JP3062563B2 - Conductive polymer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel conductive polymer composition applicable to electronic devices such as batteries, electrochromic displays and capacitors, antistatic materials and electromagnetic wave shielding materials.

[0002]

2. Description of the Related Art Conventionally known as conductive polymers are polyacetylene,
There are those using electrons as charge carriers, such as polypyrrole, polythiophene, polyaniline, and polyphenylenevinylene. Among them, polypyrrole is used as a solid electrolyte for a solid electrolytic capacitor because of its relatively high strength (Japanese Patent Laid-Open No. 63-158829). Also, polyaniline is used as a positive electrode active material of secondary batteries because it is repeatedly doped and undoped electrochemically and has a larger doping capacity than other conductive polymers (27th edition). Battery debate, 3A05L).

[0003] Known methods for producing these polymers include a method of chemically oxidizing and polymerizing using an oxidizing agent (chemical polymerization method) and a method of electrochemically oxidizing and polymerizing (electrolytic polymerization method). I have.

Among them, chemical polymerization is generally easy to synthesize in large quantities. However, the resulting conductive polymer is inferior in formability because it is a powder and is insoluble and infusible. When used as a conductive material, it is necessary to disperse and apply it to a binder. The characteristics are poor as in the case of using powder.

On the other hand, in the electrolytic polymerization method, a film-like conductive polymer is obtained. However, in the case of a conductive polymer such as polypyrrole, a film having high film strength can be obtained, but in the case of a conductive polymer such as polyaniline or polythiophene, the film strength is low. In addition, the disadvantages common to conductive polymers obtained by the electrolytic polymerization method are that the size of the conductive polymer film obtained is limited by the size of the electrodes, and furthermore, that a thin film is formed on an insulator. Needs to be provided with a conductive pre-coat layer. Conventionally, it has been difficult to obtain a large-area conductive polymer film or a conductive polymer layer due to such defects.

Recently, in order to overcome such disadvantages,
By polymerizing a compound having an alkyl group or an alkoxyl group at the 3-position of a 5-membered heterocyclic compound such as pyrrole or thiophene as a monomer, a conductive polymer soluble in a solvent or a conductive polymer having thermoplasticity can be obtained. (Macromolecules, 20, 217 (1
987)). Among them, the polythiophene derivatives have excellent drawability, but have a drawback of poor stability of electric conductivity. Further, the polypyrrole derivative is expensive in monomer and often has difficulty in synthesis.

Further, it has recently been found that polyaniline obtained by a chemical polymerization method becomes soluble in a solvent when undoped (Japanese Patent Laid-Open No. 3-28229). This polyaniline gives a tough film by heat treatment and gives a self-supporting film with high electric conductivity by re-doping with a protonic acid etc. It is excellent. However, when applied on another substrate as an antistatic treatment agent, depending on the substrate, it is necessary to use a binder in combination because there is a problem in adhesion and flexibility, and the conductivity inherent in polyaniline is impaired. Results.

On the other hand, this soluble polyaniline can be used as a positive electrode active material of a secondary battery. Since the shape of the soluble polyaniline can be variously changed, the electrode design is easier than a method using a polyaniline obtained by a conventional chemical polymerization method or electrolytic polymerization method as a positive electrode active material. However, a common problem with secondary batteries using polyaniline, polythiophene, or polypyrrole as a positive electrode active material is that diffusion of anions due to charge and discharge becomes rate-limiting, which hinders the realization of large-capacity secondary batteries. However, this problem cannot be overcome even when this solvent-soluble polyaniline is used as a positive electrode active material of a secondary battery.

An object of the present invention is to provide a novel conductive polymer composition which can solve the above problems and has excellent moldability. Another object of the present invention is to provide a conductive polymer composition which can be a new conductive material by having both electron conductivity and ion conductivity.

