JPH07116292B2 - Polyaniline derivative and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a gellable polyaniline derivative and a method for producing the same.

[0002]

2. Description of the Related Art Recently, polyaniline is a new electronic material,
Wide range of conductive materials such as battery electrode materials, antistatic materials, electromagnetic shielding materials, photoelectric conversion elements, optical memories, functional elements such as various sensors, display elements, various hybrid materials, transparent conductors, various terminal devices, etc. The application to is being studied.

However, in general, polyaniline has a π
Since the conjugated system is highly developed, the polymer main chain is rigid and the interactions between the molecular chains are strong, and since many strong hydrogen bonds exist between the molecular chains, it is insoluble in most organic solvents. In addition, since it does not melt even when heated, it has poor moldability and has a major drawback that it cannot be processed into a film.

For that purpose, for example, a base material having a desired shape such as a polymer material fiber or a porous material is impregnated with a monomer,
This monomer is polymerized by contact with an appropriate polymerization catalyst or by electrolytic oxidation to form a conductive composite material,
Alternatively, the same composite material was obtained by polymerizing the monomers in the presence of the thermoplastic polymer powder.

On the other hand, polyaniline soluble only in N-methyl-2-pyrrolidone has been synthesized by devising the polymerization catalyst and reaction temperature (M.Abe et al .; J. Chem. Soc., C).
hem.Commun., 1989,1736). However, this polyaniline was hardly dissolved in other general-purpose organic solvents, and its application range was limited.

Further, there is also known a method in which the soluble polyaniline is subjected to incomplete reduction treatment with hydrazine to form intermolecular crosslinks by hydrogen bond and gelation (O.Oka et al .; Jpn. .J.Appl.Phys., 29 (1990) L679).
However, in that case, it was difficult to control the degree of crosslinking, and there was a problem in workability.

On the other hand, many gel-like polymer compounds have been known for a long time, and processing techniques such as gel stretching have been developed for processing fibers and films of polymer compounds.

[0008]

SUMMARY OF THE INVENTION The present invention is intended to solve the above problems in the prior art. That is, an object of the present invention is to provide a processable polyaniline derivative which easily swells and gels with an organic solvent or water, and a method for producing the same.

[0009]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventor has found that polyaniline can be gelated with an organic solvent or water by reacting it with a polyether having haloformyl groups at both ends. It was found that such a polyaniline derivative was obtained, and the present invention was completed.

The polyaniline derivative of the present invention has the following formula (I):

[Chemical 7] The number average molecular weight of the structural unit represented by
The reduced polyaniline of 00000 is represented by the following general formula (II) XOC-Y-COX (II) [wherein, X is chlorine, bromine or iodine, and Y is a polyether structure represented by the following structural formula (III). Yes, m = 1
It is 0 to 200.

[Chemical 8] In the formula, R represents hydrogen or an alkyl group. ] The compound obtained by reacting with a polymer compound having a haloformyl group at both ends, represented by the following formula (IV)

Embedded image (wherein Y has the same meaning as described above), and the number of nitrogen atoms forming the cross-linking points of the cross-linked structure is 5 to 40 of the nitrogen atoms in polyaniline. %
It is a polyaniline derivative characterized by being present in.

The polyaniline derivative of the present invention is produced as follows. That is, using aniline at a low temperature, for example, -20 to +5, using ammonium persulfate as an oxidizing agent.
The aniline oxidation polymer obtained by oxidative polymerization at a temperature in the range of 0 ° C. is first treated with ammonia to obtain a soluble polyaniline. Then, this is treated with an excess of hydrazine to give a number average molecular weight of 2 represented by the general formula (I).
000-500000 [measured by GPC (N-methyl-2-pyrrolidone solvent), polystyrene-reduced number average molecular weight] to obtain reduced polyaniline. Hydrazine treatment
Soluble polyaniline is dispersed in water, and hydrazine in an amount equivalent to or more than nitrogen atom in polyaniline, preferably 3 times or more, is added under a nitrogen atmosphere, and 24 hours or more, 0 to 30 ° C.
By stirring at.

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.

This reduced polyaniline is treated with an amide solvent,
For example, it is dissolved in N-methyl-2-pyrrolidone or N, N-dimethylacetamide, and a polymer compound having haloformyl groups at both ends is added under a nitrogen atmosphere to give -10
The polyaniline derivative of the present invention is synthesized by performing the reaction in the temperature range of up to + 50 ° C. and further removing the hydrogen halide generated during the reaction with aqueous ammonia. The polymer compound represented by the general formula (II) having a haloformyl group at both ends is reduced so that the amount of the haloformyl group is 5 to 40% of the nitrogen atom of the reduced polyaniline of the general formula (I). Add to type polyaniline.

