising a repeating unit represented by Z is various aromatic dicarboxylic acids) has been proposed (JP-A-5-310921).

As the diamine component of this kind of aromatic polyamide, an aromatic diamine composed of phenylene is mainly used. By using an aromatic diamine having naphthalene, further improvement in mechanical properties, heat resistance and the like are achieved. No attempt has been made.

Polymers containing naphthalene in the skeleton are generally expected to have the following two physical properties. That is, the higher planar symmetry element of the naphthalene ring brings about higher-order symmetric elements, and the long conjugate wavelength brings about various physical properties such as mechanical and light. On the other hand, however, these characteristics make it difficult to handle the resin in terms of poor solubility, poor moldability, etc., and improvements in this respect are desired.

Based on the finding that the naphthylene skeleton and the methyl group protruding from the naphthalene play an important role in high heat resistance and easy solubility, the present inventors have made use of the dimethylnaphthalene skeleton itself as a new wholly aromatic system. A polyarylene ether ketone as a polymer material has been proposed (Japanese Patent Laid-Open No. 6-234848). This polymer is a wholly aromatic polyarylene ether ketone having a naphthalene skeleton in the main chain, has a high melting point, a high glass transition point, excellent mechanical strength, and relatively good processability, so it can be used as a super engineering plastic. Be expected.

[0006]

DISCLOSURE OF THE INVENTION The present inventors further researched a new aromatic polymer having a dimethylnaphthalene skeleton, and as a result, when a dibenzoyldimethylnaphthalene derivative and an aminophenol were reacted,
A novel aromatic diamine compound is obtained, and by polycondensing this with a dicarboxylic acid, a new aromatic polyamide that is expected to be used as a super engineering plastic that has excellent mechanical strength and heat resistance and relatively good processability. It has been found that (aramid resin) and aromatic polyimide resin can be obtained.

The present invention has been made based on the above findings, and an object of the present invention is to provide super engineering plastics having excellent mechanical strength and heat resistance, and relatively good workability, and a novel method for obtaining the same. Another object of the present invention is to provide an aromatic diamine compound which is another monomer and a method for producing the same.

[0008]

The present invention provides a compound represented by the following general formula (I):

Embedded image Relates to a novel aromatic diamine compound.

The present invention also provides the following general formula (II)

Embedded image (In the above formula, X represents a halogen atom) is a method for producing an aromatic diamine represented by the above general formula (I), which comprises reacting halobenzoyldimethylnaphthalene with aminophenoxide.

Further, the present invention provides the following general formula (III)

Embedded image (In the formula, Y is a condensed polycyclic aromatic group having 20 or less carbon atoms or the following formula (IV)

Embedded image Or one or more groups selected from the group consisting of However, Z is a direct bond, -O-, -S-, -SO _{2
-, - CO-, CH 2 -} , - C (CH 3) 2 - or -
C (CF ₃ ) ₂ −, R is an alkyl group, an alkoxy group, a halogen group or a phenyl group having 1 to 4 carbon atoms, a represents 0, 1 or 2, b represents 0 or an integer of 1 to 4. . ) Relates to an aromatic polyamide comprising a repeating unit represented by

Furthermore, the present invention provides the following general formulas (V) and (VI):

[Chemical 12]

Embedded image (In the formula, W represents a tetravalent aromatic hydrocarbon group) The present invention relates to an aromatic polyamic acid and an aromatic polyimide each having a repeating unit.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The substitution position of a methyl group in the aromatic diamine represented by the above general formula (I) of the present invention is
The naphthalene nucleus may be at any of the 2,3,4 position and the 6,7,8 position, but a 2,6-position substitution product is preferable.

