JPH05247203A - Production of conductive organic polymer - Google Patents

Abstract

PURPOSE:To quickly dope an imino-p-phenylene polymer to obtain a polyaniline excellent in the stability of conductivity by treating the polymer with a combination of hydrogen peroxide and a poly basic organic acid. CONSTITUTION:An organic polymer (a) having an imino-p-phenylene unit represented by the formula as the main structural repeating unit is doped with a solution of both a polybasic organic acid and hydrogen peroxide, thereby giving a conductive organic polymer. For the strength and other properties of a conductive polyaniline film to be obtained, the polymer (a) is preferably one which in an undoped state is soluble in an organic solvent and has an intrinsic viscosity, [eta], as measured in N-methyl-2-pyrrolidone at 30 deg.C of 0.40dl/g or higher. Preferred examples of the acid include an organic disulfonic acid and a polymeric acid.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a conductive organic polymer.

[0002]

2. Description of the Related Art Generally, a conductive organic polymer called polyaniline has a general formula

[0003]

[Chemical 2]

A quinonediimine / phenylenediamine type polyaniline having a quinonediimine structural unit and a phenylenediamine structural unit represented by the following as main repeating units is doped with a protonic acid. It is generally said that the protonation of nitrogen in the quinonediimine structural unit of such polyaniline is essential for the development of conductivity. Here, m and n each represent a mole fraction of the quinonediimine structural unit and the phenylenediamine structural unit in the repeating unit, and 0 <m <1,
0 <n <1 and m + n = 1.

A film made of such a conductive polyaniline is prepared by dissolving a solvent-soluble quinonediimine / phenylenediamine type polyaniline in a suitable solvent and casting it as described in JP-A-3-28229. It can be obtained by performing drying treatment (proton acid doping) by immersing it in a proton acid aqueous solution after drying and making it into a film.

Further, Japanese Patent Application Laid-Open No. 3-52929 discloses that
General formula

[0007]

[Chemical 3]

An imino-p-phenylene type polyaniline having an imino-p-phenylene structural unit represented by the following as a main repeating unit is dissolved in a solvent, and an appropriate oxidizing agent is added thereto, followed by casting and film formation, Obtaining a conductive polyaniline film is described. According to this method, the imino-p-phenylene type polyaniline is oxidized and converted into a quinone diimine / phenylenediamine type polyaniline. In this case as well, the anion of the oxidizing agent is doped in the polyaniline. Since the doping at this time involves an oxidation reaction, it is usually called oxidation doping.

As described above, in order for polyaniline to exhibit conductivity, as described above, both a quinonediimine structure and a phenylenediamine structure are necessary in the molecule, and nitrogen in the quinonediimine structure is protonated ( Must be doped). However, conventionally, in order to dope with a protonic acid like this, usually,
It takes a long time. The dope time varies depending on the type of protonic acid used, physical properties such as the film thickness and porosity of the polyaniline film, but in the case of a polyaniline film of about 20 μm, in order to have a conductivity of 1 S / cm or more, hydrochloric acid is used. It requires immersion in an aqueous solution for several hours. When p-toluenesulfonic acid is used as the acid, it may take several days. Such long doping time is disadvantageous in industrial production of the conductive polyaniline film.

On the other hand, in JP-A-60-133027 and Faraday Discuss. Chem. Soc., 88 , 317 (1989), imino-p-phenylene type polyaniline powder is added to ferric chloride in acetonitrile. Alternatively, it is shown that a quinonediimine / phenylenediamine type polyaniline can be obtained by oxidative doping treatment with hydrogen peroxide and an inorganic acid solution such as hydrochloric acid, sulfuric acid or phosphoric acid. ing.

Therefore, as described above, the oxidative doping is carried out by adding an oxidizing agent to a polyaniline solution and then forming a film, or from an imino-p-phenylene type polyaniline solution by casting first. It can also be carried out by preparing a p-phenylene type polyaniline film and then immersing the film in an aqueous solution of an oxidizing agent such as ferric chloride. This oxidative doping differs from protonic acid doping in that it involves an oxidative reaction.

