JP2943119B2 - Organic polymer, conductive organic polymer composition and method for producing them - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel high molecular weight organic polymer, a conductive organic polymer composition obtained therefrom, and a method for producing the same.

[0002]

2. Description of the Related Art A method for producing a conductive organic polymer composition comprising aniline chemically oxidized and polymerized with a chemical oxidizing agent and containing an electrolyte ion as a dopant and having an electric conductivity of 10 ^-6 S / cm or more is known. It is already known, and furthermore, in the production of the conductive organic polymer composition by such chemical oxidation polymerization, when the standard electrode potential determined as the electromotive force in the reduction half-cell reaction based on the standard hydrogen electrode is 0.6 V or more. The fact that a certain oxidizing agent is particularly preferably used has already been disclosed in JP-A-61-2.
No. 58831.

However, in general, since a conductive organic polymer composition is insoluble and infusible, it cannot be formed into a film by a casting method, so that it is difficult to develop an application of the conductive organic polymer composition. It is a major obstacle. JP-A-60-235831 and J. Polymer Sci., P.
As described in olymer Chem. Ed., 26, 1531 (1988), a film of a conductive organic polymer composition can be formed on an electrode by electrolytic oxidation polymerization of aniline. Because the forming surface is limited to the electrode surface,
It is difficult to obtain a large-area film, and the production cost is high due to electrolytic oxidation. Moreover, this film has low strength and is insoluble and infusible.

Therefore, conventionally, an intermediate soluble in an organic solvent is produced, the solution is formed into a film by a casting method, and then the intermediate is converted into a conductive polymer composition by physical or chemical means. Various methods have been proposed. However, according to this method, a treatment at a high temperature is required, or the conversion from the intermediate to the conductive polymer composition does not always proceed as theoretically. From the viewpoint, it is not practical as a method for producing a conductive organic polymer composition film.

In the field of polypyrrole or polythiophene, polymers soluble in organic solvents are known. That is,
Electrolytic oxidation polymerization of thiophene having a long-chain alkyl group as a substituent or pyrrole having an alkanesulfonic acid group as a substituent can obtain an organic solvent-soluble poly (3-alkylthiophene) and a water-soluble polypyrrolealkanesulfonic acid, respectively. it can. Any of these polymers can be obtained from the solution by a casting method. However, this method uses a special monomer and carries out electrolytic oxidation polymerization of the monomer, so that the production cost is extremely high.

On the other hand, in the field of chemical oxidative polymerization of aniline, recently, about 1/4 mole of ammonium peroxodisulfate is used as an oxidizing agent for aniline, and aniline is chemically oxidatively polymerized to form an organic solvent-soluble polymer. It has been reported that polyaniline can be obtained (A.
G. MacDiarmid et al., Synthetic Metals, 21, 21 (198
7); AG MacDiarmid et al., L. Alcacer (ed.), Con
ducting Polymers, 105-120 (D. Reidel Publishing C
o., 1987). However, this polymer is not N-methyl-2-
80% as well as pyrrolidone and dimethyl sulfoxide
Since it is also soluble in acetic acid and 60% formic acid aqueous solution, its molecular weight is low. It is also described that a self-supporting film can be obtained from a solution of a polymer such as N-methyl-2-pyrrolidone or dimethyl sulfoxide. Furthermore, it is described that a film of a conductive polymer composition doped with acetic acid can be obtained from an acetic acid solution, and the film is dedoped with ammonia. However, the undoped film has low strength due to the low molecular weight of polyaniline, and is easily broken by bending, so that it cannot be put to practical use.

It is also known that aniline can be oxidized with ammonium peroxodisulfate to obtain polyaniline soluble in tetrahydrofuran (J. T.
ang, Synthetic Metals, 24, 231 (1988). However, this polymer is also considered to have a low molecular weight from the viewpoint of dissolving in tetrahydrofuran.

[0008]

The present inventors have, in particular,
As a result of intensive studies to obtain organic solvent-soluble high molecular weight organic polymers by chemical oxidative polymerization of aniline, it has been found that, although it has a much higher molecular weight than conventionally known polyaniline, it can be used in various organic solvents in the undoped state. Soluble quinone diimine phenylenediamine type polyaniline was found, and as a result of further studies on such polyaniline, this organic solvent-soluble polyaniline was reduced with a reducing agent to give an imino-p-phenylene type solvent-soluble polyaniline. By doping this with an electron acceptor, even in the doping state, it is soluble in an organic solvent, easily becomes self-supporting by the casting method from the solution, and has a tough and flexible conductive property. A film of the polyaniline composition can be obtained, and It has found that it is possible to obtain a thin film of conductive polyaniline composition having a tough flexible if casting or coating on the timber, and have reached the present invention.

[0009]

The organic polymer according to the present invention has the general formula (I)

[0010]

Embedded image

It is composed of an imino-p-phenylene structural unit represented by the following formula, is soluble in an organic solvent in an undoped state, and is dissolved in N-methyl-2-pyrrolidone at 30 ° C.
Is characterized by having an intrinsic viscosity [η] of 0.40 dl / g or more. Hereinafter, an organic polymer comprising the imino-p-phenylene structural unit represented by the above general formula (I) and soluble in an organic solvent is referred to as an imino-p-phenylene-type solvent-soluble polyaniline.

According to the present invention, the imino-p-phenylene type solvent-soluble polyaniline according to the present invention has the general formula (II)

[0013]

Embedded image

(Wherein m and n represent the mole fractions of the quinone diimine structural unit and the phenylenediamine structural unit in the repeating unit, respectively, 0 <m <1, 0 <n <1, m +
n = 1. A) a quinone diimine structural unit and a phenylenediamine structural unit, which are soluble in an organic solvent in an undoped state and have an intrinsic viscosity [η] measured at 30 ° C. in N-methyl-2-pyrrolidone.
Is not less than 0.40 dl / g and 1600 cm ^-1 of the skeleton vibration of para-substituted benzene in the laser Raman spectrum obtained by excitation with light having a wavelength of 457.9 nm.
Reduction of an organic polymer having a ratio Ia / Ib of 1.0 or more between the intensity Ia of the Raman line of the skeleton stretching vibration appearing at a higher wave number than the Raman line intensity Ib of the skeleton stretching vibration appearing at a wave number lower than 1600 cm ^-1. It can be obtained by reduction with an agent.

Hereinafter, an organic polymer comprising a quinone diimine structural unit represented by the above general formula (II) and a phenylenediamine structural unit and soluble in an organic solvent is referred to as a quinone diimine / phenylenediamine type solvent-soluble polyaniline. In addition, the conductive organic polymer composition according to the present invention has the general formula (I)

[0016]

Embedded image

Which is composed of an imino-p-phenylene structural unit represented by the following formula, is soluble in an organic solvent in an undoped state, and is dissolved in N-methyl-2-pyrrolidone at 30 ° C.
An organic polymer having an intrinsic viscosity [η] of 0.40 dl / g or more measured by the method described above is doped with an electron acceptor. Such a conductive organic polymer composition according to the present invention thus has the unexpected and surprising property of being soluble in various organic solvents even in a doped conductive state.

The conductive organic polymer composition according to the present invention can be obtained by doping the above imino-p-phenylene type solvent-soluble polyaniline with an electron acceptor according to the present invention. First, the production of the imino-p-phenylene-type solvent-soluble polyaniline according to the present invention will be described.

The imino-p-phenylene-type solvent-soluble polyaniline has the general formula (II)

[0020]

Embedded image

(Wherein, m and n represent the molar fractions of the quinone diimine structural unit and the phenylenediamine structural unit in the repeating unit, respectively, 0 <m <1, 0 <n <1, m +
n = 1. A) a quinone diimine structural unit and a phenylenediamine structural unit, which are soluble in an organic solvent in an undoped state and have an intrinsic viscosity [η] measured at 30 ° C. in N-methyl-2-pyrrolidone.
Is not less than 0.40 dl / g and 1600 cm ^-1 of the skeleton vibration of para-substituted benzene in the laser Raman spectrum obtained by excitation with light having a wavelength of 457.9 nm.
An organic polymer in which the ratio Ia / Ib of the Raman line intensity Ia of the skeleton stretching vibration appearing at a higher wavenumber than the Raman line intensity Ib of the skeleton stretching vibration appearing at a lower wavenumber than 1600 cm ^-1 is 1.0 or more. , Quinone diimine phenylenediamine type solvent-soluble polyaniline can be obtained by reducing with a reducing agent.

Here, the quinone diimine / phenylenediamine type solvent-soluble polyaniline is prepared by adding an acid dissociation constant pKa of 3.0 or less to aniline in a solvent in the presence of a protonic acid at a temperature of 5 ° C. or less, An aqueous solution of an oxidizing agent having a standard electrode potential of 0.6 V or more, which is defined as an electromotive force in a reduction half-cell reaction based on a standard hydrogen electrode, is preferably held at a temperature of 0 ° C. or lower per 1 mol of aniline. Equivalent, defined as one mole of oxidant divided by the number of electrons required to reduce one molecule of oxidant, 2
At least an equivalent amount, preferably 2 to 2.5 equivalents, gradually added to form an oxidized polymer of aniline doped with the above protonic acid, and then obtained by dedoping the polymer with a basic substance. Can be. If the amount of the oxidizing agent is described by using a mathematical formula, the molecular weight of the oxidizing agent used is M, and the number of electrons required to reduce 1 g molecule (1 mol) of the oxidizing agent is n. Is equivalent to M / n, so that the oxidizing agent is used in the range of 2 M / n to 2.5 M / n per 1 mol of aniline.

In the above method for producing an oxidized aniline polymer doped with a protonic acid, the oxidizing agent includes manganese dioxide, ammonium peroxodisulfate, hydrogen peroxide, ferric salt, iodate and the like. Particularly preferably used. Among these, for example, ammonium peroxodisulfate and hydrogen peroxide both involve two electrons per molecule in the oxidation reaction.
Usually, an amount in the range of 1 to 1.25 mol per mol of aniline is used.

