JPH05132547A - Polypyrrole derivative and its production - Google Patents

Abstract

PURPOSE:To prepare a polypyrrole deriv. which is sol. in an org. solvent and can form a flexible and self-supporting film by introducing acyl groups into the N atoms of polypyrrole. CONSTITUTION:Polypyrrole comprising structural units of formula I and having the number of the units of 50-5,000 is reacted with metallic potassium, a potassium alkoxide, or potassium hydroxide to give poly (pyrrole-N-potassium), which is reacted with an acyl halide: RCOX [wherein X is Cl, Br, or I; and R is 3C or higher (substd.)alkyl, 3C of higher (substd.)alkenyl, (substd.)aryl, or (substd.) benzyl] to give the objective polypyrrole deriv. which comprises structural units of formulas I and II (wherein R is as defined above) and has the sum of the numbers of both units of 50-5,000 and the ratio of the number of units of formula I to that of formula II of 0.01-100. The deriv. is sol. in various org. solvents and can form a flexible and, self-supporting film.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art In recent years, conductive polymers are new electronic materials,
Used as a conductive material, such as battery electrode material, antistatic material, electromagnetic wave shielding material, photoelectric conversion element, optical memory, functional elements such as various sensors, display elements, various hybrid materials, transparent conductors, various terminal devices, etc. Applications to a wide range of fields are being studied. However, in general, polypyrrole has a highly developed π-conjugated system, so that the polymer main chain is rigid and the interaction between the molecular chains is strong, it is insoluble in most organic solvents, and it does not melt even when heated. It has poor moldability and has a major drawback that it cannot be cast or coated.

For that purpose, for example, a base material having a desired shape such as a fiber of a polymeric material or a porous body is impregnated with a monomer, and the monomer is contacted with an appropriate polymerization catalyst, or
A conductive composite material was obtained by polymerization by electrolytic oxidation, or a similar composite material was obtained by polymerizing a monomer in the presence of a thermoplastic polymer powder. Further, those having a linear alkyl group or an alkoxy group as a monomer (for example, 3-alkylpyrrole, 3-alkoxypyrrole, N-
Although it is possible to obtain a soluble polymer by using (alkylpyrrole, etc.), only a polymer having a low degree of polymerization and a poor film forming property is obtained. In addition, the conductivity during doping tends to decrease, which is a practical problem.

[0004]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems, and does not impair the original properties of polypyrrole.
An object is to provide a polypyrrole derivative that is soluble in a general-purpose solvent and has processability such as coating.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventor first produced an unsubstituted polypyrrole and then introduced a substituent such as an acyl group at the N-position of the polypyrrole. As a result, they have found that the above problems can be solved, and completed the present invention.

The present invention relates to a polypyrrole derivative and a method for producing the same, which is represented by the following formula (I):

[Chemical 3] And a structural unit represented by the following formula (II)

[Chemical 4] [Wherein R represents an alkyl group or substituted alkyl group having 3 or more carbon atoms, an alkenyl group or substituted alkenyl group having 3 or more carbon atoms, an aryl group or a substituted aryl group, or a benzyl group or a substituted benzyl group] A polymer compound comprising units, the number of structures (m) of formula (I) and the number of structures (n) of formula (II)
Is 50 to 5000, and the value of n / m is 0.01 to 1
00 is a polypyrrole derivative.

The pyrrole derivative of the present invention has a high degree of polymerization (5
0-5000) polypyrrole to poly (pyrrole-N-
Potassium) and acyl halide [RCOX: X
Represents chlorine, bromine or iodine, and R has the above-mentioned meaning], and COR is introduced into the N-position of pyrrole. Polypyrrole used in the present invention,
It is produced by the oxidative coupling reaction of pyrrole. Further, polypyrrole can be produced by coupling 2,5-dihalogenated pyrrole with a catalyst such as nickel or without a catalyst. However, this method is not so general because the monomer itself used is unstable.

