JPS6369823A - Electrically conductive material - Google Patents

Abstract

PURPOSE:To provide an electrically conductive material consisting of granules composed of primary particles having a specific particle diameter and produced by the reaction of a pyrrole compound and an oxidizing agent, giving a compression-molded article having high density, easily handleable in molding process, etc., and having high electrical conductivity. CONSTITUTION:The objective electrically conductive material consisting of dark brown or black granules composed of primary particles with average particle diameter of 0.01-0.4mu and capable of giving a compression-molded article having a density of 1-1.6g/cm<3> is produced by reacting a pyrrole compound [e.g. the compound of formula (R<1> and R<2> are H, alkyl, alkoxy, etc.)] with an oxidizing agent. The oxidizing agent is composed of e.g. a cupric compound of formula CuXm (X is ClO4<->, BF4<->, etc.; m is 1-2) and a nitrile compound of formula R(CN)n (R is alkyl, etc.; n is 1-3). The reaction of the oxidizing agent and the pyrrole compound is carried out preferably at -20-+100 deg.C for 1-100hr optionally in a solvent.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a conductive material made of a granular pyrrole polymer formed from primary particles of a specific particle size and having a large pressure-molding density. It is about profit.

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

Andimon pentafluoride, iodine, bromine, sulfur trioxide, n-
It has been known for a long time that when treated with a P-type or N-type doping agent such as butyllithium or naphthalene, the electrical conductivity is significantly improved, and the material changes from an insulator to a semiconductor to a conductor. These conductive materials, so-called conductive polymers, are available in the form of powder, particles, lumps, and films.
It can be used as it is or after being molded depending on the purpose.
Functional elements such as antistatic materials, electromagnetic wave shielding elements, photoelectric conversion elements, optical memory (bolographic memory), various sensors, etc. 2 display elements (electronic ~ lochromism)
Applications are being examined in a wide range of fields, including , Suitsuji, various hybrid materials (transparent conductive films, etc.), and various terminal devices.

Among the various conductive polymers mentioned above, polythenylene, polypyrrole, and polyaniline are conductive polymers that are more stable in air than polyacetylene, have extremely low oxidative deterioration, and are easy to handle. Investigations into various applications are currently underway.

As these polythenylene, polypyrrole, and polyaniline, 1) those obtained by electrochemical oxidative polymerization (electrolytic polymerization), and 2) those obtained by chemical oxidative polymerization using an oxidizing agent are known. 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 1q of polythenylene, polypyrrole or polyaniline in the form of a film is obtained by peeling it off from the anode after precipitation. In the case of (■), powdered polypyrrole is obtained. Conventional techniques generally use peroxides such as potassium persulfate and ammonium persulfate, acids such as nitric acid, sulfuric acid, or chromic acid, and Lewis acids such as ferric chloride, ruthenium chloride, tungsten chloride, or molybdenum chloride. Oxidative polymerization is carried out in solid phase, liquid phase, or gas phase using an oxidizing agent. It has also been proposed to carry out oxidative polymerization in an organic solvent using ferric perchlorate as an oxidizing agent (for example, MOL
.

Cryst, LiQ, crystal0 magazine, 198
5, vol. 118, pages 149-153>.

<Problems to be Solved by the Invention> However, in the case of (2) 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 does not match the size of the electrode plate. There are also problems such as the production method being complicated and expensive due to the use of electrolytic polymerization.

In the case of (2), although there is no problem like (2), the electrical conductivity of the obtained polythenylene, polypyrrole, polyaniline, etc. is low, which restricts the development of various uses and has a narrow range of application. I'm holding it.

Furthermore, in (2), when ferric perchlorate is used as an oxidizing agent in an organic solvent, the solubility of ferric perchlorate in the organic solvent is very low compared to that in an aqueous solution, making it difficult to mass-produce. In addition to being disadvantageous in manufacturing, the concentration of the doping agent in the solvent decreases by the amount of decreased solubility, resulting in the problem that the electrical conductivity of the resulting polypyrrole is extremely low. In addition, the diameter of the primary particles of the polypyrrole-forming particles that can be produced is 1 μm.
1 or more, it is bulky, causes a lot of dust scattering, and the pressure molding density is low, making it difficult to handle in the subsequent molding process for each application, making it difficult to obtain a molded product with high density, and high electrical conductivity. There is also the problem that it is difficult to obtain materials with high strength. In addition, as we handle organic solvents that are highly dangerous such as explosions,
Another problem is that various safety measures must be taken during manufacturing.

<Means for Solving the Problems> The present inventor has found that there is no problem mentioned above, that it is stable in the air, is easy to form in a V shape, is easy to handle in the molding process, etc., and is easy to process. After researching how compacting density and electrical conductivity can provide a large conductivity vJ benefit, the inventors learned that the desired purpose could be achieved by using the following means, and completed this invention. .

