JP3113709B2 - Method for producing conductive polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0007]

The present invention relates to a method for producing a conductive polymer used as a conductive material.

[0008]

2. Description of the Related Art Many methods for producing conductive polymers have been proposed. These methods can be broadly classified into an electrolytic polymerization method, a chemical polymerization method, and a chemical vapor deposition method. Among these methods, the chemical polymerization method is the most simple and can be mass-produced. In view of this point, the present inventor focused on the chemical polymerization method. In this method, for example, (1) WO89 / 01008, JP-B-63
A method of producing a conductive polymer by performing oxidative polymerization in a solution using a transition metal compound such as ferric chloride or cupric chloride as an oxidizing agent described in -284219 is known. Also, (2) a salt is added to a cupric compound such as a copper borofluoride compound and a nitrile compound such as acetonitrile described in JP-A-63-215717, and the conductive polymer is oxidized and polymerized in a solution. Methods for producing coalescence are known.

[0009]

In these methods, in the method (1), the metal salt of the oxidizing agent must be used in the production of the polymer in the amount of the reaction reagent. After the termination, a large amount of metal salt is generated, and there is a risk of environmental pollution due to waste liquid treatment. In the method (2), the starting materials used are limited to pyrrole and a pyrrole derivative, and there is a problem that the produced conductive polymer is limited to p-type. In the present invention, p-type and n-type conductive polymers can be obtained by solving such problems, and without causing a problem in waste liquid treatment after the production of the conductive polymer, and in a simple and large amount. It is intended to provide a method for producing a conductive polymer which can be produced.

[0010]

According to the present invention, there is provided a compound comprising: " 1.2 . A hydrogen atom is bonded to carbon atoms at positions 2 and 5;
1 or 2 or more, which to choose from are π-conjugated heterocyclic 5-membered cyclization compound
With the following general formula MAn [where M is V or VO
A is a halogen atom or β represented by the following chemical formula 1.
-A diketone,

[0011]

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[0012] (R is an alkyl group, a halogenated alkyl group, a group selected from phenyl group) solution n is in combination with an oxygen atmosphere vanadium compound and AlCl ₃ represented by an integer from 2 or 3 as catalyst A method for producing a conductive polymer, comprising polymerizing. 2 . 2. The method for producing a conductive polymer according to item 1, wherein pyridine is added to a solution for performing polymerization. 3 . A hydrogen atom is bonded to the carbon atom at positions 2 and 5
1 or 2 or more selected from π-conjugated 5-membered ring compounds
Is represented by the following general formula MAn wherein M is V or VO, and A is a halogen atom or β represented by the following chemical formula 1.
-A diketone,

[0013]

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(R is a group selected from an alkyl group, a halogenated alkyl group, and a phenyl group) n is an integer of 2 or 3] by using a vanadium compound catalyst represented by the following formula:
Add pyridine to the solution to be run and add solution weight in oxygen atmosphere.
A method for producing a conductive polymer, comprising: 4 . The conductive polymer according to any one of claims 1 to 3, wherein the vanadium compound catalyst is one or more selected from vanadium trichloride, vanadium tribromide, vanadium acetylacetonate, and vanadium oxyacetylacetonate. Manufacturing method. 5. The 5-membered π-conjugated heterocyclic compound has the following general formula

[0015]

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[Wherein R ₁ and R ₂ are a hydrogen atom, an alkyl group, an aryl group, an arylene group or an alkoxy group;
Is O, S, NH, NR ₃ (R ₃ is an alkyl group).] The conductive property described in any one of the above items 1 to 4, which is one or more selected from A method for producing a polymer. About.

The 5-membered π-conjugated heterocyclic compound used in the present invention includes pyrrole, thiophene, furan and derivatives thereof, and one or more of them are used.
For example, pyrrole, 3-methylpyrrole, N-methylpyrrole, 3-methyl-4-hexoxycarbonylpyrrole, 3-methyl-4-benzyloxycarbonylpyrrole, thiophene, 3-methylthiophene, 3-ethylthiophene, 3- Examples include, but are not limited to, propylthiophene, 3-butylthiophene, 3-pentylthiophene, 3-hexylthiophene, 3-heptylthiophene, 3-octylthiophene, furan, 3-methylfuran, and the like.

