JPS63243161A - Method for manufacturing conductive materials - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention <Industrial Application Field> The present invention is directed to a conductive material made of an aniline and pyrrole polymer obtained by using an oxidizing agent made of a cupric compound and a nitrile compound. '3A This relates to improvements in the manufacturing method.

<Prior art> Polymers with a military double bond in the main chain, such as polyacetylene, polyparaphenylene, polythenylene, polypyrrole, polyparaphenylenevinylene, polyaniline, etc., are arsenic pentafluoride.

Antimony pentanotide, iodine, bromine, sulfur trisulfide, n-
It has been known that when treated with a P-type or N-type doping agent such as butyl lithium or naphthalene-1 helium, the electrical conductivity is significantly improved, and the material changes from an insulator to a semiconductor or even a conductor. These conductive materials, so-called conductive polymers, are obtained in the form of powder, grains, blocks, and films, and are used as they are or in the form of a film depending on the application, and are used as antistatic materials, electromagnetic shielding materials, photoelectric conversion elements Functional elements such as optical memory (holographic memory) and various sensors 1 Display elements (Electronic 1 to Lochromism), switches, various hybrids 1 to Materials (transparent conductive films, etc.), various terminal equipment and screens is being considered for application in a wide range of fields such as storage batteries.

Among the various conductive polymers mentioned above, polythenylene, polypyrrole, polyaniline, etc. have better stability in air than polyacetylene, have very little oxidative deterioration, and are easy to handle conductive polymers. Studies are being carried out on various applications that take advantage of this technology.

Known methods for producing polythenylene, polypyrrole, polyaniline, etc. include (1) electrochemical oxidative polymerization (electrolytic polymerization), and (2) chemical oxidative polymerization using an oxidizing agent. In method (2), polythenylene, polypyrrole, or polyaniline is deposited in the form of a film on the anode used for electrolytic polymerization.

After the precipitation, a film of polythenylene, polypyrrole or polyaniline is obtained by peeling it off from the anode. In addition, in method (■), peroxides such as potassium persulfate and ammonium peroxide, acids such as nitric acid, sulfuric acid, or chromic acid, and Lewis acids such as ferric chloride, ruthenium chloride, tungsten chloride, or molybdenum chloride are used. Powdered polypyrrole is obtained by carrying out oxidative polymerization in the same phase, liquid phase or gas phase using an oxidizing agent such as an acid. It has also been proposed to perform oxidative polymerization in an organic solvent using ferric perchlorate as an oxidizing agent to obtain a similar powdered polypyrrole (for example, MOL, Cryst, LiQ, C
rVSt, magazine, 1985 vol 118 no. 149
~153 pages).

However, in the above method (■), polythenylene, polypyrrole, and polyaniline are produced in the form of a film on the anode as described above, so the size of the product is regulated by the size of the electrode plate, which is a big problem in terms of seedling production. In addition to being constrained,
Since the electrolytic polymerization method is used, the manufacturing method is complicated and there is 1 loss.
- There are disadvantages such as being high.

In addition, in the case of method (2), although there are no disadvantages as in (2), the electrical conductivity of the resulting polythenylene, polypyrrole yaborianiline, etc. is low, which limits its application to various uses and has a narrow range of application. I am experiencing some inconvenience.

Furthermore, in method (2), when ferric perchlorate is used as an oxidizing agent in an organic solvent, the solubility of ferric perchlorate in the organic solvent is lower than that in an aqueous solution, making it difficult to mass-produce. In addition, there is a problem that the electrical conductivity of the produced polypyrrole or polyaniline is low because the concentration of the doping agent in the solvent decreases by the amount of the decrease in solubility.

In addition, there is the disadvantage that various safety measures must be taken during the manufacturing process because organic solvents that are highly dangerous, such as explosives, are handled.

Therefore, the present inventor has already developed a method for polymerizing this type of conjugated compound in the presence of an oxidizing agent in which a cupric compound and a nitrile compound coexist, thereby eliminating the above disadvantages and stabilizing it in the air. Of course, we would like to propose a method for manufacturing a conductive material that has a high reaction rate, is easy to manufacture, and has high electrical conductivity (Japanese Patent Application No. 61-215296).

<Problems to be Solved by the Invention> Among the polymers of conjugated compounds thus obtained, the polymers of aniline compounds are necessarily conductive polymers with high electrical conductivity as described above. The solubility in organic solvents is relatively high, the solvent resistance is poor, and the yield is quite low after washing with a line-specific solvent consisting of 21-lyl compounds etc. to purify the reaction product. It has been found that there are problems such as the loss is low and becomes a factor of 1 to high loss when industrially produced in large quantities.

