JPH09227675A - Organic polymer, conductive organic polymer composition, and their preparation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a high-mol.wt. org. polymer comprising an imino-p- phenylene structural unit and a conductive org. polymer compsn. prepared from the org. polymer. SOLUTION: This org. polymer comprises an imino-p-phenylene structural unit represented by the formula, is soluble in dedoped state in an org. solvent, and has an intrinsic viscosity [η] of not less than 0.40dl/g as measured in N- methyl-2-pyrrolidone at 30 deg.C. The conductive org. polymer compsn. comprises the org. polymer doped with an electron receptor.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD 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 containing ionic acid as a dopant by chemical oxidative polymerization of aniline with a chemical oxidant and having an electric conductivity of 10 ^-6 S / cm or more is known. Further, in the production of a conductive organic polymer composition by such a known chemical oxidative polymerization, the standard electrode potential defined as an electromotive force in a reducing half-cell reaction with a standard hydrogen electrode as a reference is 0.6 V or more. The fact that an oxidizing agent is particularly preferably used is already disclosed in JP-A-61-2.
It is described in Japanese Patent No. 58831.

However, since the conductive organic polymer composition is insoluble and infusible in general, it cannot be formed into a film by the casting method, and therefore, in developing the application of the conductive organic polymer composition. It is a big obstacle. JP-A-60-235831 and J. Polymer Sci., P
As described in olymer Chem. Ed., 26, 1531 (1988), electro-oxidative polymerization of aniline can form a film of a conductive organic polymer composition on an electrode. Since the formation surface is limited to the electrode surface,
It is difficult to obtain a large area film, and the manufacturing cost is high because of the 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, when this method is used, treatment at a high temperature is required, or the conversion of the intermediate to the conductive polymer composition does not always proceed according to the theory. From the aspect, it is not practical as a method for producing a conductive organic polymer composition film.

Polymers soluble in organic solvents are known in the field of polypyrrole or polythiophene. That is,
A thiophene having a long-chain alkyl group as a substituent or a pyrrole having an alkanesulfonic acid group as a substituent can be electrooxidatively polymerized to obtain an organic solvent-soluble poly-3-alkylthiophene and a water-soluble polypyrrole alkanesulfonic acid, respectively. it can. A film of 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 molar amount of ammonium peroxodisulfate was made to act as an oxidant with respect to aniline to chemically oxidize aniline to dissolve it in an organic solvent. 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 N-methyl-2-
80% as well as pyrrolidone and dimethyl sulfoxide
Since it is also soluble in acetic acid and a 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 polymer N-methyl-2-pyrrolidone or dimethylsulfoxide. Further, 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 a film dedoped with ammonia. However, this undoped film has low strength because of 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 which is 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 diligent research to obtain a high molecular weight organic polymer soluble in an organic solvent by chemical oxidative polymerization of aniline, it has a much higher molecular weight than conventionally known polyaniline, but in a dedoped state, it can be used in various organic solvents. As a result of finding soluble quinonediimine / phenylenediamine type polyaniline and further researching the polyaniline, the organic solvent-soluble polyaniline was reduced with a reducing agent to obtain imino-p-phenylene type solvent-soluble polyaniline, and then, By doping it with an electron acceptor, it is still soluble in an organic solvent even in the doped state, and it has a self-sustaining property from the solution by a casting method, and is also tough and flexible. It is possible to obtain a film of the polyaniline composition, 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]

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It is composed of an imino-p-phenylene structural unit represented by the following formula, is soluble in an organic solvent in the undoped state, and is in N-methyl-2-pyrrolidone at 30 ° C.
It is characterized in that the intrinsic viscosity [η] measured in step 4 is 0.40 dl / g or more. Hereinafter, an organic polymer which is composed of the imino-p-phenylene structural unit represented by the general formula (I) and is soluble in an organic solvent is referred to as an imino-p-phenylene type solvent-soluble polyaniline.

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

[0013]

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(In the formula, m and n represent the mole fractions of the quinonediimine structural unit and the phenylenediamine structural unit in the repeating unit, and 0 <m <1, 0 <n <1, m +.
n = 1. ), A quinonediimine structural unit and a phenylenediamine structural unit, which are soluble in an organic solvent in a dedoped state, and have an intrinsic viscosity [η] measured at 30 ° C. in N-methyl-2-pyrrolidone.
Is 0.40 dl / g or more and the skeletal vibration of para-substituted benzene in the laser Raman spectrum obtained by excitation with light having a wavelength of 457.9 nm is 1600 cm ^-1.
Reduction of an organic polymer having a ratio Ia / Ib of the Raman line intensity Ia of skeletal stretching vibration appearing at a higher wave number than that and the Raman line intensity Ib of skeletal stretching vibration appearing at a lower wave number than 1600 cm ^-1 is 1.0 or more It can be obtained by reducing with an agent.

Hereinafter, an organic polymer which is composed of the quinonediimine structural unit represented by the general formula (II) and the phenylenediamine structural unit and is soluble in an organic solvent is referred to as a quinonediimine / phenylenediamine type solvent-soluble polyaniline. The conductive organic polymer composition according to the present invention has the general formula (I)

[0016]

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It is composed of an imino-p-phenylene structural unit represented by the formula (1), is soluble in an organic solvent in the undoped state, and is in N-methyl-2-pyrrolidone at 30 ° C.
The organic polymer having an intrinsic viscosity [η] of 0.40 dl / g or more measured in 1. is doped with an electron acceptor. Such a conductive organic polymer composition according to the invention thus has the unexpected and surprising property of being soluble in various organic solvents even in the doped conductive state.

The conductive organic polymer composition according to the present invention can be obtained by doping the 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.

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

[0020]

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(In the formula, m and n represent the mole fractions of the quinonediimine structural unit and the phenylenediamine structural unit in the repeating unit, and 0 <m <1, 0 <n <1, m +.
n = 1. ), A quinonediimine structural unit and a phenylenediamine structural unit, which are soluble in an organic solvent in a dedoped state, and have an intrinsic viscosity [η] measured at 30 ° C. in N-methyl-2-pyrrolidone.
Is 0.40 dl / g or more and the skeletal vibration of para-substituted benzene in the laser Raman spectrum obtained by excitation with light having a wavelength of 457.9 nm is 1600 cm ^-1.
An organic polymer having a ratio Ia / Ib of the Raman line intensity Ia of the skeletal stretching vibration appearing at a higher wave number and the Raman line intensity Ib of the skeletal stretching vibration appearing at a lower wave number than 1600 cm ⁻¹ is 1.0 or more, , Quinonediimine / phenylenediamine type solvent-soluble polyaniline can be obtained by reduction with a reducing agent.

