JP2932011B2 - Method for producing polyaniline derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a polyaniline derivative soluble in an organic solvent.

[0002]

2. Description of the Related Art In recent years, polyaniline has been used as a new electronic material and conductive material as a battery electrode material, an antistatic material,
Application to a wide range of fields, such as electromagnetic wave shielding materials, photoelectric conversion elements, optical memories, functional elements such as various sensors, display elements, various hybrid materials, transparent conductors, various terminal devices, etc., is being studied.

By the way, polyaniline generally has a highly developed π-conjugated system, so that the main chain of the polymer is rigid, the interaction between molecular chains is strong, and there are many strong hydrogen bonds between molecular chains. Since it is present, it is insoluble in most organic solvents and does not melt even by heating, so it has poor moldability and has a major drawback that it cannot be cast or coated. For this purpose, for example, fibers of a polymer material,
An aniline monomer is impregnated into a substrate having a desired shape such as a porous body, and the aniline monomer is brought into contact with an appropriate polymerization catalyst, or is polymerized by electrolytic oxidation to form a conductive composite material, or An aniline monomer is polymerized in the presence of a thermoplastic polymer powder to obtain a similar composite material.

On the other hand, by devising the polymerization catalyst and the reaction temperature,
Polyaniline soluble only in N-methyl-2-pyrrolidone has also been synthesized (M. Abe et al .: J. Am.
Chem. Soc. Chem. Commu
n. , 1989, 1736). However, this polyaniline is hardly soluble in other general-purpose organic solvents, and its application range is limited.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to provide a method for producing a polyaniline derivative soluble in a general-purpose organic solvent without impairing the inherent properties of polyaniline. And

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that the introduction of a specific substituent having an alcoholic hydroxyl group into the nitrogen atom of polyaniline solves the above problems. The inventors have found that the present invention can be solved, and have completed the present invention.

[0007] The present invention relates to a method for producing a polyaniline derivative, characterized on that structure, aniline
Is treated with ammonia to convert to soluble polyaniline,
Next, the treated polyaniline is treated with excess hydrazine
And then dissolved in amide solvents or aromatic
After dispersing in solvent, ether solvent or concentrated hydrochloric acid,
In the solution or dispersion obtained, the following general formula (I)

Embedded image (Wherein, R ¹ and R ² may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group,
Represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted benzyl group. ) In shows
By adding the oxirane compound
And the nitrogen atom of the reduced polyaniline has the formula: —CH
It is to introduce a substituent having an alcoholic hydroxyl group represented by R ¹ CH (OH) R ² (wherein R ¹ and R ² have the same meanings as described above).

[0008]

Hereinafter, the present invention will be described in detail.
In the present invention, a number average molecular weight of 2,000 to 500,000 [ GPC (NPC) obtained by oxidative polymerization of aniline at a low temperature, for example, at a temperature in the range of −20 to 50 ° C. using ammonium persulfate or the like as an oxidizing agent. -Methyl-2
-Pyrrolidone solvent), and polyaniline having a number average molecular weight in terms of polystyrene] is used. First, the polyaniline is treated with ammonia to convert it into a soluble polyaniline, and the soluble polyaniline is treated with an excess of hydrazine to produce a reduced polyaniline. The reduced polyaniline is a reduced form of the above polyaniline obtained by oxidative polymerization, and means a hydrogen atom bonded to a nitrogen atom contained in the polyaniline. In the treatment of hydrazine, a soluble polyaniline is dispersed in water, and hydrazine equivalent to or more than three times the nitrogen atom in the polyaniline is added under a nitrogen atmosphere, and the mixture is stirred at 0 to 30 ° C. for 24 hours. It is done by doing.

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.

Next, the reduced polyaniline is dissolved in an amide solvent or dispersed in an aromatic solvent, an ether solvent or concentrated hydrochloric acid, and the resulting solution or dispersion is represented by the above general formula (I). The oxirane compound is added, and the mixture is heated and reacted under a nitrogen atmosphere for several hours to 2 days to introduce a substituent having an alcoholic hydroxyl group represented by the formula: —CHR ¹ CH (OH) R ² into a nitrogen atom.

At this time, the amide solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide,
N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like can be used. As the aromatic solvent, benzene, toluene, xylene, ethylbenzene, tetralin and the like can be used. Further, as the ether-based solvent, ether, tetrahydrofuran, dioxane, and the like can be used.

In the present invention, R ¹ and R ² in the oxirane compound represented by the above general formula (I) may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl. Group,
A substituted or unsubstituted aryl group or a substituted or unsubstituted benzyl group is represented by the following.

