JPS63213518A - Production of electrically conductive material - Google Patents

Abstract

PURPOSE:To simply obtain a material having excellent electrical conductivity, by attaching a cyclic ether containing pyrrole and a polymerization catalyst to a substrate and drying to form an electrically conductive polymer on the surface and in the interior of the substrate. CONSTITUTION:A cyclic ether (e.g. tetrahydrofuran, etc.) containing pyrrole and/or a pyrrole derivative polymerization catalyst (e.g. FeCl3, etc.) is attached to a substrate (e.g. cotton cloth, etc.), dried and an electrically conductive polymer is formed on the surface or in the interior of the substrate to give the aimed material. The amount of the polymerization catalyst used is preferably 0.2-5mol. based on 1mol. pyrrole.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for manufacturing a conductive material. The conductive material obtained by the present invention has good conductivity without impairing the inherent properties of conventional materials, and can be made conductive by a simple method, so it can be used in a wide range of application fields of conductive materials. It is something.

<Conventional technology> In recent years, research has been conducted on conductive polymers in which the polymer itself is conductive, and polyacetylene, polyparaphenylene, polyphenylene sulfide, polythiophene, polypyrrole, etc. have attracted attention, and studies have been conducted in a wide range of conductive fields. ing. However, when considering the application of conductive polymers,
Material stability and moldability are major issues. First, regarding stability, when polyacetylene film is exposed to air, it reacts with oxygen and becomes brittle. Other polymers are relatively stable in the undoped state, but polymers doped with impurities are unstable in air. The only exception is polypyrrole, which is stable even in films doped with impurities. It is known that pyrrole forms an insoluble and infusible polymer when treated with an oxidizing agent. For example, the Journal of Polymer Science has shown that pyrrole can be polymerized in aqueous solution under the action of potassium persulfate, and the polymer precipitates out in the form of a fine black powder.

1089-1095. (1982). There is also a method of dissolving pyrrole in a suitable electrolytic solution and obtaining a pyrrole polymer on an electrode by electrolytic oxidation polymerization (for example, Chemical Communication, p. 635,
(1979)).

However, these stably obtained pyrrole polymers are insoluble and infusible powders or lumps, and cannot be molded into desired shapes by conventional methods. Further, in electrolytic polymerization, although a specific film-like product can be obtained, it cannot be formed into a desired shape, and moreover, there are problems such as requiring expensive equipment.

<Problems to be Solved by the Invention> In view of the above circumstances, the present invention aims to improve the moldability of conductive polymers, which had been considered a drawback in the past, and to provide a simple method for producing materials with good conductivity. The purpose is to provide.

Means for Solving the Problems> The present invention provides that in a specific organic solvent, even in the presence of FeC1,.6H80, which is a polymerization catalyst for pyrrole, polymerization of torrole hardly progresses, and a polymer of pyrrole also precipitates. A homogeneous mixed solution is obtained, and pyrrole is polymerized only by removing the organic solvent from this mixed solution, and is characterized by having the following requirements.

That is, by attaching a cyclic ether containing pyrrole and/or a pyrrole derivative and a polymerization catalyst to a substrate and drying it, a conductive polymer is produced on the surface and/or inside of the substrate. A method of manufacturing a conductive material is characterized by the following.

The compounds used in the present invention include pyrrole, N-alkylpyrrole, N-arylpyrrole, and pyrrole substituted with monoalkyl or dihalogen at the carbon atom. Usually, pyrrole is most preferably used.

As the organic solvent, cyclic ether is effectively used.

Examples of the cyclic ether include tetrahydrofuran and dioxane. It is also possible to use a mixture of these organic solvents. Further, it may be mixed with a solvent other than the cyclic ether as long as it does not impede the effects of this patent.

The pyrrole polymerization catalyst used in the present invention is mainly Fe
C15, FeC13・6H! O1CuC1g・2H wealth 0
Chlorides such as are effective.

In the present invention, a specific organic solvent, a polymerization catalyst, and pyrrole are mixed, but there are no particular restrictions on the mixing method.
It is sufficient to simply add pyrrole to a solution of a polymerization catalyst dissolved in an organic solvent and stir and mix as necessary. Furthermore, there are no particular limitations on the treatment temperature and time, and it is usually sufficient to carry out the mixing treatment at room temperature for 1 minute to 10 hours.

The amount of polymerization catalyst used is 0 per mole of pyrrole.
．． It is appropriate to use 2 to 5 moles. If the amount of polymerization catalyst is less than 0.2 moles, the polymerization of pyrrole will not proceed sufficiently, and 5 moles is sufficient to polymerize the entire amount of pyrrole.

The amount of the organic solvent may be within a range that dissolves the polymerization catalyst. After applying or dipping the thus obtained mixed solution consisting of the specific organic solvent, polymerization catalyst, and pyrrole onto the substrate, Removing the organic solvent by drying
Polypyrrole is generated on the surface and/or inside of the base material.

