JPS63243131A - 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 provides an aniline polymer which is produced by reacting an aniline compound with an oxidizing agent consisting of a cupric compound and a 21-lyl compound. The present invention relates to an improvement in a method for producing a conductive material comprising:

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

Andimony pentafluoride, iodine, bromine, tricore sulfur, n-
Bujirrichi “Kum, naphthalenna 1~Rium-like P
It has been known that when treated with a type or N type doping agent, 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, or films, and are used as they are or after being molded depending on the purpose, such as antistatic abrasives, electromagnetic shielding materials, and photoelectric conversion elements. (electronic-optical functional elements), optical memory (holographic memory), two-layer display elements (electrochromism) such as various types of Renly, switches, various hybrid materials (transparent conductive films, etc.), various terminal devices or storage batteries. Applications to a wide range of fields are being considered.

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.

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 the method (2), polythenylene, polypyrrole or polyaniline is deposited in a film form on the anode used for electrolytic polymerization, and after the deposition is peeled off from the anode, polythenylene, polypyrrole or polyaniline is obtained in the form of a film. In addition, in the method (■), peroxides such as potassium persulfate and ammonium perlaate, 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 such an oxidizing agent. It has also been proposed to perform oxidative polymerization in an organic solvent using ferric perchlorate as an oxidizing agent to obtain 1 q of similar powdered polypyrrole (for example, Mo1.Cryst, liq, Cry).
st0 magazine, 1985 vol 118 no. 149-1
page 53).

However, in method (■) 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, which is a major constraint in terms of mass production. Along with receiving
Since the electrolytic polymerization method is used, the manufacturing method is complicated and there is 1 loss.
-There are inconveniences such as being expensive.

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 polypyrrole or polyaniline produced is low because the Ct degree of the doping agent in the solvent decreases by the decrease in solubility.

In addition, there is the disadvantage that various safety measures must be taken during the manufacturing process because a line-specific solvent with a high risk of explosion is handled.

On the other hand, JP-A No. 60-58430 proposes a method for producing conductive powdery pyrrole polymers in which pyrroles are treated with an oxygen-containing oxidizing agent in the presence of a conductive salt in a solution. has been done.

・However, in this method, peroxides such as peroxoacid or its salt or hydrogen peroxide are used as the above oxygen-containing oxidizing agent, so there is a risk of explosion and abnormalities in the storage and handling reaction port). It is necessary to be very careful about this, and when mass-producing it industrially, it has extremely large drawbacks in terms of handling safety.

Therefore, the present inventors have discovered that by polymerizing this type of conjugated compound in the presence of an oxidizing agent made of a cupric compound and a nitrile compound, the above-mentioned disadvantages and drawbacks can be avoided, and the method can be used in air. We proposed a method for manufacturing a conductive material that is not only stable but also has a high reaction rate, is easy to manufacture, and has high electrical conductivity (Japanese Patent Application No. 61-2152).
June 9).

<Problems to be Solved by the Invention> However, among the polymers of conjugated compounds obtained in this way, the polymer of aniline compounds is a conductive outer polymer with high electrical conductivity as described above. , has a relatively high solubility in organic solvents and poor solvent resistance, and the yield after washing with organic solvents such as nitrile compounds to purify the reaction product is quite low, making it difficult to use industrially. When producing in large quantities, there are problems that can cause losses of 1 to 100%.

<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 made of an aniline polymer by reacting an aniline compound in the presence of an oxidizing agent formed by coexisting a cupric compound and a nitrile compound. The present invention resides in a method for producing a conductive material, the gist of which is allowing a salt to coexist during the reaction.

As the cupric compound used in the present invention, for example, the general formula % formula % (1) (wherein, X is C20-1BF4-1 AsF -1PF -1SbF6-1CH3C6H
4SO3-, CF3SO3-, ZrF6-"', T
i F6- or 5iF6-, and m represents an integer of 1 to 2. ) are mentioned.

Further, the nitrile compound used in the present invention includes, for example, the general formula % 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 are used, a single or different two or more cupric compounds, and a single or two or more different 21-lyl compounds. It is possible to avoid reaction between the compound and the oxidizing agent.

