JPH05170904A - Polyaniline derivative and its production - Google Patents

Abstract

PURPOSE:To obtain a polyaniline derivative soluble in an organic solvent even by increase in the number of N atoms by crosslinking, forming a flexible self- supporting film by reacting a polyaniline with a polyether containing COOHs at both ends. CONSTITUTION:(A) A reduction type polyaniline comprising a structural unit of formula I, having 2,000-500,000 number-average molecular weight, obtained by treating an aniline oxidative polymer with ammonia to give a soluble type polyaniline and further treating the polyaniline with hydrazine is reacted with (B) a polymer compound of formula II [X is polyether structure of formula III ((m) is 10-200; R is H or alkyl)] containing COOHs at both ends in the presence of an N,N'-disubstituted carbodiimide (e.g. diethylcarbodiimide) to give a polyaniline derivative having a crosslinking structure of formula IV and the number of N atoms by crosslinking of 0.1-20% N atoms of polyaniline. The polyaniline derivative is soluble in various kinds of organic solvents and can be formed into a flexible self-supporting film by casting.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a highly conductive organic polymer and a method for producing the same, and more particularly to a polyaniline derivative which is soluble in an organic solvent and gives a flexible self-supporting film and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, a group of electrically conductive organic polymers has been attracting attention. Among them, polyaniline is a new electronic material, a conductive material, as a battery electrode material, an antistatic material, an electromagnetic shielding material, a photoelectron conversion material. Applications to a wide range of fields such as devices, optical memories, functional devices such as various sensors, display devices, various hybrid materials, transparent conductors, various terminal devices, etc. are being studied. However, in general, polyaniline has a highly developed π-electron conjugated organic polymer, so that the polymer main chain is rigid and the interaction between the molecular chains is strong, and there are many strong hydrogen bonds between the molecular chains. Therefore, it is insoluble in most organic solvents, and does not melt even when heated, so that it has poor moldability and cannot be processed into a film. For this purpose, for example, a base material having a desired shape such as a fiber of a polymer material or a porous body is impregnated with a monomer, and the monomer is polymerized by contact with an appropriate polymerization catalyst or by electrolytic oxidation to conduct a conductive composite material. Alternatively, or in the presence of the thermoplastic polymer powder, the monomer is polymerized to obtain a similar composite material. On the other hand, N is changed by devising the polymerization catalyst and reaction temperature.
Polyaniline soluble only in -methyl-2-pyrrolidone has been synthesized (M. Abe et al .; J. Ch.
em. Soc. Chem. Commun. , 198
9, 1736). However, this polyaniline was hardly dissolved in other general-purpose organic solvents and its application range was limited. Polyaniline derivatives soluble in organic solvents have also been synthesized using various aniline derivatives, but it has not been possible to provide a film having sufficient flexibility. Furthermore, it is also possible to produce a similar polymer by reacting a polyether-based polymer having a haloformyl group at both ends with a reduced polyaniline,
In this case, if the number of nitrogen atoms involved in crosslinking exceeds 5% of the nitrogen atoms of polyaniline, there is a problem that gelation occurs rapidly and coating or casting becomes difficult.

[0003]

SUMMARY OF THE INVENTION The present invention is intended to solve the above-mentioned problems in the prior art. That is, an object of the present invention is to provide a polyaniline derivative which is soluble in an organic solvent even when the number of nitrogen atoms involved in crosslinking is increased, and provides a flexible self-supporting film, and a method for producing the same. is there.

[0004]

Means for Solving the Problems As a result of extensive studies to solve the above problems, the present inventor has found that polyaniline and a polyether having carboxyl groups at both ends are N, N '.
-By reacting in the presence of disubstituted carbodiimides, a polyaniline derivative is obtained which is soluble in an organic solvent and gives a flexible self-supporting film even if the number of nitrogen atoms involved in crosslinking increases. As a result, they have completed the present invention. The polyaniline derivative of the present invention has the following formula (I)

[Chemical 6] The number average molecular weight of the structural unit represented by
Reduced polyaniline of 00000 and the following general formula (II) HOOC-X-COOH (II) [wherein, X is a polyether structure represented by the following structural formula (III), m = 10 to 200, R Is a hydrogen atom or an alkyl group. ]

[Chemical 7] Which is obtained by reacting a polymer compound having a carboxyl group at both ends with the presence of N, N'-disubstituted carbodiimides, represented by the following formula (IV):

[Chemical 8] (Wherein X has the same meaning as described above), and the number of nitrogen atoms participating in the crosslinking is 0.1 to 20% of the nitrogen atoms of polyaniline. It is a characteristic polyaniline derivative.

