JPH075733B2 - 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 application 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 inventors have found that the above problems can be solved by sulfonamidating the nitrogen atom of polyaniline, and the present invention It came to completion.

The present invention relates to a method for producing a polyaniline derivative, which is characterized in that the reduced polyaniline is reacted with a sulfonyl halide represented by the following general formula (I) to give a nitrogen atom of the reduced polyaniline. Sulfonamidating an atom. RSO ₂ X (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,
Further, it is dissolved in an amide solvent or dispersed in an aromatic solvent or an ether solvent, and then the sulfonyl halide represented by the general formula (I) is added to the obtained solution or dispersion to give the reduced polyaniline. It is characterized by sulfonamidating a nitrogen atom.

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), polystyrene-equivalent number average molecular weight] is used. First, this polyaniline is treated with ammonia to be converted into soluble polyaniline, and this soluble polyaniline is treated with excess hydrazine to produce reduced polyaniline. 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 with hydrazine involves dispersing a soluble polyaniline in water, and equivalent amount or more, preferably 3 or more, with respect to the nitrogen atom in the polyaniline.
Add more than twice the amount of hydrazine under a nitrogen atmosphere and leave for 24 hours
It is performed by stirring at -30 ° C.

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. Then, the reduced polyaniline is sulfonamided. In the sulfonamidation, reduced polyaniline is dissolved in an amide solvent or dispersed in an aromatic solvent or an ether solvent, and the obtained solution or dispersion is charged with the sulfonyl halide represented by the general formula (I). In addition, it can be performed by stirring in a temperature range of −10 to 100 ° C. under 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 sulfonyl 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, a substituted or unsubstituted It represents an unsubstituted benzyl group, X represents a bromine atom or a chlorine atom, and examples of R include the following. 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, A linear alkyl group such as docosyl, 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 at least one of hydrogen atoms thereof is a halogen atom, a cyano group, a nitro group. Examples thereof include those substituted with a 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.

Preferred specific examples include 1-butanesulfonyl chloride, 1-octanesulfonyl chloride, p-toluenesulfonyl chloride, benzylsulfonyl chloride, benzenesulfonyl chloride and the like.

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

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

The N-sulfonamidated polyaniline produced according to the present invention is not only soluble in N-methyl-2-pyrrolidone and N, N-dimethylacetamide but also halogenated with chloroform, dichloroethane, dichloromethane or the like. A film which is soluble in a hydrocarbon solvent and an ether solvent such as tetrahydrofuran and which is dissolved in these solvents can be cast to obtain a good self-supporting film. Further, 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. .

[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 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, 1 g of p-toluenesulfonyl chloride (50 mol% relative to the nitrogen atom of reduced polyaniline) was added, and stirring was continued for 6 hours, It was made to react. Pour this solution into 1 liter of water while stirring,
The precipitate was separated by filtration, dried, and then dedoped with aqueous ammonia to obtain 1.5 g of a polyaniline derivative having a sulfonamidated nitrogen atom. Sulfonamidation was confirmed by absorption at 1350 and 1160 cm ⁻¹ in the infrared absorption spectrum. From the reaction yield, it was found that the nitrogen atom substitution rate was 29%. This polyaniline derivative was not only soluble in N-methyl-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. In addition, the film before doping is the above-mentioned N-
Methyl-2-pyrrolidone, N, N-dimethylacetamide, chloroform, dichloroethane, dichloromethane,
It could be dissolved in an organic solvent such as tetrahydrofuran.

Example 2 In Example 1, 1.1 g of 1-butanesulfonyl chloride was used instead of p-toluenesulfonyl chloride.
(50 mol with respect to the nitrogen atom of reduced polyaniline
%) To obtain 1.4 g of a polyaniline derivative having a sulfonamidated nitrogen atom in the same procedure. Sulfonamidation is characterized by infrared absorption spectra of 1350 and 1
It was confirmed by absorption at 160 cm ^-1 . From the reaction yield, it was found that the nitrogen atom substitution rate was 30%.

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 0.05 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.

Example 3 In Example 1, 1-octanesulfonyl chloride 1.2 was used instead of p-toluenesulfonyl chloride.
g (50 mol relative to the nitrogen atom of reduced polyaniline
%), And 1.6 g of a polyaniline derivative in which a nitrogen atom was sulfonamidated was obtained by the same procedure. Sulfonamidation is characterized by infrared absorption spectra of 1350 and 1
It was confirmed by absorption at 160 cm ^-1 . From the reaction yield, it was found that the nitrogen atom substitution rate was 30%.

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.

Example 4 In Example 1, 1 g of benzylsulfonyl chloride (50 mol% based on the nitrogen atom of reduced polyaniline) was used in place of p-toluenesulfonyl chloride, and the nitrogen atom was subjected to sulfonamidation by the same procedure. 1.3 g of the obtained polyaniline derivative was obtained. Sulfonamidation
1350 and 1160c in the infrared absorption spectrum
It was confirmed by absorption of m ^-1 . From the reaction yield, it was found that the substitution rate of nitrogen atoms was 18%.

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 0.05 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, this polyaniline is insoluble in chloroform and tetrahydrofuran, and
The free-standing film obtained was insoluble in any organic solvent.

[0026]

INDUSTRIAL APPLICABILITY According to the present invention, by converting the nitrogen atom of reduced polyaniline to sulfonamidation , 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.

Claims (3)

[Claims] 1. A reduced polyaniline having the following general formula (I):
A method for producing a polyaniline derivative, characterized in that the nitrogen atom of reduced polyaniline is sulfonamided by reacting with a sulfonyl halide represented by RSO ₂ X (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 sulfonyl halide represented by the following general formula (I) is added to the obtained solution or dispersion to sulfonamidate the nitrogen atom of the reduced polyaniline to obtain a polyaniline derivative. Production method. RSO ₂ X (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 above-mentioned is subjected to sulfonamide formation.
Or the method for producing the polyaniline derivative according to the item 2.