Specific examples of the oxidative coupling polymerization method include a polymerization method using an oxidant catalyst and an electrochemical polymerization method. Among them, the polymerization method using an oxidant catalyst is important. It is preferable as a means to obtain the coalesced inexpensively and easily. Examples of these polymerization catalysts include compounds known as Lewis acids such as aluminum chloride, iron chloride, molybdenum chloride, tungsten chloride, tin chloride, antimony chloride and arsenic pentafluoride. Of these, those having no or weak oxidizing power, such as aluminum chloride, are preferably used in combination with an oxidizing agent such as cupric chloride, manganese dioxide and oxygen.

The polypyrrole used in the present invention can be easily obtained at room temperature by adding these oxidant catalysts to pyrrole in an atmosphere of an inert gas such as nitrogen or argon. If necessary, an inert solvent such as chloroform, dichloromethane, tetrahydrofuran, ether or the like may be added to the reaction system, which is a preferable method because the reaction can be easily controlled. Further, the system can be heated if necessary.

The electrochemical oxidative polymerization method is carried out in an electrolyte solution in which pyrrole is dissolved at a potential of 0.1 to 30 V under conditions of constant current, constant voltage, constant potential, etc. at low temperature, preferably -3.
It is carried out at 0 to 20 ° C. As a solvent constituting the electrolyte solution, water, alcohol, ether, propylene carbonate, methylene chloride, nitrobenzene, nitromethane, acetonitrile, benzonitrile, and other organic solvents, and mixed solvents thereof are used. Examples of the electrolyte that constitutes the electrolyte solution include protonic acids such as hydrochloric acid, sulfuric acid, borofluoric acid, and perchloric acid, benzenesulfonic acid, p-toluenesulfonic acid, alkylsulfonic acid, alkylbenzenesulfonic acid, acetic acid, and trifluoroacetic acid. Organic acids or salts thereof, lithium perchlorate, lithium tetrafluoroborate,
An electrolyte salt such as lithium hexafluoroarsenate, tetrabutylammonium tetrafluoroborate, or tetrabutylammonium perchlorate is used.

The electrodes are preferably noble metal electrodes such as gold and platinum, nickel, chromium and carbon electrodes, as well as glass electrodes obtained by vapor-depositing stannic oxide and indium oxide on glass. Further, these electrochemical oxidative polymerizations are preferably carried out in an inert gas such as argon or nitrogen.

Since the powder of polypyrrole obtained by any of the above methods or the film on the electrode contains a dopant, it is necessary to carry out a dedoping treatment and then carry out the N-potassiumation reaction in the next step. The dedoping treatment is not particularly limited, but it is exposed to ammonia vapor, followed by thorough washing with water, thorough washing with ammonia water, sufficient washing with a solvent that dissolves the oxidizer catalyst, and then exposure to ammonia vapor, electrochemical It is possible to perform a reduction treatment or to use them together.

The polypyrrole thus obtained is brought into contact with metal potassium or reacted with a potassium alkoxide to give poly (pyrrole-N-potassium) at room temperature.
Can be obtained. 4 with potassium hydroxide
It is also possible to similarly obtain poly (pyrrole-N-potassium) by heating at 0 to 130 ° C. These reactions are also preferably carried out in an inert gas. The reaction at this time can also be carried out in an inert halogen-based or ether-based solvent or in an alcohol.

The poly (pyrrole-N-potassium) thus obtained and the acyl halide [RCOX: X and R have the above-mentioned meanings] are directly or in an inert solvent at low temperature, preferably from -20 to 10 The substituent COR can be introduced into the N-position of polypyrrole by allowing it to act at ° C.

Examples of the alkyl group having 3 or more carbon atoms for R include propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, hexadecyl group, Linear alkyl group such as docosyl group, isobutyl group, isopentyl group,
Branched alkyl groups such as neopentyl group and isohexyl group,
A cyclic alkyl group such as a cyclohexyl group, and at least one of hydrogen atoms thereof is a cyano group, a nitro group, a phenyl group,
Examples thereof include a substituted alkyl group substituted with an alkoxy group and the like.