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.

The polymer compound having a haloformyl group at both ends represented by the general formula (II) has the general formula X ¹ OC-Y-COX ¹ (V) [wherein Y has the above-mentioned meaning, X ¹ can be easily derived from a dicarboxylic acid, a dicarboxylic acid ester or a dicarboxylic acid salt represented by a hydroxyl group, an alkoxy group or OM (M is an alkali metal or quaternary ammonium).

From the dicarboxylic acid, the C of the dicarboxylic acid
An inorganic halogen compound such as phosphoryl chloride, thionyl chloride, phosphorus pentachloride or phosphorus trichloride is added to OX ^{1 in} an equivalent amount or more and reacted in an inert solvent such as benzene to form a haloformyl group at both ends used in the present invention. It is possible to obtain a polymer compound having In this case, zinc chloride, pyridine,
You may add iodine, triethylamine, etc. as a catalyst. Alternatively, from the same dicarboxylic acid, acid halides such as benzoyl chloride, phthalic acid chloride and oxalic acid chloride, α, α-dihalogenoethers, halogenated alkylamines, triphenylphosphine / tetracarboxylic acid can be used for the dicarboxylic acid. Obtained by reacting an organic halide such as an organic phosphorus halide such as carbon chloride, pyrocatealkylphosphotrichloride, diethylhalophosphochloride, triphenylhalophosphobromide in an inert solvent such as benzene or chlorobenzene. You can

From the dicarboxylic acid ester, a polymer compound having a haloformyl group at both ends used in the present invention is obtained by reacting the dicarboxylic acid ester with a triphenylhalophosphohalide or its complex with boron fluoride. Obtainable. From a carboxylate salt, a polymer compound having a haloformyl group at both ends used in the present invention by reacting an inorganic halogen compound such as phosphoryl chloride or phosphorus pentachloride or a complex of thionyl chloride and dimethylformamide with respect to the dicarboxylate salt. Can be obtained. In addition to this, there is no problem as long as it is a reaction capable of converting a carboxyl group to a haloformyl group, and a polymer compound having haloformyl groups at both ends used in the present invention can be obtained.

The number of nitrogen atoms forming the cross-linking points of the cross-linked structure of the formula (IV) is 5-40% of the nitrogen atoms in the polyaniline.
Must be within the range. When the number of nitrogen atoms forming the cross-linking points of the cross-linking structure of the formula (IV) is higher than 40%, a gel having a swelling degree that can be processed cannot be obtained. Again 5
If it is lower than%, it will be dissolved and gelation will not be possible.

The polyaniline derivative of the present invention produced as described above is an amide solvent such as N-methyl-2-pyrrolidone or N, N-dimethylacetamide,
It is possible to gel with halogenated hydrocarbon solvents such as chloroform, dichloroethane, dichloromethane, ether solvents such as tetrahydrofuran, amine solvents such as pyridine, polar solvents such as dimethylsulfoxide, etc. It is possible to manufacture fibers and fibers. Further, the processed products such as the film and the fiber show a high conductivity of 10 ⁻³ to 10 S / cm when doped with an acceptor dopant.

The dopant used here is not particularly limited, and any dopant can be used as long as it is used as a dopant in doping the aniline-based conductive polymer. For example, iodine, bromine, chlorine, halogen compounds such as iodine trichloride, sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, protic acid such as borofluoric acid, various salts of the protic acid, aluminum trichloride, iron trichloride, Examples thereof include Lewis acids such as molybdenum chloride, antimony chloride and arsenic pentafluoride, and various compounds such as acetic acid, trifluoroacetic acid, benzenesulfonic acid, p-toluenesulfonic acid and other organic acids.

The method for doping these compounds is not particularly limited, and any known method can be used. Generally, the gel of the polyaniline derivative, or a molded product thereof, and the dopant compound may be brought into contact with each other, and it can be carried out in a gas phase or a liquid phase. Alternatively, a method of electrochemically doping in the solution of the above-mentioned protonic acid or its salt can be used.

[0022]

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
The solution was cooled to −10 ° C., slowly added dropwise to the aniline solution described above, and stirring was continued at −10 ° C. for 6 hours. The number average molecular weight thus obtained was 12000 [GPC
The aniline-oxidized polymer having a number average molecular weight in terms of polystyrene measured in (N-methyl-2-pyrrolidone solvent)] was thoroughly washed with water, and then dedoped with ammonia water.

The soluble polyaniline thus obtained was
It was dispersed in 00 ml 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. The reduced polyaniline thus obtained (number average molecular weight 12000) 1
g under a nitrogen stream 50 ml of N-methyl-2-pyrrolidone
Dissolve completely in.

