JPS63256617A - Manufacture of electrically conductive polymer - Google Patents

Abstract

PURPOSE:To produce an electrically conductive stable polymer, by making electrically conductive a polymer resin containing a polymerization catalyst in a reaction system containing a heterocyclic compound in an atmosphere having a relative humidity above a specified value. CONSTITUTION:A polymer resin containing a polymerization catalyst is made electrically conductive in a reaction system containing a heterocyclic compound in an atmosphere having a relative humidity above a certain value, preferably more than 60% RH. For this purpose, the polymer resin may be exposed to the reaction system for a certain period or it may be a continuous method wherein a continuous polymer film is passed through the reaction system at a certain speed. As the heterocyclic compound to be used, for example, pyrrole, thiophene, furan, aniline, and an alkyl-substituted derivative thereof and a derivative thereof can be mentioned. From the point of view of the stability of the electrically conductive polymer that will be obtained, pyrrole is preferably used.

Description

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

In particular, the present invention relates to a method for producing conductive polymers by chemical vapor phase polymerization of heterocyclic compounds.

<Prior Art and its Problems> It has been well known for a long time that heterocyclic compounds can be borinared with an oxidizing agent to obtain insoluble and infusible polymers.

For example, when pyrrole is treated with inorganic acids, ferric chloride, benzoquinone, hydrogen peroxide, etc., pyrrole Bratz chemistry (
Advances in Heterocycle
ic Chemistry) Volume 15, Page 67 (1
973).

Similarly, furans, thiophenes, and other heterocyclic compounds,
Substituted products and derivatives thereof also become polymers.

On the other hand, it is also known that film-like polymers such as pyrrole, furan, and thiophene can be obtained by electrolytic polymerization in the presence of an appropriate organic electrolyte.
cation) 635 pages (1979), Japan Journal of Applied Physics (Ja
pan Journal of Applied
Physics) Volume 21 (1982), Polymer Preprint Japan (Polymer Preprint Japan)
There are many other reports including 33 volumes (1984) of prints Japan).

Since these reports all involve electrolytic polymerization, it is difficult to produce a large-area membranous product (film);
Since the adhesion between the electrode substrate and the product is poor and only a thin film can be obtained, there are problems such as a lack of mechanical strength and uniformity.

In order to solve these problems, improvements are being made gradually in terms of both devices and methods.

Recently, it has been reported that a conductive polymer can be formed on the surface and inside of a polymer resin containing a polymerization medium by contacting it with a heterocyclic compound. No. 61-111336, JP-A-61-157522
No. and many other publications.

The conductive polymer thus obtained is obtained by chemical oxidation of a heterocyclic compound using a polymerization catalyst in a polymer resin. However, the state of the conductive polymer changes depending on the phase state of the heterocyclic compound, ie, liquid phase or gas phase, as the reaction type.

In the case of liquid phase, conductive polymers can be obtained in a short time, but
The result is a highly branched, irregular polymer that tends to become insoluble and infusible.

On the other hand, in the case of a gas phase, the resulting conductive polymer has a highly regular structure with few branches and has excellent conductivity, but there are problems such as a long reaction time. there were.

In particular, in the formation of conductive polymers by chemical oxidation of heterocyclic compounds, the polymerization catalyst, the polymer resin holding it, the type of heterocyclic compounds, the reaction temperature, the heterocyclic The uniformity and reproducibility of the resulting conductive polymer vary depending on the amount of water vapor coexisting with the compounds, making it difficult to obtain a stable conductive polymer.

Means for solving the above problems In order to solve the above problems, heterocyclic compound vapor and water vapor are allowed to coexist, and the relative humidity is at least 6.
By chemically oxidizing a polymer resin containing a polymerization catalyst in a reaction system controlled to exceed 0% RH,
Settled.

