JPS63289023A - Electroconductive material - Google Patents

Abstract

PURPOSE:To obtain an electroconductive material which has a low solubility in an organic solvent, can be easily produced and has a high electric conductivity, by reacting an aniline compound with an acid and polymerizing this aniline compound with an oxidizing agent comprising a cupric compound and a nitrile compound. CONSTITUTION:An aniline compound (e.g., aniline or phenylaniline) is previously reacted with an acid (e.g., HBF3 or HCl). The reaction product is polymerized with an oxidizing agent comprising a cupric compound (e.g., CuCl2 or CuTiF6) and a nitrile compound (e.g., acetonitrile or benzonitrile) to produce a polymer of the aniline compound. This aniline compound polymer is used as an electroconductive material. As the aniline compound is previously reacted with the acid in this way, the obtained aniline compound polymer has a low solubility in an organic solvent, the filtrability of the polymer from the reaction solution is good and its moldability is good.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a conductive material made of an aniline polymer obtained by a polymerization reaction using an oxidizing agent made of a cupric compound and a nitrile compound. It is.

<Prior art> Polymers with conjugated double bonds in their main chains, such as polyacetylene, polyparaphenylene, polythenylene, polypyrrole, polyparaphenylene vinylene, polyaniline, etc., are arsenic pentafluoride.

Antimony pentafluoride, iodine, bromine, sulfur trioxide, n-
It has been known that when treated with a P-type or N-type doping agent such as butyl lithium or sodium naphthalene, 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, can be used in the form of 1 q of powder, lump, or film.
1. It can be used as it is or molded depending on the purpose,
Antistatic materials, electromagnetic wave shielding materials, photoelectric conversion elements (electronic
optical functional device), optical memory (holographic memory)
Applications are being considered in a wide range of fields, including functional elements such as various sensors, two display elements (electrochromism), switches, various hybrid materials (transparent conductive films, etc.), various terminal devices, and storage batteries.

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

It is known that these polythenylene, polypyrrole, polyaniline, etc. can be produced by (1) electrochemical oxidative polymerization (electrolytic polymerization) or (2) chemical oxidative polymerization using an oxidizing agent. In the case of (2), polythenylene, polypyrrole, or polyaniline is deposited in the form of a film on the anode used for electrolytic polymerization, and is peeled off from the anode after the precipitation to form a film of polythenylene,
Polypyrrole or polyaniline is obtained. In the case of using the agent,
Powdered polypyrrole is produced by oxidative polymerization in solid phase, liquid phase or gas phase.

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, Mo1.
LiQ, cryst1 magazine, 1985 vol.11
8, pp. 149-153).

Furthermore, it has been reported by A, G, (3reen et al.) that emeraldine, an octopod of aniline, is produced from an aqueous solution containing aniline-hydrochloride using an oxidizing agent such as hydrogen peroxide. (J, Chem, 3oc
, Section 2388 (1910)).

However, in the case of (■) above, 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, resulting in a large increase in productivity. In addition to being subject to restrictions, there are disadvantages such as the production method being complicated and high cost because the electrolytic polymerization method is used.

In addition, in the case of ■, although there is no inconvenience like ■,
Polythenylene, polypyrrole yaborianiline, etc. have low electrical conductivity, which limits their use in various applications and limits their range of application.

Furthermore, in (2), when ferric perchlorate is used as an oxidizing agent in an organic solvent, the solubility of ferric perchlorate in an organic solvent is lower than that in an aqueous solution, so there is a problem in (1) productivity. This is disadvantageous due to restrictions on production, and the concentration of the doping agent in the solvent decreases by the amount of decrease in solubility, resulting in a disadvantage that the electrical conductivity of the polypyrrole or polyaniline produced is low. In addition, there is also the drawback that various safety measures must be taken during the manufacturing process because organic solvents that are highly dangerous, such as explosives, are handled.

On the other hand, in the case of (2), since peroxides such as hydrogen peroxide are used as the oxidizing agent, it is necessary to be careful about the safety during storage, handling, and reaction, and when mass-producing them industrially, However, it has extremely large drawbacks in terms of handling and safety. In addition, emeraldine, which is an octamer of aniline, has poor solvent resistance to organic solvents.
Another drawback is that it has a fairly high solubility.

Therefore, the present inventor has already developed a method of reacting a conjugated compound in the presence of an oxidizing agent comprising a cupric compound and a nitrile compound, thereby eliminating the above-mentioned disadvantages and disadvantages and being stable in the air. Needless to say, 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 conjugated compounds thus obtained, the polymer of the aniline compound is a conductive polymer with high electrical conductivity as described above, but it Not only is the solubility of the polymer relatively high, but also the particle size of the polymer to be jqed is small, resulting in poor filterability of the polymer when separating and purifying the product, which limits productivity. There is a problem in that these particles aggregate and solidify after washing and drying, making it extremely difficult to mold the polymer into any desired shape.

