JPH06220191A - Polyaniline derivative and its production - Google Patents

Abstract

PURPOSE:To obtain the subject derivative providing a self-supporting film showing flexibility, soluble in an organic solvent or capable of being gelatinized, by reacting a reduction type polyaniline with a specific polythiourea compound. CONSTITUTION:First, an aniline oxidation polymer is treated with ammonia to give a soluble aniline polymer, which is treated with an excessive amount of hydrazine to give a reduction type polyaniline having an imino-1,4-phenylene unit and 2,000500,000 number-average molecular weight. Then the reduction type polyaniline is reacted with a polythiourea compound of formula I [W1 and W2 are halogen or XCN (X is S or O), etc.; A<3> is direct bond and 1-30C bifunctional hydrocarbon; A<4> is direct bond, 1-30C halogen-substituted bifunctional hydrocarbon, etc.; RP is polythiourea of formula II (RP<1> and RP<2> are 1-30C bifunctional nonaromatic hydrocarbon, its halogen-substituted group, etc.; (k) is 1-500)] containing functional groups to be reacted with an aromatic secondary amine at both ends, having 100-100,000 number-average molecular weight to give the objective derivative comprising a polyaniline of formula III as a main chain, having a crosslinking structure of formula IV (A1 and A2 are direct bond, etc.).

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]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventor reacted reduced polyaniline with a polyurethane compound having a functional group capable of reacting with an aromatic secondary amine at both ends. Thus, it was found that a polyaniline derivative having a crosslinked structure, capable of being soluble or gelled in an organic solvent, and capable of forming a flexible self-supporting film is obtained, and the present invention is completed. I arrived.

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
0000 polyaniline as the main chain, and the main chain is represented by the following formula (II)

[Chemical 8]

[Wherein RP represents a polythiourea chain having an average molecular weight of 100 to 100,000 represented by the following formula (III),

[Chemical 9] (In the formula, RP ¹ and RP ² represent a divalent non-aromatic hydrocarbon group having 1 to 30 carbon atoms or a halogen or alkoxycarbonyl substitution product thereof, and k represents an integer of 1 to 500). ¹ represents a linking group selected from the following formulas (1) to (10),

[0008]

[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 above, p means an integer of 0 to 2, and A ² represents a linking group selected from the following formulas (1 ′) to (10 ′),

[0009]

[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.
A reduced polyaniline having imino-1,4-phenylene as a structural unit and having a number average molecular weight of 2000 to 500000 was produced, and then the following formula (IV) W ¹ -A ³ -RP-A ⁴ -W ² (IV)

[Wherein W ¹ and W ² each represent a functional group selected from the following formulas (a) to (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 substitution product thereof, -R-C (= X)-, -R-NH-C (=
X) -, - R-SO p - or -RP ² -NHCS-
(However, R, X, RP ² and p have the same meanings as described above.), A ⁴ is a direct bond, and has 1 to 30 carbon atoms.
Divalent hydrocarbon group or halogen-substituted product thereof, -C
(= X) -R -, - C (= X) -NH-R -, - SO p
-R- or -CSNH-RP ² - (provided that, R, X,
RP ² and p have the same meaning as described above. ),
However, when W ¹ and W ² represent the intramolecular carbomonoanhydride group of the formula (c), A ³ and A ⁴ are respectively> 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 has the same meaning as described above. ] It is characterized by reacting with a polythiourea 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 (10), and the linking group A ² is represented by the formulas (1 ') to (). 10 '), 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] In the formula, RP ¹ and RP ² are linear or branched aliphatic groups such as methylene, ethylene, trimethylene, hexamethylene, decamethylene, propylene and cyclohexylene. Hydrocarbon group or alicyclic hydrocarbon group,
It represents a divalent non-aromatic hydrocarbon group having 1 to 30 carbon atoms or a halogen or alkoxycarbonyl substitution product thereof, and specifically, the following can be exemplified.