The protonic acid used in the oxidative polymerization of aniline is not particularly limited as long as it has an acid dissociation constant pKa of 3.0 or less. Examples thereof include hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, and fluorinated acid. Hydrofluoric acid, phosphoric hydrofluoric acid,
Hydrofluoric acid, inorganic acids such as hydroiodic acid, benzenesulfonic acid, aromatic sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid, alkanesulfonic acids such as ethanesulfonic acid, phenols such as picric acid, Examples thereof include aromatic carboxylic acids such as m-nitrobenzoic acid, and aliphatic carboxylic acids such as dichloroacetic acid and malonic acid. Also, polymeric acids can be used. Examples of such a polymer acid include polystyrene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, and polyvinyl sulfate.

The amount of protonic acid used depends on the mode of reaction of the oxidizing agent used. For example, in the case of manganese dioxide, the oxidation reaction is represented by MnO ₂ + 4H ⁺ + 2e ⁻ → Mn ²⁺ + 2H ₂ O.
It is necessary to use a protonic acid capable of supplying a double molar amount of protons. Also, in the case of hydrogen peroxide, since the oxidation reaction is represented by H ₂ O ₂ + 2H ⁺ + 2e ⁻ → 2H ₂ O, a proton acid capable of supplying at least twice the amount of protons of hydrogen peroxide to be used is used. There is a need. On the other hand, in the case of ammonium peroxodisulfate,
Since the oxidation reaction is represented by S ₂ O ₈ ²⁻ + 2e ⁻ → 2SO ₄ ²⁻ , it is not particularly necessary to use a protonic acid. However, in the present invention, even when ammonium peroxodisulfate is used as the oxidizing agent, it is preferable to use a protonic acid in an equimolar amount with the oxidizing agent.

As a solvent in the oxidative polymerization of aniline, aniline, a protonic acid and an oxidizing agent are dissolved.
Those that are not oxidized by an oxidizing agent are used. Water is most preferably used, however, if necessary, alcohols such as methanol and ethanol, nitriles such as acetonitrile, N-methyl-2-pyrrolidone, polar solvents such as dimethyl sulfoxide, ethers such as tetrahydrofuran, Organic acids such as acetic acid can also be used.
Also, a mixed solvent of these organic solvents and water can be used.

In the preparation of oxidized aniline polymers doped with such a protonic acid, the temperature of the reaction mixture should always be 5 during the oxidation reaction of the aniline, especially during the addition of the oxidizing agent solution to the aniline solution. It is important to keep it below ° C. Therefore, the oxidant solution must be added slowly to the aniline so that the temperature of the reaction mixture does not exceed 5 ° C. When the oxidizing agent is added rapidly, the temperature of the reaction mixture also increases due to external cooling,
A low molecular weight polymer is produced, or a solvent-insoluble oxidized polymer is produced even after dedoping described later.

In particular, in the above oxidation reaction, it is preferable to keep the reaction temperature at 0 ° C. or lower. The intrinsic viscosity [η] measured at 30 ° C. in N-methyl-2-pyrrolidone by dedoping the doped aniline oxide polymer thus obtained (the same applies hereinafter).
Can obtain a high-molecular-weight quinonediimine / phenylenediamine-type solvent-soluble polyaniline having a molecular weight of 1.0 dl / g or more.

Since the oxidized aniline polymer doped with the protonic acid used forms a salt with the protonic acid, the oxidized polymer of aniline is usually used at a high concentration at which a self-supporting film can be prepared. Does not dissolve in organic solvents. It is well known that salts of high molecular weight amines are generally poorly soluble in many organic solvents. However, a quinonediimine-phenylenediamine-type solvent-soluble polyaniline can be obtained by dedoping the aniline oxidized polymer insoluble in an organic solvent.

Further, the oxidized polymer of aniline doped with the protonic acid used is dedoped to obtain a quinonediimine / phenylenediamine type solvent-soluble polyaniline, which is, for example, an N-methyl-2-pyrrolidone dilute solution. For example, by doping with an organic acid such as malonic acid, a doped polyaniline composition can be obtained while maintaining solvent solubility.

The dedoping of the oxidized aniline polymer doped with a protonic acid is a kind of neutralization reaction. Therefore, any basic substance capable of neutralizing a protonic acid as a dopant may be used. Although not limited, preferably, aqueous ammonia, sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide,
A metal hydroxide such as calcium hydroxide is used. In the dedoping, a basic substance may be directly added to the reaction mixture after the oxidative polymerization of aniline, or the basic substance may be allowed to act after the polymer composition is once isolated.

The doped polymer composition obtained by oxidative polymerization of aniline usually has a conductivity of 10 ⁻⁶ S / cm or more and exhibits a blackish green color.
It is purple or purple-colored copper. This discoloration is because the amine nitrogen of the salt structure in the polymer composition was changed to a free amine. The conductivity is usually on the order of 10 ^-10 S / cm.

The undoped quinonediimine / phenylenediamine-type solvent-soluble polyaniline thus obtained has a high molecular weight and is soluble in various organic solvents. Such organic solvents include N-methyl-2-
Examples include pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, 1,3-dimethyl-2-imidazolidinone, and sulfolane. The solubility depends on the average molecular weight of the polymer and the solvent, but 0.5 to 100% of the polymer is dissolved, and a solution of 1 to 30% by weight can be obtained.

In particular, this quinone diimine / phenylenediamine type solvent-soluble polyaniline is N-methyl-2-
Shows high solubility in pyrrolidone, usually 20 to 20
100% dissolves to give a 3-30% by weight solution. However, it does not dissolve in tetrahydrofuran, 80% acetic acid aqueous solution, 60% formic acid aqueous solution, acetonitrile and the like.

Accordingly, such a quinone diimine / phenylenediamine type solvent-soluble polyaniline can be dissolved in an organic solvent and formed into a film by a casting method. For example, after casting a quinone diimine phenylenediamine type solvent-soluble polyaniline solution on a glass plate, by selecting the conditions of heating and drying the solvent,
It is possible to obtain a free-standing film which is uniform, tough and excellent in flexibility.

In this film preparation, in order to obtain a film that is tough and excellent in flexibility, the intrinsic viscosity [η] is 0.4.
It is desirable to use 0 or more of the above-mentioned quinone diimine / phenylenediamine type solvent-soluble polyaniline.

Further, a film obtained by casting a quinone diimine / phenylenediamine type solvent-soluble polyaniline has different properties depending on the drying conditions of the solvent. Usually, when the intrinsic viscosity [η] is cast on a glass plate with an N-methyl-2-pyrrolidone solution of a soluble polymer having 0.40 or more, and the solvent is dried,
When the drying temperature is 100 ° C. or lower, the obtained film is still not sufficiently strong, and the N-methyl-2
Partially soluble in pyrrolidone. However, if the drying temperature is 1
When the temperature is 30 ° C. or higher, the resulting film has excellent flexibility, is very tough, and does not crack even when bent. Further, the film obtained in this manner has N
-Does not dissolve in methyl-2-pyrrolidone, nor does it dissolve in concentrated sulfuric acid. Thus, the solvent insolubilization of the polymer by drying the solvent at a high temperature after casting is considered to be due to the crosslinking of the polymer molecules due to the coupling of radicals present in the polymer or generated upon heating.

The quinonediimine / phenylenediamine-type solvent-soluble polyaniline is represented by the general formula (IR) based on elemental analysis, infrared absorption spectrum, ESR spectrum, laser Raman spectrum, thermogravimetric analysis, solubility in a solvent, and visible to near infrared absorption spectrum. II)

[0039]

Embedded image

(Wherein, m and n represent the mole fractions of the quinone diimine structural unit and the phenylenediamine structural unit in the repeating unit, respectively, 0 <m <1, 0 <n <1, m +
n = 1. ) Is a polymer comprising a quinone diimine structural unit and a phenylenediamine structural unit.

A film obtained by insolubilizing a solvent using the quinone diimine / phenylenediamine type solvent-soluble polyaniline by the casting method also shows substantially the same infrared absorption spectrum as that of the solvent-soluble polymer. From the absorption spectrum, ESR spectrum, laser Raman spectrum, thermogravimetric analysis, solubility in solvent, visible to near-infrared absorption spectrum, etc., it is considered that the polymer has a crosslinked structure but substantially the same repeating unit.

Here, the characteristics of the quinone diimine / phenylenediamine type solvent-soluble polyaniline obtained from the laser Raman spectrum will be described in comparison with conventionally known so-called polyaniline.

In general, there is vibration spectroscopy as a means for obtaining information on vibrations between atoms constituting a substance, including infrared spectroscopy and Raman spectroscopy. Infrared spectroscopy is active in vibrational modes that result in dipole moment changes,
Raman spectroscopy is active on vibrations that cause a change in polarizability. Therefore, the two are in a complementary relationship, and generally, the vibration mode that appears strongly in infrared spectroscopy is weak in Raman spectroscopy, while the vibration mode that appears strongly in Raman spectroscopy is weak in infrared spectroscopy. .

An infrared absorption spectrum is obtained by detecting the energy absorption between vibrational levels, and a Raman spectrum occurs when a molecule is excited by light irradiation and then falls to a higher ground state vibrational level. It is obtained by detecting scattered light (Raman scattering). At this time, the vibration energy level can be known from the energy difference of the scattered light with respect to the irradiation light.

Usually, a Raman spectrum is obtained by excitation with visible light from an argon laser or the like. Here, when the sample has an absorption band in the visible region, it is known that a very strong Raman ray can be obtained if the irradiation laser light and the absorption band wavelength match. This phenomenon is called resonance Raman effect, according to this, 10 ⁴ to 10 ⁵ times the strong Raman lines of normal Raman line is obtained. According to such a resonance Raman effect, information of a chemical structure part excited by the wavelength of the irradiated laser light can be obtained with more enhanced information. Therefore, by measuring the Raman spectrum while changing the wavelength of the laser light to be irradiated, the chemical structure of the sample can be more accurately analyzed. Such a feature is a feature of Raman spectroscopy that does not exist in infrared spectroscopy.

