JPS60226527A - Aromatic polythioether amide polymer and its production - Google Patents

Abstract

PURPOSE:To obtain the titled polymer having excellent heat resistance and moldability and useful as a material of fiber, film and paint, by reacting a specific diamine having thioether bond with an aromatic dicarboxylic acid (chloride). CONSTITUTION:An aromatic polythioether amide polymer having the recurring unit of formula II (Ar is 6-30C aromatic ring) can be produced either by dispersing an aromatic diamine having a thioether bond and containing >=50mol% diamine of formula I (X is 1-10C bivalent hydrocarbon group, O, SO, CO, etc.; a is 0 or 1; Y is 1-20C alkyl, 6-20C aryl, etc.; b and c are 0-4) in an alkaline aqueous solution, adding a solution obtained by dissolving an aromatic dicarboxylic acid chloride in an organic solvent to the above dispersion, and carryingt out the polycondensation of the components, or by dissolving the above aromatic diamine and aromatic dicarboxylic acid in an organic acid amide or organic sulfoxide, adding a condensation agent (e.g. tertiary amine) to the solution, and carrying out the polycondensation of the components.

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the present invention] - Industrial field of application The present invention relates to an aromatic polyamide having a thioether bond and a method for producing the same. The aromatic polyamide of the present invention has excellent heat resistance and moldability, and is useful as a fiber film and coating material.

[Conventional technology and its problems]

Aromatic polyamide resins synthesized from aromatic diamines and aromatic dicarboxylic acids or their chlorides have attracted attention for their excellent heat resistance and flame retardancy, and have been actively researched and developed. However, aromatic polyamides generally have a high melting point (in air, many have a melting point higher than the thermal decomposition onset temperature, making injection molding or extrusion molding difficult.
It has poor solubility in common organic solvents (which is extremely inconvenient when forming fibers, films, coatings, etc.).

Therefore, processability is improved by lowering the melting point as a copolymer or by dissolving it in a solvent.

Such an aromatic polyamide with improved processability is produced by a method of copolymerizing an aliphatic component (!l?
2-109592, Japanese Unexamined Patent Publication No. 53-94397),
A method of introducing a connecting functional group into the Tbl main chain or imparting flexibility (U.S. Pat. No. 3,505,288, JP-A-52-1999)
23198, JP-A-53-10469s), (
Methods of random copolymerization of cl aromatic components ('I? 1983-104697, !I? 1988-88427, US Pat. No. 4,410,684) are known. However, the polyamides obtained by these techniques cannot be said to have a sufficient balance between processability and heat resistance.

[Configuration of the present invention]

The present invention provides an aromatic polyamide having a retathioether bond that has a good balance between moldability and heat resistance, and a method for producing the same.

That is, the first aspect of the present invention provides an aromatic polythioetheramide polymer having the following repeating units.

[Wherein, X is a divalent hydrocarbon group having 1 to 1 carbon atoms, -0
-1-8O-2S 02'! Tan indicates -CO-. a is 0 or 1; when a is 0, the aromatic rings are bonded to each other without X; YH
1 represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, an aryol group having 6 to 20 carbon atoms, a halogen group, or a nitro group, respectively. They may be the same or different.

b and C are the same or different integers of θ to 4, and Ar is an aromatic ring having 6 to 30 carbon atoms].

The second aspect of the present invention is to react an aromatic diamine having a thioether bond containing 50 moles or more of the diamine represented by the general formula (I) with an aromatic dicarboxylic acid chloride to form an aromatic diamine having the following repeating unit. Provides a method for producing a polythioetheramide polymer [wherein XI-j is a divalent hydrocarbon group having 1 to 10 carbon atoms, -〇-1-SO-1-s02- or -CO- shows. auO or 1, and when a is 0, it means that the aromatic rings are bonded to each other without the presence of X. Y is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, -.rogen group or nitro group ( 7. They may be the same or different from each other.

b and CU represent integers from 0 to 4 that are the same or different from each other. Moreover, Ar is J which is an aromatic ring having 6 to 30 carbon atoms.

