JPH0737508B2 - Polyaniline derivative and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a gellable polyaniline derivative and a method for producing the same.

[0002]

2. Description of the Related Art Recently, polyaniline is a new electronic material,
As a conductive material, a wide range of fields such as battery electrode materials, antistatic materials, electromagnetic wave shielding materials, photoelectric conversion elements, optical memories, functional elements such as various sensors, display elements, various hybrid materials, transparent conductors, various terminals, etc. The application to is being studied. However, in general, polyaniline has a π
Since the conjugated system is highly developed, the polymer main chain is rigid and the interactions between the molecular chains are strong, and since many strong hydrogen bonds exist between the molecular chains, it is insoluble in most organic solvents. In addition, since it does not melt even when heated, it has poor moldability and has a major drawback that it cannot be processed into a film.

For that purpose, for example, a base material having a desired shape such as a polymer material fiber or a porous material is impregnated with a monomer,
This monomer is polymerized by contact with a suitable polymerization catalyst or by electrolytic oxidation to form a conductive composite material,
Alternatively, the same composite material was obtained by polymerizing the monomers in the presence of the thermoplastic polymer powder. On the other hand, a polyaniline soluble only in N-methyl-2-pyrrolidone has been synthesized by devising the polymerization catalyst and the reaction temperature (MA.
be et al. J .; Chem. Soc. , Che
m. Commun. , 1989, 1736). But,
This polyaniline was also insoluble in other general-purpose organic solvents and its application range was limited.

On the other hand, many gel-like polymer compounds have been known for a long time, and processing techniques such as gel stretching have been developed for processing fibers and films of polymer compounds. Polyaniline has also been attempted to gel, and for example, a method of forming an intermolecular crosslink by hydrogen bond to form a gel by subjecting the soluble polyaniline to an incomplete reduction treatment with hydrazine is known. (O. Oka et al .; Jpn.
J. Appl. Phys. , 29 (1990) L67
9). However, in that case, it was difficult to control the degree of crosslinking, and there was a problem in workability.

[0005]

SUMMARY OF THE INVENTION The present invention is intended to solve the above problems in the prior art. That is, it is an object of the present invention to provide a processable polyaniline derivative which easily swells and gels with an organic solvent, and a method for producing the same.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventor has found that polyaniline can be gelled with an organic solvent by reacting polyaniline with polybutadiene having an isocyanate group at both ends. The inventors have found that a derivative can be obtained, and completed the present invention.

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

[Chemical 7]

A reduced polyaniline having a number average molecular weight of 2,000 to 500,000 composed of structural units represented by
Formula (II) OCN-X-NCO (II) [In the formula, X represents a poly (1,2-butadiene) structure represented by the following structural formula, and m is an integer of 10 to 200. ]

[Chemical 8] Which is obtained by reacting with a polymer compound having an isocyanate group at both ends, represented by the following formula (III):

[0009]

[Chemical 9] (Wherein X has the same meaning as described above), and the number of nitrogen atoms forming a crosslinking point is present in 15 to 40% of the nitrogen atoms in polyaniline. And

The polyaniline derivative of the present invention is manufactured as follows. That is, aniline is used at a low temperature, for example, -20 to 50 by using ammonium persulfate as an oxidant.
The aniline oxidation polymer obtained by oxidative polymerization at a temperature in the range of ° C is first treated with ammonia to obtain a soluble polyaniline. Then, this is treated with an excess of hydrazine to give a compound having a number average molecular weight of 2,000 represented by the above formula (I).
0-500,000 [measured with GPC (N-methyl-2-pyrrolidone solvent), polystyrene-equivalent number average molecular weight]
A reduced polyaniline of is obtained. The hydrazine treatment involves dispersing soluble polyaniline in water, adding an equivalent amount or more, preferably 3 times or more, of hydrazine to the nitrogen atoms in the polyaniline under a nitrogen atmosphere, and stirring at 0 to 30 ° C. for 24 hours. Can be done by.

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

This reduced polyaniline is mixed with an amide solvent such as N-methyl-2-pyrrolidone or N, N.
-Dissolved in dimethylacetamide, added a polymer compound having an isocyanate group at both ends under a nitrogen atmosphere,
The reaction is performed in the temperature range of -10 to 50 ° C to synthesize the polyaniline derivative of the present invention. As the amide solvent, N
-Methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like can be used.