The catalyst used in the present invention is a vanadium compound represented by the following general formula. MAn [where M is V
Or VO, A is a halogen atom or a β-diketone represented by the following formula:

[0019]

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(R is a group selected from an alkyl group, a halogenated alkyl group and a phenyl group) n is an integer of 2 or 3. The reason is that, in the case of iron chloride, an oxidizing agent that makes iron trivalent divalent However, the reaction from divalent to trivalent is difficult, and it is difficult to work as a catalyst cycle. Also, copper chloride can work in bivalent and monovalent catalytic cycles,
With a catalytic amount, it is difficult to obtain a polymer by oxidatively polymerizing the substituted monomer in an oxygen atmosphere. Therefore, the present inventor has focused on vanadium compounds which are considered to have stronger oxidizing power than copper and can work in a catalytic cycle, and as a result of intensive research, have found that the vanadium compounds are most suitable as polymerization catalysts for monomers. .

According to the present invention, a conductive polymer is produced by solution polymerization in an oxygen atmosphere. Specific examples of the vanadium compound include vanadium trichloride, vanadium tribromide, vanadium acetylacetonate, and vanadium oxyacetate. Acetyl acetonate and the like can be mentioned. The amount of the vanadium compound to be used is preferably 0.01 to 1 mole, and most preferably 0.1 to 0.6 mole, per 1 mole of the π-conjugated 5-membered ring compound.

AlCl ₃ is used in combination as a catalyst, and its amount is preferably 5 mol or less per 1 mol of the vanadium compound. When the amount is 5 mol or more, the polymer becomes a mere addition polymer, the π-conjugated chain becomes short, and the electric conductivity is remarkably reduced. Pyridine can be used in combination with the catalyst, and the amount of the pyridine is 0.1 to 1 mol of the vanadium compound.
1 to 5 moles is preferred.

The solvent used is a general organic solvent, preferably acetonitrile, nitromethane, nitrobenzene, ethanol, methanol, chloroform and the like. Although the amount of use is not particularly limited,
It is preferably 2- to 75-fold the molar amount of 1-membered ring compound.

As the reaction conditions in the present invention, the reaction temperature is 0 to 90 ° C., preferably 20 to 60 ° C. The reaction time is 1 to 100 hours after oxygen substitution, and preferably 3 to 48 hours. The polymer obtained according to the present invention is a black, brown, tan or red-brown powdery substance, and can be doped with various dopants. Dopant used is halogen such as _{I 2,} As
^{_{F 5 2-, SbF 5 -,}} ClO 4 - can be improved electrical conductivity by doping the like.

[0025]

In the present invention, the present inventor believes that the reaction proceeds additionally with a Lewis acid, then hydrogen is extracted by the vanadium compound and oxygen, and the conjugate chain is extended. The vanadium compound plays two roles of the above-mentioned addition and hydrogen abstraction, and advances the polymerization reaction.
When aluminum chloride is used in combination with the vanadium compound,
It is thought that aluminum chloride acts as a stronger Lewis acid, facilitating the addition reaction, and improves the polymer yield. When pyridine is used in combination, it is considered that the form of the polymer changes, and electron transfer between molecules is likely to occur. As a result, the electric conductivity is improved by 2 to 4 digits. The conductive polymer obtained by the present invention is a secondary battery, a transistor,
Used as antistatic agent, electromagnetic wave shielding agent, etc.

[0026]

EXAMPLES Example 1 V was placed in a 50 ml two-necked flask purged with nitrogen under a nitrogen stream.
Cl ₃ 0.787g (5mmol) and AlCl ₃ 0.
667 g (5 mmol) was weighed, 13 ml of dry acetonitrile was slowly added, and the mixture was stirred for about 1 hour. To this solution was added dropwise pyrrole 1.68g (25 mm ol), and stirred for an additional 2 hours. Thereafter, the inside of the reaction system was replaced with oxygen, and the mixed solution was stirred at 60 ° C. for 24 hours. After completion of the reaction, 6N-hydrochloric acid was added to the reaction solution to stop the reaction, and the produced polypyrrole was filtered off. 6N- residue
It was washed several times with hydrochloric acid, then with alcohol, and then with water until the pH of the filtrate was 7. The product obtained is
Vacuum drying was performed at 24 ° C. for 24 hours to obtain 1.844 g of a black powdery substance. An elemental analysis of this material showed
Matched with polypyrrole. Conductivity measurement was performed as follows. 50 mg of the product was weighed and pressed at 4000 kg / cm ² for 10 minutes using a 10 mmψ tablet press with a press machine (Hydraulic cylinder manufactured by Yuken Kogyo Co., Ltd.) to produce pellets having a diameter of 10 mm and a thickness of 1 mm. . The electrical conductivity of the obtained pellets was measured by a four-point probe method using Loresta-AP / MCP-400 manufactured by Mitsubishi Yuka Corporation. The conductivity at this time is 2.0 × 10−
6 Scm-1.

