JPH04293927A - Production of polyaniline derivative - Google Patents

Abstract

PURPOSE:To obtain the title derivative soluble in a general-purpose organic solvent without detriment to the properties inherent in polyaniline by introducing specified alcoholic substitutents into the nitrogen atoms of a reduced form of polyaniline by reaction with a specified oxirane compound. CONSTITUTION:A polyaniline derivative is produced by introducing alcoholic substituents of formula II (wherein R<1> and R<2> are each H, (substituted)alkyl, (substituted)alkenyl, (substituted)aryl or (substituted)benzyl into the nitrogen atoms of a reduced form of polyaniline by reaction with an oxirane compound of formula I. This derivative is soluble not only in N-methyl-2-pyrrolidone and N,N-dimethylacetamide but also in various solvents such as chloroform, tetrahydrofuran and ethanol, and the resulting solution can cause a good self-supporting film by casting.

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 to solve the above problems, the present inventors have found that the above problems can be solved by introducing a specific substituent having an alcoholic hydroxyl group to the nitrogen atom of polyaniline. We have found a solution to this problem and have completed the present invention.

The present invention relates to a method for producing a polyaniline derivative, and its structural feature is that reduced polyaniline has the following general formula (I) (wherein R1 and R2 may be the same or different). often represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted benzyl group, respectively).
The oxirane compound represented by the formula: -CHR1 CH(OH) is reacted with the nitrogen atom of the reduced polyaniline.
The objective is to introduce a substituent having an alcoholic hydroxyl group represented by R2 (wherein R1 and R2 have the same meanings as above).

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, by dispersing the reduced polyaniline in an aromatic solvent, an ether solvent, or concentrated hydrochloric acid, and then adding and reacting the oxirane compound represented by the above general formula (I) to the obtained solution or dispersion, the nitrogen of the reduced polyaniline can be dissolved. The atom has the formula: -CHR1 CH(
It is characterized by introducing a substituent having an alcoholic hydroxyl group represented by OH)R2.

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,
Polyaniline having a number average molecular weight of 000 to 500,000 [measured by GCP (N-methyl-2-pyrrolidone solvent), calculated as 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, an ether solvent, or concentrated hydrochloric acid, and the resulting solution or dispersion is added with the compound represented by the general formula (I). The oxirane compound is added and reacted by heating under a nitrogen atmosphere for several hours to two days, thereby introducing a substituent having an alcoholic hydroxyl group represented by the formula: -CHR1 CH(OH)R2 into the nitrogen atom.

[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, R1 and R2 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, It represents a substituted or unsubstituted aryl group or a substituted or unsubstituted benzyl group, and examples thereof include the following.

Examples of substituted or unsubstituted alkyl groups 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, docosyl group, etc. Straight chain alkyl groups, isobutyl groups, isopentyl groups, neopentyl groups, branched chain alkyl groups such as isohexyl, cyclic alkyl groups such as cyclohexyl, and one or more of their hydrogen atoms are halogen atoms, cyano groups, nitro groups, Examples include those substituted with an alkoxy group, an ester group, or a hydroxyl group. Substituted or unsubstituted alkenyl groups include butenyl group, pentenyl group,
a hexenyl group, and one or more of their hydrogen atoms,
Examples include those substituted with a halogen atom, a cyano group, a nitro group, an alkoxy group, an ester group, or a hydroxyl group. The substituted or unsubstituted aryl group includes a phenyl group, and one or more hydrogen atoms of the phenyl group substituted with an alkyl group, a phenyl group, a halogen atom, a cyano group, a nitro group, an alkoxy group, an ester group, or a hydroxyl group. I can give 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, an ester group, and a hydroxyl group.

[0015] Preferred oxirane compounds include:
Examples include: Propylene oxide, 1,2
- Dodecylene oxide, styrene oxide, epichlorohydrin, epibromohydrin, glycidyl methacrylate, etc. can be mentioned.

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

It is desirable that the polyaniline obtained in the above manner, in which the alcoholic hydroxyl group is introduced into the nitrogen atom, is subjected to a dedoping treatment with aqueous ammonia as a post-treatment.