That is, the present invention is a granular conductive material made of a pyrrole polymer obtained by reacting a pyrrole compound and an oxidizing agent, and is a granular material formed from primary particles with an average particle size of 0.01 to 0.4 μm. Yes, pressure molding density is 1-1.6M
+J3 The conductive material of the present invention uses a single or two or more different types of pyrrole compounds, and for example, a single or different two or more types of pyrrole compounds. By reacting a dicopper compound with an oxidizing agent consisting of a single or two or more different di-1-lyl compounds,
I can do it.

The above-mentioned pyrryl compound used in the present invention includes, for example, the general formula (wherein R and R2 are a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an allyloxy group, an amino group, an alkylamino group, The compound represents an arylamino group, and R3 represents a hydrogen atom, an argyl group, or an aryl group.

Further, the oxidizing agent used in the present invention has the general formula % (wherein, X is CJ2o4-, BF4-1AsF-
1PF -1SbF6-1CH3C6H4SO3-1
CF3SO3'''', ZrF6'-1T i re- or S i R6-, m represents an integer from 1 to 2, and t
, > with the general formula % formula % (3) (wherein R represents an alkyl group, alkenyl group, or aryl group that may have a substituent, and n is an integer of 1 to 3) Use a nitrile compound shown in

Among the pyrrole compounds represented by the general formula (1) above, pyrrole compounds having no substituents at the 2 and 5 positions of the pyrrole ring skeleton structure are preferred. Also, for details, see R1,
R2 is a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, 5
CC-butyl group, tert-butyl group, me-1-xy group,
]~oxy group, n-propoxy group, isopropoxy group,
n-11~oxy group, phenyl group, 1~ruyl group, naphthyl group, phenoxy group, methylphenoxy group, naphthoxy group, amino group, dimethylamino group, diethylamino group,
represents a phenylamino group, a diphenylamino group, a methylphenylamino group, a phenylbootthylamine group, and R
3 is a hydrogen atom, methyl group, ethyl group, n-propyl group,
Isopropyl group, n-butyl group, isobutyl group, 5ec
- Does not represent a butyl group, tert-butyl group, phenyl group, tolyl group, or naphthyl group.

Specifically, pyrrole compounds include pyrrole, N
-Methylpyrrole, N-ethylpyrrole, N-phenylpyrrole, N-naphdylpyrrole, N-methyl-3-methylpyrrole, N-methyl-3ethylpyrrole, N-phenyl-3methylpyrrole, N-phenyl-3ethylpyrrole, 3- Methylpyrrole, 3-ethylpyrrole, 3-
n-propylpyrrole, 3-iso-70pyrrole, 3-n-butylpyrrole, 3-methoxypyrrole, 3
-Propoxypyrrole, 3-n-propoxypyrrole,
3-n-butylhexypyrrole, 3-phenylpyrrole,
3-1 ~ Ruylpyrrole, 3-naphthylpyrrole, 3-
Phenoxypyrrole, 3-methylphenoxypyrrole,
3-naph I~xythiophene, 3-aminopyrrole, 3
-dimethylaminopyrrole, 3-diethylaminopyrrole, 3-diphenylaminopyrrole, 3-methylphenylaminopyrrole, 3-phenylnaphthylaminepyrrole and the like.

Specifically, the cupric compound represented by the general formula (2) has Cu (CJ204 >2, Cu (BF4 >2
, Cu (PF6)2, Cu(△sF6)2,
Cu (SbF6)2, Cu (CH3C6)14
S O3) 2 , Cu (CF3303 >2,
CuZrF6, CuT! FB, CuS! FB
These are usually used as compounds with water of crystallization or as aqueous solutions.

In the 21-lyl compound represented by the general formula (3), =
11-, R is a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, 5ec-
Butyl group, 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, hydroxypropylene group.

group, hydroxybutyl group, methoxyethyl group, methoxyethyl group, methoxyethyl group, ethoxymethyl group, hexyethyl group, cyanomethyl group, cyanethyl group,
Cyanopropyl group, cyanopropyl group, cyanopentyl group, cyanohexyl group, carboxymethyl group, carboxypropyl group, phenyl group, naphthyl group, tolyl group, hydroxyphenyl group, hydroni-Vcypufyl group, metho-nidiphenyl group, Engineering 1 ~xyphenyl group, methoxyethyl group, cyanone 1-yl group, dicyanophenyl group, cyanotolyl group, dicyano 1-ruyl group, cyanonaph=12-del group, carboxyphenyl group, carboxytolyl group, etc.