The aromatic diamine compound represented by the general formula (I) is a so-called Williamson ether synthesis reaction of the halobenzoyldimethylnaphthalene represented by the general formula (II) with an aminophenoxide, for example, 4-aminophenoxide. It is obtained by The halobenzoyldimethylnaphthalene which is the starting material in this case is obtained by reacting dimethylnaphthalene with a halogenated benzoic acid halide in the presence of a Lewis acid catalyst, as disclosed in JP-A-6-234848. You can The halogen in this halobenzoyldimethylnaphthalene is fluorine, chlorine, bromine or the like, but one having fluorine as a substituent is particularly preferable because the reaction proceeds easily.

On the other hand, it is preferable to use an alkali metal salt such as sodium or potassium as the aminophenoxide. In the production method of the present invention, first, aminophenol is mixed with an organic solvent such as benzene, toluene or xylene. Under heating under reflux, potassium carbonate, sodium carbonate,
Aminophenoxide is reacted with an alkali such as potassium hydroxide or sodium hydroxide, and halobenzoyldimethylnaphthalene is added thereto to carry out the above Williamson ether synthesis reaction. It may be mixed with aminophenol from the beginning, and this is preferable because the reaction operation is simpler.

The conditions of the above-mentioned Williamson ether synthesis reaction are generally performed, for example, in the presence of an organic solvent such as benzene, toluene and xylene, halobenzoyldimethylnaphthalene is added to 1 mol of aminophenoxide in an amount of 0. It is advisable to add 75 to 1 mol and carry out at a temperature of 150 to 240 ° C. for 1 to 8 hours.

The resulting reaction product is m-cresol,
Purification is carried out by recrystallization with a polar solvent such as N-methyl-2-pyrrolidone, pyridine, N, N-dimethylacetamide, tetrahydroxyfuran or a mixed solvent of these polar solvents and a poor solvent such as water or alcohol. be able to.

The aromatic diamine compound represented by the above general formula (I) of the present invention is converted into a polyamide by polycondensation with a dicarboxylic acid derivative and by a reaction with a tetracarboxylic acid derivative into a polyimide via a polyamic acid. be able to. All of these polyamides, polyamic acids and polyimides are novel polymers that have not yet been known, and are wholly aromatic polymers having a dimethylnaphthalene skeleton, which are excellent in heat resistance and strength and have relatively good processability. It has unique physical properties such as

The aromatic polyamide of the above general formula (III) of the present invention comprises an aromatic diamine compound represented by the above general formula (I) and a condensed polycyclic aromatic group, or the above general formula (IV).
It is a polycondensation product with an aromatic dicarboxylic acid having a group of, an aromatic dicarboxylic acid dihalide, an aromatic dicarboxylic acid dialchelate or diarylate.

As a polycondensation method, a method generally known as a method for producing polyamide can be used. For example, when an aromatic dicarboxylic acid is used as a raw material, sulfuric anhydride, thionyl chloride, sulfite ester, picryl chloride, phosphorus pentoxide, oxy In the presence of a condensing agent such as phosphorus chloride, phosphite-pyridine type, triphenylphosphine-hexachloroethane type, propylphosphoric anhydride-N-methyl-2-pyrrolidone type, N, N-dimethylformamide, N , N-
Dimethylacetamide, N-methyl-2-pyrrolidone,
In an organic solvent such as pyridine, chloroform, toluene,
It can be polycondensed at 10 to 150 ° C.

When dicarboxylic acid dihalide is used, trimethylamine, triethylamine, N, N-dimethylbenzylamine, N, N-dimethylcyclohexylamine, N, N-dimethylaniline, N-methylpyrrolidine, N-methylpiperidine, N -Methylmorpholine, pyridine, α-picoline, 2,4-lutidine, quinoline, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium acetate, potassium acetate, ethylene oxide, propylene oxide Polycondensation in the presence of a dehydrohalogenating agent such as, for example, 60 ° C. or lower in the above organic solvent, and 100 to 300 ° C. in the above organic solvent when a dialkyl chelate or diarylate is used as a raw material. it can.