For example, a polymer of trimethylenediamine and ethylenediisothiocyanate, a polymer of trimethylenediamine and trimethylenediisothiocyanate, a polymer of trimethylenediamine and tetramethylenediisothiocyanate, Polymers of methylene diamine and hexamethylene diisothiocyanate, polymers of trimethylene diamine and octamethylene diisothiocyanate, polymers of tetramethylene diamine and ethylene diisothiocyanate, tetramethylene diamine and trimethylene di Polymer with isothiocyanate, polymer with tetramethylenediamine and tetramethylenediisothiocyanate, polymer with tetramethylenediamine and hexamethylenediisothiocyanate, tetramethylenediamine and octamethylenediii Polymers of thiocyanate, polymers of pentamethylene diamine and tetramethylene diisothiocyanate, polymers of pentamethylene diamine and pentamethylene diisothiocyanate, polymers of hexamethylene diamine and ethylene diisothiocyanate,
Polymers of hexamethylenediamine and trimethylenediisothiocyanate, polymers of hexamethylenediamine and tetramethylenediisothiocyanate, polymers of hexamethylenediamine and hexamethylenediisothiocyanate, hexamethylenediamine and octa Polymer with methylenediisothiocyanate, polymer with hexamethylenediamine and decamethylenediisothiocyanate, polymer with heptamethylenediamine and heptamethylenediisothiocyanate, octamethylenediamine and octamethylenediisothiocyanate , A polymer of nonamethylenediamine and nonamethylenediisothiocyanate, a polymer of decamethylenediamine and decamethylenediisothiocyanate, undecamethylenediamine and undecamethylenediiso It can be exemplified polythiourea oligomer of the polymer such as the Oshianato.

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.
Represents alkylene of 8 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 to give a number average molecular weight of 2000 to 5 having an imino-1,4-phenylene structure as a structural unit.
A reduced polyaniline of 00000 [measured with GPC (N-methyl-2-pyrrolidone solvent), polystyrene-equivalent number average molecular weight] is obtained. The hydrazine treatment is carried out by dispersing a soluble polyaniline in water or methanol, adding hydrazine in an amount equal to or more than the nitrogen atom in the polyaniline, preferably 3 times or more under a nitrogen atmosphere, for 24 hours or more,
It is performed by stirring at 0 to 30 ° C. The reduced polyaniline is typically n = 0 in the formula (I), but is oxidized by a small amount of oxygen present in the atmosphere during the above reaction or by being exposed to air after the reaction. In some cases, m: n may approach 1: 1.

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 2000, it becomes difficult to obtain a flexible self-supporting film or fiber from the finally formed polyaniline derivative. On the other hand, 500000
If it exceeds, the solubility or swelling property 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 the reduced polyaniline, polythiourea having functional groups (W ¹ ) (W ² ) which react with an aromatic secondary amine at both ends, represented by the above formula (IV), is used. The main point of the present invention in which the compound is used is to cross-link the polyaniline main chain with a cross-linking chain composed of a suitable polythiourea, and the connecting portion between the cross-linking chain and the polyaniline main chain, that is, A ¹ and A ² The structure 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. On the other hand, when the polythiourea chain is made of an aromatic hydrocarbon, the degree of freedom of the crosslinked chain can be increased, and the solubility and the swelling property can be imparted. Further, by using polythiourea as the cross-linked chain, the stability of the cross-linked product at the time of doping can be expected more than in the case of having the urea-based cross-linked chain.

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

Examples of the polythiourea 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, isothiocyanate at both ends condensed with excess diisothiocyanate component. Polythiourea compound having a nato group, and converting the terminal amino group of a polythiourea compound having an amino group at both ends obtained by condensation with an excess of a diamine component into a functional group capable of reacting with an aromatic secondary amine. A polythiourea compound obtained by
Alternatively, a polythiourea compound obtained by converting an isothiocyanate group and an amino group at both ends of a polythiourea compound obtained by condensation of an approximately equivalent amount of diamine and diisothiocyanate into a functional group capable of reacting with an aromatic secondary amine. Examples thereof include urea compounds.

For example, the following compounds may be mentioned. A polythiourea compound condensed with excess diamine component is used as a starting material, and its terminal amino group is reacted with trimellitic anhydride or halogenated trimellitic anhydride to form a cyclic acid anhydride structure at the terminal, Those having an isocyanate structure at the end by reaction with diisocyanate, those having an isothiocyanate structure at the end by reacting with excess diisothiocyanate, disulfinyl halide,
It is reacted with each of disulphenyl halide, disulfonyl halide, and dihalide, and is reacted with a sulfinyl halide, sulfenyl halide, sulfonyl halide, or halide structure having an epoxy ring-containing halide such as epihalohydrin. The end of which has an epoxy structure, a halogenated hydrocarbon having a double bond at the end, for example, an allyl halide, or a carboxylic acid having a double bond at the end, for example, allyl acetic acid, Examples thereof include a structure having a double bond, which is then oxidized to an epoxy ring structure, a structure which is treated with phosgene to convert an amino group into an isocyanate group, and the like.

