JP2683996B2 - Polyaniline derivative and method for producing the same - Google Patents

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 can form a flexible 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 as a battery electrode material, an antistatic material,
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, and various terminal devices, is being studied. However, polyaniline generally has a highly developed π-conjugated system, so the polymer main chain is rigid, the interaction between molecular chains is strong, and there are many strong hydrogen bonds between molecular chains. Since they are almost insoluble in organic solvents and do not melt even when heated, they have a major drawback that they have poor moldability and cannot be processed into films or the like.

For this purpose, for example, fibers of a polymer material,
A monomer having a desired shape such as a porous body is impregnated with the monomer,
The 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 form a similar composite material. I was getting it. On the other hand, by devising the polymerization catalyst and the reaction temperature, 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. In addition, polyaniline derivatives soluble in organic solvents have been synthesized utilizing various aniline derivatives, but a film having sufficient flexibility could not be obtained. On the other hand, it is known that a polymer compound can be processed using a technique such as gel stretching, gel spinning, or gel formation if gelation is possible.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances 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 has found that reduced polyaniline and a reactive polyamide 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):

Embedded image (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)

Embedded image

[Wherein, RP represents a polyamide chain represented by the following formula (III) and having an average molecular weight of 200 to 100,000,

Embedded image (In the formula, RP ¹ represents an alkylene group having 1 to 10 carbon atoms, and RP ² has an ether or polyether structure.
Carbon consisting of alkylene group and / or phenylene group
It represents a divalent group of the number 2 to 60, and k represents an integer of 1 to 500. ) A ¹ represents a linking group selected from the following formulas (1) to (4) ,

[0008]

Embedded image (In the formula, R is the number of carbon atoms which may have an ether bond.
1-10 alkylene groups, phenylene groups or -C thereof
Represents an OOH-substituted product or a polyoxyethylene group
You . ) A ² is to Table Wa selected linking groups from the following formula (1 ') to (4').

[0009]

Embedded image (Wherein R has the same meaning as described above.)], And the number of nitrogen atoms involved in the crosslinked structure is 0.01 of the nitrogen atoms of the main chain polyaniline.
５０50%. The above general formula
(I) is not a monomer representing a block copolymer, but a polymer
Nylene diamine structural unit (in the brackets on the left side of the formula (I)
Formula) and quinonediimine structural unit (right parenthesis of formula (I)
Is random within the range of n and m, respectively.
Means polyaniline with random structure bound to
You.

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 (f) ,

Embedded image (Wherein, Hal is Wath. Table halogen atom) A ³ is
Methylene group, -R-C (= O)-, -R-NH-C (=
O)-or -R-SO _2- (where R is as defined above)
Have righteousness. ) , A ⁴ is a methylene group, —C
(= O) -R-, -C (= O) -NH-R- or -S
O ₂ —R— (where R has the same meaning as defined above) , provided that W ¹ and W ² represent an intramolecular carboxylic acid anhydride group of formula (c), A ³ and A ⁴ is
> R ¹ -C (= O)-or -C (= O) -R respectively
¹ <(wherein R ¹ represents a benzene ring ), and RP has the same meaning as described above . ] It reacts with the polyamide compound which has the functional group which reacts with an aromatic secondary amine shown in 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), but in the present invention, in order to improve the solubility or to improve the fluidity during gelation, An ether structure, more preferably a polyether structure, is introduced into the crosslinked chain. In the present invention, the number of nitrogen atoms involved in the crosslinked structure represented by the above formula (II) is 0.01 to 5 of the nitrogen atoms of polyaniline.
It must be in the range of 0%. 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 (4) , and the linking group A ² is represented by the formulas (1 ') to (4 ). 4 ′) , 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 an ether bond
An alkylene group having 1 to 10 carbon atoms which may have
Enylene group or its -COOH substitution product, or polio
It represents a xyethylene group, and specific examples of the alkylene group include straight chain and branched chain aliphatic hydrocarbon groups such as methylene, ethylene, trimethylene, hexamethylene and propylene.