[0010]

Means for Solving the Problems The conductive polymer composition of the present invention is a group consisting of (A) polyaniline, (B) a homopolymer, a block copolymer and a random copolymer of an alkylene oxide monomer. A crosslinked product obtained by crosslinking a terminal acryloyl or methacryloyl-modified product of at least one alkylene oxide polymer selected from the group consisting of: (C) (a) an anion of a protonic acid, and (b) tetracia
Noquinodimethane, chloranil and tetracyanoethylene
And at least one selected from the group consisting of (c) an alkali metal salt and (d) an alkaline earth metal salt.

In the present invention, the component (A) and the component (B) are mutually dissolved and molecularly dispersed to form a polymer alloy comprising a composite of the components (A) and (B). Component (A) and / or (B) in polymer alloy
The component shows electronic conductivity and / or ionic conductivity by forming a complex with the component (C).

Further, since the components (A) and (B) are completely compatible with each other, the polymer alloy formed has an interpenetrating network structure (IPN structure). Shows unprecedented flexibility.

Hereinafter, in the present invention, the component (A)
Adding a component (C) to the component (B) or a complex of the component (A) and the component (B) to form a complex is referred to as "dope".

The polyaniline as the component (A) used in the present invention is prepared by dispersing or dissolving aniline in a solvent such as water or methanol, and then adding ammonium persulfate, hydrogen peroxide, or carbon dioxide in the presence of a protic acid such as sulfuric acid or hydrochloric acid. It can be easily obtained by adding an oxidizing agent such as manganese and polymerizing to obtain a doped polyaniline, which is further subjected to a dedoping treatment with a base such as ammonia or sodium hydroxide. Further, a material obtained by reducing undoped polyaniline can also be used.

The crosslinked product of the terminal acryloyl or methacryloyl modified product of the alkylene oxide polymer (B) is selected from the group consisting of homopolymers, block copolymers and random copolymers of alkylene oxide monomers. A crosslinked product obtained by crosslinking a terminal acryloyl or methacryloyl modified product of at least one type of alkylene oxide polymer, which is usually subjected to an addition (ring-opening) polymerization reaction of an alkylene oxide with an active hydrogen compound described later, Esterification reaction of acrylic acid, methacrylic acid, etc., or dechlorination reaction of acrylic acid chloride, methacrylic acid chloride, etc., to introduce an acryloyl or methacryloyl group at the terminal, followed by crosslinking by an appropriate crosslinking method. Can be Further, the terminal of the alkylene oxide polymer, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate,
After reacting with isocyanates such as 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and then reacting with hydroxyethyl acrylate, hydroxyethyl methacrylate, etc., an acryloyl or methacryloyl group is introduced into a terminal, and then an It can also be obtained by crosslinking with a crosslinking method.

As the active hydrogen compound, monohydric alcohols such as methanol and ethanol, ethylene glycol,
Dihydric alcohols such as propylene glycol and 1,4-butanediol, polyhydric alcohols such as glycerin, trimethylolpropane, sorbitol, sucrose and polyglycerin, monoethanolamine, ethylenediamine, diethylenetriamine, 2-ethylhexylamine, hexa Examples include amines such as methylene diamine, and phenolic active hydrogen-containing compounds such as bisphenol A and hydroquinone.

Examples of the alkylene oxide monomer include ethylene oxide, propylene oxide, 1,2-epoxybutane, 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyheptane, and 1,2-epoxyoctane. , 1,2-epoxynonane or the like having 2 to 9 carbon atoms
Α-olefin oxide, and α having 10 or more carbon atoms
Any of olefin oxide, styrene oxide and the like can be used, but ethylene oxide, propylene oxide and 1,2-epoxybutane are particularly preferable.

In the polymerization reaction, a basic catalyst such as sodium methoxide, sodium hydroxide, potassium hydroxide, lithium carbonate, triethylamine, potassium tert-butoxide and an acidic catalyst such as perchloric acid and boron trifluoride are used. Particularly, a basic catalyst is preferably used.

