JPS62119237A - Dopant for electrically-conductive high polymer compound - Google Patents

Abstract

PURPOSE:The titled dopant useful for various electrode materials such as electrochromic elements, secondary battery, etc., because of high electrical conductivity and reversible doping and dedoping, consisting of a specific fluorine- containing alkanesulfonic acid ion system. CONSTITUTION:A dopant of a fluorine-containing alkanesulfonic acid ion shown by the formula (n is 3-20 integer, especially preferably 3-10 integer; X is H or F) is introduced into an electrically-conductive polymer such as polypyrrole, polythiophene, etc., by electrochemical method, chemical method, etc.

Description

Detailed Description of the Invention a. Industrial Field of Application The dopant for conductive organic polymer compounds of the present invention is obtained by doping an organic polymer compound known to provide a conductive paid polymer compound. It is used to make the organic polymer compound electrically conductive. These conductive organic polymer compounds can be formed into, for example, flexible films or good coatings to be used in various flexible switches, sensors, EMI materials, antistatic materials, photoelectric conversion elements or their protective layers, etc. Various uses are possible.

In addition to high conductivity, the conductive polymer has doping,
Since it has redox properties that allow reversible dedoping, it is also useful as a material for various electrodes such as electrochromic devices and secondary batteries.

b. Prior Art Organic polymer compounds that can be doped to exhibit conductivity include, for example, polyacetylene, polythiophene,
Various types of polypyrrole, polyaniline, etc. are known, and the dopants used to dope them are also 12,
Cl04-, AsFs-.

Various ions such as PF6- and p-toluenesulfonic acid ions are known.

However, conductive organic polymer compounds doped with these dopants still have problems in the high degree of conductivity they exhibit or in stability under usage conditions, and are not practical.

In order to solve these problems, efforts are being made to search for new organic polymer compounds.

Unlike such conventional attempts, the present inventors were able to achieve the present invention while intensively studying ways to solve the problems of conventional conductive organic polymer compounds by improving dopants. This is what happened.

C9 Constitution of the Invention The present invention is based on the following general formula (I) It is a dopant for a fluorine-containing alkanesulfonic acid ion-based conductive organic polymer compound represented by the following.

In the formula, X is a hydrogen atom or a fluorine atom, and in the formula 2□', n is 3 to 20. Preferably 3-15. Particularly preferably 3
~10 integer. When n exceeds 20, it is difficult to obtain raw materials, and when n is less than 3, it is difficult to exhibit the water repellent effect due to fluorine content.

The conductive polymers used in the present invention include polypyrrole, polythiophene, and polyaniline.

Examples include polyfurans and their derivatives.

Electrochemical methods and chemical methods are generally used to introduce the fluorine-containing alkanesulfonic acid ion dopant into these conductive polymers. The former method is suitably applied to charge transfer complex type conductive polymers such as polypyrrole, polythiophene, and polyfuran.

A specific explanation will be given below using polypyrrole.

The amount of the dopant to be doped is in the range of 5 to 100 mol%, preferably 10 to 60 mol%, based on the virole ring. If it is less than that, high conductivity will not be exhibited, and if it is more than that, it is impossible to introduce it due to repulsion between dopants, which is not preferable.

To dope polypyrrole with the above dopant,
The dopant may be doped after the polypyrrole is synthesized, but it is convenient to dope the dopant at the same time as the polypyrrole is synthesized. That is, for example, virol and/or its derivatives are placed in an electrolytic solution consisting of an electrolyte, a solvent, and optionally a small amount of water, using a platinum plate as a working electrode (hereinafter referred to as WE) and a platinum plate as a counter electrode (hereinafter referred to as CE). Alternatively, it can be obtained by performing conventionally known electrolytic polymerization using conventionally known general-purpose materials.

B: The electrolyte used in the above reaction is a fluorine-containing alkanesulfonic acid and/or a salt thereof represented by the following formula % (in the formula, X and n are as defined above). Examples of the salt include quaternary ammonium salts such as tetraethylammonium salt, tetrabutylammonium salt, and triethylbenzylammonium salt, and monovalent metal salts such as sodium salt, potassium salt, and silver salt.