<Means for Solving the Problems> The present inventor has intensively studied a method for producing aniline polymers that does not have the above problems, and has found that the intended purpose can be achieved by using the following means. This invention was successfully completed.

That is, the present invention provides a method for producing a conductive material comprising a polymer of an aniline compound in the presence of an oxidizing agent comprising a cupric compound and a nitrile compound, in which a part of the aniline compound is Alternatively, there is a method for producing a conductive material, the gist of which is to add a pyrrole compound after polymerizing the entire material.

As the cupric compound used in the present invention, for example, the general formula % formula % (1) (wherein, X is C20-1BF4-1 ASF -1PF -1SbF6-1- C[]
]3C6H4SO3-1CF3SO31ZrF-1
Represents T i F6- or S i F6-, m is 1
Represents an integer between ~2. ) is removed.

Further, the nitrile compound used in the present invention has the general formula % (2) (wherein R represents an alkyl group, alkenyl group, or aryl group that may have a substituent, and n is 1 represents an integer of 3 to 3).

In the production method of the present invention, a single or two or more different aniline compounds and a pyrrole compound are used, and a single or two or more different cupric compounds and a mono-
Alternatively, the reaction with an oxidizing agent consisting of two or more different nitrile compounds can be avoided.

The aniline compounds used in the present invention include, for example, (wherein R1 and R2 represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an allyloxy group, an amine group, an alkylamino group, an arylamino group, R3 and R4 represent a hydrogen atom, an alkyl group, or an aryl group.

The above-mentioned pyrrole compounds used in the present invention include, for example, the general formula (wherein R5 and R6 are hydrogen atoms, alkyl groups, alkoxy groups, aryl groups, allyloxy groups, amino groups, alkylamino groups, arylamino R7 represents a hydrogen atom, an alkyl group, or an aryl group.

Specifically, the cupric compound represented by the general formula (1) includes Cu(0°C04)2, Cu(BF4)2, Cu(PF6)2, Cu
(ASF6)2, Cu (SbF6)2, cu
(CH3C61-14SO3) 2 , Cu
(CF3SO3)2, Cu5iF6, CuTiF6
, Cu5iF6, and choleraba is usually used as a compound with water of crystallization or as an aqueous solution.

In the 21-helyl compound represented by the general formula (2), R is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a 5ec-butyl group, a tert-butyl group, Vinyl group, methylvinyl group, dimethylvinyl group, ethylvinyl group, diethylvinyl group, n-propylvinyl group, n-butylvinyl group, phenylvinyl group, naphthylvinyl group, hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, hydroxy Butyl group, methoxyfer group, methoxyethyl group, methoxyphenyl group, xymethyl group, xyedyl group, cyanomethyl group, cyanethyl group, cyanopropyl group, cyanobutyl group, cyanopentyl group, cyanohexyl group , carboxymethyl group, carboxyethyl group, carboxypropyl group, phenyl group, naphthyl group,
Tolyl group, hydroxyphenyl group, hydroxyethyl group, methoxyphenyl group, 1-xyphenyl group, methoxyfer group, cyanophenyl group, dicyanophenyl group, cyanotolyl group, dicyano-ruyl group, cyanonaphthyl group, carboxyphenyl group, Represents carboxy 1-ruyl group, etc. Such nitrile compounds include, specifically, acetonitrile, n-propionitrile, isopropionitrile, n-butyronitrile, isobutyronitrile, tert-butyronitrile, acrylonitrile, methylacrylonitrile, ethyl Acrylonitrile, phenylacrylonitrile, acetone cyanohydrin, methylene cyanohydrin, ethylene cyanohydrin, propylene cyanohydrin, methoxyacetonitrile, ethoxyacetonitrile, methoxypropioni-1-lyl, malondin-1-lyl, aziboni-1-helyl,
Cyanoacetic acid, cyanopropionic acid, cyanobutyric acid, benzonitrile, nano 1-2l-lyl, methylbenzonitrile, hydroxybenzonitrile, phthalonitrile, 1-lycyanobenzene, methoxybenzoni 1-tru, carboxybenzoni 1- Examples include Lil.

In the aniline compound represented by the above general formula (3), R1 and R2 are hydrogen atoms, methyl groups, ethyl groups, n-
Propyl group, isopropyl group, n=butyl group, isobutyl group, 5ec-butyl group, tert-butyl group, methoxy group, 1-oxy group, n-propoxy group, n-butoxy group, phenyl group, tolyl group, naphthyl group group, phenoxy group, methylphenoxy group, naphthoxy group, amino group, dimethylamine group, diethylamino group, phenylamino group, diphenylamino group, methylphenylamino group, phenylnaphthylamine group, R3 and R4 are hydrogen atoms, methyl groups , ethyl group, "]-propyl group, and isopropyl represent n-butyl group, phenyl group, tolyl group, and naphthyl group.