The number average molecular weight of the alkylene oxide polymer is preferably from 100 to 20,000.

The method of crosslinking the terminal acryloyl or methacryloyl modified product of the alkylene oxide polymer includes the following:
Heating is effective in addition to irradiation with actinic radiation such as ultraviolet rays, visible rays, and electron beams. At that time, if necessary, start photopolymerization of trimethylsilylbenzophenone, benzoin, 2-methylbenzoin, 4-methoxybenzophenone, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, benzoin methyl ether anthraquinone, or the like. It is also effective to add an initiator and a polymerization initiator such as benzoyl peroxide and methyl ethyl ketone peroxide.

In order to obtain the conductive polymer composition of the present invention,
For example, the component (A) and the modified terminal acryloyl or methacryloyl of the alkylene oxide polymer are dissolved in a common solvent such as dimethyl sulfoxide, dimethylformamide, N-methyl-2-pyrrolidone,
This is heated and dried to remove the solvent and to carry out a crosslinking reaction to obtain a composite of the component (A) and the component (B), and the composite may be doped with the component (C). Alternatively, the crosslinking may be performed by irradiating with actinic radiation during or before or after the solvent removing step. Further, the component (A) and / or the component (B) are
After doping the components, these may be mixed to obtain a conductive polymer composition.

That is, the polyaniline of the component (A) is usually insoluble in a solvent in a doped state, but is treated with a reducing agent such as hydrazine, phenylhydrazine or hydrazine hydrochloride, and then treated with tetracyanoquinodimethane. By doping with an electron accepting substance such as chloranil or tetracyanoethylene, a conductive polyaniline that is soluble in a solvent even in a doped state is obtained. Therefore, if polyaniline doped with such an electron acceptor is used,
It is not necessary to dope after forming the composite. When polyaniline or a reduced form thereof is used as the component (A) in a normal undoped state, after forming the complex, the complex is added to a protonic acid such as perchloric acid, sulfuric acid, or paratoluenesulfonic acid. By immersion treatment, the anion of the protonic acid can be easily doped. Further, an electrochemical doping method is also possible.

Furthermore, in the conductive polymer composition of the present invention, since a crosslinked product of a terminal acryloyl or methacryloyl modified product of an alkylene oxide polymer is compounded as the component (B), an alkali metal salt or an alkali metal salt is used. It is possible to dope the crosslinked product of the alkylene oxide polymer terminal acryloyl or methacryloyl modified product in the composite using an earth metal salt. These salts can be doped into the terminal acryloyl or methacryloyl modified product of the alkylene oxide polymer before forming the complex, or can be doped using a salt solution after forming the complex. It is.

The alkali metal salt or alkaline earth metal salt to be doped into the component (B) is not particularly limited. For example, LiI, LiCl, LiClO ₄ , LiSCN, LSC
iBF ₄ , LiAsF ₆ , LiCF ₃ SO ₃ , LiCF
₃ CO ₂ , LiHgI ₃ , NaI, NaSCN, NaB
r, CaCl ₂ , Ca (SCN) ₂ , Ca (ClO ₄ )
_{2 and the} like are preferred.

When the terminal acryloyl or methacryloyl modified product of the alkylene oxide polymer is doped in advance, an alkali metal salt, an alkaline earth metal salt such as acetone, methanol or tetrahydrofuran, and the terminal acryloyl or methacryloyl polymer of the alkylene oxide polymer are used. A method can be used in which these are mixed using a common solvent for the denatured product and then the solvent is distilled off. In the case of doping after the formation of the complex, a method of immersing the complex in a solvent in which an alkali metal salt or an alkaline earth metal salt is dissolved is suitably used.

The conductive polymer composition of the present invention has a mixed electron / ion conductivity because its structure contains a polymer chain having electron conductivity and ionic conductivity. Therefore, it can be suitably used as an electrode for a secondary battery. It is also possible to express only one of electron conductivity and ion conductivity as needed.

