JPH06256511A - Polyaniline derivative and its production - Google Patents

Abstract

PURPOSE:To obtain a polyaniline derivative having a crosslinked structure obtained by the reaction of a reduced-type polyaniline with a specific polythiourethane and capable of forming a self-supporting flexible film and fiber soluble in or gelatinizable with an organic solvent. CONSTITUTION:This polyaniline derivative contains a polyaniline having the structure of formula I [(m) and (n) are >=0; m/(n+m) is 0-1; m+n is 10-5,000] and a number-average molecular weight of 2,000-500,000 as a main chain, which forms a crosslinked structure expressed by formula II [RP is polythiourethane chain of formula III having a number-average molecular weight of 220-100,000; RP<1> is 1-30C bivalent non-aromatic hydrocarbon group, etc.; RP<2> is 1-30C bivalent non-aromatic hydrocarbon group, etc.; (k) is 1-50; A<1> is R, etc.; R is direct bond, etc.; A<2> is R-C(=X), etc.; X is O or S] wherein the number of nitrogen atoms participating in the crosslinked structure is 0.01-50% of the nitrogen atoms of the polyaniline of the main chain. The derivative can be produced by treating a soluble aniline polymer with excess hydrazine and reacting the obtained reduced-type aniline polymer with a polythiourethane.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyaniline derivative which is soluble or gellable in an organic solvent and is capable of forming a flexible and self-supporting film, and a method for producing the same.

[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, photoelectric conversion elements, optical memories, functional elements such as various sensors, display elements, various hybrid materials, transparent conductors, various terminal devices, etc. are being studied. However, 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 exist between the molecular chains. Since it is almost insoluble in organic solvents and does not melt even when heated, it has poor moldability and cannot be processed into a film.

For that purpose, for example, fibers of polymeric materials,
Impregnate a base material of a desired shape such as a porous body with a monomer,
This monomer is polymerized by contact with a suitable polymerization catalyst or by electrolytic oxidation to form a conductive composite material, or alternatively, the monomer is polymerized in the presence of a thermoplastic polymer powder to prepare a similar composite material. I was getting. On the other hand, N-methyl-
Polyaniline soluble only in 2-pyrrolidone has been synthesized (M. Abe et al .; J. Chem. So.
c. Chem. Commun. , 1989, 173
6). However, this polyaniline was hardly dissolved in other general-purpose organic solvents, and its application range was limited. Although polyaniline derivatives soluble in organic solvents have been synthesized by utilizing various aniline derivatives, it was not possible to provide a film having sufficient flexibility. On the other hand, it is known that a polymer compound can be processed by using techniques such as gel stretching, gel spinning, and gel formation, if gelation is possible.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above situation in the prior art. That is, an object of the present invention is to provide a polyaniline derivative that is soluble or gellable in an organic solvent and can form a flexible self-supporting film or fiber, and a method for producing the same.

[0005]

As a result of intensive studies to solve the above problems, the present inventor has found that reduced polyaniline and a polythiourethane compound having a functional group capable of reacting with an aromatic secondary amine at both ends are used. It was found that by reacting, a polyaniline derivative having a cross-linking structure, capable of being soluble or gelling in an organic solvent and capable of forming a flexible self-supporting film, was obtained, and the present invention was completed. Came to do.

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

[Chemical 7] (In the formula, m and n mean integers of 0 or more, and m / (n
+ M) = 0 to 1, m + n = 10 to 5000. ) The number average molecular weight of the structural unit represented by
The main chain is made of polyaniline of 0,000, and the main chain is represented by the following formula (II).

[Chemical 8] [In the formula, RP represents a polythiourethane chain having a number average molecular weight of 220 to 100,000 represented by the following formula (III),

[0007]

[Chemical 9] (In the formula, RP ¹ represents a divalent non-aromatic hydrocarbon group having 1 to 30 carbon atoms, and PR ² represents a divalent non-aromatic hydrocarbon group having 1 to 30 carbon atoms or a halogen or alkoxy thereof. Represents a carbonyl substituent, and k represents an integer from 1 to 500.)

A ¹ represents a linking group selected from the following formulas (1) to (11),

[Chemical 10] (In the formula, R is a direct bond, a divalent hydrocarbon group having 1 to 30 carbon atoms, or a halogen or —COOM substitution product thereof (wherein M is a hydrogen atom, Li, Na, K, Cs, Rb or NH _4). X represents an oxygen atom or a sulfur atom, Y represents an oxygen atom, a sulfur atom or NH, and B represents a hydrocarbon group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms. , RP ² has the same meaning as described above, and p means an integer of 0 to 2),

A ² represents a linking group selected from the following formulas (1 ') to (11'),

[Chemical 11] (In the formula, R, X, Y, B, RP ² and p have the same meanings as described above.) Represents a group selected from the group consisting of: ] The number of the nitrogen atoms involved in the crosslinked structure is 0.01 to 50% of the nitrogen atoms of the main chain polyaniline.