Example 2-3 Using the monomers and catalysts shown in Table 1, a conductive polymer was produced in the same manner as in Example 1 under the polymerization conditions shown in Table 1. The obtained polymer was subjected to elemental analysis and found to be consistent with polypyrrole.

[0028]

[Table 1]

Examples 4 to 10 Conductive polymers were produced in the same manner as in Example 1 by using the monomers and catalysts shown in Table 2 under the polymerization conditions shown in Table 2. The obtained polymer was subjected to elemental analysis and found to be consistent with the calculated values. The conductivity was measured in the same manner as in Example 1 after doping in an iodine atmosphere for 24 hours after the preparation of the pellet.

[0030]

[Table 2]

[0031] Using the example 1 1 to 1 4 Table 3 shows the monomer and catalyst, after the mixture was stirred for 1 hour was added acetonitrile, pyridine 0.40ml was added and after stirring for further 1 hour, the polymerization conditions shown in Table 3 Then, a conductive polymer was produced in the same manner as in Example 1. The obtained polymer was subjected to elemental analysis and found to be consistent with polypyrrole.

[0032]

[Table 3]

Examples 15 and 16 Conductive polymers were produced in the same manner as in Examples 11 to 14 using the monomers and catalysts shown in Table 4 and under the polymerization conditions shown in Table 4. The obtained polymer was subjected to elemental analysis and found to be consistent with the calculated values. The measurement of the conductivity was performed according to Examples 4-1.
Performed similarly to 0 .

[0034]

[Table 4]

Comparative Example VCl ₃ was changed to 1.33 g of AlCl _3, and 60
The reaction was carried out in the same manner as in Example 1 except that the reaction was carried out at ℃. As a result, 0.415 g of a brown powdery substance was obtained. Elemental analysis of this material indicated that it was consistent with the pyrrole addition polymer. When the conductivity was measured in the same manner as in Example 1, it was 10 ⁻¹⁰ Scm ⁻¹ or less.

[0036]

According to the production method of the present invention, a conductive polymer can be produced in an oxygen atmosphere using a catalytic amount of a metal salt without using a reactive reagent amount of a metal salt as in the prior art. Even when mass production is carried out, almost water is generated instead of a large amount of metal salt, and there is no environmental pollution due to waste liquid treatment. Further, in the production method according to the present invention, a polymer of a π-conjugated 5-membered ring compound such as thiophene and a thiophene derivative can be produced without being limited to a polymer of pyrrole and a pyrrole derivative, and p-type and n-type can be produced. A conductive polymer is obtained.

Claims (5)

(57) [Claims] 1. A hydrogen atom is bonded to carbon atoms at positions 2 and 5.
1 or selected from the π-conjugated 5-membered heterocyclic compound
Two or more of the following general formula MAn [where M is V or VO
Ri, A is represented by a halogen atom or the following of 1 beta-wearer's own hair
A ton, [0001] [Formula 1] [0002] (R is an alkyl group, a halogenated alkyl group, a group selected from phenyl group) solution n is in combination with an oxygen atmosphere vanadium compound and AlCl ₃ represented by an integer from 2 or 3 as catalyst A method for producing a conductive polymer, comprising polymerizing. 2. The method for producing a conductive polymer according to claim 1, wherein pyridine is added to a solution for performing polymerization. 3. A hydrogen atom is bonded to carbon atoms at positions 2 and 5.
1 or selected from the π-conjugated 5-membered heterocyclic compound
Two or more are represented by the following general formula MAn wherein M is V or VO, A is a halogen atom or a β-diketone represented by the following chemical formula 1, [0004] (R is an alkyl group, a halogenated alkyl group, selected group phenyl group) polymerization using a vanadium compound catalyst represented by the n is an integer of 2 or 3]
Add pyridine to the solution to be run and add solution weight in oxygen atmosphere.
A method for producing a conductive polymer, comprising: 4. The method according to claim 1, wherein the vanadium compound catalyst is one or more selected from vanadium trichloride, vanadium tribromide, vanadium acetylacetonate, and vanadium oxyacetylacetonate. A method for producing a conductive polymer. 5. A 5-membered π-conjugated heterocyclic compound represented by the following general formula: [Wherein R ₁ and R ₂ are a hydrogen atom, an alkyl group, an aryl group, an arylene group or an alkoxy group;
Is O, S, NH, or NR ₃ (R ₃ is an alkyl group). 5. The conductive material according to claim 1, wherein A method for producing a polymer.