Since the components (A) and (B) are completely compatible, the formed composite becomes a polymer alloy having an interpenetrating network structure (IPN structure).
Shows flexibility not found in a single film containing only components.

[0028]

EXAMPLES Examples of the synthesis of polyaniline are shown below.

Synthesis Example 1 (Synthesis of undoped polyaniline) In a 1-liter four-necked flask equipped with a stirrer, a thermometer, a cooling tube, and a dropping funnel, 20 g of aniline, 18 ml of hydrochloric acid,
And 250 ml of water were added. After cooling to 0 ° C., a solution of 49 g of ammonium persulfate dissolved in 120 g of water was dropped from the dropping funnel over 4 hours. After stirring for 1 hour after the completion of the dropwise addition, the precipitated solid was separated by filtration, washed with water, and then washed with methanol until the filtrate became transparent. Then, this solid was dispersed in 500 ml of 4N aqueous ammonia and stirred for 4 hours. After completion of the stirring, the solid was separated by filtration, washed with water until the filtrate became neutral, and then washed with methanol until the filtrate became transparent. The filtered solid was dried under vacuum to obtain 10.2 g of dark brown undoped polyaniline. It was soluble in N-methyl-2-pyrrolidone.

Synthesis Example 2 (Reduction of undoped polyaniline reduced product)
Synthesis) 2 g of the undoped polyaniline obtained in Synthesis Example 1 was N-
It was dissolved in 98 g of methyl-2-pyrrolidone, and 0.8 g of phenylhydrazine was added to this solution. After the completion of the reaction, the precipitate was reprecipitated with acetone. The precipitated solid was separated by filtration, washed with acetone, and then dried to give the gray title polyaniline 1.6.
g was obtained.

Next, an example of the synthesis of a terminal acryloyl or methacryloyl-modified alkylene oxide polymer will be described.

Synthesis Example 3 (Terminal of alkylene oxide polymer
Synthesis of acryloyl-modified product B-1) Starting from 212 g of diethylene glycol and using 4 g of potassium hydroxide as a catalyst, 1,78 g of ethylene oxide
After reacting 8 g at 120 ° C. for 8 hours in a 5-liter autoclave, desalting and purification were carried out to obtain 1,950 g of an ethylene oxide homopolymer having a number average molecular weight of 1,000 (calculated from a hydroxyl value).

Next, 1,000 g of the above polymer, 180 g of acrylic acid, 2,000 g of toluene and 10 g of sulfuric acid as a catalyst were charged, and a reaction was carried out for 10 hours while removing water under stirring and reflux. Perform salt purification,
Terminal acryloyl-modified ethylene oxide polymer 1,05
0 g was obtained.

Synthesis Example 4 (Terminal of alkylene oxide polymer
Synthesis of acryloyl-modified product B-2) Starting from 212 g of diethylene glycol, using 12 g of potassium hydroxide as a catalyst, ethylene oxide 1,8
After reacting 94 g and 1,894 g of propylene oxide in a 5-liter autoclave at 120 ° C. for 8 hours, desalting and purification were carried out, and the number average molecular weight was 4,000.
3,980 g of an ethylene oxide-propylene oxide random copolymer (calculated from the hydroxyl value) was obtained.

Next, 1,000 g of the above polymer, 43.3 g of acrylic acid, 2,000 g of toluene, and 10 g of sulfuric acid as a catalyst were charged. Thereafter, the same procedure as in Synthesis Example 3 was carried out to give an acryloyl-terminal-modified ethylene oxide-propylene oxide random copolymer 1 , 015 g.

Synthesis Example 5 (Terminal of alkylene oxide polymer
Synthesis of acryloyl-modified B-4) Using 184 g of glycerin as a starting material, 12.0 g of potassium hydroxide as a catalyst, and 3,816 g of ethylene oxide
Was reacted in a 5 liter autoclave at 130 ° C. for 4 hours, followed by desalting and purification, and the number average molecular weight was 2,2.
3,940 g of an ethylene oxide homopolymer having a molecular weight of 000 (calculated from the hydroxyl value) was obtained.