On the other hand, polyethylene oxide diglycolic acid (molecular weight ≈3000, manufactured by Kawaken Fine Chemical Co., Ltd.), which is a polyether having a carboxyl group at the end of the amount.
0.825 g was dissolved in 10 ml of dry benzene,
1 ml of oxalic acid chloride was added, and the mixture was heated at 50 ° C. for 2 hours and then at 80 ° C. for 1 hour to distill off benzene, unreacted oxalic acid chloride, and the like. 0.830 with a polyether having a chloroformyl group at the end
g (chloroformyl group 5 mol per aniline unit
%)Obtained. The presence of chloroformyl group showed absorption at 1795 cm ^-1 in IR spectrum,
It was confirmed that the absorption at 0 cm ^-1 had disappeared.

This was dissolved in 10 ml of dried chloroform and slowly added dropwise to the above polyaniline solution.
The reaction was continued for 4 hours at room temperature with stirring. 11 of this solution
Was poured into water with stirring, the precipitate was filtered off, and the hydrogen halide formed during the reaction was further removed with aqueous ammonia,
When dried, 1.820 g of the polyaniline derivative of the present invention
Obtained. When the infrared absorption spectrum was measured, it was 1650 cm ^-1 (C = O expansion / contraction) and 2850 to 2950 cm ^-1 (aliphatic C-H expansion / contraction) due to the structure of the above formula (IV).
Was observed to be absorbed. From the reaction yield, the number of nitrogen atoms forming the cross-linking point of the structure of formula (IV) was 5% of the nitrogen atoms in polyaniline.

1 g of the obtained polyaniline derivative was added to 5 g of N-methyl-2-pyrrolidone and stirred at room temperature to form a gel, which could be formed into a film by spinning or stretching.
Further, when this film was dipped in a 20% aqueous hydrochloric acid solution for 24 hours and was doped and dried, the conductivity was 0.5 S / cm. Further, instead of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, pyridine, chloroform, dichloroethane,
Similar gelation was possible using an organic solvent such as dichloromethane or tetrahydrofuran. Furthermore, this gel was swellable with water and alcohol such as methanol and ethanol, and could be processed.

Example 2 1.650 g of polyethylene oxide diglycolic acid having a carboxyl group at both ends (molecular weight ≈3000, manufactured by Kawaken Fine Chemicals Co., Ltd.) was used in Example 1 and the polyaniline derivative of the present invention was prepared by the same procedure. 2.640 g was obtained. When the infrared absorption spectrum was measured, absorptions of 1650 cm ⁻¹ (C═O stretching) and 2850 to 2950 cm ⁻¹ (aliphatic C—H stretching) due to the structure of the above formula (IV) were observed. . From the reaction yield, the number of nitrogen atoms forming the cross-linking point in the structure of formula (IV) was 10% of the nitrogen atoms in polyaniline.

1 g of the obtained polyaniline derivative was added to 5 g of N-methyl-2-pyrrolidone and stirred at room temperature to form a gel, which could be formed into a film by spinning or stretching.
Further, when this film was dipped in a 20% hydrochloric acid aqueous solution for 24 hours and was doped and dried, the conductivity was 0.3 S / cm. Further, instead of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, pyridine, chloroform, dichloroethane,
Similar gelation was possible using an organic solvent such as dichloromethane or tetrahydrofuran. Furthermore, this gel was swellable with water and alcohol such as methanol and ethanol, and could be processed.

Example 3 In Example 1, 6.60 g of polyethylene oxide diglycolic acid having a carboxyl group at both ends (molecular weight ≈3000, manufactured by Kawaken Fine Chemicals Co., Ltd.) was used, and the polyaniline derivative of the present invention was prepared by the same procedure. 7.55 g was obtained. When the infrared absorption spectrum was measured, it was found to be 1650 cm ^-1 (C = O stretching) due to the structure of the above formula (IV), 285
Absorption of ^{0 to} 2950 cm ^-1 (aliphatic C-H stretch) was observed. From the reaction yield, the number of nitrogen atoms forming the cross-linking point in the structure of formula (IV) is 40% of the nitrogen atoms in polyaniline.
Met.

1 g of the obtained polyaniline derivative was added to 5 g of N-methyl-2-pyrrolidone and stirred at room temperature to form a gel, which could be formed into a film by spinning or stretching.
Further, when this film was dipped in a 20% hydrochloric acid aqueous solution for 24 hours and was doped and dried, the conductivity was 0.05 S / cm. Further, instead of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, pyridine, chloroform, dichloroethane,
Similar gelation was possible using an organic solvent such as dichloromethane or tetrahydrofuran. Furthermore, this gel was swellable with water and alcohol such as methanol and ethanol, and could be processed.