FIG. 1 shows that in N-methyl-2-pyrrolidone
A disk-shaped sample of undoped quinonediimine / phenylenediamine-type solvent-soluble polyaniline having an intrinsic viscosity [η] of 1.2 dl / g measured at 30 ° C. was irradiated at an excitation wavelength of 457.9 nm. It is the obtained laser Raman spectrum. The assignment of the Raman line is as follows. 1622 and 1591 cm ^-1 are the skeleton stretching vibration of para-substituted benzene, 1489 and 1479 cm -1.
^-1, stretching vibration of C = C and C = N quinonediimine structure, 1220 cm ^-1 mixed C-N stretching vibration and C-C stretching vibration, 1185 and 1165 cm ^-1-plane bending of the C-H Vibration.

FIG. 2 shows Y. Furukawa et al., Synth.
t., 16, 189 (1986) is a laser Raman spectrum obtained by irradiating the undoped polyaniline shown in T., 16, 189 (1986) at an excitation wavelength of 457.9 nm. This polyaniline is obtained by electrolytic oxidation polymerization of aniline on a platinum electrode.

As shown in FIG. 1, quinone diimine
The phenylenediamine type solvent-soluble polyaniline, among the skeletal vibration of para-substituted benzene, the Raman line intensity appears at lower frequency than the Raman line intensity Ia and 1600 cm ^-1 skeletal stretching vibration appearing at the number of high wave than 1600 cm ^-1 I
b and the ratio Ia / Ib is 1.0 or more. On the contrary,
Conventionally known polyanilines including the polyaniline shown in FIG. 2 have the above-mentioned ratio Ia / 1b smaller than 1.0, including those based on chemical oxidative polymerization.

The Raman lines at 1622 and 1591 cm ^-1 are
Both are based on the skeleton stretching vibration of para-substituted benzene. In the polyaniline in the reduced state, since it does not have a quinone diimine structure, a Raman line is generated only at 1621 cm ^-1. However, in the undoped polyaniline having the quinone diimine structure, 1622 and 1
A Raman line appears at 591 cm ^-1 . These Raman lines exhibit excitation wavelength dependence as shown in FIG.

The excitation wavelength is 488.0 nm to 476.5 nm.
As a result, Ia / Ib changes as the wavelength is changed to 457.9 nm on the short wavelength side. That is, at 488.0 nm, Ia / Ib is smaller than 1.0, but at 457.9 nm,
1.0 or more, compared to 488.0 nm.
The Ia / Ib intensity is reversed. This reversal phenomenon will be explained as follows.

FIG. 4 shows the quinone diimine complex according to the present invention.
Electronic Spec of Nilendiamine-type Solvent Soluble Polyaniline
Indicates a torr. The peak at 647 nm corresponds to quinone diimine
Reduction of phenylenediamine-type solvent-soluble polyaniline
Due to the quinone diimine structure
The peak at 334 nm
Since the strength is increased by reducing aniline,
Π-π of substituted benzene ^*Probably due to the transition. Figure
4 shows the Raman excitation wavelength described above. Where para substitution
For the benzene skeleton stretching vibration band, set the excitation wavelength
Change from 488.0 nm to 457.9 nm on the short wavelength side
Then, 1591cm^-11622cm compared to the band^-1
The resonance condition of the resonance Raman effect of the band
It is thought that the relative intensity change described above occurs.
You.

Next, in the spectra shown in FIGS.
1591cm^-1And 1622cm^-1Intensity of Raman line of
But the same excitation wavelength (457.9 nm)
The differences will be explained as follows. That is,
N, N 'as model compound of phenylenediamine structure
1617 cm of diphenyl-p-phenylenediamine ^-1
Modeling quinone diimine structure with Raman lines only
N, N'-diphenyl-p-benzoquinonedi as compound
1568cm imin^-1And 1621cm^-1With Raman line
Therefore, as shown in (a) below, quinone diimine
Structure and non-conjugated para-substituted benzene ring excites short wavelength light
1622cm increased in strength at^-1Has a Raman line of
As shown in (b), it is conjugated to a quinone diimine structure
The para-substituted benzene ring is 1591 cm^-1And 1622cm^-1
Is presumed to have the Raman line of

[0053]

Embedded image

From the results of the elemental analysis, it is considered that the number of quinone diimines and the number of phenylenediamines are almost equal in the quinone diimine / phenylenediamine solvent-soluble polyaniline. From the connection mode between the structure and the phenylenediamine structure, as shown in (c), an alternating copolymer chain of a quinonediimine structure and a phenylenediamine structure,
As shown in (d), it is classified into two types: a block copolymer chain having a quinone diimine structure and a phenylenediamine structure. In the figure, a para-substituted benzene ring indicated by an arrow indicates a benzene ring that is not conjugated to quinone diimine. In the above alternating copolymer chain, for example, two per octamer chain unit, In a united chain, for example, three per octamer chain unit. If the chain unit is longer, the difference in the number of quinone diimines and non-conjugated benzene rings in both will be even greater. This difference is 1
It can be said that the difference between the relative intensities of the Raman lines at 591 cm ^-1 and 1622 cm ^-1 appears.

[0055]

Embedded image

The quinone diimine / phenylenediamine type solvent-soluble polyaniline contains a large amount of a quinone diimine structure and a non-conjugated benzene ring because the Ia / Ib ratio in the laser Raman spectrum is 1.0 or more. It is considered to have the above-mentioned block copolymer chain.

The organic solvent solubility of the quinone diimine / phenylenediamine type solvent-soluble polyaniline is reasonably explained by having such a block copolymer chain. Generally, the imine nitrogen (-N =) in the quinone diimine structure is replaced by a nearby secondary amino group hydrogen (-NH).
-) Is known to form a hydrogen bond with (Macr
omolecules, 21, 1297 (1988)), the hydrogen bonds between the secondary amino groups are not strong.

Therefore, when polyaniline has the above-mentioned alternating copolymer chain, a strong network of hydrogen bonds as shown in (f) is formed. It is considered that the conventionally known polyaniline is insoluble in many organic solvents even in the undoped state, because it forms such a strong network of hydrogen bonds. On the other hand, when the polymer chain is the block copolymer-like chain like the solvent-soluble polyaniline in the undoped state according to the present invention, the block chains usually have different lengths, so that (e) As seen in (2), even when the phenylenediamine structure portion and the quinonediimine structure portion are adjacent to each other, many hydrogen bonds cannot be formed, and the solvent penetrates between the polymer chains and forms a hydrogen bond with the solvent. To be dissolved in the organic solvent. If the block chains have exactly the same length in all parts, they will form a network of hydrogen bonds as described above, but since the probability of having such a structure is extremely small, it is usually ignored. obtain.

[0059]

Embedded image

[0060]

Embedded image

Further, such an interchain interaction is explained by the in-plane bending vibration of the laser Raman spectrum. The Raman line at 1162 cm ^-1 attributed to the CH in-plane bending vibration of the undoped quinone diimine / phenylenediamine type solvent-soluble polyaniline shown in FIG. 1 indicates that the polyaniline is reduced and all imine nitrogens When converted to a secondary amino nitrogen, there is a high wave number shift to 1181 cm ^-1 .

As described above, the quinone diimine / phenylenediamine type solvent-soluble polyaniline in the undoped state has two Raman lines at 1165 and 1185 cm ^-1 which are attributed to the CH in-plane bending vibration. This 1185 cm ^-1 Raman line is not found in the conventionally known undoped polyaniline,
11 belonging to CH in-plane bending vibration in reduced state
It shows a value close to 81 cm ^-1 .

From these points, it is considered that the quinone diimine / phenylenediamine type solvent-soluble polyaniline has a block copolymer chain in the undoped state and has an atmosphere of a reduced structure. This suggests that the polymer has high solubility in organic solvents despite its high molecular weight. As described above, the quinonediimine / phenylenediamine-type solvent-soluble polyaniline disclosed herein is a novel polymer having a structural chain different from conventionally known polyaniline.

As described above, an oxidized polymer doped with a protonic acid obtained by oxidative polymerization of aniline has, as a repeating unit, a quinone diimine structural unit and a phenylenediamine structural unit in a block copolymer chain. Therefore, in the state doped with a protonic acid, it is described as having conductivity only by an acid-base reaction without an oxidation-reduction reaction.
This conductive mechanism was provided by AG MacDiarmid et al. (AG MacDiarmid et al., J. Chem. Soc., Chem. C.
ommun., 1987, 1784), by doping with a protonic acid, as shown below, the quinone diimine structure is protonated, which takes a semiquinone cation radical structure and has conductivity. Such a state is called a polaron state.

[0065]

Embedded image

As described above, the quinone diimine / phenylenediamine type solvent-soluble polyaniline can be dissolved in an organic solvent and formed into a self-supporting film by a casting method. Into a film to obtain a composite film. Such a film can be easily made conductive by doping it with a protonic acid. Here, the pKa value of the protonic acid is 4.
8 or less can be used.

Before doping, the film has a reflected light color of copper and a transmitted light color of blue, but after doping with a protonic acid, the reflected light has a blue color and the transmitted light has a green color. Further, after doping, a near infrared region (1000
２０００2000 nm) changes significantly. That is, before doping, near-infrared light is almost reflected, but after doping, near-infrared light is almost absorbed.

The conductivity of the conductive film obtained by doping depends on the pKa value of the protonic acid used.
The pKa value of 4.8 for the doping of oxidized aniline polymers.
The following protic acids are effective, and when a pKa value of 1 to 4.8 is used, the conductivity of the resulting film is higher as the pKa value is smaller, that is, as the acidity is stronger. However, when the pKa value is less than 1, the conductivity of the resulting film no longer changes and is almost constant. However, of course, a protonic acid having a pKa value of 1 or less may be used, if necessary.

As described above, the conductivity of a conductive film obtained by doping a quinone diimine / phenylenediamine type solvent-soluble polyaniline with a protonic acid is usually 10 ⁻⁶ S / cm or more, and in many cases, 10 ⁻⁴ S / cm. /
cm or more.

This conductive film is also tough and does not break easily even when bent. However, this conductive film is doped with a protonic acid, similarly to the conductive polymer prepared in the presence of a protonic acid. Due to cross-linking by coupling of radicals generated in the evaporation step, they do not dissolve in the above-mentioned organic solvents.

However, according to the present invention, by reducing the above-mentioned quinonediimine / phenylenediamine-type solvent-soluble polyaniline with a reducing agent, more imino-p-phenylene-type solvent-soluble polyaniline soluble in various organic solvents can be obtained. An organic solvent-soluble conductive polymer-complex can be obtained by oxidatively doping the solvent-soluble imino-p-phenylene-type polyaniline with an electron acceptor.