As the aromatic dicarboxylic acid having the above condensed polycyclic aromatic group or the group of the general formula (IV),
4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, phthalic acid, methylphthalic acid, ethylphthalic acid, methoxyphthalic acid, ethoxyphthalic acid, chlorophthalic acid, bromophthalic acid, isophthalic acid, methylisophthalic acid Acid, ethylisophthalic acid, methoxyisophthalic acid, ethoxyisophthalic acid, chloroisophthalic acid, bromoisophthalic acid, terephthalic acid, methylterephthalic acid, ethylterephthalic acid, methoxyterephthalic acid, ethoxyterephthalic acid, chloroterephthalic acid, bromoterephthalic acid, 4 , 4'-biphenylzocarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-diphenyl sulfide dicarboxylic acid, 4,4'-benzophenone dicarboxylic acid, 4,4 '
-Diphenyl sulfone dicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid, 2,2-bis (4-carboxyphenyl) propane, 2,2-bis (4-carboxyphenyl) -1,1,1,3,3,3 3-hexafluoropropane etc. can be illustrated.

Further, as the aromatic dicarboxylic acid dihalide, dichloride and dibromide of the above aromatic dicarboxylic acid, and as the aromatic dicarboxylic acid alkylate and arylate, dialkyl ester having 1 to 10 carbon atoms, diphenyl ester, di ( Fluorophenyl) ester, di (chlorophenyl) ester, di (bromophenyl) ester, di (methylphenyl) ester, di (ethylphenyl) ester, di (propylphenyl) ester
Ester, di (isopropylphenyl) ester, di (butylphenyl) ester, di (isobutylphenyl) ester, di (t-butylphenyl) ester, di (methoxyphenyl) ester, di (ethoxyphenyl) ester, di (nitrophenyl) ) Ester, di (phenylphenyl) ester, dinaphthyl ester and the like.

The aromatic polyamic acid represented by the general formula (V) of the present invention is an intermediate of the aromatic polyimide represented by the general formula (VI), and contains the aromatic diamine compound represented by the general formula (I). It is a reaction product with an aromatic tetracarboxylic dianhydride. In this reaction, in an organic solvent, aromatic tetracarboxylic acid dianhydride 0.95 to 1.50 is added to 1 mol of the aromatic diamine compound represented by the general formula (I).
It is obtained by reacting 05 mol at a temperature of 0 to 70 ° C. for 1 to 5 hours. As the organic solvent, xylene, toluene, dimethylsulfoxide, N, N'-dimethylformamide, N, N'-diethylformamide, N, N'-dimethylacetamide, N-methyl-2.
-Pyrrolidone, N-vinyl-2-pyrrolidone, phenol, cresol, xylenol, hexamethylphosphoramide, γ-butyrolactone and the like can be used alone or in combination.

Specific examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,
3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride Anhydrous, bis (3,4-
Dicarboxyphenyl) ethane dianhydride, bis (3,4
-Dicarboxyphenyl) ether dianhydride, 1,1-
Bis (3,4-dicarboxyphenyl) ethane dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 2, Examples thereof include 3,6,7-anthracene tetracarboxylic dianhydride and 1,2,7,8-phenylene tetracarboxylic dianhydride. These are used alone or in combination of two or more. be able to.

The aromatic polyimide of the general formula (VI) of the present invention is obtained by dehydration ring closure of the aromatic polyamic acid of the general formula (V). For this dehydration ring-closing reaction, any of the usual thermal or chemical dehydration ring-closing methods can be preferably adopted.

As the above thermal dehydration ring-closing method, 200
It can be performed by heating at ~ 300 ° C for 5 to 180 minutes.