The quinonediimine / phenylenediamine type solvent-soluble polyaniline is added to 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 5 ° C. or less, An aqueous solution of an oxidant having a standard electrode potential of 0.6 V or more, which is defined as an electromotive force in a reducing half-cell reaction with a standard hydrogen electrode as a reference, is preferably maintained at a temperature of 0 ° C. or lower per 1 mol of aniline. An equivalent amount, defined as the amount of one mole of oxidant divided by the number of electrons required to reduce one molecule of oxidant, 2
It is obtained by gradually adding an equivalent amount or more, preferably 2 to 2.5 equivalents to form an oxidized polymer of aniline doped with the above-mentioned protic acid, and then dedoping this polymer with a basic substance. You can The amount of the above-mentioned oxidizing agent will be described using a mathematical formula. When 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, the reducing agent is Therefore, the above-mentioned oxidizing agent is used in the range of 2 M / n to 2.5 M / n with respect to 1 mol of aniline.

In the method for producing an aniline oxidation polymer doped with the above-mentioned protonic acid, the oxidizing agent may be manganese dioxide, ammonium peroxodisulfate, hydrogen peroxide, ferric salt, iodate or the like. Particularly preferably used. Of 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 1 mol of aniline is used.

The protonic acid used in the oxidative polymerization of aniline is not particularly limited as long as the acid dissociation constant pKa value is 3.0 or less, and examples thereof include hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, and borofluoride. Hydrofluoric acid, phosphorohydrofluoric acid,
Inorganic acids such as hydrofluoric acid and hydroiodic acid, aromatic sulfonic acids such as benzenesulfonic acid and p-toluenesulfonic acid, alkanesulfonic acids such as methanesulfonic acid and 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 protic acid used depends on the reaction mode 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 protic acid in an equimolar amount to the oxidizing agent.

As a solvent in the oxidative polymerization of aniline, aniline, a protonic acid and an oxidizing agent are dissolved, and
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 production of the oxidative polymer of aniline doped with such a protonic acid, the temperature of the reaction mixture is kept at 5 during the oxidation reaction of aniline, particularly during the addition of the oxidizing agent solution to the aniline solution. It is important to keep below ℃. 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 oxidant is rapidly added, the temperature of the reaction mixture rises even by cooling from the outside,
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] (hereinafter the same) measured at 30 ° C. in N-methyl-2-pyrrolidone by dedoping the aniline oxide polymer in the doped state thus obtained.
It is possible to obtain a quinone diimine / phenylenediamine type solvent-soluble polyaniline having a high molecular weight of 1.0 dl / g or more.

Since the above-mentioned oxidative polymer of aniline doped with a protic acid forms a salt with a protic acid, in many cases, the concentration is usually high enough to prepare a self-supporting film. It does not dissolve in organic solvents. Generally, it is well known that salts of high molecular weight amines are poorly soluble in many organic solvents. However, the quinone diimine / phenylenediamine type solvent-soluble polyaniline can be obtained by dedoping the organic polymer-insoluble aniline oxidation polymer.

In this manner, the oxidative polymer of aniline doped with the protonic acid used is dedoped to obtain a quinonediimine / phenylenediamine type solvent-soluble polyaniline, which is used as a dilute solution of N-methyl-2-pyrrolidone, for example. For example, when doped with an organic acid such as malonic acid, a polyaniline composition in a doped state can be obtained while being soluble in a solvent.

Since the dedoping of the aniline oxide polymer doped with the above-mentioned protonic acid is a kind of neutralization reaction, a basic substance which can neutralize the protonic acid as a dopant is particularly preferable. 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, the basic substance may be added directly 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 polymer composition in the doped state obtained by the oxidative polymerization of aniline usually has a conductivity of 10 ^-6 S / cm or more and exhibits a black green color, but after dedoping,
It is a purple or purplish copper color. This discoloration is because the amine nitrogen of the salt structure in the polymer composition was changed to a free amine. The electrical conductivity is usually on the order of 10 ^-10 S / cm.

The dedoped 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-
Pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, 1,3-dimethyl-2-imidazolidinone, sulfolane and the like can be mentioned. The solubility depends on the average molecular weight of the polymer and the solvent, but 0.5 to 100% of the polymer dissolves and a solution of 1 to 30% by weight can be obtained.

Particularly, this quinonediimine / phenylenediamine type solvent-soluble polyaniline is N-methyl-2-
It shows high solubility in pyrrolidone and is usually 20 to
100% dissolves and a 3-30 wt% solution can be obtained. However, it does not dissolve in tetrahydrofuran, 80% acetic acid aqueous solution, 60% formic acid aqueous solution, acetonitrile or the like.

Therefore, the quinonediimine / phenylenediamine type solvent-soluble polyaniline can be dissolved in an organic solvent and formed into a film by the casting method. For example, after casting a quinonediimine 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 self-supporting film that is uniform, tough, and has excellent flexibility.

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

Furthermore, the film obtained by casting the quinonediimine / phenylenediamine type solvent-soluble polyaniline has different properties depending on the drying conditions of the solvent. Usually, when casting an N-methyl-2-pyrrolidone solution of a soluble polymer having an intrinsic viscosity [η] of 0.40 or more on a glass plate and drying the solvent,
When the drying temperature is 100 ° C. or lower, the strength of the obtained film is not sufficiently high, and the N-methyl-2
-Partially soluble in pyrrolidone. However, the drying temperature is 1
When the temperature is 30 ° C. or higher, the obtained film has excellent flexibility, is extremely tough, and does not crack even when bent. The film thus obtained is N
-Not soluble in methyl-2-pyrrolidone, nor in concentrated sulfuric acid. Thus, it is considered that the solvent insolubilization of the polymer by solvent drying at a high temperature after casting is due to the cross-linking of the polymer molecules by the coupling of radicals existing in the polymer or generated during heating.

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

[0039]

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

A film obtained by using the quinonediimine / phenylenediamine type solvent-soluble polyaniline to insolubilize the solvent by the casting method also shows an infrared absorption spectrum substantially the same 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 and the like, it is considered that they have a cross-linked structure but substantially the same repeating unit.

The characteristics of the quinonediimine phenylenediamine type solvent-soluble polyaniline obtained from the laser Raman spectrum will now be described in comparison with so-called polyaniline which is conventionally known.

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

An infrared absorption spectrum is obtained by detecting 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.