As the base material used in the present invention, various synthetic polymers, natural polymers, inorganic materials, etc. are used. Any material that can be applied or dipped can be used. For example, thermosetting resins such as phenolic resins, urea resins, melamine resins, unsaturated polyester resins, alkyd resins, epoxy resins, silicone resins, chloride resins, etc. Thermoplastic resins such as vinyl resin, polyethylene ml polypropylene resin, styrene resin, methacrylic resin, and polyamide resin, natural polymers such as cellulose, starch, and natural rubber,
Polymer compounds such as inorganic polymers such as glass, silica, and alumina, and inorganic materials such as metals and ceramics, as well as cotton, linen, silk, wool, rayon, Kiepura, acetate, vinylon, nylon, vinylidene, and vinyl chloride fibers. Also effective are fibers and cloths such as acrylic fibers and polyester fibers, and papers such as high-quality paper, art paper, coated paper, kraft paper, glassine paper, Japanese paper, cardboard paper, and filter paper.

There are no particular restrictions on the method of applying the pyrrole liquid, but there are methods such as immersing the substrate in the mixed liquid, casting the mixed liquid on the substrate,
All commonly used deposition methods can be used, such as surface coating with a coater and spray coating.

There are also no particular restrictions on the drying method for removing the organic solvent; natural drying is usually sufficient, but if the organic solvent is difficult to evaporate, drying under reduced pressure or raising the drying temperature may be effective. It is true.

If the adhesion between the substrate and the film is poor, adding a soluble polymer compound to the mixture will improve the bond between the film and the substrate and improve the adhesion. can.

<Examples> Hereinafter, examples will be specifically described. In addition, the electrical conductivity in Examples was measured by the four-probe method.

Example-1 Tetrahydrofuran 20yR1 in a beaker with a capacity of 50d
After dissolving 68104 g of FeC1z',
1 g of pyrrole was added and stirred for 30 minutes. The mixture was a dark yellow, transparent, homogeneous solution. A polyvinyl chloride film was dipped into this mixed solution and uniformly wetted. At this time, the color of the film was black, which is typical of polypyrrole, and it did not polymerize, but as it was left as it was for 3 to 5 minutes, as the tetrahydrofuran was evaporated and dried, pyrrole polymerized on the film surface, and it was combined with polyvinyl chloride. A composite film was produced. The color tone of the obtained film was black, and the state of polymer formation was uniform. Also, the conductivity of the film is
It was 10-''S/al.

Example 2 A conductive material was prepared in the same manner as in Example 1, except that cotton cloth, polyester nonwoven fabric, nylon cloth, and high quality paper were used as the base materials.

Table 1 shows the color tone, polymer formation status, and electrical conductivity of the obtained conductive material.

Table 1 - Example 3 The conductive fabric obtained by operating in the same manner as in Example 1, but using dioxane instead of tetrahydrofuran, and using nylon cloth as the base material, was black in color and produced a polymer. The situation was homogeneous. Also, the conductivity of the film is 10-'S
/am.

Example-4 The same procedure as in Example-3 was carried out, except that t-butanol was used instead of dioxane. The color tone of the conductive cloth was black, and the state of polymer formation was uniform.

The conductivity of the film was 10-'S/value.

Example-5 The same procedure as in Example-1 was carried out, except that instead of the dipping method, the mixed solution was coated onto a polyvinyl chloride film using an applicator so that the polypyrrole film thickness was 10 μm. The color tone of the obtained conductive film was black, and the state of polymer formation was uniform. Also, the conductivity of the film is 1O-tS/
It was cm.

Example 6 The procedure was carried out in the same manner as in Example 1, except that 20 methanol was further added to the mixture. The color tone of the obtained conductive film was black, and the state of polymer formation was uniform. The conductivity of the film was 10''S/am.

Comparative Example-1 The same procedure as in Example-1 was carried out, except that acetone was used instead of tetrahydrofuran. The mixture was reddish brown. The color tone of the obtained conductive film was reddish brown, and the state of polymer formation was uniform.

The conductivity of the film was less than 10-'S/cn.

Comparative Example-2 Operated in the same manner as in Example-1, except that FeC1,.6H!
40g of 0 was used. FeC15.6H1O was not completely dissolved, and when 1 g of pyrrole was added, a large amount of black lumps were formed.

<Effects of the invention> As described above, by implementing the method of the present invention,
It becomes possible to produce a moldable conductive material by a simple method, and in particular, it is possible to impart conductivity to a molded body having a complicated shape, which is extremely valuable industrially.

Claims (1)

[Claims] 1) A conductive polymer is formed on the surface and/or inside of the substrate by attaching a cyclic ether containing pyrrole and/or a pyrrole derivative and a polymerization catalyst to a substrate and drying it. A method for producing a conductive material, the method comprising: producing a conductive material. 2) The method for producing a conductive material according to claim 1, wherein the cyclic ether is tetrahydrofuran or dioxane.