The method for producing a polyaniline derivative of the present invention comprises treating a soluble aniline polymer obtained by treating an aniline oxidation polymer with ammonia, and treating the soluble aniline polymer with an excess of hydrazine.
To produce a reduced form of polyaniline having a number average molecular weight from 2,000 to 500,000 for the imino-1,4-phenylene structural unit, then the following formula ^{(IV) W 1 -A 3 -RP} -A 4 -W 2 (IV) [wherein W ¹ and W ² are respectively represented by the following formulas (a) to
Represents a functional group selected from (h),

[Chemical 12] (In the formula, Hal represents a halogen atom, and X, Y, B
And p have the same meaning as described above. ),

A ³ is a direct bond, a divalent hydrocarbon group having 1 to 30 carbon atoms or a halogen-substituted product thereof, --R--C (=
X) -, - R-NH -C (= X) -, - R-SO p -,
-RP ¹ -SCONH-RP ² -NHCO- or -R
P ² —NHCO— (wherein R, X, RP ¹ , RP ² and p have the same meanings as described above), and A ⁴ is
Direct bond, divalent hydrocarbon group having 1 to 30 carbon atoms or halogen substitution product thereof, -C (= X) -R-, -C (= X)
_{-NH-R -, - SO p} -R -, - CONH-RP 2 -
NHCOS-RP ¹ -or -CONH-RP ^2- (provided that R, X, RP ¹ , RP ² and p have the same meanings as defined above), provided that W ¹ and W ² are of the formula (c). When representing an intramolecular carboxylic acid anhydride group,
A ³ and A ⁴ each represent> R ¹ -C (= O)-or -C (= O) -R ¹ <(wherein R ¹ represents a trivalent hydrocarbon group having 1 to 30 carbon atoms). , And R
P has the same meaning as above. ] It is characterized by reacting with a polythiourethane compound having a functional group which reacts with an aromatic secondary amine at both ends.

The present invention will be described in detail below. The polyaniline derivative of the present invention is characterized by having a crosslinked structure represented by the above formula (II).
The number of nitrogen atoms involved in the crosslinked structure represented by I) needs to be in the range of 0.01 to 50% of the nitrogen atoms of polyaniline. When the number of nitrogen atoms involved in the cross-linking structure is higher than 50%, the polyaniline derivative produced has reduced conductivity, and at the same time is difficult to dissolve or gel in an organic solvent, resulting in a problem in processability. . On the other hand, if it is less than 0.01%, the solubility is not much different from that of polyaniline.

In the crosslinked structure represented by the above formula (II), the linking group A ¹ is selected from the formulas (1) to (11), and the linking group A ² is represented by the formulas (1 ') to (1'). 11 ′), and these linking groups do not affect the physical properties of the polyaniline derivative of the present invention, including solubility and film-forming property. R in the linking group is a direct bond, a divalent hydrocarbon group having 1 to 30 carbon atoms, when the linking group has the formulas (1), (7), (1 ') and (7'). Alternatively, it is preferably a halogen or —COOM substitution product thereof, and when the linking group is other, it is preferably a divalent hydrocarbon group having 1 to 30 carbon atoms, or a halogen or —COOM substitution product thereof. More specifically, the divalent hydrocarbon group having 1 to 30 carbon atoms will be described below. For example, straight-chain and branched-chain aliphatic hydrocarbon groups such as methylene, ethylene, trimethylene, hexamethylene, propylene, and phenylene. Examples thereof include aromatic hydrocarbon groups and hydrocarbon groups containing an aromatic ring such as 2,2-diphenyltrimethylene.

RP is the following formula (III)

[Chemical 13] Represents a polythiourethane chain having a number average molecular weight of 220 to 100,000, wherein RP ¹ is methylene,
Divalent non-aromatic hydrocarbon groups having 1 to 30 carbon atoms, such as straight-chain or branched-chain aliphatic hydrocarbon groups or alicyclic hydrocarbon groups such as ethylene, trimethylene, hexamethylene, decamethylene, propylene and cyclohexylene. Represents RP
² is a linear or branched aliphatic hydrocarbon group such as methylene, ethylene, trimethylene, hexamethylene, decamethylene, propylene, cyclohexylene, vinylene, etc., an alicyclic hydrocarbon group or an alkenylene group, etc. Represents a valent non-aromatic hydrocarbon group or a halogen or alkoxycarbonyl substitution product thereof, and k is 1 to 500.
Represents the integer.

