JPH07179577A - Production of organic conductor and organic conductor produced by the process - Google Patents

Abstract

PURPOSE:To easily obtain an organic conductor stable at high temperature and extremely useful as electrode, optical function element, cell, etc., by carrying out electrolytic polymerization in the presence of magnetic field having a specific magnetic field intensity. CONSTITUTION:This conductor is produced by carrying out the electrochemical polymerization of a monomer and/or oligomer (preferably thiophene and its derivative) on the surface of an electrode, in an electrolytic solution in the presence of magnetic field having a field intensity of >=1Oe, preferably >=1.3T. The reaction is preferably carried out by electrolytic oxidation. Concretely, an electrolyte solution is prepared by using thiophene as the monomer, tetrabutylammonium tetrafluoroborate as the electrolyte and propylene carbonate as the solvent, dipping a working electrode composed of platinum and a counter electrode composed of copper into the electrolyte solution and applying a potential of 5V to the electrode pair while applying a magnetic field of 1,500Oe with a permanent magnet perpendicular to the direction of the electric field.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an organic conductor, more specifically, a high-strength organic conductor useful for electrodes, optical functional devices, batteries, nonlinear optical materials, various sensors, electromagnetic shields, FETs and the like. Regarding the method.

[0002]

2. Description of the Related Art The synthesis of an organic conductor is carried out by a chemical polymerization method in which a monomer is polymerized using an oxidant or a catalyst, a method in which an intermediate made of a non-conjugated polymer is heat-treated, an electrolytic polymerization method and the like. Has been. Here, the electrolytic polymerization method means that the working electrode and the counter electrode, and if necessary, the reference electrode are immersed in an electrolytic solution containing a monomer (or an oligomer) and a supporting electrolyte, and a voltage is applied to the monomer so that the monomer is electrochemically reacted. A polymer that can be easily obtained by electrolytic oxidation or electrolytic reduction on the electrode surface to generate in situ reactive reactive species such as cation radicals and anion radicals, which are polymerized into a polymer. Since it also has a high conductivity, it is also suitable for actual manufacturing and application.

However, some of the organic conductors synthesized by the electrolytic polymerization method are insufficient in physical properties such as electric conductivity and strength, and are not satisfactory in production such as yield. However, there is a drawback that it cannot be said to be stable especially at high temperatures, and the usable range was limited. Therefore, in order to improve the electric conductivity, electrolytic polymerization is performed while applying a magnetic field (Japanese Patent Laid-Open No. 64-79221), and in order to improve the yield, a magnetic field for flowing an electrolytic solution is used. A method of carrying out electrolytic polymerization in the presence (Japanese Patent Laid-Open No. 3-19092).
No. 2, JP-A-3-263424) and the like have been proposed.

[0004]

Certainly, according to these methods, the electric conductivity and the yield are improved, but the obtained organic conductor is not stable at high temperature.
The usable range was limited.

Therefore, an object of the present invention is to solve the above-mentioned problems, that is, to provide a method for producing an organic conductor which is stable at high temperature easily, and an organic conductor which is stable at high temperature produced by the method. To provide.

[0006]

According to the present invention, in an electrolytic solution containing a monomer and / or an oligomer, an electrochemical polymerization reaction is caused to occur on the surface of an electrode on the monomer and / or oligomer in the electrolytic solution. The reaction is 1
Provided is a method for producing a high temperature stable organic conductor, which is characterized in that it is carried out in the presence of a magnetic field of Oe or higher, and a high temperature stable organic conductor formed by the method is provided.

The method for producing an organic conductor of the present invention and the organic conductor obtained by the method will be described in detail below. The method of the present invention is characterized by forming an organic conductor that is stable at high temperature by performing electrolytic polymerization in a magnetic field. If the applied magnetic field strength is less than 10 Oe (Oersted), it is almost the same as the geomagnetism and no effect is seen.
e or more is required. As a result of diligent studies by the present inventor, the organic conductor obtained by electrolytic polymerization in a magnetic field has a higher decomposition temperature of the polymer than that obtained by electrolytic polymerization without applying a magnetic field, and It was found that the higher the magnetic field strength, the higher the decomposition temperature of the polymer. In particular, when the magnetic field strength is set to a strong magnetic field of 1.3 T (tesla) or more, the decomposition temperature becomes very high and stable at high temperature,
It can overcome the drawbacks of conventional organic conductors and is very important for practical use. This is because the molecular weight of the polymer becomes larger when electrolytically polymerized in a magnetic field than when electrolytically polymerized in a non-magnetic field. For example, when 3-dodecylthiophene is electropolymerized in a magnetic field, the molecular weight of the polymer is about 10
In contrast, when electropolymerization is carried out in a strong magnetic field of 8T, it is distributed up to about 700,000. From this, the decomposition temperature becomes high, and the organic conductor becomes stable at high temperature.

The magnetic field may be applied by any means such as a permanent magnet or a permanent magnet incorporated in a magnetic circuit, a Helmholtz coil, a solenoid coil, an electromagnet, a superconducting magnet, or any other magnetic field. It doesn't matter. Of course, both the stationary magnetic field and the pulsed magnetic field can be used.

Examples of the monomer or oligomer used in the present invention include aromatic compounds containing amino acids or hydroxyl groups, heterocyclic compounds, benzene and 2
Many substances such as polycyclic hydrocarbon compounds having one or more condensed aromatic rings, compounds having a vinyl group, acetylene and derivatives thereof can be used. Further, when thiophene and its derivative are used as the monomer here, the above-mentioned effects are remarkably observed.

