JPH01201322A - Production of conductive polymer composition - Google Patents

Abstract

PURPOSE:To obtain a conductive polymer having a high-MW and being soluble in an organic solvent, by oxidizing a 1,2-disubstituted benzene through electrolysis in a solution containing a complexing agent and doping the obtained polymer with an impurity. CONSTITUTION:A 1,2-disubstituted benzene having an electron-donating substituent such as an alkyl group or an alkoxyl group (e.g., o-xylene) is dissolved in a solvent containing a complexing agent or an electrolyte. Said complexing agent is exemplified by a Friedel-Crafts catalyst such as AlCl3, said electrolyte is exemplified by an organic ammonium salt such as Et4NBF4, and said solvent is exemplified by nitromethane. The concentrations of said 1,2-disubstituted benzene, said complexing agent and said electrolyte added are each preferably 0.01-10mol./l. This solution is subjected to oxidation through electrolysis for 5-30hr by using a Pt electrode and a voltage of 2-10V to obtain a polymer. The obtained polymer is purified by washing with water, removal of unreacted substances, etc., and optionally molded, and doped with an electron-accepting dopant such as iodine.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to a method for producing a conductive polymer composition.

(Prior Art) A conductive polymer is a high molecular compound having metallic or semiconductor-like electrical conductivity. Such conductive polymers are used in various fields such as various electronic materials and antistatic coating materials.

Examples of conductive polymers include polyacetylene, polypyrrole, polythiophene, and the like. These are relatively easy to synthesize and have excellent conductivity and safety. As a method for obtaining such a conductive polymer, for example, as disclosed in JP-A-58-187432, a conductive or semiconductive polymer is obtained by electrolytically polymerizing benzene, its derivatives, heterocyclic compounds, etc. A manufacturing method is disclosed. However, in such conventional production methods, the polymerization reaction proceeds disorderly, causing complex intermolecular crosslinks,
The result is a polymer that is insoluble in organic solvents. for example,
Even in the manufacturing method of the above-mentioned publication, the conductive polymer obtained is substantially insoluble in the solvent, and the polymer may be obtained as a film formed on the anode plate.
It is usually obtained as a porous, brittle mass. Such conductive polymers have drawbacks such as limited molding methods, and therefore their uses are limited.

(Problems to be Solved by the Invention) The present invention solves the above-mentioned conventional problems, and its purpose is to produce a conductive polymer composition that is soluble in organic solvents even if it has a high molecular weight. The goal is to provide a way to send money.

(Means for Solving the Problems) The substituent of the L2-disubstituted benzene used in the present invention is preferably an electron-donating functional group, such as an alkyl group or an alkoxy group, and the above-mentioned 1,2-disubstituted Examples of benzene include O-xylene, 0-diethylbenzene, 0-dimethoxybenzene, and α-jethoxybenzene.

Examples of the complexing agent used in the present invention include aluminum chloride, aluminum bromide, and antimony chloride, which are used as Friedel-Craft catalysts.

The electrolytes used in the present invention include compounds such as organic 4-treated ammonium salts, inorganic salts, protic acids, and esters, such as tetraethylammonium tetrafluoroborate, tetra-n-butylammonium perchlorate, and tetrabromide. Examples include methylammonium, lithium perchlorate, ammonium sulfate, and sulfuric acid.

The solvent used in the present invention may be any solvent as long as it can dissolve the 1,2-disubstituted benzene, such as nitromethane, acetonitrile, benzonitrile, nitromenzene,
Examples include propylene carbonate, tetrahydrofuran, dimethyl sulfoxide, dimethyl formamide, etc.
Nitromethane, acetonitrile, dimethyl sulfoxide are preferably used.

In the present invention, a polymer is obtained by electrolytically oxidizing 1,2-disubstituted benzene in a solvent containing a complexing agent or an electrolyte, and the concentration of 1,2-disubstituted benzene added to the solvent is 0. .01 to 10 mol/1 is preferable, and the concentration of the complexing agent or electrolyte added to the solvent is 0.01 to 10 mol/1.
2 is preferred.

Incidentally, the complexing agent and the electrolyte may be used alone or in combination. Also, since the complexing agent cannot impart conductivity in an organic solvent, it is necessary to ensure that the organic medium contains a small amount of water.

Any conventionally known method can be used to obtain the polymer by electrolytic oxidation. For example, an electrode is immersed in a solvent containing the above-mentioned 1,2-disubstituted benzene and a complexing agent or an electrolyte, and a potentiostatic method or constant Examples include a method of polymerizing by applying a voltage using a potential method.

