KR20040094468A - A diaminocarbazole compound, polyazometine synthesized with the diaminocarbazole compound, and preparation method thereof - Google Patents

Abstract

PURPOSE: Diaminocarbazole derivatives are provided to be advantageously used as intermediates in a polyazomethine preparation. Polyazomethines obtained by using the diaminocarbazole derivatives have excellent solubility in organic solvent or mixed organic solvent with water, thereby improving the processability and applications of the electroconductive polymer material obtained by doping the polyazomethine. CONSTITUTION: The diaminocarbazole derivatives are represented by a formula 1, wherein R is hydrogen, alkyl having C50 or less, hydroxyalkyl, alkylarylhydroxy, arylhydroxy, carboxyalkyl, alkylester, arylester and alkylarylester group. The diaminocarbazole derivatives are produced by: substituting the hydrogen of N-H bond in the carbazole ring with one selected from alkyl, hydroxyalkyl, alkylarylhydroxy, arylhydroxy, carboxyalkyl, alkylester, arylester and alkylarylester group in the presence of sodium hydride or potassium carbonate as a catalyst; dissolving the resulted N-substituted carbazole derivatives into a mixed solvent of acetic acid and anhydride thereof to introduce two nitro groups by using Cu(NO3)2·2.5H2O as a nitrating agent; dissolving the resulted product into ethyl alcohol and hydrochloric acid and adding SnCl2 thereto to reduce the nitro groups to imino groups. Polyazomethines are represented by a formula 2, wherein R is hydrogen, alkyl having C50 or less, hydroxyalkyl, alkylarylhydroxy, arylhydroxy, carboxyalkyl, alkylester, arylester and alkylarylester group; Z is N-R1 or CR2R3, wherein R1, R2 and R3, being independent from each other, are same as defined for R; and n is 2-500000.

Description

Diaminocarbazole derivative compound, polyazomethine synthesized therefrom, and preparation method thereof {A DIAMINOCARBAZOLE COMPOUND, POLYAZOMETINE SYNTHESIZED WITH THE DIAMINOCARBAZOLE COMPOUND, AND PREPARATION METHOD THEREOF}

The present invention relates to a diaminocarbazole derivative compound which can be used as an intermediate in the synthesis of a polyazomethine derivative which is an electrically conductive polymer, a polyazomethine synthesized therefrom, and a method for preparing the same.

Informatization, which began in the late 20th century, has a profound effect on the daily lives of individuals beyond the industrial and defense sectors, and this phenomenon is rapidly expanding worldwide. In the information age, developments in the fields of electrical, electronics, telecommunications, and defense are inevitable, and diversification and miniaturization of electronic equipment, and expansion of the electromagnetic frequency band used by these equipment are being pursued. As a result, electromagnetic interference between electromagnetic waves in electrical and electronic materials and circuits has emerged as a major problem in technical terms. On the other hand, environmentally, controversy over whether or not electromagnetic waves are harmful to human body is gradually spreading.

In general, electromagnetic shielding has been made of a metal or metal oxide material of which electrical properties are well known, but these materials are heavy and opaque, difficult to process into thin films, difficult to realize desired colors, and expensive. In addition, although the electromagnetic wave is shielded by reflecting the electromagnetic wave, there is a disadvantage in that there is no absorption ability of the electromagnetic wave. Therefore, there is a great need to develop new high performance electromagnetic shielding and absorbing materials that can replace these metal and metal oxide materials.

In order to solve these problems, fiber reinforced composite materials, materials with conductive surface treatments on plastics, materials with conductive fillers mixed with plastics, and the like have been researched and developed as substitutes for metals and metal oxides.

However, due to the recent increase in electromagnetic interference regulations at home and abroad, it is generally difficult to effectively cope with the related regulations by using fiber-reinforced composite materials and various plastic materials. Therefore, conductive polymers and composite materials having added conductivity to these materials There is growing interest in. Representative examples of such electrically conductive polymers include polyaniline, polythiophene, polypyrrole, polyparaphenylene, polyparaphenylenevinylene, polyacetylene, polyazomethine and the like. In general, the electrical conductivity of these electrically conductive polymers is highly dependent on the choice of dopant and the degree of doping. However, most of these conductive polymer materials are insoluble or have poor solubility, causing many problems in processing.