The polyaniline derivative of the present invention is manufactured as follows. That is, an aniline oxidation polymer obtained by oxidative polymerization of aniline or an aniline water-soluble salt at a low temperature, for example, a temperature in the range of −20 to 50 ° C. (conductivity: 10 ⁻⁶ , using ammonium persulfate or the like). S
/ Cm or more) is first treated with ammonia to obtain soluble polyaniline. Then, this is treated with an excess of hydrazine to obtain a number average molecular weight of 200 represented by the general formula (I).
A reduced polyaniline having a molecular weight of 0 to 500000 (measured with GPC (N-methyl-2-pyrrolidone solvent) and converted into polystyrene number average molecular weight) is obtained. The hydrazine treatment is carried out by dispersing a soluble polyaniline in water, adding an equivalent amount or more, preferably 3 times or more, of hydrazine to a nitrogen atom in the polyaniline under a nitrogen atmosphere and stirring at 0 to 30 ° C. for 24 hours or more. By doing. The obtained reduced polyaniline is soluble in N-methyl-2-pyrrolidone or N, N-dimethylacetamide, but other general-purpose organic solvent,
For example, it is almost insoluble in chloroform and tetrahydrofuran. Next, a polyether having a carboxyl group at both ends is dissolved in an amide-based solvent, and N, N'-disubstituted carbodiimides having an equivalent amount or more to the terminal carboxyl group are added while cooling to -10 to 10 ° C. Stirring is continued at that temperature for ˜4 hours, then the reduced polyaniline is added, and stirring is continued for another 1 to 6 hours while slowly returning to room temperature. The reaction mixture is poured into dilute hydrochloric acid and the polymer formed is precipitated. Since this polymer is doped with hydrochloric acid, the polyaniline derivative of the present invention can be produced by exposing it to ammonia vapor, washing it with water and dedoping. As the amide solvent, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone or the like can be used. ..

The polymer compound having carboxyl groups at both ends used in the present invention is represented by the general formula (II). HOOC-X-COOH (II) [In the formula, X is a polyether structure represented by the following structural formula (III), m = 10 to 200, and R is an alkyl group.

[Chemical 9] In the formula, R represents a hydrogen atom or an alkyl group. ] What is represented by is used. The N, N'-disubstituted carbodiimides used in the present invention are compounds represented by the following structural formula (V) R'-N = C = NR "(V), wherein R'and R "" Is an aliphatic or aromatic group, which may be the same or different, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, and a 3- group. Alkyl group such as dimethylaminopropyl group, cyclic alkyl group such as cyclohexyl group, phenyl group, p-tolyl group, m-tolyl group, p-N, N-dimethylaminophenyl group, p-chlorophenyl group, p-nitrophenyl And aryl groups such as p-cyanophenyl group. Specifically, diethylcarbodiimide, diisopropylcarbodiimide, dicyclocarbodiimide, diphenylcarbodiimide, di-p-tolylcarbodiimide, 1-ethyl-3-
(3-dimethylaminopropyl) carbodiimide and the like. The nitrogen atoms involved in the crosslinking of formula (IV) must be in the range of 0.1 to 20% on average of the nitrogen atoms of polyaniline. When the ratio of the nitrogen atoms involved in the crosslinking of the formula (IV) is higher than 20% of the nitrogen atoms of polyaniline, gelation occurs and there is a problem in preparation of paints and the like. Also, 0.1%
If it is lower, there is a problem that sufficient solubility cannot be obtained and sufficient flexibility is not obtained.