The Raman spectrum is usually obtained by excitation with visible light from an argon laser or the like. Here, it is known that when the sample has an absorption band in the visible region, a very strong Raman line can be obtained when the irradiation laser beam and the absorption band wavelength thereof match. This phenomenon is called the resonance Raman effect, and according to this, a strong Raman line 10 ⁴ to 10 ⁵ times as strong as a normal Raman line can be obtained. According to the resonance Raman effect, information on the chemical structure portion excited by the wavelength of the irradiated laser light is more emphasized and obtained. Therefore, the chemical structure of the sample can be analyzed more accurately by measuring the Raman spectrum while changing the wavelength of the laser light to be irradiated. 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 sample of quinonediimine / phenylenediamine type solvent-soluble polyaniline powder in the undoped state having an intrinsic viscosity [η] of 1.2 dl / g measured at 30 ° C. was irradiated at an excitation wavelength of 457.9 nm on a disk-shaped sample. It is the obtained laser Raman spectrum. The assignment of the Raman line is as follows. 1622 and 1591 cm ^-1 are skeleton stretching vibrations of para-substituted benzene, 1489 and 1479 cm.
^-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 It is vibration.

FIG. 2 shows Y. Furukawa et al., Synth. Me.
It is a laser Raman spectrum obtained by irradiating the polyaniline in the undoped state shown in T., 16, 189 (1986) at an excitation wavelength of 457.9 nm. This polyaniline was obtained by electrolytic oxidative 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
The ratio Ia / Ib with b is 1.0 or more. On the contrary,
All of the conventionally known polyanilines including the polyaniline shown in FIG. 2, including those produced by chemical oxidative polymerization, have the above ratio Ia / 1b smaller than 1.0.

The Raman lines at 1622 and 1591 cm ^-1 are
Both are based on the skeleton stretching vibration of para-substituted benzene. Since polyaniline in the reduced state does not have a quinonediimine structure, Raman lines are generated only at 1621 cm ⁻¹ , but in the undoped polyaniline having a quinonediimine structure, 1622 and 1
Raman lines appear at 591 cm ^-1 . These Raman lines exhibit excitation wavelength dependence as shown in FIG.

Excitation wavelength from 488.0 nm to 476.5 nm
Ia / Ib changes as the wavelength is changed to 457.9 nm on the short wavelength side. That is, when 488.0 nm, Ia / Ib is smaller than 1.0, but when 457.9 nm,
It is 1.0 or more, compared to when it is 488.0 nm.
The Ia / Ib intensity is reversed. This reversal phenomenon will be explained as follows.

FIG. 4 shows a quinone diimine compound according to the present invention.
Electron spectroscopy of nylenediamine type solvent-soluble polyaniline
Indicates a torr. The peak at 647 nm is quinone diimine
Reduction of phenylenediamine type solvent soluble polyaniline
It disappears due to the quinone diimine structure.
The peak at 334 nm is expected to
The strength is increased by reducing aniline.
Π-π of substituted benzene ^*It seems to be derived from the transition. Figure
4 shows the Raman excitation wavelength described above. Where para substitution
For the band of the benzene skeleton stretching vibration,
Change from 488.0 nm to 457.9 nm to shorter wavelength side
Then, 1591 cm^-11622 cm compared to other bands^-1
The resonance condition of the resonance Raman effect of the band becomes more advantageous
It is thought that the above-mentioned changes in relative intensity will occur.
You.

Next, in the spectra shown in FIG. 1 and FIG.
1591 cm^-1And 1622 cm^-1Raman line relative intensity
Though they have the same excitation wavelength (457.9 nm)
Instead, the difference will be explained as follows. That is,
N, N 'as model compounds of phenylenediamine structure
1617 cm of -diphenyl-p-phenylenediamine ^-1
Modeling quinonediimine structure with Raman line only
N, N'-diphenyl-p-benzoquinonedi as a compound
Imine is 1568 cm^-1And 1621 cm^-1Raman line on
Therefore, as shown in (a) below, quinone diimine
The para-substituted benzene ring, which is not conjugated with the structure, excites short-wavelength light.
1622 cm with increased strength^-1Has the Raman line of
As shown in (b), it is conjugated with a quinone diimine structure.
Para-substituted benzene ring is 1591 cm^-1And 1622 cm^-1
It is estimated to have a Raman line of.

[0053]

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From the results of elemental analysis, it is considered that the number of quinonediimines and the number of phenylenediamines are almost equal in the quinonediimine / phenylenediamine type solvent-soluble polyaniline. Therefore, the quinonediimine / phenylenediamine type solvent-soluble polyaniline structural chain is From the coupling mode between the structure and the phenylenediamine structure, as shown in (c), an alternating copolymeric chain of a quinonediimine structure and a phenylenediamine structure,
As shown in (d), it is classified into two types, that is, a block copolymeric chain having a quinonediimine structure and a phenylenediamine structure. In the figure, the para-substituted benzene ring indicated by an arrow represents a benzene ring that is non-conjugated with quinonediimine, and in the above alternating copolymeric chain, for example, there are two per octamer chain unit and the block copolymerization In coalescing chains, for example, there are three per octamer chain unit. When the chain unit is longer, the difference between the numbers of quinonediimine and the non-conjugated benzene ring in both is further increased. This difference is 1
It can be said that this appears as a difference in the relative intensities of Raman lines at 591 cm ^-1 and 1622 cm ^-1 .

[0055]

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In the quinonediimine / phenylenediamine type solvent-soluble polyaniline, since the Ia / Ib ratio in the laser Raman spectrum is 1.0 or more, many benzene rings not conjugated with the quinonediimine structure are contained, and thus, It appears to have the block copolymeric chain.

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

Therefore, when polyaniline has the alternating copolymeric chain, it forms a strong network of hydrogen bonds as shown in (f). 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 copolymeric chain as in the solvent-soluble polyaniline in the undoped state according to the present invention, the block chains usually have different lengths. ), Even if the phenylenediamine structure part and the quinonediimine structure part are adjacent to each other, many hydrogen bonds cannot be formed, the solvent penetrates between the polymer chains, and hydrogen bonds with the solvent. And is dissolved in the organic solvent. If every part of the block chain had the exact same length, it would form a hydrogen bond network as described above, but since the probability of having such a structure is extremely small, it is usually ignored. obtain.

[0059]

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[0060]

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Further, such interchain interaction can be explained from the C—H in-plane bending vibration of the laser Raman spectrum. The Raman line at 1162 cm ^-1 attributed to the C-H in-plane bending vibration of the quinonediimine / phenylenediamine type solvent-soluble polyaniline in the undoped state shown in FIG. When converted to secondary amino nitrogen, it undergoes a high wavenumber shift to 1181 cm ^-1 .

As described above, the quinonediimine / phenylenediamine type solvent-soluble polyaniline has two Raman lines of 1165 and 1185 cm ⁻¹ which are attributed to the C—H in-plane bending vibration in the dedoped state. This 1185 cm ^-1 Raman line is not found in the conventionally known undoped polyaniline.
Attributable to C-H in-plane bending vibration in the reduced state 11
A value close to 81 cm ^-1 is shown.

