JPH1180420A - Production of conductive composition and conductive composition obtained therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition having high conductivity and high environmental stability by chemically polymerizing a polymerizable monomer in an aqueous medium containing a salt containing a transition metal ion and a benzyl alcohol derivative. SOLUTION: A benzyl alcohol derivative, a polymerizable monomer selected among pyrrole, thiophene, aniline or derivatives thereof and optionally an anionic surfactant are added to an aqueous solution of a salt containing a transition metal ion, the mixture is agitated for a specified time, and the formed precipitate is separated by filtration, washed with water and dried to obtain a conductive composition containing a conjugated double bond containing a conductive polymer such as polypyrrole. The benzyl alcohol derivative used is one having an electron-attracting substituent selected among nitro, cyano, hydroxyl, etc. The transition metal ion used is selected among a trivalent iron ion, a divalent copper ion, a hexavalent molybdenum ion and a hexavalent chromiumn ion, and the anion constituting the salt is selected among a sulfate ion, a chloride ion, nitrate ion, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a conductive composition and a conductive composition, and more particularly to a method for producing a conductive composition containing a conductive polymer having a conjugated double bond, and a conductive composition. It is about.

[0002]

2. Description of the Related Art In general, conjugated double bond conductive polymers represented by polypyrrole, polythiophene and polyaniline can be produced by chemical oxidation polymerization and electrolytic polymerization.

Here, in the case of using electrolytic polymerization, it is difficult to mass-produce the conductive polymer because the conductive polymer is formed in a film on the electrode. In such a case, there is no such restriction, and in principle, a large amount of conductive polymer can be obtained relatively easily by the reaction between the polymerizable monomer and an appropriate oxidizing agent.

[0004]

However, the polymerization rate of the chemical polymerization depends on the oxidizing agent used, and when ammonium persulfate or hydrogen peroxide having a high polymerization rate is used, the electric conductivity is high and the heat resistance is high. There is a problem that it is difficult to obtain a conductive polymer having excellent properties.

[0005] This is interpreted as follows: a highly active oxidizing agent has a high probability of causing undesirable side reactions, thereby producing a polymer having low structural regularity or not increasing the degree of polymerization.

To solve such a problem, for example, 3
Divalent iron ion, divalent copper ion, hexavalent chromium ion,
An inorganic acid salt containing a transition metal ion such as hexavalent molybdenum ion is often used as an oxidizing agent.

Further, for example, an organic acid salt comprising a sulfonic acid group and such a metal ion is also used.

[0008] The conjugated double bond conductive polymer has a characteristic that when an anion or a cation is incorporated as a dopant, its unique electrical, optical and chemical properties are exhibited. Since the stability also tends to be greatly affected by the type of dopant, it is necessary to consider such a point when doping these materials.

Here, the conjugated double bond polymer in the present invention is assumed to be anion-doped.

In general, inorganic acid ions have a small ion size and are easily diffused. In particular, under high temperature and high humidity, a relatively fast de-doping reaction is caused. It is difficult to realize the molecule.

In the case of a polyvalent anion such as a sulfate ion, two binding sites close to each other within the same polymer chain or between polymer chains are prepared in order to be incorporated as a dopant. In addition to having to do so, furthermore, when incorporated as a dopant, the small ionic size causes steric crowding, resulting in distortion of the polymer backbone, resulting in low electrical conductivity.

On the other hand, in the case of an organic anion having a bulky structure, it is considered that the polymer skeleton is not distorted and diffusion due to heat is suppressed. And heat resistance and moisture resistance.

In fact, it is known that polypyrrole having excellent heat and moisture resistance can be obtained by doping with, for example, anthraquinone sulfonate or alkylnaphthalene sulfonate (JP-A-3-93214).
JP-A-2-130906).

However, such a transition metal salt having a relatively large molecule as an anion generally has low solubility in water, and thus is introduced as a direct dopant into a conjugated double bond polymer by oxidative polymerization in an aqueous medium. It is difficult.

Therefore, in order to obtain a conductive high molecular polymer doped with a bulky organic anion as described above and having excellent electric conductivity and environmental stability, it is necessary to carry out polymerization in an organic solvent. there were.

However, organic solvents are overwhelmingly expensive as compared with water, and are often flammable and toxic. Therefore, when mass production is to be carried out, it is necessary to take measures to prevent such disasters. However, there has been a problem that the apparatus is large and complicated, and the resulting conductive composition is expensive.

