JP2537710B2 - 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,
As a conductive material, it is used in a wide range of fields such as battery electrode materials, antistatic materials, electromagnetic wave 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 of is being considered.

[0003] However, conventional polyaniline has π
Since the conjugated system is highly developed, the main chain of the polymer is rigid and the interaction between the molecular chains is strong, and since there are many strong hydrogen bonds between the molecular chains, it is insoluble in most organic solvents. In addition, since they are not melted by heating, they have poor moldability and cannot be processed into films or the like.

For this purpose, for example, a base material having a desired shape such as a fiber made of a polymer material or a porous material is impregnated with an aniline monomer, and the monomer is polymerized by contact with an appropriate polymerization catalyst or by electrolytic oxidation. , In a conductive composite material, or in the presence of a thermoplastic polymer powder,
A similar composite material was obtained by polymerizing the monomers. However, in this case, there are limits to the combination of materials, shape, etc.
There was a problem that the application range was narrow.

On the other hand, N can be changed by devising the polymerization catalyst and reaction temperature.
Polyaniline soluble only in -methyl-2-pyrrolidone has been synthesized (M. Abe et al .; J. Ch.
em. Soc. Chem. Commun. , 198
9, 1736). However, this polyaniline is hardly soluble in other general-purpose organic solvents and its application range is limited.

A method is also known in which the soluble polyaniline is subjected to a reduction treatment with an appropriate amount of hydrazine to form intermolecular crosslinks by hydrogen bond and gelation (0.0ka 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 terms of workability.

On the other hand, 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. There was a strong demand for polyaniline to be easily swelled in an organic solvent and to be gelated.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems in the prior art. That is, an object of the present invention is to provide a polyaniline derivative which can be easily swollen / gelled with an organic solvent and can be processed into a wide range of applications, 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 a gelling polyaniline derivative can be obtained by reacting reduced polyaniline with diepoxide and crosslinking the same. The present invention has been completed and the present invention has been completed.

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

[Chemical 9] The number average molecular weight of the structural unit represented by
000000 of reduced polyaniline is represented by the following general formula (II)

[Chemical 10] [In the formula, X is a terminal-substituted or substituted alkylene group or a group represented by the following general formula (III) —CH ₂ — (O—R—O—CH ₂ CH (OH) CH ₂ ) _n— O—R— O-CH ₂ - represent (n = 0~2) (III) . In this case, R in the general formula (III) represents a terminally-substituted or substituted alkylene group, a terminally-substituted or substituted arylene group, a group represented by the general formula (IV), a substituted product of the group, and a hydrogenated product of the group.

[Chemical 11] Incidentally, Z is a direct _{bond, -CH 2 -, - CH (} CH 3)
_{-, - C (CH 3)} 2 -, - (C 6 H 11) C (CH 3)
_{-, - C (CF 3)} 2 -, - O -, - S -, - SO 2 -
And a substituted alkylene group which constitutes X in the general formula (II), a substituted alkylene group and a substituted arylene group which constitutes R in the general formula (III), and substitution of a substitution product which constitutes the group of the general formula (IV) A halogen atom, a cyano group, a nitro group, an alkyl group, or an alkoxy group corresponds to the group. ] It is made to react with a diepoxide represented by the following formula (V)

[Chemical 12] (In the formula, X has the same meaning as described above.) The crosslinked structure represented by the formula (1) is present in 0.1 to 25 mol% of the nitrogen atom of polyaniline.

The polyaniline derivative of the present invention is produced as follows. That is, using aniline at a low temperature, for example, -20 to 50, using ammonium persulfate as an oxidizing agent.
The aniline oxidation polymer obtained by oxidative polymerization at a temperature in the range of ° C is first treated with ammonia to obtain soluble polyaniline. Then, this is treated with an excess of hydrazine to obtain a number average molecular weight of 20 represented by the general formula (I).
A reduced polyaniline of 00-500000 [polystyrene-equivalent number average molecular weight measured by GPC (N-methyl-2-pyrrolidone solvent)] is obtained. The hydrazine treatment is carried out by dispersing a soluble polyaniline in water, adding an equivalent amount or more, preferably 3 times or more, of hydrazine to the nitrogen atom in the polyaniline under a nitrogen atmosphere, and 0 to 30 ° C. for 24 hours.
By stirring at.