The polyaniline produced by the present invention in which the alcoholic hydroxyl group is introduced into the nitrogen atom is:
It is not only soluble in N-methyl-2-pyrrolidone and N,N-dimethylacetamide, but also in chloroform,
It is soluble in halogenated hydrocarbon solvents such as dichloroethane and dichloromethane, ether solvents such as tetrahydrofuran, and alcohol solvents such as methanol, ethanol, and propanol, and can be formed by cast molding using a solution dissolved in these solvents. , a film with good self-supporting properties can be obtained. In addition, the formed film can be obtained by doping it in a protic acid such as hydrochloric acid, sulfuric acid, fluoroboric acid, perchloric acid, etc.
It exhibits a high conductivity of 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
was completely dissolved in 30 ml of N-methyl-2-pyrrolidone, and after the atmosphere was sufficiently replaced with nitrogen, 0.6 ml of propylene oxide was added.
4g (100m for the nitrogen atom of reduced polyaniline)
ol%) was added thereto, and stirring was continued at 80° C. for 12 hours to cause a reaction. This solution was poured into 1 liter of water with stirring, the precipitate was filtered off, and after drying, a polyaniline derivative in which nitrogen atoms were replaced by dedoping treatment with aqueous ammonia was obtained.
I got g. The reaction yield revealed that the nitrogen atom substitution rate was 31%. The presence of alcoholic hydroxyl groups was confirmed by the absorption at 3355 cm −1 in the infrared absorption spectrum.

[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 0.01 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, tetrahydrofuran, and methanol.

Example 2 1 g of reduced polyaniline used in Example 1 was added to 6
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.
Made it react. The precipitate was filtered, dried, and dedoped with aqueous ammonia to obtain 1.4 g of a polyaniline derivative in which nitrogen atoms were substituted. From the reaction yield, the substitution rate of nitrogen atoms is 2
It was found to be 6%. The presence of alcoholic hydroxyl groups was confirmed by the absorption at 3355 cm −1 in the infrared absorption spectrum.

[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 0.01 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, tetrahydrofuran, and methanol.

Example 3 In Example 1, instead of propylene oxide,
Using 1.3 g of styrene oxide (100 mol % with respect to the nitrogen atom of reduced polyaniline), 1.5 g of a polyaniline derivative in which the nitrogen atom was substituted was obtained in the same manner. The reaction yield revealed that the nitrogen atom substitution rate was 38%. The presence of alcoholic hydroxyl groups was confirmed by the absorption at 3355 cm −1 in the infrared absorption spectrum.

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, tetrahydrofuran, and methanol.

Example 4 In Example 1, instead of propylene oxide,
Using 2 g of 1,2-dodecylene oxide (100 mol% with respect to the nitrogen atom of reduced polyaniline), a polyaniline derivative in which the nitrogen atom was substituted using the same procedure was prepared by 1.7
I got g. The reaction yield revealed that the nitrogen atom substitution rate was 34%. The presence of alcoholic hydroxyl groups was confirmed by the absorption at 3355 cm −1 in the infrared absorption spectrum.

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, tetrahydrofuran, and methanol.

Example 5 In Example 2, 1.02 g of epichlorohydrin (100 mol % based on the nitrogen atom of the reduced polyaniline) was used in place of glycidyl methacrylate, and a polyaniline derivative in which the nitrogen atom was substituted was prepared in the same manner as in Example 2. 1.6g
Obtained. The reaction yield revealed that the nitrogen atom substitution rate was 59%. The presence of alcoholic hydroxyl groups was confirmed by the absorption at 3355 cm −1 in the infrared absorption spectrum.

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, tetrahydrofuran, and methanol.

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.

[0031]

According to the present invention, by introducing a substituent having an amino group represented by the formula: -CHR1 CH(NH2)R2 into the nitrogen atom of reduced polyaniline, the original properties of polyaniline are not impaired. It is possible to produce a polyaniline derivative that is soluble in organic solvents and has excellent processability such as film formation and coating.

Claims (3)

[Claims] [Claim 1] The following general formula (I
) (wherein R1 and R2 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, a substituted or unsubstituted benzyl group) ) is reacted with an oxirane compound represented by the formula: -CHR1 CH(OH
) A method for producing a polyaniline derivative, which comprises introducing a substituent having an alcoholic hydroxyl group represented by R2 (wherein R1 and R2 have the same meanings as above). 2. Polyaniline is treated with ammonia to convert it to soluble polyaniline, then treated with excess hydrazine to convert it to reduced polyaniline, and then dissolved in an amide solvent, or aromatic solvent, ether type After dispersing in a solvent or concentrated hydrochloric acid, the resulting solution or dispersion is mixed with the following general formula (I) (wherein R1 and R2 may be the same or different, and each is 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).
By adding and reacting an oxirane compound represented by the formula: -C to the nitrogen atom of the reduced polyaniline.
A method for producing a polyaniline derivative, which comprises introducing a substituent having an alcoholic hydroxyl group represented by HR1 CH(OH)R2 (wherein R1 and R2 have the same meanings as above). [Claim 3] 10 nitrogen atoms of reduced polyaniline
% or more of the formula: -CHR1 CH(OH)R2 (in the formula,
R1 and R2 have the same meanings as above. 3. The method for producing a polyaniline derivative according to claim 1 or 2, characterized in that a substituent having an alcoholic hydroxyl group represented by the following formula is introduced.