JPS62256831A - Aromatic polyamide resin and its production - Google Patents

Abstract

PURPOSE:To produce the title resin excellent in solubility in an organic solvent, resistance to heat softening and thermal deterioration and mechanical properties, by polycondensing a specified dicarboxylic acid or its dihalide or diester with a specified aromatic diamine. CONSTITUTION:A 5,6-bis(4-ethoxycarboxyphenyl)-3-substituted-astriazine of formula IV, obtained by reacting 4,4'-bis(ethoxycarbonyl)benzene with an amidrazone of formula I (wherein R is alkyl or formula II or III, R<1> is H, halogen, lower alkyl or lower alkoxyl) is hydrolyzed with a basic compound and then acidified to obtain a dicarboxylic acid of formula V or its dihalide or diester (A). Component A is polycondensed with an aromatic diamine (B) of formula VI (wherein Ar is a bivalent group having an aromatic ring) to obtain an aromatic polyamide resin having no diketone group in the molecule, comprising repeating units of formula VII (wherein Ar is a bivalent group derived by removing the amino groups from the aromatic diamine) and having a logarithmic viscosity of 0.2-5dl/g (0.5g/100ml concn. sulfuric acid at 30 deg.C).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel aromatic polyamide resin and a method for producing the same.

[Conventional technology]

Conventionally, fully aromatic polyamide resins synthesized from aromatic diamines and aromatic dicarboxylic acids have been known, and have attracted attention for their excellent heat resistance, and have been used as electrical insulation materials, high-temperature materials, etc. In recent years, much importance has been placed on the research and development of seeds in order to use them as materials for protective clothing.

In addition, as a polyamide containing a triazine ring, Macromolecular Chemist IJ-(Makromol
.

Chem, Vol. 186, p. 483 (1985). That is, the polyamide has the general formula [A] (where % Ar' in formula 1 is a polyamide having 7 groups of rose elm and a repeating unit, which is synthesized in advance, and reacted with amide hydrazone to form the above general formula [A]. It is obtained by converting a part of the diketone group in A] into a group represented by the general formula (), and a diketone group always remains in the molecule.

[Problem that the invention seeks to solve]

However, the above-mentioned wholly aromatic polyamide resins usually have poor solubility in organic solvents, and are extremely inconvenient for forming films, coatings, and the like.

In addition, the above-mentioned polyamide resin having a triazine ring is
Although it exhibits excellent solubility in polar solvents such as N-methylpyrrolidone, it has poor thermal stability and is impractical because diketone groups remain.

[Means for solving problems]

The first invention is based on the general formula [I] ] , lower alkyl group or lower alkoxy group.

Ar is a divalent residue of an aromatic diamine excluding the amino group) Aromatic polyamide resin having a repeating unit (However, the molecule does not contain a diketone group)
Regarding K.

The lower alkyl group and lower alkoxy group in the above ratio and R and IK preferably have 1 to 3 carbon atoms.

This polyamide resin was prepared by dissolving 0.5 g of the resin in concentrated sulfuric acid (concentration 96%, specific gravity 1.84) and making 100ml of the resin. The logarithmic viscosity of the solution at 30tZ" is 0.2 to 5 dl/
Preferably, it is g. If this viscosity is too low, the mechanical strength of the resin tends to decrease, and if it is too high, the solubility of the resin in organic solvents tends to be poor.

Note that the above logarithmic viscosity (ηl++h) is ηlnh =
(log (η/ηo)) / C (where η
and η0 represent the viscosity of the solution and the viscosity of the solvent, respectively, and the flow times of the solution and liquid medium when measured using an Ubbelohde dilution capillary viscometer are t and 1o, respectively.
In this case, η/ηo = t/t o and C
is the resin concentration (g/di) of the solution.

The aromatic polyamide resin according to the present invention is soluble in polar solvents such as N-methylpyrrolidone, dimethylsulfoxide, and dimethylacetamide.

The second invention relates to a method for producing the aromatic polyamide resin according to the first invention.