Further, in the case of using chemical oxidative polymerization, the conductive polymer is generally obtained in powder form, and furthermore, since the polymer skeleton is formed of conjugated double bonds, in most cases, For example, it is difficult to perform post-processing such as heat melting or dispersion in a solvent, and it is also difficult to uniformly coat the solid surface as it is.

For this reason, attempts have been made to mix a suitable binder or introduce a suitable substituent into the polymer main chain, solubilize the solvent in a solvent, and then provide the film for film formation.

However, when mixed with a binder, a decrease in electrical conductivity due to the effect of dilution of the conductive polymer is inevitable. Therefore, it is necessary to maintain a high level of electrical conductivity of the original conductive polymer. There was a problem that did not become.

On the other hand, when solubilization is intended, there is a problem that the selection of substituents is limited in view of the balance between imparting solubility and the properties of the conductive polymer, for example, electric conductivity or environmental stability. there were.

Further, there is also a problem that it is difficult to produce a polymerizable monomer having a substituent, and the resulting conductive polymer tends to be expensive.

In order to solve the above-mentioned problems of the prior art, the present invention provides a conductive composition containing a conjugated double bond conductive polymer and having high environmental stability such as high thermal stability. Is obtained in a short time with high yield.

[0023]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art, and has a conjugated double bond conductivity by chemical polymerization in an aqueous medium containing a transition metal inorganic acid salt and a benzyl alcohol derivative. A method for producing a conductive composition containing a polymer, a method for producing a conductive composition containing a conjugated double bond conductive polymer by chemical polymerization in an aqueous medium to which anionic surfactant has been added, or such a method. It is a conductive composition obtained by a simple manufacturing method.

With the above structure, a highly conductive conductive composition containing a conjugated double bond conductive polymer and having high environmental stability such as high thermal stability can be obtained in a short time and with a high yield. be able to.

[0025]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS In the method for producing a conductive composition according to the present invention, a step of preparing a polymerizable monomer and a step of preparing a salt containing a transition metal ion capable of polymerizing the polymerizable monomer are provided. And a step of preparing an aqueous medium containing benzyl alcohol derivative, and a step of chemically polymerizing the polymerizable monomer using the aqueous medium, a conductive composition containing a conjugated double bond conductive polymer. It is a manufacturing method.

According to this structure, an undesired side reaction is suppressed by the interaction between the benzyl alcohol derivative and the polymerizable monomer having a conjugated double bond. A double bond polymer is obtained, and a conductive composition containing a conjugated double bond conductive polymer and having high environmental stability such as high thermal stability can be obtained in a short time and in a high yield. can get.

Alternatively, as in claim 2, a step of preparing a polymerizable monomer, and water containing a salt containing a transition metal ion capable of polymerizing the polymerizable monomer, a benzyl alcohol derivative, and an anionic surfactant. A method for producing a conductive composition containing a conjugated double bond conductive polymer, comprising a step of preparing a medium and a step of chemically polymerizing the polymerizable monomer using the aqueous medium.

Here, in addition to the effect of the addition of the benzyl alcohol derivative, the surfactant incorporates a polymerizable monomer having high hydrophobicity into the micelle. By forming a temporary insoluble salt with the cation and adsorbing the polymerizable monomer on the surface thereof, the polymerization reaction proceeds at those locations, thereby accelerating the polymerization reaction.

Furthermore, most conductive polymers exhibit conductivity in an oxidized state. For example, in the case of polypyrrole, the charge deficiency in the oxidized state is 1 to 3 per pyrrole ring.
It is about electronic.

This charge deficiency is compensated by the dopant anion. However, when a surfactant is used, the surfactant anion is present in the vicinity of the produced polymer, so that it is easily taken in as a dopant. If the surfactant anion is present at a higher concentration than is sufficient as a dopant for the formed conjugated double bond polymer, it will be predominantly included as a dopant. .

Since the surfactant anion is bulky and has a higher molecular weight than the anion derived from the transition metal salt, the doping does not distort the skeleton structure of the conjugated double bond conductive polymer, and furthermore, the doping is also possible. Since the electric conductivity is increased and the equivalent concentration of the dopant per conductive polymer repeating unit is constant, the higher the molecular weight, the higher the yield of the obtained conductive polymer. To increase.

Accordingly, a conductive composition containing a conjugated double bond conductive polymer and having higher conductivity and higher environmental stability such as higher thermal stability can be obtained in a shorter time and in a higher yield. Will be done.

Here, the anionic surfactant may be sulfonic acid, esterified sulfuric acid,
Alternatively, it is more preferable to include an esterified phosphoric acid-based activator in order to ensure the manifestation of its action.