The third aspect of the present invention is to convert an aromatic diamine having a thioether bond represented by the general formula (1) (Y)b (Y)c (I) and an aromatic dicarboxylic acid into an organic acid amide or an organic sulfoxide. The present invention provides a method for producing a polymer having the following repeating unit, which is characterized by dissolving the polymer and polycondensing the same in the presence of a condensing agent and a tertiary amine [wherein, X has 1 to 1 carbon atoms] It represents a divalent hydrocarbon group of 10, -〇-1-SO-1-802- or -CO-.a is O-straddling 1, and when a lJ'-0, X is an aromatic ring without represents that they are bonded to each other.Y
H1 represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aralgyl group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a -rogen group, or a nitro group, respectively. They may be the same or different.

5. UMI,,Elyoa6L'F1!14fK60
~4°.・; Represents. Moreover, Ar is an aromatic ring having 6 to 30 carbon atoms].

[Aromatic diamine]

Examples of the medium for the aromatic diamine having a thioether bond represented by the general formula (I) used in the present invention are shown below, and 2.2
-bis(4-(4-aminophenylthio)phenyl)propane, 1.1,1,3,3.3-hexafluoromethyl-2,2-bis(4-(4-aminophenylthio)phenyl) Furonon, a, 4'-his (4-7ε nophenylthio) diphenyl ether, 4,47-bis (4
-aminophenylthio)benzophenone, 4,4'-bis(4-aminophenylthio)diphenyl sulfoxide, 4,4'-bis(4-aminophenylthio)diphenyl sulfone, 3,3'-bis(4-7-bis(4-aminophenylthio)), /phenylthio)diphenylsulfone, 4+4'bis(4-aminophenylthio)biphenyl, 2.2',6.6'-tetramethyl-4,4'-bis(4-7minophenylthio)biphenyl, etc. can be used.

A part of these aromatic amines (less than 50 mol %, preferably 5 to 30 mol %) is replaced with aromatic diamine represented by general formula (n) or aromatic diamine represented by general formula (1) H2N -A! It may be replaced with r-NH2(H) to improve the solubility and moldability of the resulting aromatic polyamide [wherein, yt-r is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms] group, an aralkyl group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a nitro group across a rogene group, and even if they are the same as each other,
It's okay to be different. dU.

The numbers 'fr between ~20, e and fl-j represent integers of θ~4 that are the same or different from each other. A', ru, an aromatic ring having 6 to 30 carbon atoms].

As the aromatic diamine represented by the above formula (II), 4
．． 4'-bis(4-aminophenylthio)diphenyl sulfide, 1,4-bis(4-aminophenylthio)benzene, 1,3-bis(4-aminophenylthio)benzene, α,ω-diaminopo IJ(1 ,4-phenylene)
Examples include oligomers.

Further, the aromatic diamine represented by the formula ([11)] includes p-phenylenediamine, m-phenylenediamine, 4
-1+ru 1,3-phenylenecyabane, 5-methyl-
1,3-phenylenediamine, 4,4'-cyabanobiphenyl, 4,4'-diaminodiphenyl ether, 41
4'-diaminodiphenylsulfide, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylsulfoxide, 4,4'-diaminodiphenylsulfone,
4.4'-diaminodiphenylmethane, 2.2-his(
4-aminophenyl)propa7.1.4-bis(4-aminophenoxy)benzene, 1.4-bis(4-aminobenzoyl)benzene, 1.4-bis(4-aminobenzenesulfonyl)benzene, 4. 4'-bis(4-aminophenoxy)diphenylmethane Jk, 4.4'-bis(4-aminophenoxy)diphenyl sulfide, 4.
4'-bis(4-aminophenoxy)benzophenone,
4.4'-bis(4-aminophenoxy)diphenylsulfone, 4.4'-bis(4-aminophenoxy)diphenylmethane, 2.2-his(4-(4-aminophenoxy)phenyl)pronoξone, 4 .4'-bis(4-
Amino(nzoyl)diphenyl ether, 4.4'-?
"Su(4-7minobenzoyl)benzophenone, 4.4
'-bis(4-aminobenzoyl)diphenylsulfoxide, 4.4'-his(4-a is nobenzoyl)diphenylsulfone, 4.4'-bis(4-aminobenzoyl)diphenylmethane, 2,2-bis(4 -(4-aminobenzoyl)phenyl)propane, 4,4'-bis(4
-aminobenzenesulfonyl)diphenyl ether, <
, 4'-his(4-aminobenzenesulfonyldiphenyl sulfide, 4.4'-his(4-aminobenzenesulfonyl)benzophenone, 4.a'-his(4-aminobenzenesulfonyl)diphenyl sulfoxide, 4
．． 4'-His(4-aminobenzenesulfonyl)diphenylsulfones 4+4'-His(4-aminobenzenesulfonyl)diphenylmethane, 2.2-bis(4-(
t-4-aminobenzenesulfonyl)phenyl]pronoξ, etc. can be mentioned.

