JPH062819B2 - Method for producing conductive composite - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a pyrrole polymer composition.
Specifically, it relates to a method for producing a composition in which a polymer of pyrrole is supported on thermoplastic resin particles.

[Conventional technology]

It is already well known that a 5-membered heterocyclic compound forms a polymer with an oxidizing agent. For example, it is known that pyrrole and its derivatives can form insoluble and infusible polypyrrole with inorganic acids, iron chloride, benzoquinone, ozone, etc. Advancing in heterocyclic chemistry 15
Volume 67 (1973). The thus-obtained polypyrrole is insoluble and infusible, and has problems that it is difficult to mold and also has a low bulk specific gravity and is difficult to handle. On the other hand, for example, a method of electrolytically polymerizing pyrrole in the presence of a specific particulate carrier is shown. (JP Sho
59-168010) [Problems to be Solved by the Invention] The above-described method for electrolytically polymerizing pyrrole in the presence of a particulate carrier has a problem that a special apparatus and an electrolyte are required.

[Means for solving problems]

The present inventors have earnestly studied a method for solving the above problems and obtaining a pyrrole polymer composition at a low cost by a simple method, and arrived at the present invention.

That is, the present invention, after adding pyrrole to the solution in which the oxidant is dissolved and mixed, the volume obtained by separating the insoluble matter and the thermoplastic resin particles are brought into contact with each other, and then, as it is or filtered,
In the method for producing a conductive composite, the thermoplastic resin particles are caused to carry a pyrrole polymer by evaporating and removing the solvent after decantation.

As the oxidizing agent used in the present invention, inorganic acids, metal compounds and the like are effective, and sulfuric acid, hydrochloric acid, nitric acid, chlorosulfonic acid and the like are mentioned as specific examples of the inorganic acid, and the metal compound is known as a Lewis acid. A compound is preferably used, and aluminum, tin, titanium, zirconium,
Specific examples include chlorides, sulfates, nitrates and acetylacetonate compounds of metals such as chromium, manganese, iron, copper, molybdenum, tungsten, ruthenium, palladium and platinum. Further, peroxodisulfuric acid or percarbonate salts can also be preferably used. Furthermore, organic compounds such as benzoquinone and diazonium salts can also be used. It is also possible to use these oxidizing agents as a mixture of two or more species.

As the thermoplastic resin particles used in the present invention, any known one can be used, and pellets, powders, beads, etc. may have any shape, but preferably,
It has a shape that allows the oxidant solution to easily penetrate. Examples of the thermoplastic resin include industrially available ones such as polypropylene, polyethylene, polystyrene, polyvinyl chloride, styrene-acrylonitrile copolymer, polyester, polycarbonate and polyisoprene.

The solvent for dissolving the oxidizing agent is not limited as long as the oxidizing agent is soluble and the thermoplastic resin particles are insoluble, but preferably alcohols, halogenated hydrocarbons, and direction group hydrocarbons. , Ethers, water, etc., and preferably one capable of dissolving 0.01 g or more of the above-mentioned oxidizing agent in 1 part.

The amount of pyrrole used in the present invention is 0.1 to 100 mol, and usually 1 to 10 mol, per 1 mol of the oxidizing agent.

The mixing of pyrrole in the oxidant solution is not particularly limited in terms of temperature, time and mixing method, and it is sufficient to perform the mixing at room temperature for several minutes to several tens of minutes. After mixing, the insoluble matter is separated and removed. As the separation method, an ordinary method such as decantation or another method can be adopted.

The method of bringing the thus obtained homogeneous solution into contact with the thermoplastic resin particles is not particularly limited, but it is usual to disperse and mix the thermoplastic resin particles in the solution. The thermoplastic resin particles thus brought into contact with the solution can be used as they are, or after the solvent is removed by evaporation, decantation or the like, the solvent can be removed by evaporation to obtain a thermoplastic resin composition carrying a pyrrole polymer.

Here, the method of removing the solvent is not particularly limited, and a method of evaporating and removing by heating, a method of treating under a stream of air, oxygen, nitrogen, or other gas can be adopted.

〔The invention's effect〕

By carrying out the method of the present invention, it is possible to disperse a polymer of pyrrole in a relatively large amount ratio with respect to the thermoplastic resin, and a composite composition having high electric conductivity can be obtained.

〔Example〕

 Hereinafter, the present invention will be described with reference to examples.

Example 1 10 g of ferric chloride-6 hexahydrate as an oxidant, 50 ml of methanol
5 ml of pyrrole is slowly added to a solution of 20 ml of methanol in a solution with vigorous stirring. After the addition, the mixture was stirred at room temperature for a uniform time, and the insoluble matter was passed through to obtain a uniform solution. Add 10 ml of this solution to polypropylene (# 600 pas
s) 2.5 g was added and the solvent was removed under a stream of air with stirring and then washed with methanol. The yield of the obtained composite was 2.7 g, which was heated and pressed at 240 ° C. to be molded into a sheet. When the molded product was measured for specific resistance by a two-terminal method using silver paste, it was 6.1 × 10 ⁸ Ωcm.

Example 2 The operation of forming a composite by impregnating polypropylene with a solution in Example 1 was repeated three times. Complex yield is 3.
It was 1 g and the specific resistance was 3.6 × 10 ⁵ Ωcm.

Example 3 Example 2 was repeated except that polystyrene was used instead of polypropylene. The yield of the obtained composite was 2.9 g, and the specific resistance was 3.2 × 10 ⁷ Ωcm.

Claims (1)

[Claims] 1. A solution obtained by adding pyrrole to a solution in which an oxidant is dissolved and mixing, and then separating a solution obtained by separating insolubles from the thermoplastic resin particles, and then contacting the solution as it is or after filtration and decantation with a solvent. A method for producing an electrically conductive composite, characterized in that a pyrrole polymer is supported on the thermoplastic resin particles by evaporating and removing the polymer.