JPH04332730A - Production of polyaniline derivative - Google Patents

Abstract

PURPOSE:To obtain a derivative soluble in organic solvent, having excellent processability and useful as electronic material, etc., without deteriorating the characteristic feature of the original polymer by reacting a reduced-type polyaniline with a specific isocyanate compound, etc., thereby introducing carbamoyl group, etc., to nitrogen atom. CONSTITUTION:A polyaniline is treated with ammonia and the obtained soluble polyaniline is converted to a reduced-type polyaniline by treating with excess hydrazine. The reduced-type polyaniline is dissolved in an amide-type solvent or dispersed in an aromatic solvent or an ether solvent. The obtained solution or dispersion is made to react with an isocyanate compound or isothiocyanate compound of formula [R is (substituted) >=2C alkyl, (substituted) alkenyl, (substituted) aryl or (substituted) benzyl; X is O or S] to introduce carbamoyl group or thiocarbamoyl group to the nitrogen atom and obtain the objective derivative.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing polyaniline derivatives soluble in organic solvents.

0002

[Prior Art] In recent years, polyaniline has been used as a new electronic material and conductive material for battery electrode materials, antistatic materials, electromagnetic wave shielding materials, photoelectronic conversion elements, optical memories, functional elements such as various sensors, display elements, and various hybrids. material,
Applications to a wide range of fields such as transparent conductors and various terminal devices are being considered.

By the way, polyaniline generally has a highly developed π-conjugated system, so the main chain of the polymer is rigid, the interactions between the molecular chains are strong, and there are many strong hydrogen bonds between the molecular chains. Because of its presence, it is insoluble in most organic solvents 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, fibers of polymeric materials,
By impregnating a base material of a desired shape such as a porous body with an aniline monomer and bringing this aniline monomer into contact with a suitable polymerization catalyst, or by polymerizing it by electrolytic oxidation, or alternatively, Similar composite materials have been obtained by polymerizing aniline monomers in the presence of thermoplastic polymer powders.

On the other hand, by modifying 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.
Commun. , 1989, 1736). However, this polyaniline is also hardly soluble in other general-purpose organic solvents, and its applicability is limited.

[0005]

[Problems to be Solved by the Invention] The purpose of the present invention is to solve the above problems and provide a method for producing polyaniline derivatives that are soluble in general-purpose organic solvents without impairing the inherent properties of polyaniline. It is said that

[0006]

[Means for Solving the Problems] As a result of intensive studies aimed at solving the above problems, the present inventors discovered that the above problems could be solved by converting the nitrogen atom of polyaniline into carbamoyl or thiocarbamoylate. The invention was completed.

[0007] The present invention relates to a method for producing a polyaniline derivative, and the structural feature thereof is that reduced polyaniline has the following general formula (I) R-NCX (I
) (wherein 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, and X is an oxygen atom or a sulfur atom The purpose of the present invention is to introduce a carbamoyl or thiocarbamoyl group into the nitrogen atom of reduced polyaniline by reacting an isocyanate or isothiocyanate compound represented by the following formula.

More specifically, the present invention involves treating aniline with ammonia to convert it into soluble polyaniline, then treating it with excess hydrazine to convert it into reduced polyaniline, and further dissolving it in an amide solvent. Alternatively, after dispersing in an aromatic solvent or an ether solvent, the resulting solution or dispersion is reacted with an isocyanate or an isothiocyanate compound represented by the above general formula (I) to obtain a reduced polyaniline. It is characterized by introducing a carbamoyl or thiocarbamoyl group into the nitrogen atom.

The present invention will be explained in detail below. In the present invention, the number average molecular weight 2, which is 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,
000 to 500,000 (measured by GCP (N-methyl-2-pyrrolidone solvent), number average molecular weight in terms of polystyrene) is used. First, this polyaniline is treated with ammonia to convert it into soluble polyaniline, and this soluble polyaniline is treated with excess hydrazine to produce reduced polyaniline. Note that the term "reduced polyaniline" refers to a reduced form of the polyaniline obtained by oxidative polymerization, in which a hydrogen atom is bonded to a nitrogen atom contained in polyaniline. In the treatment of hydrazine, soluble polyaniline is dispersed in water, hydrazine is added in an amount equivalent to or more, preferably 3 times or more, to the nitrogen atoms in polyaniline under a nitrogen atmosphere, and the mixture is heated for 24 hours.
This is done by stirring at 30°C.