Accordingly, there is an urgent need to provide a new conductive polymer material having excellent solubility in an organic solvent or a mixed solvent of organic solvent and water.

Accordingly, a first object of the present invention is to provide a diaminocarbazole derivative compound which can be used as an intermediate in the preparation of polyazomethine and a method for producing the same.

It is a second object of the present invention to provide a polyazomethine and a method for producing the same, which are excellent in solubility in an organic solvent or a mixed solvent of water and an organic solvent synthesized from the diaminocarbazole derivative compound.

A third object of the present invention is to provide an electrically conductive polymer material obtained by doping the polyazomethine according to the present invention with a dopant.

Figure 1 shows the results of the thermal stability test of the polyazomethine polymer prepared in Examples 4 and 5 of the present invention.

The object of the present invention as described above is achieved by providing a diaminocarbazole derivative compound represented by the following formula (1), polyazomethine represented by the formula (2), and a method for preparing the same.

In the formula, R is selected from the group consisting of hydrogen, an alkyl group having up to 50 carbon atoms, a hydroxyalkyl group, an alkylarylhydroxy group, an arylhydroxy group, a carboxyalkyl group, an alkylester group, an arylester group and an alkylarylester group.

In Chemical Formula 2, R is the same as in Chemical Formula 1, Z is NR ₁ or CR ₂ R ₃ , wherein R ₁ , R ₂ and R ₃ are each independently hydrogen, an alkyl group having 50 or less carbon atoms, or a hydride. It is selected from the group consisting of an oxyalkyl group, an alkylarylhydroxy group, an arylhydroxy group, a carboxyalkyl group, an alkylester group, an arylester group, and an alkylarylester group, n has a value of 2-500,000.

The diaminocarbazole derivative compound of the present invention represented by Formula 1 may be prepared according to the method described below via the reaction route shown in Scheme 1 below.

The first step is to dissolve the carbazole in a suitable solvent, and then, using a base catalyst, the hydrogen atom of the carbazole NH bond, using an alkyl group, hydroxyalkyl group, alkylarylhydroxy group, arylhydroxy group, carboxyalkyl group, It is substituted by the substituent selected from the group which consists of an alkyl ester group, an aryl ester group, and an alkyl aryl ester group. Tetrahydrofuran is used as the reaction solvent, and sodium hydride (NaH) or potassium carbonate (K ₂ CO ₃ ) is preferably used as the base catalyst, but is not necessarily limited thereto.

The second step is to introduce two nitro groups into the carbazole ring. As the reaction solvent, a mixed solvent composed of acetic acid and acetic anhydride, and copper nitrate 2.5 hydrate (Cu (NO ₃ ) ₂ .2.5H ₂ O) may be used as the nitrating agent, but are not necessarily limited thereto. It is preferable to keep the reaction temperature at 0 ° C by using an ice bath, because when the nitrating agent is added, the reaction temperature rises to 100 ° C or more by exotherm, and there is a risk of explosion. Compounds in which R is hydrogen are obtained by direct nitration of carbazole.

The third step is to reduce the nitro group to an amino group using a reducing agent to obtain a diaminocarbazole derivative compound represented by Chemical Formula 1. A mixed solution of acetic acid and hydrochloric acid may be used as the reaction solvent, and tin chloride (SnCl ₂ ) may be used as the reducing agent.

The polyazomethine of the present invention represented by Chemical Formula 2 may be prepared by copolymerizing the diaminocarbazole derivative of Chemical Formula 1 with carbazole dialdehyde or fluorenedialdehyde comonomer represented by Chemical Formula 3 below.

In formula, Z is NR <_1> or CR <_2> R <_3> , and said R <_1> , R <_2> and R <_3> are respectively independently hydrogen, an alkyl group of 50 carbon atoms, a hydroxyalkyl group, an alkylarylhydroxy group, an arylhydroxy group, and a carboxyalkyl group , Alkyl ester group, aryl ester group and alkyl aryl ester group.