Further, as a chemical dehydration ring-closing method, in the presence of a dehydrating agent and a catalyst, at a temperature of 20 to 400 ° C.,
It is preferable to react for 0.2 to 20 hours. Examples of the dehydrating agent include aliphatic acid anhydrides, aromatic acid anhydrides, N, N'-dialkylcarbodiimides, lower fatty acid halides, halogenated lower fatty acid halides, halogenated lower fatty acid anhydrides and allyl phosphons. The acid dihalide, thionyl halide and the like may be used alone or in admixture of two or more, and may be used in an amount of 0.1 to 10 mol per repeating unit of the aromatic polyamic acid. Examples of the catalyst include aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as dimethylaniline, and heterocyclic tertiary amines such as pyridine, β-picoline, and isoquinoline, either alone or in combination. It is advisable to mix the above and use 0.01 to 4 mol per repeating unit of aromatic polyamic acid.

The aromatic polyamide of the above general formula (III) and the aromatic polyimide of the above (VI) are crystalline and generally excellent in mechanical properties and heat resistance depending on the molecular weight and the kind of dicarboxylic acid. ing. In addition, since aromatic polyamide has a moderate solubility in many organic solvents, it is an excellent super engineering plastic that is easy to process. Aromatic polyimide also has good solvent solubility in its precursor aromatic polyamic acid. Therefore, both can be widely used for applications such as molding materials, fibers and films.

[0029]

【Example】

[Example 1] (Synthesis of 1,5-bis- [4- (4-aminophenoxy) benzoyl] -2,6-dimethylnaphthalene) 0.05 mol of 4-aminophenol was added to a container replaced with an inert gas. 0.1 mol of potassium carbonate, 100 ml of N-methyl-2-pyrrolidone and 20 ml of toluene were weighed out, and toluene was heated under reflux for 1 hour. Then, the reaction vessel was air-cooled and 1,5- (4-fluorobenzoyl)-
0.025 mol of 2,6-dimethylnaphthalene was added,
The reaction was carried out at 180 ° C for 3 hours. This was again air-cooled, the reaction solution was poured into 700 ml of water, stirred for a while, and the precipitated solid was collected by filtration under reduced pressure. The obtained crude product was recrystallized twice from a N, N-dimethylacetamide / methanol mixed solvent (50/50 vol ratio), washed with methanol, and dried under reduced pressure to obtain a purified product.

About this purified product, melting point, elemental analysis, ¹
1 H-NMR (solvent: DMSO-d ₆ ), ¹³ C-NMR
(Solvent: DMSO-d ₆ ), infrared absorption spectrum analysis and the like were performed to identify the structure. The measurement results were as follows.

(1) Melting point (° C.): 275.5-277.
0

(2) Elemental analysis (%): The results of the elemental analysis are as follows, and 1,5-bis- [4- (4-aminophenoxy) benzoyl] -2,6-dimethylnaphthalene (molecular formula: _{C 34 H 30 O 4 N 2} ) in good agreement with the elemental content calcd.

[Table 1]

(3) ¹ H-NMR (solvent: DMSO-
d ₆ ) (δppm): ¹ H-NMR spectrum showed the following chemical shifts. 2.19
(S, 6H), 5.12 (s, br, 4H), 6.63
(D, 4H), 6.82 (d, 4H), 6.91 (d,
4H), 7.38 (s, 4H), 7.68 (d, 4H) These chemical shifts and couplings confirmed the presence of a substituent and a substitution position such as an amino group and a methyl group in the molecule.

(4) ¹³ C-NMR (solvent: DMSO-
d ₆ ) (δppm): The following chemical shifts were confirmed by the ¹³ C-NMR spectrum. 18.9, 1
15, 116, 121, 125, 128, 129, 13
1, 131, 132, 136, 144, 146, 197

Due to this chemical shift, carbonyl group (197 ppm), methyl group (18.9 ppm),
The presence of carbon atoms constituting the aromatic ring (115 to 146 ppm) was confirmed.

(5) IR (KBr) (cm ^-1 ): Infrared absorption spectrum shows that amino group (3352, 344)
6), ether group (1269), ketone group (164
The absorption based on 0) was confirmed, and their existence was confirmed.