The resulting 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, this reduced polyaniline is dissolved in an amide solvent or dispersed in an aromatic solvent or an ether solvent, and the isocyanate represented by the general formula (I) is added to the resulting solution or dispersion. Alternatively, an isothiocyanate compound is added and reacted by heating in a nitrogen atmosphere for several hours to two days to convert the nitrogen atom of the reduced polyaniline into carbamoyl or thiocarbamoylate.

[0012] At that time, as the amide solvent, N-methyl-2-pyrrolidone, N,N-dimethylacetamide,
N,N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone, etc. can be used. As the aromatic solvent, benzene, toluene, xylene, ethylbenzene, tetralin, etc. can be used. Further, as the ether solvent, ether, tetrahydrofuran, dioxane, etc. can be used.

In the present invention, R in the isocyanate or isothiocyanate compound represented by the above general formula (I) is a substituted or unsubstituted alkyl group having 2 or more carbon atoms, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted alkenyl group. represents an aryl group, a substituted or unsubstituted benzyl group,
Examples of these include:

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, Straight chain alkyl groups such as hexadecyl group and docosyl, branched chain alkyl groups such as isobutyl group, isopentyl group, neopentyl group, isohexyl, cyclic alkyl groups such as cyclohexyl, and one or more of their hydrogen atoms are halogen atoms, cyano Examples include those substituted with a group, a nitro group, a phenyl group, an alkoxy group, or the like. Substituted or unsubstituted alkenyl groups include butenyl groups, pentenyl groups, hexenyl groups, and those in which one or more of their hydrogen atoms are substituted with a halogen atom, cyano group, nitro group, phenyl group, or alkoxy group, etc. can be given. Substituted or unsubstituted aryl groups include phenyl groups, 1-naphthyl groups, and those in which one or more hydrogen atoms are substituted with an alkyl group, a halogen atom, a cyano group, a nitro group, a phenyl group, an alkoxy group, etc. I can give you what I have. Further, examples of the substituent in the substituted benzyl group include a halogen atom, a cyano group, a nitro group, an alkoxy group, and an ester group.

Preferred examples of these isocyanates or isothiocyanate compounds include the following. n-propyl isocyanate, n-butyl isocyanate, octyl isocyanate, dodecyl isocyanate, p-chlorophenylisocyanate, anisyl isocyanate, n-propyl isothiocyanate, n
-butylisothiocyanate, octylisothiocyanate, dodecylisothiocyanate, p-chlorophenylisothiocyanate, anisylisothiocyanate, and the like.

In the present invention, the carbamoylation or thiocarbamoylation with the isocyanate or isothiocyanate compound is carried out so that carbamoyl or thiocarbamoyl groups are introduced into 10% or more of the nitrogen atoms of the reduced polyaniline. is preferred. When the introduction rate is less than 10%, sufficient solubility in organic solvents cannot be obtained.

The polyaniline derivative obtained by carbamoylation or thiocarbamoylation as described above is preferably dedoped with aqueous ammonia as a post-treatment.

The above-mentioned polyaniline derivative in which a carbamoyl group or thiocarbamoyl group is introduced into the nitrogen atom produced by the present invention is not only soluble in N-methyl-2-pyrrolidone and N,N-dimethylacetamide, but also It is soluble in halogenated hydrocarbon solvents such as chloroform, dichloroethane, and dichloromethane, and ethereal solvents such as tetrahydrofuran, and a film with good self-supporting properties is obtained by cast molding using a solution dissolved in these solvents. be able to. The formed film can also be prepared by doping it in a protic acid such as hydrochloric acid, sulfuric acid, fluoroboric acid, or perchloric acid.
It exhibits a high electrical conductivity of 3 to 10-1 S/cm.

[0019]

[Examples] The present invention will be explained below with reference to Examples. Example 1 Dissolve 4.1 g of aniline and 21.9 g of concentrated hydrochloric acid in water and make 1
00 ml and cooled to -5°C. 21.9g of concentrated hydrochloric acid,
Dissolve 6.28g of ammonium persulfate in water and add 100m
This solution was also cooled to -5°C, slowly added dropwise to the above aniline solution, and stirring was continued at -5°C for 4 hours. The number average molecular weight thus obtained was 12,000 (GP
The polyaniline (measured in C,N-methyl-2-pyrrolidone solvent, number average molecular weight in terms of polystyrene) was thoroughly washed with water, and then dedoped with aqueous ammonia. 200 m of soluble polyaniline thus obtained
1 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 off-white reduced polyaniline.