According to the fourth aspect of the present invention, the use of a benzyl alcohol derivative having at least one electron-withdrawing substituent on the benzene ring can be achieved by using a polymerizable monomer having an electron-withdrawing substituent and a conjugated double bond. By the interaction of, undesirable side reactions are suppressed, a conjugated double bond conductive polymer having a skeleton with excellent structural regularity is formed, and a polymer having high electrical conductivity is obtained more reliably. More preferred.

More specifically, as described in claim 5,
It is preferable to use a benzyl alcohol derivative having an electron-withdrawing substituent selected from a nitro group, a cyano group, a hydroxyl group, a carboxyl group, an aldehyde group and a methyl ketone group.

According to a sixth aspect of the present invention, the transition metal ion is selected from trivalent iron ions, divalent copper ions, hexavalent molybdenum ions and hexavalent chromium ions. It is preferable from the standpoint of reliable expression.

Further, the anions constituting the salt containing a transition metal ion include sulfate, chloride, nitrate, perchlorate, hexacyanoferrate, benzenesulfonate, and toluene. It is preferable to be selected from sulfonic acid ions and sulfonic acid ions containing an alkyl group having 6 or less carbon atoms, when the conductive composition is used for an electrolyte of a capacitor without adversely affecting the dielectric.

As described in claim 8, it is preferable that the polymerizable monomer is pyrrole, thiophene, aniline or a derivative thereof because of its high conductivity.

On the other hand, the conductive composition of the present invention comprises
As described, a conductive composition comprising a conductive polymer having a conjugated double bond doped with an anion, which is manufactured by the method for manufacturing a conductive composition according to any one of claims 1 to 7. .

More specifically, as described in claim 10, a conductive composition containing pyrrole as a repeating unit,
As described in claim 11, a conductive composition containing thiophene as a repeating unit, or as described in claim 13, a conductive composition containing aniline as a repeating unit, and when thiophene is contained as a repeating unit, More specifically, as described in claim 12, thiophene is
Preferably, it is 3,4-ethylenedioxythiophene.

With this configuration, the conductive composition of the present invention is a conductive composition having high conductivity and high environmental stability such as high thermal stability.

Hereinafter, each embodiment of the present invention will be described in detail. (Embodiment 1) First, a first embodiment of the present invention will be described.

First, in this embodiment, 10.7 g of ferric sulfate n-hydrate (containing 0.02 mol as ferric sulfate) as an oxidizing agent containing a transition metal ion is dissolved in 100 g of water. Thus, an oxidizing agent solution was prepared.

Next, 5 g of a pyrrole monomer was added to this solution.
(0.75 mol), p-nitrobenzyl alcohol
A solution prepared by dissolving 15 g (0.0075 mol) in 100 g of water was added, and the mixture was polymerized with stirring at 25 ° C. and atmospheric pressure for 1 hour.

Then, the obtained precipitate is separated by filtration, washed with water until the filtrate becomes neutral, further washed with ethanol, and dried under reduced pressure at about 50 ° C. for several hours to form a conjugated double bond. A conductive composition containing polypyrrole, which is a conductive polymer, was obtained.

Then, after measuring the yield of the conductive composition, a part thereof was pulverized in a mortar to produce a disc-shaped pellet having a diameter of 13 mm at a pressure of about 30 MPa, which was subjected to measurement of electric conductivity.

The electric conductivity was measured using a resistivity meter Loresta AP manufactured by Mitsubishi Yuka Corporation and a four-terminal probe M.
CP-T400 was used.

The obtained yield and measured values of the electric conductivity were
It is shown in the following (Table 1).

[0049]

[Table 1]

(Comparative Example 1) As Comparative Example 1, polypyrrole was prepared in the same manner as in Embodiment 1, except that a monomer solution to which no benzyl alcohol derivative was added was used. Was measured.

The results are shown in the above (Table 1). As is clear from the comparison between Comparative Example 1 and Embodiment 1 in (Table 1), the conductive composition according to Embodiment 1
It was found that an excellent effect was obtained in that the electric conductivity was high.

In addition, elemental analysis of polypyrrole revealed that the ratio of sulfur element to nitrogen element was larger for polypyrrole obtained in a system containing p-nitrobenzyl alcohol.

From this point, also, in the chemical polymerization of the polymerizable monomer, the coexistence of the benzyl alcohol derivative results in the formation of polypyrrole having a high regularity in the structure, resulting in an increase in the conjugate length and an increase in the doping ratio. It is determined that the electrical conductivity has improved.

FIG. 1 shows the effect of the addition ratio of p-nitrobenzyl alcohol on the electrical conductivity and yield of polypyrrole.

