JPS61159455A - Production of electrically conductive resin composite material - Google Patents

Abstract

PURPOSE:To obtain a resin composite material which is inexpensive, can be molded and is electrically conductive, by treating a five-membered heterocylic compd.-impregnated thermoplastic resin in a soln. of an oxidizing agent which does not dissolve the resin. CONSTITUTION:A five-membered heterocylic ring compd.-impregnated thermo plastic resin is brought into contact with a soln. contg. a dissolved oxidizing agent which does not dissolve said five-membered compd. and said resin. Examples of the five-membered compds. are pyrrole, thiophene, furan and their derivatives, among which pyrrole and its derivatives are preferred, because they have high reaction rate and gives composite materials having high electrical conductivity. Examples of the oxidizing agents are inorg. acids and metallic compds. The treatment is usually carried out at room temp. for several min to several tens of hr.

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 in the presence of oxidizing agents, such as virol, inorganic acids, iron chloride, and benzoquinone.

Advances, ins, heterocyclics, and chemistry (Advances 1nHeter) can be turned into polymers such as pyrrole black and pyrrole red by ozone,
Cyclic Chemistry, Volume 15, Page 67 (1973). Similarly, Fran and .

Derivatives of thiophene also form polymers. On the other hand, it is also known that film-like polymers of pyrrole, furan, and thiophene can be obtained by electrolytic polymerization in the presence of an appropriate electrolyte (
For example, chemical communication (J, C, S,
(Chemical Communication)1
979 635 pages, Japan Journal
of Applied Physics Volume 21 (19
1982) L562, ib id, vol. 23 (1984) L527).

[Problem to be solved by the invention]

However, with conventional methods, the polymer obtained is insoluble and infusible and cannot be molded into the desired shape, and with electrolytic polymerization, although it is possible to form a specific film, the desired shape cannot be obtained. However, there was a problem in that it could not be made into a shape of 1, and moreover, it required expensive equipment.

The inventors of the present invention have conducted extensive 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 polymer, it is possible to create a composite resin that is inexpensive, moldable, and conductive. The present invention has been completed based on the discovery that a resin composite with a high viscosity can be obtained.

[Means for solving problems]

That is, 1. the present invention involves contact treatment of a thermoplastic resin impregnated with a 5-membered heterocyclic compound in a liquid medium containing an oxidizing agent that does not substantially dissolve the 5-membered heterocyclic compound and the thermoplastic resin. A method for producing a conductive resin composite, characterized by:

The thermoplastic resin used in the present invention is not particularly limited, and many commercially available polymers can be used, such as polyethylene, polypropylene, polyvinyl chloride,
Styrene-acrylonitrile copolymer, polycarbonate, polyester.

Polyisopropylene and other materials manufactured on an industrial scale can be used.

Examples of the 5-membered heterocyclic compound used in the present invention include pyrrole, thiophene, furan, and their derivatives, and among them, pyrrole and its derivatives have a fast reaction rate and a high electrical conductivity of the resulting complex. Derivatives of are preferably used.

In the present invention, methods for impregnating a thermoplastic resin with a 5-membered heterocyclic compound include, for example, a method of co-pulverizing the above-mentioned two, a method of mixing and heating the 5-membered heterocyclic compound, or a method of heating the 5-membered heterocyclic compound. Examples include a method of melt-mixing a compound of the formula and a thermoplastic resin and then molding it into a desired shape, and there are no particular restrictions on the schedule. Further, there is no particular restriction on the shape of the product when it is brought into contact with a solution in which an oxidizing agent is dissolved, and it may be in the form of a final product, pellets, or powder.

The oxidizing agent used in the present invention is an inorganic acid.

Metal compounds are effectively used. For example, inorganic acids include sulfuric acid, hydrochloric acid, nitrate, chlorosulfonic acid, etc.
Metal compounds include various compounds known as Lewis acids: aluminum, tin, titanium, zirconium, chromium, manganese, iron.

Specific examples include chlorides, sulfates, nitrates, and acetylacetonate compounds of copper, molybdenum, tungsten, ruthenium, palladium, and platinum. Furthermore, organic compounds such as benzoquinone and diazonium salts can also be used. These oxidizing agents may be used alone or in combination of two or more.

The solvent used to dissolve the oxidizing agent may be any solvent as long as it dissolves the oxidizing agent and does not substantially dissolve the five-membered heterocyclic compound and the thermoplastic resin.

In the present invention, there are no special restrictions on the contact method,
It is sufficient to simply add a thermoplastic resin impregnated with a five-membered heterocyclic compound to a solution containing an oxidizing agent and stir and mix as necessary. There are no particular restrictions on the temperature and time of the contact treatment, but it is usually sufficient to carry out the contact treatment at room temperature for several minutes to several tens of hours. The five-membered heterocyclic compound and the oxidizing agent are generally used in amounts of 0.01 to 0.5 parts by weight and 0.001 to 0.5 parts by weight, respectively, per part of the thermoplastic resin.

The conductive resin composite thus obtained is subjected to filtration or static separation to remove unnecessary oxidizing agents, and, if necessary, heated or dried under reduced pressure to remove unreacted 5-membered heterocyclic compounds.

Obtained. Conductive resin composite as required.

A molded product of a desired shape can be formed by hot melt molding or compression molding, and in the case of a molded product before contacting with an oxidizing agent solution, the above-mentioned excess oxidizing agent and five-membered heterocyclic compound are simply removed. The desired molded product can be obtained by just using the above method.

[For production]

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 it is moldable and has high conductivity. It is believed that a complex is obtained.

〔Effect of the invention〕

By implementing the method of the present invention, a moldable conductive resin composite can be easily obtained and is of high industrial value.

〔Example〕

The present invention will be explained below with reference to Examples.

Example 1 2 g of pyrrole-impregnated polypropylene obtained by co-pulverizing 4 parts by weight of polypropylene with 1 part by weight of pyrrole,
It was dispersed in a solution of 0.1f of iron chloride dissolved in 10ml of water and subjected to contact treatment for 5 hours with stirring.

After contact treatment and filtration, a polypyrrole composite was obtained.

When it was dry weighed, it was 1.81, and it is estimated that 12.5 wt% polypyrrole was obtained based on polypropylene. The specific resistance of the hot-pressed sheet is 5.
I x 10'Ω·l.

Example 2 Polycarbonate (Kijin Kasei) was used instead of polypropylene
The treatment was carried out in the same manner as in Example 1, except that Panlite L-1250 (trade name: Panlite L-1250) was used. The specific resistance of the hot-pressed sheet was 2.8 x 10'Ω.

Example 3? 3 parts by weight of polyvinyl chloride (trade name Vinicron 4000M manufactured by Mitsui Toatsu Chemical Co., Ltd.) and α
- 1 part by weight of methylstyrene oligomer was added and kneaded with a roll to form a sheet with a thickness of 1 inch. The obtained sheet is K
t St 04101/l in an aqueous solution containing 20
After contacting for a period of time and then separating and drying the sheet, the specific resistance was measured and found to be 4.5 x 1030mm.

Claims (1)

[Claims] 1. A thermoplastic resin impregnated with a five-membered heterocyclic compound is contact-treated in a liquid medium in which an oxidizing agent that does not substantially dissolve the five-membered heterocyclic compound and the thermoplastic resin is dissolved. A method for producing a conductive resin composite.