Examples of the substituted or unsubstituted alkyl group include ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, hexadecyl, docosyl and the like. A linear alkyl group, an isobutyl group, an isopentyl group, a neopentyl group, a branched chain alkyl group such as isohexyl, a cyclic alkyl group such as cyclohexyl, and one or more of those hydrogen atoms are a halogen atom, a cyano group, a nitro group, Examples include those substituted by an alkoxy group, an ester group, or a hydroxyl group. As a substituted or unsubstituted alkenyl group, a butenyl group, a pentenyl group, a hexenyl group, and one or more of those hydrogen atoms are substituted with a halogen atom, a cyano group, a nitro group, an alkoxy group, an ester group, or a hydroxyl group. You can give things. As the substituted or unsubstituted aryl group, a phenyl group and one or more hydrogen atoms of the phenyl group are an alkyl group, a phenyl group, a halogen atom,
Examples include those substituted by a cyano group, a nitro group, an alkoxy group, an ester group or a hydroxyl group. Examples of the substituent in the substituted benzyl group include a halogen atom, a cyano group, a nitro group, an alkoxy group, an ester group and a hydroxyl group.

Preferred oxirane compounds include:
The following can be exemplified. Propylene oxide, 1,2
-Dodecylene oxide, styrene oxide, epichlorohydrin, epibromohydrin, glycidyl methacrylate and the like.

In the present invention, the substituent having an alcoholic hydroxyl group is one of the nitrogen atoms of reduced polyaniline.
It is preferable to carry out the reaction so as to be introduced at 0% or more. If the introduction ratio is less than 10%, sufficient solubility in an organic solvent cannot be obtained.

The polyaniline obtained by introducing the alcoholic hydroxyl group into the nitrogen atom obtained as described above is desirably subjected to dedoping treatment with aqueous ammonia as a post-treatment.

The polyaniline produced by the present invention, wherein the alcoholic hydroxyl group is introduced into the nitrogen atom,
Chloroform, as well as soluble in N-methyl-2-pyrrolidone and N, N-dimethylacetamide
Dichloroethane, it is soluble in halogenated hydrocarbon solvents such as dichloromethane, ether solvents such as tetrahydrofuran, and alcohol solvents such as methanol, ethanol, and propanol, and is cast using a solution dissolved in these solvents. A good self-supporting film can be obtained. Further, the formed film is doped in a protonic acid such as hydrochloric acid, sulfuric acid, borofluoric acid, perchloric acid, etc., so that 10 ⁻³ to 10 ⁻¹ S /
cm.

[0019]

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 obtain 1
Make up to 00 ml and cool to -5 ° C. Concentrated hydrochloric acid 21.9 g,
Dissolve 6.28 g of ammonium persulfate in water and add 100 m
The solution was also cooled to -5 ° C and slowly added dropwise to the aniline solution, and stirring was continued at -5 ° C for 4 hours. The thus obtained number average molecular weight of 12,000 (GP
Polyaniline (measured in a C, N-methyl-2-pyrrolidone solvent, number average molecular weight in terms of polystyrene) was sufficiently washed with water, and further dedoped with ammonia water. The soluble polyaniline obtained in this way is 200 m
1 ml 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 an off-white reduced polyaniline.

1 g of the reduced polyaniline thus obtained
Was completely dissolved in 30 ml of N-methyl-2-pyrrolidone, and sufficiently purged with nitrogen.
64 g (100 per nitrogen atom of reduced polyaniline)
mol%), stirring was continued at 80 ° C. for 12 hours to cause a reaction. This solution was poured into 1 liter of water while stirring, and the precipitate was separated by filtration, dried and dedoped with ammonia water to replace the nitrogen atom-substituted polyaniline derivative.
2 g were obtained. From the reaction yield, it was found that the substitution rate of nitrogen atoms was 31%. The presence of the alcoholic hydroxyl group was confirmed by the absorption at 3355 cm ^{-1 in} the infrared absorption spectrum.

This polyaniline derivative is N-methyl-
In addition to being soluble in 2-pyrrolidone, it showed good solubility in organic solvents such as chloroform, dichloroethane, dichloromethane, and tetrahydrofuran. Further, from a chloroform solution of this polyaniline derivative, a free-standing film could be obtained by casting. The conductivity was 0.01 S / cm when sulfuric acid was doped. The film before doping could be dissolved in the above-mentioned organic solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, chloroform, dichloroethane, dichloromethane, tetrahydrofuran, and methanol.

Example 2 1 g of the reduced polyaniline used in Example 1 was
Dispersed in 30 ml of N hydrochloric acid, 1.56 g of glycidyl methacrylate was added thereto, and stirring was continued at 80 ° C. for 12 hours.
Reacted. The precipitate was separated by filtration, dried, and dedoped with ammonia water to obtain 1.4 g of a polyaniline derivative substituted with a nitrogen atom. From the reaction yield, the nitrogen atom substitution rate was 2
It turned out to be 6%. The presence of the alcoholic hydroxyl group was confirmed by the absorption at 3355 cm ^{-1 in} the infrared absorption spectrum.

This polyaniline derivative is N-methyl-
In addition to being soluble in 2-pyrrolidone, it showed good solubility in organic solvents such as chloroform, dichloroethane, dichloromethane, and tetrahydrofuran. Further, from a chloroform solution of this polyaniline derivative, a free-standing film could be obtained by casting. The conductivity was 0.01 S / cm when sulfuric acid was doped. The film before doping could be dissolved in the above-mentioned organic solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, chloroform, dichloroethane, dichloromethane, tetrahydrofuran, and methanol.

