JPS6197332A - Production of electroconductive polymer - Google Patents

Abstract

PURPOSE:To make it possible to use a polymerization solution containing a substance which is corrosive to electrodes, by performing an operation of immersing electrodes in the polymerization solution under application of a voltage between them in the electrochemical production of an electroconductive polymer film. CONSTITUTION:In the formation of an electroconductive polymer film on the surface of an electrode by immersing, for example, a NESA glass electrode (an electroconduc tive film comprising a thin SnO2 film formed on the surface of glass) in a polymeriza tion solution and electrochemically polymerizing the solution, it is impossible to per form such formation if the polymerization solution contains a component which degrades and dissolves said electroconductive film. However, such an electroconductive film can be formed by previously applying a voltage sufficient to allow the polymeriza tion reaction to proceed in the reaction system to the electrodes and immersing the electrodes under application of the voltage in the polymerization solution. Thus, the surface of the electrode can be protected and the reaction can proceed uniformly and satifactorily because when the electrode is immersed in the solution, the electroconductive polymer film can be formed on its surface before the degradation of the electrode occurs.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing a conductive polymer,
More specifically, the present invention relates to a method for producing conductive polymers using an electrochemical method.

[Conventional technology]

BACKGROUND OF THE INVENTION With recent advances in science and technology, demands for display elements for electronics, high-efficiency batteries, sensors, etc. are increasing, and the development of a wide variety of conductive polymers is required.

The method of synthesizing conductive polymers by electrochemical oxidation has the advantage that the produced polymer can be obtained in the form of a film attached to the Flu plate, and therefore the area of the film can be controlled, and It is also possible to create an element in which arbitrary conductive polymers are laminated by performing reactions in different polymerization solutions. Furthermore, this method is excellent in that the thickness or doping state of the film can be controlled arbitrarily. Reflecting these advantages, conductive polymers produced by electrochemical oxidation are expected to be applied as display elements for electronics, and to date, applications of polythiophene, polypyrrole, etc. as display elements have been reported. . These application examples use a conductive polymer synthesized in the form of a film on Nesa glass by an electrochemical method, and utilize changes in the absorption spectrum caused by this electrophoresis reduction reaction.

[Problem that the invention seeks to solve]

However, Nesa glass electrodes are made by coating the glass surface, which is an insulator, with a very thin gold-plated oxide film, and therefore do not contain components that dissolve the gold R oxide film in the polymerization solution, such as Hcla H2S 04HNO3p H
If a strong acid such as e l O4 was contained, it could not be used as an electrode. As a result, there have been many materials that are expected to be used as materials for display elements, but whose practical application has been delayed due to the late stage.

[Means to resolve the gap]

The present invention has been made in view of the above points,
In general, the purpose is to provide a technology for synthesizing conductive polymers, and in particular, to provide methods for synthesizing conductive polymers on electrode surfaces, especially when polymerization solutions containing components that dissolve or degrade the electrode surface are used. The purpose is to provide film forming technology.

The method for synthesizing the conductive polymer P of the present invention is characterized by applying a voltage to the electrode in advance and then immersing the electrode in a polymerization solution in the conductive polymer synthesis reaction using an electrochemical oxidation method. .

The conductive polymer synthesis reaction in the present invention includes, among general electrochemical polymerization reactions, a reaction in which a polymerization solution containing a component that dissolves or deteriorates an electrode is combined with an electrode. , does not include other electrochemical polymerization reactions. This combination is HCI t H2SO41HNO
These are a combination of a strong acid such as 3 or HO104 and an electrode made of a metal, a metal resistant material, a semiconductor, or a compound semiconductor, and a combination of a polymer anticonductor and a solvent that degrades it.

Here, metals include the I group excluding hydrogen, the ■ group, the So group excluding hydrogen, the ■ group excluding carbon and silica, the ■ group, and ■, ■, ■.
These are elements belonging to each subgroup a of the group and various alloys that are mixtures thereof. Semiconductors include Sl, Gθ, Se, B, etc., and compound semiconductors include m-v compounds such as QaAs and InSb, and InGaAs, which is a combination thereof.
■-■ compounds such as AIQaAs and ZnS%cas.

