JPS61127736A - Production of electrically conductive resin composite - Google Patents

Abstract

PURPOSE:To obtain the titled moldable composite having high electrical conductivity, and containing a large amount of a 5-membered heterocyclic compound in uniformly dispersed state, by impregnating an oxidizing agent to a thermoplastic resin particles, and stirring the particles in a solution containing a 5-membered heterocyclic compound as a solute. CONSTITUTION:An oxidizing agent is impregnated in thermoplastic resin particles, and the particles are stirred in a solution produced by dissolving a 5-membered heterocyclic compound in a liquid medium which is essentially a nonsolvent of said oxidizing agent and thermoplastic resin. The oxidizing agent is e.g. sulfuric acid, chlorosulfonic acid, aluminum chloride, etc. The amount of the 5-membered heterocyclic compound polymer is preferably 0.1-0.2pt.wt. per 1pt. of the thermoplastic resin.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a method of manufacturing a conductive composite.

Specifically, the present invention relates to a method for producing a conductive resin composite comprising a thermoplastic resin and a five-membered heterocyclic compound polymer.

[Conventional technology]

It is well known that five-membered heterocyclic compounds form insoluble and infusible polymers when oxidizing agents are used.For example, pyrrole is formed into polymers such as pyrrole black and pyrrole red when inorganic acids, iron chloride, benzoquinone, ozone, etc. Advances in Heterocyclic Chemistry (A
dvances 1nHeterocyclic C
hemistry) Volume 15, page 67 (1973). Similarly, derivatives of furan and thiophene also form polymers. On the other hand, it is also known that membrane-like polymers of virol, furan, and thiophene can be obtained by electrolytic polymerization in the presence of an appropriate electrolyte (for example, Chemical Co., Ltd.
mmunication) 1979655 pages,
Japan Journal of Applied Physics (Japan J, Apl, Physics) Vol. 21 L562 (1982), Vol. 26 L527 (1982)
1984)).

[Problem to be solved by the invention]

However, with conventional methods, the resulting polymer is insoluble and infusible and cannot be molded into a desired shape, and with electrolytic polymerization, although it can be made into a specific film shape, it is difficult to shape the polymer. There was a problem that it was not possible to form the desired shape, and moreover, expensive equipment was required.

The inventors of the present invention have conducted intensive studies on ways to solve the above problems, and have found that by using a specific polymerization method to create a composite resin of a thermoplastic resin and a five-membered heterocyclic compound, a resin composite that can be molded at low cost and is conductive. The present invention was completed based on the discovery that the present invention can be obtained by the following methods.

[Means for solving problems]

That is, the present invention is characterized in that thermoplastic resin particles impregnated with an oxidizing agent are stirred in a liquid medium in which a five-membered heterocyclic compound that does not substantially dissolve the oxidizing agent and the thermoplastic resin is dissolved. This is a method for manufacturing a conductive resin composite.

As the oxidizing agent used in the present invention, inorganic acids and metal compounds are effectively used. For example, inorganic acids include sulfuric acid,
Examples include hydrochloric acid, nitric acid, chlorosulfonic acid, etc., and examples of metal compounds include various compounds known as Lewis acids,
Specifically, examples include chlorides, sulfates, nitrates, and acetylacetonate compounds of aluminum, dB, -f-7, zirconium, chromium, manganese, iron, copper, molybdenum, tungsten, ruthenium, palladium, platinum, etc. Examples include: Furthermore, organic compounds such as be/noquinone and diazonium salts can also be used. These oxidizing agents may be used alone or in combination of two or more.

The thermoplastic resin particles used in the present invention can be of any shape, including pellets, powder,
Commercially available shapes such as beads can be used as they are. For example, those manufactured on an industrial scale such as polyethylene, polypropylene, polyvinyl chloride, styrene-acrylonitrile copolymer, polycarbonate, polyester, and polyinopropylene can be used.

In the present invention, as for the shape of the thermoplastic resin particles, the shape of the particles before being impregnated with the above-mentioned oxidizing agent may be maintained as it is, or the shape of the particles may be changed when impregnated with the oxidizing agent as described later. , it is sufficient that the shape is suitable for easy dispersion during contact treatment with a five-membered heterocyclic compound.

In the present invention, there is no particular restriction on the method of impregnating the thermoplastic resin with the oxidizing agent, and the following method can be adopted. For example, a method in which a thermoplastic resin is dispersed in a solution containing an oxidizing agent, a method in which a thermoplastic resin and an oxidizing agent are dissolved in a solvent and then precipitated in a poor solvent for both, and a method in which a crystalline thermoplastic resin and an oxidizing agent are heated Examples include a method of dissolving and then cooling and solidifying the resin, and a method of co-pulverizing the oxidizing agent and the thermoplastic resin.