The obtained reduced polyaniline 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 converted into N-methyl-2
-Dissolved in pyrrolidone or N, N-dimethylacetamide, or dispersed in an aromatic solvent or ether solvent, and added the diepoxide under a nitrogen atmosphere,-
A cross-linking reaction is performed within a temperature range of 10 to 100 ° C. to synthesize a cross-linked polyaniline derivative of the present invention.

In this case, as the solvent for the reduced polyaniline, in addition to N-methyl-2-pyrrolidone and N, N-dimethylacetamide described above, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3- An amide solvent such as dimethyl-2-imidazolidinone can be used. Further, as the aromatic solvent, benzene, toluene, xylene, ethylbenzene, tetralin and the like can be used, and further, as the ether solvent, ether,
Tetrahydrofuran, dioxian, etc. can be used.

The diepoxide used in the present invention has the general formula (II):

[Chemical 13] [In the formula, X is a terminally-substituted or substituted alkylene group or a group represented by the general formula (III): —CH ₂ — (O—R—O—CH ₂ CH (OH) CH ₂ ) _n— O—R—O. --CH _2- (n = 0 to 2) represents (III). In this case, R in the general formula (III) represents a terminally-substituted or substituted alkylene group, a terminally-substituted or substituted arylene group, a group represented by the general formula (IV), or a substitution product or a hydrogenated product of the group.

Embedded image Incidentally, Z is a direct _{bond, -CH 2 -, - CH (} CH 3)
_{-, - C (CH 3)} 2 -, - (C 6 H 11) C (CH 3)
_{-, - C (CF 3)} 2 -, - O -, - S -, - SO 2 -
And a substituted alkylene group which constitutes X in the general formula (II), a substituted alkylene group and a substituted arylene group which constitutes R in the general formula (III), and substitution of a substitution product which constitutes the group of the general formula (IV). A halogen atom, a cyano group, a nitro group, an alkyl group, or an alkoxy group corresponds to the group. ] What is represented by is used.

The alkylene group represented by X in the above general formula (II) is a methylene group, an ethylene group, a propylene group,
Examples thereof include a butylene group, a hexylene group and an octylene group. Examples of the substituted alkylene group in which one or more hydrogen atoms of the alkylene group are substituted with a halogen atom, a nitro group or an alkoxy group include tetrafluoroethylene, octafluorobutylene, 2-methoxyoctylene and the like. Further, as the group represented by the above formula (IV) and its substitution product or its hydrogenated product, 4,4′-biphenylene, 3,4-biphenylene,

Embedded image And the like.

Preferred diepoxides represented by the general formula (II) are 1,7-octadiene diepoxide, ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether and 2,2-
Bis [4- (2,3-epoxypropoxy) phenyl]
Propane, 2,2-bis [3,5-dibromo-4-
(2,3-epoxypropoxy) phenyl] propane,
Bis [4- (2,3-epoxypropoxy) phenyl]
Examples include methane.

It is necessary to carry out the reaction with the diepoxide so that the average cross-linking structure is in the range of 0.1 to 25 mol% per aniline unit. If the crosslinked structure has a ratio higher than 25 mol%, a sufficient degree of swelling in an organic solvent cannot be obtained. On the other hand, if it is less than 0.1 mol%, it will be dissolved and gelation will not be possible.

The polyaniline derivative obtained as described above is desirably subjected to a dedoping treatment with aqueous ammonia as a post-treatment. 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, a halogenated hydrocarbon solvent such as chloroform, dichloroethane or dichloromethane, or tetrahydrofuran. It is possible to form a gel with an ether solvent, an amine solvent such as pyridine, and a polar solvent such as dimethylsulfoxide, and it is possible to produce a self-supporting film or fiber from the obtained gel. Further, the processed products such as films and fibers and gels exhibit high electric 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. Specific examples include 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, Examples thereof include various compounds such as Lewis acids such as iron trichloride, molybdenum chloride, antimony chloride and arsenic pentafluoride, and organic acids such as acetic acid, trifluoroacetic acid, benzenesulfonic acid and p-toluenesulfonic acid.