Specific examples of such nitrile compounds include acetonitrile, n-propionitrile, inpropionitrile, n-butyronitrile, imbutyronitrile, tert-butyronitrile, acrylonitrile, methylacrylonitrile, ethyl Acrylonitrile, phenyl acrylonitrile, acetone cyanohydrin, methylene cyanohydrin, ethylene cyanohydrin, propylene cyanohydrin, methoxyacetonitrile, methoxypropionitrile, malondi Nitrile, adiponitrile, cyanoacetic acid, cyanopropionic acid, cyanoacetic acid, benzonitrile, nano 1-nitrile, methylbenzoni-i-lyl, hydroxybenzoni-1-lyl, phthalonitrile, tricyanobenzene, methoxybenzoni-1-helyl, carboxybenzonitrile Examples include.

The amount of the cupric compound represented by the general formula (2) is 0.01 to 10.0 to 1.0 to 1 mole of the pyrrole compound.
It is 0 times the molar amount, preferably 0.1 to 50 times the molar amount.

The dil-lyl compound represented by the general formula (3) is used in combination with the cupric compound described above, and examples of its usage include the following methods.

1) After allowing a nitrile compound and a cupric compound to coexist in advance, they are allowed to interact with a pyrrole compound.

2) A cupric compound is allowed to act on a system in which a pyrrole compound and a dilyl compound coexist.

3) A 21-lyl compound is allowed to act on a system in which a pyrrole compound and a cupric compound coexist.

4) A system in which a cupric compound and a di-lyl compound coexist is allowed to act on a system in which a pyrrole compound and a nitrile compound coexist.

5) A reaction product of a cupric compound and a nitrile compound is isolated in advance and allowed to react with a pyrrole compound.

The coexistence of such a nitrile compound significantly accelerates the reaction between the pyrrole compound and the oxidizing agent, and even in a system where substantially no oxidative polymerization reaction occurs, the oxidative polymerization reaction can easily proceed. discovered.

The amount of the di-lyl compound represented by the general formula (3) is 0.01 to 10.0001 per mole of the cupric compound.
The amount is 8 moles, preferably 0.1 to 1,000 times the mole.

When the 21-lyl compound is a liquid substance, it can be used as a reaction solvent, or when it is a solid substance, any solvent can be used, such as water, alcoholic solvents such as methanol and ethanol, te1-lahydrofuran, Common organic solvents such as dione, benzene, i-toluene, dichloromethane, dichloroethane, and acetic acid can be used.

The reaction temperature is -50°C to 150'C, preferably -20'C to 100'C. The reaction time is related to the reaction temperature, but is usually 0.5 to 200 hours, preferably 1.0 hours.
It is 100 hours.

A cupric compound represented by the general formula (2) and example = 1
5- For example, the reaction with the pyrol-based compound represented by the general formula (1) above can be carried out in any phase, such as the same phase, liquid phase, or gas phase; is preferable.

The reaction product is a dark brown to black powdery substance, and in the case of the reaction in the presence of the above solvent, after the reaction is completed, the solvent is removed by a conventional method, and then a liquid di-1-lyl compound such as acetonitrile, propionitrile, etc. The reaction product is washed and purified several times with a solvent such as, and the by-product cuprous compound is dissolved and removed.
product can be obtained.

The product is a conductive material consisting of aggregates of various shapes in which primary particles with an average particle diameter of 0.01 to 0.4 μm, preferably 0.02 to 0.35 μm, are pressurized. The molding density is 1 to 1.6 Mcm3, preferably 1
．． 1 to 1.5 o/cm3.

The aggregates of -order particles are connected at arbitrary lengths in one, two, and three dimensions, forming aggregates with various shapes such as linear, branched, and irregular shapes. And -
Since the secondary particles are smaller than conventional granular conductive materials, the voids between the particles become smaller during pressure molding, making it possible to form a compact with high density. As a result, the material M'i+ having higher electrical conductivity is used, and the filling weight per predetermined volume is increased, so that higher functionality is achieved.

<Function> By using the above-mentioned means, it is possible to create a granular conductive material Fl that does not have the problems of the conventional methods, is easy to handle in the molding process, has a high pressure molding density, is easy to manufacture, and has high electrical conductivity. can be obtained.

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

Example 1 Pyrrole 8.0 +11 (0,
12 moles) and 450 mf1 of acetocolyl were added to this solution at room temperature (15 to 12 moles) while stirring under a nitrogen atmosphere.
45% = 17-Cu (Br4 >2 aqueous solution 189.7 + 11 (0
, 36E/L) and 1 to 150 m of acetonate was added dropwise over 15 minutes.

As the mixture was added, heat generation was observed, and the reaction liquid immediately turned black, and a powdery solid was precipitated in the reaction liquid, giving the appearance of a slurry. After continuing stirring for 2 hours, the mixture was left at room temperature overnight. When the reaction product was separated, a black powdery substance mixed with white crystals was obtained. This was mixed with 600 m of acetonitrile, [
The white crystalline material was removed by repeated washing with 1 ml of water 4 times, and 12.4 q of black powder was obtained by drying under reduced pressure at a temperature of 60'C.