In the present invention, there is no particular restriction on the method of incorporating the polymerization catalyst into the polymer resin, and depending on the stability and solubility of the polymerization catalyst, a hot melt mixing method, a method in which the polymerization catalyst is dissolved in a solvent, etc. A method of dissolving the resin to form a solution and then forming it into a film. After mixing and dispersing resin powder or particles in a solvent in which a polymerization catalyst has been dissolved, the solvent is removed, or heat and pressure are simultaneously applied to form a film. Various methods can be used, such as applying a polymerization catalyst dissolved in a solvent to a resin nonwoven fabric or microporous material and drying it, or then hot pressing to fix it.

The polymer resin containing the polymerization catalyst used in the present invention may be any resin as long as it can support and hold the polymerization catalyst.
It must not cause deterioration and must have excellent compatibility with the polymerization catalyst. Specifically, cellulose, starch,
Natural polymer compounds such as casein and natural rubber, semi-synthetic polymer compounds such as methyl cellulose, hydroxyethyl cellulose, and carboxymethyl cellulose, polyvinyl alcohol, polyvinyl acetate, polycarbonate, polyvinyl butyral, polyacrylate, polymethacrylate, polyethylene, polypropylene, polystyrene, and Acrylonitrile, polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, polyvinylidene cyanide, polybutadiene, polyisoprene, polyether, polyester, polyamide,
Examples include organic synthetic polymer compounds such as silicone, polyvinylpyrrolidone, polyacrylamide, and polyethylene glycol, and compounds composed of one or more of these derivatives.

Basically, any oxidizing agent may be used as the polymerization catalyst used in the present invention, but the difference in oxidizing power affects the conductivity of the conductive polymer obtained, and Since the polymerization catalyst itself is stabilized as a dopant in the resulting conductive polymer, metal halides such as ferric chloride, cupric chloride, and ferric bromide, and perchloric acid are used as polymerization catalysts. Perchlorates such as ferric are preferred,
The reaction system consisting of a heterocyclic compound and water vapor, etc. may be in any form as long as the relative humidity can be controlled to exceed 60%RH@, and the above-mentioned heterocyclic compound may be used. It is possible to control the relative humidity by putting the compound and water in the same reaction system, or by supplying an inert gas as a carrier to each separately from outside the reaction system to control the relative humidity.

In addition, because heterocyclic compounds are chemically oxidized in the gas phase on the surface and inside of the polymer resin containing the polymerization catalyst,
In order to increase the gas diffusivity within the reaction system, provide a gas circulation function, and increase the reactivity, it is also necessary to provide a temperature distribution between the atmospheric temperature within the reaction system and the cough polymer resin.

In the present invention, as a method for making the polymer resin containing a polymerization catalyst conductive in the reaction system, the polymer resin may be exposed to the reaction system for a certain period of time, or the polymer resin in a continuous state may be exposed to the reaction system for a certain period of time. A continuous method may be used in which the film is passed through the reaction system at a constant speed.

Furthermore, the heterocyclic compounds used in the present invention include virols and substituted virols, such as N-alkylvirols, N-arylvirols, monoalkylvirols substituted in the 3-position and monohalogenated virols, Dialkylviroles and dihalogenated virols substituted in the 3- and 4-positions, thiophenes, substituted thiophenes, such as monoalkylthiophenes substituted in the 3-position, monohalogenated thiophenes, dialkyl substituted in the 3- and 4-positions. Thiophene, aniline and derivatives thereof, such as
N-alkylaniline, N-dialkylaniline, halogenated aniline, dihalogenated aniline, halogenated-
N-alkylaniline, halogenated-N-dialkylaniline, dihalogenated-N-dialkylaniline, dihalogenated-N-acetylaniline, phenylenediamine, and its substituted N-alkylphenenediamine, N-N'- Dialkylphenylene diamine, N-
Examples include N'-dialkylphenylenediamine and N-N''-dialkylphenylenediamine, and one type or a combination of two or more of the above compounds may be used.From the viewpoint of stability of the resulting conductive polymer, virole It is preferable to use

<Function> When chemical vapor phase polymerization is carried out in a controlled reaction system at a temperature exceeding the relative temperature in the reaction system by at least 60% RH, a conductive polymer with little branching and excellent regularity is produced in a uniform manner in a short reaction time. Stable products can be obtained with good reproducibility.