As the alkenyl group having 3 or more carbon atoms, an alkenyl group such as an allyl group, a butenyl group, a pentenyl group and a hexenyl group, and at least one hydrogen atom thereof is a cyano group, a nitro group, a phenyl group or an alkoxy group. A substituted alkenyl group substituted with, for example, can be mentioned.

As the aryl group, a phenyl group, a tolyl group, a 1-naphthyl group, a 2-naphthyl group and the like, and at least one hydrogen atom thereof is a cyano group, a nitro group, a phenyl group,
Examples thereof include a substituted aryl group substituted with an alkoxy group and the like. Further, examples of the substituent of the substituted benzyl group include a cyano group, a nitro group, a phenyl group, an alkoxy group and the like. Specific examples of preferable acyl halides include caproyl chloride, crotonoyl bromide,
Examples thereof include p-methoxybenzoyl chloride and the like.
In the present invention, the introduction reaction of the substituent to the N-position of polypyrrole is preferably performed so that 1 to 100% of the N-position of polypyrrole is substituted. If the substitution at the N-position is less than 1%, sufficient solubility in an organic solvent cannot be obtained.

The substituent C at the N-position prepared according to the invention is
The polypyrrole introduced with OR is soluble in amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylacetamide, halogenated hydrocarbon solvents such as chloroform, dichloroethane and dichloromethane, and ether solvents such as tetrahydrofuran. is there.

A good self-supporting film can be obtained by casting from a solution in which the polypyrrole derivative is dissolved in these solvents. The obtained film is a protic acid such as hydrochloric acid, sulfuric acid, hydrofluoric acid, and perchloric acid, an organic acid such as benzenesulfonic acid, p-toluenesulfonic acid, acetic acid, and trifluoroacetic acid, iodine, bromine, chlorine, and trifluoroacetic acid. Halide compounds such as iodine chloride, aluminum trichloride, iron trichloride, molybdenum chloride, tungsten chloride, antimony chloride, arsenic pentafluoride, Lewis acids such as sulfur trioxide, nitrosyl hexafluoroantimonate, nitrosyl hexafluoroarsenate, trifluoro By doping with an oxidizing agent such as nitrosyl methanesulfonate, an alkali metal such as lithium, sodium, potassium, rubidium, or cesium, or a tetraalkylammonium salt, 10 ^-3 to 10 -10
^It shows a high conductivity of ³ S / cm.

The method of doping these dopants is not particularly limited, and it is generally sufficient that the dopant and the polymer of the present invention are brought into contact with each other, and it is often carried out in a gas phase or a liquid phase. Alternatively, lithium perchlorate, lithium tetrafluoroborate, lithium hexafluoroarsenate, tetrabutylammonium tetrafluoroborate,
A method of electrochemically doping with an electrolyte solution containing an electrolyte salt such as tetrabutylammonium perchlorate is also possible.

[0021]

【Example】

Example 1 Under a nitrogen stream, 24 g of anhydrous ferric chloride was added to 300 ml of chloroform, and then 3 g of pyrrole was added to the mixture at 30 ° C. for 1 hour.
Stir for 20 hours. The reaction mixture was added to 1 liter of methanol and well stirred, and then the solid matter was filtered off, thoroughly washed with methanol, water, methanol containing ammonia water, and water in this order, and dried under reduced pressure to obtain 2.7 g of polypyrrole. Was obtained. The average degree of polymerization of this polymer was about 150, which was estimated from the degree of polymerization of 2,5-ditritiated pyrrole synthesized under the same conditions, which was determined by measuring the specific activity. The number of repeating structures is 15
0].

This is dispersed in methanol, 1.14 g of potassium methoxide is added, and the mixture is stirred at room temperature for 5 hours. Remove methanol and unreacted potassium methoxide,
Thoroughly washed and dried. This was dispersed in tetrahydrofuran, 3 g of caproyl chloride was added, and the mixture was allowed to stand at room temperature for 24 hours.
Stirring was continued for hours. The solid matter is filtered off and thoroughly washed with methanol, water, methanol containing ammonia water, and water in this order,
It was dried under reduced pressure to obtain 3.64 g of polymer.