Specifically, such aniline-based compounds include aniline, methylaniline, ■ thylaniline, n-propylaniline, isopropylaniline, n-butylaniline, methoxyaniline, ethoxyaniline, n-propoxyaniline, phenylaniline, toluylaniline,
naphthylaniline, phenoxyaniline, methylphenoxyaniline, naphthoxyaniline, aminoanisone,
Dimedylaminoaniline, dietylaminoaniline, phenylaminoaniline.

Examples include diphenylaminoaniline, methylphenylaminoaniline, and phenylnaphthylaminoaniline.

Among the pyrrole compounds represented by the above general formula (4), pyrrole compounds that do not have a substituent at the 2.5 position of the five-membered ring structure are preferred. In addition, for details, please refer to R, R
"represents a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-ethyl group, isobutyl group, 5e
c-butyl group, tert-butyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-1
1-oxy group, phenyl group, 1-ruyl group, naphthyl group,
Represents a phenoxy group, methylphenoxy group, naphthoxy group, amino group, dimethylamino group, diethylamino group, phenylamino group, diphenylamino group, methylphenylamino group, phenylnaphthylamino group, and R7 is a hydrogen atom, methyl group, or ethyl group. , n-propyl group, isopropyl group, n-butyl group, isobutyl group, 5ec-butyl group, tert-butyl group, phenyl group, tolyl group, and naphthyl group.

Specifically, pyrrole compounds include pyrrole, N-
Methylpyrrole, N-ethylpyrrole, N-phenylpyrrole, N-naphthylpyrrole, N-methyl-3-methylpyrrole, N-methyl-3-ethylpyrrole, N-phenyl-3-methylpyrrole, N-phenyl-3 -Ethylpyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-n-propylpyrrole, 3-iso-propylpyrrole, 3-n-butylpyrrole, 3-methyl-xypyrrole, 3-ethoxypyrrole, 3-n -propoxypyrrole, 3-n-butoxypyrrole, 3-phenylpyrrole, 3-1~ruylpyrrole, 3-naphthylpyrrole,
3-phenoxypyrrole, 3-methylphenoxypyrrole, 3-natoxythiophene, 3-aminopyrrole,
Examples include 3-dimethylaminopyrrole, 3-diethylaminopyrrole, 3-diphenylaminopyrrole, 3-methylphenylaminopyrrole, and 3-phenylnaphthylaminopyrrole.

The scope of use of the cupric compound represented by the above general formula (1) is:
0 per mole of the total mole of the aniline compound and pyrrole compound represented by the above general formulas (3) and (4)
．． It is 1 to 100 times the mole, preferably 1 to 50 (8 moles).

Further, the di-lyl compound represented by the above general formula (2) is used in coexistence with the cupric compound, and the method of using it in the present invention includes, for example, the following method.

1) A nitrile compound and a cupric compound are made to coexist in advance to partially or completely produce a polymer of an aniline compound, and then a pyrrole compound is added to produce a polymer of this pyrrole compound.

2) A cupric compound is applied to a system in which an aniline compound and a nitrile compound coexist to form part or all of the aniline compound polymer, and then a pyrrole compound is added to form this pyrrole compound. to produce a polymer of

3) A di-I-lyl compound is applied to a system in which an aniline compound and a cupric compound coexist to avoid forming part or all of the aniline compound polymer, and then a pyrrole compound is added to form this polymer. A polymer of pyrrole compound is produced.

4) Avoiding the coexistence of a cupric compound and a nitrile compound on a system in which an aniline compound and a 21-lyl compound coexist, a polymer of the aniline compound is partially or completely formed. Then, a pyrrole compound is added to produce a polymer of this pyrrole compound.

5) After isolating the reaction product of the cupric compound and the nitrile compound in advance and reacting it with the aniline compound to partially or completely produce a polymer of the aniline compound,
A pyrrole compound is added to form a polymer of the pyrrole compound.

6) After partially or completely forming a polymer of an aniline compound with an oxidizing agent consisting of a cupric compound and a nitrile compound, a pyrrole compound is added, and the oxidizing agent is further added to form the pyrrole compound. Produces polymers of compounds.

The amount of the 21-lyl compound represented by the general formula (2) to be used is 0.01 to 10.000 times the mole of the cupric compound, preferably 0.1 to i,oo.