From these points, it is considered that the quinonediimine / phenylenediamine type solvent-soluble polyaniline has a block copolymer chain in the dedoped 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 that of conventionally known polyaniline.

As described above, the oxidative polymer obtained by the oxidative polymerization of aniline and doped with a protonic acid has, as a repeating unit, a quinonediimine structural unit and a phenylenediamine structural unit in a block copolymeric chain. Therefore, it is described as having conductivity by the acid-base reaction alone without being accompanied by the redox reaction in the state of being doped with a protonic acid.
This conduction mechanism is due to AG MacDiarmid et al. (AG MacDiarmid et al., J. Chem. Soc., Chem. C.
ommun., 1987, 1784), as shown below, the quinonediimine structure is protonated by doping with a protonic acid, and this has a semiquinone cation radical structure and is conductive. Such a state is called a polaron state.

[0065]

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As described above, the quinonediimine / phenylenediamine type solvent-soluble polyaniline can be dissolved in an organic solvent to form a self-supporting film by the casting method, and can be cast on a suitable substrate by the casting method. It is also possible to obtain a composite film by forming a composite film. And such a film can easily be made conductive by doping it with a protic acid. Here, as a protonic acid, the pKa value is 4.
8 or less can be used.

Before the film is doped, the reflected light has a copper color and the transmitted light has a blue color, but after the film is doped with a protonic acid, the reflected light has a blue color and the transmitted light has a green color. After doping, the near infrared region (1000
(-2000 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.
A pKa value of 4.8 is used for doping aniline oxide polymer.
The following protic acids are effective, and when a protic acid having a pKa value of 1 to 4.8 is used, the smaller the pKa value, that is, the stronger the acidity, the higher the conductivity of the obtained film. However, when the pKa value is less than 1, the conductivity of the resulting film is almost unchanged and is almost constant. However, as a matter of course, if necessary, a protonic acid having a pKa value of 1 or less may be used.

Thus, the electroconductivity of the electroconductive film obtained by doping the quinonediimine / phenylenediamine type solvent-soluble polyaniline with the protonic acid is usually 10 ⁻⁶ S / cm or more, and in most cases 10 ⁻⁴ S. /
cm or more.

This conductive film is also tough and does not easily break when bent. However, since this conductive film is doped with a protonic acid as in the case of a conductive polymer prepared in the presence of a protonic acid, for the reasons described above, the heating of the solvent during the film preparation was also performed. It does not dissolve in the above-mentioned organic solvent due to the crosslinking due to the coupling of radicals generated in the evaporation step.

However, according to the present invention, imino-p-phenylene type solvent-soluble polyaniline more soluble in various organic solvents can be obtained by reducing the quinonediimine / phenylenediamine type solvent-soluble polyaniline described above with a reducing agent. Further, 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 the reducing agent because it does not produce a residue after the reduction reaction.

The method for reducing the quinonediimine / phenylenediamine type solvent-soluble polyaniline with the above-mentioned reducing agent may be a usual reduction reaction method, and is not particularly limited. For example, quinonediimine / phenylenediamine type solvent-soluble polyaniline is added to N-methyl-2.
-Dissolving in an organic solvent such as pyrrolidone and adding the reducing agent to the solution; dissolving the reducing agent in an organic solvent such as N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, etc., and adding quinonediimine A phenylenediamine-type solvent-soluble polyaniline may be added, or a quinonediimine / phenylenediamine-type solvent-soluble polyaniline may be dispersed in a non-solvent to carry out a reduction reaction in a heterogeneous system.

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

However, as described above, 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. To give conductivity,
Undesirable side reactions may occur or imino-p-
When a solution of a phenylene-type solvent-soluble polyaniline is stored for a long period of time, the molecular weight may be reduced due to the molecular chain scission of the polymer. Therefore, when excess reducing agent is used,
It is desirable that the imino-p-phenylene type solvent-soluble polyaniline obtained 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 a wider variety of organic solvents than phenylenediamine type solvent-soluble polyaniline. For example, imino-p-phenylene type solvent-soluble polyaniline is well soluble in dimethylformamide, dimethylacetamide, dimethylsulfoxide and the like at a high concentration of several wt% or more.

As described above, the imino-p-phenylene type solvent-soluble polyaniline is more soluble in the organic solvent as described in the structural analysis by Raman spectrum of quinone diimine / phenylenediamine type solvent-soluble polyaniline. It seems that the hydrogen bond between the polymer chains is significantly weakened because the quinonediimine structure in the polymer disappears due to the reduction.

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

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

The imino-p-phenylene type solvent-soluble polyaniline can be doped by various methods. For example, doping can be performed by adding an electron acceptor to a solution of imino-p-phenylene type solvent-soluble polyaniline. In this case, Imino-
The p-phenylene-type solvent-soluble polyaniline may be used in a solution state obtained by reducing the quinonediimine / phenylenediamine-type solvent-soluble polyaniline, and, if necessary, imino-p-phenylene-type solvent-soluble polyaniline. Is purified by a reprecipitation method, etc.
A solution may be prepared by dissolving it in a solvent such as -methyl-2-pyrrolidone.

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

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

[0083]

Embedded image

A quinone skeleton represented by

[0085]

[Chemical 21]

(In the formula, R represents an alkyl group, and s is 1 to
4 is an integer. ) Quinodimethane skeleton represented by

[0087]

Embedded image

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

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. Therefore, specific examples of such an electron acceptor 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,
2-trifluoromethyl-7,7,8,8-tetracyanoquinodimethane and the like can be mentioned.

As the inorganic electron acceptor, those having a standard hydrogen electrode as a reference and a standard electrode potential defined as an electromotive force of a reduction half-cell reaction of −0.80 V or more are preferably used. A specific example is (standard electrode potential (E ₀ ) in parentheses
(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 (0.75V), I ₂ (0.5355)
V), K ₃ Fe (CN) ₆ (0.358V), RuCl ₃
(0.2487V), CuCl ₂ (0.153V), SnC
l ₄ (0.15V), PbCl ₂ (-0.126V), VC
_{l 3 (-0.255V), CoCl 2} (-0.28V), Z
nCl ₂ (-0.7618V), and the like can be given.

These inorganic electron acceptors are N-methyl-
From the viewpoint of solubility in 2-pyrrolidone, anhydrous is used.
Is preferred. Imino-p-phenylene type solvent soluble poly
An electron acceptor used for doping aniline
The amount depends on the type, for example, TCNQ
In the case of, imino-p-phenylene type solvent-soluble polyol
Per imino-p-phenylene structural unit possessed by niline,
With a small amount of 0.15 equivalents, the resulting complex is 10 ⁰
It has high conductivity in the S / cm range. In general, imino-
Imino-p of p-phenylene type solvent-soluble polyaniline
-Up to 0.5 equivalent per phenylene structural unit
Conductivity of the complex obtained by increasing the reaction amount of the body
However, on the other hand, there is a tendency that the strength of the film after film formation decreases.
In the direction.