RP is the following formula (III)

Embedded image In the formula, RP ¹ represents an alkylene group having 1 to 10 carbon atoms such as methylene, ethylene, trimethylene, hexamethylene, propylene and cyclohexylene.
And represents a divalent non-aromatic hydrocarbon group having 1 to 30 carbon atoms such as a straight chain or branched chain aliphatic hydrocarbon group or an alicyclic hydrocarbon group. RP ² is an alkylene group and / or a phenylene group having an ether or polyether structure.
Represents become more divalent group having 2 to 60 carbon atoms, specifically, ethylene oxyethylene, propylene-oxy propylene, ethylene oxyethylene oxyethylene, 3,
6,9-trioxaundecylene, 3,6,9,12-
Tetraoxatetradecylene, (ethylenedioxy) diphenylene, phenyleneoxyphenylene, and polyoxyethylene structure (hexamer, 10mer, 20mer, 9
0-mer etc.) and the like. Further, k represents an integer of 1 to 500.

Specifically, for example, ethylenediamine
Diethylene glycol acid polycondensate, tetramethylene diamine / triethylene glycol acid polycondensate, tetramethylene diamine / oxydibenzoic acid polycondensate, hexamethylene diamine / diethylene glycol acid polycondensate, hexamethylene diamine / 3,3'-oxydi Propionic acid polycondensate, octamethylene diamine / dipropylene glycol acid polycondensate, decamethylene diamine / polyethylene oxide (PEO) diacid (about 6-mer, 10-mer, 20
Polyamide oligomers such as polycondensates).

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).

Embedded image (In the formula, A ⁵ is an alkylene group having 1 to 10 carbon atoms or a fluorine atom;
Represents a phenylene group , A ⁶ represents an alkylene having 1 to 8 carbon atoms, 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 oxidant.
The aniphosphorylated 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 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, a polyamide compound represented by the above formula (IV) and having functional groups (W ¹ ) (W ² ) which react with an aromatic secondary amine at both ends. The main point of the present invention in which is used is to cross-link the polyaniline main chain with a cross-linked chain composed of a suitable polyamide chain, and the connecting portion of the cross-linked chain and the polyaniline main chain, that is, the structure of A ¹ and A ² 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.

[0020] The terminal functional groups of the polyamide compound of the formula ^{(IV) (W 1, W} 2), specifically, Cal
Boxyl group, haloformyl group, isocyanate group, sulphate
Examples thereof include a phenyl halide group, an oxirane ring and an intramolecular cyclic carboxylic acid anhydride group. As the RP, those exemplified above can be mentioned.

Examples of the polyamide 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, a polyamide having a carboxyl group at both ends which is obtained by condensing an excess dicarboxylic acid component. Compound,
A polyamide compound obtained by converting a terminal amino group of a polyamide compound having amino groups at both ends obtained by condensing with an excess of a diamine component into a functional group that reacts with an aromatic secondary amine, or almost equivalent amount Polyamide compounds obtained by converting the carboxyl groups and amino groups at both ends of the polyamide compound obtained by the condensation of the diamine and the dicarboxylic acid into functional groups that react with the aromatic secondary amine.

For example, the following compounds may be mentioned. Polyamide compound condensed with excess diamine component was used as the starting material, and its terminal amino group was reacted with trimellitic anhydride.
By reacting with a cyclic acid anhydride structure at the end, by reacting with excess diisocyanate at the end by reacting with an isocyanate structure, by reacting with excess disulfonyl halide
Examples thereof include those having a sulfonyl halide structure at the terminal and those having an epoxy structure at the terminal by reacting with a halide having an epoxy ring such as epihalohydrin .
Further, those having a carboxyl group and an amino group at the terminal obtained by condensing using a diamine component and a dicarboxylic acid component in approximately equivalent amounts, for example, those treated with phosgene to be converted into a haloformyl group and an isocyanate group, respectively. You can also give it.

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

Embedded image (In the formula, A ⁶ and RP have the same meanings as described above.)

The reaction between the reduced polyaniline and the polyamide 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, A polyamide 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 to an amide-based solution, and the mixture is added under a nitrogen stream for 1 to 48 hours at a temperature of -10 to 80 ° C. Continue stirring within the range. 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 to precipitate the polymer formed. By further treating the resulting polymer with aqueous ammonia,
The polyaniline derivative of the present invention can be produced.

