JPH06107788A - Polyaniline derivative and its production - Google Patents

Abstract

PURPOSE:To obtain the subject derivative soluble in organic solvent, having excellent flexibility and useful for electronic material, electrically conductive material, etc., by reacting a specific reduced-type polyaniline with a specific polyester compound. CONSTITUTION:The objective derivative containing nitrogen atoms participating in the crosslinked structure accounting for 0.01-50% of the nitrogen atoms of a polyaniline is produced by treating an oxidized aniline polymer with ammonia to form a soluble aniline polymer, treating the polymer with excess hydrazine to obtain a reduced-type polyaniline containing imino-1,4-phenylene unit as a structural unit and having a number-average molecular weight of 2,000-500,000 and reacting the polyaniline with a polyester compound having functional groups reactive with aromatic secondary amine at both terminals and expressed by formula I [W<1> and W<2> are HOOC, Hal (Hal is halogen), etc.; A<3> is direct bond, 1-30C bivalent hydrocarbon group, etc.; A<4> is direct bond, 1-30C bivalent hydrocarbon group, etc.; RP is a polyester chain having an average molecular weight of 1,000-100,000 and expressed by formula II (RP<1> and RP<2> are 1-30C bivalent hydrocarbon group; (k) is 1-500)].

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 can be formed into an organic solvent or can be gelled, and can form a flexible, self-supporting film, and a process 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 extensive studies to solve the above problems, the present inventor reacted reduced polyaniline with a polyester 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 6] (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 7]

[In the formula, RP represents a polyester chain having an average molecular weight of 100 to 100,000 represented by the following formula (III), and-(O-RP ¹ -OCO-RP ² -CO) _k -O-RP ¹ -O- (III) (In the formula, RP ¹ and RP ² each have 1 to 3 carbon atoms.
0 represents a divalent hydrocarbon group, one of which represents an aromatic hydrocarbon group, the other represents a non-aromatic hydrocarbon group, and k represents an integer of 1 to 500. ) A ¹ represents a linking group selected from the following formulas (1) to (10),

[0008]

[Chemical 8] (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. , P represents an integer of 0 to 2), A ² represents a linking group selected from the following formulas (1 ′) to (10 ′),

[0009]

[Chemical 9] (In the formula, R, X, Y, B and p have the same meanings as described above.) Represents a group selected from the group consisting of: ]
Is formed, and the number of 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 10] (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 ¹ -OCO-RP
^2- CO- (however, R, X, RP ¹ , RP ² and p
Has the same meaning as 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- or -CO-RP ² -COO
-RP ^1- (however, R, X, RP ¹ , RP ² and p
Has the same meaning as above. ), Where W represents an intramolecular carboxylic acid anhydride group of formula (c),
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 reacts with the polyester 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).
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 branched structure is higher than 50%, the generated polyaniline derivative has a problem that conductivity is lowered. Also,
If it is less than 0.01%, the solubility will not be 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 having 1 to 30 carbon atoms is described as a straight-chain or branched-chain aliphatic hydrocarbon group such as methylene, ethylene, trimethylene, hexamethylene and propylene, and aromatic carbon such as phenylene. Examples thereof include a hydrogen group and a hydrocarbon group containing an aromatic ring such as 2,2-diphenyltrimethylene.

RP has an average molecular weight of 100 to 100,000 represented by the following formula (III)-(O-RP ¹ -OCO-RP ² -CO) _k -O-RP ¹ -O- (III). In the formula, RP ¹ and RP ² are each a divalent hydrocarbon group having 1 to 30 carbon atoms, for example, methylene, ethylene, trimethylene, hexamethylene, propylene, cyclohexylene, vinylene, phenylene,
_{-C 6 H 4 CH 2 -,} - C 6 H 4 C (CH 3) 2 C 6 H
_{It represents a} divalent straight-chain or branched-chain aliphatic hydrocarbon or cycloaliphatic hydrocarbon such as 4- and biphenylylene. However, in that case, ^one of RP ¹ and RP ² is an aromatic hydrocarbon group, and the other is a non-aromatic hydrocarbon group. When both RP ¹ and RP ² represent an aromatic hydrocarbon group, the solubility or swelling property in an organic solvent decreases, so one of them must be a non-aromatic hydrocarbon group. . When both are non-aromatic hydrocarbon groups, the heat resistance tends to decrease. Further, k represents an integer of 1 to 500. Specifically, poly (oxyethylene oxyphthaloyl),
Poly (oxyethyleneoxyisophthaloyl), poly (oxyethyleneoxycarbonylbiphenylenecarbonyl), poly (oxybiphenyleneoxysuccinyl), poly (oxyphenyleneoxysebacoil), poly (oxynaphthyleneoxyadipoyl), Poly (oxyphenylene methylene phenylene oxyadipoyl),
Examples thereof include polyester oligomers having a structure such as poly (oxyphenylenepropane 2-ylidenephenyleneethyleneoxysebacoil).