The polyaniline derivative of the present invention produced as described above is an amide solvent such as N-methyl-2-pyrrolidone or N, N-dimethylacetamide, a halogenated hydrocarbon solvent such as chloroform, dichloroethane or dichloromethane. It can be dissolved in ether solvents such as and tetrahydrofuran, amine solvents such as pyridine, and polar solvents such as dimethyl sulfoxide. It is possible to produce free-standing films and fibers from this solution. Furthermore, processed products such as this film and fiber are
1 by doping with an acceptor dopant
It shows a high conductivity of 0 ^{−3 to} 10 S / cm. The dopant used here is not particularly limited, and any dopant can be used as long as it is used as a dopant in doping the aniline-based conductive polymer. Specific examples include iodine, bromine, chlorine, halogen compounds such as iodine trichloride, sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, protic acid such as borofluoric acid, various salts of the protic acid, aluminum trichloride, Lewis acids such as iron trichloride, molybdenum chloride, antimony chloride and arsenic pentafluoride, acetic acid, trifluoroacetic acid, benzenesulfonic acid, p
-Various compounds such as organic acids such as toluenesulfonic acid may be mentioned. The method of doping these compounds is not particularly limited, and any known method can be used. Generally, the gel of the derivative of polyaniline, or a molded product thereof and the dopant compound may be brought into contact with each other, and it can be carried out in a gas phase or a liquid phase. Alternatively, a method of electrochemically doping in the solution of the above-mentioned protonic acid or its salt can be used.

[0008]

EXAMPLES The present invention will be described below with reference to examples. Example 1. 4.1 g of aniline and 21.9 g of concentrated hydrochloric acid are dissolved in water to make 100 ml, and cooled to -5 ° C. Concentrated hydrochloric acid 2
1.9 g and 6.28 g of ammonium persulfate were dissolved in water to make 100 ml, this solution was also cooled to -10 ° C, slowly added dropwise to the above aniline solution, and stirring was continued at -10 ° C for 6 hours. The number average molecular weight of 1200 thus obtained
An aniline-oxidized polymer of 0 (measured in GPC, N-methyl-2-pyrrolidone solvent, polystyrene-reduced number average molecular weight) was obtained. This was thoroughly washed with water, and then dedoped with aqueous ammonia to obtain a soluble polyaniline. Next, the soluble polyaniline was dispersed in 200 ml of water, and 50 ml of hydrazine was added under a nitrogen atmosphere.
The mixture was continuously stirred at room temperature for hours, filtered and dried to obtain an off-white reduced polyaniline. 1 g of the reduced polyaniline thus obtained (number average molecular weight 12000) was added under a nitrogen stream under N 2 atmosphere.
-Completely dissolved in 10 ml of methyl-2-pyrrolidone. On the other hand, polyethylene oxide diglycolic acid (molecular weight ≈3000, manufactured by Kawaken Fine Chemicals Co., Ltd.), which is a polyether having carboxyl groups at both ends, is 0.8.
Dissolve 25 g in 30 ml N-methyl-2-pyrrolidone and cool to 0 ° C. Add 0.1134 g of dicyclohexylcarbodiimide and continue stirring at 0 ° C. for 1 hour. The reduced polyaniline solution was added thereto, and the reaction was continued for 6 hours while gradually returning to room temperature. This solution was poured into 11 diluted hydrochloric acid with stirring, the precipitate was filtered off, exposed to ammonia vapor and washed with water to remove hydrogen halide, and dried to obtain 1.78 g of the polyaniline derivative of the present invention. ..

When the infrared absorption spectrum was measured,
1650 cm ^-1 (C = O due to the structure of the above formula (IV)
(Stretching), 2850-2950 cm ^-1 (aliphatic C-H stretching)
Was observed to be absorbed. From the reaction yield, the number of nitrogen atoms involved in the crosslinking of formula (IV) is 5% on average of the nitrogen atoms of polyaniline.
Met. 1 g of the obtained polyaniline derivative was put in 5 g of N-methyl-2-pyrrolidone, dissolved at room temperature, and a very flexible film was obtained by casting. Further, when this film was dipped in a 20% aqueous solution of sulfuric acid for 24 hours, doped, and dried, the conductivity was 0.5 S / cm. Also, instead of N-methyl-2-pyrrolidone, N,
Similar processing was possible using an organic solvent such as N-dimethylacetamide, N, N-dimethylformamide, pyridine, chloroform, dichloroethane, dichloromethane or tetrahydrofuran.