Generally, oxidative doping has an advantage that it takes a shorter time than protonic acid doping, but on the other hand, when an oxidizing agent such as ferric chloride is used, hydrogen chloride is used as a dopant. In addition, when hydrogen peroxide and methanesulfonic acid are combined, methanesulfonic acid is a dopant, so that there is a problem in stability of conductivity after doping with polyaniline.

[0013]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention As a result of intensive studies conducted by the present inventors in order to solve the above-mentioned problems in the conventional doping of polyaniline, the inventors have found that a specific oxidizing agent and a protonic acid are used in combination. , The above imino
The p-phenylene type polyaniline can be rapidly doped, and by doing so,
The present invention has been completed by finding that polyaniline having excellent conductivity stability can be obtained.

[0014]

The method for producing a conductive organic polymer according to the present invention is represented by the general formula (I)

[0015]

[Chemical 4]

An organic polymer having an imino-p-phenylene structural unit represented by the following as a main repeating unit does not have an anion itself with a polyvalent organic acid, and a reductant after an oxidation reaction produces an anion. It is characterized in that it is treated with a solution in which an oxidizing agent which does not exist is dissolved. The polyaniline used in the present invention is an organic polymer having an imino-p-phenylene structural unit represented by the general formula (I) as a main repeating unit and soluble in an organic solvent in a dedoped state. According to the present invention, the above-mentioned imino-p-phenylene-type polyaniline is N-methyl-2-diamine in consideration of the strength of the obtained conductive polyaniline film.
Intrinsic viscosity [η] measured at 30 ℃ in pyrrolidone is 0.4
It is preferably 0 dl / g or more.

Such polyaniline is disclosed in JP-A-3-5.
As described in detail in Japanese Patent No. 2929, the general formula (II)

[0018]

[Chemical 5]

(In the formula, m and n represent the mole fractions of the quinonediimine structural unit and the phenylenediamine structural unit in the repeating unit, and 0 <m <1, 0 <n <1, m +.
n = 1. ) Is an organic polymer having a quinonediimine structural unit and a phenylenediamine structural unit as main repeating units, and is obtained by reducing an organic polymer soluble in an organic solvent in a dedoped state with a reducing agent. be able to.

Examples of the reducing agent include phenylhydrazine, hydrazine, hydrazine hydrate, hydrazine sulfate,
Hydrazine compounds such as hydrazine hydrochloride and reductive metal hydride compounds such as lithium aluminum hydride and lithium borohydride are preferably used. Hydrazine hydrate or phenylhydrazine is particularly preferably used as the reducing agent because it does not produce a residue after the reduction reaction.

The oxidizing agent used in the method of the present invention does not have an anion itself, and the reductant after the oxidation reaction does not produce an anion. Further, the oxidizing agent is preferably soluble in a suitable solvent. It is an agent. In the present invention, for example, hydrogen peroxide is preferably used as the oxidizing agent. In the method according to the present invention, a polyvalent organic acid is used as the protonic acid, and in particular, organic disulfonic acid, especially alkanedisulfonic acid or arenedisulfonic acid is preferably used. Examples of the organic polysulfonic acid containing such an organic disulfonic acid include, for example, ethanedisulfonic acid, propanedisulfonic acid, butanedisulfonic acid, pentanedisulfonic acid, hexanedisulfonic acid, heptanedisulfonic acid, octanedisulfonic acid, nonanedisulfonic acid, Decanedisulfonic acid, benzenedisulfonic acid, naphthalene disulfonic acid, naphthalene trisulfonic acid, naphthalene tetrasulfonic acid, anthracene disulfonic acid, anthraquinone disulfonic acid, phenanthrene disulfonic acid, fluorenone disulfonic acid, carbazole disulfonic acid, diphenyl methane disulfonic acid, biphenyl Disulfonic acid, terphenyl disulfonic acid, terphenyl trisulfonic acid, naphthalene sulfonic acid-formalin condensate, phenanthrene sulfonic acid- Rumarin condensate, anthracene sulfonic acid - formalin condensate, fluorene sulfonic acid - formalin condensate, carbazole sulphonic acid - can be exemplified formalin condensates. The position of the sulfonic acid group in the aromatic ring is arbitrary.