The introduction of the caproyl group is from 2850 to 2950.
This was confirmed by the presence of an infrared absorption band resulting from CH stretching of the caproyl group at cm ^-1 . Further, the ratio of the structure of the structural formula (I) to the structure of the structural formula (II) was n / m≈0.30 when calculated from the hydrogen intensity of NH of proton NMR and the hydrogen intensity of methyl of the caproyl group. .. This polymer is N-
Methyl-2-pyrrolidone, N, N-dimethylacetamide, chloroform, dichloroethane, dichloromethane,
It showed good solubility in organic solvents such as tetrahydrofuran. Furthermore, a self-supporting film could be obtained by casting from a chloroform solution of this polymer.
The conductivity was 20 S / cm when iodine was doped.

Example 2 In place of caproyl chloride in Example 1, 3.1 g of crotonoyl bromide was used, and the same treatment as described below was carried out.
A polymer of Introduction of crotonoyl group is 2950 cm
^-1 was confirmed by the presence of an infrared absorption band due to CH stretching. Further, the ratio of the structure of the structural formula (I) to the structure of the structural formula (II) was calculated from the intensity of NH hydrogen of proton NMR and the intensity of methyl hydrogen of crotonoyl group, and n / m≈
It was 0.16. This polymer is N-methyl-2-
It showed good solubility in organic solvents such as pyrrolidone, N, N-dimethylacetamide, chloroform, dichloroethane, dichloromethane and tetrahydrofuran. Furthermore, a self-supporting film could be obtained by casting from a chloroform solution of this polymer. The conductivity was 24 S / cm when iodine was doped.

Example 3 In place of caproyl chloride in Example 1, 3.5 g of p-methoxybenzoyl chloride was used, and the same treatment as described below was carried out to obtain 3.54 g of a polymer. The introduction of the p-methoxybenzoyl group was confirmed by the presence of an infrared absorption band resulting from CH stretching of methyl of the p-methoxybenzoyl group at 2950 cm ^-1 . Further, the ratio of the structure of the structural formula (I) to the structure of the structural formula (II) depends on the intensity of NH hydrogen of proton NMR and p-
It was n / m≅18 when calculated from the intensity of methyl hydrogen in the methoxybenzoyl group. This polymer is N-methyl-2-pyrrolidone, N, N-dimethylacetamide, chloroform, dichloroethane, dichloromethane,
It showed good solubility in organic solvents such as tetrahydrofuran. Furthermore, a self-supporting film could be obtained by casting from a chloroform solution of this polymer.
The conductivity was 20 S / cm when iodine was doped.

Example 4 In a propylene carbonate solution containing 20 mmol of pyrrole and 10 mmol of tetraethylammonium tetrafluoroborate, using a platinum plate as an electrode, a constant voltage of 1.5 V and an electric quantity of 1 C were obtained under an argon atmosphere at −20 ° C. The electrolytic polymerization was carried out. Since the polymer film grown on the platinum plate contains a dopant, it is dedoped by applying a potential of -0.1 V, and further washed with ammonia water and water in this order.
It was dried under reduced pressure. The weight of the polymer exfoliated from the electrode was 0.
It was 1 g. The average degree of polymerization of this polymer was about 250, which was estimated from the degree of polymerization determined by measuring the specific activity of 2,5-ditritiated pyrrole synthesized under the same conditions [shown by structural formula (I)]. The number of repeating structures is 25
0].