The polymer compound having an isocyanate group at both ends used in the present invention is represented by the formula (II) OCN-X-NCO (II) [wherein, X is a poly (1,2- Butadiene) structure, and m is an integer of 10 to 200. ]

[Chemical 10] What is represented by is used.

In the polyaniline derivative of the present invention, the number of nitrogen atoms forming the cross-linking points in the cross-linking structure of the above (III) must be in the range of 15-40% of the nitrogen atoms in polyaniline. When the number of nitrogen atoms forming the cross-linking points of the cross-linked structure of (III) is higher than 40%, a gel having a swelling degree that can be processed cannot be obtained. On the other hand, if it is lower than 15%, it will be dissolved and cannot be gelled.

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. Alternatively, gelation is possible with an ether solvent such as tetrahydrofuran, an amine solvent such as pyridine, and a polar solvent such as dimethyl sulfoxide, and a self-supporting film or fiber can be produced from the obtained gel. Further, the processed product such as this film or fiber shows a high conductivity of 10 ⁻³ to 10 S / cm when doped with an acceptor dopant.

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, Examples thereof 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. The method of doping these compounds is not particularly limited, and any known method can be used. Generally, a gel of a derivative of polyaniline or a molded product thereof may be brought into contact with a dopant compound, and it can be performed 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.

[0017]

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 were dissolved in water to prepare 1
Make up to 00 ml and cool to -5 ° C. Concentrated hydrochloric acid 21.9 g,
Dissolve 6.28 g of ammonium granulate in water and add 100 ml.
This solution was also cooled to −10 ° C., and was slowly added dropwise to the aniline solution, and stirring was continued at −10 ° C. for 6 hours. The number average molecular weight thus obtained was 22,000 (G
An aniline-oxidized polymer having a polystyrene-equivalent number average molecular weight (measured in a solvent of PC and N-methyl-2-pyrrolidone) was obtained. After thoroughly washing this with water, dedoping treatment was further performed with aqueous ammonia. The soluble polyaniline thus obtained was dispersed in 200 ml of water, 50 ml of hydrazine was added under a nitrogen atmosphere, the mixture was continuously stirred at room temperature for 24 hours, filtered and dried to obtain an off-white reduced polyaniline.

1 g of the reduced polyaniline (number average molecular weight 22,000) thus obtained was completely dissolved in 30 ml of N-methyl-2-pyrrolidone, and after sufficiently substituting with nitrogen, a polyisocyanate having isocyanate groups at both ends was prepared. (1,2-
Butadiene) 50% by weight butyl acetate solution [TP-10
01, manufactured by Nippon Soda Co., Ltd., molecular weight about 1000 (m = about 18)] 1.65 g was added and the reaction was continued by stirring at room temperature for 4 hours. This solution was poured into 1 liter of water while stirring, the precipitate was filtered and dried to obtain 1.82 g of the polyaniline derivative of the present invention. When the infrared absorption spectrum was measured, it was found to be 165 due to the structure of the above formula (III).
0 cm ^-1 (C = O expansion and contraction), 2850-2950 cm
Absorption of ^-1 (aliphatic C-H stretch) was observed. From the reaction yield, the number of nitrogen atoms forming the cross-linking points in the structure of formula (III) was 15% of the nitrogen atoms in polyaniline.

1 g of the obtained polyaniline derivative was put into 5 g of N-methyl-2-pyrrolidone and stirred at room temperature to gel, which could be formed into a film by spinning or stretching.
The film was very flexible and did not break or break when bent. Furthermore, when this film was dipped in a 20% hydrochloric acid aqueous solution for 24 hours and was then dried, the conductivity was 0.5 S / cm. Further, instead of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, pyridine,
Similar gelation was possible using an organic solvent such as chloroform, dichloroethane, dichloromethane and tetrahydrofuran.