<Means for Solving the Problems> The inventors of the present invention have intensively studied methods for producing aniline polymers that do not have these problems, and have found that the intended purpose can be achieved by using the following means. After learning what was possible, he completed this invention.

That is, the present invention provides a conductive material made of a polymer of an aniline compound obtained by polymerizing an aniline compound with an oxidizing agent made of a cupric compound and a nitrile compound, wherein the aniline compound is It is a conductive material that is made by reacting with.

As the cupric compound used in the present invention, for example, the general formula % formula % (1) (wherein, X is Cβ0-1BF4.-1 AS F -1CJ2-.5O4-1PF6-1Sb
F -1CH3C6H4SO3-1CF S〇 -1C
6H5SO3-1 ZrF '''-1T i F6- or S i F6
-, and m represents an integer of 1 to 2. ) are mentioned.

The 21-lyl compound used in the present invention has, for example, the general formula R(CN), (2) (wherein R is an alkyl group which may have a substituent, It represents an alkenyl group or an aryl group, and n represents an integer of 1 to 3.

) Examples include nitrile compounds represented by:

When producing the conductive material of the present invention, a product obtained by reacting a single or two or more different aniline compounds with an acid is used, and a single or two or more different cupric compounds are used. The compound can be reacted with an oxidizing agent consisting of a single nitrile compound or two or more different nitrile compounds.

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 amino group, an alkylamino group, an arylamino group, R3 and R4 represent a hydrogen atom, an alkyl group, or an aryl group.

The acid used in the present invention includes, for example, the general formula % formula % (4) (wherein, Y is CbuO-18F4-1 ASF6-1Cλ-1SO4-1PF6-1SbF
~, Cl-13C6H4So3-1CF3SO3-1C
6H5SO3-1 ZrF6=,”represents rlF6- or 5iF6-,
a represents an integer of 1-2. ).

Specifically, the cupric compound represented by the general formula (1) is CuCJ22, Cu (CJ204>2, Cu
(BF4)2, Cu (PF6)2, Cu (
AsF6 >2, Cu(SbF6)2, Cu(CH
3C6H4803)2, Cu(CF3S03)2, Cu(C6H5S03)2, CuSO4, CUZ
r R6, CuT i R6, QuSf R6,
These are usually used as compounds with water of crystallization or as aqueous solutions.

In the nitrile 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, or a vinyl group. , methylvinyl group,
Dimethyl vinyl group, ethyl vinyl group, diethyl vinyl group, n-propyl vinyl group, n-butyl vinyl group, phenyl vinyl group, naphthyl vinyl group, hydroxymethyl group,
Hydroxyethyl group, hydroxypropyl group, hydroxybutyl group, methoxymethyl group, methoxyethyl group, methoxypropyl group, ethoxymethyl group, ethoxyethyl group, cyanomethyl group, cyanoethyl group, cyanopropyl group, cyanobutyl group, cyanopentyl group, cyano Hexyl group, carboxymethyl group, carboxyethyl group, carboxypropyl group, phenyl group, naphthyl group, tolyl group, hydroxyphenyl group, hydroxynaphthyl group, methoxyethyl group, ethoxyphenyl group, methoxyethyl group, cyanophenyl group, dicyanophenyl group group, cyanotolyl group, dicyanotolyl group, cyanoethyl group, carboxyphenyl group, carboxytolyl group, etc. Specifically, such nitrile compounds include acetonitrile, n-propionitrile, isopropionitrile, n-butyronitrile, isobutyronitrile, t
ert-butyronitrile, acrylonitrile, medyl acrylonitrile, ethyl acrylonitrile, phenyl acrylonitrile, ace 1-cyanhydrin, medilene cyanohydrin, edilene cyanohydrin, propylene cyanohydrin, meth-1-xyace 1-nitrile,
1-xyacetic nitrile, 1-methoxypropionitrile,
Malonzini 1~lyl, adiponitrile, cyanacetic acid, cyanopropionic acid, cyanobutyric acid, benzonitrile, naphthonitrile, methylbenzonitrile, hydroxybenzonitrile, phthalonitrile, tricyanobenzene, me1
~xybenzonitrile, carboxybenzonitrile, etc.

In the aniline compound represented by the above general formula (3), R1 and R2 are hydrogen atoms, methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, isobutyl groups, 5ec-butyl groups, tert- Butyl group, methoxy group, ethoxy group, n-propoxy group, n-butoxy group,
Phenyl group, tolyl group, naphthyl group, phenoxy group,
It represents a methylphenoxy group, a naphthoxy group, an amino group, a dimethylamino group, a diethylamino group, a phenylamino group, a diphenylamino group, a methylphenylamino group, a phenylnaphthylamino group, and R3 and R4 are a hydrogen atom, a methyl group, an ethyl group, n-propyl group, isopropyl group,
Represents n-butyl group, phenyl group, tolyl group, and naphthyl group.

