JPH04161427A - Production of halogenated aniline polymer - Google Patents

Abstract

PURPOSE:To obtain the subject polymer having excellent workability, stable in air, exhibiting high fire resistance and useful as electromagnetic radiation shielding material, solar cell, magnetic material, electrode material, etc., by polymerizing a specific halogenated aniline derivative in the presence of a specific amount of an oxidizing agent. CONSTITUTION:The objective polymer is produced by polymerizing 1mol of a halogenated aniline derivative of formula (at least one of R1 to R4 is halogen substituent and the others are H, 1-5C alkyl or alkoxy) (e.g. o-chloroaniline or 2-chloro-3-methylaniline) in the presence of 1.5-5 oxidation equivalent of an oxidizing agent (e.g. ferric perchlorate).

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a method for producing a halogenated aniline polymer.

[Conventional technology]

Aniline derivatives are used as electrode materials for plastic batteries, EM
It is a compound useful for I materials, organic ferromagnetic materials, antistatic agents, various sensors, etc. Among aniline polymers, halogenated aniline polymers, especially chloroaniline polymers,
It is a substance that is attracting attention as an organic magnetic material. Polyaniline derivatives obtained by oxidative polymerization of halogen-containing aniline are soluble in organic solvents and do not require the addition of other materials, unlike substances such as polypyrrole, polythiophene, etc. obtained by electrolytic polymerization or chemical oxidative polymerization. , can provide conductive materials that can be cast or coated. Furthermore, it is characterized by superior flame resistance compared to other polyaniline derivatives.

[Problem to be solved by the invention]

Conventionally, oxidative polymerization of aniline in the presence of an oxidizing agent has been known as a typical method for producing aniline polymers, and it has also been used for oxidative polymerization of alkyl-substituted or alkoxy-substituted aniline derivatives. There is. However, no method for polymerizing halogenated aniline was known. And in the case of halogenated aniline derivatives,
There is a problem in that polymerization is difficult to proceed due to the high oxidation potential, and so far, no method for practically producing halogenated aniline derivatives has been known. The present invention has been made in view of the above problems. Therefore, an object of the present invention is to provide a method for producing a halogenated aniline polymer in which oxidative polymerization of halogenated aniline proceeds smoothly.

[Means to solve the problem]

As a result of studies, the present inventor found that the oxidative polymerization reaction proceeds smoothly by using a specific amount of an oxidizing agent, and has completed the present invention. The method for producing a halogenated aniline polymer of the present invention comprises a halogenated aniline derivative represented by the following general formula (I) (in the formula, at least one of R1 to R4 is substituted with a halogen atom, and the other substituents are , hydrogen atom, carbon number 1~
5 represents an alkyl group or an alkoxy group. ) to 1 mole of the above halogenated aniline derivative.
It is characterized by polymerization in the presence of 5 to 5 oxidizing equivalents of an oxidizing agent. The present invention will be explained in detail below. In the present invention, the halogenated aniline derivative represented by the above general formula (I) includes O-chloroaniline, m-
Chloroaniline, 2-amino-6-chlorotoluene, 3
-Amino-4-chlorotoluene, 2-amino-4-chlorotoluene, 2-chloro-3-methylaniline, 2-bromo-3-methylaniline, 2-chloro-3-ethylaniline, 2-bromo-3- Dithylaniline, 2-chloro-3, -(n-propyl)aniline, 2-chloro-4-
(n-butyl)aniline, 2-bromo-3-(n-butyl)aniline, 2-methoxy-5-chloroaniline, 2
-Butyl-5-fluoroaniline, m-fluoroaniline, 0-fluoroaniline, 0-bromoaniline, m-
Examples include, but are not limited to, bromoaniline, 0-iodoaniline, m-iodoaniline, and the like. In the present invention, oxidative polymerization can be easily carried out by mixing and stirring the above-mentioned halogenated aniline derivative and an oxidizing agent in an aqueous medium at room temperature. Examples of the oxidizing agent to be used include the following. (1) Trivalent iron compounds such as trivalent iron perchlorates, hydrohalides, balates, sulfates, and potassium ferricyanide; (2) Trivalent iron compounds such as chromic anhydride and potassium dichromate; Examples include hexavalent chromium compounds, (3) persulfate compounds such as sodium persulfate, potassium persulfate, and ammonium persulfate. These oxidizing agents need to be used in an amount of 2 to 5 oxidizing equivalents per mole of the halogenated aniline derivative. When the above oxidizing agent is used, the anion contained in the oxidizing agent is incorporated as a dopant into the halogenated aniline derivative produced, but in order to make these doping effects even more effective, it is necessary to add hydrochloric acid and odor to the reaction system. Inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, methanesulfonic acid, p-1
- An organic acid such as luenesulfonic acid can be present. The halogenated aniline polymer obtained as described above is a polymer (771nch-0,1-1,2 (reduced viscosity)) consisting of repeating units represented by the following general formula (n), and is A conductive substance soluble in (wherein R1-
R4 has the same meaning as above. ) Therefore, by dissolving this halogenated aniline polymer in an organic solvent, for example,
By forming a surface coating layer by applying or spraying on various solid surfaces such as metals, semiconductors, synthetic resins, ceramics, paper-like materials, etc., and then removing the organic solvent,
A conductive film can be formed on the surface of these solids. Various organic solvents can be used to dissolve the halogenated aniline polymer produced by the present invention, such as aliphatic and aromatic ketones, ethers, esters, amides, nitriles, Carbonates, carboxylic acids, halides, sulfolane compounds, nitro compounds, sulfoxides, lactams, lactones,
Examples include saturated and unsaturated heterocyclic compounds. Specifically, aliphatic and aromatic ketones include acetone, diethyl ketone, methylpropyl ketone, hydroxyacetone, methoxyacetone, phenylacetone,
4-phenylbutanone-2, etc.: Ethers include tetrahydrofuran, dioxane, dimethyl ether, dimethyl ether, methyl ethyl ether, dimethoxyethane, jetoxymethane, methyl glycol, anisole, 1.2-dimethoxybenzene, 1.4-dimethoxybenzene. , 1.3-dioxolanes; As esters, methyl acetate, ethyl acetate, trimethyl orthoformate, ethyl oxalate, trimethyl phosphate esters;
Amides include formamide, N-methylformamide, dimethylformamide, N-methylacetamide, dimethylacetamide, N-methylpropioamide,
Hexamethylphosphoramide, etc.; Nitriles include:
Acetonitrile, valeronitrile, benzonitrile, etc.;
Carbonates include propylene carbonate, ethylene carbonate, dimethyl carbonate; carboxylic acids include formic acid, acetic acid, benzoic acid, oxalic acid, etc.;
Examples of halogen compounds include dichloromethane, chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene,
As sulfolane compounds such as benzoyl chloride, benzenesulfonyl chloride, benzenesulfonyl dichloride, benzenethiophosphonyl dichloride, methanesulfonyl chloride, chloride, acetyl benzylide bromide, dimethylsulfamyl chloride, ethyloxalyl chloride, chlorosulfonylacetyl chloride, etc. are sulfolane, 3-methylsulfolane, etc.; nitro compounds include nitromethane, nitrobenzene, etc.; sulfoxides include dimethyl sulfoxide, etc.; lactams include N-methylpyrrolidone, etc.; lactones include:
Examples include γ-butyrolactone.

