JPH075734B2 - Method for producing polyaniline derivative - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD 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 for battery electrode materials, antistatic materials,
Application to a wide range of fields such as electromagnetic wave shielding materials, optoelectronic conversion elements, optical memories, functional elements such as various sensors, display elements, various hybrid materials, transparent conductors, various terminal devices, etc. is being studied.

In general, polyaniline has a highly developed π-conjugated system, so that the polymer main chain is rigid, the interaction between the molecular chains is strong, and many strong hydrogen bonds are present between the molecular chains. Since it is present, it is insoluble in most organic solvents, and it does not melt even when heated. Therefore, it has poor moldability and has a major drawback that it cannot be cast or coated. To that end, for example, fibers of polymeric materials,
A substrate having a desired shape such as a porous body is impregnated with an aniline monomer, and the aniline monomer is brought into contact with a suitable polymerization catalyst, or is polymerized by electrolytic oxidation to form a conductive composite material, or, A similar composite material is obtained by polymerizing the aniline monomer in the presence of the thermoplastic polymer powder.

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

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above problems and provide a method for producing a polyaniline derivative soluble in a general-purpose organic solvent without impairing the original properties of polyaniline. I am trying.

[0006]

As a result of intensive studies to solve the above problems, the present inventor has found that the above problems can be solved by sulfenamidating the nitrogen atom of polyaniline. Has been completed.

The present invention relates to a method for producing a polyaniline derivative, which is characterized in that the reduced polyaniline is reacted with a sulfenyl halide represented by the following general formula (I) to give a reduced polyaniline derivative. The purpose is to sulfenamidate the nitrogen atom. RSX (I) (In the formula, R represents a substituted or unsubstituted alkyl group having 2 or more carbon atoms, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted benzyl group,
X represents a bromine atom or a chlorine atom. )

More specifically, polyaniline is treated with ammonia to be converted into soluble polyaniline, and then with excess hydrazine to be converted into reduced polyaniline, which is further dissolved in an amide solvent or an aromatic solvent. Alternatively, after dispersing in an ether solvent, the sulfenyl halide represented by the above general formula (I) is added to the obtained solution or dispersion to react with each other, whereby the nitrogen atom of the reduced polyaniline is sulfenamidated. It is characterized by doing.

The present invention will be described in detail below.
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, a temperature in the range of -20 to 50 ° C using ammonium persulfate or the like as an oxidant. -Methyl-2
-Pyrrolidone solvent), and polyaniline in the range of polystyrene-equivalent number average molecular weight] is used. First, this polyaniline is treated with ammonia to be converted into a soluble polyaniline, and this soluble polyaniline is treated with an excess of hydrazine to produce a reduced polyaniline. In addition,
The reduced polyaniline means a reduced product of the above polyaniline obtained by oxidative polymerization, in which a hydrogen atom is bonded to a nitrogen atom contained in the polyaniline. The treatment of hydrazine is carried out by 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. By doing.

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.

Next, this reduced polyaniline is sulfenamidated. The sulfenamidation is carried out by dissolving reduced polyaniline in an amide-based solvent or dispersing it in an aromatic solvent or an ether-based solvent, and adding the resulting solution or dispersion to the sulfenyl group represented by the general formula (I) It can be carried out by adding a halide and stirring in a temperature range of −10 to 100 ° C. in a nitrogen atmosphere.

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. As the aromatic solvent, benzene, toluene, xylene, ethylbenzene, tetralin or the like can be used. As the ether solvent, ether, tetrahydrofuran, dioxane or the like can be used.

In the present invention, R in the sulfenyl halide represented by the general formula (I) is a substituted or unsubstituted alkyl group having 2 or more carbon atoms, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group or a substituted group. Alternatively, it represents an unsubstituted benzyl group, X represents a bromine atom or a chlorine atom, and R is as follows.

Examples of the substituted or unsubstituted alkyl group having 2 or more carbon atoms include ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, Hexadecyl group, linear alkyl group such as docosyl, isobutyl group, isopentyl group, neopentyl group, branched chain alkyl group such as isohexyl, cyclic alkyl group such as cyclohexyl, and one or more of their hydrogen atoms are halogen atom, cyano Examples thereof include those substituted with a group, a nitro group, an alkoxy group or a hydroxyl group. Examples of the substituted or unsubstituted alkenyl group include butenyl group, pentenyl group, hexenyl group, and those in which one or more hydrogen atoms thereof are substituted with a halogen atom, a cyano group, a nitro group, an alkoxy group or a hydroxyl group. be able to. The substituted or unsubstituted aryl group includes a phenyl group and one in which one or more hydrogen atoms of the phenyl group are substituted with an alkyl group, a phenyl group, a halogen atom, a cyano group, a nitro group, an alkoxy group or a hydroxyl group. I can give you. Further, examples of the substituent in the substituted benzyl group include a halogen atom, a cyano group, a nitro group, an alkoxy group and a hydroxyl group.

Specifically, 1-octane sulphenyl chloride, p-toluene sulphenyl chloride, o-
Examples thereof include nitrophenylsulfenyl chloride.

In the present invention, the sulfenamidation reaction is preferably carried out so that 10% or more of the nitrogen atoms of the reduced polyaniline are sulfenamidated. When the sulfenamidation is less than 10%, sufficient solubility in an organic solvent cannot be obtained.

The N-sulfenamidated polyaniline obtained as described above is desirably subjected to dedoping treatment with aqueous ammonia as a post-treatment.

