JPH0413722A - Production of polyaniline derivative - Google Patents

Abstract

PURPOSE:To obtain the title derivative soluble in an organic solvent and having excellent processabilities such as formation of film and coating without impairing original characteristics of polyaniline by adding an acyl halide to a polyaniline solution and reacting the acyl halide with the solution. CONSTITUTION:A polyaniline is preferably treated with ammonia to give a soluble polyaniline, which is then treated with excess hydrazine to prepare a reducing type polyaniline. Then the reducing type polyaniline is dissolved in N-methyl-2-pyrrolidone or N,Ndimethylacetamide to afford a polyaniline solution. An acyl halide is dropwise added to the solution and reacted with the solution to provide the aimed derivative amidated in N position of the above-mentioned reducing type polyaniline.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for producing polyaniline derivatives soluble in organic solvents.

<Prior art> In recent years, polyaniline has been used as a new electronic material and conductive material, as a battery electrode material, antistatic material, electromagnetic shielding material, photoelectric conversion element, optical memory, functional elements such as various sensors,
Applications to a wide range of fields such as display elements, various hybrid materials (transparent conductors), and various terminal devices are being considered.

However, in general, polyaniline has a highly developed π-conjugated system, the polymer chains are rigid, the interactions between the molecular chains are strong, and there are many strong hydrogen bonds between the molecular chains. It is insoluble in any organic solvent and does not melt even when heated, so it has poor moldability and has the major drawback of not being able to be cast or coated.

For this purpose, for example, a base material of a desired shape such as a polymer fiber or a porous body is impregnated with a monomer, and this monomer is polymerized by contact with an appropriate polymerization catalyst or by electrolytic oxidation to form a conductive composite material. Alternatively, similar composite materials have been obtained by polymerizing monomers in the presence of thermoplastic polymerization powders.

In contrast, recent advances in polymerization catalysts and reaction temperatures have led to N-
A polyaniline soluble only in methyl-2-pyrrolidone has been synthesized (M, Abe et al.: J.

Chew, Soc, +Ches, Com*un, +
1989.1736) @ However, this polyaniline was also hardly soluble in other general-purpose organic solvents, and its applicability was limited.

<Problems to be Solved by the Invention> The present invention aims to solve the above-mentioned problems and provide polyaniline that is soluble in general-purpose solvents without impairing the inherent properties of polyaniline.

<Means for solving the problem> As a result of intensive studies to solve the above problem, the inventor has found that
We have discovered a method for producing polyaniline derivatives, which is characterized by dropping an acyl halide into a polyaniline solution and reacting it to amidate the N-position of the polyaniline, and have completed the present invention.

That is, the method for producing a polyaniline derivative of the present invention is as follows:
Polyaniline obtained by oxidative polymerization of aniline at low temperature using ammonium persulfate or the like as an oxidizing agent is treated with ammonia to obtain soluble polyaniline, and then treated with excess hydrazine to obtain reduced polyaniline. . The thus obtained reduced polyaniline is soluble in N-methyl-2-pyrrolidone or N,N-dimethylacetamide, but is almost insoluble in other organic solvents such as chloroform and tetrahydrofuran. This reduced polyaniline is converted into N-methyl-2-pyrrolidone or N,N
- The polyaniline derivative having an amidated N position of the present invention is synthesized by dissolving it in dimethylacetamide and reacting it by dropping an acyl halide under a nitrogen atmosphere.

The acyl halide used in the present invention has the formula: RCO
It is represented by It may be any alkyl group, such as one with a branched structure such as isopentyl, neopentyl, and isohexyl, or a cyclic group such as cyclohexyl, or an alkenyl group such as butenyl, pentenyl, or hexenyl, and one or more of these hydrogens is a halogen. It may be substituted with an atom, a cyano group, a nitro group, a phenyl group, an alkoxy group, a hydroxyl group, or the like.

The N-amidated polyaniline derivative of the present invention obtained as described above is preferably dedoped with aqueous ammonia in order to remove impurities as a post-treatment.

The polyaniline derivatives of the present invention are not only soluble in N-methyl-2-pyrrolidone or N,N-dimethylacetamide, but also soluble in chloroform, dichloroethane, dichloromethane, etc., and ethers such as tetrahydrofuran. It is soluble in various solvents, and films with good self-supporting properties can be obtained by casting from these solutions. Further, these films exhibit a high electrical conductivity of 10-3 to 10-'S/(2) when doped with protic acids such as hydrochloric acid, sulfuric acid, fluoroboric acid, and perchloric acid.

In addition, in the polyaniline derivative of the present invention, it is necessary that 10% or more of the nitrogen atoms contained in the reduced polyaniline be amidated; if less than 10% is amidated, the polyaniline derivative of the present invention will not dissolve in an organic solvent. Unable to fully achieve goals.

<Example> The present invention will be explained below with reference to Examples.