Examples of the reducing agent include phenylhydrazine, hydrazine, hydrazine hydrate, hydrazine sulfate,
Hydrazine compounds such as hydrazine hydrochloride and reductive metal hydride compounds such as lithium aluminum hydride and lithium borohydride are preferably used. Hydrazine hydrate or phenylhydrazine is particularly preferably used as a reducing agent since no residue is produced after the reduction reaction.

The method for reducing the quinone diimine / phenylenediamine type solvent-soluble polyaniline with the above reducing agent may be a conventional reduction reaction method, and is not particularly limited. For example, quinone diimine / phenylenediamine type solvent-soluble polyaniline is converted to N-methyl-2.
-Dissolving in an organic solvent such as pyrrolidone, adding the above reducing agent to this solution, dissolving the reducing agent in an organic solvent such as N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, and adding quinonediimine. A method of adding phenylenediamine-type solvent-soluble polyaniline or a method of dispersing quinonediimine / phenylenediamine-type solvent-soluble polyaniline in a non-solvent and performing a reduction reaction in a heterogeneous system can be used.

According to the present invention, the reduction reaction is carried out by adding quinone diimine / phenylenediamine type solvent-soluble polyaniline to the polyaniline in an amount of 0.1 to 15% by weight, preferably 0.5 to 10% by weight.
It is performed in a solution containing. The reducing agent may be usually used in an amount equivalent to the amount of quinone diimine in the quinone diimine / phenylenediamine type solvent-soluble polyaniline, but may be used in an amount exceeding the equivalent in order to accelerate the progress of the reaction.

However, when an excessive reducing agent is used, the obtained imino-p-phenylene-type solvent-soluble polyaniline is directly doped with an electron acceptor in a solution state to give a polymer. When imparting conductivity,
Causing undesired side reactions or imino-p-
When the phenylene-type solvent-soluble polyaniline solution is stored for a long period of time, the molecular weight may be reduced due to molecular chain cleavage of the polymer. Therefore, when an excess reducing agent is used,
It is desirable that the obtained imino-p-phenylene-type solvent-soluble polyaniline is separated and purified by a reprecipitation method, and then doped.

The imino-p-phenylene-type solvent-soluble polyaniline thus obtained is quinone diimine.
It has better solubility in various organic solvents than phenylenediamine-type solvent-soluble polyaniline. For example, imino-p-phenylene-type solvent-soluble polyaniline is well dissolved in dimethylformamide, dimethylacetamide, dimethylsulfoxide and the like at a high concentration of several weight% or more.

The reason why the imino-p-phenylene-type solvent-soluble polyaniline is more soluble in the organic solvent is that, as described in the structural analysis of the quinonediimine-phenylenediamine-type solvent-soluble polyaniline by the Raman spectrum, the polymer chain is dissolved. It is considered that the quinone diimine structure in the polymer disappeared by reduction, so that hydrogen bonds between polymer chains were greatly weakened.

In this reduction reaction, the molecular chain is generally not substantially cleaved at the time of the reaction, and the resulting imino-p-phenylene-type solvent-soluble polyaniline is obtained from the initial quinonediimine / phenylenediamine-type solvent-soluble polyaniline. It is confirmed from the measurement of the intrinsic viscosity [η] of the resulting imino-p-phenylene-type solvent-soluble polyaniline that the polymer has the high molecular weight. The resulting imino-p-phenylene-type solvent-soluble polyaniline usually has an intrinsic viscosity [η] of 0.40 dl / g or more measured in N-methyl-2-pyrrolidone at 30 ° C.

The conductive organic polymer according to the present invention can be obtained by bringing the imino-p-phenylene-type solvent-soluble polyaniline into contact with an electron acceptor and doping.

The doping of the imino-p-phenylene type solvent-soluble polyaniline can be carried out by various methods. For example, doping can be performed by adding an electron acceptor to a solution of an imino-p-phenylene-type solvent-soluble polyaniline. In this case, imino
The p-phenylene-type solvent-soluble polyaniline may be used in the state of a solution obtained by reducing quinone diimine / phenylenediamine-type solvent-soluble polyaniline, and if necessary, imino-p-phenylene-type solvent-soluble polyaniline. Is purified by a reprecipitation method or the like.
It may be dissolved in a solvent such as -methyl-2-pyrrolidone to form a solution.

As another method, an electron acceptor may be dissolved in a solvent, and an imino-p-phenylene-type solvent-soluble polyaniline may be added as a powder to the solution. Thus, when the electron acceptor is brought into contact with the imino-p-phenylene-type solvent-soluble polyaniline, it is confirmed that the color of the solution changes and an imino-p-phenylene-type solvent-soluble polyaniline-electron acceptor complex is formed. Is done.

In the present invention, as the electron acceptor,
Both organic and inorganic electron acceptors can be used. In the present invention, an organic electron acceptor preferably used is a compound represented by the general formula (III) Q- [A] _p (wherein Q is

[0083]

Embedded image

A quinone skeleton represented by

[0085]

Embedded image

Wherein R is an alkyl group, and s is 1 to
4 is an integer. ) Quinodimethane skeleton represented by

[0087]

Embedded image

A naphthoquinodimethane skeleton represented by the formula or an ethylene skeleton represented by the formula> C = C <, A represents a monovalent electron-withdrawing group which may be different from each other, and p represents 1 to 4 is an integer. ).

In the above, the electron-withdrawing group is preferably a fluorine atom, a chlorine atom, a bromine atom, a cyano group, a nitro group or a trifluoromethyl group. Accordingly, specific examples of such electron acceptors include, for example, tetrachloro-
p-benzoquinone (chloranil), 2,3-dichloro-5,
6-dicyano-p-benzoquinone, tetrabromo-p-
Benzoquinone, tetrafluoro-p-benzoquinone, 7,
7,8,8-tetracyanoquinodimethane (TCNQ), 2-
Methyl-7,7,8,8-tetracyanoquinodimethane, 2,5-
Dimethyl-7,7,8,8-tetracyanoquinodimethane, 11,1
1,12,12-tetracyano-2,6-naphthoquinodimethane,
Tetracyanoethylene, 2,5-dinitrobenzoquinone,
Examples thereof include 2-trifluoromethyl-7,7,8,8-tetracyanoquinodimethane.

As the inorganic electron acceptor, those having a standard electrode potential defined as an electromotive force of a reduction half-cell reaction of -0.80 V or more based on a standard hydrogen electrode are preferably used. As a specific example, (the standard electrode potential (E ₀ )
(CRC Handbook of Chemistry and Physics, 68th ed.
(CRC Press), D151-D158. ). ), For example, HgCl ₂ (0.92 V), FeCl ₃ (0.77 V).
V), SbCl ₅ (0.75 V), I ₂ (0.5355)
V), K ₃ Fe (CN) ₆ (0.358 V), RuCl ₃
(0.2487V), CuCl ₂ (0.153V), SnC
_{l 4 (0.15V), PbCl 2} (-0.126V), VC
l ₃ (−0.255 V), CoCl ₂ (−0.28 V), Z
nCl ₂ (−0.7618 V) and the like.

These inorganic electron acceptors are N-methyl-
From the viewpoint of solubility in 2-pyrrolidone, an anhydride is used.
Is preferred. Imino-p-phenylene-type solvent-soluble poly
Electron acceptor used for doping aniline
Varies depending on the type, for example, TCNQ
In the case of the above, an imino-p-phenylene type solvent-soluble polymer
Per imino-p-phenylene structural unit of nirin,
With a small amount of 0.15 equivalents, the resulting complex is 10 ⁰
It has high conductivity on the order of S / cm. Generally, imino-
Imino-p of p-phenylene-type solvent-soluble polyaniline
-Up to 0.5 equivalents per phenylene structural unit
By increasing the amount of reaction of the body, the conductivity of the resulting complex
However, the strength of the film after film formation tends to decrease.
In the direction.

The doping of the imino-p-phenylene-type solvent-soluble polyaniline is usually performed using a solution of 0.1 to 15% by weight, preferably 0.5 to 10% by weight of the imino-p-phenylene-type solvent-soluble polyaniline. It is done.
According to the present invention, as described above, by doping the imino-p-phenylene-type solvent-soluble polyaniline in a solution state, a complex in a doped state can be obtained as a solution without causing precipitation.

Therefore, according to the present invention, a self-standing film of the complex can be obtained by casting or coating the complex solution on a glass plate or the like, followed by drying and peeling. In forming such a complex into a film, the concentration of the complex solution is preferably 3 to 10% by weight in terms of the concentration of the imino-p-phenylene-type solvent-soluble polyaniline. Further, according to the present invention, the complex can be immediately formed into a thin film on the substrate by casting or coating the complex solution on an appropriate substrate. Preferably, 0.05 to 2% by weight of the complex solution is converted to a concentration of imino-p-phenylene-type solvent-soluble polyaniline by spin coating, bar coating on a suitable substrate such as a glass plate or a polymer film. The complex can be thinned on the substrate by thinning and drying by an appropriate means such as a method.

In making such a conductive imino-p-phenylene type solvent-soluble polyaniline-electron acceptor complex into a film or a thin film, in order to speed up or facilitate the drying of the solvent, the complex solution may be acetone, acetonitrile or the like. , Isopropyl alcohol, and tetrahydrofuran. The self-supporting film of the complex thus obtained usually has a conductivity of at least 10 ^-2 S / cm. When the complex is formed into a thin film on a substrate, a complex thin film having a surface resistance of 10 ⁸ Ω / □ or less can be easily obtained.

As described above, the quinone diimine / phenylenediamine type solvent-soluble polyaniline in the undoped state has a high intrinsic viscosity [η] of not less than 1.0 dl / g measured at 30 ° C. in N-methyl-2-pyrrolidone. Even when having a molecular weight, it is soluble in aprotic polar organic solvents such as N-methyl-2-pyrrolidone. As described above, this solubility has a structure in which a quinone diimine structure portion and a phenylenediamine structure portion are connected in a block manner, and therefore, a hydrogen bond between an imine nitrogen and a secondary amino group is formed. Is likely to be generated between polymer chains.