FIG. 1 also clearly shows the effect of improving the electric conductivity depending on the addition ratio of p-nitrobenzyl alcohol.

As described above, according to the present embodiment, typically, ferric sulfate n-hydrate is used as an oxidizing agent, and p-nitrobenzyl alcohol is allowed to coexist with the aqueous medium polymerization system, thereby obtaining electric power. A conductive composition having high conductivity was obtained.

(Embodiment 2) Next, a second embodiment of the present invention will be described.

In this embodiment, instead of the p-nitrobenzyl alcohol used in the first embodiment, equimolar amounts of (A) m-nitrobenzyl alcohol, (B) o-nitrobenzyl alcohol, and (C) p-nitrobenzyl alcohol -Hydroxybenzyl alcohol, (D) p-oxymethylbenzoic acid, (E)
A conductive composition containing polypyrrole was prepared in the same manner as in Embodiment 1 except that a monomer solution to which p-oxymethylbenzaldehyde and (F) p-oxymethylacetophenone were added was used, and after a similar treatment. The yield and electrical conductivity were measured.

The results are shown in the above (Table 1). As is clear from the comparison between Embodiment 2 in Table 1 and Comparative Example 1, the conductive composition according to the present embodiment obtained an excellent effect in terms of high electric conductivity. There was found.

As described above, according to the present embodiment, ferric sulfate n-hydrate is typically used as the oxidizing agent, and various benzyl alcohol derivatives are allowed to coexist in the aqueous medium polymerization system. A high conductive composition could be obtained.

(Embodiment 3) Next, a third embodiment of the present invention will be described.

In the present embodiment, instead of the oxidizing agent solution obtained by dissolving 0.02 mol of ferric sulfate n-hydrate in 100 g of water, the same equivalent of each of (A) cupric sulfate and (B) ) A conductive composition was prepared in the same manner as in Embodiment 1 except that an oxidizing agent solution obtained by dissolving sodium phosphate molybdate and (C) ammonium dichromate in 100 g of water was used. The yield and electrical conductivity were measured.

The results are shown in the above (Table 1). Comparative Example 2 As Comparative Example 2, each (A) cupric sulfate was used as an oxidizing agent by the same operation as in Embodiment 3, except that a monomer solution to which no benzyl alcohol derivative was added was used.
Polypyrrole was prepared using (B) sodium phosphomolybdate and (C) ammonium dichromate, and after the same treatment, the yield and electric conductivity were measured.

The results are shown in the above (Table 1). As is clear from the comparison between Comparative Example 2 and Embodiment 3 in (Table 1), the conductive composition according to Embodiment 3 exhibited an excellent effect in terms of high electric conductivity. There was found.

As described above, also according to the present embodiment, various transition metal salts are used as oxidizing agents, and typically, p-nitrobenzyl alcohol is allowed to coexist in the aqueous medium polymerization system, thereby obtaining a conductive material having high electric conductivity. A composition could be obtained.

(Embodiment 4) Next, a fourth embodiment of the present invention will be described.

In this embodiment, instead of the oxidizing agent solution obtained by dissolving 0.02 mol of ferric sulfate n-hydrate in 100 g of water, the same amount of each of (A) ferric chloride and (B) ) Ferric perchlorate, (C) ferric nitrate, (D) potassium hexacyanoferrate (IV), (E) ferric benzenesulfonate,
(F) Ferric p-toluenesulfonate, (G) Conductive composition in the same manner as in Embodiment 1, except that an oxidizing agent solution obtained by dissolving ferric n-hexylsulfonate in 100 g of water was used. A product was prepared, and after the same treatment, the yield and the electric conductivity were measured.

The results are shown in the above (Table 1). (Comparative Example 3) As Comparative Example 3, each (A) ferric chloride was used as an oxidizing agent in the same manner as in Embodiment 4 except that a monomer solution to which no benzyl alcohol derivative was added was used.
(B) ferric perchlorate, (C) ferric nitrate, (D) potassium (IV) hexacyanoferrate, (E) ferric benzenesulfonate, (F) ferric p-toluenesulfonate ,
(G) Polypyrrole was prepared using ferric n-hexylsulfonate, and after the same treatment, the yield and the electric conductivity were measured.

The results are shown in the above (Table 1). As is clear from the comparison between Comparative Example 3 and Embodiment 4 in (Table 1), the conductive composition according to Embodiment 4 exhibited an excellent effect in terms of high electrical conductivity. There was found.

As described above, also in the present embodiment, various transition metal salts are used as oxidizing agents, and p-nitrobenzyl alcohol is typically allowed to coexist with the aqueous medium polymerization system, thereby obtaining a conductive material having high electric conductivity. A composition could be obtained.