[Aromatic dicarboxylic acid chloride]

Examples of the aromatic dicarboxylic acid chloride used in the present invention include terephthalic acid chloride, isophthalic acid chloride, 4,4'-biphenyl dicarboxylic acid chloride, 4,4'-diphenyl ether dicarboxylic acid chloride, and 4,4'-diphenyl sulfide dicarboxylic acid chloride. Acid chloride, 4,4'-benzophenonedicarboxylic acid chloride, 4,4'-diphenylsulfonedicarboxylic acid chloride, 4,4'-diphenylmethanedicarboxylic acid chloride, 1,5-naphthalenedicarboxylic acid chloride, etc. .

[Aromatic dicarboxylic acid]

Examples of aromatic dicarboxylic acids used in the present invention include terephthalic acid, inphthalic acid, 4,4'-biphenyl dicarboxylic acid, 414'-diphenyl ether dicarboxylic acid, and 4,4'-diphenyl sulfide dicarboxylic acid.
Examples include 414'-benzophenone dicarboxylic acid, 4,t'-diphenylsulfone dicarboxylic acid, 4+4'-diphenylmethane dicarboxylic acid, and 1,5-naphthalene dicarboxylic acid.

[Production method of polyamide]

Second invention: In the present invention, all known methods can be employed as they are in the reaction of aromatic diamine and aromatic dicarboxylic acid chloride. For example, this can be achieved by an interfacial polycondensation method, a solution polycondensation method, or the like.

Regarding the interfacial polycondensation method, known water-soluble neutralizing agents are used. For example, sodium hydroxide, potassium hydroxide,
Examples include inorganic alkalis such as sodium carbonate, potassium carbonate, and sodium hydrogen carbonate. The amount of alkali used is in the range of 0.3 to 3 equivalents, preferably 0.5 equivalents based on the number of moles of the reactive group of the aromatic dicarboxylic acid chloride.
~1,5 equivalents.

Aromatic polythioetheramide is produced by dispersing an aromatic diamine in an aqueous solvent containing the above-mentioned water-soluble neutralizer, and adding a solution of an aromatic dicarboxylic acid chloride dissolved in an organic solvent to the solution and reacting the same. I can do it.

Examples of the organic solvent include ketone solvents such as cyclohexanone, diisobutyl ketone, acetophenone, and p-methylacetophenone, methylene chloride, chloroform,
Carbon tetrachloride, 1,1.1-) IJ dichlortane, 1
．． Examples include rhodanized hydrocarbon solvents such as 1,2,2-tetrachloroethane. In order to obtain a high molecular weight substance, cyclohexanone, p-methylacetophenone, etc. are preferred. Further, the reaction temperature is in the range of 0 to 100°C, preferably 3 to 50°C.

- The reaction time is in the range of 1 minute to 10 hours, preferably 5 minutes to 3 hours.

In the case of the solution polycondensation method, a known tertiary amine may be used as a total neutralizing agent. For example, triethylamine, tributylamine, pyridine, quinoline, pyrimidine, 2
．． Examples include 6-lutidine. However, when an organic acid amide is used as a reaction solvent for these compounds, it is not necessarily necessary to add it. When a neutralizing agent is used, the amount used is preferably 0.3 to 3.0 equivalents based on the number of moles of the reactive group of the aromatic dicarboxylic acid chloride. On the other hand, organic acid amides and organic sulfoxides are preferred as reaction solvents. For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-methyl-ε-caprolactam, hexamethylphosphoramide, tetramethylurea, dimethylsulfoxide and the like can be mentioned.