From the above results, the purified product obtained above is 1,5-bis- [4- (4-aminophenoxy) benzoyl] -2,6-dimethylnaphthalene represented by the formula (I). It was confirmed that there is.

[Examples 2 to 3] (Low temperature solution polycondensation of aromatic diamine and isophthalic acid dichloride or terephthalic acid dichloride) As aromatic carboxylic acid dichlorides, isophthalic acid dichloride (Example 2) and terephthalic acid dichloride (implementation) Example 1 was used, and the container of Example 1 was replaced with an inert gas.
1,5-bis- [4- (4-aminophenoxy) obtained in
Benzoyl] -2,6-dimethylnaphthalene 1 mmo
l, 6 ml of dried N-methyl-2-pyrrolidone were weighed out, and with stirring, 1 mmol of isophthalic acid dichloride
Or dry N containing 1 mmol of terephthalic acid dichloride
-Add 2 ml of methyl-2-pyrrolidone solution and
The reaction was performed at 100 ° C. for 1 hour. Then, the reaction solution was air-cooled, and 2 m of N-methyl-2-pyrrolidone solution was added thereto.
After the addition of 1 liter, the reaction solution was poured into 200 ml of methanol. Then, the mixture was heated under reflux as it was, the precipitated solid was washed, the solid matter was recovered by vacuum filtration, and dried under reduced pressure at 200 ° C. Yields 96% by weight (Example 1) and 94% by weight
It was (Example 2).

The above solid was dissolved in N-methyl-2-pyrrolidone and the logarithmic viscosity was measured at 30 ° C.
It was 73 (Example 1) and 0.57 (Example 2). In addition, for these solids, elemental analysis, ¹ H
-MNR (solvent: DMSO-d ₆₎ and ¹³ C-NMR
(Solvent: DMSO-d ₆₎ was analyzed. The result is as follows.

(1) Elemental analysis The results of elemental analysis are as follows.
Elemental content of the polycondensate of the above aromatic diamine and isophthalic acid or aromatic diamine and terephthalic acid (molecular formula:
C ₄₆ H ₃₃ O ₆ N ₂ ) in good agreement.

[Table 2]

(2) ¹ H-NMR (solvent: DMSO-
d ₆ ) From the ¹ H-NMR spectrum of the polycondensate obtained in Example 2, the following chemical shift (δ ppm) was obtained. : 2.20 (s, 6H), 7.08 (d, 4H),
7.18 (d, 4H), 7.39 (s, 4H), 7.7
2 (tor m, 6H), 7.88 (d, 4H),
8.14 (d, 2H), 8.53 (s, 1H), 10.
5 (s, 2H) From this, it was confirmed that the compound has a structure such as a methyl group, an amino group, and an aromatic ring.

Further, ¹ H-of the polycondensate obtained in Example 3
The NMR spectrum is as shown in FIG. 1. From this, it was confirmed that this polycondensate was an aromatic polyamide similar to that of Example 2 (but having a terephthalic acid component as an acid component).

(3) ¹³ C-NMR (solvent: DMSO-
d ₆ ) The following chemical shift (δ ppm) was obtained from the ¹³ C-NMR spectrum of the polycondensate obtained in Example 2. : (Δppm): 19.0, 117, 121, 12
2, 125, 128, 129, 129, 131, 13
1, 131, 132, 135, 136, 136, 15
0, 163, 165, 197 From this, a methyl group (19.0 ppm), a carbonyl group (197 ppm), an aromatic ring (116 to 185 pp)
The presence of carbon atoms constituting m) was confirmed.

Further, ¹³ C of the polycondensation product obtained in Example 3 was used.
-The NMR spectrum is as shown in FIG. 2, and it was confirmed that the polymer was the same as that of Example 2 except that the acid component was terephthalic acid.