(Fifth Embodiment) Next, a fifth embodiment of the present invention will be described.

In this embodiment, the pyrrole monomer 0.1.
075 mol, each (A) thiophene monomer,
(B) A conductive composition was prepared in the same manner as in Embodiment 1, except that 3,4-ethylenedioxythiophene (Baytron M manufactured by Bayer) and (C) aniline were used. And the electrical conductivity was measured.

The results are shown in the above (Table 1). (Comparative Example 4) As Comparative Example 4, each of (A) thiophene monomer, (B) 3, 4 -Polypyrrole was prepared using ethylenedioxythiophene (Baytron M manufactured by Bayer) and (C) aniline, and after the same treatment, the yield and electric conductivity were measured.

The results are shown in the above (Table 1). As is clear from the comparison between Comparative Example 4 and Embodiment 5 in (Table 1), the conductive composition according to Embodiment 5 exhibited an excellent effect in terms of high electrical conductivity. There was found.

As described above, also according to the present embodiment, by using a typical transition metal salt as an oxidizing agent and allowing various monomers and typically p-nitrobenzyl alcohol to coexist in an aqueous medium polymerization system, the electric conductivity is improved. A highly conductive composition could be obtained.

(Embodiment 6) Next, a sixth embodiment of the present invention will be described.

In this embodiment, except that 0.005 mol of sodium alkylnaphthalenesulfonate (average molecular weight: 332) is further added to the monomer solution.
A conductive composition was prepared in the same manner as described above, and after the same treatment, the yield and the electric conductivity were measured.

The results are shown in the following (Table 2).

[0079]

[Table 2]

Comparative Example 5 As Comparative Example 5, polypyrrole was prepared in the same manner as in Embodiment 6 except that a monomer solution to which p-nitrobenzyl alcohol was not added was used. The conductivity was measured.

The results are shown in the above (Table 2). As is clear from the comparison between Comparative Example 5 and Embodiment 6 in (Table 2), the conductive composition according to Embodiment 6
It was found that an excellent effect was obtained in that the electric conductivity was high.

Further, as is apparent from the comparison between Embodiment 1 in (Table 1) and Embodiment 6 in (Table 2), the coexistence of an anionic surface-forming chemical agent significantly increased the yield. You can see that it is.

FIG. 2 shows the yield and electrical conductivity of polypyrrole obtained when the concentration of sodium alkylnaphthalenesulfonate was changed in this embodiment.

Further, FIG. 2 also shows the results obtained when only sodium alkylnaphthalenesulfonate was added without adding p-nitrobenzyl alcohol and the concentration was changed.

Here, the doping rate of the polypyrrole prepared under the main polymerization conditions is estimated to be about 25 mol% from the ratio of sulfur to nitrogen obtained by elemental analysis. Assuming, the concentration required to fill all dopants with surfactant anions is calculated to be 0.022M.

That is, in FIG. 2, the reason why the electrical conductivity and the yield linearly increase to the vicinity of this concentration is considered to be that the surfactant anion having a large molecular weight is preferentially taken in as a dopant.

In FIG. 2, in the region where the concentration of the surfactant is 0.022 M or more, the electric conductivity slightly decreases.
It is considered that the reason why the yield was still slightly increased is that the dopant of polypyrrole became occupied by the surfactant anion, and that which was not consumed as the dopant was adsorbed on the hydrophobic polypyrrole surface.

From this point as well, in the chemical polymerization of the polymerizable monomer, polypyrrole having a high structural regularity is formed by coexisting p-nitrobenzyl alcohol and the surfactant sodium alkylnaphthalenesulfonate. Also, it is judged that since the molecular weight is formed by a surfactant anion having a molecular weight larger than that of the oxidant anion, the electric conductivity is increased and the yield is further increased.

FIG. 3 shows the effect of the presence or absence of a surfactant on the polymerization rate. In FIG. 3, in the system to which the surfactant was added, the yield reached saturation after almost 30 minutes, whereas in the case of the non-added system and the addition of sodium β-naphthalenesulfonate having no surfactant effect, It can be seen that it takes more than 2 hours for the yield to reach saturation.

This is because the pyrrole monomer is incorporated into the micelles of the surfactant and the polymerization reaction proceeds by a so-called emulsion polymerization mechanism, or it is formed temporarily between the surfactant anion and the iron (III) cation. It is considered that the polymerization rate was increased because the pyrrole monomer was adsorbed on the surface of the insoluble precipitated fine particles to form innumerable reaction initiation points.

