JPH04372623A - Polyaniline derivative and its production - Google Patents

Abstract

PURPOSE:To obtain a derivative which is soluble in various solvents and can give a self-supporting flexible film when cast by giving thereto a specified crosslinked structure and specifying the number of the nitrogen atoms forming crosslinking points. CONSTITUTION:A polyaniline derivative which has a crosslinked structure of formula II derived by reacting a polyaniline in the reduced form having a number-average molecular weight of 2000-50000 and comprising structural units of formula I with a polymeric compound having an NCO group at each terminal and represented by the formula: OCN-X-NCO [wherein X is a poly(1,2-butadiene) structure of formula II (wherein m is 10-200)] and has the number of the nitrogen atoms forming crosslinking points in the range of 0.1-15% based on the total nitrogen atoms in the polyaniline.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to polyaniline derivatives which are soluble in various organic solvents and which can be cast or cast to form flexible, self-supporting films, and a method for producing the same.

0002

[Prior Art] In recent years, polyaniline has been used as a new electronic material.
As a conductive material, it can be used in a wide range of fields such as battery electrode materials, antistatic materials, electromagnetic shielding materials, photoelectronic conversion elements, optical memories, functional elements such as various sensors, display elements, various hybrid materials, transparent conductors, and various terminal devices. Applications are being considered.

By the way, conventional polyaniline has a highly developed π-conjugated system, so the main chain of the polymer is rigid, 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 it has poor moldability and has the major disadvantage that it cannot be processed into films or the like.

For this purpose, for example, fibers of polymeric materials,
A conductive composite material can be obtained by impregnating a base material of a desired shape such as a porous body with a monomer made of aniline and bringing the monomer into contact with a suitable polymerization catalyst, or by polymerizing it by electrolytic oxidation. also polymerized the monomer in the presence of thermoplastic polymer powder to obtain similar composite materials.

On the other hand, by modifying the polymerization catalyst and reaction temperature, N
- Polyaniline soluble only in methyl-2-pyrrolidone has been synthesized (M. Abe et al.; J. Ch.
em. Soc. , Chem. Commun. , 1989
, 1736). However, this polyaniline is also hardly soluble in other general-purpose organic solvents, so its range of application is limited. Furthermore, the polymers obtained by either method do not have sufficient flexibility, which limits their range of use.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned problems in the prior art. That is, an object of the present invention is to provide a polyaniline derivative that is easily dissolved in an organic solvent and can be formed into a flexible, self-supporting film by casting or flow-spreading, and a method for producing the same.

[0007]

[Means for Solving the Problems] As a result of intensive studies to solve the above-mentioned problems, the present invention has been developed by reacting reduced polyaniline with polybutadiene having isocyanate groups at both ends, and by reacting reduced polyaniline with polybutadiene having isocyanate groups at both ends. It has been discovered that polyaniline derivatives soluble in various organic solvents can be obtained by having a specific amount of the crosslinked structure of formula (III), and the present invention has been completed.

The polyaniline derivative of the present invention has the following formula (
I)

Number average molecular weight consisting of the structural unit represented by [Chemical 7] 2,000~
500,000 reduced polyaniline was converted into the following general formula (
II) OCN-X-NCO (I
I) [wherein, X is poly(1,2-
butadiene) structure. m=10~200]

It is obtained by reacting with a polymer compound having isocyanate groups at both ends represented by the following formula (II
I)

A polyaniline characterized in that the crosslinked structure represented by [Formula 9] (wherein X has the same meaning as above) exists in a range of 0.1% or more and less than 15% of the nitrogen atoms of the polyaniline. It is a derivative.

The polyaniline derivative of the present invention is produced as follows. That is, aniline oxidation polymerization obtained by oxidative polymerization of aniline at a low temperature, for example, in the range of -20 to 50°C, using ammonium persulfate or the like as an oxidizing agent in the presence of a protonic acid such as hydrochloric acid, sulfuric acid, or nitric acid. The coalescence is first treated with ammonia to obtain soluble polyaniline. Thereafter, this was treated with excess hydrazine to obtain a number average molecular weight of 2,000 to 5 as represented by the above general formula (I).
00,000 (measured by GPC, N-methyl-2-pyrrolidone solvent, number average molecular weight in terms of polystyrene) is obtained. In the hydrazine treatment, soluble polyaniline is dispersed in water, hydrazine is added in an amount equivalent to or more, preferably 3 times or more, to the nitrogen atoms in the polyaniline under a nitrogen atmosphere, and the mixture is stirred at 0 to 30°C for 24 hours. To do this.