Specifically, a polymer of ethanedithiol and tetramethylene diisocyanate, a polymer of propanedithiol and tetramethylene diisocyanate, a polymer of tetramethylene dithiol and tetramethylene diisocyanate, tetramethylene Polymer of dithiol and hexamethylene diisocyanate, polymer of hexamethylene dithiol and tetramethylene diisocyanate, polymer of hexamethylene dithiol and lysine diisocyanate, polymer of hexamethylene dithiol and isophorone diisocyanate Examples thereof include polythiourethane oligomers such as polymers of octamethylenedithiol and dicyclohexyldiisocyanate.

In the present invention, specific examples of the crosslinked structure represented by the formula (II) include those represented by the following formulas (II-1) to (II-4).

[Chemical 14] (In the formula, A ⁵ represents an alkylene group having 1 to 10 carbon atoms, an alkenylene group or a phenylene group, and A ⁶ represents 1 carbon atom.
~ 8 represents an alkylene group, and RP has the same meaning as described above. )

The polyaniline derivative of the present invention is manufactured as follows. That is, aniline is used at a low temperature, for example, -20 to 20 using ammonium persulfate or the like as an oxidizing agent.
An aniline oxidation polymer obtained by oxidative polymerization at a temperature in the range of 50 ° C. is first treated with ammonia to obtain a soluble polyaniline. Then, the soluble polyaniline is treated with an excess of hydrazine, and the number average molecular weight of the imino-1,4-phenylene structure as a structural unit is 2,000 to
A reduced polyaniline of 500,000 [measured with GPC (N-methyl-2-pyrrolidone solvent), polystyrene-equivalent number average molecular weight] is obtained. The hydrazine treatment is carried out by dispersing soluble polyaniline in water or methanol, adding hydrazine in an equivalent amount or more, preferably 3 times or more, to the nitrogen atom in the polyaniline under a nitrogen atmosphere, and at 0 to 30 ° C. for 24 hours or more. By stirring at.

The reduced polyaniline thus obtained is soluble in N-methyl-2-pyrrolidone and N, N-dimethylacetamide, but almost insoluble in other general-purpose organic solvents such as chloroform or tetrahydrofuran.
In the present invention, when the number average molecular weight of the polyaniline main chain is lower than 2,000, it becomes difficult to obtain a flexible self-supporting film or fiber from the finally formed polyaniline derivative. 500,00
When it exceeds 0, the solubility or swellability in a solvent becomes insufficient, which is not preferable in terms of workability such as casting and gel stretching.

In order to introduce the above-mentioned crosslinked structure into this reduced polyaniline, polythio having a functional group (W ¹ ) (W ² ) which reacts with an aromatic secondary amine at both ends represented by the above formula (IV). A urethane compound is used. The main point of the present invention is to cross-link the polyaniline main chain with a cross-linking chain composed of a suitable polythiourethane, and the connecting portion of the cross-linking chain and the polyaniline main chain, that is, the structure of A ¹ and A ² is It does not significantly affect the physical properties of the derivative of the present invention, including solubility and film-forming property. Therefore, both ends of the crosslinked chain may be linked by a functional group that reacts with the secondary aromatic amine.

Specific examples of the terminal functional groups (W ¹ , W ² ) of the polythiourethane compound in the above formula (IV) include halogen atom, carboxyl group, haloformyl group,
Isocyanate group, isothiocyanate group, sulfinyl halide group, sulfenyl halide group, sulfonyl halide group, oxirane ring, aziridine ring, thiirane ring,
Examples thereof include a phosphinyl halide group, a thiophosphinyl halide group and an intramolecular cyclic carboxylic acid anhydride group. Further, in the groups represented by A ³ and A ⁴ , the hydrocarbon group having 1 to 30 carbon atoms includes straight-chain and branched-chain aliphatic hydrocarbon groups such as methylene, ethylene, trimethylene, hexamethylene, propylene, and phenylene. And the like, and hydrocarbon groups containing an aromatic ring such as 2,2-diphenyltrimethylene. As the RP, those exemplified above can be mentioned.

Examples of the polythiourethane compound represented by the above formula (IV) having a functional group capable of reacting with an aromatic secondary amine at both ends include, for example, an isocyanate at both ends condensed with excess diisocyanate component. Polythiourethane compound having a group, and converting the terminal mercapto group of the polythiourethane compound having a mercapto group at both ends obtained by condensing with excess dithiol component into a functional group that reacts with an aromatic secondary amine By reacting the polythiourethane compound obtained by the above or an isocyanate group and a mercapto group at both ends of the polythiourethane compound obtained by condensation of almost equivalent amounts of dithiol and diisocyanate with an aromatic secondary amine. The polythiourethane compound etc. which are obtained by converting into a group are mentioned.