The required amount of these electrolytes is such that the electrolyte is dissolved in the form of a solution and that the electric current necessary for the reaction to proceed is obtained. .3 mol or more, and the maximum amount is the amount at which the electrolyte is saturated as an electrolytic solution. Of course, there is no problem even if there is something more than that. The electrolyte concentration in commonly used electrolyte solutions varies depending on the solvent, the type of electrolyte, and the amount of water used if desired.
,.

(However, it is usually 0.OOIM/u (mol,
! >i: 1 to 2 M/u, preferably 0.05 Mzl or 1 to 0.5 M/u.

? The solvent used in the reaction must be stable under the voltage required for polymerization of the virol compound, have high solubility in the electrolyte and water, and be liquid during the reaction. Examples of such solvents include water, acetonitrile, benzonitrile, propylene carbonate, nitrobenzene, and the like. Moreover, these solvents can also be used in a mixed state.

The role of water used as required is to increase the effectiveness of electrolytes,
This improves the form in which polypyrrole is precipitated.

The amount used varies depending on the type of electrolyte used, and the concentration of water in the electrolytic solution is from 0.1 M/day to 5 M/day, preferably from 0.3 M/day to 3 M/u.

The release material used in the reaction is deficient in the electrode reaction,
Any general-purpose material may be used as long as it does not undergo deterioration, and platinum and gold are not particularly specified.

In addition to metals such as copper and nickel, conductive materials such as 3N02, InzOz, or similar conductive materials, and carbon electrodes that are larger than those of the electrodes generally generate photo-electrolytic voltages of 1.0 volt or higher, although not inferior. but,
Preferably 1.5 volts or more, particularly preferably 12 volts or more, and 10.0! from the stability of the electrolytic reaction solvent! ″
□ Bolt: Desirably less than 100 ft. The electrolytic current is the current density at the anode: 0.0011A/C1i~10rAA/CI! ,
Preferably 0.01 mA/ci ~5 l1lA
/cd, particularly preferably 0.5m A/cd~3
mA/ci.

The reaction temperature is -50°C to 100°C, preferably -40°C to 50°C.

On the other hand, Example Eva, C104-, AS Fs-.

',,Ff? The dopants in polypyrrole containing known dopants such as Fs- and p-toluenesulfonic acid ions can be electrochemically exchanged with a fluorine-containing alkanesulfonic acid ion-based dopant.

Next, doping using a chemical method will be explained.

Chemical methods are preferably used for polyionic complex type conductive polymers such as polyaniline.

In this case, the general introduction method is to replace the acid added to polyaniline with fluorine-containing alkanesulfonic acid, or to introduce inorganic materials such as fluorine-containing alkanesulfonic acid coexisting with
For example, hydrohalic acid in the polyaniline by treatment with an organic base.

This is achieved by removing an acid such as sulfuric acid, nitric acid, perhydric acid, or phosphoric acid, and then treating with a fluorine-containing alkali sulfonic acid represented by the above formula (II).

-Medium: Process at medium, room temperature or under heating. In the latter case, for example, the method of MacDiarmid et al.

al,, ACS Polymer rep
rint), Vol. 25, p. 248), in the presence of the fluorine-containing alkanesulfonic acid.

Hereinafter, the present invention will be further explained in detail.

The electrical conductivity during the test was calculated by the four-terminal method from the voltage and current measured using a digital voltmeter 34568 manufactured by Hewlett-Paracard.

Example 1 A separable 1000 d glass electrolytic cell equipped with two electrode inlets, a nitrogen inlet pipe and an exhaust port had a length of 5 as an anode.
α, rt14cm platinum plate, [1]5ctr as counter electrode
A copper foil with a length of 40 Ctn was installed.

The entire electrolytic cell was immersed in a cooled bath so that the temperature could be controlled.