As the solvent for dissolving these monomers or oligomers, for example, aprotic solvents such as acetonitrile, benzonitrile, propylene carbonate, protic solvents such as methanol and ethanol, water and many others are used. can do.
Further, as the electrolyte, for example, LiBF ₄ , LiCl
Many substances can be used, including O ₄ , LiPF ₆ , LiAsF ₆ , p-toluenesulfonate, and m-nitrobenzenesulfonate, and depending on the type of monomer to be polymerized and the conditions of polymerization, these substances can be used. An appropriate combination of is selected as the electrolytic solution.

When the above-mentioned electrolytic polymerization is carried out by electrolytic oxidation, for example, aromatic compounds containing amino acids or hydroxyl groups, heterocyclic compounds, benzene and polycyclic compounds having two or more condensed aromatic rings. Since a large number of monomers such as hydrocarbon compounds and compounds having vinyl groups can be polymerized, typical organic conductor monomers such as polythiophene, polypyrrole, polyaniline, polyparaphenylene, polyazulene, and polypyrene are used. it can.

The shape of the organic conductor formed by the above-mentioned manufacturing method is various electrolysis conditions, the material and shape of the electrodes to be used, the distance between electrodes, the electrode (or electrode pair)
Various things can be obtained according to the direction of the applied magnetic field with respect to. In particular, when this shape is a film or a thin film (usually obtained when the electrode pair is a parallel plate), not only can it itself be a functional material, but it can also be combined with other materials or bonded. Since it becomes easy, it can be applied to various fields such as electric fields, optical fields, energy fields, and chemical fields by utilizing the advantage of being stable at high temperature.

[0013]

EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereby.

Example 1 An electrolyte solution was prepared by using thiophene (5.0M) as a monomer, tetrabutylammonium tetrafluoroborate (0.4M) as an electrolyte, and propylene carbonate as a solvent. The electrolytic cell is filled with this electrolytic solution, and a working electrode (anode) made of platinum and a counter electrode (cathode) made of copper
The electrode pair of was immersed. By applying a voltage of 5 V to this electrode pair and polymerizing thiophene on the working electrode,
Formed polythiophene. At this time, the magnetic field was applied using a permanent magnet, and the magnetic field strength was set to 1,500 Oe. For comparison, the formation of polythiophene was carried out also when no magnetic field was applied.

FIG. 1 shows a case where no magnetic field is applied and a case of 1,50
The TG (thermogravimeter) curve of the formed polythiophene when a magnetic field of 0 Oe is applied is shown. It can be seen from FIG. 1 that when a magnetic field of 1,500 Oe is applied, the temperature at which the weight decreases decreases to the high temperature side. This indicates that the decomposition temperature of polythiophene increased, and it can be seen that polythiophene electrolytically polymerized in a magnetic field is stable up to a higher temperature than in the case where no magnetic field is applied.

Example 2 A magnetic field was applied using a superconducting magnet and the magnetic field strength was 1.3 T.
And polythiophene were formed under the same conditions as in Example 1, except that 8T was used. Fig. 2 shows T in each case.
A G curve is shown (also shown in the case of no magnetic field). From FIG.
A similar TG curve is obtained when the magnetic field strength is 1.3 T or more, and there is no magnetic field or 1,500 O of Example 1.
As compared with the case of e, it is found that the weight is gently reduced with increasing temperature, and that the magnetic field is stable up to a higher temperature when the magnetic field is 1.3 T or more.

[0017]

In the method for producing an organic conductor according to the first aspect of the present invention, when the monomer and / or oligomer in the electrolytic solution undergoes an electrochemical polymerization reaction on the surface of the electrode, the reaction is performed in a magnetic field of 1 Oe or more. Since it is configured to be carried out in the presence, it is possible to manufacture a stable organic conductor at high temperature.

In the method for producing an organic conductor according to the second aspect, since a constitution in which a polymerization reaction is caused by electrochemically performing electrolytic oxidation is added, a typical organic conductor monomer can be used. Is added.

In the method for producing an organic conductor according to the third aspect of the present invention, since the strength of the magnetic field is 1.3 T or more, it is possible to produce a stable organic conductor at a higher temperature.

In the method for producing an organic conductor according to claim 4, since the monomer and / or oligomer contains at least thiophene and / or its derivative,
Furthermore, it becomes possible to manufacture a stable organic conductor at a higher temperature.

Since the organic conductor according to claim 5 is stable at high temperatures, it is extremely useful for electrodes, optical functional devices, batteries and the like.

The organic conductor according to claim 6 has a film shape or a thin film shape, and therefore has an effect of broadening the range of application.

[Brief description of drawings]

FIG. 1 shows a TG (therm of a polythiophene obtained when a magnetic field of 1,500 Oe is applied and a polythiophene obtained when a magnetic field is not applied in Example 1.
The gravimeter curve is shown.

FIG. 2 shows TG curves of polythiophene obtained when a magnetic field of 1.3 T and 8 T was applied and polythiophene obtained when a magnetic field was not applied in Example 2.

Claims (6)

[Claims] 1. In an electrolytic solution containing a monomer and / or an oligomer, in causing an electrochemical polymerization reaction of the monomer and / or the oligomer in the electrolytic solution on the electrode surface, the reaction is performed in a magnetic field of 1 Oe or more. A method for producing an organic conductor that is stable at high temperature, characterized in that it is carried out in the presence. 2. The method for producing an organic conductor according to claim 1, wherein a polymerization reaction is caused by electrochemically performing electrolytic oxidation. 3. The method for producing an organic conductor according to claim 1, wherein the strength of the applied magnetic field is 1.3 T or more. 4. The method for producing an organic conductor according to claim 1, wherein the monomer and / or oligomer contains at least thiophene and / or a derivative thereof. 5. A high-temperature-stable organic conductor formed by the manufacturing method according to claim 1. 6. The organic conductor according to claim 5, which has a film shape or a thin film shape.