It is necessary in twice the mole.

If the nitrile compound is a liquid substance, it can be used as a reaction solvent, or if it is a solid substance, it can be used as an arbitrary solvent, such as water, alcoholic solvents such as methanol or ethanol, tetrahydrofuran, dioquinane, benzene, etc. - Common organic solvents such as toluene, dichloromethane, dichloroethane, acetic acid, etc. can be used.

The amount of the pyrrole compound represented by general formula (4) is:
The amount is 0.01 to 10 times, preferably 0.05 to 5 times, per mole of the aniline compound.

Moreover, this pyrrole compound is added at the time when the polymer of the aniline compound is partially or completely formed.

The reaction temperature is -50°C to 150°C, preferably -20'C to 100°C. Reaction 11; Ii depends on the reaction temperature, but is usually 0.1 to 200 hours, preferably 0.2 to 100 hours.

The reaction product is a dark brown to black powdery substance, and in the reaction in the presence of the above solvent, the reaction is completed.The solvent is removed by a conventional method. For example, by washing and purifying the reaction product several times with a solvent such as ace-1-2-lyl or propionitrile, and dissolving and removing by-product cuprous compounds, a product with higher conductivity can be obtained. It is preferable because you can get things.

<Function> By using the above method, it is possible to obtain a conductive material made of an aniline and pyrrole polymer that has low solubility in organic solvents, a high yield during production, is easy to produce, and has high electrical conductivity. Can be done.

<Example> The manufacturing method of the present invention will be specifically explained with reference to Examples below.

Example 1 2.8 g (0.03 mol) of aniline and 150 mN of aretonyl were placed in a round bottom flask at 1°C, and the solution was added to room temperature (15-20') while stirring under a nitrogen atmosphere.
C) 45% Cu(BF4)2 aqueous solution prepared in advance in 63.2 (] (00.12 mol) and acetonitrile 7
5 mJ) was added dropwise over 15 minutes.

As the mixture was added, heat generation was observed, and the reaction liquid immediately turned black. Powder-like solid matter was precipitated in the reaction liquid, and the reaction liquid took on the form of a slurry. After continuing stirring for 2 hours, the mixture was left at room temperature overnight. Thereafter, 0.67 g (0.01 mol) of pyrrole was added dropwise over 5 minutes while stirring.

Heat generation was observed as the mixture was added, and stirring was continued for 2 hours.
I left it for 14 hours overnight at room temperature. When the reaction product was separated, a black powdery substance mixed with white crystals was obtained. This was washed 4 times with 600 ml of acetonitrile to remove the white crystalline material, and when dried under reduced pressure at a temperature of 60'C, 4.0 g of a black powdery material was obtained.

Elemental analysis of this black powder substance revealed that it was C55.96.
%, )-13,70%, N12.49%, F20.57
Assuming % L nitrogen is 1, C5,2, 14.1
, N1, Fl, 2 was 1d. Also, separately
As a result of analyzing the copper content zone, it was found that copper o,
It was ooi. This means that C
This shows that u(BF4)2 is reacted, and especially the anion portion thereof is added.

In addition, as a result of measuring the electrical conductivity of this black powdery substance by the two-terminal method, it was found to be 1.4 × 10-10-2
8C was obtained, and it was found to be one of the leading semiconductors with conductivity in the semiconductor region.

The electrical conductivity was measured as follows. First, the black powder obtained by the above treatment was ground sufficiently finely in a mortar, and then pressure-molded into a disk shape with a diameter of 1Qmm (5 tons/
c1) Shita. Next, this disk sample was sandwiched between two copper cylinders made by the same person, a load of 1.2 KCl was applied from the top, and the conductor leads were taken out from the upper and lower copper cylinders, respectively, and a digital multimeter (Takedariken TR6851) was placed.
), and the electrical conductivity of the disk sample was measured by this meter.

Comparative Example 1 The reaction and washing were carried out in the same manner as in Example 1 except that the above operation of adding pyrrole later was not carried out. As a result, the product was considerably dissolved in acetonitrile, which is an organic solvent, and The amount of black powdery substance was less than 1.0 L or 1 U.

Comparative Example 2 0.67 g (0.03 mol) of pyrrole and 150 mN of acetonitrile were placed in a round-bottomed flask at 1°C.
) 45% CIJ(Br4)2 aqueous solution 63 prepared in advance with
．． 2 g (0.12 mol) and ace I-21~lyl 75m
The mixture was added dropwise over 15 minutes.