In the present invention, the thermoplastic resin particles impregnated with the oxidizing agent obtained by the above method are then dispersed in a solvent that does not substantially dissolve the oxidizing agent and the thermoplastic resin, and stirred with a five-membered heterocyclic compound described below. Treat contact. Any solvent may be used as long as it does not substantially react with the oxidizing agent and the five-membered cyclic compound and does not substantially dissolve the oxidizing agent and the thermoplastic resin. For example, in the case of a combination of polypropylene and metal halides, low-temperature pen/tan, hexa/
, be/zene, toluene, etc. can be used. It is not necessary to add the entire amount of the five-membered heterocyclic compound at once; it can also be added gradually, and this method is particularly effective when using a solvent that is difficult to dissolve the five-membered heterocyclic compound. It is. The stirring process is generally carried out using a conventional stirring blade, but it can also be carried out by circulating stirring with a slurry pump or the like.

There are no particular restrictions on the temperature and time of the stirring contact treatment, but in order to obtain a resin composite with good conductivity,
It is preferable to select the temperature and time such that the amount of the polymer of the five-membered heterocyclic compound in the resin composite relative to the thermoplastic resin becomes a weight ratio of 0.1 to 2.

In particular, the reaction proceeds sufficiently at room temperature.

In the present invention, the five-membered heterocyclic compound includes pyrrole,
Examples include furan, thiophene, seleno7e/, tellurophene and derivatives thereof.

The conductive resin composite thus obtained is separated from the unreacted five-membered heterocyclic compound and the solvent by separation using a filtration device. At this time, it is possible to remove the oxidizing agent if necessary, but when a Lewis acid is used as the oxidizing agent, the oxidizing agent acts as a dopant and improves conductivity, so the unreacted oxidizing agent is simply removed. It is sufficient to simply remove the elementary five-membered cyclic compound.

〔Effect of the invention〕

By carrying out the method of the present invention, it is possible to obtain a composite in which a comparatively large amount of a five-membered heterocyclic compound polymer is uniformly dispersed, so that a conductive composite that is moldable and has high conductivity can be obtained. can be easily obtained and has high industrial value.

〔Example〕

The present invention will be explained below with reference to Examples. Note that parts in the examples indicate parts by weight.

Example 1 Oxidizing agent-impregnated resin 201 obtained by co-pulverizing 1 part of ferric chloride with 4 parts of polypropylene and 25 parts of n-hexane were placed in a glass container, stirred, and then mixed with virol 5. O
Add rall. After stirring at room temperature for 24 hours, the resulting polypyrrole composite was washed with 7-talohexane and dried. The yield of complex was 2.81. Further, the specific resistance of the truly breathed sheet was 8, OXl[+3 Ωcm.

Example 2 The same operation sound as in Example 1 was carried out using high-grade resin "Balenox" (trademark, manufactured by Nohio Chemical Co., USA) instead of polyglopylene. The yield of polypyrrole composite is 2.62, and the specific resistance of the press note is 1.7X
It was 105 cm.

Example 5 Oxidizing agent-impregnated resin 1 obtained by impregnating 1 part of ferric chloride into 10 parts of polypropylene in methanol and then drying.
25 mg of 01 and 7 chlorohexane were placed in a glass container, and 4.0 ml of pyrrole was added while stirring. After stirring at room temperature for 4 hours, the resulting polypyrrole composite was washed with methanol and dried. The specific resistance of the hot-pressed notes was 1.5 x 10'rLcm.

Example 4 Thiophenone 5.0 mef was used instead of virol,
The same operation as in Example 1 was performed except that the reaction time was 96 hours. The yield was 2.61 and the specific resistance of the pressed sheet was 6.5 x 10106Q.

Example 5 The same operation as in Example 1 was carried out except that 5.0 mef of furan was used instead of pyrrole and the reaction time was changed to 96 hours.

The yield was 2.71, and the specific resistance of the press sheet was 7.
It was F3×105QCm.

Claims (1)

[Claims] 1. A conductive resin characterized in that thermoplastic resin particles impregnated with an oxidizing agent are stirred in a liquid medium in which a five-membered heterocyclic compound that does not substantially dissolve the oxidizing agent and the thermoplastic resin is dissolved. Method of manufacturing the composite.