In the present invention, specific examples of the polythiourea compound represented by the above formula (IV) include the following formula (IV-
The compounds represented by 1) to (IV-4) can be exemplified.

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

The reaction between the reduced polyaniline and the polythiourea 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 polyaniline. To the amide-based solution, the polythiourea 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 the mixture is mixed under a nitrogen stream for 1 to 48 hours at -10 to 80 ° C. Continue stirring at the temperature range of. 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 an amide-based solution of polythiourea having carboxyl groups at both ends, N, N'-disubstituted carbodiimides in an amount equal to or more than the terminal carboxyl groups are added while cooling to -10 to 10 ° C, and the temperature is kept for 1 to 4 hours. After continuing stirring at 1, the above reduced polyaniline is added, and the stirring is continued for 1 to 48 hours while slowly returning to room temperature. 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
-Substituted or unsubstituted alkyl group such as propyl group, n-butyl group, t-butyl group and 3-dimethylaminopropyl group, cyclic alkyl group such as cyclohexyl group, phenyl group, p-tolyl group, p-N, N -Dimethylaminophenyl group, p-chlorophenyl group, p-nitrophenyl group,
It represents a substituted or unsubstituted aryl group such as p-cyanophenyl group. ), More specifically, diethylcarbodiimide, diisopropylcarbodiimide, dicyclohexylcarbodiimide, diphenylcarbodiimide, di-p-tolylcarbodiimide, 1-
Examples include ethyl-3- (3-dimethylaminopropyl) carbodiimide and the like.

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. This conversion of the terminal carboxylic acid group to a haloformyl group is carried out by converting the dicarboxylic acid which is the polythiourea compound represented by the general formula (IV), the ester of the dicarboxylic acid (lower alcohol ester such as methyl and ethyl) or the dicarboxylic acid thereof. It can be easily carried out from a salt (alkali metal salt, ammonium salt, etc.) by the following method.

That is, from dicarboxylic acid, an equivalent amount or more of an inorganic halogen compound such as phosphoryl chloride, thionyl chloride, phosphorus pentachloride, phosphorus trichloride is added to the dicarboxylic acid and reacted in an inert solvent such as benzene. A polythiourea 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 / Carbon tetrachloride, pyrocatekyl phosphotrichloride,
It can also be obtained by adding an organic halide such as an organic phosphorus halide such as diethylhalophosphochloride or triphenylhalophosphobromine and reacting it in an inert solvent such as benzene or chlorobenzene.

From the dicarboxylic acid ester, a polythiourea compound having haloformyl groups at both ends used in the present invention is obtained by using a triphenylhalophosphohalide or a complex thereof with boron fluoride for the dicarboxylic acid ester. be able to. From the dicarboxylate,
For the dicarboxylic acid salt, an inorganic halogen compound such as phosphoryl chloride or phosphorus pentachloride or a complex of thionyl chloride and dimethylformamide can be used to obtain a polythiourea compound having haloformyl groups at both ends used in the present invention. 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, whereby a polythiourea compound having haloformyl groups at both ends used in the present invention can be obtained. it 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 thereof include halogen compounds such as iodine, bromine, chlorine and iodine trichloride, sulfuric acid, hydrochloric acid, nitric acid, perchlorates, protic acids such as borofluoric acid, various salts of the above protic acids, and trichloride. Aluminum, iron trichloride, molybdenum chloride, antimony chloride, arsenic pentafluoride and other Lewis acids, acetic acid, trifluoroacetic acid, benzene sulfonic acid, p-toluene sulfonic acid and other organic acids, polyethylene sulfonic acid, polyethylene carboxylic acid, polyacrylic Examples thereof include various compounds such as acids and polymer acids such as polystyrene sulfonic acid. 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-oxidized polymer having a number average molecular weight of 12000 (measured in GPC, N-methyl-2-pyrrolidone solvent, polystyrene equivalent number average molecular weight) was thoroughly washed with water, and then dedoped with aqueous ammonia. Processed. Disperse the obtained soluble polyaniline in 200 ml of water, and in a nitrogen atmosphere 50 ml
Hydrazine was added, and stirring was continued at room temperature for 24 hours, filtered and dried to obtain an off-white reduced polyaniline (number average molecular weight 12000, 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 polythiourea compound having an isothiocyanate group at both ends was synthesized as follows. Hexamethylene diisothiocyanate and decamethylene diamine were reacted at a molar ratio of 1.05: 1.00. The amount of terminal isothiocyanate group was 2.01, and the average molecular weight was 2,550. (W ¹ = W ² = NCS, A ³
_{= - (CH 2) 6 -NHCS-} , A 4 = -CSNH-
(CH ₂ ) ₆ −) 1.399 g of this product was added to N-methyl-
After dissolving in 2-pyrrolidone (NMP), the amide solution of the reduced polyaniline was added, and the mixture was stirred for 8 hours while slowly returning to room temperature. The reaction mixture was poured into alcohol to precipitate the produced polymer. The obtained polymer was further treated with aqueous ammonia to obtain 2.256 g of the polyaniline derivative of the present invention.