Since the iron (III) cation is consumed during the polymerization reaction, the insoluble salt is considered to disappear with the progress of the polymerization reaction. This is supported by the fact that it is confirmed that almost no iron is present.

As described above, according to the present embodiment, a typical transition metal salt is used as an oxidizing agent, and p-nitrobenzyl alcohol and a surfactant sodium alkylnaphthalenesulfonate are typically used in a medium polymerization system. Take the configuration to coexist, that is, in the chemical polymerization of the polymerizable monomer,
By having p-nitrobenzyl alcohol coexist, polypyrrole with high structural regularity was formed, and by further coexisting an anionic surfactant, the anion was preferentially incorporated as a dopant. As a result, it was possible to obtain a conductive polymer composition having improved electric conductivity and increased yield.

(Embodiment 7) Next, a seventh embodiment of the present invention will be described.

In the present embodiment, instead of the p-nitrobenzyl alcohol used in the sixth embodiment, equimolar amounts of each of (A) m-nitrobenzyl alcohol, (B) o-nitrobenzyl alcohol, and (C) p-hydroxybenzyl alcohol, (D) p-oxymethylbenzoic acid, (E)
A conductive composition containing polypyrrole was prepared in the same manner as in Embodiment 6, except that a monomer solution to which p-oxymethylbenzaldehyde and (F) p-oxymethylacetophenone were added was used, and after the same treatment. The yield and electrical conductivity were measured.

The results are shown in the above (Table 2).
As is clear from the comparison between the results of Embodiment 7 in Table 2 and the results of Comparative Example 5, the conductive composition according to the present embodiment has an excellent effect in terms of high electric conductivity. It turned out that it was done.

Further, as is apparent from the comparison between Embodiment 2 in (Table 1) and Embodiment 7 in (Table 2), the coexistence of an anionic surface-forming chemical agent significantly increased the yield. You can see that it is.

As described above, also in this embodiment, ferric sulfate n-hydrate is typically used as the oxidizing agent, and various benzyl alcohol derivatives and the surfactant sodium alkylnaphthalenesulfonate are typically used in an aqueous medium. By coexisting in the polymerization system, a conductive composition having high electric conductivity could be obtained in high yield.

(Eighth Embodiment) Next, an eighth embodiment of the present invention will be described.

In the present embodiment, the equivalent amounts of sodium (A) sodium dodecylbenzenesulfonate, (B) sodium alkylsulfonate (average molecular weight 328), A conductive composition was prepared in the same manner as in Embodiment 6, except that a pyrrole monomer solution in which (C) potassium dodecyl sulfate and (D) sodium hexyl phosphate (acid equivalent: 181) were dissolved in 100 g of water was used. After treatment, the yield and electrical conductivity were measured.

The results are shown in the above (Table 2). (Comparative Example 6) As Comparative Example 6, a polypyrrole was prepared in the same manner as in (A) to (D) of Embodiment 8, except that a monomer solution to which p-nitrobenzyl alcohol was not added was used. After the treatment, the yield and the electric conductivity were measured.

The results are shown in the above (Table 2). As is clear from the comparison between Comparative Example 6 and Embodiment 8 in (Table 2), the conductive composition according to Embodiment 8 exhibited an excellent effect in terms of high electric conductivity. There was found. The yield was equivalent to that of the sixth embodiment.

As described above, also in the present embodiment, when the polymerizable monomer is chemically polymerized, the p-nitrobenzyl alcohol and various anionic surfactants are typically allowed to coexist in the aqueous medium polymerization system, so that the electric conductivity is improved. A highly conductive composition was obtained in high yield.

(Embodiment 9) Next, a ninth embodiment of the present invention will be described.

In the present embodiment, an equivalent amount of (A) cupric sulfate and (B) are replaced with an oxidizing agent solution obtained by dissolving 0.02 mol of ferric sulfate n-hydrate in 100 g of water. A conductive composition was prepared in the same manner as in Embodiment 6, except that an oxidizing agent solution obtained by dissolving sodium phosphomolybdate and (C) ammonium dichromate in 100 g of water was used. The conductivity was measured.

The results are shown in the above (Table 2). (Comparative Example 7) As Comparative Example 2, each (A) cupric sulfate was used as an oxidizing agent by the same operation as in Embodiment 9 except that a monomer solution to which no benzyl alcohol derivative was added was used.
Polypyrrole was prepared using (B) sodium phosphomolybdate and (C) ammonium dichromate, and after the same treatment, the yield and electric conductivity were measured.