1 g of the thus obtained reduced polyaniline (number average molecular weight 12,000) was completely dissolved in 30 ml of N-methyl-2-pyrrolidone, the atmosphere was sufficiently replaced with nitrogen, and 0.47 g of n-propylisocyanate ( 60 mol%) based on the nitrogen atoms of reduced polyaniline
Stirring was continued for an hour to allow reaction. This solution was poured into 1 liter of water with stirring, and the precipitate was filtered off. After drying, it was dedoped with aqueous ammonia to obtain 1.2 g of a polyaniline derivative in which nitrogen atoms were carbamoylated. Carbamoylation was confirmed by absorption near 1650 and 3400 cm −1 in the infrared absorption spectrum. The reaction yield revealed that the nitrogen atom substitution rate was 42%.

[0021] This polyaniline derivative has 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, a self-supporting film could be obtained by cast molding from a chloroform solution of this polyaniline derivative. The conductivity was 0.07 S/cm when doped with sulfuric acid. Furthermore, the film before doping could be dissolved in the aforementioned organic solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, chloroform, dichloroethane, dichloromethane, and tetrahydrofuran.

Example 2 The nitrogen atom was carbamoylated in the same manner as in Example 1, using 1.2 g of dodecyl isocyanate (50 mol % based on the nitrogen atom of the reduced polyaniline) instead of n-propylisocyanate. 1.4 g of polyaniline derivative was obtained. Carbamoylation was confirmed by absorption near 1650 and 3400 cm −1 in the infrared absorption spectrum. The reaction yield revealed that the nitrogen atom substitution rate was 33%.

[0023] This polyaniline derivative has 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, a self-supporting film could be obtained by cast molding from a chloroform solution of this polyaniline derivative. The conductivity was 0.02 S/cm when doped with sulfuric acid. Furthermore, the film before doping could be dissolved in the aforementioned organic solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, chloroform, dichloroethane, dichloromethane, and tetrahydrofuran.

Example 3 In Example 1, 0.84 g of p-chlorophenylisocyanate (50 mol % based on the nitrogen atom of the reduced polyaniline) was used in place of n-propylisocyanate, and the nitrogen atom was converted to carbamoyl in the same manner as in Example 1. 1.2 g of the polyaniline derivative obtained was obtained. Carbamoylation was confirmed by absorption near 1650 and 3400 cm −1 in the infrared absorption spectrum. From the reaction yield, the substitution rate of nitrogen atoms is 2
It was found to be 4%.

This polyaniline derivative has 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, a self-supporting film could be obtained by cast molding from a chloroform solution of this polyaniline derivative. The conductivity was 0.09 S/cm when doped with sulfuric acid. Furthermore, the film before doping could be dissolved in the aforementioned organic solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, chloroform, dichloroethane, dichloromethane, and tetrahydrofuran.

Example 4 The nitrogen atom was carbamoylated in the same manner as in Example 1, using 0.82 g of anisyl isocyanate (50 mol % based on the nitrogen atom of the reduced polyaniline) instead of n-propylisocyanate. 1.3 g of the polyaniline derivative obtained was obtained. Carbamoylation was confirmed by absorption near 1650 and 3400 cm −1 in the infrared absorption spectrum. The reaction yield revealed that the nitrogen atom substitution rate was 37%.

This polyaniline derivative has 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, a self-supporting film could be obtained by cast molding from a chloroform solution of this polyaniline derivative. The conductivity was 0.01 S/cm when doped with sulfuric acid. Furthermore, the film before doping could be dissolved in the aforementioned organic solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, chloroform, dichloroethane, dichloromethane, and tetrahydrofuran.

Example 5 In Example 1, 0.55 g of n-propyl isothiocyanate (50 mol % based on the nitrogen atom of the reduced polyaniline) was used in place of n-propyl isocyanate, and the nitrogen atom was removed in the same manner as in Example 1. 1.2 g of a thiocarbamoylated polyaniline derivative was obtained. Thiocarbamoylation was confirmed by absorption near 1250 cm −1 in the infrared absorption spectrum. The reaction yield revealed that the nitrogen atom substitution rate was 36%.

This polyaniline derivative has 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, a self-supporting film could be obtained by cast molding from a chloroform solution of this polyaniline derivative. The conductivity was 0.07 S/cm when doped with sulfuric acid. Furthermore, the film before doping could be dissolved in the aforementioned organic solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, chloroform, dichloroethane, dichloromethane, and tetrahydrofuran.