Next, 1,000 g of the above polymer, 130 g of acrylic acid, 2,000 g of toluene, and 10 g of sulfuric acid as a catalyst were charged. Thereafter, in the same manner as in Synthesis Example 3, 1,040 g of an acryloyl-terminal-modified ethylene oxide polymer was obtained.

Synthesis Example 6 (Terminal of alkylene oxide polymer
Synthesis of acryloyl-modified product B-5) Using 92 g of glycerin as a starting material and 9 g of potassium hydroxide as a catalyst, reacting 2,326 g of ethylene oxide and 581 g of propylene oxide in a 5-liter autoclave at 120 ° C. for 8 hours, followed by dehydration. After salt purification, number average molecular weight 3,000 (calculated from hydroxyl value)
2,994 g of an ethylene oxide-propylene oxide random copolymer was obtained.

Next, 1,000 g of the above polymer, 87 g of acrylic acid, 2,000 g of toluene and 10 g of sulfuric acid as a catalyst were charged, and thereafter, as in Synthesis Example 3, 1,030 g of an acryloyl-terminal-modified ethylene oxide-propylene oxide random copolymer was obtained. I got

Synthesis Example 7 (alkylene oxide polymer terminal
Synthesis of acryloyl-modified product B-6) After reacting 2,454 g of ethylene oxide and 2,454 g of propylene oxide for 8 hours at 120 ° C. in a 10-liter autoclave using 92 g of glycerin as a starting material and 10 g of potassium hydroxide as a catalyst. Then, desalting and purification were performed to obtain 4,990 g of an ethylene oxide-propylene oxide random copolymer having a number average molecular weight of 5,000 (calculated from the hydroxyl value).

Then, 1,000 g of the above polymer, 52 g of acrylic acid, 2,000 g of toluene, and 10 g of sulfuric acid as a catalyst were charged. Thereafter, as in Synthesis Example 3, 1,010 g of an acryloyl-terminal-modified ethylene oxide-propylene oxide random copolymer was obtained. I got

Synthesis Example 8 (Terminal of alkylene oxide polymer
Synthesis of methacryloyl-modified product B-7) After reacting 1,382 g of ethylene oxide and 5,526 g of propylene oxide at 120 ° C. for 8 hours in a 10-liter autoclave using 92 g of glycerin as a starting material and 21 g of potassium hydroxide as a catalyst. After desalting and purification, 6,990 g of an ethylene oxide-propylene oxide random copolymer having a number average molecular weight of 7,000 (calculated from the hydroxyl value) was obtained.

Next, 1,000 g of the above polymer, 44 g of methacrylic acid, 2,000 g of toluene, and 10 g of sulfuric acid as a catalyst were charged. Thereafter, as in Synthesis Example 3, 1,005 g of a methacryloyl-terminal-modified ethylene oxide-propylene oxide random copolymer was prepared. I got

Synthesis Example 9 (alkylene oxide polymer terminal
Synthesis of Acryloyl Modified Product B-11) Using 182 g of sorbitol as a starting material and 9 g of potassium hydroxide as a catalyst, 1,409 g of ethylene oxide was first reacted at 120 ° C. for 4 hours in a 5-liter autoclave, and then, 2-epoxybutane 1,40
After reacting 9 g at 120 ° C. for 7 hours, desalting and purification were carried out to obtain 2,990 g of an ethylene oxide-1,2-epoxybutane block copolymer having a number average molecular weight of 3,000 (calculated from a hydroxyl value).

Next, 1,000 g of the above polymer, 173 g of acrylic acid, 2,000 g of toluene, and 10 g of sulfuric acid as a catalyst were charged, and the acryloyl-terminal-modified ethylene oxide-1,2-epoxybutane block copolymer was used in the same manner as in Synthesis Example 3. 1,050 g of the combined product was obtained.