The aromatic diamine is dissolved in the above reaction solvent, a neutralizing agent is added if necessary, and an aromatic dicarboxylic acid chloride is added to this solution and reacted to produce a polyamide having the following repeating unit. “6. :, :#”tl”
"6.,: This polyamide has the formula (II) or the formula (
By using the aromatic diamine shown in III), the following units may be included in the polyamide molecule.

5 to 10 weight percent lithium in the production of polyamide,
It may be advantageous to add calcium chloride, rhodan calcium, etc. to the reaction system to significantly increase solubility. In this case, the reaction temperature ranges from 30°C to +100°C, preferably from -20°C to +30°C. Reaction time is 5 minutes to 10 minutes
The time is preferably in the range of 30 minutes to 5 hours.

[Manufacturing method of the third invention] The method of manufacturing a polyamide by total polycondensation of an aromatic diamine and an aromatic dicarboxylic acid can also be adopted in all known methods as is, except for the raw materials. For example, this can be achieved by a direct polycondensation method, etc.

The aromatic polythioetheramide polymer of the present invention is produced by dissolving an aromatic diamine and an aromatic dicarboxylic acid in an organic acid amide or an organic sulfoxide, and adding a tertiary amine or the like as a condensing agent to the solution and reacting the same. can do. Examples of this solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N
-Methylpyrrolidone, N-methyl-ε-caprolactam, hexamethylphosphoramide, tetramethylurea, dimethylsulfoxide and the like. As the condensing agent, phosphorus-based condensing agents such as triphenyl phosphite are preferred. Examples of the tertiary amine include pyridine, quinoline, pyrimidine, 2,6-lutidine, triethylamine, and tributylamine. The condensing agent is used in an amount of 1 to 2 based on the number of moles of the reactive group of the aromatic dicarboxylic acid.
It is desirable to use equivalent amounts. Tertiary amines may be used in excess. Furthermore, it may be convenient to synthesize by adding 1 to 10 weight percent lithium, calcium chloride, calcium rhodan, etc., if necessary. Also, the reaction temperature is 0
-200°C, reaction time ranges from 30 minutes to 20 hours.

〔polyamide〕

The polyamide thus produced is an aromatic polythioetheramide polymer having the following repeating unit.
-1-8O-1-8O2- or -C〇-. a is 0 or 1, and when a is 00, it means that the aromatic rings are bonded to each other without X. Y is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, and 6 to 2 carbon atoms.
o represents an aryl group, a halogen group, or a nitro group, which may be the same or different from each other.

b and C represent integers from θ to 4 that are the same or different from each other. Moreover, Ar is an aromatic ring having 6 to 3 carbon atoms].

This polyamide may have the following units in its molecule.

The glass transition temperature of the polyamide thus obtained is approximately 150 to 28011°C for the homopolymer and approximately 200 to 350°C for the copolymer.

〔purification〕

Diluting a solution containing an aromatic polythioetheramide polymer produced by any of the methods above with a solvent that does not dissolve the polymer and is easily compatible with the reaction solvent,
The polyamide is isolated by precipitating the polymer and removing it in an oven.

[Processing, usage]

When molding the polymer of the present invention, various known filler components can be included. Typical examples of filler components include (a) fibrous filler, glass fiber, carbon fiber,
Boron fibers, aramid fibers, alumina fibers, silicon carbide fibers, etc., fb) Inorganic fillers: Myriki, talc, clay, graphite, carbon black, silica, asbestos, molybdenum sulfide, magnesium oxide,
Examples include calcium oxide.

The polymer of the present invention can be used for various electrical and electronic parts, housings, automobile parts, aircraft interior materials, sliding parts, gears, insulating materials, heat-resistant films, heat-resistant panels, heat-resistant fibers,
It can be used in a wide range of applications.

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 A stirring rod, a thermometer, and a dropping funnel were set in a No. 11 Mitsuro flask, and 2. OI was dissolved in 40 resistant water and placed in a flask. Next, 4.4'-bis (4
-a is nophenylthio) diphenylsylt7s,
s Og (!: 2.509 g of 4,4'-diaminodiphenyl ether was added, stirred vigorously at 5° C., and dispersed in the aqueous solution.