Doping of the imino-p-phenylene type solvent-soluble polyaniline is usually carried out 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. Will be performed.
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-supporting film of a complex can be obtained by casting or coating such a 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, the concentration of the imino-p-phenylene type solvent-soluble polyaniline is converted to 0.05 to 2% by weight of the complex solution on a suitable substrate such as a glass plate or a polymer film by spin coating or bar coating. The complex can be formed into a thin film on the substrate by making it into a thin film and drying it by an appropriate means such as a method.

In order to form a film or a thin film of such a conductive imino-p-phenylene type solvent-soluble polyaniline-electron acceptor complex, in order to accelerate or facilitate the drying of the solvent, the complex solution is acetone or acetonitrile. A solvent such as isopropyl alcohol or tetrahydrofuran may be contained. The self-supporting film of the complex thus obtained usually has an electric conductivity of 10 ^-2 S / cm or more. Further, when the complex is formed into a thin film on the substrate, a complex thin film having a surface resistance of 10 ⁸ Ω / □ or less can be easily obtained.

As described above, the quinonediimine / phenylenediamine type solvent-soluble polyaniline in the undoped state has a high intrinsic viscosity [η] of 1.0 dl / g or more measured at 30 ° C. in N-methyl-2-pyrrolidone. Even when it has 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 the quinone diimine structure portion and the phenylenediamine structure portion are connected in a block-like manner, and therefore, the hydrogen bond between the imine nitrogen and the secondary amino group. Is believed to be difficult to form between polymer chains.

However, if this is doped with a protic acid which is a mineral acid such as hydrochloric acid or sulfuric acid, it becomes insoluble in the solvent. That is, the imine nitrogen is protonated and has a polaron structure, which has a new electronic structure and becomes conductive (electroconductive), while it has a salt structure, which makes it 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 solvent-soluble conductive organic polymer composition in a doped state can be obtained.

However, when the imino-p-phenylene-type solvent-soluble polyaniline is reduced by reducing the quinonediimine-phenylenediamine-type solvent-soluble polyaniline according to the present invention, the quinonediimine structure is completely eliminated. The bond becomes extremely weak, and as a result, the solubility in various organic solvents is increased and the organic solvent is dissolved in various organic solvents. Therefore, if the imino-p-phenylene type solvent-soluble polyaniline is subjected to oxidative doping with an electron acceptor within the range of appropriate conditions, the solvent solubility can be maintained in the doped state.

The reason why a solvent-soluble polyaniline in a doped state can be obtained by doping with an imino-p-phenylene type solvent-soluble polyaniline is not necessarily clear yet, but it is not clear that it is quinonediimine / phenylenediamine type solvent-soluble. Unlike the case of doping with polyaniline, it seems that the solvent solubility is maintained for some reason in the doped state because it passes through imino-p-phenylene type solvent-soluble polyaniline, which is excellent in solvent solubility.

Factors for maintaining the solvent solubility of the imino-p-phenylene type solvent-soluble polyaniline in the doped state are the concentration of the imino-p-phenylene type solvent-soluble polyaniline solution at the time of doping, the type of electron acceptor used, The reaction amount of the electron acceptor with respect to the imino-p-phenylene type solvent-soluble polyaniline and the concentration in the solution can be mentioned. But in general,
When a relatively small amount of electron acceptor is used for imino-p-phenylene type solvent-soluble polyaniline, that is, when the doping ratio is low, the obtained complex in the doped state is
Highly soluble in solvent.

Thus, the fact that the imino-p-phenylene type solvent-soluble polyaniline is soluble in the doped state shows absorption of polaron (cation radical) of polyaniline in the near infrared region in the electronic spectrum of the solution. It is clear from the fact that absorption of anion radicals of TCNQ is observed in the visible region, and that the hyperfine structure (hfs) is observed in the ESR spectrum of the solution. The above-mentioned ultrafine structure shows a mixture of cation radicals of polyaniline and anion radicals of TCNQ in a dissolved state.

[0101]

INDUSTRIAL APPLICABILITY As described above, the imino-p according to the present invention
The phenylene type solvent-soluble polyaniline is doped with an electron acceptor to give a polymer complex having conductivity while being soluble in the solvent. That is, according to the present invention, a solvent-soluble conductive organic polymer composition 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 thin film having a large area.

Therefore, the solvent-soluble conductive organic polymer composition according to the present invention can be used in a wide variety 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, since the conductive thin film is electronically conductive, it is not affected by moisture or water.
The base material can be stably provided with high antistatic performance. In the production of release sheets and adhesive tapes,
Antistatic properties can be imparted by forming a thin film of the conductive organic polymer composition according to the present invention on a substrate. Further, it can be suitably used as a solid electrolyte in a solid electrolytic capacitor or an electromagnetic wave shielding material in various electronic devices. It is also possible to obtain the conductive fiber immediately by ordinary spinning.

[0103]

EXAMPLES The present invention will be described below with reference to examples and 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 6 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) was 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 a sulfuric acid aqueous 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.

Then, 980 g (4.295 mol) of ammonium peroxodisulfate was added to 2293 g of distilled water in a beaker and dissolved to prepare an aqueous oxidant 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 tube 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.

A temperature rise is observed in the reaction mixture during this powder precipitation, but again in accordance with the invention.
In order to obtain a high molecular weight polymer, the temperature in the reaction system is 0 ° C.
It is important to keep the temperature below, preferably -3 ° C or lower. 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 filtered, washed with water, washed with acetone, and vacuum dried at room temperature to obtain 430 g of a black-green polymer composition powder. This was pressure molded into a disk with a diameter of 13 mm and a thickness of 700 μm, and van der
When its conductivity was measured by the Poe method, it was 14S.
/ Cm.

(Production of Quinonediimine / Phenylenediamine-Type Solvent-Soluble Polyaniline by Dedoping of Conductive Organic Polymer Composition) 350 g of the above doped conductive organic polymer composition powder was added to 4 L of 2N ammonia water, and the solution was added automatically. The mixture was stirred with a homomixer at a rotation speed of 5000 rpm for 5 hours. The mixture turned from black green to bluish purple. The powder was filtered off with a Buchner funnel, 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. Then, the powder was vacuum dried at room temperature for 10 hours to obtain 280 g of a blackish brown dedoped polymer powder.
I got

This polymer was soluble in N-methyl-2-pyrrolidone and had a solubility of 8 per 100 g of the solvent.
It was g (7.4%). Also, use this as a solvent at 30 ℃
The intrinsic viscosity [η] measured in 1. was 1.23. This polymer had a solubility of 1% or less in dimethyl sulfoxide and dimethylformamide. Tetrahydrofuran,
It was practically insoluble in pyridine, 80% acetic acid aqueous solution, 60% formic acid aqueous solution and acetonitrile.

