JPH0324120A - Production of conductive polymer - Google Patents

Abstract

PURPOSE:To obtain a conductive polymer having both a high electric conductivity and excellent processability by converting an oxidation-unpolymerizable compound into an oxidation-polymerizable monomer with light or heat and polymerizing the obtained monomer through oxidation. CONSTITUTION:This process comprises the steps of converting an oxidation- unpolymerizable compound into an oxidation-polymerizable monomer with light or heat and polymerizing the obtained monomer through oxidation. Examples of the oxidation-polymerizable monomers include compounds having a five-membered heterocyclic structure such as pyrrole, isoindole, naphtho[1,2- c]pyrrole, pyrrolo[3,4-b]pyridine, [3,4-c]pyrrole, pyrrolo[3,4-c]pyrrole and 1,3- dihydro derivatives thereof. Although the precursor compound used in the formation of the above monomer is not particularly limited so far as it can be converted into the above monomer with light or heat, an example includes the formation of the above monomer by a photo-reaction of an aromatic sulfonamide compound.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing a conductive polymer having high conductivity and excellent stability in a doped state. The conductive polymer produced by the method of the present invention is used as a conductive material, a semiconductor material, an electrode material, a display material, and an electromagnetic wave shielding material in the fields of electrical and electronic industries. (Prior Art) In recent years, conductive polymers have attracted attention as new materials that have various properties not found in metals. Although poly(acetylene), a typical conductive polymer, has achieved conductivity comparable to that of metals, problems with its stability still remain.

On the other hand, poly(aniline) is used as an electrode material for secondary batteries.
Poly(virol) has been put into practical use in aluminum electrolytic capacitors. Considering these points, it is thought that the development of applications for conductive polymers will continue in the future, not only as a substitute for metals, but also in applications where they can be applied even with lower conductivity. Up until now, a major problem that has been a major obstacle to the practical application of conductive polymers is that most conductive polymers are insoluble and infusible, and have extremely low processability. The following method has been proposed as a typical means to solve this problem. (1) A method of developing solubility and meltability in solvents by introducing an alkyl group, a hydrophilic substituent, etc. into the side chain of a polymer. (2) A force method in which precursor polymers with excellent workability are combined, processed into an arbitrary shape, and then converted into a conductive material through heat treatment or the like.

(3) A method in which a photopolymerizable material consisting of an oxidative polymerizable monomer, a photosensitizer, and an oxidizing agent is applied to a substrate, and a conductive layer is formed in the irradiated area by light irradiation.

However, the above method (1) has problems such as difficulty in introducing substituents and a decrease in RM properties due to changes in processability. In addition, although the method (2) can obtain a product having high conductivity, there are problems such as requiring high-temperature heat treatment and being applicable only to polymers with a limited structure. Furthermore, in method (3), although it is easy to form a pattern of the conductive layer using a conductive polymer, there is a problem that the conductivity of the conductive layer is low. It could not be said that it was sufficient to change the molecular resistance. (What the invention seeks to solve! lJal) The present invention solves the problem of obtaining a conductive polymer having both high conductivity and excellent processability.

(Means for Solving the Problems) The present inventors are satisfied with the points mentioned in J.2. After much research, we found that a compound that does not have oxidative polymerizability is treated with light or heat to form a monomer that can be oxidatively polymerized, and the process of oxidatively polymerizing the obtained monomer. We have discovered that the above problems can be solved by combining them, and have completed the present invention.

In the present invention, oxidatively polymerizable monomers include virol, isoindole, nut (1.2-e) virol, naphl/[2.3-cl virol, and virol!
3.4-b] pyridine, virolo[3.4-cl pyridine, furano[3.4-1-. ] Virol, Chieno [3.4
-Hetero5-membered rings such as e3-pyrrole, seleno[3.4-cl-bytol, telluro[3.4-cl-byrol, vilolo[3.4-cl-virol, and their 1,3-dioxetol] Examples include compounds having a structure.