0.1 g of potassium methoxide was added to this in methanol, and the mixture was stirred at room temperature for 10 hours. Methanol and unreacted potassium methoxide were removed, thoroughly washed and dried. 0.2 g of caproyl chloride was added to this in tetrahydrofuran, and stirring was continued at room temperature for 48 hours. The film is thoroughly washed with methanol, water, methanol containing ammonia water, and water in this order, and dried under reduced pressure to 0.1.
5 g of polymer was obtained. Introduction of a caproyl group is 2850
Confirmed by the presence of an infrared absorption band due to CH stretching of the caproyl group at ˜2950 cm ⁻¹ . In addition, structural formula (I)
The ratio of the structure to the structural formula (II) structure is N in proton NMR.
When calculated from the strength of hydrogen of H and the strength of hydrogen of methyl of caproyl group, it was n / m≈0.43. This polymer showed good solubility in organic solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, chloroform, dichloroethane, dichloromethane and tetrahydrofuran. Furthermore, a self-supporting film could be obtained by casting from a chloroform solution of this polymer. The conductivity was 15 S / cm when doped with iodine.

[0029]

INDUSTRIAL APPLICABILITY The derivative of the present invention in which an acyl group is introduced at the N-position of polypyrrole is soluble in various organic solvents, and a cast and flexible self-supporting film can be obtained. Processing by a method such as working is also possible, and further, these films and processed products can exhibit high conductivity by doping. Therefore, it is very useful for various purposes as an electronic device material and a conductive material as an organic semiconductor, an organic conductor and the like.

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[Procedure amendment]

[Submission date] May 19, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 2

[Correction method] Change

[Correction content]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0005

[Correction method] Change

[Correction content]

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventor first produced an unsubstituted polypyrrole, and then introduced a substituent consisting of an acyl group at the N-position of polypyrrole. As a result, they have found that the above problems can be solved, and completed the present invention.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction content]

The polypyrrole derivative of the present invention is obtained by reacting an unsubstituted polypyrrole consisting of the structural unit represented by the structural formula (I) [the number of structural units m = 50 to 5000] with metal potassium, potassium alkoxide or potassium hydroxide. Poly (pyrrole-N-potassium), and an acyl halide [RCOX: X is chlorine, bromine or iodine, R is an alkyl group having 3 or more carbon atoms or a substituted alkyl group, an alkenyl group having 3 or more carbon atoms. Or a substituted alkenyl group, an aryl group or a substituted aryl group, or a benzyl group or a substituted benzyl group]. Polypyrrole used in the present invention,
It is produced by the oxidative coupling reaction of pyrrole. Further, polypyrrole can be produced by coupling 2,5-dihalogenated pyrrole with a catalyst such as nickel or without a catalyst. However, this method is not so general because the monomer itself used is unstable.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction content]

The polypyrrole derivative produced by the present invention is an amide solvent such as N-methyl-2-pyrrolidone or N, N-dimethylacetamide, a halogenated hydrocarbon solvent such as chloroform, dichloroethane or dichloromethane, and an ether such as tetrahydrofuran. It is soluble in system solvents.

Claims (2)

[Claims] 1. The following formula (I): And a structural unit represented by the following formula (II): [Wherein R represents an alkyl group or substituted alkyl group having 3 or more carbon atoms, an alkenyl group or substituted alkenyl group having 3 or more carbon atoms, an aryl group or a substituted aryl group, or a benzyl group or a substituted benzyl group] A polymer compound comprising units, the number of structures (m) of formula (I) and the number of structures (n) of formula (II)
Is 50 to 5000, and the value of n / m is 0.01 to 1
00 is a polypyrrole derivative. 2. An unsubstituted polypyrrole comprising the structural unit represented by the structural formula (I) [the number of structural units n = 50 to
5000] is reacted with metal potassium, potassium alkoxide or potassium hydroxide to give poly (pyrrole-N-potassium), and an acyl halide [RCOX: X
Represents chlorine, bromine or iodine, and R represents an alkyl group or substituted alkyl group having 3 or more carbon atoms, an alkenyl group or substituted alkenyl group having 3 or more carbon atoms, an aryl group or substituted aryl group, or a benzyl group or substituted benzyl group. ] The method for producing a polypyrrole derivative according to claim 1, characterized in that