(4) IR spectrum analysis The infrared absorption spectra of FIG. 5 (Example 2) and FIG. 6 (Example 3) were obtained. From the infrared absorption spectrum of FIG. 5, absorption based on an amide group, an ether group, and an aromatic ring was recognized, and the existence of these was confirmed.

From the above various analysis results, Examples 2 and 3
The solid obtained in 1. has a molecular formula: C ₄₆ H ₃₃ O ₆ N ₂
And in formula (III) Y is 1,3 phenylene and 1,4 phenylene, i.e. 1.5-bis- [4- (4-aminophenoxy) benzoyl] -2,6-dimethyl It was confirmed to be a polycondensate of naphthalene and isophthalic acid (Example 2) and terephthalic acid (Example 3).

Further, in order to measure the physical properties of the obtained aromatic polyamide, the crystallinity by X-ray diffraction, the glass transition temperature by a differential scanning calorimeter, and the 5% weight loss temperature by a thermogravimetric analyzer were measured, Separately from this, the solubility in a solvent was measured. The result is as follows.

(5) X-ray Diffraction Analysis (Powder Method) The X-ray diffraction charts of FIG. 3 (Example 2) and FIG. 4 (Example 3) were obtained, and the polyamide obtained from this was a crystalline polymer. It was confirmed.

(6) Glass transition temperature Example 2: 277 ° C. Example 3: 305 ° C.

(7) 5% weight loss temperature Example 2: 440 ° C. Example 3: 458 ° C.

(8) Solubility in Solvents The results of examining the solubilities in various solvents were as follows.

[Table 3]

From the above results, the polyamide of the present invention is
Since it has excellent heat resistance and excellent solubility in organic solvents,
It can be seen that melt molding is easy.

[Example 4] (High-temperature direct polycondensation of aromatic diamine with isophthalic acid) 1,5 obtained in Example 1 in a container replaced with an inert gas
-Bis- [4- (4-aminophenoxy) benzoyl]
1 mmol of 2,6-dimethylnaphthalene and isophthalic acid, 0.13 g of calcium chloride, 0.13 g of lithium chloride, and 2.5 m of dried N-methyl-2-pyrrolidone.
Triphenyl phosphite 2 is weighed and stirred with stirring.
mmol and pyridine 0.5 mmol were added, the temperature was raised to 100 ° C. to react for 3 hours, and then the mixture was air-cooled to room temperature. Next, this reaction solution was poured into 100 ml of methanol to form a precipitate, and the mixture was heated under reflux for 1 hour as it was. The solid content was collected by vacuum filtration and dried under reduced pressure at 210 ° C.

From the results of NMR analysis, IR analysis and elemental analysis, it was confirmed that the obtained solid content was the same polymer as the aromatic polyamide of Example 2 obtained by polycondensation with isophthalic acid dichloride. It was

[Examples 5 to 6] (Synthesis of aromatic polyamic acid by polycondensation of aromatic diamine and pyromellitic dianhydride or benzophenonetetracarboxylic dianhydride) As aromatic tetracarboxylic dianhydride Pyromellitic dianhydride (Example 5) and benzophenonetetracarboxylic dianhydride (Example 6) were used, and the 1,5-bis- [4 -(4-
Aminophenoxy) benzoyl] -2,6-dimethylnaphthalene (10 mmol) and dry N-methyl-2-pyrrolidone (50 ml) are weighed and stirred, and a small amount of pyromellitic dianhydride (10 mmol) or benzophenonetetracarboxylic dianhydride (10 mmol) is added in a small amount. Each was added to the reaction solution. After stirring as it was for 24 hours, the solution was cast as it was on a glass plate. This was dried under reduced pressure at room temperature.

The obtained solid was dissolved in N-methyl-2-pyrrolidone and the logarithmic viscosity was measured at 30 ° C.
It was 0.78 (Example 5) and 0.70 (Example 6).