The results are shown in the above (Table 2). As is clear from the comparison between Comparative Example 7 and Embodiment 9 in (Table 2), the conductive composition according to Embodiment 9 exhibited an excellent effect in terms of high electric conductivity. There was found. In addition, an increase in the yield is apparent from comparison with the third embodiment.

As described above, also in the present embodiment, the electric conduction is achieved by using various transition metal salts as oxidizing agents, and typically coexisting p-nitrobenzyl alcohol and an anionic surfactant in the aqueous medium polymerization system. A highly conductive composition was obtained in high yield.

(Embodiment 10) Next, the first embodiment of the present invention will be described.
Embodiment 0 will be described.

In the present embodiment, an equivalent amount of (A) ferric chloride and (B) are replaced with an oxidizing agent solution obtained by dissolving 0.02 mol of ferric sulfate n-hydrate in 100 g of water. Ferric perchlorate, (C) ferric nitrate, (D) hexacyanoferrate (I
V) potassium, (E) ferric benzenesulfonate,
A conductive composition was prepared in the same manner as in Embodiment 6, except that an oxidizing agent solution obtained by dissolving (F) ferric p-toluenesulfonate and (G) ferric n-hexylsulfonate in 100 g of water was used. After preparing and performing the same treatment, the yield and the electric conductivity were measured.

The results are shown in the above (Table 2). (Comparative Example 8) As Comparative Example 8, each of (A) ferric chloride and (B) was used as an oxidizing agent in the same manner as in Embodiment 6, except that a monomer solution to which p-nitrobenzyl alcohol was not added was used. Ferric perchlorate, (C) ferric nitrate, (D)
Potassium (IV) hexacyanoferrate, (E) ferric benzenesulfonate, (F) ferric p-toluenesulfonate,
(G) Polypyrrole was prepared using ferric n-hexylsulfonate, and after the same treatment, the yield and the electric conductivity were measured.

The results are shown in the above (Table 2). As is clear from the comparison between Comparative Example 8 and Embodiment 10 in (Table 2), the conductive composition according to Embodiment 10 exhibited an excellent effect in terms of high electric conductivity. There was found. In addition, an increase in the yield is apparent from comparison with the fourth embodiment.

As described above, also in this embodiment, various transition metal salts are used as oxidizing agents, and p-nitrobenzyl alcohol and a typical anionic surfactant coexist in an aqueous medium polymerization system. As a result, a conductive composition having high electric conductivity could be obtained at a high yield.

Embodiment 11 Next, the first embodiment of the present invention will be described.
One embodiment will be described.

In this embodiment, the pyrrole monomer 0.1.
(A) a thiophene monomer,
(B) A conductive composition was prepared in the same manner as in Embodiment 6, except that 3,4-ethylenedioxythiophene (Baytron M manufactured by Bayer) and (C) aniline were used. And the electrical conductivity was measured.

The results are shown in the above (Table 2). (Comparative Example 9) As Comparative Example 9, each (A) was used as a polymerizable monomer in the same manner as in Embodiment 5, except that a monomer solution to which p-nitrobenzyl alcohol was not added was used.
Polypyrrole was prepared using a thiophene monomer, (B) 3,4-ethylenedioxythiophene (Baytron M manufactured by Bayer) and (C) aniline, and after the same treatment, the yield and the electric conductivity were measured.

The results are shown in the above (Table 2). As is clear from the comparison between Comparative Example 9 and Embodiment 11 in (Table 2), the various conductive compositions according to Embodiment 11 exhibited excellent effects in terms of high electrical conductivity. It has been found.

As described above, also in this embodiment, a typical metal salt is used as an oxidizing agent, and various monomers, typically p-nitrobenzyl alcohol, and a typical anionic surfactant are polymerized in an aqueous medium. By coexisting in the system, a conductive composition having high electric conductivity could be obtained in high yield.

In the above embodiments, pyrrole, thiophene,
Only the case where 3,4-ethylenedioxythiophene and aniline are repeated has been described. For pyrrole and aniline, these derivatives may be used, and for thiophene, other derivatives may be used. Any polymer can be used as long as it is polymerized to lead to a conjugated double bond conductive polymer, and is not limited to these.

Further, these may be arbitrarily combined and included. In the above embodiments, the surfactant is a sulfonate, an esterified sulfate and an esterified phosphate, but an anionic surfactant which generates an organic acid anion is used. If so, it is of course not limited to these.

Further, in the above embodiments, the case where iron ions, copper ions, chromium ions, and molybdenum ions are used as transition metal ions in the oxidizing agent has been representatively described. For example, a cerium ion or an inorganic acid salt containing manganese may be used,
As long as a conjugated double bond polymer can be obtained from the polymerizable monomer, the same can be used.