Example 1 Aniline 4.1g, t! Dissolve 21.9 g of hydrochloric acid in water to make 100 ml, and cool to -5°C. Concentrated hydrochloric acid 21.9
g, 6.2 FKg of ammonium persulfate was dissolved in water to make 10 QmIt, and this solution was also cooled to -5°C.
It was slowly added dropwise to the previous aniline solution, and stirring was continued at =5°C for 4 hours. After thoroughly washing the aniline polymer thus obtained with water, it was further subjected to dedoping treatment with aqueous ammonia.

1 g of the polyaniline thus obtained was completely dissolved in 20 ml of N-methyl-2-pyrrolidone, the atmosphere was sufficiently purged with nitrogen, and 0.5 g of octanoyl chloride was added.
After stirring for a while, the reaction was allowed to proceed. This solution was added to water in Step 11 with stirring, the precipitate was filtered off, dried, and dedoped with aqueous ammonia to obtain 1 g of the polymer of the present invention in which the N-position was amidated. This polymer was not only soluble in N-methyl-2-pyrrolidone, but also showed good solubility in organic solvents such as chloroform, dichloroethane, dichloromethane, and tetrahydrofuran. Further, when a self-supporting film obtained by casting from a chloroform solution of this polymer of the present invention is doped with sulfuric acid, the conductivity is 0.
It was 1 s/cIl. In addition, the above-mentioned cast film before doping was prepared using the aforementioned N-methyl-2-pyrrolidone, N,N-dimethylacetamide, chloroform,
It could be dissolved in organic solvents such as dichloroethane, dichloromethane, and tetrahydrofuran.

Example 2 In place of octanoyl chloride in Example 1, 1
- Using 0.2 g of hexenoyl bromide, a polymer of the present invention was obtained in which the N-position was amidated using the same procedure. This polymer is not only soluble in N-methyl-2-pyrrolidone, but also chloroform, dichloroethane, dichloromethane,
It showed good solubility in organic solvents such as tetrahydrofuran.

Furthermore, when a self-supporting film obtained by casting from a chloroform solution of this polymer was doped with sulfuric acid, the conductivity was 0.05 S/cm.

In addition, the cast film before doping is N
-Methyl-2-pyrrolidone, N+N-cy/tylacetamide, chloroform, dichloroethane, dichloromethane, tetrahydrofuran, and other lsl solvents.

Example 3 A polymer of the present invention in which the N-position was amidated was obtained in the same manner as in Example 1 using 0.2 g of methyl-n-amylacetyl chloride instead of octanoyl chloride. This polymer was not only soluble in N-methyl-2-pyrrolidone, but also showed good solubility in @containing solvents such as chloroform, dichloroethane, dichloromethane, and tetrahydrofuran. Furthermore, when a self-supporting film obtained by casting from a chloroform solution of this polymer of the present invention is doped with sulfuric acid, the conductivity is 0.03 S/(2).
Met. In addition, the above-mentioned cast film before doping includes the aforementioned N-methyl-2-pyrrolidone, N,N-dimethylacetamide, chloroform, dichloroethane,
It can be dissolved in organic solvents such as dichloromethane and tetrahydrofuran.

Comparative Example: Dissolve 4.1 g of aniline and 21.9 g of concentrated hydrochloric acid in water.
00 mA' and cooled to -5°C. Concentrated hydrochloric acid 21.9g
, dissolve 6.28 g of ammonium persulfate in water and add 100 g of ammonium persulfate.
mj! After closing, this solution was also cooled to -5°C, slowly added dropwise to the aniline solution prepared above, and stirring was continued at -5°C for 4 hours. After thoroughly washing the aniline polymer thus obtained with water, it was further subjected to dedoping treatment with aqueous ammonia.

The polyaniline thus obtained was soluble in N-methyl-2-pyrrolidone, and a self-supporting film could be obtained from this solution. However, the obtained polyaniline was insoluble in chloroform and tetrahydrofuran, and the free-standing film obtained from the above N-methyl-2-pyrrolidone solution was insoluble in any organic solvent.

<Effects of the invention> The present invention provides the following effects by amidating the N-position of polyaniline.
It is a manufacturing method that can obtain polyaniline derivatives that are soluble in organic solvents and have excellent processability such as film formation and coating without impairing the original properties of polyaniline.
Very useful.

Claims (4)

[Claims] (1) A method for producing a polyaniline derivative, which comprises dropping an acyl halide into a polyaniline solution and reacting it to amidate the N-position of the polyaniline. (2) After treating polyaniline with ammonia to obtain soluble polyaniline, this is treated with excess hydrazine to create reduced polyaniline, and then the reduced polyaniline is converted into N-methyl-2- Pyrrolidone or N,N
- A method for producing a polyaniline derivative, which comprises dissolving it in dimethylacetamide to obtain a polyaniline solution, dropping an acyl halide into the polyaniline solution to cause a reaction, and amidating the N-position of the reduced polyaniline. (3) The acyl halide has 5 carbon atoms as an acyl group.
3. The method for producing a polyaniline derivative according to claim 1 or claim 2, wherein the method comprises the above-described method and contains chlorine or bromine as the halide. (4) One of the nitrogen atoms contained in the reduced polyaniline
3. The method for producing a polyaniline derivative according to claim 1, wherein 0% or more of the polyaniline derivative is amidated.