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 a polyamide amide solution having carboxyl groups at both ends, N, N'-disubstituted carbodiimides having an equivalent amount or more to the terminal carboxyl groups are added while cooling to -10 to 10 ° C, and at that temperature for 1 to 4 hours. After continuing the stirring, the above amide solution of 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 groups such as -propyl group, n-butyl group, t-butyl group, 3-dimethylaminopropyl group, cyclic alkyl groups such as cyclohexyl group, phenyl group, p-tolyl group, p-N, N -Dimethylaminophenyl group, p-chlorophenyl group, p-nitrophenyl group,
represents a substituted or unsubstituted aryl group such as a p-cyanophenyl group; And more specifically, diethylcarbodiimide, diisopropylcarbodiimide, dicyclohexylcarbodiimide, diphenylcarbodiimide, di-p-tolylcarbodiimide, 1-
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. The conversion of the terminal carboxylic acid group to a haloformyl group is carried out by dicarboxylic acid which is a polyamide compound represented by the general formula (IV), ester of the dicarboxylic acid (lower alcohol ester such as methyl and ethyl) or salt of the dicarboxylic acid. (Alkali metal salt,
It can be easily carried out 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 or phosphorus trichloride is added to the dicarboxylic acid and reacted in an inert solvent such as benzene. A polyamide 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 polyamide compound having haloformyl groups at both ends used in the present invention can be obtained by using a triphenylhalophosphohalide or a complex thereof with boron fluoride for the dicarboxylic acid ester. You can From the dicarboxylic acid salt, an inorganic halogen compound such as phosphoryl chloride or phosphorus pentachloride or a complex of thionyl chloride and dimethylformamide is used for the dicarboxylic acid salt, and a polyamide compound having a haloformyl group at both ends used in the present invention is obtained. Obtainable. 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 polyamide compound having haloformyl groups at both ends used in the present invention can be obtained. .

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.

Since the polyaniline derivative of the present invention does not change the length of the main chain of polyaniline during its production, the value of m + n is n of the reduced polyaniline starting material.
Is the same as the value of. 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 with an oxidizing agent or electrochemically, the value of m is increased, and with a reducing agent,
Alternatively, if the polyaniline derivative of the present invention is electrochemically reduced, the value of m decreases. Note that m / (n + m) is
Peaks derived from quinoid structure (chemical shift 138 ppm / TMS) and peaks derived from benzenoid (chemical shift 122 ppm / TM) in ¹³ C NMR spectrum.
It can be determined from the respective intensity ratios with S).

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. Lewis acids such as aluminum, iron trichloride, molybdenum chloride, antimony chloride and arsenic pentafluoride, organic acids such as acetic acid, trifluoroacetic acid, benzenesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid and camphorsulfonic acid, Various compounds such as polyethylene sulfonic acid, polyethylene carboxylic acid, polyacrylic acid, polystyrene sulfonic acid and other polymeric acids can be mentioned. The method of doping these compounds is not particularly limited, and any known method can be used. In general, a polyaniline derivative, a gel thereof, or a molded product thereof may be brought into contact with a dopant compound, and the reaction can be performed in a gas phase or a liquid phase. Alternatively, a method of electrochemically doping in a solution of the above-described protonic acid or a salt thereof can also be used.

[0034]

EXAMPLES The present invention will be described below with reference to examples. Example 1 2.0 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 dropped into the above aniline solution,
For 6 hours. The thus-obtained aniline-oxidized polymer having a number average molecular weight of 21,000 (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 obtained soluble polyaniline was dispersed in 200 ml of water, and 50 m under nitrogen atmosphere.
l of 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 21,000, m + n = about 115). 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 polyamide compound having carboxyl groups at both ends was synthesized as follows. Polyethylene oxide (PEO) diacid (average molecular weight 400) and hexane-1,6-diamine were reacted at a molar ratio of 1.05: 1.00. The amount of terminal carboxyl groups is 2.0
1, the average molecular weight was 3,700. This thing 2.03
1 g was dissolved in benzene and reacted with an excess of oxalyl chloride to chloroformate the end groups. (W ¹ =
^{W 2 = COCl, A 3 =} - (CH 2) p -CO-, A 4
_{= -CO- (CH 2) p -} , provided that p = 5 to 7) above after removing the oxalyl chloride unreacted to a tetrahydrofuran solution of chloroformylation polyamide end groups, which had been cooled to 0 ℃ Was added to the amide-based solution of reduced polyaniline and the mixture was stirred for 6 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 2.89 g of the polyaniline derivative of the present invention.