The second invention is a dicarboxylic acid represented by the formula (wherein R is the same as in the general formula [I]) or its cybaride or diester and the general formula [■] H2N-几2-NH2CIID ( However, R2 represents a divalent group having an aromatic ring)
The present invention relates to a method for producing an aromatic polyamide resin, which is characterized in that a polyamide resin having a repeating unit represented by the general formula [I] is obtained by polycondensing an aromatic diamine represented by the formula [I].

In the second invention, the polycondensation method may be a low temperature polycondensation method, a direct polycondensation method, an active ester method, etc., and is not particularly limited.

The low temperature polycondensation method will be explained next.

The di-ride of the dicarboxylic acid is preferably used in an amount of 0.9 to 1.2 equivalents per equivalent of the aromatic diamine,
In the presence of tertiary amines such as triethylamine, tripropylamine, tributylamine, triamylamine, inorganic acid acceptors such as propylene oxide, styrene oxide, 1,2-niboquinodes such as chlorhexene oxide, N-
The reaction is carried out in a non-reactive polar organic solvent such as methylpyrrolidone or dimethylacetamide at a temperature ranging from minus ten degrees Celsius to the reflux temperature of the organic solvent.

The direct polycondensation method will be explained next.

The above dicarboxylic acid and the above aromatic diamine are used in equivalent or almost equal amounts, triphenyl phosphite, phosphorus trichloride,
The reaction is carried out in the presence of a phosphorous catalyst such as a condensed phosphoric acid ester and pyridine or its basic derivative in a non-reactive polar organic solvent similar to that described below at a temperature within the range from room temperature to reflux temperature. let In this case, the phosphoric acid catalyst is used in an equivalent or nearly equivalent amount to the dicarboxylic acid or the aromatic diamine, and the pyridine or its derivative is used in an amount of 10 molar or more based on the dicarboxylic acid or the aromatic diamine. preferable.

The active ester method will be explained next.

A benzotriazyl ester is produced by the reaction of the dicarboxylic acid cybalide and 1-hydroxybenzotriazole, and an equivalent or nearly equivalent amount of this ester and the above aromatic diamine are used, and the same non-reactive polar organic solvent as above is used. The reaction is carried out at room temperature or higher.

The reaction solution obtained as described above is compatible with a lower alcohol such as methanol and the above organic solvent such as water,
The aromatic polyamide resin according to the present invention can be recovered by pouring a large excess of a solvent which is a poor solvent relative to the resin to obtain a precipitate, which is then filtered and dried.

In addition, the above literature (macromolecular chemistry)
Polyamide resin containing some triazine rings can also be obtained by the polymer reaction described in .
Conversion to a triazine ring is not possible because it is a polymer reaction.

The dicarboxylic acid represented by the general formula [II] can be produced as follows.

In other words, 4. 4'-bis(ethquincarphonyl)benzyl and amithracine represented by the general formula CIV) H R, -CCIVINHN H2 (wherein R is the same as in the general formula CI) are combined with N-methyl-2 -PyD React in lydone to give the general formula [V] (however, the formula in the formula is the same as in the general formula CI)
5,6-bis(4-ethoquinocarboxy7phenyl)-3-substituted-a s -) riazine represented by is obtained.

Next, this is dissolved in an ethanol aqueous solution, hydrolyzed with a strong basic compound such as potassium hydroxide, and further acidified (for example, about I) H1 with a hydrochloric acid aqueous solution to obtain the dicarboxylic acid represented by the general formula [II]. can be obtained. This dicarboxylic acid civalide can be obtained by heating and refluxing the dicarboxylic acid together with a large excess of a halogenating agent such as thionyl chloride, thionyl bromide, or phosphorus pentachloride, and several dimethylformamides. Amitracin represented by the above general formula [■] includes the following. Among these, 2-picolinoamidrazo/,
Acetamithracine is particularly representative.

As the aromatic diamine represented by the above general formula (III), a diamine having an aromatic ring is used, and examples thereof include compounds represented by the general formula 0).

In the above formula, R+' l R', R', 几8. R’.