For example, the following compounds may be mentioned. Polythiourethane compound condensed with excess dithiol component as a starting material, and its terminal mercapto group reacted with trimellitic acid anhydride or halogenated trimellitic acid anhydride to form a cyclic acid anhydride structure at the terminal, excess Of which the terminal was made to have an isocyanate structure by reacting with the diisocyanate of, the terminal of which was made to react with an excess of diisothiocyanate to be an isothiocyanate structure, disulfinyl halide, disulphenyl halide, disulfonyl halide Reacting with each of them, the terminal of which has a sulfinyl halide, sulfenyl halide, sulfonyl halide structure, or a halide having an epoxy ring such as epihalohydrin, which has an epoxy structure of the terminal, and a double bond at the terminal Halogenated hydrocarbons having, for example Allyl halide, or carboxylic acid having a double bond at the terminal, for example, allyl acetic acid, to form a structure having a double bond at the terminal, and then oxidize this to form an epoxy ring structure, pentachloride Examples thereof include those treated with phosphorus to convert the mercapto group to halogen.

In the present invention, specific examples of the polythiourethane compound represented by the above formula (IV) include the following formula (IV
Examples thereof include compounds represented by -1) to (IV-4).

[Chemical 15] (In the formula, A ⁶ and RP have the same meanings as described above.)

The reaction between the reduced polyaniline and the polythiourethane compound represented by the above formula (IV) having a functional group (W ¹ , W ² ) which reacts with an aromatic secondary amine at both ends is carried out by the above-mentioned reduced type. To the amide-based solution of polyaniline, a polythiourethane compound having a functional group that reacts with an aromatic secondary amine at both ends or a solution obtained by dissolving it in an organic solvent is added, and under a nitrogen stream for 1 to 48 hours, -10 to -10. Stirring is continued in the temperature range of 80 ° C. If necessary, pyridine or a tertiary amine such as triethylamine or diethylaniline may be added to carry out the reaction. The reaction mixture is poured into alcohol or water and the polymer formed is precipitated. The polyaniline derivative of the present invention can be produced by further treating the obtained polymer with aqueous ammonia.

The terminal functional group is a carboxyl group (a).
In this case, the polyaniline derivative of the present invention can be obtained via the following route. To the amide-based solution of polythiourethane having a carboxyl group at both ends, N, N'-disubstituted carbodiimides having an equivalent amount or more to the terminal carboxyl group are added while cooling to -10 to 10 ° C, and the mixture is added for 1 to 4 hours. After continuing stirring at the temperature, the above reduced polyaniline was added, and while slowly returning to room temperature,
Continue stirring for 48 hours. The reaction mixture is poured into alcohol and the polymer formed is precipitated. By further treating the obtained polymer with aqueous ammonia, the polyaniline derivative of the present invention can be produced.

The N, N'-disubstituted carbodiimides used here have the following structural formula (V) R'-N = C = NR "(V) (wherein R'and R" are They may be the same or different, for example, methyl group, ethyl group, n-propyl group, i
-Propyl group, n-butyl group, t-butyl group, substituted or unsubstituted alkyl group such as 3-dimethylaminopropyl group, cyclic alkyl group such as cyclohexyl group, phenyl group, m-tolyl group, p-tolyl group, It represents a substituted or unsubstituted aryl group such as p-N, N-dimethylaminophenyl group, p-chlorophenyl group, p-nitrophenyl group and p-cyanophenyl group. ), More specifically, diethylcarbodiimide, diisopropylcarbodiimide, dicyclohexylcarbodiimide, diphenylcarbodiimide, di-p-tolylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide and the like. To be

Further, the carboxylic acid group at the terminal is converted into a haloformyl group, and the polyaniline derivative of the present invention can be produced by the above method. The conversion of the terminal carboxylic acid group to a haloformyl group is carried out by dicarboxylic acid which is a polythiourethane compound represented by the general formula (IV), ester of the dicarboxylic acid (lower alcohol ester such as methyl and ethyl) or dicarboxylic acid thereof. It can be easily carried out by the following method from the salt (alkali metal salt, ammonium salt, etc.).

That is, from dicarboxylic acid, an equivalent amount or more of an inorganic halogen compound such as phosphoryl chloride, thionyl chloride, phosphorus pentachloride or phosphorus trichloride is added to the dicarboxylic acid and reacted in an inert solvent such as benzene. A polythiourethane compound having haloformyl groups at both ends used in the present invention can be obtained. In this case, zinc chloride, pyridine, iodine, triethylamine or the like may be added as a catalyst. Also, from dicarboxylic acid, acid halides such as benzoyl chloride, phthalic acid chloride and oxalic acid chloride, α, α-dihalogenoethers, halogenated alkylamines, triphenylphosphine / Add organic halides such as organic phosphorus halides such as carbon tetrachloride, pyrocatetyl phosphotrichloride, diethylhalophosphochloride, triphenylhalophosphobromine and react in an inert solvent such as benzene and chlorobenzene. You can also get it.