Table 1 shows examples of the terminal acryloyl-modified and methacryloyl-terminal modified alkylene oxide polymers that can be used in the present invention.

[0047]

[Table 1]

Example 1 Synthesis Example 4 was prepared by dissolving 0.5 g of the polyaniline powder obtained in Synthesis Example 1 in 9.5 g of N-methyl-2-pyrrolidone.
0.5 g of the alkylene oxide polymer terminal acryloyl modified product (B-2) obtained in the above and 0.001 g of benzoyl peroxide
Was added and stirred to make them compatible with each other. This solution was cast on a glass plate and dried at 150 ° C. for 30 minutes to carry out a crosslinking reaction to obtain a self-supporting film having a deep blue gloss. This film was immersed in a 20% aqueous solution of p-toluenesulfonic acid for 24 hours. After completion of the immersion, the film was washed with water, further washed with acetone, and then dried to obtain a dark blue self-supporting film.

The electrical conductivity (conductivity) of this film is 2.1 S / cm in terms of electron conductivity, and the frequency dependence of the electrical conductivity is small. The tensile strength was 820 kgf / cm ² and the elongation was 250%.

Example 2 A solution of 0.5 g of the polyaniline powder obtained in Synthesis Example 2 in 9.5 g of N-methyl-2-pyrrolidone was added to a solution of 7,7,
8,8-tetracyanoquinodimethane (TCNQ) was added to 0.
002 g were added. Next, the alkylene oxide polymer terminal acryloyl-modified product (B-1) 0.2 obtained in Synthesis Example 3 was added.
g and benzoyl peroxide 0.001 g were added, and the mixture was stirred well to dissolve. This solution was cast on a glass plate to form a solution.
Crosslinking was performed by heating at 1 Torr and 160 ° C. for 60 minutes to obtain a self-supporting film showing a deep blue color.

The conductivity of this film is 0.8 S / cm, which is electronically conductive, and the frequency dependence of the conductivity (10 Hz to 10 Hz).
200 kHz). Tensile strength is 890kgf /
cm ² , and the elongation percentage was 105%.

Example 3 To a solution of 0.5 g of the polyaniline powder obtained in Synthesis Example 1 in N-methyl-2-pyrrolidone was added 0.05 g of lithium perchlorate, and the terminal of the alkylene oxide polymer obtained in Synthesis Example 6 was added. 0.5 g of the acryloyl-modified product (B-5) and 0.002 g of benzoyl peroxide were added and dissolved by stirring. This solution was cast on a glass plate and dried at 150 ° C. for 30 minutes to obtain a self-supporting film exhibiting dark blue gloss.

The conductivity of this film at room temperature is 10
⁻⁵ S / cm, and the temperature dependence of the conductivity is based on the WLF (Williams-Landel-Fe) characteristic of ion conduction.
(ryry) type dependence.

The film was immersed in a 10% HClO ₄ solution for 10 hours, washed with methanol and dried to obtain a dark blue flexible self-supporting film. The conductivity of this film is 2.3 S / cm electronic conductivity and 10 ⁻⁵ S / c.
It shows the ionic conductivity of m. Tensile strength is 780
kgf / cm ² and the elongation were 195%.

Example 4 0.5 g of the polyaniline powder obtained in Synthesis Example 2 was added to a solution prepared by dissolving 0.005 g of TCNQ in 9.5 g of N-methyl-2-pyrrolidone. Next, the alkylene oxide polymer terminal methacryloyl modified product (B-
7) Addition of 0.005 g of 2-methylbenzoin to 0.5 g, irradiation of ultraviolet rays at an intensity of 7 mW / cm ^{2 to} carry out a crosslinking reaction, and doping of lithium perchlorate with 0.04 g, alkylene oxide polymer terminal 0.4 g of a crosslinked product of a methacryloyl-modified product was added and dissolved by stirring. This solution was cast on a glass plate and dried at 150 ° C. for 30 minutes to obtain a self-supporting film exhibiting dark blue gloss.