Rlo and R1'' each independently represent hydrogen, a lower alkyl group, a lower alkoxy group, chlorine or bromine, and R''
and R113 each independently represent hydrogen, a methyl group, an ethyl group, a trifluoromethyl group, or a trichloromethyl group. Substituents similar to these are the above general formulas], [■]
In and [■], K may also be bonded to the be/zene ring.

In the above general formula], A is a bond, -〇-1 (J
QR+" -C-. Here, RL4 and R" are each 1 (,
+5 Stands up to indicate hydrogen, methyl group, ethyl group, trifluoromethyl group or trichloromethyl group.

Examples of the aromatic diamine include meta-phenylene diamine, para-phenylene diamine, meta-tolylene diamine, para-tolylene diamine, 4,4'-diaminodiphenyl ether, 3. 3'-dimethy/l/-4,4'-diaminodiphenyl ether, 3°3'-dimethoxy-4
, 4'-diaminodipheni/l/Z-f/l/, 3.
3'-diaminodiphenyl ether, 3.4'-
Diaminodiphenyl ether, 4,4'-benzidino,
4,4'-diaminodiphenylthioether, a,
3'-Diaminodiphenylthioether, 3.3'-diethoxy/-4,4'-diaminodiphenylthioether, 3.3'-diaminodiphenylthioether, 4.4'-diaminobenzophenone, 3.3'-dimethyl-4,4'-diaminobencif s-/:y+, L3'-diaminodiphenylmethane.

4.4'-diaminodiphenylmethane, 3.3'-dimethoxy-4,4'-diaminodiphenylmethane, 2,
2'-bis(4-aminophenyl)propa/, 2.2'
-bis(3-aminophenyl)fluorane, 4.4'-
Diaminodiphenylsulfoxide, 4,4'-diaminodiphenylsulfone.

3.3'-diaminodiphenylsulfone, benti di/,
3.3'-dimethylbenzidine, 3,31-dimethylbenzidine, 3. 3'-diaminobiphenyl, 2,
2-bis(4-(4-aminophenoxy)phenyl)furopane, 2,2-bis[3-methyl-4-(4-aminophenoxy)phenyl]propa/, 2,2-bis[3-
Chloro-4-(4-aminophenoxy)phenyl]propane, 2.2-bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]propane, 1. 1-
Bis(4-(4-aminophenoxy)phenyl)ethane, 1,1-bis[3-chloro-4-(4-aminophenoxy)phenyl]ethane, bis[4-(4-aminophenoxy)phenyl]methane, Bis[3-methyl-4-(
Examples include 4-aminophenoxy/)phenyl]methane.

In order to improve the organic solvent solubility of the aromatic polyamide resin according to the present invention, the aromatic diamine is preferably a compound represented by the general formula α■] or [■],
Furthermore, in order to improve the heat resistance of the resin, the general formula C'vil
: Compounds represented by l are preferred.

The polyamide resin according to the present invention contains terephthalic acid, inphthalic acid, 4.4'-diphenyl ether dicarboxylic acid, 4.4'-diphenylsulfone dicarboxylic acid as a carboxylic acid component.4. It may contain aromatic dicarboxylic acids such as 4'-diphenylcarboxylic acid and 1,5-naphthalene dicarboxylic acid. These are used in an amount of 30 molar or less based on the total carboxylic acid component. If these amounts are too large, the organic solvent solubility will decrease. Further, as a carboxylic acid component, an aliphatic dicarboxylic acid such as adipic acid and sepa//acid may be contained in an amount of 10 molti or less based on the total carboxylic acid component. Too much aliphatic dicarboxylic acid tends to reduce heat resistance. Similarly, as a diamine component, aliphatic diamines such as hexamethylene 5-amine and ethylene diamine may be included, but they are used in an amount of 10 mole or less based on the total diamine. Too much aliphatic diamine reduces heat resistance. The above-mentioned aromatic dicarboxylic acids and aliphatic dicarboxylic acids are used as they are or as cibarides or diesters by polymerization methods.

[Effect]

Because the aromatic polyamide resin according to the present invention has a bulky triazine ring in its main chain, it has far superior organic solvent solubility compared to conventional wholly aromatic polyamide resins, and It has far superior heat resistance compared to polyamide resins containing rings and diketone groups.