In the present invention, a polymer acid is preferably used as the polyvalent organic acid. Examples of such a polymer acid include polyvinyl sulfonic acid, polyvinyl sulfuric acid, polystyrene sulfonic acid, sulfonated styrene-butadiene copolymer, polyallyl sulfonic acid, polymethacryl sulfonic acid, poly-2-acrylamido-2-methylpropane. Examples thereof include sulfonic acid and polyhalogenated acrylic acid. Sulfonated polyaniline and fluorine-containing polymers known as Nafion (registered trademark of Dupont, USA) are also suitably used as the polymer acid.

According to the present invention, the above-mentioned oxidizing agent and polyvalent organic acid are dissolved in water or an appropriate solvent such as an organic solvent to prepare a dope solution, and the dope solution is imino- Doping the polyaniline by contacting it with p-phenylene type polyaniline. Preferred specific examples of such a dope solution include an aqueous solution of 1,2-ethanedisulfonic acid in hydrogen peroxide.

The concentration of such a dope solution is appropriately selected depending on the temperature of the doping treatment, the film thickness of the polyaniline, the electric conductivity of the target conductive polyaniline, and the like.
For example, in the case of an aqueous solution of 1,2-ethanedisulfonic acid in hydrogen peroxide, the concentration of 1,2-ethanedisulfonic acid is 5 to
It is preferable that the concentration is 30% by weight and the concentration of hydrogen peroxide is about 5 to 30% by weight. Generally, the higher the concentration of the dope solution, the shorter the time required for the doping process, but if it is too high, problems such as deterioration of the mechanical strength of the polyaniline film occur.

The temperature of the doping process is usually 1
The temperature is in the range of 0 to 40 ° C., but if necessary, the doping process can be performed at a higher temperature to shorten the required time. However, if the temperature is too high, problems such as deterioration in mechanical strength of the polyaniline film occur, which is not preferable. According to the method of the present invention, the doping treatment is performed by bringing the polyaniline film into contact with the above-mentioned dope solution. More specifically, it is carried out by a method such as immersing polyaniline in a dope solution with stirring, if necessary, coating the polyaniline film with the dope solution, or spraying the dope solution. After such doping treatment, the film is preferably washed with an appropriate solvent such as ethanol and dried to remove the dope liquid from the polyaniline. This is because when the dope solution remains in the polyaniline film, it may adversely affect the conductivity and the like. A basic solvent containing water may dedope the protonic acid doped into polyaniline, and therefore, washing with such a solvent should be avoided. Ultrasonic cleaning is one effective cleaning method.

[0026]

According to the method of the present invention, polyaniline can be doped in a short time, and the conductive polyaniline obtained has excellent conductivity stability.

[0027]

EXAMPLES The present invention will be described below with reference to examples and reference examples, but the present invention is not limited to these examples. Reference Example 1 (Production of quinonediimine / phenylenediamine type conductive polyaniline in a doped state by oxidative polymerization of aniline)
6000 g of distilled water in a 10 liter separable flask equipped with a stirrer, a thermometer and a straight pipe adapter,
360 ml of 6% hydrochloric acid and 400 g (4.295 mol) of aniline were charged in this order to dissolve the aniline. Separately, while cooling with ice water, distilled water 149 in a beaker
Add 434 g (4.295 mol) of 97% concentrated sulfuric acid to 3 g,
A sulfuric acid aqueous solution was prepared by mixing. This sulfuric acid aqueous solution was added to the separable flask, and the entire flask was cooled to -4 ° C in a low temperature constant temperature bath.