Example 2 Polyethylene oxide diglycolic acid, which is a polyether having carboxyl groups at both ends (molecular weight = 300
No. 0, manufactured by Kawaken Fine Chemical Co., Ltd.) was used, and 3.293 g of dicyclohexylcarbodiimide was used, and 4.25 g of the polyaniline derivative of the present invention was obtained in the same manner as in Example 1. The infrared absorption spectrum was measured and found to be 1650 cm due to the structure of the above formula (IV).
^-1 (C = O expansion and contraction), 2850 to 2950 cm ^-1 (aliphatic C
-H stretching) was observed. From the reaction yield, the formula (IV)
The number of nitrogen atoms participating in the crosslinking of was an average of 20% of the nitrogen atoms of polyaniline. Obtained polyaniline derivative 1
g was placed in 5 g of N-methyl-2-pyrrolidone, dissolved at room temperature and cast to give a very flexible film. Furthermore, this film is added to a 20% sulfuric acid aqueous solution for 2 minutes.
When immersed for 4 hours, doped and dried, the conductivity is 0.0
It was 5 S / cm. Also, similar processing can be performed by using an organic solvent such as N, N-dimethylacetamide, N, N-dimethylformamide, pyridine, chloroform, dichloroethane, dichloromethane, or tetrahydrofuran instead of N-methyl-2-pyrrolidone. It was

Example 3 Polyethylene oxide diglycolic acid, which is a polyether having carboxyl groups at both ends (molecular weight = 300
0, manufactured by Kawaken Fine Chemicals Co., Ltd. 0.0165
g, 0.0023 g of dicyclohexylcarbodiimide
0.990 g of the polyaniline derivative of the present invention was obtained in the same manner as in Example 1 except that the polyaniline derivative was used. When the infrared absorption spectrum was measured, it was found to be 16 due to the structure of the above formula (IV).
Absorption of 50 cm ^-1 (C = O stretching) and 2850 to 2950 cm ^-1 (aliphatic C-H stretching) was observed. From the reaction yield, the number of nitrogen atoms involved in the crosslinking of formula (IV) was 0.1% on average of the nitrogen atoms of polyaniline. 1 g of the obtained polyaniline derivative was added to 5 g of N-methyl-2-pyrrolidone,
It melted at room temperature and was cast to give a very flexible film. Further, when this film was dipped in a 20% sulfuric acid aqueous solution for 24 hours to be doped and dried, the conductivity was 0.1 S / cm. Also, instead of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N
The same processing was possible using an organic solvent such as dimethylformamide, pyridine, chloroform, dichloroethane, dichloromethane and tetrahydrofuran.

Example 4 Polyethylene oxide diglycolic acid, which is a polyether having carboxyl groups at both ends (molecular weight≈100)
0, 1.098 g of Kawaken Fine Chemicals Co., Ltd.,
In the same manner as in Example 1 except that 0.452 g of dicyclohexylcarbodiimide was used, 1.990 g of the polyaniline derivative of the present invention was obtained. The infrared absorption spectrum was measured and found to be 1650 cm due to the structure of the above formula (IV).
^-1 (C = O expansion and contraction), 2850 to 2950 cm ^-1 (aliphatic C
-H stretching) was observed. From the reaction yield, the formula (IV)
The number of nitrogen atoms participating in the crosslinking of was an average of 20% of the nitrogen atoms of polyaniline. Obtained polyaniline derivative 1
g was placed in 5 g of N-methyl-2-pyrrolidone, dissolved at room temperature and cast to give a very flexible film. Furthermore, this film is added to a 20% sulfuric acid aqueous solution for 2 minutes.
When immersed for 4 hours, doped and dried, the conductivity is 0.0
It was 1 S / cm. Also, similar processing can be performed by using an organic solvent such as N, N-dimethylacetamide, N, N-dimethylformamide, pyridine, chloroform, dichloroethane, dichloromethane, or tetrahydrofuran instead of N-methyl-2-pyrrolidone. It was