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 11] (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 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.

To introduce the above-mentioned crosslinked structure into the reduced polyaniline, a polyester compound represented by the above formula (IV) and having functional groups (W ¹ ) (W ² ) which react with an aromatic secondary amine at both terminals. Is used. The main point of the present invention is to cross-link the polyaniline main chain with a cross-linking chain made of a suitable polyester, 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 have a great influence on the physical properties of the derivative of the present invention including the 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 and W ² ) of the polyester compound in the above formula (IV) include a halogen atom, a carboxyl group, a haloformyl group, an isocyanate group, an isothiocyanate group, and a sulfinyl halide. Examples thereof include a 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 polyester 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 polyester having a carboxyl group at both ends which is obtained by condensing excess dicarboxylic acid component. -Based compound, a polyester-based compound having haloformyl groups at both ends condensed with excess dicarboxylic acid halide, and a terminal hydroxyl group of a polyester-based compound having hydroxyl groups at both ends obtained by condensation with excess diol component as an aromatic group Two
A carboxyl group and a hydroxyl group at both terminals of a polyester compound obtained by converting into a functional group capable of reacting with an amine or a polyester compound obtained by condensation of an approximately equivalent amount of a diol and a dicarboxylic acid are converted to an aromatic secondary amine. Examples thereof include polyester compounds obtained by converting into reactive functional groups.

For example, the following compounds may be mentioned. Polyester compound condensed with excess diol component is used as a starting material, and its terminal hydroxyl group is reacted with trimellitic anhydride or halogenated trimellitic anhydride to form a cyclic acid anhydride structure at the terminal, and excess diene Those having an isocyanate structure at the end by reacting with an isocyanate, those having an end having an isothiocyanate structure by reacting with excess diisothiocyanate, disulfinyl halide,
By reacting with each of disulfenyl halide and disulfonyl halide, the terminal of each is a sulfinyl halide,
Those having a sulfenyl halide or sulfonyl halide structure, those having an epoxy structure at the end by reaction with a halide having an epoxy ring such as epihalohydrin, halogenated hydrocarbon having a double bond at the end, for example, allyl halide , Or a carboxylic acid having a double bond at the end, for example, allyl acetic acid to form a structure having a double bond at the end, and then oxidize this to an epoxy ring structure, treated with phosphorus pentachloride Examples thereof include halogenated hydroxyl groups.

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

[Chemical 12] (In the formula, A ⁶ and RP have the same meanings as described above.)

Reduced polyaniline and an aromatic second group at both ends
The reaction with the polyester compound represented by the above formula (IV) having a functional group (W ¹ , W ² ) that reacts with an amine is carried out by reacting with an amide solution of the reduced polyaniline and with an aromatic secondary amine at both ends. The polyester compound having a functional group or a solution obtained by dissolving it in an organic solvent is added, and stirring is continued in a temperature range of −10 to 80 ° C. for 1 to 48 hours under a nitrogen stream. 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 polyester 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 at that temperature for 1 to 4 hours After continuing the stirring, the reduced polyaniline is added, and the temperature is slowly returned to room temperature, and the stirring is further continued for 1 to 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 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. The conversion of the terminal carboxylic acid group to a haloformyl group is carried out by dicarboxylic acid which is a polyester 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. From (alkali metal salt, ammonium salt, etc.), 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 polyester 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 / Obtained by adding an organic halide such as an organic phosphorus halide such as carbon tetrachloride, pyrocatetyl phosphotrichloride, diethylphosphochloride, triphenylphosphobromide, etc. and reacting in an inert solvent such as benzene or chlorobenzene. You can also

From the dicarboxylic acid ester, a polyester compound having haloformyl groups at both ends used in the present invention can be obtained by using a triphenylphosphohalide or a complex thereof with boron fluoride for the dicarboxylic acid ester. it 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 polyester 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 polyester 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.