Next, 980 g (4.295 mol) of ammonium peroxodisulfate was added to 2293 g of distilled water in a beaker and dissolved to prepare an oxidizing agent aqueous solution. The entire flask was cooled in a low temperature constant temperature bath, while maintaining the temperature of the reaction mixture at -3 ° C or lower, while stirring, to an acidic aqueous solution of aniline salt, using a tubing pump, using a straight pipe adapter, the above ammonium peroxodisulfate aqueous solution. 1 ml
The mixture was gradually added dropwise at a rate of not more than / minute. At first, the colorless and transparent solution changes from greenish blue to blackish green as the polymerization proceeds.
Then, a black-green powder was deposited.

A temperature rise is observed in the reaction mixture at the time of this powder precipitation, but in order to obtain a high molecular weight polymer,
It is important to keep the temperature in the reaction system at 0 ° C or lower, preferably -3 ° C or lower. After the powder is deposited, the dropping rate of the aqueous solution of ammonium peroxodisulfate may be slightly increased, for example, about 8 ml / min. However, also in this case, it is necessary to monitor the temperature of the reaction mixture and adjust the dropping rate so as to keep the temperature at −3 ° C. or lower. Thus, after the dropping of the aqueous ammonium peroxodisulfate solution was completed over 7 hours, the stirring was continued for another 1 hour at a temperature of -3 ° C or lower.

The obtained polymer powder was filtered, washed with water, washed with acetone, and vacuum dried at room temperature to obtain a black-green quinonediimine / phenylenediamine type conductive polyaniline powder 4
30 g was obtained. This was pressure-molded into a disk having a diameter of 13 mm and a thickness of 700 μm, and by a van der Pauw method,
The conductivity was measured and found to be 14 S / cm. (Production of Quinonediimine / Phenylenediamine-Type Solvent-Soluble Polyaniline by Dedoping of Conductive Organic Polymer) The doped conductive polyaniline powder 35
0 g was added to 4 liters of 2N ammonia water, and the mixture was stirred with an auto homomixer at a rotation speed of 5000 rpm for 5 hours. The mixture changed from black green to blue purple.

The powder was filtered off with a Buchner funnel, washed repeatedly with distilled water while stirring in a beaker until the filtrate became neutral, and then washed with acetone until the filtrate became colorless. did. Then, the powder was vacuum dried at room temperature for 10 hours to obtain 280 g of a dark brown dedoped solvent-soluble quinone diimine / phenylenediamine type polyaniline powder. This polyaniline is N-methyl-2-
It is soluble in pyrrolidone and its solubility is 100 g of the same solvent.
To 8 g (7.4%). Also, the intrinsic viscosity [η] measured at 30 ° C. using this as a solvent was 1.23.

Example 1 1.49 g of phenylhydrazine was dissolved in 90 g of N-methyl-2-pyrrolidone, and then 10 g of the solvent-soluble quinonediimine / phenylenediamine type polyaniline obtained in Reference Example 1 was dissolved with stirring. It was At this time, the solution changed its color from dark blue to light black brown, and at the same time, it was confirmed that nitrogen gas was generated. This solution was filtered under reduced pressure with a G2 filter.

The solvent-soluble imino-p-phenylene type polyaniline solution thus obtained was cast on a glass plate, squeezed with a glass rod, and then N-methyl-2-pyrrolidone in a hot air circulation dryer. Was evaporated, and the obtained polyaniline film was peeled from the glass plate. The film thickness was 20 to 30 μm. This film is 3
After immersing in an aqueous solution containing 0% by weight of 1,2-diethanesulfonic acid and 15% by weight of hydrogen peroxide for 10 minutes, the film was taken out, washed with ethanol, and dried at 60 ° C. for 30 minutes. The electric conductivity of this film was 10.7 S / cm. The electric conductivity of the film after being immersed in distilled water for 10 days was 0.5 S / cm. This conductivity corresponds to 4.7% before immersion.