Then, it can be formed into a film or coating using the same casting method as conventional solvent-soluble resins.
The films have excellent heat softening and heat deterioration resistance, as well as excellent mechanical properties, and are suitable for use as electrical and electronic insulating materials, heat-resistant adhesives, and high-temperature materials. This resin can also be used in the form of a solution by dissolving it in a solvent. In this case, the solvent used is a polar organic solvent such as dimethylformamide, dimethylacetamide, or N-methylpyrrolidone.

〔Example〕

Synthesis examples and examples related to the present invention are shown below.

Synthesis Example 1 5.6-bis(4-ethoxycarbonylphenyl)-3
-(2-pyridyl)-as-triazine (BEPyT
4,4'-bis(ethquincarbonyl)benzyl was added to a 100-meter four-hole flask equipped with a ball condenser with a ram tube, a thermometer with a nitrogen inlet tube, and a stirring device. 14.0 g (3,95X 10-2moj)
and dissolved in NMP40m/ under nitrogen. 5 within the system
At 0C, add 6.15 g of 2-picolinoamiderazone (
A solution of 4,52x 10-2+no7) dissolved in NMP40- was added dropwise from the dropping funnel over a period of 2 hours.

After dropping, the temperature was raised to 90C over 1.5 hours, and the temperature was increased to 90C.
The reaction was carried out at C for 3 hours. After the reaction is completed, cool to room temperature,
The resulting yellow precipitate was filtered with suction, washed with water, and then dried. Then ethanol:water=1:1
It was recrystallized from a mixed solvent of

The yield was 13.6g. The obtained crystal showed the following physical properties.

Yellow powder melting point (m, p,): 165.2-166.4 C
(KBr method) νC=N 1620cm
-'cyC-0 (α-diketone) 1680cy-'disappearance (
CDCl2) 4.45 ppm Q 4H
CH28, 461) I) m m 13t-I Ar elemental analysis: C (Feed 1-■ (%) N (%) C26
H2204N 4 Calculated value: 68.71 4.88
12.33 Actual value: 68.56 4.92 12.27
Synthesis Example 2 5,6-bis(4-carboxyphenyl)-3-(2-
pyridyl) -a s-) riazine (BCPyT) synthetic ball condenser, thermometer, and a stirring device.
5,6-bis(4-ethoxycarbonylphenyl)-3-(2-viridi/l/)-a in a four-bottle flask.
s-triazine 14.7 g (3,23X 10-
2mot) and heated to dissolve in 99ml of ethanol. Here, 5.6 g (0.10 mot) of potassium hydroxide was added to 20.0 g of distilled water. OmJ, dissolved in 20.0 m of ethanol, was added, and the mixture was heated under reflux for 3 hours. A yellow precipitate formed during the process. After cooling to room temperature, it was poured into a beaker and distilled water was added to dissolve it. Add 2N hydrochloric acid to this, pH = 1
A yellow precipitate was formed. Suction filter this,
The filtrate was washed with distilled water until it became neutral. Recrystallized from dimethyl sulfoxide. The yield was 9.08g.

The physical properties are shown below.

Yellow powder.

m, p, : 354 C (DTA) ■ R:
νOH3448cm −1 CKBr method) V C=0 1700cm −
'νC=N 1620cm -1NMR
:8.30ppm m 14H aromatic COOH (DMC
ooH(D Elemental analysis: C candy H% Nchi C22HI
4N404 Calculated value 66.33 3.54 14.
06 Actual value 66.13 3.62 14.10 Synthesis example 3 5.6-bis(4-ethoxycarbonylphenyl) -
3-mefk-as-triasif (BEMe'lr)
13.9 g of 4,4'-bis(ethoxycarbonyl)benzyl (3,92xlO -2mo7) and dissolved in NMP25- under nitrogen. Here, 5.0 g of acetamithracine hydrochloride group (4,6Xi O""mo
t) and 20 ml of NMP plus 8 ml of propylene oxide
．． Od (1,2X 10-1 mol) was added. After stirring at room temperature for 1.5 hours, the mixture was completely dissolved. Another 0.
After stirring for 5 hours, the temperature was increased to 90C for 1 hour, and the temperature was increased to 90C for 3 hours.
After reacting for a while, the color changed from transparent yellow to transparent red.