Further, the following analysis and physical property measurement were performed on this solid substance. (1) ¹ H-NMR (solvent DMSO-d ₆ ) (2) ¹³ C-NMR (solvent: DMSO-d ₆ ) (3) IR spectrum (KBr method) The analysis results are as shown in the table below. is there.

[Table 4]

As a result of examining the analysis charts obtained by the above-mentioned respective analysis methods in comparison with the analysis chart of the aromatic polyamide of Example 2, the polymers obtained in Examples 5 and 6 were represented by the formula (V). Aromatic polyamic acid shown (however, W
There is a fifth embodiment in tetravalent benzene Kakuzanmoto (C ₆ H _2), in Example 6 tetravalent benzophenone residues (C ₆ H ₃
COC ₆ H ₃ )).

(4) Solubility in Solvents The results of measuring the solubilities in various organic solvents are shown in the table below. Since the solubilities in organic solvents are relatively good, molding at the stage of this polyamic acid was carried out. By heat-treating this and imidizing it, a polyimide having a desired shape can be obtained.

[Table 5]

Examples 7 to 8 (Synthesis of Aromatic Polyimide from Aromatic Polyamic Acid) The polyamic acid obtained in Examples 5 and 6 above was cast on a glass plate, and the hot air blowing dryer was used. 1 at 100 ° C, 200 ° C, and 300 ° C under air flow
It heat-processed for time and was imidized. The obtained film was peeled off from the glass plate in methanol, and the film was heated at 150 ° C
It dried under reduced pressure for hours.

The obtained solid substance was subjected to IR spectrum analysis to obtain IR spectra of FIG. 13 (Example 7) and FIG. 15, and the analysis results are shown in Example 5 and Example 6.
IR analysis result of aromatic polyamic acid of (Fig. 9, Fig. 12)
As a result of a comparison with the polymers obtained in Examples 7 and 8, the polymers obtained in Examples 7 and 8 were aromatic polyimides represented by the formula (VI) (however, in Example 5, the tetravalent benzene nucleus residue (C ₆ H
₂ ) and in Example 6, it was confirmed to be a tetravalent benzophenone residue (C ₆ H ₃ COC ₆ H ₃ ).

As a result of X-ray diffraction analysis, FIG.
The X-ray diffraction charts of (Example 7) and FIG. 16 (Example 8) were obtained. As a result, it was confirmed to be a crystalline polymer, and the 5% weight loss temperature using a thermogravimetric analyzer was 4
70 ° C. (Example 7) and 478 ° C. (Example 8),
It was found that all were polyimides having excellent heat resistance.

[0063]

INDUSTRIAL APPLICABILITY The novel aromatic diamine of the present invention can be converted into a polyamide by polycondensation with an aromatic dicarboxylic acid derivative, or a polyimide via a polyamic acid by reacting with a tetracarboxylic acid derivative. The obtained aromatic polyamide and aromatic polyimide have a high melting point, a high glass transition point, excellent mechanical strength, and relatively good workability, and are used for electric / electronic parts, automobile parts, precision instrument parts, and spacecraft. Since it can be used as a material for devices and the like, it is extremely useful as a monomer for obtaining such super engineering plastics.

[Brief description of drawings]

FIG. 1 is a ¹ H-NMR chart of a polycondensate of 1,5-bis- [4- (4-aminophenoxy) benzoyl] -2,6-dimethylnaphthalene and terephthalic acid.

FIG. 2 is a ¹³ C-NMR chart of a polycondensate of 1,5-bis- [4- (4-aminophenoxy) benzoyl] -2,6-dimethylnaphthalene and terephthalic acid.

FIG. 3 is an X-ray diffraction chart of a polycondensate of 1,5-bis- [4- (4-aminophenoxy) benzoyl] -2,6-dimethylnaphthalene and isophthalic acid.