Example 2 The polyaniline film obtained in Example 1 was immersed in an aqueous solution containing 10% by weight of polyvinylsulfonic acid and 15% by weight of hydrogen peroxide for 10 minutes, and then the film was taken out.
It was washed with ethanol and dried at 60 ° C. for 30 minutes. The electric conductivity of this film was 7.2 S / cm. In addition, the electric conductivity after dipping this film in distilled water for 10 days is 2.
It was 5 S / cm. This conductivity corresponds to 35% before immersion.

Comparative Example 1 The polyaniline film obtained in Example 1 was dipped in a 30% by weight aqueous solution of 1,2-ethanedisulfonic acid for 10 minutes, then taken out and washed with ethanol.
It was dried at 0 ° C. for 30 minutes. The conductivity of this film is 8.0
It was × 10 ^-4 S / cm.

Comparative Example 2 The polyaniline film obtained in Example 1 was immersed in an aqueous solution of 10% by weight of polyvinyl sulfonic acid for 30 minutes, then the film was taken out, washed with ethanol and dried at 60 ° C. for 30 minutes. . The conductivity of this film is 0.29S
/ Cm.

Comparative Example 3 The polyaniline film obtained in Example 1 was dipped in a 20% by weight ferric nitrate aqueous solution for 10 minutes, taken out, washed with ethanol and dried at 60 ° C. for 30 minutes. The conductivity of this film was 11.6 S / cm. The electric conductivity of the film after being immersed in distilled water for 10 days was 2.3 × 10 ⁻⁴ S / cm. This conductivity corresponds to 0.002% before immersion.

Comparative Example 4 The polyaniline film obtained in Example 1 was immersed in an aqueous solution containing 10% by weight of methanesulfonic acid and 7.5% by weight of hydrogen peroxide for 10 minutes, and then the film was taken out and washed with ethanol. And dried at 60 ° C. for 30 minutes. The electric conductivity of this film was 7.4 S / cm. The conductivity of this film after immersion in distilled water for 10 days is 1.5 × 10.
^{It was -3} S / cm. This conductivity corresponds to 0.02% before immersion.

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[Procedure amendment]

[Submission date] November 24, 1992

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[Claims]

[Chemical 1] Of an electrically conductive organic polymer characterized by subjecting an organic polymer having an imino-p-phenylene structural unit represented by the following as a main repeating unit to a doping treatment with a solution in which hydrogen peroxide is dissolved together with a polyvalent organic acid. Production method.

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[0013]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems in the conventional doping of polyaniline, and as a result, peroxidation with polyvalent organic acids has been carried out.
By using hydrogen as an oxidant , the above imino-
The p-phenylene type polyaniline can be rapidly doped, and by doing so,
The present invention has been completed by finding that polyaniline having excellent conductivity stability can be obtained.

[Procedure amendment 3]

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An organic polymer having an imino-p-phenylene structural unit represented by the following as a main repeating unit is treated with a solution in which hydrogen peroxide is dissolved together with a polyvalent organic acid. The polyaniline used in the present invention is an organic polymer having an imino-p-phenylene structural unit represented by the general formula (I) as a main repeating unit and soluble in an organic solvent in a dedoped state.
According to the present invention, in consideration of the strength and the like of the conductive polyaniline film to be obtained, the imino-p-phenylene type polyaniline is treated at 30 ° C. in N-methyl-2-pyrrolidone.
It is preferable that the intrinsic viscosity [η] measured in step 4 is 0.40 dl / g or more.