Example 5 In place of the polyethylene oxide diglycolic acid having carboxyl groups at both ends in Example 1, 0.825 g of polypropylene oxide diglycolic acid having a carboxyl group at both ends (molecular weight about 3000) was used. Is the same as in Example 1 except that the polyaniline derivative 1.82 of the present invention is
0 g was obtained. When the infrared absorption spectrum was measured,
1650 cm ^-1 (C = O due to the structure of the above formula (IV)
(Stretching), 2850-2950 cm ^-1 (aliphatic C-H stretching)
Was observed to be absorbed. From the reaction yield, the number of nitrogen atoms involved in the crosslinking of formula (IV) is 5% on average of the nitrogen atoms of polyaniline.
Met. 1 g of the obtained polyaniline derivative was put in 5 g of N-methyl-2-pyrrolidone and dissolved by stirring at room temperature, and it was possible to form a film by casting. Furthermore,
When this film was immersed in a 20% hydrochloric acid aqueous solution for 24 hours, doped, and dried, the conductivity was 0.5 S / cm.
Further, instead of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide,
Similar processing was possible using an organic solvent such as pyridine, chloroform, dichloroethane, dichloromethane and tetrahydrofuran.

Example 6 In place of polyethylene oxide diglycolic acid having carboxyl groups at both ends in Example 1, 1.650 g of polypropylene oxide diglycolic acid (having a molecular weight of about 3000) having carboxyl groups at both ends was used. Is a polyaniline derivative of the present invention 2.64 in the same manner as in Example 1.
0 g was obtained. When the infrared absorption spectrum was measured,
1650 cm ^-1 (C = O due to the structure of the above formula (IV)
(Stretching), 2850-2950 cm ^-1 (aliphatic C-H stretching)
Was observed to be absorbed. From the reaction yield, the number of nitrogen atoms involved in the crosslinking of formula (IV) is 10 on average of the nitrogen atoms of polyaniline.
%Met. 1 g of the obtained polyaniline derivative was put in 5 g of N-methyl-2-pyrrolidone and dissolved by stirring at room temperature, and it was possible to form a film by casting. Further, when this film was dipped in a 20% hydrochloric acid aqueous solution for 24 hours to be doped and dried, the conductivity was 0.3 S / cm. Also, instead of N-methyl-2-pyrrolidone, N, N
Similar processing was possible using an organic solvent such as -dimethylacetamide, N, N-dimethylformamide, pyridine, chloroform, dichloroethane, dichloromethane and tetrahydrofuran.

Example 7 In place of the polyethylene oxide diglycolic acid having carboxyl groups at both ends in Example 1, 0.549 g of polypropylene oxide diglycolic acid (having a molecular weight of about 1000) having carboxyl groups at both ends was used. Is a polyaniline derivative of the present invention 1.54 in the same manner as in Example 1.
g was obtained. When the infrared absorption spectrum was measured, absorptions of 1650 cm ^-1 (C = O stretching) and 2850 to 2950 cm ^-1 (aliphatic CH stretching) due to the structure of the above formula (IV) were observed. From the reaction yield, the number of nitrogen atoms involved in the crosslinking of formula (IV) is 10% of the nitrogen atoms of polyaniline on average.
Met. 1 g of the obtained polyaniline derivative was put in 5 g of N-methyl-2-pyrrolidone and dissolved by stirring at room temperature, and it was possible to form a film by casting. Furthermore,
When this film was immersed in a 20% hydrochloric acid aqueous solution for 24 hours, doped, and dried, the conductivity was 0.5 S / cm.
Further, instead of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide,
Similar processing was possible using an organic solvent such as pyridine, chloroform, dichloroethane, dichloromethane and tetrahydrofuran.