Example 4 Polyethylene oxide diglycolic acid having a carboxyl group at both ends used in Example 1 (molecular weight ≈3000,
0.549 g of polyethylene oxide diglycolic acid (molecular weight≈1000, manufactured by Kawaken Fine Chemical Co., Ltd.) was used in place of Kawaken Fine Chemical Co., Ltd., and 1.54 g of the polyaniline derivative of the present invention was obtained by the same procedure as described below. The infrared absorption spectrum was measured and found to be 1650 cm ^-1 (C = O stretching) due to the structure of the above formula (IV), 2850
Absorption of ˜2950 cm ⁻¹ (aliphatic C—H stretching) was observed. From the reaction yield, the number of nitrogen atoms forming the cross-linking point in the structure of formula (IV) was 10% of the nitrogen atoms in polyaniline.

1 g of the obtained polyaniline derivative was added to 5 g of N-methyl-2-pyrrolidone and stirred at room temperature to form a gel, which could be formed into a film by spinning or stretching.
Further, when this film was dipped in a 20% aqueous hydrochloric acid solution for 24 hours and was doped and dried, the conductivity was 0.5 S / cm. Further, instead of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, pyridine, chloroform, dichloroethane,
Similar gelation was possible using an organic solvent such as dichloromethane or tetrahydrofuran. Furthermore, this gel was swellable with water and alcohol such as methanol and ethanol, and could be processed.

Example 5 In Example 4, 2.196 g of polyethylene oxide diglycolic acid having a carboxyl group at both ends (molecular weight ≈1000, manufactured by Kawaken Fine Chemicals Co., Ltd.) was used, and the polyaniline derivative of the present invention was prepared by the same procedure. 3.185 g was obtained. When the infrared absorption spectrum was measured, it was 1650 cm ^-1 (C = O expansion / contraction) and 2850 to 2950 cm ^-1 (aliphatic C-H expansion / contraction) due to the structure of the above formula (IV).
Was observed to be absorbed. From the reaction yield, the number of nitrogen atoms forming the cross-linking point in the structure of formula (IV) was 20% of the nitrogen atoms in polyaniline.

1 g of the obtained polyaniline derivative was added to 5 g of N-methyl-2-pyrrolidone and stirred at room temperature to form a gel, which could be formed into a film by spinning or stretching.
Further, when this film was dipped in a 20% aqueous hydrochloric acid solution for 24 hours and was doped and dried, the conductivity was 0.5 S / cm. Also, instead of N-methyl-2-pyrrolidone,
N, N-dimethylacetamide, N, N-dimethylformamide, pyridine, chloroform, dichloroethane,
Similar gelation was possible using an organic solvent such as dichloromethane or tetrahydrofuran. Furthermore, this gel was swellable with water and alcohol such as methanol and ethanol, and could be processed.

[0035]

INDUSTRIAL APPLICABILITY The polyaniline derivative of the present invention can be gelled with various organic solvents or water, can be processed by other molding techniques such as gel drawing and spinning, and shows high conductivity by doping, It is very useful as a material and a conductive material for various purposes.

[Chemical 9]

Claims (2)

[Claims] 1. The following formula (I): The number average molecular weight of the structural unit represented by
The reduced polyaniline of 00000 is represented by the following general formula (II) XOC-Y-COX (II) [wherein, X is chlorine, bromine or iodine, and Y is a polyether structure represented by the following structural formula (III). Yes, m = 1
It is 0 to 200. [Chemical 2] In the formula, R represents hydrogen or an alkyl group. ] The compound obtained by reacting with a polymer compound having a haloformyl group at both ends, represented by the following formula (IV): (Wherein Y has the same meaning as described above), and the number of nitrogen atoms forming the cross-linking points of the cross-linking structure is 5 to 4 of the nitrogen atoms in polyaniline.
Polyaniline derivative characterized by being present in 0%. 2. An aniline-oxidized polymer is treated with ammonia to obtain a soluble polyaniline, and then treated with hydrazine to obtain the following formula (I): The number average molecular weight of the structural unit represented by
The reduced polyaniline of 00000 is represented by the following general formula (II) XOC-Y-COX (II) [wherein, X is chlorine, bromine or iodine, and Y is a polyether structure represented by the following structural formula (III). Yes, m = 1
It is 0 to 200. [Chemical 5] In the formula, R represents hydrogen or an alkyl group. ] The compound represented by the following formula (IV): characterized by reacting with a polymer compound having haloformyl groups at both ends. (Wherein Y has the same meaning as described above), and the number of nitrogen atoms forming the cross-linking point of the cross-linked structure is 5 to 4 of the nitrogen atoms in polyaniline.
A method for producing a polyaniline derivative which is present in 0%.