Z is NR ₁ the cover joldi aldehyde comonomers in the above formula (3) can be synthesized in the same way as that shown in Scheme 2 below.

First, the carbazole is dissolved in a suitable solvent, and then the hydrogen atom of the NH bond is substituted with an alkyl group, a hydroxyalkyl group, an alkylarylhydroxy group, an arylhydroxy group, a carboxyalkyl group, an alkylester group, or an aryl having up to 50 carbon atoms using a base catalyst. Reaction with a substance selected from the group consisting of ester groups and alkylaryl ester groups yields carbazoles wherein Z is NR ₁ . The reaction conditions are the same as in the first step of preparing the compound of Formula 1.

Next, two aldehyde groups are introduced into an unsubstituted carbazole or a carbazole derivative compound in which Z is NR ₁ to obtain a carbazole dialdehyde. In this reaction, dimethylformamide and phosphorous oxychloride can be used as a reactant, and 1,1,2-trichloroethane can be used as a reaction solvent.

In Formula 3, the fluorenedialdehyde comonomer in which Z is CR ₂ R ₃ may be prepared by a method as described below through a reaction route as shown in Scheme 3 below.

In the first step, one or two hydrogen atoms in the methylene position of the fluorene pentagonal ring are each an alkyl group, a hydroxyalkyl group, an alkylarylhydroxy group, an arylhydroxy group, a carboxyalkyl group, an alkylester group or an aryl ester having up to 50 carbon atoms. Substituted by a substituent selected from the group consisting of a group and an alkylaryl ester group. In this reaction, it is preferable to use tetrahydrofuran as a solvent and n-butyllithium which is a strong base catalyst as a catalyst.

In the second step, two of the eight fluorene ring hydrogens in the product of the first step are replaced with halogen atoms. The halogen atom is preferably bromine. In this case, propylene carbonate may be used as the reaction solvent, and N-bromosuccinimide may be used as the brominating agent.

The third step is to react the product of the second step with dimethylformamide in the presence of a base catalyst to replace the two bromine atoms introduced previously with an aldehyde group to obtain fluorenedialdehyde comonomers. Tetrahydrofuran can be used as the reaction solvent, and n-butyllithium can be used as the base catalyst.

By using a diaminocarbazole derivative synthesized through the same process as described above as the main monomer, and using a carbazole dialdehyde derivative or a fluorenedialdehyde derivative as a comonomer in the solution state, the polya represented by the formula (2) Gets Jometin Any organic solvent can be used as the polymerization solvent, but is preferably selected from the group consisting of o-, m- and p-cresol, chloroform, tetrahydrofuran, dimethylformamide and N-methylpyrrolidone.

The polymerization was carried out by placing a diaminocarbazole derivative compound represented by the formula (1) and a carbazole dialdehyde or fluorenedialdehyde derivative compound represented by the formula (3) in a dried solvent in a reactor and depressurizing to continuously remove water generated during the polymerization reaction. You can proceed in such a way.

The polymerization reaction may take several hours to 24 hours depending on the type of starting material, and the reaction temperature may range from room temperature to 130 ° C. Although the polymerization reaction proceeds even at room temperature, the temperature is raised when it is necessary to remove the generated water. In the case where the polymerization reaction proceeds at room temperature, a salt such as lithium chloride capable of absorbing the water generated during the polymerization process is added to the polymerization reaction medium. In this case, a basic solvent is used as the solvent.

By increasing the polymerization time or by carrying out the polymerization reaction at a temperature of 100 ° C. or higher, the molecular weight of the resulting copolymer can be increased. The polyazomethine polymer of the present invention prepared by the same method as described above has a weight average molecular weight in the range of 1,000 to 500,000.

Polyazomethine according to the present invention represented by the formula (2) is characterized in that the polymer main chain has a π-conjugated structure, and at the same time excellent solubility in an organic solvent or a mixed solvent of organic solvent and water by a substituent present in the side chain Excellent workability.