As the mixture was added, heat generation was observed, and the reaction liquid immediately turned black. Powder-like solid matter was precipitated in the reaction liquid, and the reaction liquid took on the form of a slurry. After stirring for 2 hours, the mixture was left at room temperature overnight, and the aniline 2.8 (] (00,0
3 mol was added dropwise over 5 minutes.

Heat generation was observed as the mixture was added, and stirring was continued for 2 hours.
It was left at room temperature overnight. After this, washing in the same manner as in Example 1,
Upon drying, the product was quite soluble in the organic solvent and the H content of 1 q of black powder material after washing was 2.0 g.

Comparative Example 3 Aniline 2.8 (] (00,
04 mol of pyrrole, 0.67 Cl (0.01 mol) and 150 mβ of acetonyl-lyl were added to this solution while stirring under a nitrogen atmosphere, and 45% CLJ (prepared in advance) was added at room temperature (15-20°C). BF4)2 aqueous solution 63.2
A mixture of 0.0 (0.12 mol) and acetonitrile 75 mN was added dropwise over 15 minutes.

As the mixture was added, heat generation was observed, and the reaction liquid immediately turned black, powdery solids precipitated in the reaction liquid, and the solution took on the form of a slurry. One barley that had been continuously stirred for 2 hours was left overnight at room temperature, and then washed and dried in the same manner as in Example 1.
The product was highly soluble in the organic solvent and the amount of black powdery material recovered after the washing process was 2.0 g.

From the above results, it was confirmed that by adding pyrrole after part or all of the aniline polymer is produced, a reaction product that does not dissolve in the organic solvent can be obtained by the washing treatment.

Example 2゜In place of aniline, Or1~-1~Luidine was used as 3,18[
], N-methylpyrrole instead of pyrrole, aig
An experiment was carried out in the same manner as in Example 1 except that 4.5 g of black powder material was used (q). From the elemental analysis of the obtained black material, it was determined that nitrogen was 1. Assuming, C6,2, [ ]3.2 , N1.O, Fl,1
The equivalent of (qta).

Moreover, the electrical conductivity of this black material is 1.0×10-2
3 Cm-1 tea ivy.

Examples 3 to 14 Various aniline compounds and pyrrole compounds were used, and these were reacted with various cupric compounds and 21-lyl compounds in the same manner as in Example 1. The test results of the obtained dark brown to black powder are shown in Table 1.

In addition, when the above reaction was carried out using an organic solvent other than a nitrile compound, the molten soot used is also shown in Table 1.

<Effects of the Invention> As described above, according to the production method of the present invention, a polymer containing an aniline compound that has low solubility in organic solvents and good solvent resistance, is easy to produce, and has high electrical conductivity. There are many types of conductive materials, and their practical value is extremely important.

Claims (1)

[Scope of Claims] 1. A method for producing a conductive material comprising a polymer of an aniline compound in the presence of an oxidizing agent comprising a cupric compound and a nitrile compound, the method comprising: A method for producing a conductive material, which comprises adding a pyrrole compound after polymerizing part or all of the material. 2. The cupric compound has the general formula CuX_m (1) (wherein, X is ClO_4^-, BF_4^-, AsF_
6^-, PF_6^-, SbF_6^-, CH_3C_
6H_4SO_3^-, CF_3SO_3^-, ZrF
_6^-^-, TiF_6^-^- or SiF_6^
-^-, and m represents an integer of 1 to 2. ) The method according to claim 1, which is a cupric compound represented by: 3. The nitrile compound has the general formula R(CN)_n (2) (wherein R represents an alkyl group, alkenyl group, or aryl group that may have a substituent, and n is The method according to claim 1, wherein the nitrile compound is a nitrile compound represented by: 4. The above aniline compound has the general formula ▲ Numerical formula, chemical formula, table, etc. ▼・・・・・・(3) (In the formula, R^1 and R^2 are hydrogen atoms, alkyl groups, alkoxy groups, aryl group, allyloxy group, amino group, alkylamino group, or arylamino group, and R^3 and R^4 represent a hydrogen atom, an alkyl group, or an aryl group. A method according to claim 1. 5. The above pyrrole compound has the general formula ▲ Numerical formula, chemical formula, table, etc. ▼・・・・・・(4) (In the formula, R^5 and R^6 are hydrogen atoms, alkyl groups, alkoxy groups, represents an aryl group, an allyloxy group, an amino group, an alkylamino group, or an arylamino group, and R^7 represents a hydrogen atom, an alkyl group, or an aryl group). The method described in item 1. 6. The method according to claim 1, characterized in that the reaction product is washed with a liquid nitrile compound.