The method for doping these compounds is not particularly limited, and any known method can be used. Generally, the gel of the derivative of polyaniline, or the molded product thereof and the dopant compound may be brought into contact with each other, and it can be carried out in the gas phase or the liquid phase. Alternatively, a method of electrochemically doping in a 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 ml
This solution was also cooled to −5 ° C., slowly added dropwise to the aniline solution described above, and stirring was continued for 4 hours at −5 ° C. to obtain a number average molecular weight of 12000 (GPC, in N-methyl-2-pyrrolidone solvent). An aniline oxidation polymer having a measured polystyrene equivalent number average molecular weight) was obtained. After thoroughly washing this with water, dedoping treatment was further performed with aqueous ammonia. 200 ml of the soluble polyaniline thus obtained
Of water, 50 ml of hydrazine was added under a nitrogen atmosphere, and stirring was continued at room temperature for 24 hours, followed by filtration and drying to obtain an off-white reduced polyaniline.

1 g of the reduced polyaniline (number average molecular weight: 12000) thus obtained was completely dissolved in 30 ml of N-methyl-2-pyrrolidone, and after thoroughly substituting with nitrogen,
A solution in which 0.078 g of 1,7-octadiene diepoxide (5 mol% based on the aniline unit) was completely dissolved in 5 ml of N-methyl-2-pyrrolidone was added, and stirring was continued for 6 hours to cause a reaction. This solution was poured into 11 water with stirring, the precipitate was filtered off, dried and then dedoped with aqueous ammonia to obtain 1.078 g of a nitrogen atom-crosslinked polyaniline derivative. Crosslinking was confirmed by infrared absorption spectrum at 2950 cm ^-1 . From the reaction yield, the cross-linked structure of the formula (V) was 5% on average with respect to the aniline unit.

When 1 g of the obtained polyaniline derivative was added to 10 g of N-methyl-2-pyrrolidone and stirred at room temperature, it gelated, and it was possible to form a film by spinning or stretching. When this film was dipped in a 20% aqueous hydrochloric acid solution for 24 hours and was then dried, the conductivity was 1.5 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.

Example 2 In the same manner as in Example 1, except that 0.312 g of 1,7-octadiene diepoxide (20 mol% based on aniline unit) was used, 1.281 g of a polyaniline derivative having a nitrogen atom crosslinked therein was subjected to the same procedure as described below. Obtained. The existence of cross-linked structure is 29
It was confirmed by an infrared absorption spectrum at 50 cm ^-1 . From the reaction yield, the cross-linked structure of the formula (V) was 18% on average with respect to the aniline unit.

1 g of the obtained polyaniline derivative was put in 10 g of N-methyl-2-pyrrolidone and stirred at room temperature to gel, and it was possible to form a film by spinning or stretching. When this film was dipped in a 20% hydrochloric acid aqueous solution for 24 hours and was then dried, the conductivity was 1.0 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.

Example 3 In Example 1, ethylene glycol diglycidyl ether was added in place of 1,7-octadiene diepoxide.
Using 191 g (10 mol% relative to the aniline unit), 1.172 g of a polyaniline derivative having a nitrogen atom cross-linked was obtained in the same procedure as described below. The presence of crosslinked structure is 2950
It was confirmed by an infrared absorption spectrum at cm ^-1 . From the reaction yield, the crosslinked structure of the formula (V) is 9% on average with respect to the aniline unit.
Met. 1 g of the obtained polyaniline derivative was put in 10 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.
When this film was dipped in a 20% hydrochloric acid aqueous solution for 24 hours and was then dried, the conductivity was 0.5 S / cm. Also, instead of N-methyl-2-pyrrolidone, N,
Similar gelation was possible using organic solvents such as N-dimethylacetamide, N, N-dimethylformamide, pyridine, chloroform, dichloroethane, dichloromethane and tetrahydrofuran.