Example 8 In place of the polyethylene oxide diglycolic acid having carboxyl groups at both ends in Example 1, 2.169 g of polypropylene oxide diglycolic acid (having a molecular weight of about 1000) having carboxyl groups at both ends was used. Is a polyaniline derivative of the present invention 3.18 in the same manner as in Example 1.
5 g was obtained. When the infrared absorption spectrum was measured,
1650 cm ^-1 (C = O due to the structure of the above formula (IV)
(Stretching), 2850-2950 cm ^-1 (aliphatic C-H stretching)
Was observed to be absorbed. From the reaction yield, the number of nitrogen atoms involved in the crosslinking of the formula (IV) is 20 on average of the nitrogen atoms of polyaniline.
%Met. 1 g of the obtained polyaniline derivative was put in 5 g of N-methyl-2-pyrrolidone and dissolved by stirring at room temperature, and it was possible to form a film by casting. Further, when this film was dipped in a 20% hydrochloric acid aqueous solution for 24 hours, doped, and dried, the conductivity was 0.5 S / cm. Also, instead of N-methyl-2-pyrrolidone, N,
Similar processing was possible using an organic solvent such as N-dimethylacetamide, N, N-dimethylformamide, pyridine, chloroform, dichloroethane, dichloromethane or tetrahydrofuran. The polypropylene oxide diglycolic acid having carboxyl groups at both ends used in Examples 5 to 8 was a polypropylene glycol having both end hydroxyl groups (a molecular weight of about 3000 Wako Pure Chemical Industries, Ltd.) in the presence of potassium carbonate and platinum-activated carbon. As a catalyst, an aqueous solution was refluxed for 12 hours to oxidize a hydroxyl group into a carboxyl group. The number of terminal groups was 2.01 by volumetric analysis, and it was confirmed that almost 100% was oxidized to be a carboxyl group.

INDUSTRIAL APPLICABILITY The polyaniline derivative of the present invention has a cross-linking structure between polyanilines formed of a dicarboxylic acid having a polyether structure, is soluble in various organic solvents, and is cast and is free-standing. It can be processed by obtaining a film having good properties and can be processed by coating, etc., and shows high conductivity by doping, and is very useful for various applications as an electronic material and a conductive material.

[Procedure amendment]

[Submission date] July 21, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0004

[Correction method] Change

[Correction content]

[0004]

Means for Solving the Problems As a result of extensive studies to solve the above problems, the present inventor has found that polyaniline and a polyether having carboxyl groups at both ends are N, N '.
-By reacting in the presence of disubstituted carbodiimides, a polyaniline derivative is obtained which is soluble in an organic solvent and gives a flexible self-supporting film even if the number of nitrogen atoms involved in crosslinking increases. As a result, they have completed the present invention. The polyaniline derivative of the present invention has the following formula (I)

[Chemical 6] The number average molecular weight of the structural unit represented by
000000 of reduced polyaniline and the following general formula (I
I) HOOC-X-COOH (II) [In the formula, X is a polyether structure represented by the following structural formula (IIl), m = 10 to 200, and R is a hydrogen atom or an alkyl group. ]

[Chemical 7] Which is obtained by reacting a polymer compound having a carboxyl group at both ends with the presence of N, N′-disubstituted carbodiimides, represented by the following formula (IV):

[Chemical 8] (Wherein X has the same meaning as described above), and the number of nitrogen atoms participating in the crosslinking is 0.1 to 20% of the nitrogen atoms of polyaniline. It is a characteristic polyaniline derivative.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0006

[Correction method] Change

[Correction content]

The polymer compound having carboxyl groups at both ends used in the present invention is represented by the general formula (II). HOOC-X-COOH (II) [wherein, X is a polyether structure represented by the following structural formula (III), m = 10 to 200, and R is an alkyl group.