The above-mentioned aniline compounds used in the present invention include, for example, the general formula (wherein R1 and R2 are hydrogen atoms, argyl groups, alkoxy groups, aryl groups, allyloxy groups, amino groups, alkylamino groups, and arylamino groups. (where R3 and R4 represent a hydrogen atom, an alkyl group, or an aryl group).

On the other hand, the salt used in the present invention is, for example, an organic or inorganic salt or double salt that is soluble in the reaction system containing the oxidizing agent and easily dissociates into ions in this reaction system, and has the general formula % formula % ( 4) (In the formula, M is an alkali metal or a quaternary alkylammonium group, X is a perchlorate ion, a fluorine metal anion, or a sulfonic acid anion, and a represents an integer of 1 to 2. ) are listed.

Specifically, the cupric compound represented by the general formula (1) is Cu (Cff104 >2, Cu (BF )
, Cu(PF6)2, Cu(AsF3)2, C
u(SbF6)2, Cu(CH3C6F(45O
3)2, Cu(CF3S03)2, CuZrF6
,CuT! FB, CLJS! FB, which 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, hydroxyethyl group, methoxymethyl group, methoxynatyl group,
Methoxypropyl group, oxymethyl group, ethoxyethyl group, cyanmethyl group, cyanethyl group, cyanopropyl group, cyanobutyl group, cyanopentyl group, cyanohexyl group, carboxymethyl group, carboxypropyl group, phenyl group, naphthyl group group, tolyl group, hydroxyphenyl group, hydroxynaphthyl group, methoxynaphthyl group, ethoxyphenyl group, methoxynaphthyl group, cyanophenyl group, dicyanophenyl group, cyanotolyl group, dicyano-1-ruyl group, cyanonaphthyl group, carboxyphenyl group, Represents a carboxytolyl group, etc. Examples of such nitrile compounds include ', ace-1-nitrile, n-propionitrile, isopropionitrile, n-butyronitrile,
Isobutyronitrile, tert-butyronitrile, acrylonitrile, methylacrylonitrile, ethyl acrylonitrile, phenyl acrylonitrile, ace1-cyanhydrin, medilene cyanohydrin, ethylene cyanohydrin, propylene cyanohydrin, -21~lyl, ethoxyacetoni1~lyl, me1
~xypropionitrile, malondinitrile, adiponitrile, cyanacetic acid, cyanopropionic acid, cyanoacetic acid, benzonitrile, naphthonitrile, methylbenzonilyl, hydroxybenzonitrile, phthalonitrilyl, lycyanobenzene, melilyl ~xybenzonitrile, lypoxybenzonitrile, 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, sec-butyl groups, tert- Butyl group, methoxy group, 1~xy group, n-propoxy group, n-11~xy group, phenyl group, tolyl group, naphthyl group, phenoxy group, methylphenoxy group, naphthoxy group, amine group, dimethylamino group, represents a diethylamino group, a phenylamino group, a diphenylamino group, a methylphenylamino group, a phenylnaphthylamino group, R and R4 are hydrogen atoms,
It represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a phenyl group, a tolyl group, and a naphthyl group.

Specific examples of such aniline compounds include aniline, methoxyaniline, ethylaniline, n-propylaniline, isopropylaniline, n-butylaniline, methoxyaniline, hegycyaniline, n-propoxyaniline, phenylaniline, -ruylaniline, naphdylaminoaniline, phenoxyaniline, methylphenoxyaniline, nano 1 - xyaniline, amineaniline, dimedylaminoaniline, diethylaminoaniline, phenylaminoaniline.

Examples include diphenylaminoaniline, methylphenylaminoaniline, and phenylnaphthylamineaniline.

Specifically, the salt represented by the above general formula (4) is Li
Cβ04, L i BF4, L i As Fe
, LiPF6, LiSbF6, LiSbF6, LiTi
F6, Li2SiF6, L i 2 B10Cff110. CH3C
6to'4SO3Li.