The infrared absorption spectrum was measured and found to be 1350 cm ^-1 (-due to the crosslinked structure of the above-mentioned formula (II).
NH-CS-NH-structure), 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 9% of the nitrogen atoms of polyaniline.
Met. In addition, from the ¹³ C NMR spectrum, m / (n
+ M) = 0.48. 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,
Similar gelation was possible using an organic solvent such as dichloroethane, dichloromethane and tetrahydrofuran.

Example 2 For a polythiourea compound having amino groups at both ends, octamethylene diisothiocyanate synthesized as follows and tetramethylene diamine were reacted at a molar ratio of 1.00: 1.50. . The amount of terminal isothiocyanate groups was 0.01, and the average molecular weight was 2720. This was reacted with trimellitic anhydride chloride to obtain a polythiourea compound having an acid anhydride structure at both ends. The average molecular weight was 3020. (W ¹ = W ² = carboxylic acid _{^{anhydride, A 3 => C 6 H}} 3 -CO-, A 4 = -CO-C 6 H
₃ <) 6.629 g of this product was taken and added to a solution of 1 g of reduced polyaniline dissolved in 30 ml of N-methyl-2-pyrrolidone and reacted at 40 ° C. for 6 hours to obtain 7.452 g of the polyaniline derivative of the present invention. It was

The infrared absorption spectrum was measured and found to be 1360 cm ^-1 (-due to the crosslinked structure of the formula (II).
NH-CS-NH-structure), 1650 cm ^-1 (amide C
= O expansion and contraction), 2850 to 2950 cm ^-1 (aliphatic C-H)
(Stretching) was observed. Furthermore, 1600, 150
General formula (I) at ⁰ , 1300, 1170, 820 cm ^-1
The absorption pattern peculiar to polyaniline shown by was observed, 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 formula (II) was about 39% of the nitrogen atoms of polyaniline.
Further, from the ¹³ C NMR spectrum, m / (n + m) =
It was 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, this film is placed in a 20% hydrochloric acid aqueous solution for 24 hours.
When it was dipped for a period of time and dried, the conductivity was 0.00
It was 9 S / cm. Further, instead of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N
-Similar gelation was possible using an organic solvent such as dimethylformamide, pyridine, chloroform, dichloroethane, dichloromethane and tetrahydrofuran.

Example 3 A polythiourea compound having amino groups at both ends was obtained from decamethylenediamine and dicyclohexyldiisothiocyanate in the same manner as in Example 2. This was reacted with epichlorohydrin to obtain a polythiourea compound having epoxy groups at both ends. The average molecular weight was 3100. (W ¹ = W ² = epoxy group, A ³ =
A ⁴ = methylene group) 3.402 g of this product was taken, and 1 g of reduced polyaniline was added to N-methyl-2-pyrrolidone 30.
It was added to a solution dissolved in ml and reacted at 40 ° C. for 8 hours to obtain 4.233 g of the polyaniline derivative of the present invention.