On the other hand, 2.541 i of terephthalic acid chloride and 2.54 i of inophthalic acid chloride were added to 120 M of cyclohexanone.
The acid chloride solution was poured into the flask from the dropping funnel. At this time, the total reaction temperature was kept at 15°C or less. After 20 minutes, 100ml of water and 80ml of cyclohexanone were added to the reaction solution, and then 200ml of acetone was added to the reaction solution.
1 to precipitate the polymer.

The polymer was separated, washed with hot water, and then dried in a vacuum oven (100°C, 8 hours). Yield 11.69 (yield xo0
9b). The glass transition temperature of this polymer was 208°C. Also, the intrinsic viscosity ij0.89dl/J? (o, s%
DMSO solution, 30°C).

When the infrared absorption spectrum of this polymer was measured, the absorption derived from amide was found to be 1640.1515α-1.
Absorption derived from ether at 1240αm, 11451
Absorption derived from 11C sulfone, absorption derived from vc thioether at 1070 cm', and absorption derived from aromatic ring at 805 cm' were observed.

Example 2 A gun was manufactured in the same manner as in Actual Gun Example 1 using raw materials having the following composition.

Cyclohexanone 120 d Polymer yield 13.2 g (100%). Glass transition temperature 250°C. Intrinsic viscosity 0.4 s d l /-g (0
, 2% NMP solution, 30°C).

TR spectrum (Figure 1): 1640, 1520cIr
L (amide), 1080cm' (thioether), so
scm (aromatic ring).

Example 3 A stirring bar, a thermometer, and a dropping funnel were set in a 500g Mitsuro flask, and 10.7g'k of 4,4'-bis(4-aminophenylthio)benzophenone and 50d of dry N-methylpyrrolidone were added. Melt it and put it in a flask. -5
While stirring at °C, a 50M solution of isophthalic acid chloride 5.08.9 in dry N-methylpyrrolidone was poured into the flask from the dropping funnel.

At this time, the reaction temperature f was kept at or below 0°C. Stirring was continued at 0°C for 2 hours, and then the reaction solution was poured into acetone to precipitate the polymer.The polymer was separated, washed with hot water, and then dried in a vacuum oven (100°C, 8 hours).
. Polymer yield “°°bar°°1・””Transition 2°’°”
, ;°C, softening point 310°C. Intrinsic viscosity o, 9c+dJ/
, V (0.5% DMSO solution, 30°C).

Infrared absorption TR spectrum: 16'40.1512CI
rv' (amide), 1640C1rv1 (ketone), 1
070m' (thioether), 810cm" (aromatic ring)
.

Example 4 Polyamide was produced in the same manner as in Example 1 using raw materials having the following composition.

Polymer yield 14.09 (100%). Glass transition temperature 229°C, softening point 322°C. Intrinsic viscosity 0.4°5dρ
/g (0.5% DMSO solution, 30°C).

TR spectrum (Figure 2): 1645.1520cr
iv' (7 mito), 164 scm" (keto y), 1
080c108O' (thioether), 825儂-1 (
Aromatic ring.

Example 5 A test was carried out using the same apparatus and method as in Example 1 using raw materials having the following composition.

Yield 13.9 g (99 inches). Glass transition temperature 227℃
, softening point 300°C. Intrinsic viscosity o, s s dl/, li
'(0.5% DMS08 solution, 30°C).

TR spectrum: 1s4o, 1510c+rL (amide), 1640crri' (ketone), 1070cm
'(thioether), 810 cm' (aromatic ring).

When this polymer was compression molded at 320°C, a pale yellow, strong resin plate was obtained.

Example 6 Polyamide was produced in the same manner as in Example 1 using raw materials having the following composition.

Yield 14.7 jj (99 chi). Glass transition temperature 18
8℃, softening point 262℃, intrinsic viscosity 0.4t d17g
(0.5% DMSO solution, 30°C).

TR spectrum: 1650.1510 crIL (amide), 1150 (IYA (sulfone), 1070 cm (
Example 7 A polyamide was produced in the same manner as in Example 1 using raw materials having the following composition.

(Terephthalic acid chloride 2.54,!l? Collection Jl
t4.9, 1iT (100 regrets). Glass transition temperature 199
°C, softening point 284 °C. Intrinsic viscosity 0.63 dl/1 (0,
5% DMSO solution, 30°C).