The monomers listed in L can be converted into conductive polymers by ordinary electrolytic oxidative polymerization or chemical oxidative polymerization using an oxidizing agent.

As for the specific means, the precursor compound used in the preparation of the monomer has no oxidative polymerizability and is capable of oxidative polymerization by light irradiation or heat irradiation.
Although it is not particularly limited as long as it is converted into a monomer, a specific example thereof includes the production of the above-mentioned monomer by a photoreaction of an aromatic sulfonamide compound.

Aromatic sulfonamide compounds such as balatluenesulfonamide and napucrenesulfonamide undergo a cleavage reaction of nitrogen-sulfur bonds when irradiated with light to produce amine compounds. Compounds having a structure in which an aromatic sulfonamide group is introduced into the nitrogen atom contained in the five-membered ring of the above monomer generally have a high oxidation potential and are not easily oxidized. Therefore, by using these compounds as precursors and irradiating them with light, it becomes possible to produce the above-mentioned monomers that can be polymerized regioselectively. Furthermore, oxidative polymerization can be carried out in this state to regioselectively produce a conductive polymer. The wavelength of the light used for light irradiation is not particularly limited, but in order to more efficiently control the monomer, it is preferable to use light having a wavelength in the ultraviolet m81 region. The precursor compound capable of producing an oxidatively polymerizable monomer by thermal irradiation may be in any of the gas, solid, liquid, or solution states, and may be added to other matrix polymers. It may be in a distributed state.
In the case of electrolytic oxidative polymerization, the oxidative polymerization reaction of monomers obtained by light irradiation or thermal irradiation can be carried out by a method commonly used for electrolytic polymerization of virol, thiophene, etc.
Solvents used in electropolymerization generally include acetonitrile, penzonitrile, brobionitrile, dioxane, tetrahydrofuran, sulfolane, propylene carbonate, nitrobenzene, N. Examples include N-dimethylformamide and dimethyl sulfoxide. In addition, the electrolytes used include tetraethylammonium bromide, tetraethylammonium chloride, tetra n-
butylammonium bromide, tetra n-butylammonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium chloride, tetra n-
Butylammonium bark chlorate, lithium bark chlorate, lithium tetrafluoroborate, tetraethylammonium tetraphroborate, tetra n-butylammonium hexafluoroantimony, tetra n-butylammonium hexafluorophosphate, benzenesulfonic acid potassium salt , toluenesulfonic acid sodium salt, sulfur, hydrochloric acid, trifluoroacetic acid, etc. These electrolyte anions are incorporated into the polymer as dopant during electrolytic polymerization. Furthermore, in the case of chemical oxidative polymerization using an oxidizing agent, the produced monomer can be converted into the polymer by contacting it with the oxidizing agent. At that time, the oxidant is in a gaseous state,
It may be in a liquid state, solid state, or solution state. When the oxidizing agent is in a solution state, the solvent used includes dichloromethane, chloroform, carbon tetrachloride, dichloroethane, tetrachloroethane, nitromethane, nitroethanenitrobenzene, chlorobenzene, N-methyl-2-pyrrolidone, carbon disulfide, etc. can be mentioned. In addition, as an oxidizing agent used in oxidative polymerization, tetrachlor-1
．． Quinone oxidizing agents such as 2-penzoquinone, tetrachlor-1,4-penzoquinone, 2,3-dichloro-5,6-dicyano-1.4penzoquinone, halogen oxidizing agents such as iodine, bromine, chlorine, nitric acid, hydrochloric acid , chlorides, sulfates and nitrates of inorganic acids such as sulfuric acid or metals such as aluminum, tin, chromium, manganese, iron, copper, molybdenum, tungsten, ruthenium, palladium and platinum, as well as sodium persulfate, potassium persulfate, Examples include persulfates such as ammonium persulfate. In the monomer biochemical process by light irradiation, monomers can be more efficiently grown by coexisting one or more compounds selected from water, alcoholic solvents, reducing agents, and electron-donating compounds. It becomes possible to keep the body in good health. Furthermore, by using a monomer precursor having an electron-donating group such as an alkoxy group as a substituent, it is also possible to obtain a polymer having high electrical conductivity in a high yield. (Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples, but the technical scope of the present invention is not limited by these Examples. Example 1 N,N-
The mixture was reacted in dimethylformamide to obtain N-paratolylsulfonyl-1,3-dihydroisoindole. 5.0 g of the obtained white needle-shaped crystals and 50.0 g of poly(methyl methacrylate) (molecular weight: 10,000) were dissolved in 200 g of chloroform and formed into a film by a casting method. Next, the film was partially irradiated with ultraviolet rays for 2 hours using a 200 W high-pressure mercury lamp, and then the film was heated to 0.1
When it was immersed in an aqueous M ferric chloride solution, the light source part had turned black. When the conductivity of this part was measured using the DC four-probe method, it was found to be 3. OX10-'S/ell. Example 2 N-valatrylsulfonyl-l,3- used in Example 1
When N-valatrylsulfonylisoindole was used in place of dihydroisoindole and film formation, ultraviolet ray irradiation, and oxidizing agent treatment were performed in the same manner, the irradiated area turned dark green.