1. In the upper gas chemical polymerization reaction, the voltage to be applied in advance is selected so that the polymerization reaction proceeds in each reaction system. The speed at which the electrode is immersed in the polymerization solution is not particularly limited, but is preferably Q-] mm /8 el O or more in order to obtain a film-like polymer with a uniform thickness.

[Effect]

The method for synthesizing a conductive polymer according to the present invention is carried out by gradually immersing an electrode to which a voltage has been previously applied in a polymerization solution containing a component that dissolves and deteriorates the electrode. When a singing reaction is performed under these conditions, when the electrode is inserted, the surface of the electrode is retained by the polymerization reaction of the conductive polymer before the electrode dissolves or deteriorates, and the subsequent polymerization reaction proceeds uniformly. do. Furthermore, in the case of a solvent containing a strong acid or the like, applying a voltage may have the effect of reducing the hydrogen ion concentration near the electrode surface and suppressing the progress of deterioration.

Therefore, melting or deterioration of the electrode surface is not a problem at all, and the electrode can be protected from repeated use. JSS Rough Examples] The present invention will be specifically explained below with reference to Examples.
The present invention is not limited to these arrangements.

(Comparative Example 1) A 0.1 Mn2 S 04 aqueous solution is charged in a glass polymerization container, 0.05 mol of aniline is added thereto, and the mixture is stirred for about 30 minutes to dissolve. Nesa glass was immersed as an electrode in this polymerization solution, and immediately the potential width was 10.2V-10V and the scanning speed was 0. When a scanning voltage of IV/sec was applied, no product was observed on the electrode surface even after 30 minutes. Further, almost no current flowed, and the electrical resistance of the surface of the electrode taken out was extremely high, making it impossible to use it as an electrode again.

(Example 1) Another Nesa glass electrode was immersed in the same polymerization solution as in Comparative Example 1 while a constant voltage of 04 V was applied in advance. Immediately, the scanning voltage was changed to the same conditions as the previous time, and the formation of a torme-conducting polymer polyaniline film was confirmed. The film taken out after the reaction was completed showed properties completely equivalent to those obtained when an acid-resistant platinum electrode was used.

The electrical resistance of the Nesa Glass surface after the electrode was ultrasonicated in water and the film was peeled off was the same as before the reaction.
Repeated use was possible.

(Comparative Example 2) A polyacetylene film polymerized from acetylene gas using Ziegler and Natsuta catalysts was brought into contact with iodine gas and then attached to a polymerization cell under an argon gas atmosphere.

This was taken out into the air and immediately charged with the same polyaniline polymerization solution as in Example 1, with a potential width of -02V to loV,
Scanning speed 0. When a scanning voltage of IV/sec was applied, polyacetylene began to deteriorate immediately after charging the polymerization solution and decomposed within several minutes. It was impossible to produce polyaniline.

(Example 2) The same polyaniline polymerization solution as in Comparative Example 2 was charged into a famous container,
The polyacetylene set as an electrode in argon gas was taken out into the air, and immediately immersed in the polymerization solution while a constant voltage of 04 V was applied. When the scanning voltage was changed to a potential width of -02 V to lO2 and a scanning speed of 01 V/sea, the formation of a conductive polymer polyaniline film was confirmed. Further, in this case, no deterioration or decomposition of polyacetylene was observed.

〔Effect of the invention〕

The method for synthesizing conductive polymers of the present invention makes it possible to use combinations of materials that were previously difficult to use. This allows the electrode to be used repeatedly.

By using the conductive polymer synthesis method of the present invention, by combining various polymerization solutions, more complex elements such as metals, semiconductors, polymer semiconductors, or shaved products of these can be laminated or combined as desired. It also becomes possible to develop new elements.

Patent applicant: Six King Soap Company , Kumakuno (patent attorney Moto Keibu)

Claims (1)

[Claims] 1. A method for producing a conductive polymer using an electrochemical oxidative polymerization method, characterized in that a voltage is applied to the electrode in advance and the electrode is immersed in a polymerization solution. Method of manufacturing molecules. 2. The method for producing a conductive polymer according to claim 1, wherein one or both of the electrodes is a thin film of metal, metal oxide, semiconductor, compound semiconductor, or polymer semiconductor. 3. The method for producing a conductive polymer according to claim 1 or 2, wherein the polymerization solution contains a component that degrades or dissolves the electrode surface.