The infrared absorption spectrum was measured and found to be 1340 cm ^-1 (-due to the crosslinked structure of the formula (II).
NH-CS-NH-structure), 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 cross-linked structure of the formula (II) is about 19 of the nitrogen atoms of polyaniline.
%Met. In addition, from the ¹³ C NMR spectrum, m /
(N + m) = 0.47. 1 g of the obtained polyaniline derivative was added to 5 g of N-methyl-2-pyrrolidone,
When the mixture was stirred at room temperature, it gelated and 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. 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.

Example 4 A polythiourea compound having amino groups at both ends, which was synthesized from nonamethylenediamine and nonamethylenediisothiocyanate in the same manner as in Example 2, was reacted with succinic anhydride and then phosphorus oxychloride. And the end was chloroformylated. The average molecular weight was 1950. ^{(W 1 = W 2 = COCl} , A 3 = -C (= O) CH
^{_{2 CH 2 -, A 4 =}} -CH 2 CH 2 C (= O) -) takes this one 0.214 g, the reduced polyaniline 1 g N
-Methyl-2-pyrrolidone was added to a solution dissolved in 30 ml and reacted at 40 ° C for 6 hours to obtain 1.193 g of the polyaniline derivative of the present invention.

The infrared absorption spectrum was measured and found to be 1360 cm ^-1 (-due to the crosslinked structure of the above-mentioned formula (II).
NH-CS-NH-structure), 1650 cm ^-1 (amide C
= O expansion and contraction), 2850 to 2950 cm ^-1 (aliphatic C-H)
(Stretching) was observed. Furthermore, 1600, 150
General formula (I) at ⁰ , 1300, 1170, 820 cm ^-1
The absorption pattern peculiar to polyaniline shown by was observed, 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 formula (II) was about 2% of the nitrogen atoms of polyaniline. Further, from the ¹³ C NMR spectrum, m / (n + m) = 0.
It was 48. 1 g of the obtained polyaniline derivative was N-
When placed in 5 g of methyl-2-pyrrolidone and stirred at room temperature, it gelated, and it was possible to form a film by spinning or stretching. Further, when this film was dipped in a 20% hydrochloric acid aqueous solution for 24 hours and was then dried, the conductivity was 1.5 S /
It was cm. Similar gelation is also possible 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 A polythiourea compound having amino groups at both ends was synthesized as follows. That is, 1.30: nonamethylene diisothiocyanate and undecamethylene diamine:
The reaction was carried out at a molar ratio of 1.00. The amount of terminal isothiocyanate groups was 0.01, and the average molecular weight was 2500. The polythiourea having amino groups at both ends was reacted with benzenedisulfonyl chloride to convert the ends into sulfonyl chloride groups. The average molecular weight was 3140. ^{(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 1.713G, added to a solution of reduced polyaniline 1g of N- methyl-2-pyrrolidone 30 ml,
The reaction was carried out at 40 ° C. for 6 hours to obtain 2.601 g of the polyaniline derivative of the present invention.

The infrared absorption spectrum was measured and found to be 1360 cm ^-1 (-due to the cross-linked structure of the above formula (II).
NH-CS-NH-structure), 1351 cm ^-1 and 11
76 cm ^-1 (S (= O) ₂ expansion / contraction), 2850-2950
Absorption of cm ^-1 (aliphatic C-H stretch) was observed. Further, 1600, 1500, 1300, 1170, 820
An absorption pattern peculiar to the polyaniline represented by the general formula (I) was observed at 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 crosslinked structure of formula (II) was about 10% of the nitrogen atoms of polyaniline. In addition, m / (n + m) = 0.49 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, this film is 20%
When it was dipped in a hydrochloric acid solution for 24 hours and then dried,
The conductivity was 0.07 S / cm. Similar gelation is also possible 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 6 A polythiourea compound having amino groups at both ends was synthesized as follows. That is, 1.30 of decamethylenediamine and decamethylenediisothiocyanate:
The reaction was carried out at a molar ratio of 1.00. The amount of terminal amino groups was 2.01, and the average molecular weight was 1950. This polythiourea having amino groups at both ends was reacted with trimellitic anhydride chloride to obtain a polythiourea compound having an acid anhydride structure at both ends. The average molecular weight was 2250. (W ¹ = W ² = carboxylic acid anhydride, A ³ => C _{6
^{H 3 -CO-, A 4 = -CO}} -C 6 H 3 <) takes this one 6.174G, added to a solution of reduced polyaniline 1g of N- methyl-2-pyrrolidone 30 ml,
The reaction was carried out for 16 hours at 40 ° C. to obtain 7.182 g of the polyaniline derivative of the present invention.