The present invention also relates to an electrically conductive polymer material obtained by doping a polyazomethine prepared by the same method as described above with a suitable doping agent.

In order to dope a polyazomethine with a processing or dopant, the polyazomethine must first be dissolved in a suitable solvent. At this time, all of the acid solution or a mixed solution of organic solvent and water may be used as the solvent. , Naphthalene acid, dimethyl sulfate, diethyl sulfate, dipropyl sulfate, di (2-ethylhexyl) sulfosuccinate, 4-sulfophthalic acid, malonic acid, 1,1,2-trichloroethane, chloroform, At least one selected from the group consisting of dichloromethane, tetrahydrofuran, dimethylformamide, propylenecarbonate, N-methyl pyrrolidone and m-cresol.

The polyazomethine may be dissolved in an organic solvent or a mixed solution of organic solvent and water and then doped into the polyazomethine using an acid, salt or iodine as the dopant. The doping agent is preferably sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, dodecylbenzenesulfonic acid, camphorsulfonic acid, sulfosalicylic acid, toluenesulfonic acid, benzenesulfonic acid, sulfic acid, naphthalene acid, dimethylsulfate, diethylsulfate, di At least one selected from the group consisting of propylsulfate, di (2-ethylhexyl) sulfosuccinate, 4-sulfophthalic acid and malonic acid. 1M solution is used when acid or base is used as dopant. In most cases doping is carried out by placing 1 g of polymer in 10 ml of 1 M dopant solution and stirring for 24 to 48 hours.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the embodiments are only examples of the present invention, and the scope of the present invention is not limited thereto.

Monomer Production Example

Example 1

Preparation of 3,6-diamino-9-[(2-ethyl) hexyl] carbazole

10 g of carbazole was dissolved in 100 ml of tetrahydrofuran, 15.2 ml of 2- (ethyl) hexylbromide was added, followed by 6.5 g of sodium hydride as a catalyst and reacted at 78 ° C. for 24 hours. After the reaction was completed, neutralized with 2M hydrochloric acid solution, ethyl acetate and water were added to separate the organic layer, and ethyl acetate was removed under reduced pressure to obtain a yellow liquid, which was then chromatographed to give 9-[(2-ethyl ) Hexyl] carbazole was obtained (yield 91%).

10 g of copper (II) nitrate 2.5 hydrate (Cu (NO ₃ ) ₂ .2.5H ₂ O) was added to a mixture of 30 ml of acetic acid and 30 ml of acetic anhydride at 0 ° C., followed by 9-[( 5 g of 2-ethyl) hexyl] carbazole were added and stirred for 1 hour. The reaction mixture was poured into excess water to form a precipitate which was filtered off and the solid was dried in vacuo to give 3,6-dinitro-9-[(2-ethyl) hexyl] carbazole in 87% yield.

10 ml of hydrochloric acid, 60 ml of acetic acid and 22 g of tin chloride were added to a vessel equipped with a reflux apparatus, and 3 g of 3,6-dinitro-9-[(2-ethyl) hexyl] carbazole was added to the mixture. The reaction mixture was refluxed for 24 hours. The reaction solution was neutralized with sodium hydroxide solution, the resulting precipitate was filtered off, and the filtered solid was vacuum dried at 100 ° C. This solid was again dissolved in tetrahydrofuran and the insoluble salts were filtered off to afford the desired compound in 87% yield. The data confirmed this is as follows.