Example 3 In Example 1, instead of propylene oxide,
Using 1.3 g of styrene oxide (100 mol% based on the nitrogen atom of the reduced polyaniline), 1.5 g of a polyaniline derivative having a nitrogen atom substituted was obtained in the same procedure. From the reaction yield, it was found that the substitution rate of nitrogen atoms was 38%. The presence of the alcoholic hydroxyl group was confirmed by the absorption at 3355 cm ^{-1 in} the infrared absorption spectrum.

This polyaniline derivative is N-methyl-
In addition to being soluble in 2-pyrrolidone, it showed good solubility in organic solvents such as chloroform, dichloroethane, dichloromethane, and tetrahydrofuran. Further, from a chloroform solution of this polyaniline derivative, a free-standing film could be obtained by casting. The conductivity was 0.01 S / cm when sulfuric acid was doped. The film before doping could be dissolved in the above-mentioned organic solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, chloroform, dichloroethane, dichloromethane, tetrahydrofuran, and methanol.

Example 4 In Example 1, instead of propylene oxide,
Using 2 g of 1,2-dodecylene oxide (100 mol% based on the nitrogen atom of reduced polyaniline), a polyaniline derivative having a nitrogen atom substituted in the same procedure as 1.7 was obtained.
g was obtained. From the reaction yield, it was found that the substitution rate of nitrogen atoms was 34%. The presence of the alcoholic hydroxyl group was confirmed by the absorption at 3355 cm ^{-1 in} the infrared absorption spectrum.

This polyaniline derivative is N-methyl-
In addition to being soluble in 2-pyrrolidone, it showed good solubility in organic solvents such as chloroform, dichloroethane, dichloromethane, and tetrahydrofuran. Further, from a chloroform solution of this polyaniline derivative, a free-standing film could be obtained by casting. The conductivity was 0.01 S / cm when sulfuric acid was doped. The film before doping could be dissolved in the above-mentioned organic solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, chloroform, dichloroethane, dichloromethane, tetrahydrofuran, and methanol.

Example 5 In Example 2, instead of glycidyl methacrylate, 1.02 g of epichlorohydrin (100 mol% based on the nitrogen atom of reduced polyaniline) was used, and a polyaniline derivative having a nitrogen atom substituted by the same procedure was used. 1.6
g was obtained. From the reaction yield, it was found that the substitution rate of nitrogen atoms was 59%. The presence of the alcoholic hydroxyl group was confirmed by the absorption at 3355 cm ^{-1 in} the infrared absorption spectrum.

This polyaniline derivative is N-methyl-
In addition to being soluble in 2-pyrrolidone, it showed good solubility in organic solvents such as chloroform, dichloroethane, dichloromethane, and tetrahydrofuran. Further, from a chloroform solution of this polyaniline derivative, a free-standing film could be obtained by casting. The conductivity was 0.01 S / cm when sulfuric acid was doped. The film before doping could be dissolved in the above-mentioned organic solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, chloroform, dichloroethane, dichloromethane, tetrahydrofuran, and methanol.

Comparative Example 4.1 g of aniline and 21.9 g of concentrated hydrochloric acid were dissolved in water to obtain 1
Make up to 00 ml and cool to -5 ° C. Concentrated hydrochloric acid 21.9 g,
Dissolve 6.28 g of ammonium persulfate in water and add 100 m
The solution was also cooled to -5 ° C and slowly added dropwise to the aniline solution, and stirring was continued at -5 ° C for 4 hours. The polyaniline thus obtained was sufficiently washed with water, and then dedoped with ammonia water. The polyaniline thus obtained was soluble in N-methyl-2-pyrrolidone, and a self-supporting film could be obtained from this solution. However, the resulting polyaniline was insoluble in chloroform and tetrahydrofuran, and the resulting free-standing film was insoluble in any organic solvent.

[0031]

According to the present invention, by introducing a substituent having an amino group represented by the formula: -CHR ¹ CH (NH ₂ ) R ² into a nitrogen atom of reduced polyaniline, the original characteristics of polyaniline can be improved. A polyaniline derivative which is soluble in an organic solvent and excellent in processability such as film formation and coating can be produced without impairment.

Claims (2)

(57) [Claims] 1. Polyaniline is converted to a soluble polyaniline by treating it with ammonia, and then converted to a reduced polyaniline by treating it with an excess of hydrazine. The polyaniline is further dissolved in an amide solvent, or is dissolved in an aromatic solvent or an ether solvent. After dispersing in a solvent or concentrated hydrochloric acid, the resulting solution or dispersion is added to the following general formula (I): (Wherein, R ¹ and R ² may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group,
Represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted benzyl group. ) To react with the oxirane compound represented by the formula: -CH
A method for producing a polyaniline derivative, comprising introducing a substituent having an alcoholic hydroxyl group represented by R ¹ CH (OH) R ² (wherein R ¹ and R ² have the same meanings as described above). . 2. 10% of nitrogen atoms of reduced polyaniline
As described above, the formula: —CHR ¹ CH (OH) R ² (wherein R ¹ and R ² are
It has the same meaning as above. Claim 1, characterized by introducing a substituent having an alcoholic hydroxyl group represented by)
Method for producing a serial mounting of polyaniline derivatives.