JPS62109820A - Production of heterocyclic five-membered ring compound polymer composition - Google Patents

Abstract

PURPOSE:The form the titled polymer composition useful as an electrically conductive filler, supported carrier, etc., on a solid acid, by bringing a heterocyclic five-membered ring compound into contact with the solid acid. CONSTITUTION:A heterocyclic five-membered ring compound, e.g. pyrrole, furan, thiophene, selenophene or tellurophene, etc., is brought into contact with a solid acid, e.g. acid clay, bentonite or cation exchange resin, to form the aimed polymer on the solid acid. The above-mentioned compound may be brought into contact with the solid acid by a method for bringing the solid acid into contact with the heterocyclic five-membered ring compound monomer or a monomer composition prepared by diluting with a solvent or passing the monomer gas through a fluidized bed containing the solid acid for contact of both or pulverizing and mixing both solid acid and monomer in a ball mill.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a five-membered heterocyclic compound polymer composition.

[Conventional technology]

Five-membered heterocyclic compound polymers are known as organic compounds whose electrical properties can be controlled from insulators to conductors, and can be used as electrical conductors or semiconducting materials. In addition, because of its good thermal stability, it can be used as a heat-resistant material, and can also be used as a catalyst for photodecomposition of water and organic substances, and as a material for various sensors.

As a method for polymerizing five-membered heterocyclic compounds, it is known that powdery or bulk polymers can be obtained by reaction with an oxidizing agent (Atopansis of Heterocyclic Chemistry, Vol. 15, p. 67, 1973). etc.), and
Recently, it has been reported that a powder or film of a five-membered heterocyclic compound is formed on an electrode substrate by an electrochemical polymerization method (Journal Op Chemical Society Chemical Comunication 1979 635, Japan Journal of Applied Physics). 2
1 L567 (1982), 1 bid competition L52
7 (1984)).

[Problem that the invention seeks to solve]

However, it is possible to some extent to synthesize composites of these five-membered heterocyclic compound polymers and carriers by polymerizing the five-membered heterocyclic compound monomers using an oxidizing agent in the presence of the carrier. However, since the polymer produced is insoluble and infusible to heat and solvents, it is impossible to separate the composite with the carrier from the polymer without the carrier, and the difference between the carrier and the polymer is impossible. There is a problem that the bonding strength is not very strong and the carrier and polymer are easily separated.

An object of the present invention is to provide a method for producing a five-membered heterocyclic compound polymer composition that solves these problems.

c) Means for Solving the Problems] As a result of intensive studies by the present inventors to solve these problems, the present inventors found that by using a specific carrier, a heavy hetero5-membered cyclic compound strongly bonded to the carrier can be produced. The present invention was completed by discovering that coalescence can be obtained.

That is, the present invention provides a five-membered heterocyclic compound polymer composition, characterized in that the five-membered heterocyclic compound is brought into contact with a solid acid to form a polymer of the five-membered heterocyclic compound on a solid acid. It is a method of manufacturing something.

In the present invention, in order to produce a composite of the carrier and the hetero five-membered cyclic compound polymer, a solid acid is used as the carrier and the hetero five-membered cyclic compound polymer is brought into contact with the solid acid. Good.

The solid acids used in the present invention include natural clay minerals such as acid clay, bentonite, kaolin, montmorillonite, kujirite, and phlorizin, solidified acids prepared by adhering sulfuric acid, phosphoric acid, malonic acid, etc. to silica gel or alumina and calcining them. , cation exchange resins, silica/alumina, silica/magnesia, silica/boria, various zeolites, heteropolyacids, zinc oxide, aluminum oxide, titanium oxide, vanadyl pentoxide, cane oxide, and other oxides.

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

The method for producing a five-membered heterocyclic compound polymer composition is to simply bring the five-membered heterocyclic compound into contact with a solid acid (there is no need to use other oxidizing agents, so the production process is simple). is extremely easy.

Specifically, a five-membered heterocyclic compound monomer or a seven-member composition prepared by diluting it with a solvent is contacted with a solid acid, or a monomer gas is passed through a solid acid in a fluidized bed to form a solid. The contact treatment may be carried out by contacting the acid and the monomer, or by placing the solid acid and the monomer in a ball mill and pulverizing and mixing them.

The reaction time and reaction temperature may be appropriately determined depending on the type of five-membered heterocyclic compound and reaction conditions.

A five-membered heterocyclic compound polymer composition can be obtained without any special treatment by simply removing the excess monomer after contacting the solid acid and the five-membered heterocyclic compound monomer.

〔Example〕

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

Example 1 3 ml of virol was added to 10 g of acid clay (dried at 200° C. for 3 hours) and mixed uniformly. The surface of the acid clay gradually turned black. After 40 hours, unreacted virol was removed by drying under reduced pressure at 150°C to obtain a black composite.

As a result of elemental analysis, this composite contained 5% by weight of polypyrrole.

Example 2 Cation exchange resin 'DOWEX50W' as solid acid
(trademark) and brought it into contact with virol vapor,
The cation exchange resin turned black in 1 hour, and after 24 hours, it was dried under reduced pressure and the change in weight was examined, and it was found that 10% by weight of polypyrrole had been produced.

Examples 3 to 6 Furan (Example 3), thiophene (
Polymerization was carried out in the same manner as in Example I except for using Example 4), selenophene (Example 5), or tellurophene (Example 6), and 8% by weight of polyfuran, 7% by weight of polythiophene, and 7% by weight of polyselenophene, respectively. , a composite containing 4% by weight of polytellurophene was obtained.

〔Effect of the invention〕

The composition obtained by the present invention can be used as a conductive filler and as a carrier catalyst utilizing the catalytic effect of a five-membered heterocyclic compound polymer, and has great industrial utility value.

Claims (1)

[Claims] 1. A method for producing a five-membered heterocyclic compound polymer composition, which comprises contacting the five-membered heterocyclic compound with a solid acid to produce a five-membered heterocyclic compound polymer on the solid acid.