Specific examples of such aniline compounds include aniline, methylaniline, ethylaniline, n-propylaniline, isopropylaniline, n-butylaniline, methoxyaniline, toxyaniline, n-propoxyaniline, phenylaniline, and toluyl. Aniline, naphthylaniline, phenoxyaniline, methylphenoxyaniline, naphthoxyaniline, aminoaniline, dimethylaminoaniline, diethylaminoaniline, phenylaminoaniline.

Examples include diphenylaminoaniline, methylphenylaminoaniline, and phenylnaphthylamineaniline.

Specifically, the acid represented by the above general formula (4) is
04, HBF4, HAsF6, ICβ, Machi SO4, HPF6, HSbF6, CH3C6H4SO3 1. CF3 so, 1, C6F+5 SO3H, 12 T i
R6, H2S I R6, and these are usually dissolved in an organic solvent such as alcohol, ether, or nitrile, or used as an aqueous solution.

When the aniline compound and the oxidizing agent are reacted, it can be carried out in the presence of a conductive material. Powdered or granular conductive materials are used, specifically acetylene black and activated carbon.

Metal powder, inorganic oxide, etc., preferably acetylene black. The amount used is o, ooi to 100 times (weight ratio) relative to the aniline compound, preferably 0.005 to 50 times (weight ratio).

The amount of the cupric compound represented by the general formula (1) to be used is o, oi per mole of the aniline compound represented by the general formula (3) treated with the acid represented by the general formula (4).
~100 mil 100 times the mole or 0.5 to 50 times the mole.

Further, the nitrile compound represented by the general formula (2) is used in coexistence with the cupric compound, and examples of its usage include the following method.

1) A nitrile compound and a cupric compound are allowed to coexist in advance, and then treated with an aniline compound and an acid are allowed to act.

2) A cupric compound is allowed to act on a system in which the aniline compound and the acid-treated material coexist with the nitrile compound.

3) Avoid applying a nitrile compound to the system in which the aniline compound and the acid-treated material coexist with the cupric compound.

4) A system in which a cupric compound and a nitrile compound coexist is applied to a system in which a nitrile compound and a compound treated with an aniline compound and an acid coexist.

5) A reaction product of a cupric compound and a nitrile compound is isolated in advance and allowed to react with an aniline compound and an acid-treated product.

The amount of the nitrile compound represented by the general formula (2) to be used is 0.01 to ooo times, preferably 0.1 to 1,000 times, per mole of the cupric compound. .

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, dioxylane, or benzene. , toluene, dichloromethane, dichloroethane, acetic acid, and other common organic solvents.

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

The reaction temperature is -50°C to 150°C, preferably -22°C.
It is 0°C to 100°C. The reaction time is related to the reaction temperature, but is usually 0.5 to 200 hours, preferably 1.0 to 100 hours.
It's time.

The reaction product is a dark brown to black powdery substance, and in the reaction in the presence of the above solvent, the solvent is removed by a conventional method after the reaction is completed.In the present invention, a liquid nitrile compound such as acetonitrile, It is preferable to wash and purify the reaction product several times with an organic solvent such as propionitrile to dissolve and remove by-product cuprous compounds, since a product with higher conductivity can be obtained.

<Function> By using the above means, it is possible to obtain an aniline polymer that has low solubility in organic solvents, has good filterability of the product from the reaction solution, and can be easily molded into any shape,
It is possible to obtain a conductive material with high productivity, easy manufacture, and high electrical conductivity.

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

18.6 g of aniline (0.2 mo
1) was taken, and while stirring under a nitrogen atmosphere, a 42% HBF4 aqueous solution 41.
8a (0.2 mol) was added dropwise over 10 minutes.

As the mixture was added, heat generation was observed, and the reaction solution became cloudy, and a powdery solid was precipitated in the reaction solution to form a slurry. After stirring for 30 minutes, the reaction solution was heated to room temperature (15-20℃).
) and 316.2 g (0.6 mol) of a 45% Cu(BF4)2 aqueous solution prepared in advance with 30 g of acetonitrile.
00 mixture was added dropwise over 15 minutes.

As the mixture was added, a slight heat generation was observed, and the reaction liquid immediately turned black, and a powdery solid was precipitated in the reaction liquid to form a slurry. After continuing stirring for 2 hours, the mixture was left at room temperature overnight.

Thereafter, the reaction product was separated into a furnace to obtain a black powdery substance mixed with white crystalline substances.