From the dicarboxylic acid ester, a polythiourethane compound having haloformyl groups at both ends used in the present invention is prepared by using a complex of triphenylhalophosphohalide or its boron fluoride with respect to the dicarboxylic acid ester. Obtainable. From the dicarboxylic acid salt, a polythiourethane having a haloformyl group at both ends used in the present invention is prepared by using an inorganic halogen compound such as phosphoryl chloride or phosphorus pentachloride or a complex of thionyl chloride and dimethylformamide with respect to the dicarboxylic acid salt. The compound can be obtained. In addition to these, any method may be used as long as it is a reaction capable of converting a carboxylic acid group to a haloformyl group, thereby obtaining a polythiourethane compound having haloformyl groups at both ends used in the present invention. You can

As the amide solvent used in the present invention, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl- 2-
Examples include imidazolidinone.

The polyaniline derivative of the present invention does not change the length of the polyaniline main chain during its production. Further, the value of m / (n + m) can be controlled by oxidizing or reducing the obtained polyaniline derivative of the present invention. That is, when the polyaniline derivative of the present invention is oxidized using an oxidizing agent or electrochemically, m
When the polyaniline derivative of the present invention is reduced with a reducing agent or electrochemically, the value of m decreases. In addition, m / (n + m) is a peak (chemical shift 138) derived from a quinoid structure in a ¹³ C NMR spectrum.
ppm / TMS) and the peak derived from benzenoid (chemical shift 122 ppm / TMS).

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, or a halogenated hydrocarbon solvent such as chloroform, dichloroethane or dichloromethane. It can be dissolved or gelled in an ether solvent such as tetrahydrofuran, an amine solvent such as pyridine, and a polar solvent such as dimethyl sulfoxide. From this solution or gel it is possible to produce free standing films or fibers. Further, the processed product such as this film or fiber shows 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 when doping the aniline-based conductive polymer. Specific examples include halogen compounds such as iodine, bromine, chlorine and iodine trichloride, protic acids such as sulfuric acid, hydrochloric acid, nitric acid, perchloric acid and borofluoric acid, various salts of the protic acid, and aluminum trichloride. Lewis acid such as iron trichloride, molybdenum chloride, antimony chloride and arsenic pentafluoride, acetic acid, trifluoroacetic acid, benzenesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, camphor sulfonic acid and other organic acids, polyethylene Various compounds such as polymeric acids such as sulfonic acid, polyethylene carboxylic acid, polyacrylic acid and polystyrene sulfonic acid can be mentioned. The method of doping these compounds is not particularly limited, and any known method can be used. Generally, a derivative of polyaniline, a gel thereof or a molded product thereof and a 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 a solution of the above-mentioned protonic acid or its salt can be used.

[0034]

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 100 ml and cooled to -5 ° C. On the other hand, concentrated hydrochloric acid 2
1.9 g and 6.28 g of ammonium persulfate were dissolved in water to make 100 ml. After cooling this solution to -10 ° C, it was slowly added dropwise to the above aniline solution, and -10 ° C.
The stirring was continued for 6 hours. The thus obtained aniline oxidation polymer having a number average molecular weight of 12,000 (GPC, measured in a solvent of N-methyl-2-pyrrolidone, polystyrene equivalent number average molecular weight) was thoroughly washed with water, and then washed with aqueous ammonia. A dedoping process was performed. The soluble polyaniline thus obtained was dispersed in 200 ml of water, and the water content was 50 m under a nitrogen atmosphere.
1 hydrazine was added, stirring was continued at room temperature for 24 hours, filtered and dried to obtain an off-white reduced polyaniline (number average molecular weight 12,000, m + n = about 130). 1 g of the reduced polyaniline thus obtained was completely dissolved in 30 ml of N-methyl-2-pyrrolidone under a nitrogen stream.

On the other hand, a polythiourethane compound having an isocyanate group at both ends was synthesized as follows. Tetramethylene diisocyanate and hexane-1,
6-Dithiol was reacted at a molar ratio of 1.05: 1.00. The amount of terminal isocyanate groups was 2.01, and the number average molecular weight was 1,600. (W ¹ = W ² = NCO, A ³
_{= - (CH 2) 6 -NHCO-} , A 4 = -CONH-
(CH ₂ ) ₆ −) 0.878 g of this product was dissolved in N-methyl-2-pyrrolidone (NMP), and then the above amide solution of reduced polyaniline was added, and the mixture was slowly warmed to room temperature while adding 6 more. Stirring was continued for hours. The reaction mixture was poured into alcohol to precipitate the produced polymer. The obtained polymer was further treated with aqueous ammonia to obtain 2.01 g of the polyaniline derivative of the present invention.