Melting Point: 134 ℃

¹ H NMR (δSO, δ for TMS): 7.23 (s, 2H), 7.20 (d, 2H), 6,85 (m, 2H), 4.94 (s, 2H), 4.11 (d, 2H), 2.11 (s, 1H), 1.37-1.23 (m, 10H), 0.95-0.86 (m, 6H)

IR (KBr, cm ^-1 ): 3373, 3281, 3190, 2920, 2859, 1621, 1580, 1488, 1325, 1203, 877, 791

Elemental analysis calculated from C ₂₀ H ₂₇ N ₃ : C; 77.83, H; 8.79, N; 13.58

Found: C; 78.12, H; 8.34, N; 13.59

Example 2

Preparation of 9-[(2-ethyl) hexyl] -3,6-carbazoledialdehyde

5 g of 9-[(2-ethyl) hexyl] carbazole was dissolved in 30 ml of 1,1,2-trichloroethane, 16.7 ml of dimethylformamide and 16.8 ml of phosphorus oxychloride were added at 0 ° C, The reaction was carried out at 110 ° C. for 24 hours. The reaction mixture was neutralized with potassium hydroxide solution, extracted with ethyl acetate, and then ethyl acetate was darkened. The residue was chromatographed using ethyl acetate: hexane in a ratio of 1: 10 to separate the target compound, and the separated product was recrystallized from a small amount of ethyl acetate and excess hexane to obtain 3.6 g of the pure target compound.

Melting Point: 112 ℃

¹ H NMR (ClCl ₃ , δ for TMS): 10.02 (s, 1H), 8.55 (s, 2H), 7.99 (s, 2H), 7.43 (d, 2H), 4.15 (d, 2H), 1.97 ( m, 1H), 1.28-1.15 (m, 10H), 0.85-0.71 (m, 6H)

IR (KBr, cm ^-1 ): 2945, 2863, 1640, 1587, 1473, 1320, 1196, 875, 783

Elemental analysis calculated from C ₂₂ H ₂₅ NO ₂ : C; 78.77, H; 7.53, N; 4.18

Found: C; 79.02, H; 7.89 N; 4.37

Example 3

Preparation of 9,9-dibutyl-2,7-fluorenedialdehyde

Under a nitrogen atmosphere, 4.24 g of fluorene was dissolved in 60 ml of tetrahydrofuran, the temperature was lowered to -78 ° C using dry ice, 8 g of butyl bromide were added, and 21.5 ml of n-butyllithium was added, 5 The reaction was carried out for a time. Water was poured into the reaction mixture, followed by extraction with diethyl ethyr. The solvent was removed under reduced pressure to obtain 6.6 g (yield 93%) of 9,9-dibutylfluorene.

Under a nitrogen atmosphere, 5 g of 9,9-dibutylfluorene was dissolved in 80 ml of propylene carbonate, and 3.84 g of N-bromosuccinimide was added, followed by reaction for 2 hours. The reaction mixture was poured into excess water to form a precipitate, which was filtered to give a white solid. The solid was recrystallized from hexane to give 6.7 g of 2,7-dibromo-9,9-dibutylfluorene.

Under a nitrogen atmosphere, 5 g of 2,7-dibromo-9,9-dibutylfluorene was dissolved in 50 ml of tetrahydrofuran, the temperature was lowered to -78 ° C using dry ice, and n-butyllithium 5 ml was added. Then, 27 ml of dimethylformamide was added and reacted for 4 hours. Water was added to the reaction mixture, extraction was performed with diethyl ether, and the solvent was removed. The residue obtained was subjected to column chromatography using ethyl acetate: hexane in a ratio of 1: 10 to obtain a white solid. This solid was recrystallized from hexane to give 2.87 g of 9,9-dibutyl-2,7-fluorenedialdehyde.

Melting Point: 121 ℃

¹ H NMR (CLCl ₃ , δ for TMS): 10.08 (s, 1H), 7.95-7.88 (m, 6H), 2.08 (t, 4H), 1.08 (m, 4H), 0.65 (t, 6H), 0.52 (m, 4H)

IR (KBr, cm ^-1 ): 2990, 2872, 1670, 1581, 1493, 1227, 1184, 895, 788

Elemental analysis calculated from C ₂₃ H ₂₆ O ₂ : C; 82.6, H; 7.84

Found: C; 82.62, H; 8.16

Polymer Preparation

Example 4

0.5 g of 3,6-diamino-9-[(2-ethyl) hexyl] carbazole prepared in Example 1 and 9-[(2-ethyl) hexyl] -3,6-carba prepared in Example 2 Zoldialdehyde was dissolved in 10 ml of m-cresol using the same equivalent weight and polymerized at room temperature for 24 hours under reduced pressure to 50 cmHg to remove the water produced as a by-product to obtain polyazomethine in 81% yield. The prepared polymer was subjected to saxlet extraction using methanol as a solvent to remove the low molecular weight polymer, thereby obtaining a high molecular weight polymer having a weight average molecular weight of 1,000 to 500,000.