When the infrared absorption spectrum was measured, absorptions of 1650 cm ^-1 (amide C = O stretching) and 2850 to 2950 cm ^-1 (aliphatic CH stretching) due to the cross-linking structure of the above formula (II) were measured. Was recognized. In addition, 1600,
Absorption patterns peculiar to the polyaniline represented by the general formula (I) were observed at 1500, 1300, 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 crosslinked structure of formula (II) was about 10% of the nitrogen atoms of polyaniline. In addition, from the ¹³ C NMR spectrum, m / (n + m)
= 0.4. When 1 g of the obtained polyaniline derivative was put in 5 g of N-methyl-2-pyrrolidone and stirred at room temperature, it gelled, and a film could be formed by spinning or stretching. Furthermore, this film is placed in a 20% hydrochloric acid aqueous solution for 24 hours.
Conductivity is 1.0S when it is dipped for a period of time and dried.
/ Cm. In addition, the same gel can be obtained by using an organic solvent such as N, N-dimethylacetamide, N, N-dimethylformamide, pyridine, chloroform, dichloroethane, dichloromethane, tetrahydrofuran, m-cresol in place of N-methyl-2-pyrrolidone. Was possible.

Example 2 A polyamide compound having amino groups at both ends was synthesized as follows. 3,3'-oxydipropionic acid and hexane-1,6-diamine were reacted at a molar ratio of 1.00: 1.50. The amount of terminal amino groups was 2.01. This was reacted with trimellitic anhydride chloride to obtain a polyamide compound having an acid anhydride structure at both ends.
The average molecular weight was 2100. (W ¹ = W ² = carboxylic acid _{^{anhydride, A 3 => C 6 H}} 3 -CO-, A 4 = -CO
-C ₆ H ₃ <) 4.610 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 6 hours to obtain 5.412 g of the polyaniline derivative of the present invention.

When the infrared absorption spectrum was measured, absorptions of 1650 cm ^-1 (amide C = O stretching) and 2850 to 2950 cm ^-1 (aliphatic CH stretching) due to the crosslinked structure of the above formula (II) were measured. Was recognized. In addition, 1600,
Absorption patterns peculiar to the polyaniline represented by the general formula (I) were observed at 1500, 1300, 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 crosslinked structure of formula (II) was about 38% of the nitrogen atoms of polyaniline. In addition, from the ¹³ C NMR spectrum, m / (n + m)
= 0.40. 1 g of the obtained polyaniline derivative
Was put in 5 g of N-methyl-2-pyrrolidone and agitated at room temperature to form a gel, which could be formed into a film by spinning or stretching. Furthermore, this film was dipped in a 20% hydrochloric acid aqueous solution to 2
After doping for 4 hours and drying, the conductivity was 0.0
It was 4 S / cm. Further, instead of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N
-Dimethylformamide, pyridine, chloroform, dichloroethane, dichloromethane, tetrahydrofuran,
Similar gelation was possible using an organic solvent such as m-cresol.

Example 3 A polyamide compound having amino groups at both ends was obtained from propylenediamine and 4,4'-ethylenedioxybenzoic acid in the same manner as in Example 2. This terminal amino group was reacted with epichlorohydrin to obtain a polyamide 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 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 4.342 g of the polyaniline derivative of the present invention.

When the infrared absorption spectrum was measured, absorptions of 1650 cm ^-1 (amide C = O stretching) and 2850 to 2950 cm ^-1 (aliphatic CH stretching) due to the cross-linking structure of the above formula (II) were measured. Was recognized. In addition, 1600,
Absorption patterns peculiar to the polyaniline represented by the general formula (I) were observed at 1500, 1300, 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 crosslinked structure of formula (II) was about 19% of the nitrogen atoms of polyaniline. In addition, from the ¹³ C NMR spectrum, m / (n + m)
Was 0.48. 1 g of the obtained polyaniline derivative
Was put in 5 g of N-methyl-2-pyrrolidone and agitated at room temperature to form a gel, which could be formed into a film by spinning or stretching. Furthermore, this film was dipped in a 20% hydrochloric acid aqueous solution to 2
When it was dipped for 4 hours and then dried, the conductivity was 0.1.
S / cm. Further, instead of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, pyridine, chloroform, dichloroethane, dichloromethane, tetrahydrofuran, m-
Similar gelation was possible using an organic solvent such as cresol.