Elemental analysis of the black substance is C45, 28%, H2, 63%, N
12.48%, F 24.12%, and carbon 4.0%.
Assuming that, C4,0,+-+2.8,NO,95,F
o, equivalent to 33 was obtained. Separately, the copper content was analyzed and found to be 4.0 carbon and 0.001 copper. This indicates that Cu (Br4>2) has reacted with pyrrole, and especially its anion portion has been added.The primary particle size of this black powder was measured using a scanning electron microscope. As a result, the average particle diameter was 0.1 μm.The electrical conductivity of this black substance was measured using the two-terminal method, and as a result, it was found to be 1.2×10-'5 cm-1, which indicates that the conductivity of the semiconductor region It was found that it is an organic semiconductor with .

The electrical conductivity was measured as follows. First, the black powder obtained by the above treatment was pulverized sufficiently finely in a mortar and then pressure-molded into a disk shape with a diameter of 10 mm (51 to 112 mm/Cl).Then, this disk sample was placed between two copper plates made by the same person. Sandwiched between cylinders, 1.2Kg from the top
After applying a load of
6851), and the electrical conductivity of the disc crimp was measured using this meter.

The pressure-molding density of the above-mentioned pressure-molded polypyrrole molded product was 1.4 MC113, and the molded product was dense.

For comparison, ferric perchlorate Fe ((
929.4 g of this
was uniformly dissolved in 7000+ ml of water, and while stirring under a nitrogen atmosphere, pyrrole 120.8 (] (1,
8m, Q) was added dropwise to carry out a polymerization reaction of pyrrole.

The obtained black powder has an average primary particle size of 0.6 μm, is extremely bulky, and easily scatters, and the pressure-molded polypyrrole molded body has a pressure-molded density of 0.8 a/cl.
It was l13. The electrical conductivity of this polypyrrole was 7.6X 10-23C...-1.

Example 2 An experiment was conducted in the same manner as in Example 1 except that 9.7 g of N-methylpyrrole was used instead of pyrrole.
2.6 g of black powdery material was obtained.

From the elemental analysis of the obtained black material, assuming that carbon is 5.0, C, H, N1. . , 5.0 5.1 ``., I got the equivalent of 28.

This indicates that Cu (BF4 >2) reacted with N-methylpyrrole, and in particular, the anion portion thereof was added.

The electrical conductivity of this black material was 4.2 x 10'SCm-1, the average secondary particle diameter was 0.2 µm, and the compacted compact density was 1.3 MCIII'.

Examples 3 to 11 Various pyrrole compounds were used, and reactions between these and various cupric compounds were performed in the same manner as in Example 1. Table 1 shows the inspection results of the obtained dark brown to black powder. In addition, when the reaction was carried out using a solvent other than the 21-lyl compound, the solvent used is shown in Table 1.

Effect of Kimei> As described above, according to the present invention, it is easy to manufacture,
A wide variety of organic semiconductors can be obtained that are easy to handle in the molding process, have high pressure molding density and high electrical conductivity, and have excellent oxidation resistance, and their practical value is extremely high. Thus, the organic semiconductor of the present invention can be used as an antistatic material, an electromagnetic shielding material,
It can be applied to a wide range of fields such as electronic-optical functional devices, optical memories, various 4-no-1 display devices, switches, and various terminal devices.

Claims (1)

[Claims] 1. A granular conductive material made of a pyrrole polymer obtained by reacting a pyrrole compound and an oxidizing agent, and formed from primary particles with an average particle size of 0.01 to 0.4 μm. A conductive material characterized in that it is a granular material, molded under pressure, and has a density of 1 to 1.6 g/cm^3. 2. The above-mentioned conductive material has a general formula ▲ mathematical formula, chemical formula, table, etc. represents an amino group or an arylamino group, and R^3 represents a hydrogen atom, an alkyl group, or an aryl group.) A pyrrole compound represented by the general formula CuX_m (2) (wherein, are ClO_4^-, BF_4^-, ASF_
6^-, PF_6^-, SbF_6^-, CH_3C_
6H_4SO_3^-, CF_3SO_3^-, ZrF
6^-^-, TiF6^-^- or SiF6^-^-
, and m represents an integer of 1 to 2. ) A cupric compound represented by the general formula R(CN)_n (3) (wherein R represents an alkyl group, alkenyl group, or aryl group that may have a substituent, 2. The conductive material according to claim 1, wherein the conductive material is obtained by reacting a nitrile compound represented by the formula (n represents an integer of 1 to 3) with an oxidizing agent.