The length of the polyaniline main chain of the polyaniline derivative of the present invention does not change 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. However, if the solubility in a solvent is important, it is preferable that the rigid quinonediimine structure is small, that is, m <n. If the self-supporting property and flexibility of the film are important, m> n is preferable. Therefore, for the reasons described above, the value of m / (n + m) suitable for film molding is usually in the range of 0.10 to 0.60 for the polyaniline derivative of the present invention. Note that m /
(N + m) is a peak derived from a quinoid structure in the ¹³ C NMR spectrum (chemical shift 138 ppm / TMS)
And benzenoid-derived peak (chemical shift 122p
pm / TMS) and their respective intensity ratios.

The polyaniline derivative of the present invention produced as described above is an amide solvent such as N-methyl-2-pyrrolidone or N, N-dimethylacetamide, a halogenated hydrocarbon solvent such as chloroform, dichloroethane or dichloromethane. 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.

[0032]

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 polyester compound having a carboxyl group at both ends was synthesized as follows. Terephthalic acid and ethylene glycol were reacted at a molar ratio of 1.05: 1.00 first at 160 ° C. for 20 hours and further reduced pressure. The amount of terminal carboxyl groups was 2.01, and the average molecular weight was 1,900. (W ¹ = W ² = C
_{^{OOH, A 3 = -C 6 H}} 4 -CO-, A 4 = -CO-C
₆ H ₄ − 1.043 g of this product was dissolved in N-methyl-2-pyrrolidone, and N, N′-dicyclohexylcarbodiimides having a terminal carboxyl group and an equivalent amount or more were added while cooling to −10 to 10 ° C. Stirring is continued for 4 hours at that temperature, then the above amide solution of reduced polyaniline is added,
While slowly returning to room temperature, stirring was continued for 1 to 48 hours. The reaction mixture was poured into alcohol to precipitate the polymer under purification. The obtained polymer was further treated with aqueous ammonia to obtain 2.01 g of the polyaniline derivative of the present invention.

[0034] was measured infrared absorption spectrum, 1740 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) = 0.46. 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.

Example 2 A polyester compound having hydroxyl groups at both ends was synthesized as follows. Biphenyldicarboxylic acid and ethylene glycol were mixed at a molar ratio of 1.00: 1.50 to give 1
The reaction was carried out at 60 ° C. for 20 hours under reduced pressure. The amount of terminal carboxyl groups is 0.01, the degree of polymerization is about 11,
The average molecular weight was 1800. This was reacted with trimellitic anhydride chloride to obtain a polyester compound having an acid anhydride structure at both ends. The 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 5.212 g of the polyaniline derivative of the present invention.

The result of having measured an infrared absorption spectrum, 1740 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 37% 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% hydrochloric acid aqueous solution for 24 hours and was then dried, the conductivity was 0.01 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 3 Example 2 was prepared from propylene glycol and isophthalic acid.
A polyester compound having hydroxyl groups at both ends was obtained in the same manner as in (1). After sodiumating this end,
By reacting with epichlorohydrin, a polyester having epoxy groups at both ends was obtained. The average molecular weight was 2600. (W ¹ = W ² = epoxy group, A ³ = A ⁴ = methylene group) Take 2.854 g of this product and 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 3.212 g of the polyaniline derivative of the present invention.

The result of having measured an infrared absorption spectrum, 1740 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 16% 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 0.1 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 The polyester having hydroxyl groups at both ends synthesized in Example 2 was treated with sodium hydride at the end to react with 3-chloropropylamine, and then treated with phosgene to form an isocyanate at the end. Converted Average molecular weight is 1960
Met. (W ¹ = W ² = NCO, A ³ = A ⁴ = trimethylene group) Take 0.215 g of this product and 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 1.210 g of the polyaniline derivative of the present invention.

The result of having measured an infrared absorption spectrum, 1740 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-
It was put in 5 g of 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 1.1 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 5 The polyester having hydroxyl groups at both ends synthesized in Example 2 was reacted with benzenedisulfonyl chloride to form a sulfonyl chloride at the ends. The average molecular weight was 2150. ^{(W 1 = W 2 = SO} 2 Cl, A 3 = -C 6 H 4
-SO _2- , A ⁴ = -SO ₂ -C ₆ H ₄ ) 1.180 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 2.152 g of the polyaniline derivative of the present invention.