Example 2 A 50% by weight butyl acetate solution of poly (1,2-butadiene) having isocyanate groups at both ends in Example 1 [TP-1001, manufactured by Nippon Soda Co., Ltd., molecular weight about 10].
00 (m = about 18)] 2.20 g was added, and 2.03 g of the polyaniline derivative of the present invention was obtained by the same procedure.
When the infrared absorption spectrum was measured, the above formula (III)
1650 cm ^-1 (C = O expansion and contraction) due to the structure of, 28
Absorption of 50 to 2950 cm ^-1 (aliphatic C-H stretch) was observed. From the reaction yield, the number of nitrogen atoms forming the cross-linking point in the structure of formula (III) is 20% of the nitrogen atoms in polyaniline.
%Met.

1 g of the obtained polyaniline derivative was put in 10 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. The film was very flexible and did not break or break when bent. Further, when this film was dipped in a 20% hydrochloric acid aqueous solution for 24 hours and was doped and dried, the conductivity was 0.05 S / cm. Also, N
-In place of methyl-2-pyrrolidone, N-dimethylacetamide, N, N-dimethylformamide, pyridine, chloroform, dichloroethane, dichloromethane,
Similar gelation was possible using an organic solvent such as tetrahydrofuran.

Example 3 A 50% by weight butyl acetate solution of poly (1,2-butadiene) having isocyanate groups at both ends in Example 1 [TP-1001, manufactured by Nippon Soda Co., Ltd., molecular weight: about 10].
00 (m = about 18)] 4.40 g was added, and the same procedure was followed to obtain 3.13 g of the polyaniline derivative of the present invention.
When the infrared absorption spectrum was measured, the above formula (III)
1650 cm ^-1 (C = O expansion and contraction) due to the structure of, 28
Absorption of 50 to 2950 cm ^-1 (aliphatic C-H stretch) was observed. From the reaction yield, the number of nitrogen atoms forming the cross-linking point in the structure of formula (III) is 40% of the nitrogen atoms in polyaniline.
%Met.

1 g of the obtained polyaniline derivative was put in 10 g of N-methyl-2-pyrrolidone and stirred at room temperature to gel, which could be formed into a film by spinning or stretching. The film was very flexible and did not break or break when bent. Further, when this film was dipped in a 20% hydrochloric acid aqueous solution for 24 hours and doped, and dried, the conductivity was 0.005 S / cm. Also,
Instead of N-methyl-2-pyrrolidone, N-dimethylacetamide, N, N-dimethylformamide, pyridine, chloroform, dichloroethane, dichloromethane,
Similar gelation was possible using an organic solvent such as tetrahydrofuran.

[0024]

INDUSTRIAL APPLICABILITY The polyaniline derivative of the present invention can be gelled with various organic solvents and can be processed by other molding techniques such as gel drawing and spinning. Further, since it exhibits high conductivity by doping, it is very useful for various purposes as an electronic material and a conductive material.

Claims (2)

[Claims] 1. The following formula (I): The number average molecular weight of the structural unit represented by
The reduced polyaniline of 500,000 is represented by the following formula (II) OCN-X-NCO (II) [wherein, X represents a poly (1,2-butadiene) structure represented by the following structural formula, and m represents 10 to 10]. It is an integer of 200. ] [Chemical 2] A compound obtained by reacting with a polymer compound having an isocyanate group at both ends, represented by the following formula (III): (Wherein X has the same meaning as described above), and the number of nitrogen atoms forming a crosslinking point is present in 15 to 40% of the nitrogen atoms in polyaniline. And a polyaniline derivative. 2. The aniline-oxidized polymer is treated with ammonia to give a soluble aniline polymer, and then treated with an excess of hydrazine to obtain a compound represented by the following formula (I): The number average molecular weight of the structural unit represented by
500,000 reduced polyaniline was produced, and the polyaniline was prepared from the following formula (II) OCN-X-NCO (II) [wherein, X represents a poly (1,2-butadiene) structure represented by the following structural formula. , M is an integer of 10 to 200. ] [Chemical 5] Characterized by reacting with a polymer compound having an isocyanate group at both ends, represented by the following formula (III): (Wherein X has the same meaning as described above), and the number of nitrogen atoms forming the cross-linking point is 15 to 40% of the nitrogen atoms in polyaniline. Production method.