The obtained reduced polyaniline is soluble in N-methyl-2-pyrrolidone or N,N-dimethylacetamide, but is almost insoluble in other general-purpose organic solvents such as chloroform and tetrahydrofuran.

[0011] This reduced polyaniline is treated with an amide solvent,
For example, -1
The polyaniline derivative of the present invention is synthesized by carrying out the reaction in a temperature range of 0 to 50°C.

In this case, as a solvent for the reduced polyaniline, in addition to the above-mentioned N-methyl-2-pyrrolidone and N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphoric triamide, 1,3 −
An amide solvent such as dimethyl-2-imidazolidinone can be used.

The polymer compound having isocyanate groups at both ends used in the present invention has the general formula (II): OCN-X
-NCO (II) [wherein, X is a poly(1,2-butadiene) structure represented by the following structural formula. m=10~200]

[Chemical formula 10] The one represented by is used.

In the polyaniline derivative of the present invention, the number of nitrogen atoms forming the crosslinking points of the crosslinked structure of the above formula (III) is 1% or more of the nitrogen atoms in the polyaniline.
It is necessary that it be within a range of less than 5%. The formula (III
) the number of nitrogen atoms forming crosslinking points in the crosslinked structure is 15%
At higher ratios, the conductivity drops rapidly and gelation occurs. Further, if it is lower than 0.1%, solubility decreases and sufficient flexibility cannot be obtained.

The polyaniline derivative of the present invention produced as described above can be prepared using an amide solvent such as N-methyl-2-pyrrolidone or N,N-dimethylacetamide, an amine solvent such as pyridine, or a polar solvent such as dimethyl sulfoxide. It can be dissolved in a solvent, and from the resulting solution it is possible to produce self-supporting films and fibers. Furthermore, processed products such as films and fibers are
1 by doping with an acceptor dopant.
It exhibits 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 when doping an aniline conductive polymer. Specific examples include halogen compounds such as iodine, bromine, chlorine, and iodine trichloride, protonic acids such as sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, and fluoroboric acid, various salts of the protonic acids, aluminum trichloride, Examples include various compounds such as Lewis acids such as iron trichloride, molybdenum chloride, antimony chloride, and arsenic pentafluoride, and organic acids such as acetic acid, trifluoroacetic acid, benzenesulfonic acid, and p-toluenesulfonic acid.

There are no particular limitations on the method of doping these compounds, and for example, the polyaniline derivative and the dopant compound may be brought into contact in a gas phase or a liquid phase. Alternatively, a method of electrochemical doping in a solution of the protonic acid or its salt can also be used.

[0018]

[Examples] The present invention will be explained below with reference to Examples. Example 1. Dissolve 4.1g of aniline and 21.9g of concentrated hydrochloric acid in water and make 1
00 ml and cooled to -5°C. 21.9g of concentrated hydrochloric acid,
Dissolve 6.28g of ammonium persulfate in 100ml of water.
This solution was also cooled to -5°C, slowly added dropwise to the above aniline solution, and stirred for 4 hours at -5°C to give a number average molecular weight of 12,000 (GPC, N-methyl-2-
An aniline oxidized polymer having a polystyrene-equivalent number average molecular weight measured in a pyrrolidone solvent was obtained. After thoroughly washing this with water, it was further subjected to dedoping treatment with aqueous ammonia. 200 m of soluble polyaniline thus obtained
1 of water, 50 ml of hydrazine was added under a nitrogen atmosphere, stirring was continued at room temperature for 24 hours, filtered and dried to obtain off-white reduced polyaniline.