With respect to the sample obtained by molding the powder of the quinonediimine / phenylenediamine type solvent-soluble polyaniline in the undoped state into a disk shape, the excitation wavelength was 457.9 nm.
FIG. 1 shows the laser Raman spectrum obtained by irradiation with.

For comparison, Y. Furukawa et al., Syn
FIG. 2 shows a laser Raman spectrum obtained by irradiating the polyaniline in the undoped state shown in th. Met., 16, 189 (1986) at an excitation wavelength of 457.9 nm. This polyaniline was obtained by electrolytic oxidative polymerization of aniline on a platinum electrode.

FIG. 3 shows the result of measuring the Raman spectrum in the range of 1400 to 1700 cm ⁻¹ by changing the wavelength of the laser excitation light. Excitation wavelength is 48
As the wavelength is changed from 8.0 nm to 476.5 nm to 457.9 nm on the short wavelength side, Ia / Ib changes to 45
It is 1.0 or more at 7.9 nm, and it is shown that the Ia / Ib intensity is reversed as compared with the case of 488.0 nm. Furthermore, the electronic spectrum is shown in FIG.

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 an N-methyl-2-pyrrolidone solution of lithium bromide at a concentration of 0.01 mol / L. GP in Figure 5
The result of C measurement is shown.

From these results, the quinonediimine / phenylenediamine type solvent-soluble polyaniline had a number average molecular weight of 23,000 and a weight average molecular weight of 160000 (all converted to polystyrene). Similarly, the reaction conditions are variously changed, and the reaction is performed in N-methyl-2-pyrrolidone at 30 ° C.
Solvent-soluble polyaniline of quinonediimine / phenylenediamine type having different intrinsic viscosities [η] measured by. Table 1 shows the intrinsic viscosity [η], the number average molecular weight and the weight average molecular weight by GPC.

[0115]

[Table 1]

Reference Example 2 (Preparation of Self-Standing Film Using Soluble Aniline Oxidized Polymer) 5 g of the dedoped aniline oxidized polymer powder obtained in Reference Example 1 was added to 95 g of N-methyl-2-pyrrolidone at room temperature. To obtain a black-blue solution. When this solution was vacuum filtered with a G3 glass filter, the amount of insoluble matter 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 dissolves and 1.5% of the insoluble matter
Met.

The quinone diimine thus obtained
A solution of phenylenediamine-type solvent-soluble polyaniline was cast on a glass plate, squeezed with a glass rod, and then N-methyl-2-pyrrolidone was evaporated in a hot air circulation dryer. Then, the polymer plate was naturally peeled 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 film has different strength and solubility depending on its drying temperature. When the drying temperature is 100 ° C. or lower, the obtained film dissolves in N-methyl-2-pyrrolidone in a small amount and has relatively low strength. But,
The film obtained by heating at a temperature of 130 ° C. or higher is extremely 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 thus obtained films of the quinonediimine / phenylenediamine type solvent-soluble polyaniline in the undoped state had an electric conductivity of 10 ^-11 S / cm.
It was a stand. The film did not break even after being bent 10,000 times and had a tensile strength of 850 kg / cm ² .

Reference Example 3 (Doping with Protic Acid of Self-Standing Film) In Reference Example 2, the self-supporting film obtained by heating and drying at 160 ° C. for 2 hours was placed in 1N sulfuric acid, perchloric acid and hydrochloric acid aqueous solution at room temperature. After being soaked for 66 hours in the above, it was washed with acetone and air-dried to obtain a conductive film. The films all have a dark blue color and have an electric conductivity of 9S.
/ Cm, 13 S / cm and 6 S / cm. The tensile strength of the film doped with perchloric acid is 520 kg.
/ Cm ² .

Reference Example 4 (Spectra and structure of quinonediimine / phenylenediamine type polyaniline and insoluble film-formed polyaniline which are both soluble in the undoped state) Soluble polymer powder obtained in Reference Example 1 and Reference Example 2 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 that the residual solvent N-methyl-
Although there is a slight absorption at 1660 cm ⁻¹ which is considered to be due to 2-pyrrolidone, the two spectra are almost the same, and therefore, the polymer is insolubilized by crosslinking by heating and drying the solvent after casting the solvent-soluble polymer. However, it is observed that no major changes in chemical structure have occurred.

The results of thermogravimetric analysis of the soluble polymer powder and the insoluble polymer film are shown in FIG. All have high heat resistance. Considering that it is insoluble in concentrated sulfuric acid, the insoluble film does not decompose to a higher temperature, which indicates that the polymer molecules are crosslinked in the insoluble film.

The ESR spectrum is shown in FIG. The spin concentration is 1.2 × 10 ¹⁸ spins / g in the soluble polymer, and it is shown that the spin concentration increases as the heating temperature is increased, and the radical is generated by heating.
It is believed that the coupling of the radicals crosslinks the polymer and renders 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)

Based on this elemental analysis, C12.00 was specified.
The composition formula of the graded 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, the key standardized to C12.00
Non-diimine structural unit and phenylenediamine structural unit
Are as follows, respectively. Quinonediimine structural unit C₁₂H₈N_Two Phenylenediamine structural unit C₁₂H_TenN_Two Therefore, both the soluble polymer and the solvent-insoluble polymer are
As you can see, the quinone diimine structural unit and phenylenedia
It is a polymer composed of min structural units.

Next, reflection of the quinonediimine / phenylenediamine type solvent-soluble polyaniline film in the undoped state obtained in Reference Example 2 and the perchloric acid-doped film obtained in Reference Example 3 in the visible to near-infrared region The spectra are shown in FIG. 10, respectively. In the undoped state, almost infrared light is reflected, but after doping, near infrared light is absorbed and almost no reflection is observed. It is based on absorption by polarons or bipolarons resulting in conductivity produced by protonic acid doping.

By doping the dedoped film with perchloric acid, the ESR absorption is significantly 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 film obtained in Reference Example 2 was immersed in an aqueous solution or alcoholic solution of a protonic acid having various pKa values, and the possibility of doping was examined. Table 2 shows the electric conductivities of polymer composition films obtained by doping with a protonic acid having various pKa values. Protonic acids with pKa values below 4.8 are shown to be effective in 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 quinonediimine / phenylenediamine type solvent-soluble polyaniline obtained in Reference Example 1 was added to 97.5 g of N-methyl-2-pyrrolidone.
And dissolved under stirring. 0.82 g of phenylhydrazine was gradually added to this solution. At this time, the solution changed its color from dark blue to light black brown, and at the same time, it was confirmed that nitrogen gas was generated.