The conductivity of this film showed an electron conductivity of 0.5 S / cm and an ionic conductivity of 10 ⁻⁴ S / cm. Tensile strength is 920 kgf / cm ² , elongation is 18
It was 0%.

Example 5 0.5 g of the polyaniline powder obtained in Synthesis Example 1 was dissolved in 9.5 g of N-methyl-2-pyrrolidone. Then, an alkylene oxide polymer terminal acryloyl-modified product B-11 doped with sodium perchlorate in advance (0.06 g of sodium perchlorate was dissolved in 1 g of methanol, and the alkylene oxide polymer-terminal acryloyl-modified product obtained in Synthesis Example 9) B
After adding 0.4 g of -11 and stirring to make the mixture uniform, methanol was distilled off to dope. ) And 0.004 g of 4-methoxybenzophenone were added and dissolved by stirring. This solution was cast on a glass plate, irradiated with ultraviolet rays at an intensity of 7 mW / cm ² , and dried at 150 ° C. for 30 minutes to obtain a self-supporting film exhibiting dark blue gloss.

The conductivity of this film at room temperature is 10
^-5 S / cm, indicating ionic conductivity.

Example 6 0.5 g of the polyaniline powder obtained in Synthesis Example 1 was dissolved in 9.5 g of N-methyl-2-pyrrolidone. To this solution, 0.5 g of the alkylene oxide polymer terminal acryloyl modified product (B-6) obtained in Synthesis Example 7 was added, followed by stirring and mixing.
This solution was cast on a glass plate, crosslinked using an electron curtain type electron beam irradiation device (200 kV, 5 Mrad), and dried at 150 ° C. for 30 minutes to obtain a dark blue self-supporting film. This film was immersed in a 10% aqueous solution of perchloric acid containing 5% of lithium perchlorate for 10 hours, washed with water, further washed with methanol, and dried.

The electrical conductivity of this film showed an electron conductivity of 1.3 S / cm and an ion conductivity of 10 ⁻⁵ S / cm. Tensile strength is 600 kgf / cm ² , elongation is 130
%Met.

Comparative Example 1 0.5 g of the polyaniline powder obtained in Synthesis Example 1 was dissolved in 9.5 g of N-methyl-2-pyrrolidone. This solution was cast on a glass plate and dried at 150 ° C. for 30 minutes to obtain a red copper-colored glossy film. This film was immersed in a 20% aqueous solution of p-toluenesulfonic acid for 24 hours. After the completion of the immersion, the substrate was washed with water and acetone and then dried to obtain a dark blue self-supporting film.

The conductivity of this film is electronic conductivity.
It was 2 S / cm. Tensile strength is 680 kgf / cm ²
And the elongation was 2%.

Further, the film was immersed in 10 g of methanol containing 2 g of lithium perchlorate for 24 hours, washed with water and acetone, and dried. Then, the conductivity was measured, but no ionic conductivity was exhibited. Was.

In the examples and comparative examples, the conductivity was measured by using both the complex impedance method and the four-terminal method using a direct current.

[0065]

According to the conductive polymer composition of the present invention, electron conductivity and / or ionic conductivity can be selected according to the application. Further, since it is rich in processability and flexible, it can be applied to a wide range of uses.

Continuation of front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08L 79/00-79/08

Claims (1)

(57) [Claims] 1. The terminal acryloyl of at least one alkylene oxide polymer selected from the group consisting of (A) polyaniline, (B) a homopolymer, a block copolymer and a random copolymer of an alkylene oxide monomer. Or a crosslinked product obtained by crosslinking a methacryloyl-modified product; (C) (a) an anion of a protonic acid ;
Noquinodimethane, chloranil and tetracyanoethylene
A conductive polymer composition comprising at least one selected from the group consisting of (c) an alkali metal salt and (d) an alkaline earth metal salt.