The infrared absorption spectrum was measured and found to be 1690 cm ^-1 (C) due to the crosslinked structure of the above formula (II).
= O expansion / contraction), 1650 cm ^-1 (C = O expansion / contraction), 2850
Absorption of ˜2950 cm ⁻¹ (aliphatic C—H stretching) was observed. Furthermore, 1600, 1500, 1300, 117
An absorption pattern peculiar to the polyaniline represented by the general formula (I) was observed at 0,820 cm ^−1, and it was confirmed that the main chain had a polyaniline structure. From the reaction yield, the formula (II)
The number of nitrogen atoms involved in the crosslinked structure of was about 10% of the nitrogen atoms of polyaniline. In addition, m / (n + m) = 0.46 from the ¹³ C NMR spectrum. 1 g of the obtained polyaniline derivative was put into 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. Furthermore, when this film was dipped in a 20% aqueous hydrochloric acid solution for 24 hours and was then dried, the conductivity was 0.8 S / cm. Also, N
N-N-dimethylacetamide, N, N-dimethylformamide, pyridine, chloroform, dichloroethane, dichloromethane instead of methyl-2-pyrrolidone,
Similar gelation was possible using an organic solvent such as tetrahydrofuran.

Example 2 A polythiourethane compound having mercapto groups at both ends was synthesized as follows. Add octamethylene diisocyanate and hexane-1,6-dithiol to 1.0
The reaction was carried out at a molar ratio of 0: 1.50. The amount of terminal isocyanate groups was 0.01. This was reacted with trimellitic acid chloride chloride to obtain a polythiourethane compound having an acid anhydride structure at both ends. Number average molecular weight is 2100
Met. (W ¹ = W ² = carboxylic acid anhydride, A ³ =>
^{_{C 6 H 3 -CO-, A 4}} = -CO-C 6 H 3 <) takes this one 4.610G, reduced polyaniline 1g
Was added to a solution dissolved in 30 ml of N-methyl-2-pyrrolidone and reacted at 40 ° C. for 6 hours to obtain 5.312 g of the polyaniline derivative of the present invention.

The result of having measured an infrared absorption spectrum, 1690 cm due to the crosslinked structure of the above equation (II) ^-1 (ester C = O stretching), 1650 cm ^-1 (amide C = O stretch), 2850~2950cm ^{- 1} (Aliphatic C-H stretch)
Was observed to be absorbed. Furthermore, 1600, 1500, 1
Absorption patterns peculiar to the polyaniline represented by the general formula (I) were observed at 300, 1170 and 820 cm ^−1, and it was confirmed that the main chain had a polyaniline structure. From the reaction yield, the number of nitrogen atoms involved in the cross-linked structure of formula (II) is
It was about 38% of the nitrogen atoms of polyaniline. Also, ¹³
From the C NMR spectrum, it was m / (n + m) = 0.42. 1 g of the obtained polyaniline derivative was put into 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. Furthermore, when this film was dipped in a 20% aqueous hydrochloric acid solution for 24 hours and was then dried, the conductivity was 0.02 S / cm. 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. Met.

Example 3 A polythiourethane compound having mercapto groups at both ends was obtained from propylene dithiol and dicyclohexyl diisocyanate in the same manner as in Example 2. This was reacted with epichlorohydrin to obtain a polythiourethane compound having epoxy groups at both ends. The number average molecular weight was 2,200. (W ¹ = W ² = epoxy group, A ³ = A ⁴ = methylene group) 2.415 g of this product was taken, and 1 g of reduced polyaniline was used.
Was added to a solution dissolved in 30 ml of N-methyl-2-pyrrolidone and reacted at 40 ° C. for 8 hours to obtain 3.221 g of the polyaniline derivative of the present invention.

The result of having measured an infrared absorption spectrum, 1690 cm due to the crosslinked structure of the above equation (II) ^-1 (ester C = O stretching), 1650 cm ^-1 (amide C = O stretch), 2850~2950cm ^{- 1} (Aliphatic C-H stretch)
Was observed to be absorbed. Furthermore, 1600, 1500, 1
Absorption patterns peculiar to the polyaniline represented by the general formula (I) were observed at 300, 1170 and 820 cm ^−1, and it was confirmed that the main chain had a polyaniline structure. From the reaction yield, the number of nitrogen atoms involved in the cross-linked structure of formula (II) is
It was about 17% of the nitrogen atoms of polyaniline. Also, ¹³
From the C NMR spectrum, it was m / (n + m) = 0.47. 1 g of the obtained polyaniline derivative was put into 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. Furthermore, 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. 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.