Example 6 In Example 1, 1.2 g of dodecylisothiocyanate (50 mol % based on the nitrogen atom of the reduced polyaniline) was used instead of n-propyl isocyanate, and the nitrogen atom was converted to thiocarbamoyl using the same procedure. 1.5 g of the polyaniline derivative obtained was obtained. Thiocarbamoylation was confirmed by absorption near 1250 cm −1 in the infrared absorption spectrum. The reaction yield revealed that the nitrogen atom substitution rate was 40%.

This polyaniline derivative has 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, a self-supporting film could be obtained by cast molding from a chloroform solution of this polyaniline derivative. The conductivity was 0.009 S/cm when doped with sulfuric acid. In addition, the film before doping was prepared using the aforementioned N-methyl-2-pyrrolidone, N,N-dimethylacetamide,
It could be dissolved in organic solvents such as chloroform, dichloroethane, dichloromethane, and tetrahydrofuran.

Example 7 In Example 1, 0.93 g of p-chlorophenylisothiocyanate (
50 mol% based on the nitrogen atoms of reduced polyaniline)
Using the same procedure, 1.32 g of a polyaniline derivative in which the nitrogen atom was thiocarbamoylated was obtained. Thiocarbamoylation results in 1250 and 340 in the infrared absorption spectrum.
This was confirmed by absorption near 0 cm-1. The reaction yield revealed that the nitrogen atom substitution rate was 34%.

This polyaniline derivative has 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, a self-supporting film could be obtained by cast molding from a chloroform solution of this polyaniline derivative. The conductivity was 0.01 S/cm when doped with sulfuric acid. Furthermore, the film before doping could be dissolved in the aforementioned organic solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, chloroform, dichloroethane, dichloromethane, and tetrahydrofuran.

Example 8 In Example 1, 0.90 g of anisyl isothiocyanate (50 mol % based on the nitrogen atom of the reduced polyaniline) was used in place of n-propylisocyanate, and the nitrogen atom was converted to carbamoyl in the same manner as in Example 1. 1.1 g of the polyaniline derivative obtained was obtained. Carbamoylation was confirmed by absorption near 1250 cm −1 in the infrared absorption spectrum. The reaction yield revealed that the nitrogen atom substitution rate was 11%.

[0035] This polyaniline derivative has 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, a self-supporting film could be obtained by cast molding from a chloroform solution of this polyaniline derivative. The conductivity was 0.1 S/cm when doped with sulfuric acid. In addition, the film before doping is the N-methyl-
It could be dissolved in organic solvents such as 2-pyrrolidone, N,N-dimethylacetamide, chloroform, dichloroethane, dichloromethane, and tetrahydrofuran.

Comparative Example: Dissolve 4.1 g of aniline and 21.9 g of concentrated hydrochloric acid in water.
00 ml and cooled to -5°C. 21.9g of concentrated hydrochloric acid,
Dissolve 6.28g of ammonium persulfate in water and add 100m
This solution was also cooled to -5°C, slowly added dropwise to the above aniline solution, and stirring was continued at -5°C for 4 hours. After thoroughly washing the polyaniline 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 polyaniline obtained was insoluble in chloroform and tetrahydrofuran, and the free-standing film obtained was insoluble in any organic solvent.

[0037]

According to the present invention, by introducing a carbamoyl or thiocarbamoyl group into the nitrogen atom of reduced polyaniline, polyaniline can be soluble in organic solvents and formed into a film without impairing its original properties. It is possible to produce polyaniline derivatives with excellent processability such as coating and coating.

Claims (3)

[Claims] [Claim 1] The following general formula (I
)R-NCX (
I) (wherein 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, and X is an oxygen atom or a sulfur 1. A method for producing a polyaniline derivative, which comprises introducing a carbamoyl or thiocarbamoyl group into a nitrogen atom by reacting an isocyanate or an isothiocyanate compound represented by (representing an atom). 2. Polyaniline is treated with ammonia to convert it into soluble polyaniline, then treated with excess hydrazine to convert it into reduced polyaniline, and then dissolved in an amide solvent, or an aromatic solvent or an ether-based polyaniline. After dispersing in a solvent, the following general formula (I) R-NCX (I
) (wherein 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, and X is an oxygen atom or a sulfur atom A method for producing a polyaniline derivative, which comprises introducing a carbamoyl or thiocarbamoyl group into the nitrogen atom of the reduced polyaniline by reacting with an isocyanate or isothiocyanate compound represented by [Claim 3] 10 nitrogen atoms of reduced polyaniline
The method for producing a polyaniline derivative according to claim 1 or 2, characterized in that carbamoyl or thiocarbamoyl groups are introduced in an amount of % or more.