[Chemical 9] In the formula, R represents a hydrogen atom or an alkyl group. ] What is represented by is used. The N, N'-disubstituted carbodiimides used in the present invention are compounds represented by the following structural formula (V) R'-N = C = NR "(V), wherein R'and R "" Is an aliphatic or aromatic group, which may be the same or different, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, and a 3- group. Alkyl group such as dimethylaminopropyl group, cyclic alkyl group such as cyclohexyl group, phenyl group, p-tolyl group, m-tolyl group, p-N, N-dimethylaminophenyl group, D-chlorophenyl group, p-nitrophenyl And aryl groups such as p-cyanophenyl group. Specifically, diethylcarbodiimide, diisopropylcarbodiimide, dicyclocarbodiimide, diphenylcarbodiimide, di-p-tolylcarbodiimide, 1-ethyl-3-
(3-dimethylaminopropyl) carbodiimide and the like. The nitrogen atoms involved in the crosslinking of formula (IV) must be in the range of 0.1 to 20% on average of the nitrogen atoms of polyaniline. If the proportion of nitrogen atoms participating in the cross-linking of formula (IV) is higher than 20% of the nitrogen atoms of polyaniline,
Gelation occurs and there is a problem in the preparation of paints. In addition, 0.
If it is less than 1%, there is a problem that sufficient solubility cannot be obtained and sufficient flexibility is not obtained.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction content]

Example 8 Polypropylene oxide having carboxyl groups at both ends in Example 1 was replaced with polypropylene oxide having a carboxyl group at both ends (molecular weight: about 10).
(00) 2.169 g, but in the same manner as in Example 1 to obtain 3.185 g of the polyaniline derivative of the present invention. When the infrared absorption spectrum was measured, the above formula (I
Absorption of 1650 cm ⁻¹ (C═O stretching) and 2850 to 2950 cm ⁻¹ (aliphatic C—H stretching) due to the structure V) was observed. From the reaction yield, the number of nitrogen atoms involved in the crosslinking of formula (IV) was 20% on average of the nitrogen atoms of polyaniline. 1 g of the obtained polyaniline derivative was put into 5 g of N-methyl-2-pyrrolidone and stirred at room temperature to form a gel, which could be formed into a film by spinning or stretching. Further, this film was dipped in a 20% hydrochloric acid aqueous solution for 24 hours, doped, and dried to obtain a conductivity of 0.5 S /
It was cm. Further, similar gelation is possible by using an organic solvent such as N, N-dimethylacetamide, N, N-dimethylformamide, pyridine, chloroform, dichloroethane, dichloromethane or tetrahydrofuran instead of N-methyl-2-pyrrolidone. there were. Example 5 above
Polypropylene oxide having a carboxyl group at both terminals was used in 8, the presence of potassium carbonate polypropylene glycol having hydroxyl groups at both ends, platinum - charcoal was an aqueous solution as a catalyst was refluxed for 12 hours to oxidize the hydroxyl group to a carboxyl group It is a thing. The number of terminal groups was 2.01 by volumetric analysis, and it was confirmed that almost 100% was oxidized to be a carboxyl group.

Claims (2)

[Claims] 1. The following formula (l): The number average molecular weight of the structural unit represented by
000000 reduced polyaniline and the following general formula (II) HOOC-X-COOH (II) [wherein, X is a polyether structure represented by the following structural formula (III), and m = 10 to 200. [Chemical 2] In the formula, R represents a hydrogen atom or an alkyl group. ] The compound represented by the following formula (IV): (Wherein X has the same meaning as described above), and the number of nitrogen atoms involved in the crosslinking is 0.1 to 20% of the nitrogen atoms of polyaniline. A polyaniline derivative. 2. A soluble polyaniline obtained by treating an aniline-oxidized polymer with ammonia is treated with hydrazine,
The following formula (I): The number average molecular weight of the structural unit represented by
000000 of reduced polyaniline was prepared, and then the reduced polyaniline was converted to the following general formula (II) HOOC-X-COOH (II) [wherein X represents a polyether structure represented by the following structural formula (III)] Yes, m = 10-200. ] [Chemical 5] [In the formula, R represents a hydrogen atom or an alkyl group. ] The high molecular compound which has a carboxyl group at both ends shown by these are made to react in presence of N, N'-disubstituted carbodiimides, The manufacturing method of the polyaniline derivative characterized by the above-mentioned.