Example 4 Octamethylene diisocyanate and hexane-1,6-
Reacting dithiol in a molar ratio of 1.00: 1.50,
It was treated with sodium hydride to react with 3-chloropropionic acid and then treated with phosphorus oxychloride to chloroformate the ends. The number average molecular weight was 1,900. (W ¹ = W ² = COCl, A ³ = A ⁴ = ethylene group) 0.209 g of this product is taken to give 1 g of reduced polyaniline.
Was added to a solution dissolved in 30 ml of N-methyl-2-pyrrolidone and reacted at 40 ° C. for 6 hours to obtain 1.202 g of the polyaniline derivative of the present invention.

The result of having measured an infrared absorption spectrum, 1690 cm due to the crosslinked structure of the above equation (II) ^-1 (ester C = O stretching), 1650 cm ^-1 (amide C = O stretch), 2850~2950cm ^{- 1} (Aliphatic C-H stretch)
Was observed to be absorbed. Furthermore, 1600, 1500, 1
Absorption patterns peculiar to the polyaniline represented by the general formula (I) were observed at 300, 1170 and 820 cm ^−1, and it was confirmed that the main chain had a polyaniline structure. From the reaction yield, the number of nitrogen atoms involved in the cross-linked structure of formula (II) is
It was about 2% of the nitrogen atoms of polyaniline. Also, ¹³ C
From the NMR spectrum, it was m / (n + m) = 0.48. 1 g of the obtained polyaniline derivative was added to N-methyl-
Put it in 5 g of 2-pyrrolidone, dissolve by stirring at room temperature,
It was possible to make a film by casting. Furthermore, when this film was dipped in a 20% aqueous hydrochloric acid solution for 24 hours and was then dried, the conductivity was 1.2 S / cm.
Further, instead of N-methyl-2-pyrrolidone, N, N-
Similar processing was possible using an organic solvent such as dimethylacetamide, N, N-dimethylformamide, pyridine, chloroform, dichloroethane, dichloromethane and tetrahydrofuran.

Example 5 Octamethylene diisocyanate was reacted with hexane 1,6-dithiol in a molar ratio of 1.00: 1.50, and this was reacted with benzenedisulfonyl chloride to form a sulfonyl chloride at the terminal. . Number average molecular weight is 2150
Met. ^{(W 1 = W 2 = SO} 2 Cl, A 3 = -C 6 H
^{_{4 -SO 2 -, A 4 =}} -SO 2 -C 6 H 4 -) takes this one 1.180 g, reduced polyaniline 1g
Was added to a solution dissolved in 30 ml of N-methyl-2-pyrrolidone and reacted at 40 ° C. for 6 hours to obtain 2.012 g of the polyaniline derivative of the present invention.

When the infrared absorption spectrum was measured, it was found to be 1690 cm ^-1 (ester C = O stretching), 1351 cm ^-1 and 1176c due to the cross-linking structure of the formula (II).
m ^-1 (S (= O) ₂ expansion and contraction), 2850 to 2950 cm ^-1
Absorption of (aliphatic C-H stretch) was observed. Furthermore, 1
600, 1500, 1300, 1170, 820 cm ^-1
The absorption pattern peculiar to the polyaniline represented by the general formula (I) was observed in and it was confirmed that the main chain had a polyaniline structure. From the reaction yield, the number of nitrogen atoms involved in the crosslinked structure of the formula (II) is about 10 of the nitrogen atoms of polyaniline.
%Met. In addition, from the ¹³ C NMR spectrum, m /
(N + m) = 0.49. 1 g of the obtained polyaniline derivative was added to 5 g of N-methyl-2-pyrrolidone,
It melted when stirred at room temperature and could be formed into a film by casting. Furthermore, when this film was dipped in a 20% aqueous hydrochloric acid solution for 24 hours and was then dried, the conductivity was 0.2 S / cm. Further, instead of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N,
N-dimethylformamide, pyridine, chloroform,
Similar processing was possible using an organic solvent such as dichloroethane, dichloromethane or tetrahydrofuran.

Example 6 In the same manner as in Example 1, a polythiourethane compound having an isocyanate group at both ends was synthesized from 1,6-hexanedithiol and lysine diisocyanate. The number average molecular weight was 2,100. (W ¹ = W ² = NCO, A
_{^{3 = - (CH 2) 4}} CH (COOCH 3) NHCO-,
_{^{A 4 = -CONHCH (COOCH 3)}} (CH 2)
₄ −) 1.152 g of this product is taken, and 1 g of reduced polyaniline is used.
Was added to a solution dissolved in 30 ml of N-methyl-2-pyrrolidone and reacted at 40 ° C. for 6 hours to obtain 2.112 g of the polyaniline derivative of the present invention.