When this was washed four times with 600 mJ2 of acetonitrile, the filtration operation was easy and the white crystalline substance was removed by this operation. When the residue was dried under reduced pressure at a temperature of 60°C, 1q of 17.43 g of a black powdery substance that was hardly soluble in organic solvents was obtained.

Elemental analysis of this black powder substance revealed that C50.05
%, H3, 68%, N 10.04%, F 24.56
I got %. Assuming carbon is 6, C6, O-H5,29
・N1.03・F 18.6'-"+The desired product was obtained. Also, as a result of measuring the electrical conductivity of this black object using the two-terminal method, it was found to be 1°2X 10"Scm-'
It was found that this is an organic semiconductor 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 (5 tons/CII!2) into a disk shape with a diameter of 1Q mm. At this time, pulverization and molding could be performed extremely easily.

Next, sandwich this disc crimp between two copper cylinders of the same size, apply a load of 1.2K () from the top, take out the conductor leads from the upper and lower copper cylinders, and connect them to a digital multimeter (Takedariken TR6851). The electrical conductivity of the disk sample was then measured using this meter.

For comparison, the reaction and washing were carried out in the same manner as in Example 1 except that the l-lBF4 aqueous solution was not used. The resulting polymer had poor filterability and was difficult to wash. Also,
Drying under reduced pressure at a temperature of 60° C. yielded 1 q of a black powdery substance, 6.7 g, which is highly soluble in organic solvents. In addition, it was extremely difficult to crush and pressurize this powder.

From the above results, by using an aniline compound that has been reacted with an acid in advance to react with the oxidizing agent, a reaction product that is difficult to dissolve in organic solvents, has good filterability, and has good moldability ( It was confirmed that I would be asked.

Example 2 An experiment was conducted in the same manner as in Example 1, except that 1.8 g of acetylene black was present in the reaction system. 20.0 g of a black powdery substance that hardly dissolves in organic solvents was obtained. The material had good pulverization and moldability, and the electrical conductivity was 1.
．． It was 6x 10-1S0-1S.

Example 3 21.2 g of ortho-toluidine instead of aniline, )-
When an experiment was conducted in the same manner as in Example 1 using 19.7 g of a 37% HCJ2 aqueous solution instead of the IBF4 aqueous solution,
20.0 g of a black powdery substance was obtained that was hardly soluble in organic solvents, had good filterability, and had good moldability. From the elemental analysis of the obtained black material, assuming that carbon is 7, it is 07.01
The equivalent of (7,20-N1.01,"0.30.Fo,04 was (q).

Examples 4 to 13 The reaction products of various aniline compounds and various acids were reacted in the same manner as in Example 1 using oxidizing agents consisting of various cupric compounds and nitrile compounds. Table 1 shows the results of the examination of the obtained dark brown to black powder. In addition, when the reaction was carried out using a solvent other than the nitrile compound, the solvent used is also shown in Table 1.

<Effects of the Invention> As described above, according to the present invention, there are various types of conductive polymers made of aniline polymers that have low solubility in organic solvents, are easy to mold, are easy to manufacture, and have high electrical conductivity. , its practical value is extremely large.

Claims (1)

[Scope of Claims] 1. A conductive material consisting of a polymer of an aniline compound obtained by polymerizing an aniline compound with an oxidizing agent consisting of a cupric compound and a nitrile compound, wherein the aniline compound is A conductive material characterized in that it has been reacted with an acid in advance. 2. The cupric compound has the general formula CuX_m (1) (wherein, X is ClO_4^-, BF_4^-, AsF_
6^-, Cl^-, SO_4^-^-, PF_6^-,
SbF_6^-, CH_3C_6_H_4SO_3^-
, CF_3SO_3^-, C_6H_5SO_3^-,
ZrF_6^-^-, TiF_6^-^- or SiF
It represents _6^-^-, and m represents an integer from 1 to 2. ) The electrically conductive material 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 (representing an integer from 1 to 3) The conductive material according to claim 1, wherein the conductive material 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 conductive material according to claim 1. 5. The acid has the general formula H_aY (4) (wherein, Y is ClO_4^-, BF_4^-, AsF_
6^-, Cl^-, SO_4^-^-, PF_6^-,
SbF_6^-, CH_3C_6H_4SO_3^-,
CF_3SO_3^-, C_6H_5SO_3^-, Z
rF_6^-^-, TiF_6^-^- or SiF_
6^-^-, and a represents an integer from 1 to 2. ) The conductive material according to claim 1, wherein the conductive material is an acid represented by: 6. Claim No. 6, characterized in that the reaction between the aniline compound and the oxidizing agent is carried out in the presence of a conductive material such as acetylene black, activated carbon, metal powder, or inorganic oxide. The conductive material according to item 1. 7. The conductive material according to claim 1, wherein the reaction product of the aniline compound and the oxidizing agent is washed with a liquid nitrile compound.