CF3303 Li, NaC, 204, Na B F
4, N a S F 6, N a S b
F6, Na2ZrF6, Na2T i FB, N
a2 S! FB, N a2 B10CJ! 10゜CH3C6H4SO3N a, CF3 503
N a , Bu4NCf104 , Bu4NBF4
, Bu4NASF6 , BLJ4 NPF6, Bu4N
SbF6, (BLJ4 N)2 zr FB, (Bu4
N>27i FB, (BLJ4N>2 S i F(,, (Bu4N)2B1oCβ1o, CH3C6to14 S O3N Bu a , C
F35O°3NBu4, Et4NCβ04, Et N
BF', Et NASF6. Et4NPF6,E
t4NSbF6, (E t 4 N > 22 r F 6, (Ej4N
>2T! FB, ([j4 N>23! FB, (E t4 N>2 B10CJ210゜C1-1
Examples include 3C6H4SO3NEt4 and CF3303NEt4.

The amount of the cupric compound represented by the general formula (1) to be used is 0.01 to 100 times, preferably 0.1 to 50 times, per mole of the conjugated compound.

Further, the nitrile compound represented by the general formula (2) is used together with the cupric compound, and examples of the method for using it include the following method.

1) After allowing the 21-lyl compound and the cupric compound to coexist in advance, they are allowed to interact with the aniline compound.

2) A cupric compound is allowed to act on a system in which an aniline compound and a nitrile compound coexist.

3) A nitrile compound is applied to a system in which an aniline compound and a cupric compound coexist.

4) A system in which a cupric compound and a 21-lyl compound coexist is applied to a system in which an aniline compound and a nitrile compound coexist.

5) Isolate the reaction product of the cupric compound and the nitrile compound in advance and avoid reacting it with the aniline compound.

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

Further, the amount of the nitrile compound represented by general formula (2) used is 0.01 to 10,000 per mole of the cupric compound.
It is 0 times the molar amount, preferably 0.1 to i, ooo times the molar amount. If the nitrile compound is a liquid substance, it can be used as a reaction solvent, or if it is a solid substance, any solvent such as water, alcoholic solvents such as methanol or ethanol, tetrahydrofuran, dioxylin, etc. can be used. , benzene, toluene, dichloromethane, dichloroethane, acetic acid, and other common organic solvents.

Further, the salt represented by the general formula (4) can be used in an amount of 0.01 to 100 times, preferably 0.1 to 50 times, per mole of the aniline compound. Examples of methods for using this salt include the following methods.

1) Coexist with a nitrile compound in advance and add it to the cupric compound or aniline compound.

2) Coexist with a cupric compound in advance and add it to the di-1-lyl compound or aniline compound.

3) Coexist with the aniline compound in advance and add it to the 21-lyl compound or the cupric compound.

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 0.1 to 200 hours, preferably 0.5 to 200 hours.
It is 100 hours.

The reaction product is a dark brown to black powdery substance, and in the reaction in the presence of the above-mentioned solvent, after the reaction is completed, the solvent is removed by a conventional method, and in the present invention, a liquid 21-helyl compound, For example, if the reaction product is washed and purified several times with a solvent such as acetonitrile or propionitrile, and the by-produced cuprous compound is dissolved and removed, 1q of products with higher conductivity can be obtained. This is preferable because it can be done.

<Function> By using the above method, it has low solubility in organic solvents, good solvent resistance, high yield during production, easy production, high electrical conductivity, and safe handling. It is possible to make 1q of good aniline-based car combinations.

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

Example 1 Aniline 3.7 (J (0,0
4 mol), L i BF4y, 5g (o, oa mol)
, Ace1-21-Ril 150 mu was taken and added to this solution at air temperature (15-20'C) while stirring under a nitrogen atmosphere.
) 45% Cu (BF4>2 aqueous solution 63.
2G (0,12-El) and acetonitrile 75mN
A mixed solution was added dropwise over 15 minutes.

As the mixture was added, heat generation was observed, and the reaction liquid immediately turned black. Powder-like solids were precipitated in the reaction liquid, and the mixture took on the form of a slurry. After continuing stirring for 2 hours, the mixture was left at air temperature overnight.