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In the method according to the present invention , the oxidizing agent is
Thus, hydrogen peroxide is used . Further, in the method according to the present invention, the polyvalent organic acid is used as the protonic acid,
In particular, organic disulfonic acid, especially alkanedisulfonic acid or arenedisulfonic acid is preferably used.
Examples of the organic polysulfonic acid containing such an organic disulfonic acid include, for example, ethanedisulfonic acid, propanedisulfonic acid, butanedisulfonic acid, pentanedisulfonic acid, hexanedisulfonic acid, heptanedisulfonic acid, octanedisulfonic acid, nonanedisulfonic acid, Decanedisulfonic acid, benzenedisulfonic acid, naphthalene disulfonic acid, naphthalene trisulfonic acid, naphthalene tetrasulfonic acid, anthracene disulfonic acid, anthraquinone disulfonic acid, phenanthrene disulfonic acid, fluorenone disulfonic acid, carbazole disulfonic acid, diphenyl methane disulfonic acid, biphenyl Disulfonic acid, terphenyl disulfonic acid, terphenyl trisulfonic acid, naphthalene sulfonic acid-formalin condensate, phenanthrene sulfonic acid- Rumarin condensate, anthracene sulfonic acid - formalin condensate, fluorene sulfonic acid - formalin condensate, carbazole sulphonic acid - can be exemplified formalin condensates. The position of the sulfonic acid group in the aromatic ring is arbitrary.

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In the present invention, a polymeric acid is also preferably used as the polyvalent organic acid. As such a polymer acid, for example, polyvinyl sulfonic acid,
Examples thereof include polyvinyl sulfuric acid, polystyrene sulfonic acid, sulfonated styrene-butadiene copolymer, polyallyl sulfonic acid, polymethacryl sulfonic acid, poly-2-acrylamido-2-methylpropane sulfonic acid, and polyhalogenated acrylic acid. .. Sulfonated polyaniline and fluorine-containing polymers known as Nafion (registered trademark of Dupont, USA) are also suitably used as the polymer acid.

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According to the invention, peroxide water as oxidant
A dope solution is prepared by dissolving hydrogen and a polyvalent organic acid as a protonic acid in a suitable solvent such as water or an organic solvent, and contacting the dope solution with the imino-p-phenylene type polyaniline. The polyaniline is doped. Preferred specific examples of such a dope solution include an aqueous solution of 1,2-ethanedisulfonic acid in hydrogen peroxide.

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The solvent-soluble imino-p-phenylene type polyaniline solution thus obtained was cast on a glass plate, squeezed with a glass rod, and then N-methyl-2-pyrrolidone in a hot air circulation dryer. Was evaporated, and the obtained polyaniline film was peeled from the glass plate. The film thickness was 20 to 30 μm. This film is 3
After dipping in an aqueous solution containing 0% by weight of 1,2- ethanedisulfonic acid and 15% by weight of hydrogen peroxide for 10 minutes, the film was taken out, washed with ethanol and dried at 60 ° C. for 30 minutes. The electric conductivity of this film was 10.7 S / cm. The electric conductivity of the film after immersion in distilled water for 10 days was 0.5 S / cm. This conductivity corresponds to 4.7% before immersion.

Claims (5)

[Claims] 1. A compound represented by the general formula (I): A solution obtained by dissolving an organic polymer having an imino-p-phenylene structural unit represented by the following as a main repeating unit, together with a polyvalent organic acid, and an oxidizing agent having neither anion itself nor a reductant after oxidation reaction. A method for producing a conductive organic polymer, characterized in that the doping treatment is carried out in step 1. 2. The method for producing a conductive organic polymer according to claim 1, wherein the oxidizing agent is hydrogen peroxide. 3. The method for producing a conductive organic polymer according to claim 1, wherein the polyvalent organic acid is an organic disulfonic acid. 4. The method for producing a conductive organic polymer according to claim 1, wherein the polyvalent organic acid is a polymer acid. 5. The organic polymer is soluble in an organic solvent in a dedoped state, and has an intrinsic viscosity [η] measured at 30 ° C. in N-methyl-2-pyrrolidone of 0.40 dl / g or more. The method for producing a conductive organic polymer according to claim 1, 2, 3, or 4.