Example 4 PEO diacid (average molecular weight 1000) and hexane 1,6-
Diamine was reacted in a molar ratio of 1.00: 1.00 to give a terminal carboxyl group number of 1.0 and a terminal amino group number of 1.0.
A polyamide compound having The polyamide compound was treated with phosgene to chloroformylate and isocyanate at the ends, respectively. Average molecular weight is 450
It was 0. (W ¹ = COCl, W ² = NCO, A ³ =
_{-CH 2 O (CH 2 CH 2} O) p CH 2 -CO-, A 4
_{= -CO-CH 2 O (CH} 2 CH 2 O) p CH 2 - CO
-, provided that p = 18-20) takes this one 0.494 g, added to a solution of reduced polyaniline 1g of N- methyl-2-pyrrolidone 30 ml, and reacted for 6 hours 40 ° C., polyaniline of the present invention 1.432 g of the derivative was obtained.

When the infrared absorption spectrum was measured, the absorption of 1650 cm ^-1 (amide C = O stretching) and 2850 to 2950 cm ^-1 (aliphatic CH stretching) due to the cross-linking structure of the above formula (II) was measured. Was recognized. In addition, 1600,
Absorption patterns peculiar to the polyaniline represented by the general formula (I) were observed at 1500, 1300, 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 crosslinked structure of formula (II) was about 2% of the nitrogen atoms of polyaniline. In addition, from the ¹³ C NMR spectrum, m / (n + m)
Was 0.49. 1 g of the obtained polyaniline derivative
Was put in 5 g of N-methyl-2-pyrrolidone and agitated at room temperature to form a gel, which could be formed into a film by spinning or stretching. Furthermore, this film was dipped in a 20% hydrochloric acid aqueous solution to 2
When it was dipped for 4 hours and then dried, the conductivity was 1.7.
S / cm. Further, instead of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, pyridine, chloroform, dichloroethane, dichloromethane, tetrahydrofuran, m-
Similar gelation was possible using an organic solvent such as cresol.

Example 5 PEO diacid (average molecular weight 400) and hexane-1,6-
The diamine was reacted in a 1.00: 1.50 molar ratio.
This was reacted with benzenesulfonyl chloride to convert the terminal to a sulfonyl chloride group. Average molecular weight is 32
It was 50. ^{(W 1 = W 2 = SO} 2 Cl, A 3 = -C
₆ H ₄ —SO ₂ —, A ⁴ = —SO ₂ —C ₆ H ₄ —) 1.784 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 6 hours to obtain 2.610 g of the polyaniline derivative of the present invention.

The infrared absorption spectrum was measured and found to be 1640 cm ^-1 (amide C = O structure), 1351 cm ^-1 and 1176 cm due to the cross-linking structure of the formula (II).
^-1 (S (= O) ₂ expansion / contraction), 2850-2950 cm
Absorption of ^-1 (aliphatic C-H stretch) was observed. further,
1600, 1500, 1300, 1170, 820 cm
^-1 showed an absorption pattern peculiar to polyaniline represented by the general formula (I), 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) is about 1 of the nitrogen atoms of polyaniline.
It was 0%. In addition, from the ¹³ C NMR spectrum, m /
(N + m) = 0.48. 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. Further, when this film was dipped in a 20% hydrochloric acid aqueous solution for 24 hours and was then dried, the conductivity was 0.4 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, tetrahydrofuran, m-cresol.