FIG. 4 is an X-ray diffraction chart of a polycondensate of 1,5-bis- [4- (4-aminophenoxy) benzoyl] -2,6-dimethylnaphthalene and terephthalic acid.

FIG. 5 is an IR spectrum analysis chart of a polycondensation product of 1,5-bis- [4- (4-aminophenoxy) benzoyl] -2,6-dimethylnaphthalene and isophthalic acid.

FIG. 6 is an IR spectrum analysis chart of a polycondensate of 1,5-bis- [4- (4-aminophenoxy) benzoyl] -2,6-dimethylnaphthalene and terephthalic acid.

FIG. 7 is a ¹ H-NMR chart of polyamic acid of 1,5-bis- [4- (4-aminophenoxy) benzoyl] -2,6-dimethylnaphthalene and pyromellitic dianhydride.

FIG. 8 is a ¹³ C-NMR chart of a polyamic acid of 1,5-bis- [4- (4-aminophenoxy) benzoyl] -2,6-dimethylnaphthalene and pyromellitic dianhydride.

FIG. 9 is an IR spectrum analysis chart of a polyamic acid of 1,5-bis- [4- (4-aminophenoxy) benzoyl] -2,6-dimethylnaphthalene and pyromellitic dianhydride.

FIG. 10 ¹ H- of polyamic acid of 1,5-bis- [4- (4-aminophenoxy) benzoyl] -2,6-dimethylnaphthalene and benzophenone tetracarboxylic acid.
NMR chart.

FIG. 11 is a polyamic acid ¹³ C- of 1,5-bis- [4- (4-aminophenoxy) benzoyl] -2,6-dimethylnaphthalene and benzophenone tetracarboxylic acid.
NMR chart.

FIG. 12 is an IR spectrum analysis chart of a polyamic acid of 1,5-bis- [4- (4-aminophenoxy) benzoyl] -2,6-dimethylnaphthalene and benzophenonetetracarboxylic acid.

FIG. 13 is an IR spectrum analysis chart of a polyimide of 1,5-bis- [4- (4-aminophenoxy) benzoyl] -2,6-dimethylnaphthalene and pyromellitic dianhydride.

FIG. 14 is an X-ray diffraction chart of a polyimide of 1,5-bis- [4- (4-aminophenoxy) benzoyl] -2,6-dimethylnaphthalene and pyromellitic dianhydride.

FIG. 15 is an IR spectrum analysis chart of a polyimide of 1,5-bis- [4- (4-aminophenoxy) benzoyl] -2,6-dimethylnaphthalene and benzophenonetetracarboxylic acid.

FIG. 16 is an X-ray diffraction chart of a polyimide of 1,5-bis- [4- (4-aminophenoxy) benzoyl] -2,6-dimethylnaphthalene and benzophenonetetracarboxylic acid.

Claims (5)

[Claims] 1. A compound represented by the following general formula (I) A novel aromatic diamine compound represented by: 2. The following general formula (II): The method for producing an aromatic diamine according to claim 1, wherein a halobenzoyldimethylnaphthalene represented by the formula (X represents a halogen atom) is reacted with aminophenoxide. 3. The following general formula (III): (In the formula, Y is a condensed polycyclic aromatic group having 20 or less carbon atoms or the following formula (IV): Or one or more groups selected from the group consisting of However, Z is a direct bond, -O-, -S-, -SO _{2
-, - CO-, CH 2 -} , - C (CH 3) 2 - or -
C (CF _{3) 2} - a and, R represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a halogen group or a phenyl radical, a a is 0, 1 or 2, b is an integer of 0 or 1 to 4 Represent ) An aromatic polyamide comprising a repeating unit represented by: 4. The following general formula (V): An aromatic polyamic acid comprising a repeating unit represented by the formula (W represents a tetravalent aromatic hydrocarbon group). 5. The following general formula (VI): An aromatic polyimide comprising a repeating unit represented by the formula (W represents a tetravalent aromatic hydrocarbon group).