However, if this is doped with a protonic acid which is a mineral acid such as hydrochloric acid or sulfuric acid, the solvent becomes insoluble. That is, the imine nitrogen is protonated and has a polaron structure, has a new electronic structure and becomes conductive (electron conductive), and has a salt structure, so that it is difficult to dissolve in an organic solvent. However, as described above, if a protonic acid is selected, for example, if an organic acid such as malonic acid is used, a conductive organic polymer composition in a solvent-soluble doped state can be obtained.

However, according to the present invention, when the quinone diimine / phenylenediamine type solvent-soluble polyaniline is reduced to give an imino-p-phenylene type solvent-soluble polyaniline, the quinone diimine structure is completely lost, so that hydrogen between the polymer chains is reduced. The bonding becomes extremely weak, and as a result, the solubility in various organic solvents is increased, and the organic compounds are dissolved in various organic solvents. Therefore, if such an imino-p-phenylene-type solvent-soluble polyaniline is oxidatively doped with an electron acceptor within a range of appropriate conditions, the solvent solubility can be maintained in a doped state.

Although the reason why the doping of the imino-p-phenylene-type solvent-soluble polyaniline makes it possible to obtain a solvent-soluble doped polyaniline as described above is not necessarily clear, the quinonediimine-phenylenediamine-type solvent-soluble polyaniline is not yet clear. Unlike the case of doping with polyaniline, the solvent is once passed through imino-p-phenylene-type solvent-soluble polyaniline which is excellent in solvent solubility, so that it is considered that the solvent solubility is maintained for some reason in the doped state.

Factors for maintaining the solvent solubility of the imino-p-phenylene type solvent-soluble polyaniline in the doped state include the concentration of the imino-p-phenylene type solvent-soluble polyaniline solution at the time of doping, the type of electron acceptor used, Examples include the reaction amount of the electron acceptor with respect to the imino-p-phenylene type solvent-soluble polyaniline and the concentration in the solution. But in general,
When a relatively small amount of an electron acceptor is used for an imino-p-phenylene-type solvent-soluble polyaniline, that is, when the doping rate is low, the obtained complex in a doped state is
High solubility in solvents.

As described above, the fact that the imino-p-phenylene-type solvent-soluble polyaniline is soluble in the doped state means that the polaron (cation radical) of polyaniline is absorbed in the near infrared region in the electronic spectrum of the solution. This is evident from the fact that the absorption of the anion radical of TCNQ is observed in the visible region, and the ultrafine structure (hfs) is observed in the ESR spectrum of the solution. The ultrafine structure indicates that the cation radical of polyaniline and the anion radical of TCNQ are mixed in a dissolved state.

[0101]

As described above, the imino-p according to the present invention is
The phenylene-type solvent-soluble polyaniline is doped with an electron acceptor to give a polymer complex having conductivity while being soluble in a solvent. That is, according to the present invention, a conductive organic polymer composition soluble in a solvent can be obtained. Such a solvent-soluble conductive organic polymer composition immediately gives a self-supporting conductive film or thin film by casting or coating the solution. It is also easy to obtain a film or a thin film having a large area.

Therefore, the solvent-soluble conductive organic polymer composition according to the present invention can be used for a wide range of applications.
For example, if the conductive organic polymer composition according to the present invention is formed into a thin film on an insulating substrate, the conductive thin film is electronically conductive, without being affected by moisture or moisture.
The substrate can be stably provided with high antistatic performance. In the production of release sheets and adhesive tapes,
If a thin film of the conductive organic polymer composition according to the present invention is formed on a substrate, antistatic properties can be imparted. Furthermore, it can also be suitably used as a solid electrolyte in a solid electrolytic capacitor and an electromagnetic wave shielding material in various electronic devices. Conductive fibers can be obtained immediately by ordinary spinning.

[0103]

The present invention will be described below with reference to examples together with reference examples, but the present invention is not limited to these examples.

Reference Example 1 (Production of Doped Conductive Organic Polymer Composition by Oxidative Polymerization of Aniline) Distilled water was placed in a 10-L separable flask equipped with a stirrer, a thermometer, and a straight pipe adapter.
000g, 36% hydrochloric acid 360mL and aniline 400g
(4.295 mol) were charged in this order to dissolve the aniline. Separately, while cooling with ice water, 434 g (4.295 mol) of 97% concentrated sulfuric acid was added to 1493 g of distilled water in a beaker and mixed to prepare an aqueous sulfuric acid solution. This aqueous sulfuric acid solution was added to the separable flask, and the entire flask was cooled to −4 ° C. in a low-temperature constant temperature bath.

Next, 980 g (4.295 mol) of ammonium peroxodisulfate was added to 2293 g of distilled water in a beaker and dissolved to prepare an oxidizing agent aqueous solution. The entire flask was cooled in a low-temperature constant-temperature bath, and while maintaining the temperature of the reaction mixture at −3 ° C. or lower, the aqueous solution of ammonium peroxodisulfate was added to the acidic aqueous solution of the aniline salt from a straight pipe adapter using a tubing pump while stirring. 1m
It was gradually dropped at a rate of L / min or less. Initially, the colorless and transparent solution turned from green-blue to black-green as the polymerization proceeded, and then a black-green powder was deposited.

During the powder deposition, a rise in the temperature of the reaction mixture is observed.
In order to obtain a high molecular weight polymer, the temperature in the reaction system is set to 0 ° C.
It is important to keep the temperature below, preferably -3 ° C or less. After the powder deposition, the dropping rate of the aqueous solution of ammonium peroxodisulfate may be slightly increased, for example, to about 8 mL / min. However, also in this case, it is necessary to adjust the dropping speed so as to keep the temperature at −3 ° C. or lower while monitoring the temperature of the reaction mixture. After completion of the dropwise addition of the aqueous solution of ammonium peroxodisulfate over a period of 7 hours, stirring was continued for a further 1 hour at a temperature of -3C or lower.

The obtained polymer composition powder was separated by filtration, washed with water and acetone, and dried in vacuum at room temperature to obtain 430 g of a black-green polymer composition powder. This was pressed into a disc having a diameter of 13 mm and a thickness of 700 μm.
The conductivity was measured by the Poe method.
/ Cm.

(Production of quinonediimine / phenylenediamine-type solvent-soluble polyaniline by dedoping of conductive organic polymer composition) 350 g of the above-mentioned doped conductive organic polymer composition powder was added to 4 L of 2N aqueous ammonia. The mixture was stirred at 5,000 rpm for 5 hours with a homomixer. The mixture turned from black green to bluish purple. The powder was filtered off with a Buchner funnel and washed repeatedly with distilled water while stirring in a beaker until the filtrate became neutral, and then washed with acetone until the filtrate became colorless. Thereafter, the powder was vacuum-dried at room temperature for 10 hours to obtain 280 g of a black-brown undoped polymer powder.
I got

This polymer is soluble in N-methyl-2-pyrrolidone and has a solubility of 8 per 100 g of the same solvent.
g (7.4%). Also, use this as a solvent at 30 ° C.
The intrinsic viscosity [η] measured at 1.2 was 1.23. This polymer had a solubility of 1% or less in dimethylsulfoxide and dimethylformamide. Tetrahydrofuran,
It did not substantially dissolve in pyridine, 80% acetic acid aqueous solution, 60% formic acid aqueous solution and acetonitrile.

For a sample obtained by molding this undoped quinone diimine / phenylenediamine type solvent-soluble polyaniline powder into a disk shape, the excitation wavelength was 457.9 nm.
FIG. 1 shows a laser Raman spectrum obtained by irradiating with.

For comparison, see Y. Furukawa et al., Syn.
Th. Met., 16, 189 (1986) shows a laser Raman spectrum obtained by irradiating the undoped polyaniline at an excitation wavelength of 457.9 nm. This polyaniline is obtained by electrolytic oxidation polymerization of aniline on a platinum electrode.

FIG. 3 shows the results of measuring the Raman spectrum in the range of 1400 to 1700 cm ^-1 by changing the wavelength of the laser excitation light. 48 excitation wavelengths
As the wavelength is changed from 8.0 nm to 477.9 nm to 457.9 nm on the short wavelength side, Ia / Ib changes and 45
At 7.9 nm, the intensity is 1.0 or more, indicating that the Ia / Ib intensity is reversed as compared with the case of 488.0 nm. FIG. 4 shows an electronic spectrum.

Next, the above-mentioned organic solvent-soluble polyaniline was subjected to GPC measurement using a GPC column for N-methyl-2-pyrrolidone. As the column, three kinds of columns for N-methyl-2-pyrrolidone were used in combination.
The eluent used was a 0.01 mol / L lithium bromide N-methyl-2-pyrrolidone solution. In FIG.
The result of C measurement is shown.

From these results, it was found that the quinone diimine / phenylenediamine type solvent-soluble polyaniline had a number average molecular weight of 23,000 and a weight average molecular weight of 160,000 (both in terms of polystyrene). Similarly, the reaction conditions were variously changed, and N-methyl-2-pyrrolidone was used at 30 ° C.
To obtain quinone diimine / phenylenediamine type solvent-soluble polyanilines having different intrinsic viscosities [η] measured in the above. Table 1 shows the intrinsic viscosity [η] and the number-average molecular weight and weight-average molecular weight measured by GPC.

[0115]

[Table 1]

Reference Example 2 (Preparation of self-supporting film using soluble aniphosphorylated polymer) 5 g of the undoped aniphosphorylated polymer powder obtained in Reference Example 1 was added to 95 g of N-methyl-2-pyrrolidone. To give a black-blue solution. When this solution was vacuum-filtered with a G3 glass filter, the amount of insolubles remaining on the filter was extremely small. The filter was washed with acetone, the remaining insolubles were dried, and the weight was measured. Therefore, 98.5% of the polymer was dissolved, and 1.5% of the insoluble material was dissolved.
Met.

The thus obtained quinone diimine
A solution of the phenylenediamine-type solvent-soluble polyaniline was cast on a glass plate, and was then wrung with a glass rod. Then, N-methyl-2-pyrrolidone was evaporated in a hot air circulating drier. Thereafter, the polymer film was spontaneously peeled off from the glass plate by immersing the glass plate in cold water, thus obtaining a polymer film having a thickness of 40 μm. The film was washed with acetone and air-dried at room temperature to obtain a copper-colored film having metallic luster.