Instead of m-cresol as a solvent, a mixture of 3 ml of N-methylpyrrolidone (NMP) and 7 ml of dimethylacetamide (DMAc) is used as a cosolvent and in the reaction medium to remove the water produced during the polymerization. 0.05 g of lithium chloride was added and polymerized at room temperature, yielding the same product as above in 86% yield.

¹ H NMR (δSO, δ for TMS): 8.76 (s, 2H), 8.54 (s, 2H), 8.18-7.56 (m, 4H), 7.56 (t, 2H), 4.51 (s, 2H), 2.19 (s, 1H), 1.45-1.27 (m, 8H), 1.03-0.87 (m, 6H)

IR (KBr, cm ^-1 ): 2935, 2863, 1592, 1494, 1274, 1135, 801

Example 5

0.5 g of 3,6-diamino-9-[(2-ethyl) hexyl] carbazole prepared in Example 1 and 9,9-dibutyl-2,7-fluorenedialdehyde prepared in Example 3 were prepared. With the same equivalent It was polymerized in the same manner as in Example 4 to obtain an alternating copolymer of carbazole and fluorene in a yield of 84%.

¹ H NMR (δSO, δ for TMS): 8.85 (s, 2H), 8.21-7.89 (m, 8H), 7.62-7.29 (m, 4H), 4.25 (s, 2H), 2.19 (t, 6H) , 1.44 (m, 8H), 0.75 (m, 6H), 0.56 (t, 9H)

IR (KBr, cm ^-1 ): 2943, 2854, 1624, 1478, 1298, 1144, 818

Example 6

Solubility test

The solubility in organic solvents of the polymers prepared in Examples 4 and 5 was tested. The solubility test was performed at room temperature and visually checked to see if it became a very clear solution and if it was filtered through a 1 μm filter. In the case of visual observation, the solution was evaluated as +, completely filtered,-, and when observing both visual observation and complete filtration at ++, the results are shown in Table 1 below.

polymer chloroform Tetrahydrofuran Dimethylformamide Dimethyl sulfoxide N-methylpyrrolidone Example 5 ++ ++ ++ ++ ++ Example 4 ++ ++ ++ ++ ++

From this, it was confirmed that the polymer according to the present invention has excellent solubility in almost all solvents. Solubility in chloroform, tetrahydrofuran, dimethylformamide and N-methylpyrrolidone was particularly good.

Example 7

Electrical conductivity test

1 M sulfuric acid solution was used as a dopant and 1 g of polymer was mixed with the polymers obtained in Examples 4 and 5, respectively, using 10 ml of 1 M sulfuric acid solution, and stirred for 48 hours, and the doped polymer was filtered and dried. . The doped polymer was then pelleted using a press and the electrical conductivity was measured using 4-probe. In the case of the polymer of Example 4, the conductivity was 4.8 × 10 ⁻⁷ s / cm, and in the case of the polymer of Example 5, the conductivity was 2.4 × 10 ⁻² s / cm.

Example 8

Stability test

The thermogravimetric analyzer was tested for heat stability, and the results are shown in FIG. 1. 1 in FIG. 1 denotes the polymer of Example 4, and 5 denotes the polymer of Example 5. From Figure 1 it can be seen that the polyazomethine according to the present invention has a thermal stability up to 460 ℃.

According to the present invention, diaminocarbazole derivatives which can be used as intermediates in the preparation of polyazomethines having excellent solubility, polyazomethine copolymers prepared therefrom and methods for their preparation are provided.