Example 6 In the same manner as in Example 1, a polyamide compound having carboxyl groups at both ends was synthesized from decamethylenediamine and oxydipropionic acid. Average molecular weight is 33
00. ^{(W 1 = W 2 = COOH} , A 3 = - (C
_{H 2) 2 O (CH 2} ) 2 -CO-, A 4 = -CO- (C
_{H 2) 2 O (CH 2} ) 2 -) takes this one 1.818 g, was dissolved in N- methyl-2-pyrrolidone 10 ml, was added further dicyclohexylcarbodiimide 0.4 g, was stirred for 1 hour. The obtained solution was 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 give 2.702 g of polyaniline derivative of the present invention.
I got

When the infrared absorption spectrum was measured, absorptions of 1650 cm ^-1 (amide C = O structure) and 2850 to 2950 cm ^-1 (aliphatic C-H stretching) due to the cross-linking structure of the above formula (II) were measured. Was recognized. In addition, 1600,
Absorption patterns peculiar to the polyaniline represented by the general formula (I) were observed at 1500, 1300, 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 crosslinked structure of formula (II) was about 10% of the nitrogen atoms of polyaniline. In addition, from the ¹³ C NMR spectrum, m / (n + m)
Was 0.47. 1 g of the obtained polyaniline derivative
Was put in 5 g of N-methyl-2-pyrrolidone and agitated at room temperature to form a gel, which could be formed into a film by spinning or stretching. Furthermore, this film was dipped in a 20% hydrochloric acid aqueous solution to 2
After being dipped for 4 hours and then dried, the conductivity was 0.7.
S / cm. Further, instead of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, pyridine, chloroform, dichloroethane, dichloromethane, tetrahydrofuran, m-
Similar gelation was possible using an organic solvent such as cresol.

[0047]

INDUSTRIAL APPLICABILITY The polyaniline derivative of the present invention can be dissolved or gelled in various organic solvents, can be easily processed, and is a molded product such as a flexible self-supporting film or fiber. Can be obtained. And since these molded articles show high conductivity by doping, the polyaniline derivative of the present invention is very useful for various uses such as electronic materials and conductive materials.

Continuation of the front page (56) Reference JP-A-4-331226 (JP, A) JP-A-4-366122 (JP, A) JP-A-4-372623 (JP, A) JP-A-5-51448 (JP , A) JP 5-51449 (JP, A) JP 5-9294 (JP, A) JP 5-97999 (JP, A) JP 5-98000 (JP, A) JP 1-299608 (JP, A)

Claims (2)

(57) [Claims] 1. A compound represented by 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 2 represented by the following formula (III):
Represents 100 to 100,000 polyamide chains, (In the formula, RP ¹ represents an alkylene group having 1 to 10 carbon atoms, and RP ² has an ether or polyether structure.
Carbon consisting of alkylene group and / or phenylene group
It represents a divalent group of the number 2 to 60, and k represents an integer of 1 to 500. ) A ¹ represents a linking group selected from the following formulas (1) to (4) : (In the formula, R is the number of carbon atoms which may have an ether bond.
1-10 alkylene groups, phenylene groups or -C thereof
Represents an OOH-substituted product or a polyoxyethylene group
You . ) A ² is to Table Wa selected linking groups from the following formula (1 ') to (4'). Embedded image (Wherein R has the same meaning as described above.)], And the number of nitrogen atoms involved in the crosslinked structure is 0.01 of the nitrogen atoms of the main chain polyaniline.
The polyaniline derivative is characterized by being -50%. 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 represented by the following formula (IV) [Wherein W ¹ and W ² are each represented by the following formula (a) to
Representing a functional group selected from (f), (Wherein, Hal is Wath. Table halogen atom) A ³ is
Methylene group, -R-C (= O)-, -R-NH-C (=
O)-or -R-SO _2- (where R is as defined above)
Have righteousness. ) , A ⁴ is a methylene group, —C
(= O) -R-, -C (= O) -NH-R- or -S
O ₂ —R— (wherein R has the same meaning as described above)
Where W ¹ and W ² represent an intramolecular carboxylic acid anhydride group of formula (c), A ³ and A ⁴ are
> R ¹ -C (= O)-or -C (= O) -R respectively
¹ <(wherein R ¹ represents a benzene ring
You. ), And RP has the same meaning as above . ] The method for producing a polyaniline derivative according to claim 1, which comprises reacting with a polyamide compound having a functional group that reacts with an aromatic secondary amine at both ends.