1 g of the thus obtained reduced polyaniline (number average molecular weight 12,000) was completely dissolved in 30 ml of N-methyl-2-pyrrolidone, and after the atmosphere was sufficiently replaced with nitrogen, this solution was added with isocyanate groups at both ends. Poly(
1,2-butadiene) in butyl acetate 50% by weight solution [T
P-1001, manufactured by Nippon Soda Co., Ltd., molecular weight approximately 1,00
0 (m≈18)] was added, and the reaction was continued with stirring at room temperature for 4 hours. This reaction solution was poured into 1 liter of water with stirring, and the precipitate was filtered off and dried to obtain 1.273 g of the polyaniline derivative of the present invention. When the infrared absorption spectrum of the polyaniline derivative was measured, it was found that 16
50cm-1 (C=O expansion and contraction), 2850-2950cm
-1 (aliphatic C-H stretching) absorption was observed. From the reaction yield, the number of nitrogen atoms forming crosslinking points in the structure of formula (III) was 5% of the nitrogen atoms in polyaniline.

When 1 g of the obtained polyaniline derivative was added to 10 g of N-methyl-2-pyrrolidone and stirred at room temperature, a viscous solution was obtained, which could be formed into a film by spinning or stretching. The film in this case was extremely flexible and did not crack or break even when bent. When this film was doped with a 20% aqueous hydrochloric acid solution for 24 hours and dried, the conductivity was 1.0 S/cm. Also, instead of N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide,
Similar spinning and film formation were possible using organic solvents such as pyridine.

Example 2 A 50% by weight solution of poly(1,2-butadiene) having isocyanate groups at both ends used in Example 1 in butyl acetate [TP-1001, Nippon Soda Co., Ltd., molecular weight approximately 1.0]
00 (m≒18)], a 50% by weight solution of poly(1,2-butadiene) having isocyanate groups at both ends in ethyl acetate [TP-1002, manufactured by Nippon Soda Co., Ltd., molecular weight approximately 1,000] (m≒18)] 0.550 g, and the same procedure was followed to add 1.5 g of the polyaniline derivative of the present invention.
．． 270g was obtained. When the infrared absorption spectrum of the polyaniline derivative was measured, it was found that 1650 cm-1 (C=O stretching), 2850 cm-1 due to the structure of the above formula (III),
Absorption at ~2950 cm-1 (aliphatic C-H stretching) was observed. From the reaction yield, the number of nitrogen atoms forming crosslinking points in the structure of formula (III) is 5 of the nitrogen atoms in polyaniline.
%Met.

1 g of the obtained polyaniline derivative of the present invention
When added to 10 g of N-methyl-2-pyrrolidone and stirred at room temperature, a viscous solution was obtained, which could be formed into a film by spinning or stretching. The film in this case was extremely flexible and did not crack or break even when bent. When this film was doped with a 20% aqueous hydrochloric acid solution for 24 hours and dried, the conductivity was 0.5 S/cm. Also, instead of N-methyl-2-pyrrolidone, N
Similar spinning and film formation were possible using organic solvents such as , N-dimethylacetamide, N,N-dimethylformamide, and pyridine.

Example 3 In Example 1, a 50% by weight solution of poly(1,2-butadiene) having isocyanate groups at both ends in butyl acetate [TP-1001, manufactured by Nippon Soda Co., Ltd., molecular weight approximately 1,
000 (m≒18)] 1.100 instead of 0.550g
1.540 g of the polyaniline derivative of the present invention was obtained by the same procedure. When the infrared absorption spectrum of the polyaniline derivative was measured, it was found that 1650 cm-1 (C=O stretching), 2
Absorption from 850 to 2950 cm-1 (aliphatic C-H stretching) was observed. From the reaction yield, the number of nitrogen atoms forming crosslinking points in the structure of formula (III) was 10% of the nitrogen atoms in polyaniline.

1 g of the obtained polyaniline derivative of the present invention
When added to 10 g of N-methyl-2-pyrrolidone and stirred at room temperature, a viscous solution was obtained, which could be formed into a film by spinning or stretching. The film in this case was extremely flexible and did not crack or break even when bent. When this film was doped by soaking it in a 20% aqueous hydrochloric acid solution for 24 hours and drying, the electrical conductivity was 0.1 S/cm. Also, instead of N-methyl-2-pyrrolidone, N,
Similar spinning and films were possible using organic solvents such as N-dimethylacetamide, N,N-dimethylformamide, and pyridine.