Since the polyazomethine according to the present invention has excellent solubility and is well soluble in most organic solvents and mixed solvents of organic solvents and water, it is easy to process into various forms including thin films. In addition, since the main chain has a π-conjugated structure, it can be electrically conductive by doping with a suitable dopant, and because it has two polar imine groups per repeating unit of the main chain, it can be applied as a material for electric and electronic devices, and absorbs electromagnetic waves. Since it can be applied as a material for shielding electromagnetic waves.

Claims (8)

Diaminocarbazole derivative compounds represented by the following formula (1): [Formula 1] Wherein R is selected from the group consisting of hydrogen, an alkyl group having up to 50 carbon atoms, a hydroxyalkyl group, an alkylarylhydroxy group, an arylhydroxy group, a carboxyalkyl group, an alkylester group, an arylester group and an alkylarylester group. (a) Alkyl group, hydroxyalkyl group, alkylarylhydroxy group, arylhydroxy group, carboxyalkyl group, alkyl ester group, aryl ester group and alkylaryl ester using hydrogen atom of carbazole NH bond as base catalyst as sodium hydride or potassium carbonate Substituting with a substituent selected from the group consisting of groups, (b) The N-substituted carbazole derivative compound obtained in step (a) is dissolved in a mixed solvent of acetic acid and acetic anhydride, and two nitro groups are introduced using Cu (NO ₃ ) ₂ .2.5 H ₂ O as the nitrating agent. Steps, and (c) dissolving the product obtained in step (b) in ethyl alcohol and hydrochloric acid, and adding SnCl ₂ to reduce the nitro group to an amino group. Polyazomethine represented by the following Chemical Formula 2: [Formula 2] Wherein R is selected from the group consisting of hydrogen, an alkyl group having up to 50 carbon atoms, a hydroxyalkyl group, an alkylarylhydroxy group, an arylhydroxy group, a carboxyalkyl group, an alkylester group, an arylester group and an alkylarylester group, Z is NR ₁ or CR ₂ R ₃ , wherein R ₁ , R ₂ and R ₃ are each independently hydrogen, an alkyl group having 50 or less carbon atoms, a hydroxyalkyl group, an alkylarylhydroxy group, an arylhydroxy group, a carboxyalkyl group, or an alkyl ester. Group, aryl ester group and alkyl aryl ester group, n has a value from 2 to 500,000. 4. The polyazomethine according to claim 3, wherein the weight average molecular weight is 1,000 to 500,000. A process for preparing the polyazomethine according to claim 4, comprising copolymerizing the following compound of formula 1 with the compound represented by formula 3 in the presence of an organic solvent: [Formula 1] [Formula 3] Wherein R is selected from the group consisting of hydrogen, an alkyl group having up to 50 carbon atoms, a hydroxyalkyl group, an alkylarylhydroxy group, an arylhydroxy group, a carboxyalkyl group, an alkylester group, an arylester group and an alkylarylester group, Z is NR ₁ or CR ₂ R ₃ , and each of R ₁ , R ₂ and R ₃ is independently hydrogen, an alkyl group having 50 or less carbon atoms, a hydroxyalkyl group, an alkylarylhydroxy group, an arylhydroxy group, a carboxyalkyl group, or an alkyl ester. Group, an aryl ester group and an alkyl aryl ester group. 6. The process of claim 5 wherein said organic solvent is selected from the group consisting of o-, m- and p-cresol, chloroform, tetrahydrofuran, dimethylformamide and N-methyl pyrrolidone. An electrically conductive polymer material in which the polyazomethine according to claim 3 or 4 is doped with an acid, salt or iodine as a dopant. 8. The method of claim 7, wherein the dopant is sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, dodecylbenzenesulfonic acid, camphorsulfonic acid, sulfosalicylic acid, toluenesulfonic acid, benzenesulfonic acid, sulfic acid, naphthalene acid, dimethylsulfate, diethylsulfate, di And at least one selected from the group consisting of propylsulfate, di (2-ethylhexyl) sulfosuccinate, 4-sulfophthalic acid and malonic acid.