After cooling, it was poured into 1500 ml of distilled water, filtered under suction, washed with distilled water, and dried. It was recrystallized from a mixed solvent of ethanol:water=1:1. Yield was 12.3g.

The physical properties are shown below.

Yellow needles.

m, p, :125.3-126. ICIR Niji C
-0 (ester) 1720m-' (KBr)
vc=N 1620(771-'νC
=O(α-diketone) 1680m-' Disappearance NMR: 1.
401) pm t 6HCH3CH2 (CDC73
) 3.00ppm s 3H aromatic CH34,
46ppm q 4HCH2 7,35ppm m SHAr Elemental analysis ・0% H% N% C22H2
104N3 Calculated value: 67.51 5.41 10.
73 Actual value: 67.49 5.50 10.77 Synthesis Example 4 Synthesis of 5,6-bis(4-carboxyphenyl)-3-methyl-as-)riazine (BCMeT) Condenser with beads, thermometer, stirring In a 30 Qtd four-bottle flask equipped with a
．． 3 g (3,14X 10-2 mot) was added, 120-g of ethanol was added, and the mixture was heated and dissolved. Distilled water 20-
5.6 g of potassium hydroxide (1,OX 10” mo
t) was dissolved, and a solution containing 20 ml of ethanol was added. After heating under reflux for 4.5 hours.

The mixture was cooled to room temperature, poured into a beaker, and distilled water was added to dissolve it. 2N hydrochloric acid was added to adjust the pH to 1, and the precipitated crystals were suction filtered, washed with distilled water until the filtrate became neutral, and dried. Furthermore, it was dissolved in a KOH aqueous solution and filtered through a glass fiber filter.

The mixture was acidified with hydrochloric acid to precipitate crystals, filtered under suction, and washed with distilled water until neutral. When this was dried under reduced pressure at 6 Orr, it showed a weight loss of about 5% at around 90C in TGA. In addition, it was found from the following elemental analysis values that a monohydrate was formed.

Elemental analysis °C ■(%N%BCM
eT calculated value: 64.48 3.91 12.
53 crystal Actual value: 61.344.23 1
1.86BCMeT-HzO calculation value: 61.20 4
．． 28 11.89 Then, heat treatment was further performed at 100C for 24 hours, and when it was cooled in a desiccator, T
No weight loss was observed in GA, and the elemental analysis values also agreed well with the calculated values. Yield was 8.02 g. The physical properties are shown below.

Yellow powder.

m, p, : 314C (DTA) I R1: ν OH3450cm -' (KB
r) vC=0 1700cm-'vC=N
1620 cm-' NMR: 2.92 ppm s 3HAr-CH3
(DMSO-d6) 7.80ppm m IOH
Ar, C0OH elemental analysis ・0% H%
NchiC2□ToI2104N3 Calculated value: 67.5
1 5.41 10.73 Actual value: 67.49 5
．． 50 10.77 Example 1 0.1 g of lithium chloride and 0.3 g of cal/rum chloride were placed in a 10 rnl reaction tube equipped with a ball condenser with a chloride tube, a gas introduction tube, and a stirring device, and nitrogen 1.0 d of lower pyridine and N-methyl-pyrrolidone (NMP
) 5- was added and dissolved by heating. After cooling to room temperature,
5,6-bis(4-carboxyphenyl)-3-(2-
pyridyl)-as-)riazine 0.7968g (2,0
m mol ) and diaminodiphenyl ether 0.40
04 g (2,0 m, mot) and 0.2625 me (triphenyl phosphor) were added, heated, and 115
The reaction was carried out at C for 5 hours. After cooling to room temperature, dilute with NMP and dissolve methanol:water = 1:1 at 1400ml/! Open it inside. The resulting precipitate was filtered through a 03 glass filter, washed with methanol, and dried.