Example 4 In Example 1, 0.475 g of neopentyl glycol diglycidyl ether (20 mol% based on aniline unit) was used in place of 1,7-octadiene diepoxide, and a nitrogen atom was prepared by the same procedure. 1.451 g of a cross-linked polyaniline derivative was obtained. The existence of cross-linked structure is 29
It was confirmed by an infrared absorption spectrum at 50 cm ^-1 . From the reaction yield, the crosslinked structure of the formula (V) was 19% on average with respect to the aniline unit. 1 g of the obtained polyaniline derivative is
When 10 g of -methyl-2-pyrrolidone was added and the mixture was stirred at room temperature, it gelated, and it was possible to form a film by spinning or stretching. This film was dipped in a 20% aqueous hydrochloric acid solution for 24 hours, and was then dried to obtain a conductivity of 0.01 S / c.
It was m. Further, similar gelation can be achieved by using an organic solvent such as N, N-dimethylacetamide, N, N-dimethylformamide, pyridine, chloroform, dichloroethane, dichloromethane or tetrahydrofuran instead of N-methyl-2-pyrrolidone. there were.

Example 5 In Example 1, 0.187 g of 2,2-bis- [4- (2,3-epoxypropoxy) phenyl] propane was used instead of 1,7-octadiene diepoxide (based on aniline unit). (5 mol%) was used to obtain 1.187 g of a polyaniline derivative in which a nitrogen atom was cross-linked in the same procedure as described below. The presence of the crosslinked structure was confirmed by an infrared absorption spectrum at 2950 cm ^-1 . From the reaction yield, the crosslinked structure of the formula (V) was 5% on average with respect to the aniline unit. 1 g of the obtained polyaniline derivative was added to N-methyl-2-pyrrolidone 10
When it was added to g and stirred at room temperature, it gelated, and it was possible to form a film by spinning or stretching. When this film was dipped in a 20% hydrochloric acid aqueous solution for 24 hours and was then dried,
The conductivity was 0.1 S / cm. In addition, N-methyl-
Similar gelation was possible by using an organic solvent such as N, N-dimethylacetamide, N, N-dimethylformamide, pyridine, chloroform, dichloroethane, dichloromethane or tetrahydrofuran instead of 2-pyrrolidone.

Example 6 In Example 1, 2,2-bis- [3,5-dibromo-4- was used instead of 1,7-octadiene diepoxide.
Using 0.720 g of (2,3-epoxypropoxy) phenyl] propane (10 mol% with respect to the aniline unit), 1.648 g of a polyaniline derivative having a crosslinked nitrogen atom was obtained in the same procedure as described below. The existence of cross-linked structure is 29
It was confirmed by an infrared absorption spectrum at 50 cm ^-1 . From the reaction yield, the cross-linked structure of the formula (V) was 9% on average with respect to the aniline unit. 1 g of the obtained polyaniline derivative was N-
When 10 g of methyl-2-pyrrolidone was added and the mixture was stirred at room temperature, it gelated, and it was possible to form a film by spinning or stretching. This film was dipped in a 20% aqueous hydrochloric acid solution for 24 hours and then dried, and the conductivity was 0.05 S / cm.
Met. Further, similar gelation can be achieved by using an organic solvent such as N, N-dimethylacetamide, N, N-dimethylformamide, pyridine, chloroform, dichloroethane, dichloromethane or tetrahydrofuran instead of N-methyl-2-pyrrolidone. there were.