The strength and solubility of the film differ depending on the drying temperature. When the drying temperature is 100 ° C. or lower, the obtained film dissolves in a small amount in N-methyl-2-pyrrolidone and has relatively low strength. But,
A film obtained by heating at a temperature of 130 ° C. or more is very tough and does not dissolve in N-methyl-2-pyrrolidone or other organic solvents. Also, it does not dissolve in concentrated sulfuric acid. Thus, when heated at a high temperature, the polymer molecules are expected to crosslink with each other in the process and become insoluble.

The undoped quinone diimine / phenylenediamine type solvent-soluble polyaniline film thus obtained was measured by a direct current two-terminal method.
The conductivity was in the order of 10 ⁻¹¹ S / cm. Further, the film was not broken even after being bent 10,000 times, and the tensile strength was 850 kg / cm ² .

Reference Example 3 (Doping of Self-supporting Film with Protonic Acid) In Reference Example 2, the self-supporting films obtained by heating and drying at 160 ° C. for 2 hours were each placed in a 1N aqueous solution of sulfuric acid, perchloric acid and hydrochloric acid at room temperature. After immersion in for 66 hours, the substrate was washed with acetone and air-dried to obtain a conductive film. All films have a dark blue color and van der Pauw
As a result, the conductivity was 9 S / cm,
13 S / cm and 6 S / cm. The tensile strength of the film doped with perchloric acid is 520 kg /
cm ² . Hereinafter, the conductivity of the conductive film is
According to the van der Pau method.

Reference Example 4 (Spectrum and structure of quinone diimine / phenylenediamine type polyaniline soluble in both undoped states and polyaniline formed into an insoluble film) The soluble polymer powder obtained in Reference Example 1 and the soluble polymer powder obtained in Reference Example 2 were obtained. The FT-IR spectra of the insoluble polymer film obtained by the KBr tablet method are shown in FIGS. 6 and 7, respectively. The spectrum of the insoluble polymer film obtained in Reference Example 2 shows the residual solvent N-methyl-
Although the absorption at 1660 cm ^-1 supposedly due to 2-pyrrolidone is observed, the two spectra are almost the same, so that the solvent is insolubilized by crosslinking by heating and drying the solvent after casting of the solvent-soluble polymer. However, no significant change in the chemical structure is observed.

FIG. 8 shows the results of thermogravimetric analysis of the soluble polymer powder and the insoluble polymer film. All have high heat resistance. Considering that the insoluble film does not decompose to higher temperatures, and is insoluble in concentrated sulfuric acid, this indicates that the polymer molecules are crosslinked in the insoluble film.

FIG. 9 shows an ESR spectrum. The spin concentration of the soluble polymer is 1.2 × 10 ¹⁸ spin / g, and as the heating temperature is increased, the spin concentration increases, indicating that radicals are generated by heating.
It is believed that this radical coupling causes the polymer to crosslink and render the heated film insoluble.

Next, the results of elemental analysis of the soluble polymer and the insoluble polymer are shown below. Soluble polymer C, 77.19; H, 4.76; N, 14.86 (total 96.81) Insoluble polymer C, 78.34; H, 4.99; N, 15.16 (total 98.49)

[0125] Based on this elemental analysis, C12.00 was specified.
The composition formula of the rated soluble polymer is C _12.00H_8.82N_1.98
And the composition formula of the insoluble polymer is C_12.00H_9.11N
_1.99It is. On the other hand, similarly, a key standardized to C12.00
Non-diimine structural unit and phenylenediamine structural unit
Are as follows, respectively. Quinone diimine structural unit C₁₂H₈N_Two Phenylenediamine structural unit C₁₂H_TenN_Two Therefore, both the soluble polymer and the solvent-insoluble polymer are described above.
Quinone diimine structural unit and phenylenediamine
It is a polymer consisting of min structural units.

Next, the reflection in the visible to near infrared region of the quinonediimine / phenylenediamine type solvent-soluble polyaniline film obtained in Reference Example 2 and the perchloric acid-doped film obtained in Reference Example 3 was performed. Each spectrum is shown in FIG. In the undoped state, almost near-infrared light is reflected, but after doping, near-infrared light is absorbed, and it is recognized that there is almost no reflection. This is based on absorption by polarons or bipolarons which provides conductivity created by proton acid doping.

By doping the undoped film with perchloric acid, the ESR absorption is greatly increased and the spin concentration reaches 3.8 × 10 ²¹ spin / g.
This is derived from the generated polaron, a semiquinone radical.

Reference Example 5 The polymer films obtained in Reference Example 2 were immersed in aqueous solutions of protonic acids or alcohol solutions having various pKa values, and the possibility of doping was examined. Table 2 shows the conductivity of the polymer composition films obtained by doping with protonic acids having various pKa values. Protonic acids with a pKa value of 4.8 or less are shown to be effective for polymer doping.

[0129]

[Table 2]

Example 1 (Imino-p-phenylene type solvent-soluble polyaniline-
Preparation of TCNQ Conductive Complex Solution) 2.5 g of the quinone diimine / phenylenediamine type solvent-soluble polyaniline obtained in Reference Example 1 was mixed with 97.5 g of N-methyl-2-pyrrolidone.
And dissolved under stirring. To this solution, 0.82 g of phenylhydrazine was gradually added. At this time, the solution changed color from dark blue to light black-brown, and at the same time, generation of nitrogen gas was confirmed.

After the completion of the reaction, the reaction mixture was dropped into 1.5 L of acetone replaced with nitrogen, whereby an off-white precipitate was obtained. The precipitate was separated by filtration with a glass filter, washed several times with acetone substituted with nitrogen, and dried under reduced pressure at room temperature to obtain 2.3 g of imino-p-phenylene-type solvent-soluble polyaniline as an off-white powder. This polymer was stored in a glove box purged with argon. The intrinsic viscosity [η] of this polymer measured in N-methyl-2-pyrrolidone at 30 ° C. was 1.1.

The results of elemental analysis of this polymer are shown. C, 77.48; H, 5.26; N, 14.61; O, 1.82 ( total 99.17) on the basis of the elemental analysis, the polymer of formula according to the present invention normalized the C12.00 is a C _12.00 H _9.71 N _1.94 . On the other hand, the quinone diimine structural unit and the phenylenediamine structural unit similarly standardized to C12.00 are as follows.

Quinonediimine Structural Unit C ₁₂ H ₈ N ₂ Phenylenediamine Structural Unit C ₁₂ H ₁₀ N ₂ Therefore, imino-
The structure of p-phenylene-type solvent-soluble polyaniline is confirmed also from the result of elemental analysis.

FIG. 24 shows the FT of imino-p-phenylene type solvent-soluble polyaniline obtained by the KBr tablet method.
1 shows an IR spectrum. The imino-p-phenylene-type solvent-soluble polyaniline is characterized by extremely low absorption around 1600 cm ^-1 , which corresponds to the fact that the quinone diquimine structure is substantially eliminated by reduction in this polymer. . However, since the stretching movement of the benzene ring is also in this region, the absorption around 1600 cm ^-1 does not completely disappear even if the quinone diquimine structure substantially disappears. The absorption at 1670 cm ^-1 was due to the residual solvent N-
Based on the carbonyl group of methyl-2-pyrrolidone.

Next, separately, 0.00875 g of TCNQ was added to N
-Methyl-2-pyrrolidone was dissolved in 5.0 g. To this solution, 0.025 g of the above imino-p-phenylene-type solvent-soluble polyaniline powder was added. The solution turned from yellow to green. At this time, no precipitation occurred. Thus, a solvent-soluble imino-p-phenylene-type polyaniline-TCNQ complex solution was obtained.

The electronic spectrum of this complex solution at 300 to 1300 nm, the Raman spectrum excited at 457.9 nm, and the ESR spectrum of a solution obtained by diluting the above solution 10 times with N-methyl-2-pyrrolidone are shown in FIGS. And FIG.

In the electronic spectrum, 420, 680, 7
Since absorption specific to the anion radical of TCNQ at 50 and 840 nm and broad absorption corresponding to the radical cation (polaron) of polyaniline in the near infrared region are recognized, the solvent-soluble imino-p-phenylene-type polyaniline-TCNQ complex is observed. That is, it is confirmed that a solvent-soluble conductive polyaniline composition is formed in a doped state.

The Raman spectrum shows a spectrum peculiar to the doped polyaniline composition.
At 1285 cm ^-1 and 1330 cm ^-1 , Raman lines which are considered to be attributed to the TCNQ anion radical are observed. The presence of a large amount of radicals is apparent from the ESR spectrum. This radical is considered to be a semiquinone radical (polaron) of the doped polyaniline composition and an anion radical of TCNQ.

Example 2 (Imino-p-phenylene type solvent-soluble polyaniline-
Preparation of TCNQ Conductive Complex Powder) The complex solution obtained in Example 1 was added to a large amount of acetone to precipitate the complex, which was then separated by filtration through a glass filter and sufficiently washed with acetone. The powder thus obtained is formed into a disc and
When the conductivity was measured by the -method, it was 5.9 x 10 ^-3 S
/ Cm.

The FT-IR, Raman spectrum and ESR spectrum of this powder are shown in FIGS. 14, 15 and 16, respectively. FT-IR shows that the imino-p-phenylene type polyaniline is doped. The Raman spectrum shows a pattern different from that of the complex in the solution described above, but Raman lines due to anion radicals of TCNQ in a solid state are similarly observed at 1285 cm ⁻¹ and 1330 cm ⁻¹ . Also, the presence of a large amount of radicals is apparent from the ESR spectrum.

Example 3 (Imino-p-phenylene type solvent-soluble polyaniline-
Preparation of TCNQ conductive complex film 1) 1.0 g of the imino-p-phenylene-type solvent-soluble polyaniline obtained in Example 1 was dissolved in 9.0 g of N-methyl-2-pyrrolidone with stirring, and When 0.350 g of TCNQ was slowly added, the solution turned from pale black to deep green. However, no precipitate formed at this time.