The infrared absorption spectrum was measured and found to be 1740 cm ^-1 (ester C = O stretching), 1351 cm ^-1 and 1176c due to the cross-linked 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) = 0.48. 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. Furthermore, when this film was dipped in a 20% hydrochloric acid aqueous solution for 24 hours and was then dried, the conductivity was 0.1 S / cm. 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 6 The ends of the polyester having hydroxyl groups at both ends synthesized in Example 2 were reacted with phosphorus pentachloride to chlorinate the ends. The average molecular weight was 1840. (W ¹ = W ² = C
_{^{l, A 3 = -CH 2 CH}} 2 -OCO- (CH 2) 4 -C
^{O-, A 4 = -CO- (CH} 2) 4 -CO-O-CH 2
CH _2- ) 5.048 g of this product was taken, and 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 16 hours to obtain 5.848 g of the polyaniline derivative of the present invention.

When the infrared absorption spectrum was measured, absorptions of 1740 cm ^-1 (ester C = O stretching) and 2850 to 2950 cm ^-1 (aliphatic CH stretching) due to the cross-linking structure of the formula (II) were measured. Was recognized. In addition, 160
An absorption pattern peculiar to the polyaniline represented by the general formula (I) was observed at ⁰ , 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 48% of the nitrogen atoms of polyaniline. Further, ¹³ C NMR spectra from m / (n +
m) = 0.41. 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 0.007 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 7 The ends of the polyester having hydroxyl groups at both ends synthesized in Example 2 were reacted with hexamethylene diisocyanate to make the ends isocyanate. The average molecular weight is 214
It was 0. ^{(W 1 = W 2 = NCO} , A 3 = - (C
^{_{H 2) 6 -NHCO-, A 4}} = -CONH- (CH 2)
_6- ) 1.175 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 2.150 g of the polyaniline derivative of the present invention.

The result of having measured an infrared absorption spectrum, 1740 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.

Example 8 In the same manner as in Example 2, a polyester compound having hydroxyl groups at both ends was synthesized from bisphenol A and adipic acid. After the end was sodiumated, it was reacted with epichlorohydrin to obtain a polyester having epoxy groups at both ends. The average molecular weight was 2500. (W
¹ = W ² = epoxy group, A ³ = A ⁴ = methylene group) Take 2.744 g of this product and 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 3.212 g of the polyaniline derivative of the present invention.

The result of having measured an infrared absorption spectrum, 1740 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 0.1 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.

[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.

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[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):
It represents a polyester chain of 00～100,000, - in ^{(O-RP 1 -OCO-RP} 2 -CO) k -O-RP 1 -O- (III) ( wherein, RP ¹ and RP ^2, respectively carbon Number 1-3
0 represents a divalent hydrocarbon group, one of which represents an aromatic hydrocarbon group, the other represents a non-aromatic hydrocarbon group, and k represents an integer of 1 to 500. ) A ¹ represents a linking group selected from the following formulas (1) to (10),

[Chemical 3] (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. Representation, RP ¹ and 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 4] (Wherein R, X, Y, B, RP ¹ , RP ² and p are
It has the same meaning as described above. ) Represents a group selected from the group consisting of: ] Form a cross-linked structure,
The polyaniline derivative, wherein the number of nitrogen atoms involved in the crosslinked structure is 0.01 to 50% of the nitrogen atoms of the main chain polyaniline.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction content]

[0008]

[Chemical 8] (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. Representation, RP ¹ and 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 ′),

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction content]

[0009]

[Chemical 9] (Wherein R, X, Y, B, RP ¹ , RP ² and p are
It has the same meaning as described above. ) Represents a group selected from the group consisting of: ] Form a cross-linked structure,
The number of 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):
It represents a polyester chain of 00～100,000, - in ^{(O-RP 1 -OCO-RP} 2 -CO) k -O-RP 1 -O- (III) ( wherein, RP ¹ and RP ^2, respectively carbon Number 1-3
0 represents a divalent hydrocarbon group, one of which represents an aromatic hydrocarbon group, the other represents a non-aromatic hydrocarbon group, and k represents an integer of 1 to 500. ) A ¹ represents a linking group selected from the following formulas (1) to (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. , 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 and p have the same meanings as described above.) Represents a group selected from the group consisting of: ]
A polyaniline derivative having a crosslinked structure represented by the formula (1) above, wherein the number of nitrogen atoms involved in the crosslinked structure is 0.01 to 50% of the nitrogen atoms of the main chain polyaniline. 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 ¹ -OCO-RP
^2- CO- (however, R, X, RP ¹ , RP ² and p
Has the same meaning as 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- or -CO-RP ² -COO
-RP ^1- (however, R, X, RP ¹ , RP ² and p
Has 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 has the same meaning as above. ] The method for producing a polyaniline derivative according to claim 1, which comprises reacting with a polyester compound having a functional group which reacts with an aromatic secondary amine at both ends.