Table 1 shows the decomposition temperature yield and organic solvent solubility of the polyamide resin thus obtained. Further, the infrared absorption spectrum (KB r method) of the above polyamide resin is shown in FIG. As is clear from Figure 1, the carbonyl group of the amide bond absorbs at 1640Crn-' and at 3480 cm
-' absorption based on N H stretching vibration is observed, indicating that an amide bond is formed.

The elemental analysis results were as follows.

C (%) H (chi) N (%) Calculated value:
72.59, 3.94.14.94 Actual value: 71
．． 17. 4.01, 14.49 Example 2 Ball capacitor with calcium chloride tube.

In a 30 rnl four-bottle flask equipped with a gas inlet tube and a stirring device, 1.2 g of cal/rum chloride and 0.0 g of lithium chloride were added.
4 g+ NMP 10. Od, pyridine 4.0-
was added and heated to dissolve under nitrogen. Cool to room temperature.

Diaminodiphenyl ether 0.4004g (2.0m
mot) 5,6-bis(4-carboxyphenyl)
-3-methyl-as-triaziy 0.6706g (
2,0m mot) and triphenylphosphite 1.
Enter 05-.

Heat. After reacting at 115C for 5 hours, it was cooled to room temperature and diluted with NMP to form a methanol:water=1:1 solution 4.
00-Opened inside. The resulting precipitate was filtered through a 03 glass filter, washed with methanol, and dried.

Table 1 shows the decomposition temperature, yield, and organic solvent solubility of the polyamide resin thus obtained. Furthermore, the infrared spectrum (KBr method) of the above polyamide resin is shown in FIG.

As in Example 1, the presence of an amide bond is observed.

The results of elemental analysis are shown below.

C (%) H (attack) N (chi) Calculated value:
72.13, 4.24. 14.02 actual value + 7
0.38, 4.11, 13.52 Example 3 In Example 1, diaminodiphenyl ether 0.40
The procedure was the same as in Example 1 except that 0.216 g (2.0 mmol) of paraphenylenediamine was used instead of 0.4 g (2.0 mmol). Table 1 shows the test results.
Shown below. Moreover, the infrared absorption spectrum of the obtained polyamide resin is shown in FIG. What are the results of elemental analysis?

It was as follows.

C (%) H (%) N (%) Calculated value:
71.48. 3.86. 17.86 Actual value:
70.19. 4.00, 17.13 Example 4 Diaminodiphenyl ether in Example 1 0.40
The same procedure as in Example 1 was repeated except that 0.396 g (2.0 m mot) of diaminodiphenylmethane was used instead of 0.04 g (2.0 m mol/,). The test results are shown in Table 1. Moreover, the infrared absorption spectrum of the obtained polyamide resin is shown in FIG. What are the results of elemental analysis?

It was as follows.

C (chi) H book) N (%) calculated value:
74.99, 4.31, 14.99 Actual value:
73.43, 4.38. 14.50 Example 5 Diaminodiphenyl ether in Example 1 0.40
Example 1 except that 0.368 g (2.0 m mot) of benzidine was used instead of 0.04 g (2.0 m mol)
It was done in the same way. The test results are shown in Table 1. Moreover, the infrared absorption spectrum of the obtained polyamide resin is shown in FIG. The results of elemental analysis are as follows.

C (%) H (%) N (%'') Calculated value
: 74.71, 4.06, 15.38 Actual value: 73.00. 4.14. 14.88 Example 6 Diaminodiphenyl ether in Example 2 0.40
The same procedure as in Example 2 was carried out except that 0.216 g (2.0 m mat) of 0.04 g (2.0 m mol) was replaced with 0.216 g (2.0 m mol) of nokura phenylenediamine. The test results are shown in Table 1. Moreover, the infrared absorption spectrum of the obtained polyamide resin is shown in FIG. The results of elemental analysis are as follows.