When the reactant was separated in the furnace, 1 q of black powdery material mixed with white crystalline material was obtained. Add this to acetonitrile 600I
After repeated washing with IlfJ four times, the white crystalline material was removed, and after drying under reduced pressure at a temperature of 60° C., 3.7 g of a black powdery material was obtained.

Elemental analysis of the black substance revealed that it was C51.10%, 14.
00%, N 9.99%, F 22.35%, and assuming carbon is 6, C6, "5.6, N1.0, Fl
, 64 was obtained. Separately, as a result of analyzing the copper content, it was found that the copper content was 0 and ooi for nitrogen 1.0. This indicates that Cu(BF4)2 reacted with the polymer, and in particular, the anion portion thereof was added.

As a result of measuring the electrical conductivity of this black substance by a two-terminal method, it was found that 9 x 10-2S0-2S was obtained, and it was found to be an organic semiconductor with conductivity in a semiconductor region.

The electrical conductivity was measured as follows. First, 1 q of the black powder obtained by the above treatment was sufficiently finely ground in a mortar, and then pressure-molded (5 tons/cI12) into a disk shape with a diameter of 1 Q mm. Next, this disk sample was sandwiched between two copper cylinders of the same size, and a 1.2 kg load was applied from the top.
, take out the conductor leads from the upper and lower copper cylinders, and use a digital multimeter (Tag Dariken TR6).
851), and the electrical conductivity of the disk sample was measured using this meter.

For comparison, the reaction and washing were carried out in the same manner as in Example 1 except that LiBF4 was not used. As a result, the product was considerably dissolved in the organic solvent, and the black powdery substance after washing was 1.5%.
It was g.

From the above results, it was confirmed that by avoiding the coexistence of [1BF4 in the reaction system, 1q of the reaction product, which has low solubility in organic solvents and is difficult to dissolve in organic solvents by washing treatment, can be removed.

Example 2 4.3 g of ortho-toluidine was used instead of aniline, and L! 2 B10CJ! An experiment was carried out in the same manner as in Example 1 except that 10 was used at 19.0 ().

Elemental analysis of the black powdery substance obtained revealed that carbon content was 7.0%.
Assuming that, C7, t18.5, Ni, o -Fl
, so was obtained.

Also, the electrical conductivity of this black object is 1.0×10'S
Cm-17” Atta.

Examples 3 to 12 Various aniline compounds and various salts were used, and reactions of these with various cupric compounds and nitrile compounds were performed in the same manner as in Example 1.

Table 1 shows the results of the study on the dark brown to black powdery substance obtained.

Incidentally, when the above reaction was carried out using a solvent other than the diI-lyl compound, the solvent used is also shown in Table 1.

<Effects of the Invention> As described above, according to the production method of the present invention, a heavy aniline compound that has low solubility in organic solvents, is easy to produce, has high electrical conductivity, and has good handling safety. A wide variety of conductive materials can be obtained by combining these materials, and their practical value is extremely high.

Claims (1)

[Claims] 1. A method for producing a conductive material made of an aniline polymer by reacting an aniline compound in the presence of an oxidizing agent containing a cupric compound and a nitrile compound, A method for producing a conductive material, characterized in that a salt is allowed to coexist during the reaction. 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▲Mathematical formula, chemical formula, table, etc.▼・・・・・・(3) (In the formula, R^1 and R^2 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^3 and R^4 represent a hydrogen atom, an alkyl group, or an aryl group). The method according to claim 1. 5. The salt is soluble in the reaction system containing the oxidizing agent, and
An organic or inorganic salt or double salt that is easily ionically dissociated, with the general formula M_aX (4) (wherein M is an alkali metal or a quaternary alkylammonium group, X is a perchlorate ion, The method according to claim 1, wherein the salt is a fluorine metal anion or a sulfonic acid anion, and a represents an integer of 1 to 2. 6. The method according to claim 1, wherein the reaction product of the aniline compound and the oxidizing agent is washed with a liquid nitrile compound.