After the completion of the reaction, the reaction mixture was added dropwise to 1.5 L of acetone substituted with nitrogen, and an off-white precipitate was obtained. The precipitate was filtered by a glass filter, washed several times with nitrogen-substituted acetone, 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 whose atmosphere was replaced with argon. The intrinsic viscosity [η] of the polymer measured in N-methyl-2-pyrrolidone at 30 ° C was 1.1.

The results of elemental analysis of this polymer are shown below. 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, similarly, the quinonediimine structural unit and the phenylenediamine structural unit standardized to C12.00 are as follows, respectively.

Quinonediimine Structural Unit C ₁₂ H ₈ N ₂ Phenylenediamine Structural Unit C ₁₂ H ₁₀ N ₂ Accordingly, an imino-comprising a phenylenediamine structural unit.
The structure of p-phenylene-type solvent-soluble polyaniline is confirmed also by the results of elemental analysis.

FIG. 24 shows the FT of imino-p-phenylene type solvent-soluble polyaniline obtained by the KBr tablet method.
-IR spectrum is shown. The imino-p-phenylene type solvent-soluble polyaniline is characterized by having extremely small absorption around 1600 cm ^-1 , which corresponds to the substantial disappearance of the quinonedichimine structure due to reduction in this polymer. . However, since the stretching motion of the benzene ring is also in this region, the absorption at around 1600 cm ^-1 does not completely disappear even if the quinonedichymine structure substantially disappears. The absorption at 1670 cm ^-1 is due to the residual solvent N-
It is based on the carbonyl group of methyl-2-pyrrolidone.

Next, separately, add TCNQ 0.008775 g to N
Dissolved in 5.0 g of methyl-2-pyrrolidone. To this solution, 0.025 g of the 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 electron spectrum of this complex solution at 300 to 1300 nm, the Raman spectrum at 457.9 nm excitation, and the ESR spectrum of the solution obtained by diluting the above solution 10 times with N-methyl-2-pyrrolidone are shown in FIGS. 11 and 12, respectively. 13 and FIG.

The electronic spectrum shows 420, 680, 7
Absorption peculiar to the anion radical of TCNQ at 50 and 840 nm and broad absorption that is considered to correspond to the radical cation (polaron) of polyaniline are observed in the near infrared region. That is, it is confirmed that the solvent-soluble conductive polyaniline composition is formed in the doped state.

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

Example 2 (Imino-p-phenylene type solvent-soluble polyaniline-
Preparation of TCNQ Conductive Complex Powder) Obtained in Example 1
The complex solution was added to a large amount of acetone to precipitate the complex.
After that, this was filtered off with a glass filter and with acetone.
Thoroughly washed. The powder thus obtained is
Molded into a square and measured for electrical conductivity, it was 5.9 × 10 ^-3S
It was / 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 different pattern from the complex in the above solution, but similarly, Raman lines due to the anion radical of TCNQ in the solid state are observed at 1285 cm ⁻¹ and 1330 cm ⁻¹ . Also, the presence of a large amount of radicals is clear from the ESR spectrum.

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

The obtained solution was cast on a glass plate and dried at 60 ° C. for 1 hour to give a film thickness of 22 to 33 μm.
A self-supporting film was obtained. The electrical conductivity of these films was 1.9 to 2.6 S / cm. The Raman spectrum of the complex film is shown in FIG. It is shown to be similar to FIG.

FIG. 18 (a) shows the ESR spectrum of imino-p-phenylene type solvent-soluble polyaniline.
8 (b) shows the ESR spectrum of TCNQ, and FIG.
(c) shows an ESR spectrum of the imino-p-phenylene type solvent-soluble polyaniline composition doped with TCNQ. No radicals are found in the 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 due to polaron (semiquinone radical) and shows that the imino-p-phenylene type polyaniline is in a doped state.

Next, a self-supporting film of the above complex was added to 80-1.
Table 3 shows the electric conductivity when heat-treated at 40 ° C. for 1 hour and the electric conductivity when the film was allowed to stand at room temperature in the atmosphere for 15 days thereafter. The self-supporting film of the complex according to the present invention has a high electric conductivity when the heat treatment temperature is 100 ° C. or lower, and further, the electric conductivity shows a decrease in the electric conductivity even when left at room temperature in the air for a long time. It remains relatively slight.

[0145]

[Table 3]

Example 4 (Imino-p-phenylene type solvent-soluble polyaniline-
Preparation of TCNQ conductive complex film 2) 0.12 g of quinonediimine / 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 under stirring, 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 self-supporting film having a film thickness of 60 μm. The conductivity of this film was 8.7 S / cm. The film had a conductivity of 5.3 S / cm even after being left at room temperature in the atmosphere for 70 days. The Raman spectrum of this film is shown in FIG. It is confirmed that the Raman spectrum of the complex film shown in Example 3 is similar to that of the complex film.

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 quinonediimine / phenylenediamine type solvent-soluble polyaniline obtained in Reference Example 1 was dissolved. To this solution (10 g) was added TCNQ (0.035 g), and the mixture was stirred for 30 minutes to obtain a solution.

Then, 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 quinonediimine / 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. Then, this solution was spin-coated on a glass plate and heat-treated at 60 ° C. for 30 minutes to give 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 the conductivity of the obtained complex can be adjusted by adjusting the amount of TCNQ with respect to the imino-p-phenylene type solvent-soluble polyaniline.

FIG. 20 shows an electron spectrum at 300 to 1300 nm of the complex thin film obtained by adding 0.0450 g of TCNQ. Similar to the case of Example 1, absorption attributed to the cation radical (polaron) of near-infrared polyaniline was observed, showing that 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 quinonediimine / phenylenediamine type 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, with stirring. After stirring for 3 hours, a solution was obtained.

Then, 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 tetrahydrofuran solution of TCNQ, its electronic spectrum changed significantly as shown in FIG. This change indicates that polyaniline was changed by TCNQ from an imino-p-phenylene type polyaniline, that is, a reduction dedoped state, to an imino-p-phenylene type polyaniline-TCNQ complex, that is, an oxidized doped state. The surface resistance of this 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
N-methyl-2-pyrrolidone solution of TCNQ complex 1.0 g
Was diluted with 4 g of methyl ethyl ketone. At this time, no precipitate was formed. 300-2300 nm of this solution
The electronic spectrum of is shown in FIG.