Example 4 In Example 1, a 50% by weight solution of poly(1,2-butadiene) having isocyanate groups at both ends in butyl acetate [TP-1001, manufactured by Nippon Soda Co., Ltd., molecular weight approximately 1,
000 (m≒18)] 0.275 instead of 0.550g
1.130 g of the polyaniline derivative of the present invention was obtained by following the same procedure. When the infrared absorption spectrum of the polyaniline derivative was measured, it was found that the above formula (III)
1650 cm-1 (C=0 stretch) due to the structure of
Absorption between 2850 and 2950 cm-1 (aliphatic C-H stretching) was observed. From the reaction yield, the number of nitrogen atoms forming crosslinking points in the structure of formula (III) was 2.5% of the nitrogen atoms in the polyaniline.

1 g of the obtained polyaniline derivative of the present invention
When added to 10 g of N-methyl-2-pyrrolidone and stirred at room temperature, a viscous solution was obtained, which could be formed into a film by spinning or stretching. The film in this case was extremely flexible and did not crack or break even when bent. When this film was doped with a 20% aqueous hydrochloric acid solution for 24 hours and dried, the conductivity was 1.1 S/cm. Also, instead of N-methyl-2-pyrrolidone, N
Similar spinning and film formation were possible using organic solvents such as , N-dimethylacetamide, N,N-dimethylformamide, and pyridine.

Example 5 The reaction solution of the reduced polyaniline obtained in Example 1 and poly(1,2-butadiene) having isocyanate groups at both ends was directly cast onto a Teflon plate, and the solvent was dried. and got the film. This film was extremely flexible and did not crack or break even when bent. When the infrared absorption spectrum of the film was measured, it was found that 1650 cm-
Absorption of 1 (C=0 stretching) and 2850 to 2950 cm -1 (aliphatic C-H stretching) was observed. From the reaction yield, the formula (
The number of nitrogen atoms forming crosslinking points in the structure of III) was 5% of the nitrogen atoms in the polyaniline. When this film was doped with a 20% aqueous hydrochloric acid solution for 24 hours and dried, the conductivity was 0.1 S/cm. Furthermore, similar film formation was possible using organic solvents such as N,N-dimethylacetamide, N,N-dimethylformamide, and pyridine instead of N-methyl-2-pyrrolidone.

[0028]

[Effects of the Invention] The polyaniline derivative of the present invention is soluble in various organic solvents, can form a flexible and tough film by casting or casting, and exhibits high electrical conductivity by doping. Therefore, it is very useful for various uses as electronic materials and conductive materials.

Claims (2)

[Claims] Claim 1: A number average molecular weight of 2,000 to 2,000, consisting of a structural unit represented by the following general formula (I):
500,000 reduced polyaniline was converted into the following formula (II
) OCN-X-NCO (II)
[Wherein, X represents a poly(1,2-butadiene) structure represented by the following structural formula. m=10-200] [Formula 2] It is obtained by reacting with a polymer compound having isocyanate groups at both ends, and is represented by the following formula (II
I) It has a crosslinked structure represented by [Formula 3] (wherein, X has the same meaning as above), and the number of nitrogen atoms forming crosslinking points is 0.1% of the nitrogen atoms in polyaniline. A polyaniline derivative characterized in that the polyaniline derivative is present in a range of less than 15%. [Claim 2] The oxidized aniline polymer is treated with ammonia to obtain a soluble aniline polymer, and then treated with excess hydrazine to form a number average of structural units represented by the following formula (I) [Chem. 4] Molecular weight 2,000~
500,000 reduced polyaniline was synthesized, and then the reduced polyaniline was converted into the following formula (II) OCN-X
-NCO (II) [wherein, X
represents a poly(1,2-butadiene) structure shown by the following structural formula. m=10-200] [Formula 5] It is obtained by reacting with a polymer compound having isocyanate groups at both ends, and is represented by the following formula (II
I) has a crosslinked structure represented by [Formula 6] (wherein, X has the same meaning as above), and the number of nitrogen atoms forming crosslinking points is 0.1% of the nitrogen atoms in polyaniline. A method for producing a polyaniline derivative in which the amount is less than 15%.