TR spectrum (Figure 3): 1640.1510cm"
(amide), 1150ci” (sulfone), x070
cIrL (thioether, 815c1n (aromatic ring)) Example 8 A polyamide was produced in the same manner as in Example 1 using raw materials having the following composition.

Yield 13.1 fl (100 g). Glass transition temperature 2
43℃. Intrinsic viscosity o,s 4617g (0.5ch DMS
solution, 30°C).

TR spectrum: 1640, 15xOcIIv" (amide), 1145cIIL (sulfone), 1070c
rri (thioether), 805cwv” (aromatic ring).

Example 9 Polyamide was produced in the same manner as in Example 1 using raw materials having the following composition.

Yield 14.5.9 (99%). Glass transition temperature 230℃
. Intrinsic viscosity o,s 5 dl/g (o,s DMSO solution, 30°C).

TR spectrum: 1640.1510α (amide),
1145crrL (sulfone), 1070crn (thioether), 805crrL (aromatic ring).

Example 10 Polyamide was produced in the same manner as in Example 1 using raw materials having the following composition.

C terephthalic acid chloride 2.549 yield! 11.2.
9 (100 chi). Glass transition temperature 241°C. Intrinsic viscosity o
, s sdl/g (o, s DMSO solution, 30°C).

IR spectrum: j640.1510c* (amide),
1640cIrL (ketone, 1240cyn (ether), 107107O thioether), 8056rI
L (aromatic ring).

Example 11 Polyamide was produced in the same manner as in Example 1 using raw materials with the following composition. Yield: 12.7. li+(10(1). Glass transition temperature 2
32℃. Intrinsic viscosity 0.61dl/li (0.5chi DM
SO solution, 30°C).

When this polymer was compression molded at 300°C, a strong ocher resin plate was obtained.

IR spectrum: 1640, tsxocm (amide),
1640cIIL (ketone), 10706rIL (thioether), 805cm' (aromatic ring).

[Brief explanation of drawings]

FIGS. 1, 2 and 3 respectively show Example 2.4.
and FIG. 7 is an infrared absorption spectrum diagram of the polyamide obtained in Example 7. Patent Applicant Mitsubishi Yuka Co., Ltd. Agent Patent Attorney Hidetoshi Furukawa Agent Patent Attorney Masahisa Hase

Claims (1)

[Scope of Claims] 1) An aromatic polythioetheramide polymer having the following repeating unit [wherein, X is a divalent hydrocarbon group having 1 to 10 carbon atoms, -〇-1-SO-1-802 - or -CO-. a is 0 or 1, and when a is 0, it means that the aromatic rings are bonded to each other without U or XU. YU, alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, aralkyl group having 6 to 20 carbon atoms, 6 to 2 carbon atoms
0 aryl group...indicates a nitro group spanning a rogen group,
They may be the same or different from each other. b and cH represent integers of θ to 4 that are the same or different from each other. Moreover, Ar is an aromatic ring having 6 to 30 carbon atoms]. 2)-) Reacting an aromatic diamine having a thioether bond containing 50 moles or more of a diamine represented by the general formula (I) (Y)b (Y)c (I) with an aromatic dicarboxylic acid chloride, A method for producing an aromatic polythioetheramide polymer having the following repeating unit [wherein, X is a divalent hydrocarbon group having 1 to 10 carbon atoms, -〇-1-8O-1-802- or -CO - indicates. a is 0 or 1, and when a is 0, there is no X, VC
, indicates that the aromatic rings are bonded to each other. YU
, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, an aryl group having 6 to 2 o carbon atoms, a halogen group, or a nitro group, each of which is the same as the other. It's okay to be different. b and c represent integers of θ to 4 that are the same or different from each other. Also, Arfd is an aromatic ring having 6 to 30 carbon atoms]
. 3) The aromatic diamine represented by the general formula (I) is dispersed in an alkaline aqueous solution, and a solution of an aromatic dicarboxylic acid chloride dissolved in an organic solvent is added thereto for polycondensation to produce the entire polymer. The method according to claim 2). 4) A patent characterized in that an aromatic diamine represented by general formula (I) is dissolved in an organic acid amide or an organic sulfoxide, and an aromatic dicarboxylic acid chloride is added thereto and polycondensed to produce a polymer. The method according to claim 2).