The N-sulfenamidated polyaniline produced according to the present invention is not only soluble in N-methyl-2-pyrrolidone and N, N-dimethylacetamide, but also halogens such as chloroform, dichloroethane and dichloromethane. A film which is soluble in a modified hydrocarbon solvent and an ether solvent such as tetrahydrofuran, and which is cast in a solution dissolved in these solvents can be used to obtain a good self-supporting film. The formed film exhibits high conductivity of 10 ^-3 to 10 ^-1 S / cm when doped in a protic acid such as hydrochloric acid, sulfuric acid, hydrofluoric acid, or perchloric acid.

[0019]

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 persulfate in water to 100 m
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. The number average molecular weight thus obtained was 12,000 (GP
After sufficiently washing polyaniline having a polystyrene-equivalent number average molecular weight (measured in a C, N-methyl-2-pyrrolidone solvent) with water, dedoping treatment was further performed with aqueous ammonia. 200 m of the soluble polyaniline thus obtained
It was dispersed in 1 l 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 thus obtained
Was completely dissolved in 30 ml of N-methyl-2-pyrrolidone, and after sufficiently substituting with nitrogen, 0.87 g of p-toluenesulfenyl chloride (50 mol% with respect to nitrogen atom of reduced polyaniline) was added and stirred for 6 hours. The reaction was continued. This solution was poured into 1 liter of water with stirring, the precipitate was filtered off, dried and then dedoped with aqueous ammonia to obtain 1.5 g of a polyaniline derivative in which a nitrogen atom was sulfenamidated. From the reaction yield, it was found that the nitrogen atom substitution rate was 37%.

This polyaniline derivative is N-methyl-
It was not only soluble in 2-pyrrolidone but also showed good solubility in organic solvents such as chloroform, dichloroethane, dichloromethane and tetrahydrofuran. Furthermore, from the solution of this polyaniline derivative in chloroform, a self-supporting film could be obtained by cast molding. The conductivity was 0.01 S / cm when doped with sulfuric acid. Further, the film before doping could be dissolved in the organic solvent such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, chloroform, dichloroethane, dichloromethane and tetrahydrofuran described above.

Example 2 The same procedure as in Example 1 except that 1.04 g of o-nitrophenylsulfenyl chloride (50 mol% based on the nitrogen atom of reduced polyaniline) was used instead of p-toluenesulfenyl chloride. 1.7 g of a polyaniline derivative in which the nitrogen atom was sulfenamidated was obtained. From the reaction yield, it was found that the nitrogen atom substitution rate was 47%.

The polyaniline derivative is N-methyl-
It was not only soluble in 2-pyrrolidone but also showed good solubility in organic solvents such as chloroform, dichloroethane, dichloromethane and tetrahydrofuran. Furthermore, from the solution of this polyaniline derivative in chloroform, a self-supporting film could be obtained by cast molding. The conductivity was 0.01 S / cm when doped with sulfuric acid. Further, the film before doping could be dissolved in the organic solvent such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, chloroform, dichloroethane, dichloromethane and tetrahydrofuran described above.

Example 3 In Example 1, instead of p-toluenesulfenyl chloride, 0.99 g of 1-octane sulphenyl chloride (5 g based on the nitrogen atom of reduced polyaniline) was used.
(0 mol%), and 1.4 g of a polyaniline derivative in which a nitrogen atom was sulfenamidated was obtained by the same procedure. From the reaction yield, it was found that the nitrogen atom substitution rate was 25%.

This polyaniline derivative is N-methyl-
It was not only soluble in 2-pyrrolidone but also showed good solubility in organic solvents such as chloroform, dichloroethane, dichloromethane and tetrahydrofuran. Furthermore, from the solution of this polyaniline derivative in chloroform, a self-supporting film could be obtained by cast molding. The conductivity was 0.05 S / cm when doped with sulfuric acid. Further, the film before doping could be dissolved in the organic solvent such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, chloroform, dichloroethane, dichloromethane and tetrahydrofuran described above.

Comparative Example 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 persulfate in water to 100 m
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. The polyaniline thus obtained was thoroughly washed with water, and then dedoped with ammonia water. The polyaniline thus obtained was soluble in N-methyl-2-pyrrolidone and a free-standing film could be obtained from this solution. However, the obtained polyaniline was insoluble in chloroform and tetrahydrofuran, and the obtained self-supporting film was insoluble in any organic solvent.

[0027]

INDUSTRIAL APPLICABILITY According to the present invention, by converting the nitrogen atom of reduced polyaniline to sulfenamidation, the polyaniline is soluble in an organic solvent without impairing the original properties of polyaniline, and is formed into a film or coated. It is possible to produce a polyaniline derivative having excellent processability such as.

Claims (3)

[Claims] 1. A reduced polyaniline having the following general formula (I):
A method for producing a polyaniline derivative, which comprises reacting a sulfenyl halide represented by the formula (3) to sulfenamidate a nitrogen atom of reduced polyaniline. RSX (I) (In the formula, R represents a substituted or unsubstituted alkyl group having 2 or more carbon atoms, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted benzyl group,
X represents a bromine atom or a chlorine atom. ) 2. A polyaniline is treated with ammonia to be converted into a soluble polyaniline, which is then treated with an excess of hydrazine to be converted into a reduced polyaniline, which is further dissolved in an amide solvent or an aromatic solvent or an ether solvent. After being dispersed in a solvent, a sulfanilide represented by the following general formula (I) is added to the obtained solution or dispersion to sulfenamidate the nitrogen atom of the reduced polyaniline to obtain a polyaniline derivative. Manufacturing method. RSX (I) (In the formula, R represents a substituted or unsubstituted alkyl group having 2 or more carbon atoms, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted benzyl group,
X represents a bromine atom or a chlorine atom. ) 3. 10% of nitrogen atoms of reduced polyaniline
The method for producing a polyaniline derivative according to claim 1, wherein the above is sulfenamidated.