JPS62131029A - Production of aniline polymer - Google Patents

Abstract

PURPOSE:To obtain the titled good-regularity polymer which can give an electroconductive polymer having stable, high and desired electroconductivity and being useful for various sensors, EMI materials, antistatic use, etc., by polymerizing a specified amino compound in the presence of a chemical oxidizing agent. CONSTITUTION:1mol of an amino compound of the formula [wherein R is a (substituted) vinyl or a (substituted) aryl] is polymerized at -50-100 deg.C for 30min-1 week in water or an organic solvent (e.g., acetonitrile) in the presence of 2-10 oxidation equivalent of a chemical oxidizing agent such as a trivalent iron compound, a hexavalent chromium compound (e.g., K2Cr2O7), a persulfate compound (e.g., potassium persulfate), or a quinone compound (e.g., chloranil) and, optionally, an inorganic acid or an organic acid.

Description

[Detailed Description of the Invention] <Industrial Application Field> By doping, aniline polymer becomes a conductive polymer with high conductivity, and its stability is also good.
? It is. Furthermore, the conductivity of conductive polymers obtained from aniline polymers can be controlled over a wide range by controlling the flea of the dopant. Therefore, by utilizing these properties, various uses can be considered for various sensors, EMT materials, antistatic, etc.

In addition to high conductivity, the conductive polymer has redox properties that allow reversible doping and dedoping, and since it can be obtained in powder form, it has a large surface area, so these properties can be improved. It is useful as a secondary battery and various electrode materials.

As a method for producing aniline polymers, a method is known in which aniline itself is subjected to oxidative polymerization in the presence of a chemical oxidizing agent. However, in this method, the reaction between aniline and a chemical oxidant is an exothermic reaction, making it difficult to control the reaction.

Represents an aryl group or a substituted aryl group. The present inventors have discovered that not only can aniline polymers be obtained by using amine compounds having different structures represented by the following as raw materials, but also that the reaction is mild and side reactions are less likely to occur, leading to the completion of the present invention.

<Structure of the Invention> The present invention is based on the following general formula [I].

Represents an aryl group or a substituted aryl group. This is a method for producing an aniline polymer, which is characterized by combining an amino compound represented by 1 in the presence of a chemical oxidizing agent.

Hereinafter, specific contents of the present invention will be explained in detail.

The aniline polymer of the present invention can be easily obtained by mixing and stirring the 7-mino compound of the above formula [I] and a solution containing a chemical oxidizing agent.

Moreover, according to this method, the anions coexisting in the reaction system are simultaneously incorporated into the produced polymer as dopants, and the reaction regresses with a new electron-accepting compound, resulting in excellent regularity.

- Examples of the amino compound of the above formula [I] used in the present invention include the following.

(1) A specific example of a compound in which R in formula [I] is a vinyl group or a substituted vinyl group is N-allylaniline.

N-methallylaniline, N-crotylaniline.

Examples include γ, γ-dimethylallylaniline, γ-phenylallylaniline, and the like. N-allylaniline and N-methallylaniline are preferably used in view of the ease of obtaining the raw material It.

(i) Examples of compounds in which R in formula [I] is an aryl group or a substituted aryl group include N-benzylaniline and N-benzylaniline having a substituent on the phenyl group in the benzyl group. More specifically, N-benzylaniline, N-(1)-methylbenzyl)aniline, N-
(+)-methoxybenzyl)aniline, N-<m-methylbenzyl)aniline, N-(1-methoxybenzyl)
Examples include aniline. Among them, N-benzylaniline is used for IT 3m because of its easy availability of raw materials.

Examples of the chemical oxidizing agent used in the present invention include the following.

(1) Trivalent iron compounds such as trivalent iron hydrogen halides, 1'l salts, sulfates, perchlorates, and potassium ferricyanide: (i) Chromic anhydride, ■6 such as chromic acid Chromium compounds of high valence; (to) PerTa acid compounds such as potassium persulfate, potassium persulfate, and ammonium persulfate; (1) Quinone compounds such as chloranil; and the like.

When these oxidizing agents are used, the anions contained in the oxidizing agent are incorporated into the resulting polymer as dopants, but in order to make this doping effect even more effective, hydrochloric acid, sulfuric acid, or nitric acid is added to the reaction system.

No v11%g such as perchloric acid, acetic acid, methanesulfonic acid.

11M such as o-4-luenesulfonic acid and oxalic acid can also be present.

In the present invention, the reaction is performed in a liquid medium in order to perform the reaction mildly and efficiently.

Water or an organic solvent is used as the medium. Examples of organic solvents include acetonitrile, benzonitrile, methane, nitrobenzene, and alcohol.

The amine compound of formula [I], such as tetrahydrofuran, which easily dissolves substances and chemical oxidizing agents is preferable, but is not necessarily limited thereto.

The chemical oxidizing agent is used in an amount of 2 to 1011 oxidation equivalents, preferably 2 to 6 8 oxidation equivalents, per mole of the amino compound of the present invention. If it is less than that, the desired product can be obtained, but the yield R will be lower, and if it is more than that, the oxidizing agent will be used unnecessarily, which is not only wasteful, but also undesirable because an undesirable n1 reaction will occur.