The obtained solution was cast on a glass plate and dried at 60 ° C. for 1 hour to form a film having a thickness of 22 to 33 μm.
A self-supporting film was obtained. These films had an electrical conductivity of 1.9 to 2.6 S / cm. FIG. 17 shows the Raman spectrum of the complex film. It is shown that this is the same as FIG.

FIG. 18 (a) shows the ESR spectrum of imino-p-phenylene type solvent-soluble polyaniline, and FIG.
FIG. 8 (b) shows the ESR spectrum of TCNQ.
(c) shows the ESR spectrum of the imino-p-phenylene-type solvent-soluble polyaniline composition doped with TCNQ. No radicals are found in imino-p-phenylene-type solvent-soluble polyaniline and TCNQ, but a large amount of radicals are found in the complex. This radical is
As described above, it is based on polaron (semiquinone radical), and indicates that imino-p-phenylene-type polyaniline is in a doped state.

Next, a self-supporting film of the above complex was prepared for 80 to 1
Table 3 shows the electrical conductivity when the film was heat-treated at 40 ° C. for 1 hour and the electrical conductivity when the film was allowed to stand at room temperature and in the air for 15 days. The self-supporting film of the complex according to the present invention has a high electrical conductivity when the heat treatment temperature is 100 ° C. or lower, and the electrical conductivity is reduced even at room temperature for a long period of time in the air. Relatively slight stay.

[0145]

[Table 3]

Example 4 (Imino-p-phenylene type solvent-soluble polyaniline-
Preparation of TCNQ conductive complex film 2) 0.12 g of the quinone diimine / phenylenediamine type solvent-soluble polyaniline obtained in Reference Example 1 was added to phenylhydrazine 0.039.
g was added to a solution of 0.884 g of N-methyl-2-pyrrolidone dissolved under stirring, then 0.042 g of TCNQ was added, and the mixture was further stirred for 35 minutes.

The obtained solution was cast on a glass plate and dried to obtain a free-standing film having a thickness of 60 μm. The conductivity of this film was 8.7 S / cm. The film had an electric conductivity of 5.3 S / cm even after being left at room temperature and in the air for 70 days. FIG. 19 shows the Raman spectrum of this film. It is recognized that the Raman spectrum is the same as that of the complex film shown in Example 3.

Example 5 (Imino-p-phenylene type solvent-soluble polyaniline-
Preparation of TCNQ conductive complex thin film 1) Phenylhydrazine
In 29.7 g of N-methyl-2-pyrrolidone containing 0.1 g, 0.3 g of the quinone diimine / phenylenediamine type solvent-soluble polyaniline obtained in Reference Example 1 was dissolved. 0.035 g of TCNQ was added to 10 g of this solution and stirred for 30 minutes to obtain a solution.

Next, this solution was spin-coated on a glass plate, and heat-treated at 60 to 120 ° C. for 30 to 60 minutes.
Imino-p-phenylene-type solvent-soluble polyaniline-T
A CNQ conductive complex thin film was prepared. Table 4 shows the surface resistance of the thin film thus obtained.

[0150]

[Table 4]

Example 6 (Imino-p-phenylene type solvent-soluble polyaniline-
Preparation of TCNQ conductive complex thin film 2) Phenylhydrazine
In 29.7 g of N-methyl-2-pyrrolidone containing 0.1 g, 0.3 g of the quinone diimine / phenylenediamine type solvent-soluble polyaniline obtained in Reference Example 1 was dissolved. Various amounts of TCNQ were added to 5 g of this solution and stirred for 30 minutes to obtain a solution. Next, this solution was spin-coated on a glass plate and heat-treated at 60 ° C. for 30 minutes to obtain imino-p.
-A phenylene-type solvent-soluble polyaniline-TCNQ conductive complex thin film was prepared.

Table 5 shows the surface resistance of the thin film thus obtained. As is clear from the results shown in Table 5, it is shown that by adjusting the amount of TCNQ with respect to the imino-p-phenylene-type solvent-soluble polyaniline, the conductivity of the obtained complex can be adjusted.

FIG. 20 shows an electronic spectrum at 300 to 1300 nm of the complex thin film obtained by adding 0.0450 g of TCNQ. As in the case of Example 1, the absorption attributed to the cation radical (polaron) of the polyaniline in the near infrared is recognized, indicating that the polyaniline is in a doped state.

[0154]

[Table 5]

Example 7 (Imino-p-phenylene type solvent-soluble polyaniline-
Preparation of TCNQ Conductive Complex Thin Film 3) 0.05 g of the quinone diimine / phenylenediamine solvent-soluble polyaniline obtained in Reference Example 1 was added to 4.95 g of dimethylacetamide in which 0.035 g of phenylhydrazine was dissolved, while stirring. After stirring for 3 hours, a solution was obtained.

Next, this solution was spin-coated on a glass plate and dried under reduced pressure at room temperature to prepare an imino-p-phenylene-type solvent-soluble polyaniline thin film. When the thin film thus obtained was immersed in a solution of TCNQ in tetrahydrofuran, its electronic spectrum changed significantly as shown in FIG. This change indicates that the polyaniline was changed by TCNQ from an imino-p-phenylene-type polyaniline, that is, a reduced undoped state, to an imino-p-phenylene-type polyaniline-TCNQ complex, that is, an oxidized doped state. The surface resistance of the complex thin film in the doped state was 7.5 × 10 ⁸ Ω / □.

Example 8 (Preparation 2 of Polyaniline-TCNQ Complex Solution) Example 1
Imino-p-phenylene-type polyaniline obtained in
1.0 g of N-methyl-2-pyrrolidone solution of TCNQ complex
Was diluted with 4 g of methyl ethyl ketone. At this time, no precipitate was formed. 300-2300 nm of this solution
FIG. 22 shows the electronic spectrum of the sample.

As in the case of the first embodiment, 420, 68
At 0, 750 and 840 nm, absorption specific to the anion radical of TCNQ and broad absorption that is considered to correspond to the radical cation (polaron) of polyaniline in the near infrared region are observed.

Example 9 (Preparation of polyaniline-TCNQ complex thin film 4) Example 8
Was formed on a polyethylene terephthalate film using a wire bar and dried at 60 ° C. to obtain a green thin film. The surface resistance of this thin film is 5.
It was 4 × 10 ⁷ Ω / □. Also, this thin film is made of cotton 100
% Rubbing ten times with the web, the charging potential is 10 V
Met. The half life of the charge amount was 0.1 second. Therefore, the doped imino-p-phenylene-type solvent-soluble polyaniline-TCNQ complex is useful for producing an antistatic material.

Example 10 (Preparation of self-supporting film of polyaniline-chloranil) 1.0 g of the imino-p-phenylene-type solvent-soluble polyaniline obtained in Example 1 was added to N-methyl-2-pyrrolidone 9.
The solution was dissolved in 0 g, and 0.423 g of chloranil was gradually added to the solution. The solution turned from pale black to blue. At this time, no precipitate was formed.

The obtained solution was cast on a glass plate and dried by heating at 60 ° C. for 1 hour.
A μm freestanding film was obtained. The conductivity was 1.2 S / cm. As shown in the Raman spectrum of this film in FIG. 23, polyaniline is in a doped state.

Example 11 (Preparation of self-supporting film of polyaniline-FeCl ₃ ) 1.0 g of the imino-p-phenylene-type solvent-soluble polyaniline obtained in Example 1 was added to N-methyl-2-pyrrolidone 9.
0g, and to this solution 0.278g of anhydrous ferric chloride
Was gradually added, the solution turned from pale black to green-blue. At this time, no precipitate was formed.

The obtained solution was cast on a glass plate and dried by heating at 60 ° C. for 1 hour.
A μm flexible self-supporting film was obtained. Conductivity is 2.8
× 10 ^-2 S / cm. Similarly, a polyaniline-Lewis acid composition self-supporting film was prepared using various Lewis acids. Table 6 shows the standard electrode potential of the used Lewis acid and the conductivity of the obtained film.

[0164]

[Table 6]

Example 12 The conductive imino-p-phenylene type polyaniline-TCNQ complex solution obtained in Example 8 was coated on both sides of a polyethylene terephthalate film in the same manner as in Example 9 to obtain a green conductive polyaniline. A composite film having a thin film was obtained.

A 0.2% toluene solution of polyvinyl stearyl carbamate (release agent) was applied on one of the thin films and dried to form a release surface. Next, an acrylic pressure-sensitive adhesive was applied to a thickness of 30 μm on the other thin film, and a pressure-sensitive adhesive tape was prepared as a roll. The surface resistance of the release agent surface of this adhesive tape was 10 ⁸ Ω / □, and the charging potential of the tape when the tape outer end was peeled off from the roll was almost 0V. In addition, the antistatic performance of the ashtray was examined by visual inspection of the adsorptivity of the ashtray, flocking pile, and the like.

[Brief description of the drawings]

FIG. 1 is a laser Raman spectrum when quinone diimine phenylenediamine type solvent-soluble polyaniline in an undoped state is excited with light having a wavelength of 457.9 nm.

FIG. 2 shows a conventional polyaniline of 45
It is a laser Raman spectrum when excited with light having a wavelength of 7.9 nm.

FIG. 3 is a laser Raman spectrum when the same imino-p-phenylene-type solvent-soluble polyaniline as in FIG. 1 is excited with light having various excitation wavelengths.

FIG. 4 is an electronic spectrum of a quinonediimine / phenylenediamine type solvent-soluble polyaniline solution in N-methyl-2-pyrrolidone.

FIG. 5 is a graph showing an example of the molecular weight distribution of quinone diimine / phenylenediamine type solvent-soluble polyaniline measured by GPC.

FIG. 6 is an FT-IR spectrum of a quinonediimine / phenylenediamine-type solvent-soluble polyaniline in a dedoped state by a KBr tablet method.

FIG. 7 is an FT-IR spectrum of a solvent-insoluble film obtained by casting a quinone diimine / phenylenediamine type solvent-soluble polyaniline by a KBr tablet method.

FIG. 8 is a thermogravimetric analysis diagram of the quinone diimine / phenylenediamine type solvent-soluble polyaniline film and the insolubilized film thereof.