Then, the obtained black film had a thickness of 30 μm and an electrical conductivity of 623/Jl and 0.06 mol/Jl of virol and tetraethylammonium n-perfluorooctanesulfonate.
It was cm.

The elemental analysis value of the obtained polypyrrole was C44, 72%
, 82.84%, N11.40%, 85.40%, and CFjH3,rN y,tp (Cs Ft7
It was shown that a conductive polypyrrole was produced in which 21 mol% of the dopant was introduced into the virole ring, corresponding to S O3)I)/.

Examples 2 to 7 Films were synthesized using the same apparatus and operation as in Example 1, but varying the weighing conditions. The results are shown in Table 1.

Example 8 A separable 1000 m glass electrolytic cell equipped with two electrode inlets, a nitrogen inlet pipe, and an exhaust port was equipped with a platinum plate having a length of 5 cm and a width of 4 cta as an anode, and a width of 5α as a counter electrode.
, a copper foil with a length of 40 Crs was installed.

The entire electrolytic cell was immersed in a cooled bath, allowing temperature control.

Next, 400 mol/l of nitrobenzene solution containing 0.06 mol/l of 3-methylthiophene and 0.1 mol/l of tetraethylammonium Roperfluorooctanesulfonate was added.
d was placed in an electrolytic bath. The process was carried out for 3 hours at -5° C. and an interelectrode voltage of 6 V while introducing nitrogen.

The resulting black film had a thickness of 10 μm and an electrical conductivity of 258 parts cm.

The elemental analysis value of the obtained poly-3-methylthiophene is C3
2.9%, l-11.8%, F41.7%, 817
．． 5% and 0 units 11-↓S7. Ji (C8F/7S
03) Corresponding to #/, Che7on ring 11I! Conductive poly(3
-Methylthiophene) was shown to be produced.

Example 9 An aniline polymer was synthesized by the following method using hydrochloric acid according to the method of Matsuku Diamide described above.

I11 Mitsuro flask, 650 parts of water, 13! acid 150
9.3 parts of aniline was added. 10 while stirring at room temperature
34.2 parts of ammonium persulfate dissolved in 0 parts of water
It was dripped over a period of time. After the addition was completed, the mixture was stirred at room temperature for 12 hours, and the resulting green solid was collected by filtration.

After washing with water and acetonitrile and drying, 11C
10.6 parts of an aniline polymer containing 1 as a dopant was obtained. The conductivity of this material was 3.8t using an IR tablet press.
It was molded into a disk shape under a pressure of /cd, cut out, and measured by the four-probe method, and found to be 48/α. HCI was completely dedoped by aniline polymerization using this 11C1 as a dopant.

Two parts of the obtained dedoped aniline polymer were added to one part of water.
The sample was immersed for 24 hours in a solution prepared by dissolving 20 parts of n-perfluorooctane sulfonic acid in 0.00 parts of the sample. After filtration, it was washed with acetonitrile and dried to obtain 13 parts of green powder. From the results of elemental analysis, 0.51 n-perfluorooctanesulfone per nitrogen atom Example 10 650 parts of water, 100 parts of n-perfluorooctane sulfonic acid, and 9.3 parts of aniline were added to a Mitsuro flask. I put it in. While stirring at room temperature, 34.2 parts of ammonium persulfate dissolved in 100 parts of water was added dropwise over 1 hour. After the dropwise addition was completed, the mixture was stirred at room temperature for 12 hours. The resulting green solid was collected by filtration, washed with water and acetonitrile, and then dried to obtain 40 parts of a green-blue aniline polymer as a powder. Elemental analysis of this product confirmed that it contained 0.62 n-perfluorooctane sulfonic acid ions per 111 M of N atoms. It was molded using an infrared tablet molding machine, and the electrical conductivity was measured using a four-probe method and found to be 0.68 part cm.

Claims (1)

[Claims] The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(I
) [In the formula, n represents an integer of 3 to 20, and X represents a hydrogen atom or a fluorine atom. ] A fluorine-containing alkanesulfonic acid ion-based dopant for a conductive organic polymer compound.