JPH0556368B2 - - Google Patents

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. Specifically, the present invention relates to a method for producing a composition in which a five-membered heterocyclic compound polymer is supported on inorganic compound particles.

[Conventional technology]

It is already known that five-membered heterocyclic compounds can form polymers when treated with oxidizing agents, and pyrrole and its derivatives can form polypyrroles when treated with inorganic acids, iron chloride, non-chloride, ozone, etc.
Advances in Heterocyclic Chemistry Volume 15, 67
Page (1973), and there are also problems in that the polypyrrole thus obtained is insoluble and infusible, difficult to mold, and has a small bulk specific gravity, making it difficult to handle. In contrast, JP-A-59-
A method of electropolymerizing pyrrole in the presence of a specific particulate carrier, as shown in No. 168010, is known.

[Problems to be solved by the invention]

The above-mentioned method of electrolytically polymerizing pyrrole in the presence of a particulate carrier has the problem of requiring special equipment and an electrolyte, and in addition, since the reaction is carried out in a solution, there are problems in removing pyrrole after the polymerization reaction. .

[Means for solving problems]

The present inventors have conducted intensive studies on a method for easily and inexpensively producing a 5-membered heterocyclic compound polymer composition by solving the above problems. It was discovered that a composition supporting a polymer of a five-membered heterocyclic compound can be obtained, and the present invention was completed.

That is, the present invention is a method for producing a five-membered heterocyclic compound polymer composition, which comprises bringing inorganic compound particles impregnated with an oxidizing agent into contact with a five-membered heterocyclic compound vapor.

The inorganic compound particles serving as a carrier in the present invention are not particularly limited and may be of any kind, including metal oxides, hydroxides, carbonates, etc. Among them, oxides, for example, Magnesium oxide, alumina, silica, zinc oxide, iron oxide,
Titanium oxide, barium oxide, mixtures and eutectics thereof are preferred. Examples of copolycrystals include:
Examples include talc, mica, hydrotalcite, and those obtained by heat treatment to remove crystal water or attached water.

There is no particular restriction on the particle size of the above-mentioned inorganic compound, but usually 0.01 μm to 10 mm can be used.
0.1 to 1000μ when used as a resin filler
When used as a catalyst in a fluidized bed or fixed bed, it is preferable to use a catalyst with a diameter of about 100 μm to 10 mm.

Inorganic acids and metal compounds are effective as the oxidizing agent used in the present invention, and specific examples of the inorganic acids include sulfuric acid, hydrochloric acid, nitric acid, and chlorosulfonic acid. As the metal compound, compounds known as Lewis acids are preferably used, and metal chlorides, sulfates, etc. of aluminum, tin, titanium, zirconium, chromium, manganese, iron, copper, molybdenum, tungsten, ruthenium, palladium, platinum, etc. Specific examples include nitrates and acetylacetonate compounds. Organic compounds such as benzoquinone and diazonium salts can also be used as other oxidizing agents. These oxidizing agents may be used alone or in combination of two or more. In particular, chlorides and sulfates of iron and titanium are preferably used.

Methods for impregnating the above-mentioned inorganic compound particles with these oxidizing agents include a method of co-pulverizing the oxidizing agent and the inorganic compound particles, a method of dispersing and mixing the above-mentioned inorganic compound particles in a solution in which the oxidizing agent is dissolved, and then filtration or Examples include a method of removing the solvent by evaporation, and a method of dispersing an inorganic compound under the vapor of the oxidizing agent to adsorb the oxidizing agent.

There are no particular restrictions on the amount ratio of the oxidizing agent to the inorganic compound particles, but it is usually
Generally, the ratio is 0.0001 to 1wt.

The five-membered heterocyclic compound used in the present invention includes pyrrole, furan, thiophene, and derivatives thereof. Among them, pyrrole, N-
Pyrrole derivatives such as alkylpyrrole, N-arylpyrrole, and pyrrole substituted with an alkyl group or a halogen atom at the 3- and/or 4-position are advantageous from the viewpoint of reactivity.

In the present invention, there is no particular restriction on the method of contacting the inorganic compound particles impregnated with an oxidizing agent and the vapor of the five-membered heterocyclic compound, but the inorganic compound particles impregnated with an oxidizing agent are brought into contact with each other in a fluidized bed or fixed bed reactor. vapor of the 5-membered heterocyclic compound (nitrogen, if necessary)
A simple method is to introduce helium, argon, oxygen, or a mixture thereof.

There are no particular limitations on the contact temperature and time, and the contact temperature may be room temperature, and the contact time may be arbitrarily determined so that the ratio of the five-membered heterocyclic compound polymer becomes a desired value.

〔Effect of the invention〕

The composition of the present invention can be used as a conductive filler as a composite that has both the mechanical strength of inorganic compound particles and the conductivity of a five-membered heterocyclic compound polymer, and can also be used to remove or eliminate oxidizing agents. It can be expected to be used as a supported catalyst that takes advantage of the catalytic effects of the 5-membered heterocyclic compound polymer.

〔Example〕

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

Example 1 Talc powder (grade manufactured by Nippon Talc Co., Ltd.)
MS) and 2 g of ferric chloride were co-pulverized. This talc impregnated with ferric chloride was placed in a glass cylindrical container equipped with a glass filter with a diameter of 5 cm, and a gas containing pyrrole vapor entrained in the air was poured at 0.2 ml/1 hour.
was introduced and reacted for 20 hours. The obtained black powder was dried to obtain 11.7 g of a composition supporting about 1.7 g of polypyrrole. This item is 500Kg/cm ² as it is.
It was press-molded into a tablet shape, and its electrical conductivity was measured using the four-point probe method, and it was found to be 4.3×10 ^-1 Ωcm.

Examples 2 and 3 The same procedure was carried out except that calcium silicate manufactured by Asada Seifun Co., Ltd. (Example 2) and calcium carbonate "Sunmite #800" manufactured by Take Kagaku Kogyo Co., Ltd. (trade name, Example 3) were used as inorganic compounds. In the same manner as in Example 1, 10.5 g and 10.6 g of black particles were obtained, respectively. The electrical conductivity of each tablet-shaped product is 3.4×
10 ² Ωcm, 1.5×10 ¹ Ωcm.

Examples 4 and 5 Using 10 g each of silica gel (Example 4) and alumina (Example 5) as inorganic compounds, 2 g of ferric chloride was co-pulverized using a crusher to produce particles impregnated with an oxidizing agent. . Example 1 using the particles
reacted the same way. The obtained black particles were extracted with methanol using Soxhlet extraction for 5 hours to remove most of the ferric chloride, and when dry weighed, they were 11.3 g and 11.6 g, respectively. In addition, when we conducted elemental analysis of these, the ratio of C, H, and N was found to be
73.9:4.6:21.5 and 73.6:4.7:21.8, and it is estimated that polypyrrole is supported.

Examples 6 and 7 Black powder was prepared in the same manner as in Example 1 except that N-methylpyrrole (Example 6) and thiophene (Example 7) were used as the 5-membered heterocyclic compound.
11.0g and 10.5g were obtained. The electrical conductivities of the tablets were 8.6×10 ² Ωcm and 7.5×10 ⁵ Ωcm, respectively.

Claims (1)

[Claims] 1 Inorganic compound particles impregnated with an oxidizing agent are mixed with complex 5
1. A method for producing a five-membered heterocyclic compound polymer composition, which comprises bringing it into contact with a membered cyclic compound vapor.