The infrared absorption spectrum was measured and found to be 1340 cm ^-1 (-due to the crosslinked structure of the formula (II).
NH-CS-NH-structure), 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 50 of the nitrogen atoms of polyaniline.
%Met. In addition, from the ¹³ C NMR spectrum, m /
(N + m) = 0.41. 1 g of the obtained polyaniline derivative was added to 5 g of N-methyl-2-pyrrolidone,
When the mixture was stirred at room temperature, it gelated and 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 0.01 S / cm. Also, N-methyl-2
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 -pyrrolidone.

Example 7 In the same manner as in Example 1, a polythiourea compound having an isothiocyanate group at both ends was synthesized from 1,6-hexanediamine and lysine diisothiocyanate. The average molecular weight was 2050. (W ¹ = W ² = NCS, A
_{^{3 = - (CH 2) 4}} CH (COOCH 3) NHCS-,
_{^{A 4 = -CSNHCH (COOCH 3)}} (CH 2)
₄ -) takes this one 1.125 g, added to a solution of reduced polyaniline 1g of N- methyl-2-pyrrolidone 30 ml, and reacted for 6 hours 40 ° C., to obtain a polyaniline derivative 2.101g of the present invention It was

The infrared absorption spectrum was measured and found to be 1360 cm ^-1 (-due to the crosslinked structure of the above-mentioned formula (II).
NH-CS-NH-structure), 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) = 0.47. 1 g of the obtained polyaniline derivative was added to 5 g of N-methyl-2-pyrrolidone,
When the mixture was stirred at room temperature, it gelated and 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 doped and dried, the conductivity was 1.7 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.

[0049]

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.

[Procedure amendment]

[Submission date] March 22, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

[Correction content]

[Chemical 1] (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
0000 polyaniline as the main chain, and the main chain is represented by the following formula (II)

[Chemical 2] [Wherein, RP is an average molecular weight 1 represented by the following formula (III):
Represents a polythiourea chain of 0-100,000,

[Chemical 3] (In the formula, RP ¹ and RP ² represent a divalent non-aromatic hydrocarbon group having 1 to 30 carbon atoms or a halogen or alkoxycarbonyl substitution product thereof, and k represents an integer of 1 to 500). ¹ represents a linking group selected from the following formulas (1) to (10),

[Chemical 4] (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 (10 ′),

[Chemical 5] (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.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction content]

[0009]

[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.

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 polyaniline of 0000, and the main chain is represented by the following formula (II): [Wherein, RP is an average molecular weight 1 represented by the following formula (III):
Representing a polythiourea chain of 0-100,000, (In the formula, RP ¹ and RP ² represent a divalent non-aromatic hydrocarbon group having 1 to 30 carbon atoms or a halogen or alkoxycarbonyl substitution product thereof, and k represents an integer of 1 to 500). ¹ represents a linking group selected from the following formulas (1) to (10), and (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 (10 ′), 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 500,000 having imino-1,4-phenylene as a structural unit. A reduced polyaniline is 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 formulas (a) to
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 - or -RP ² -NHCS-
(However, R, X, RP ² and p have the same meanings as described above.), A ⁴ is a direct bond, and has 1 to 30 carbon atoms.
Divalent hydrocarbon group or halogen-substituted product thereof, -C
(= X) -R -, - C (= X) -NH-R -, - SO p
-R- or -CSNH-RP ² - (provided that, R, X,
RP ² and p have the same meaning as described above. ),
However, when W ¹ and W ² represent an intramolecular carboxylic acid anhydride group of the formula (c), A ³ and A ⁴ are respectively> R ¹ -C (= O)-or -C (= O). Represents -R ¹ <(wherein R ¹ represents a trivalent hydrocarbon group having 1 to 30 carbon atoms), and RP has the same meaning as described above. ] It is made to react with the polythiourea compound which has a functional group which reacts with an aromatic secondary amine shown in both ends, and the manufacturing method of the polyaniline derivative of Claim 1 characterized by the above-mentioned.