In the above embodiment, sulfuric acid, hydrogen chloride, nitric acid, perchloric acid, hexacyanoferric acid, benzenesulfonic acid, toluenesulfonic acid,
Although only a sulfonic acid containing an alkyl group having 6 or less carbon atoms has been described, a water-soluble salt formed from another acid and a transition metal, for example, phosphate, tetrafluoroborate, or the like can also be used. The invention is not limited to that type.

Further, in the above embodiment, the case where a derivative having a substituent at the para position is used other than nitrobenzyl alcohol, but a derivative having a substituent at the ortho or meta position may be used. And those having a plurality of substituents can be similarly used.

Further, in the above embodiments, only nitro, cyano, hydroxyl, carboxyl, aldehyde and methyl ketone groups have been described as benzyl alcohol derivatives having electron-withdrawing substituents. A benzyl alcohol derivative to which a substituent having an electron-withdrawing property is bonded can also be used.

[0124]

As described above, according to the present invention, by chemical polymerization in an aqueous medium containing a transition metal inorganic acid salt and a benzyl alcohol derivative, an anionic surfactant is added to the aqueous medium. By chemical polymerization, not only can a conductive composition containing a conjugated double bond conductive polymer be reliably produced, but also such a composition has the property of being highly conductive and highly environmentally stable. It can be realized reliably and can be obtained in a short time and in a high yield.

[Brief description of the drawings]

FIG. 1 is a diagram showing the relationship between the amount of p-nitrobenzyl alcohol added and the electrical conductivity of polypyrrole in Embodiment 1 of the present invention.

FIG. 2 is a graph showing the relationship between the amount of sodium alkylnaphthalenesulfonate added and the electrical conductivity and yield of polypyrrole in Embodiment 6;

FIG. 3 is a diagram showing the relationship between the polymerization time and the yield of polypyrrole obtained in Embodiment 6.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI H01B 1/12 H01B 1/12 G

Claims (13)

[Claims] A step of preparing a polymerizable monomer; a step of preparing an aqueous medium containing a salt containing a transition metal ion capable of polymerizing the polymerizable monomer and a benzyl alcohol derivative; Performing a chemical polymerization using a medium. A method for producing a conductive composition containing a conjugated double bond conductive polymer. 2. A step of preparing a polymerizable monomer, and a step of preparing an aqueous medium containing a salt containing a transition metal ion capable of polymerizing the polymerizable monomer, a benzyl alcohol derivative, and an anionic surfactant. Performing a chemical polymerization of a polymerizable monomer using the aqueous medium. A method for producing a conductive composition containing a conjugated double bond conductive polymer. 3. The method according to claim 1, wherein the anionic surfactant is sulfonic acid,
3. The conductive composition according to claim 2, comprising an esterified sulfuric acid or an esterified phosphoric acid-based activator. 4. The method for producing a conductive composition according to claim 1, wherein a benzyl alcohol derivative having at least one electron-withdrawing substituent on a benzene ring is used. 5. A nitro group, a cyano group, a hydroxyl group,
The method for producing a conductive composition according to claim 4, wherein a benzyl alcohol derivative having an electron-withdrawing substituent selected from a carboxyl group, an aldehyde group, and a methyl ketone group is used. 6. The transition metal ion is a trivalent iron ion,
The method for producing a conductive composition according to any one of claims 1 to 5, wherein the conductive composition is selected from valence copper ions, hexavalent molybdenum ions, and hexavalent chromium ions. 7. An anion constituting a salt containing a transition metal ion includes a sulfate ion, a chloride ion, a nitrate ion, a perchlorate ion, a hexacyanoferrate ion, a benzenesulfonic acid ion, a toluenesulfonic acid ion and a carbon number of 6 or less. The conductive composition according to any one of claims 1 to 6, wherein the conductive composition is selected from sulfonate ions containing an alkyl group. 8. The method for producing a conductive composition according to claim 1, wherein the polymerizable monomer is pyrrole, thiophene, aniline, or a derivative thereof. 9. A conductive composition produced by the method for producing a conductive composition according to claim 1 and comprising a conductive polymer having a conjugated double bond doped with an anion. 10. The conductive composition according to claim 9, comprising pyrrole as a repeating unit. 11. The conductive composition according to claim 9, comprising thiophene as a repeating unit. 12. The conductive composition according to claim 10, wherein the thiophene is 3,4-ethylenedioxythiophene. 13. The conductive composition according to claim 9, comprising aniline as a repeating unit.