C (ch) H (%) N (ch) Calculated value:
70.75. 4.21. 17.19 Actual value: 6
9.55, 4.32. 16.52 Example 7 Diaminodiphenyl ether 0.40 in Example 2
The procedure was the same as in Example 2 except that 0.396 g (2.0 m mot) of diaminodiphenylmethane was used instead of 0.04 g (2.0 m mot). Table 1 shows the test results.
Shown below. Moreover, the infrared absorption spectrum of the obtained polyamide resin is shown in FIG. The results of elemental analysis are as follows.

C (%) H (%) N (%) Calculation 1st shift:
74.83, 4.66, 14.08 actual value
: 73.04, 4.56, 13.60 Example 8 Diaminodiphenyl ether in Example 2 0.40
The procedure was the same as in Example 2 except that 0.368 g (2.0 m mob) of benzidine was used instead of 0.04 g (2.0 m mat ). The test results are shown in Table 1. Also.

The infrared absorption spectrum of the obtained polyamide resin was
As shown in the figure. The results of elemental analysis are as follows.

C (%) H (%) N (%) Calculated value:
74.52, 4.38, 14.48 Actual value: 72.70, 4.30, 13.75
Comparative Example 1 In Example 1, 0.7 of 5.6-bis(4-carboxyphenyl)-3-(2-pyridyl)-as-)riazine
The same method was used except that 0.166 g (1.0 m mot ) of terephthalic acid and 0.166 g (1.0 m rroL ) of isophthalic acid were used instead of 968 g (2.0 m mol ). The test results are shown in Table 1.

Comparative Example 2 4.4'-bis(chloroformyl)Hensyl 3.351
7g (N containing 1g of lithium chloride in 0.01 motl)
A solution of 2.002 g (0.01 mol) of diaminodiphenyl ether dissolved in -methyl-2-pyrrolidone 40- was added dropwise under a nitrogen atmosphere at room temperature while stirring. Finally triethylamine 3- was added.

After stirring at room temperature for 7 hours, the reaction product was poured into an aqueous methanol solution (380+n7!+380m/) to obtain a precipitate. After thoroughly washing with methanol and distilled water, it was dried under reduced pressure. The yield was 100%. Further, the logarithmic viscosity of the obtained resin was 0.35 dl/g (0.5 g/100-concentrated sulfuric acid, 30C).

1.9318 g of the obtained polyamide (<number of moles of repeat unit 0.005 mo7) was dissolved in N-methyl-2-pyrrolidone 25- containing 0.25 g of lithium chloride, stirred at room temperature under a nitrogen atmosphere, and then dissolved in NMP5m. Nianatamidrazone hydrochloride 0.5435g (0,005mot)
20 ml of solution and 1rn of propylene oxide
Add l(0,015mot). The mixture was stirred at room temperature for 2 hours, and then reacted at 90C for 3 hours, and the reaction solution was poured into 500 methanol to obtain a precipitate. After washing thoroughly with distilled water, it was dried under reduced pressure. The ultraviolet absorption spectrum of the obtained polymer revealed that 30% of the diketone groups were converted to triazine rings. Table 1 shows the test results for this resin.

20J Effects of the Invention Below] The aromatic polyamide resins according to the first invention and obtained according to the second invention have excellent heat resistance and solubility in organic solvents.

[Brief explanation of drawings]

Claims (1)

[Claims] 1. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] (However, in the formula, R is an alkyl group, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ , or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, where R^1 is hydrogen, halogen, lower alkyl group, or lower alkoxy group, and Ar is a divalent group other than the amino group of aromatic diamine. An aromatic polyamide resin having a repeating unit represented by (residue) (however, the molecule does not contain a diketone group). 2. Dissolve 0.5g of polyamide resin in concentrated sulfuric acid,
The logarithmic viscosity of the solution in ml at 30°C is 0.2 to 5.
dl/g. The aromatic polyamide resin according to claim 1. 3. General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] (However, in the formula, R is an alkyl group, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. There is ▼, and here,
(R^1 is hydrogen, halogen, lower alkyl group, or lower alkoxy group) or its dihalide or diester and the general formula [III] H_2N-Ar-NH_2 [III] (However, in the formula, Ar is By polycondensing aromatic diamines (which are divalent groups having an aromatic ring), the general formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] (However, in the formula, R and Ar are the same as defined above).