<Examples 1 to 6> FeC on one side of a polyester film (thickness 25 μm)
1,s・6HtO,Fe (CfO4)s・6HiO,
An acrylic resin containing each polymerization catalyst (i4 degree 20-t%) consisting of F e B rs, nH, and O is coated, and the coated film is heated at 30'C, 80% RH or more (A atmosphere ), 30''C, 270% RH (atmosphere B) in a 0.032I reaction system consisting of a pyrrole/air mixture gas for 10 minutes to form a conductive polymer on one side.

The surface resistance and light transmittance of this conductive polymer were measured, and the results are shown in Table 1.

<Comparative Examples 1 to 3> A film coated with an acrylic resin containing the same catalyst as in Examples 1 to 6 was coated on one side at 30°C and 60% RH (C atmosphere) in the same manner as in Examples 1 to 6. A conductive polymer was formed.

Table 1 shows the measurement results of the surface resistance value and light transmittance of this conductive polymer.

<Examples 7 to 12> A conductive polymer was formed on one side under the same conditions as Examples 1 to 6 except that a polyvinyl alcohol resin was used as the resin containing the polymerization catalyst.

Table 1 shows the measurement results of the surface resistance value and light transmittance of this conductive polymer.

Comparative Examples 4 to 6> A polyvinyl alcohol resin was used as the resin containing the same catalyst as in Comparative Examples 1 to 3, and the other conditions were as in Comparative Examples 1 to 3.
A conductive polymer was formed on one side under the same conditions as above.

Table 1 shows the measurement results of the surface resistance value and light transmittance of this conductive polymer.

Comparative Examples 13 to 15> A conductive polymer was formed on one side of the film under the same conditions as Examples 1 to 6, except that the atmosphere was 10° C. and 80° C. RH or higher (D atmosphere).

Table 1 shows the measurement results of the surface resistance value and light transmittance of this conductive polymer.

<Comparative Examples 7-8> A conductive polymer was formed on one side of the film under the same conditions as Comparative Examples 1-3, except that the atmosphere was 10° C. and 60° C. RH or higher (E atmosphere).

Table 1 shows the measurement results of the surface resistance value and light transmittance of this conductive polymer.

Next, for Example 1 and Example 7, the reproducibility and uniformity of conductivity were measured. The results are shown in Table 2.

At the same time, a conductive polymer was obtained under the same conditions as in Example 1 and Example 7, except that the atmosphere was changed to 30° C., 150% RH (F atmosphere). (Comparative Example 10.11) The same items were measured and the results are shown in Table 2.

Table 2 As can be seen from the results above, the humidity in the reaction system was
By controlling the temperature within a constant range exceeding %RH,
The resulting conductive polymer is uniform and stable with repeatability.

Effect〉 As mentioned above, by the gas phase polymerization method of heterocyclic compounds,
By controlling the humidity in the reaction system to obtain a conductive polymer, the resulting conductive polymer is uniform and has stable reproducibility.

Furthermore, by controlling the relative humidity to exceed at least 60% RH, the production speed of the conductive polymer was increased, and the resulting conductive polymer had uniform and stable conductivity.

Special permission person Toppan Printing Co., Ltd. Representative: Kazuo Suzuki

Claims (1)

[Claims] 1) A conductive polymer characterized by making a polymer resin containing a polymerization catalyst conductive in a reaction system containing a heterocyclic compound in an atmosphere with relative humidity above a certain level. Method of manufacturing coalescence. 2) The method for producing a conductive polymer according to claim 1), wherein the relative temperature is in a range exceeding 60% RH. 3) Claim 1) characterized in that the heterocyclic compounds are one or more compounds selected from pyrrole, thiophene, furan, anline, and alkyl substituted products and derivatives thereof. and the method for producing a conductive polymer according to item 2).