The material of the polymerized electrode is not particularly limited as long as it is a metal or conductive material that is inert to the electrolyte. for example,
Platinum is preferably used.

Conditions such as current value, voltage value, and polymerization time in electrolytic oxidation cannot be specified in part because preferred conditions vary depending on the type of monomer, solvent, complexing agent, electrolyte, etc. used.

However, electrolytic oxidation is usually carried out at a voltage value of 2 to 10 μm for 5 to 30 hours.

A polymer product obtained by such electrolytic polymerization mainly exists dissolved in an electrolytic solution. A portion of the product is deposited in the electrolytic cell or on the anode surface.

The polymer dissolved in the electrolyte can be obtained by concentrating the electrolyte. The obtained polymer is washed with water to remove electrolytes and the like, and if necessary, unreacted monomers and low molecular weight compounds are removed by reprecipitation using an appropriate solvent. The polymer thus obtained is molded into a desired shape. As mentioned above, most of the polymers obtained by the method of the present invention are soluble in solvents, so for example, they can be dissolved in a suitable organic solvent, cast on a substrate such as glass, and dried. A film can be prepared.

On the other hand, the insoluble component is, for example, made into a powder and filled into a desired mold, followed by pressure molding.

The polymer thus obtained is then doped with impurities. The impurity used for such doping is preferably an electron-accepting dopant, such as It,
CI2, Br2, ICI, lBr, AsF
3, SbF5, etc. Doping of the polymer can be carried out either in powder or bulk form. It is also possible to carry out the process after the polymer is molded.

(Example) Next, the present invention will be explained in detail.

Back layer■ 3.18 g of 0-xylene and 6.51 g of tetraethylammonium tetrafluoroborate are dissolved in 100 ml of nitromethane. The night after dissolution, argon gas was bubbled through to remove dissolved oxygen. Two platinum electrodes (reaction area: 5 Cml) were added to the obtained electrolyte under an argon gas atmosphere.
The sample was immersed at a distance of cm, and electrolytically oxidized for 20 hours by applying a voltage of 6 V without stirring. The obtained reaction solution was concentrated and washed with water to obtain a precipitate. The precipitate was filtered, dried, and then tetrahydrofuran was added to separate it into insoluble and soluble components. Insoluble components were vacuum dried to obtain 0.3 g of powder. The obtained powder was doped in an iodine atmosphere at 80° C. for 60 hours and then pressure-molded to obtain a plate-like body with a thickness of 300 μm.

The soluble components were cast on a glass plate and dried to obtain a 50 μm thick film, which was doped in an iodine atmosphere at 80° C. for 20 hours to obtain a conductive film. In addition, the soluble component is 0.6
It was g.

The weight of the obtained plate-shaped body and conductive film was measured to determine the amount of doped iodine, and the conductivity was measured by a two-probe method. The results are shown in Table 1.

Fuba Kaihi O-xylene 3.18g and aluminum chloride 6゜67
Example 1 except that g was dissolved in 100 ml of nitromethane.
0.4 g of insoluble components and 0.4 g of soluble components were prepared in the same manner as in step 1.
8 g was obtained, and the amount of doped iodine and conductivity were measured and the results are shown in Table 1.

1 liter of O-dimethoxybenzene 4.14g and aluminum chloride 6.67g to 100ml of nitromethane? 0.3 g of insoluble components and 0.5 g of soluble components were obtained in the same manner as in Example 1 except that they were dissolved, and the amount of doped iodine and t-conductivity were measured and the results are shown in Table 1. .

(Left below) Table 1 From the above table, it can be seen that the polymer composition prepared by the production method of the present invention is a conductive polymer composition having a relatively high electrical conductivity.

In particular, components soluble in organic solvents are easy to mold, and, for example, a conductive film of any thickness can be easily prepared as described above.

(Effects of the Invention) According to the present invention, a conductive polymer composition soluble in an organic solvent can be obtained. Such conductive polymer compositions are applied to a wide range of uses, including electronic devices, composites for electromagnetic shielding, and electronic components such as electrode materials for secondary batteries.

Claims (1)

[Claims] 1. A method for producing a conductive polymer composition, comprising doping an impurity into a polymer obtained by electrolytically oxidizing 1,1,2-disubstituted benzene in a solvent containing a complexing agent or an electrolyte.