Example 7 In Example 1, bis- [4- (2,3-epoxypropoxy) was used instead of 1,7-octadiene diepoxide.
Phenyl] propane (0.171 g, 5 mol% with respect to the aniline unit) was used to obtain 1.171 g of a nitrogen atom-crosslinked polyaniline derivative in the same manner as described below. The presence of the crosslinked structure was confirmed by an infrared absorption spectrum at 2950 cm ^-1 . From the reaction yield, the crosslinked structure of the formula (V) was 5% on average with respect to the aniline unit. 1 g of the obtained polyaniline derivative was added to 10 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. When this film was dipped in a 20% aqueous hydrochloric acid solution for 24 hours and was then dried, the conductivity was 0.03 S / cm. Also, N-methyl-2-
N, N-dimethylacetamide instead of pyrrolidone,
Similar gelation was possible using an organic solvent such as N, N-dimethylformamide, pyridine, chloroform, dichloroethane, dichloromethane and tetrahydrofuran.

[0032]

INDUSTRIAL APPLICABILITY The polyaniline derivative of the present invention can be gelled with various organic solvents, can be processed by gel stretching, spinning, and other molding processing techniques, and exhibits high conductivity by doping, It is very useful for various applications as an electronic material and a conductive material.

Claims (2)

(57) [Claims] 1. The following formula (I): The number average molecular weight of the structural unit represented by
000000 of reduced polyaniline is represented by the following general formula (II): [In the formula, X is a terminally-substituted or substituted alkylene group or a group represented by the general formula (III): —CH ₂ — (O—R—O—CH ₂ CH (OH) CH ₂ ) _n— O—R—O. - CH ₂ - represent (n = 0~2) (III) . In this case, R in the general formula (III) is a terminal-substituted or substituted alkylene group, a terminal-substituted or substituted arylene group or a group represented by the general formula (IV): Alternatively, it represents a substitution product of the group and a hydrogenated product of the group. Incidentally, Z is a direct _{bond, -CH 2 -, - CH (} C
_{H 3) -, - C (} CH 3) 2 -, - (C 6 H 11) C (C
_{H 3) -, - C (} CF 3) 2 -, - O -, - S -, - S
An alkylene group which represents O ₂ — and constitutes X in the general formula (II), a substituted alkylene group and a substituted arylene group which constitutes R in the general formula (III), and a substituent which constitutes a group of the general formula (IV). The substituent of is a halogen atom, a cyano group, a nitro group, an alkyl group or an alkoxy group. A compound obtained by reacting with a diepoxide represented by the following formula (V): (In the formula, X has the same meaning as described above.) The polyaniline derivative, wherein the crosslinked structure represented by 0.1 to 25 mol% of the nitrogen atoms of the polyaniline is present. 2. The aniline-oxidized polymer is treated with ammonia to obtain a soluble aniline polymer, and then treated with an excess of hydrazine to obtain a compound represented by the following formula (I): The number average molecular weight of the structural unit represented by
000000 of reduced polyaniline was synthesized, and then the reduced polyaniline was converted to the following general formula (II): [In the formula, X is a terminally-substituted or substituted alkylene group or a group represented by the general formula (III): —CH ₂ — (O—R—O—CH ₂ CH (OH) CH ₂ ) _n— O—R—O. - CH ₂ - represent (n = 0~2) (III) . In this case, R in the general formula (III) represents a terminal-substituted or substituted alkyl group, a terminal-substituted or substituted arylene group, a group represented by the general formula (IV), a substituted product of the group, or a hydrogenated product of the group. [Chemical 7] Incidentally, Z is a direct _{bond, -CH 2 -, - CH (} CH 3)
_{-, - C (CH 3)} 2 -, - (C 6 H 11) C (CH 3)
_{-, - C (CF 3)} 2 -, - O -, - S -, - SO 2 -
And a substituted alkylene group which constitutes X in the general formula (II), a substituted alkylene group and a substituted arylene group which constitutes R in the general formula (III), and substitution of a substitution product which constitutes the group of the general formula (IV). The group is a halogen atom, a cyano group, a nitro group,
An alkyl group and an alkoxy group are applicable. ] By reacting with a diepoxide represented by the following formula (V): (In the formula, X has the same meaning as described above.) A method for producing a polyaniline derivative, which comprises allowing the crosslinked structure represented by 0.1 to 25 mol% of nitrogen atoms of polyaniline to exist.