【Example】

Add 10-12N hydrochloric acid to 200-mL of water, and add 2-methyl-5
- 14.2 g of chloroaniline was dissolved. 9.8 g of 38N hydrochloric acid was added to this solution and stirred. On the other hand, as an oxidizing agent solution, (NH4)2520324□ was added to 200 g of water.
A solution was prepared by dissolving . These two solutions were mixed and stirred for several hours. The obtained oxidized polymer was separated by filtration and vacuum dried over phosphorus pentoxide to obtain 9.2 g of black powder. According to the infrared spectrum and NMR, this black powder has R "" CHa , R2, R4 in the above general formula (II).
It was confirmed that it contained a repeating unit of the structure -HlRs-CI. When this material was dissolved in methylene chloride and the absorption maximum was measured, it was confirmed to be 702n*. The black powder obtained as described above was thoroughly ground in a mortar, then pressure-molded into a disc shape with a diameter of 10 dragons, and its electrical conductivity was measured using the four-terminal method.3. 1
x 10-6s/c+a te. Examples 2 to 6 Halogenated aniline polymers were produced in the same manner as in Example 1, except that the halogenated aniline derivatives shown in Table 1 were used instead of the halogenated aniline derivatives used in Example 1. Regarding these halogenated aniline polymers, in the same manner as in Example 1, the absorption maximum in methylene chloride melting and the electrical conductivity of the press-molded product by the four-terminal method were measured. The results are shown in Table 1. The results are shown in Table 1. Margins below table 1

【Effect of the invention】

Since the method of the present invention has the above-mentioned configuration, it is possible to easily oxidatively polymerize a halogenated aniline derivative. The obtained halogenated aniline polymer has excellent workability and can be molded into any shape. Also,
The halogenated aniline polymer produced by the present invention is
Because it is stable in the air and has high flame resistance, it is extremely useful industrially as electromagnetic shielding materials, solar cells, magnetic materials, electrode materials, functional elements such as various sensors, and electronic components such as electrochromic devices. It is. Applicant Fuji Xerox Co., Ltd.

Claims (1)

[Claims] (1) Halogenated aniline derivative represented by the following general formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (I) (In the formula, at least one of R_1 to R_4 is substituted with a halogen atom, and other The substituent represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group.
A method for producing a halogenated aniline polymer, which comprises polymerizing in the presence of 5 to 5 oxidizing equivalents of an oxidizing agent.