The result of having measured an infrared absorption spectrum, 1690 cm due to the crosslinked structure of the above equation (II) ^-1 (ester C = O stretching), 1650 cm ^-1 (amide C = O stretch), 2850~2950cm ^{- 1} (Aliphatic C-H stretch)
Was observed to be absorbed. Furthermore, 1600, 1500, 1
Absorption patterns peculiar to the polyaniline represented by the general formula (I) were observed at 300, 1170 and 820 cm ^−1, and it was confirmed that the main chain had a polyaniline structure. From the reaction yield, the number of nitrogen atoms involved in the cross-linked structure of formula (II) is
It was about 10% of the nitrogen atoms of polyaniline. Also, ¹³
From the C NMR spectrum, it was m / (n + m) = 0.47. 1 g of the obtained polyaniline derivative was put into 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. Furthermore, when this film was dipped in a 20% aqueous hydrochloric acid solution for 24 hours and was then dried, the conductivity was 0.8 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.

[0047]

INDUSTRIAL APPLICABILITY The polyaniline derivative of the present invention is soluble in various organic solvents or can be gelled, can be easily processed, and can be molded into a flexible self-supporting film or fiber. You can get the goods. Since these molded products show high conductivity by doping, the polyaniline derivative of the present invention is very useful for various applications such as electronic materials and conductive materials.

Claims (2)

[Claims] 1. The following formula (I): (In the formula, m and n mean integers of 0 or more, and m / (n
+ M) = 0 to 1, m + n = 10 to 5000. ) The number average molecular weight of the structural unit represented by
The main chain is made of polyaniline of 0,000, and the main chain is represented by the following formula (II): [In the formula, RP represents a polythiourethane chain having a number average molecular weight of 220 to 100,000 represented by the following formula (III), and (In the formula, RP ¹ represents a divalent non-aromatic hydrocarbon group having 1 to 30 carbon atoms, and PR ² represents a divalent non-aromatic hydrocarbon group having 1 to 30 carbon atoms or a halogen or alkoxy thereof. Represents a carbonyl substituent, and k represents an integer of ¹ to 500.) A ¹ represents a linking group selected from the following formulas (1) to (11): (In the formula, R is a direct bond, a divalent hydrocarbon group having 1 to 30 carbon atoms, or a halogen or —COOM substitution product thereof (wherein M is a hydrogen atom, Li, Na, K, Cs, Rb or NH _4). X represents an oxygen atom or a sulfur atom, Y represents an oxygen atom, a sulfur atom or NH, and B represents a hydrocarbon group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms. , RP ² has the same meaning as described above, and p means an integer of 0 to 2), A ²
Represents a linking group selected from the following formulas (1 ′) to (11 ′), and (In the formula, R, X, Y, B, RP ² and p have the same meanings as described above.) Represents a group selected from the group consisting of: ] The number of the nitrogen atom which forms the bridge | crosslinking structure shown by these, and the number of nitrogen atoms which participate in this bridge | crosslinking structure is 0.01-50% of the nitrogen atom of the polyaniline of a main chain, The polyaniline derivative characterized by the above-mentioned. 2. A soluble aniline polymer obtained by treating an aniline-oxidized polymer with ammonia is treated with an excess of hydrazine to have a number average molecular weight of 2,000 to about 1 imino-1,4-phenylene as a structural unit. 500,000 reduced polyaniline was produced, and then the following formula (IV) W ¹ -A ³ -RP-A ⁴ -W ² (IV) [wherein W ¹ and W ² are respectively represented by the following formula (a ) ~
Representing a functional group selected from (h), (In the formula, Hal represents a halogen atom, and X, Y, B
And p have the same meaning as described above. ), A ³ is a direct bond, a divalent hydrocarbon group having 1 to 30 carbon atoms or a halogen substitution product thereof, -R-C (= X)-, -R-NH-C (=
X)-, -R-SO _p- , -RP ¹ -SCONH-RP
² -NHCO- or -RP ² -NHCO- (However,
R, X, RP ¹ , RP ² and p have the same meaning as described above. ) Represents, A ⁴ is a direct bond, a divalent hydrocarbon group or a halogen-substituted derivatives having 1 to 30 carbon atoms, -C (=
X) -R -, - C ( = X) -NH-R -, - SO p -R
^{-, - CONH-RP 2 -NHCOS} -RP 1 - or -CONH-RP ² - (provided ^{that, R, X, RP 1,} RP
² and p have the same meaning as above. ), Where W ¹ and W ² represent an intramolecular carboxylic acid anhydride group of formula (c), A ³ and A ⁴ are each> R.
^1- C (= O)-or -C (= O) -R ¹ <(wherein R ¹ represents a trivalent hydrocarbon group having 1 to 30 carbon atoms), and RP represents the above. Have the same meaning. ] It reacts with the polythiourethane compound which has the functional group which reacts with an aromatic secondary amine shown by these both ends, The manufacturing method of the polyaniline derivative of Claim 1 characterized by the above-mentioned.