The reaction temperature is -50°C to 100°C. Preferably, the temperature is between -30°C and 50°C. The reaction time is from 30 minutes to one week, and is appropriately selected depending on the relationship with the reaction temperature.

Hereinafter, the present invention will be explained in detail with reference to Examples. However, the present invention is not limited to this. Hereinafter, "Part J" refers to a heavy product. Lightning conductivity was measured by the four-probe method using a tablet made by compressing 451 powder at a molding pressure of 3800 to 9/cd.

Example 1 300 parts of m-hydrochloric acid was added to 1200 parts of water, and 18.3 parts of N-benzylaniline was added thereto. After stirring at room temperature for 30 minutes, the mixture was cooled to 5° C. and 45.6 parts of ammonium perIII acid dissolved in 200 parts of water was added dropwise over an hour. After the dropwise addition was completed, the mixture was stirred at 0 to 5°C for 24 hours.

The resulting dark green solid was collected by filtration and diluted with water and acetic acid (Br).
is shown in Figure 1a. The method of Matsukudiamitsu et al. (N.G. Matsuradiamitsu et al. American Chemical Society Polymer Preprint, (A, G.

Mac[)iaarmid, at al, ,Δ〇
Figure 1b shows the [R spectrum (K[3r)] of the aniline polymer obtained using aniline as a starting material in accordance with S.
It was shown to. The elemental analysis values (actual measurements) of the aniline polymer were as follows: C: 55.19%, H: 4.
25%, N: 10.37%
, C1: 17.12%, 1!7 according to the method of Matsuku Diamit et al. Elemental analysis value (actual value) of the aniline polymer C: 54.75%, Tol: 4,38
%, N: 10.47%,
There was good agreement with C1: 18, 19%.

In addition, the aniline polymer obtained in this example and the aniline polymer synthesized according to the method of Mac Diamid et al.
The IR spectra of the products obtained by neutralization using a 2N aqueous sodium hydroxide solution are shown in FIGS. 2a and 2b, respectively. Both spectra matched perfectly.

The conductivity of the obtained disk-shaped product was measured and found to be 1.7 S/cm.

Example 2 300 parts of concentrated hydrochloric acid was added to 1300 parts of water, and 13.3 parts of n-allylaniline was added thereto. After stirring at room temperature for 30 minutes, 34.2 parts of ammonium persulfate dissolved in 200 parts of water was added dropwise over an hour. After the dropwise addition was completed, the mixture was stirred at room temperature for 18 hours. The resulting black-rimmed solid was collected by filtration, thoroughly washed with water and acetonitrile, dried quickly, and
．． 0 parts of conductive polymer were obtained.

The black-rimmed polymer was molded into a pellet shape using a tablet molding machine in the same manner as in Example 1, and the lead index was 0.438/3.

The IR spectrum (Figure 3) of the obtained polymer treated with a 2N aqueous sodium hydroxide solution in the same manner as in Example 1 shows that it is the same as that of the aniline polymer obtained by the method of Matsudiamid et al. Since it matched with the ■R spectrum (Figure 2b) of
part was suspended.

While stirring, 29.4 parts of potassium dichromate dissolved in 100 parts of water was added at room temperature. After stirring at room temperature for 24 hours, the resulting dark green solid was collected by filtration. After thorough washing with water and acetonitrile, the product was dried to obtain 7.2 parts of a conductive polymer.

When this product was molded in the same manner as in Example 1 and the conductivity was measured, 3. It was O8/a+.

The IR spectrum of the obtained polymer treated with a 2N aqueous sodium hydroxide solution in the same manner as in Example 1 is the same as that of the aniline polymer obtained by the method of Matsukudiamid et al. (Figure 2b). ), it was identified that an aniline polymer was produced.

Example 4 18 parts of N-benzylaniline in 1000 parts of acetonitrile
．． 3 parts were dissolved. 138.6 ferric perchlorate hexahydrate dissolved in 200 parts of acetonitrile cooled to -30°C
Added a section. After the addition was completed, the product was stirred at -30°C for 48 hours and molded in the same manner as in Example 1, and the conductivity was measured to be 0.7.
It was an SS/car.

The obtained polymer was treated with 2yA constant sodium hydroxide aqueous solution in the same manner as in Example 1, and the IR spectrum was as follows.
The IR spectrum (FIG. 2b) of the aniline polymer obtained by Mack Diamit's method, which was treated in the same manner, matched the IR spectrum (FIG. 2b), so it was identified that an aniline polymer was produced.

[Brief explanation of drawings]

FIG. 18 is an IR spectrum of the reaction product of Example 1. FIG. 1b is an IR spectrum of the reaction product according to the method of Matsukdiamid et al. FIG. 28 is an IR spectrum of the reaction product of Example 1 neutralized with alkali,
FIG. 2b is an IR spectrum of the reaction product obtained by alkali neutralization according to the method of Matsukdiamid et al. FIG. 3 is a tR spectrum of the reaction product of Example 2 which was neutralized with alkali.

Claims (1)

[Claims] A method for producing an aniline polymer, which comprises polymerizing an amino compound represented by the following general formula [I] in the presence of a chemical oxidizing agent. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・［ I
] [However, in the formula, R is a vinyl group or a substituted vinyl group. Represents an aryl group or a substituted aryl group. ]