When the conductivity of this part was measured using the DC four-terminal method, it was found to be 5.
．． It was OX10-'S/cm. Example 3 N-paratolylsulfonyl used in Example 1 = 1.3-
When N-paratolylbyroro[3.4-c]pyridine was used in place of dihydroisoindole and film formation, ultraviolet ray irradiation, and oxidizing agent treatment were performed in the same manner, the irradiated area turned dark green.

When the conductivity of this part was measured using the DC four-terminal method, what was the result?
．． It was an 8 x 10 one-piece S/c seal. Example 4 A cast film was formed on a Nesa glass plate using a chloroform solution in which the precursor prepared in Example 1 and the matrix/diaphragm polymer were dissolved, and then the same as in Example 1 was irradiated with violet IA rays. Subsequently, using this as a pit electrode, the inner gold electrode as a counter electrode, and the silver/chloride wire electrode as a reference electrode, a tetra n-
Ptylammonium chloride 0. Using IM acetonitrile solution as the electrolyte, i. When electrolytically polymerized using ov c vs. silver/silver chloride electrode), the light-irradiated area turned black. When the conductivity of this part was measured using the direct slag four-probe method, it was found that
It was 1.1x 10-' S/c familiar. Example 5 N-valatrylsulfonyl-1,3-dihydronaf 1.
When [2.3-C]virol was used as a precursor and electrolytically polymerized in the same manner as in Example 4, the light-irradiated area turned blackish brown. When the conductivity of this part was measured using the DC four-probe method, it was found to be 3. OX10-'S/'CI. Comparative Example 1 A dye-containing film obtained by adsorbing a ruthenium tris-biviridine complex onto sulfonated polyolefin and a 1 liter film (thickness: 50 μm) of dioxidized polyolefin was adsorbed onto virol (0.3 μol/l and cobalt chloride). Pentaamine complex (0.04mol/
1) was immersed in an aqueous solution containing. This film was then coated with 490
When irradiated with nm light, the irradiated area turned black.
When the conductivity of this part was measured using the DC 4@T method, it was found to be 1
．． OX 10-'S/cm.

(Effects of the Invention) By adopting the manufacturing method of the present invention, problems in the processability of It-based polymers can be solved, complex shapes can be easily molded and processed, and the present invention The conductive polymer obtained by the method of the invention is used, for example, in the electrical and electronic industries as a conductive material, semiconductor material, electrode material, display material, @magnetic wave shielding material, and has countless other applications. It is a great contribution to the industry.

Claims (1)

[Claims] A conductive material comprising the steps of: converting a compound that does not have oxidative polymerizability into a monomer that can be oxidatively polymerized by light or heat; and oxidatively polymerizing the obtained monomer. method for producing a synthetic polymer.