FIG. 9 is a diagram showing a change in ESR spectrum when quinone diimine / phenylenediamine type solvent-soluble polyaniline is heated.

FIG. 10 is a reflection spectrum in the near infrared region of a quinone diimine / phenylenediamine type solvent-soluble polyaniline film in a undoped state and a film doped with perchloric acid.

FIG. 11 is an electronic spectrum of an imino-p-phenylene-type solvent-soluble polyaniline-TCNQ complex solution.

FIG. 12 is a Raman spectrum of the above complex solution at 457.9 nm excitation.

FIG. 13 is an ESR spectrum of the complex solution.

FIG. 14 is an FT-IR spectrum of a powder of an imino-p-phenylene-type solvent-soluble polyaniline-TCNQ complex.

FIG. 15 is a Raman spectrum of a powder of an imino-p-phenylene-type solvent-soluble polyaniline-TCNQ complex.

FIG. 16 is an ESR spectrum of a powder of an imino-p-phenylene-type solvent-soluble polyaniline-TCNQ complex.

FIG. 17 is a Raman spectrum of a film of an imino-p-phenylene-type solvent-soluble polyaniline-TCNQ complex.

FIG. 18 shows ESR spectra of imino-p-phenylene-type solvent-soluble polyaniline, TCNQ, and imino-p-phenylene-type solvent-soluble polyaniline-TCNQ complex.

FIG. 19 is a Raman spectrum of another imino-p-phenylene-type solvent-soluble polyaniline-TCNQ complex film.

FIG. 20 is an electronic spectrum of the complex.

FIG. 21 is an electronic spectrum obtained when an imino-p-phenylene-type solvent-soluble polyaniline is doped with TCNQ.

FIG. 22 is an electronic spectrum of an imino-p-phenylene-type solvent-soluble polyaniline-TCNQ complex solution.

FIG. 23 is a Raman spectrum of a film of an imino-p-phenylene-type solvent-soluble polyaniline-chloranil complex.

FIG. 24 is an FT-IR spectrum of imino-p-phenylene-type solvent-soluble polyaniline.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shinya Akizuki 1-1-2 Shimohozumi, Ibaraki-shi, Osaka Nippon Denko Corporation (72) Inventor Yasuhiro Umemoto 1-1-1-2 Shimohozumi, Ibaraki-shi, Osaka No. Japan Todenko Co., Ltd.

Claims (10)

(57) [Claims] 1. A compound of the general formula (I) Consisting of an imino-p-phenylene structural unit represented by the formula: is soluble in an organic solvent in the undoped state, and has an intrinsic viscosity [η] of 0.40 dl / in N-methyl-2-pyrrolidone measured at 30 ° C. An organic polymer having a weight of at least g. 2. A method of dissolving in N-methyl-2-pyrrolidone,
The organic polymer according to claim 1, which can form a solution having a concentration of 3 to 15% by weight and has an intrinsic viscosity [η] in the range of 0.40 to 1.1 dl / g. 3. A compound of the general formula (I) Consisting of an imino-p-phenylene structural unit represented by the formula: is soluble in an organic solvent in the undoped state, and has an intrinsic viscosity [η] of 0.40 dl / in N-methyl-2-pyrrolidone measured at 30 ° C. A conductive organic polymer composition, wherein an organic polymer having a weight of at least g is doped with an electron acceptor. 4. A compound of the general formula (I) Consisting of an imino-p-phenylene structural unit represented by the formula: is soluble in an organic solvent in the undoped state, and has an intrinsic viscosity [η] of 0.40 dl / in N-methyl-2-pyrrolidone measured at 30 ° C. A conductive organic polymer composition, wherein an organic polymer having a weight of at least g is doped with an electron acceptor and dissolved in an organic solvent. 5. The organic polymer can be dissolved in N-methyl-2-pyrrolidone to form a solution having a concentration of 3 to 15% by weight and the intrinsic viscosity [η] is 0.40 to 1.1 dl / g. The conductive organic polymer composition according to claim 3, wherein 6. A compound of the general formula (II) (In the formula, m and n each represent a mole fraction of the quinone diimine structural unit and the phenylenediamine structural unit in the repeating unit, and are represented by 0 <m <1, 0 <n <1, and m + n = 1.) It comprises a quinone diimine structural unit and a phenylenediamine structural unit, is soluble in an organic solvent in an undoped state, and has an intrinsic viscosity [η] of 0.40 dl measured at 30 ° C. in N-methyl-2-pyrrolidone.
/ g or more, and among the skeleton vibrations of para-substituted benzene in the laser Raman spectrum obtained by excitation with light having a wavelength of 457.9 nm, the Raman line of the skeleton stretching vibration appearing at a higher wavenumber than 1600 cm ^-1 Strength Ia and 1
A general formula (I) characterized in that an organic polymer having a ratio Ia / Ib of Raman line intensity Ib of skeleton stretching vibration having a wave number lower than 600 cm ^-1 of 1.0 or more is reduced with a reducing agent. Formula 5 Consisting of an imino-p-phenylene structural unit represented by the formula: is soluble in an organic solvent in the undoped state, and has an intrinsic viscosity [η] of 0.40 dl / in N-methyl-2-pyrrolidone measured at 30 ° C. A method for producing an organic polymer having a weight of at least g. 7. A reduction half-cell based on a standard hydrogen electrode while maintaining aniline in a solvent in the presence of a protonic acid having an acid dissociation constant pKa value of 3.0 or less, and a temperature of 0 ° C. or less The standard electrode potential determined as the electromotive force in the reaction is 0.6
An aqueous solution of an oxidizing agent having a V of not less than V
An equivalent of one mole of the oxidant divided by the number of electrons required to reduce one molecule of the oxidant, 2 to 2.5 equivalents, plus the aniline doped with the above protonic acid The oxidized polymer of formula (II) is then produced, and the polymer is dedoped with a basic substance to give a compound of the general formula (II) (In the formula, m and n each represent a mole fraction of the quinone diimine structural unit and the phenylenediamine structural unit in the repeating unit, and are represented by 0 <m <1, 0 <n <1, and m + n = 1.) It comprises a quinone diimine structural unit and a phenylenediamine structural unit, is soluble in an organic solvent in an undoped state, and has an intrinsic viscosity [η] of 0.40 dl measured at 30 ° C. in N-methyl-2-pyrrolidone.
/ g or more, and among the skeleton vibrations of para-substituted benzene in the laser Raman spectrum obtained by excitation with light having a wavelength of 457.9 nm, the Raman line of the skeleton stretching vibration appearing at a higher wavenumber than 1600 cm ^-1 Strength Ia and 1
Obtaining an organic polymer having a ratio Ia / Ib of Raman line intensity Ib of skeleton stretching vibration having a wave number lower than 600 cm ^-1 of 1.0 or more, and then reducing this organic polymer with a reducing agent. Characteristic general formula (I) Consisting of an imino-p-phenylene structural unit represented by the formula: is soluble in an organic solvent in the undoped state, and has an intrinsic viscosity [η] of 0.40 dl / in N-methyl-2-pyrrolidone measured at 30 ° C. A method for producing an organic polymer having a weight of at least g. 8. An organic polymer comprising a quinone diimine structural unit represented by the general formula (II) and a phenylenediamine structural unit is dissolved in N-methyl-2-pyrrolidone,
It can form a solution having a concentration of 30% by weight, has an intrinsic viscosity [η] in the range of 0.40 to 1.23 dl / g, and is composed of an imino-p-phenylene structural unit represented by the general formula (I). The polymer can dissolve in N-methyl-2-pyrrolidone to form a 3-15% strength by weight solution,
The method for producing an organic polymer according to claim 6 or 7, wherein the intrinsic viscosity [η] is in the range of 0.40 to 1.1 dl / g. 9. A reduction half-cell based on a standard hydrogen electrode while maintaining aniline in a solvent in the presence of a protic acid having an acid dissociation constant pKa value of 3.0 or less and a temperature of 0 ° C. or less. The standard electrode potential determined as the electromotive force in the reaction is 0.6
An aqueous solution of an oxidizing agent having a V of not less than V
An equivalent of one mole of the oxidant divided by the number of electrons required to reduce one molecule of the oxidant, 2 to 2.5 equivalents, plus the aniline doped with the above protonic acid To form an oxidized polymer of the general formula (II): (In the formula, m and n each represent a mole fraction of the quinone diimine structural unit and the phenylenediamine structural unit in the repeating unit, and are represented by 0 <m <1, 0 <n <1, and m + n = 1.) It comprises a quinone diimine structural unit and a phenylenediamine structural unit, is soluble in an organic solvent in an undoped state, and has an intrinsic viscosity [η] of 0.40 dl measured at 30 ° C. in N-methyl-2-pyrrolidone.
/ g or more, and among the skeleton vibrations of para-substituted benzene in the laser Raman spectrum obtained by excitation with light having a wavelength of 457.9 nm, the Raman line of the skeleton stretching vibration appearing at a higher wavenumber than 1600 cm ^-1 Strength Ia and 1
An organic polymer having a ratio Ia / Ib of Raman line intensity Ib of skeleton stretching vibration having a wave number lower than 600 cm ^-1 of 1.0 or more is obtained, and then the organic polymer is reduced with a reducing agent. General formula (I) Consisting of an imino-p-phenylene structural unit represented by the formula: is soluble in an organic solvent in the undoped state, and has an intrinsic viscosity [η] of 0.40 dl / in N-methyl-2-pyrrolidone measured at 30 ° C. A method for producing a conductive organic polymer composition, comprising: obtaining an organic polymer having a weight of at least g, and then doping the organic polymer with an electron acceptor. 10. An organic polymer comprising a quinone diimine structural unit represented by the general formula (II) and a phenylenediamine structural unit is dissolved in N-methyl-2-pyrrolidone,
It can form a solution having a concentration of about 30% by weight, has an intrinsic viscosity [η] in the range of 0.40 to 1.23 dl / g, and comprises an imino-p-phenylene structural unit represented by the general formula (I). The organic polymer can be dissolved in N-methyl-2-pyrrolidone to form a 3-15% strength by weight solution;
The method for producing a conductive organic polymer composition according to claim 9, wherein the intrinsic viscosity [η] is in the range of 0.40 to 1.1 dl / g.