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

Example 9 (Preparation 4 of polyaniline-TCNQ complex thin film) Example 8
The complex solution obtained in 1. was formed into a film on a polyethylene terephthalate film with 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 / □. In addition, this thin film is made of cotton 100
%, When strongly rubbed with 10% web, charging potential is 10V
Met. The half-life of the charge amount was 0.1 seconds. Therefore, the imino-p-phenylene type solvent-soluble polyaniline-TCNQ complex in the doped state is useful for manufacturing an antistatic material.

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

The obtained solution was cast on a glass plate, heated at 60 ° C. for 1 hour and dried to give a film thickness of 38.
A free-standing film of μm was obtained. The conductivity was 1.2 S / cm. The Raman spectrum of this film is shown in FIG. 23, and polyaniline is in a doped state.

Example 11 (Preparation of polyaniline-FeCl ₃ self-supporting film) 1.0 g of the imino-p-phenylene type solvent-soluble polyaniline obtained in Example 1 was used in N-methyl-2-pyrrolidone 9.
Dissolve in 0g, 0.2278g anhydrous ferric chloride in this solution
Was gradually added, the solution changed its color from pale black to green-blue. At this time, no precipitate was formed.

The obtained solution was cast on a glass plate, heated at 60 ° C. for 1 hour and dried to give a film thickness of 64.
A flexible self-supporting film of μm was obtained. Conductivity is 2.8
It was × 10 ^-2 S / cm. Similarly, polyaniline-Lewis acid composition free-standing films were prepared using various Lewis acids. Table 6 shows the standard electrode potential of the Lewis acid used and the electric 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 surfaces of polyethylene terephthalate film in the same manner as in Example 9 to give 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 on the other thin film to a thickness of 30 μm, and the roll was used to prepare a pressure-sensitive adhesive tape. The surface resistance of the release agent surface of this pressure-sensitive adhesive tape was 10 ⁸ Ω / □, and the charging potential of the tape when the outer end of the tape was peeled from the roll was almost 0V. Further, the antistatic performance was also good by the visual examination of the adsorptivity of the ashtray ash and the flocked pile.

[Brief description of drawings]

FIG. 1 is a laser Raman spectrum obtained by exciting a quinonediimine / phenylenediamine type solvent-soluble polyaniline in an undoped state with light having a wavelength of 457.9 nm.

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

FIG. 3 is a laser Raman spectrum obtained by exciting the same imino-p-phenylene type solvent-soluble polyaniline as in FIG. 1 with light having different excitation wavelengths.

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

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

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

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

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

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

FIG. 10 is a reflection spectrum in the near infrared region of a quinonediimine / phenylenediamine type solvent-soluble polyaniline film in a dedoped state and a film obtained by doping the film 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 457.9 nm excitation of the above complex solution.

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 is an ESR spectrum 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 a film of another imino-p-phenylene type solvent-soluble polyaniline-TCNQ complex.

FIG. 20 is an electronic spectrum of the complex.

FIG. 21 is an electron spectrum of imino-p-phenylene type solvent-soluble polyaniline and TCNQ doped with the polyaniline.

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.

 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Shinya Akizuki 1-2-2 Shimohozumi, Ibaraki-shi, Osaka Nitto Denko Corporation (72) Inventor Yasuhiro Umemoto 1-2-1 Shimohozumi, Ibaraki-shi, Osaka Nitto Denko Corporation

Claims (10)

[Claims] 1. A compound of the general formula (I) Of the 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] measured at 30 ° C. in N-methyl-2-pyrrolidone of 0.40 dl / An organic polymer characterized by being g or more. 2. Dissolved 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 represented by the general formula (I): Of the 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] measured at 30 ° C. in N-methyl-2-pyrrolidone of 0.40 dl / A conductive organic polymer composition, wherein an organic polymer of g or more is doped with an electron acceptor. 4. A compound of the general formula (I) Of the 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] measured at 30 ° C. in N-methyl-2-pyrrolidone of 0.40 dl / A conductive organic polymer composition, wherein an organic polymer of g or more 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, which is in the range of. 6. A compound represented by the general formula (II): (In the formula, m and n each represent a mole fraction of the quinonediimine structural unit and the phenylenediamine structural unit in the repeating unit, and 0 <m <1, 0 <n <1, m + n = 1). It is composed of a quinonediimine structural unit and a phenylenediamine structural unit, is soluble in an organic solvent in the undoped state, and has an intrinsic viscosity [η] of 0.40 dl measured at 30 ° C. in N-methyl-2-pyrrolidone.
Of the skeletal vibrations of para-substituted benzene in the laser Raman spectrum obtained by exciting with light having a wavelength of 457.9 nm, the Raman line of the skeletal stretching vibrations appearing at a wave number higher than 1600 cm ^-1 . Strength Ia and 1
A general formula (I) characterized by reducing an organic polymer having a Raman line intensity Ib ratio Ia / Ib of 1.0 or more of a skeleton stretching vibration appearing at a wave number lower than 600 cm ⁻¹ with a reducing agent. Chemical 5] Of the 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] measured at 30 ° C. in N-methyl-2-pyrrolidone of 0.40 dl / A method for producing an organic polymer having a weight of at least g. 7. A reducing half-cell based on a standard hydrogen electrode while maintaining the temperature of 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 standard hydrogen electrode as a reference. The standard electrode potential defined as the electromotive force in the reaction is 0.6
An aqueous solution of an oxidant of V or higher is added per mol of aniline
An aniline doped with the above-mentioned protic acid is added in an amount defined as the amount of 1 mol of the oxidant divided by the number of electrons required to reduce 1 molecule of the oxidant, and 2 to 2.5 equivalents are added. Of the general formula (II): ## STR00006 ## and then dedoping the polymer with a basic substance. (In the formula, m and n each represent a mole fraction of the quinonediimine structural unit and the phenylenediamine structural unit in the repeating unit, and 0 <m <1, 0 <n <1, m + n = 1). It is composed of a quinonediimine structural unit and a phenylenediamine structural unit, is soluble in an organic solvent in the undoped state, and has an intrinsic viscosity [η] of 0.40 dl measured at 30 ° C. in N-methyl-2-pyrrolidone.
Of the skeletal vibrations of para-substituted benzene in the laser Raman spectrum obtained by exciting with light having a wavelength of 457.9 nm, the Raman line of the skeletal stretching vibrations having a wave number higher than 1600 cm ^-1 Strength Ia and 1
An organic polymer having a Raman line intensity Ib of skeletal stretching vibration Ia / Ib of 1.0 or more, which appears at a wave number lower than 600 cm ^-1 , is obtained, and then the organic polymer is reduced with a reducing agent. Characterized by the general formula (I): Of the 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] measured at 30 ° C. in N-methyl-2-pyrrolidone of 0.40 dl / A method for producing an organic polymer having a weight of at least g. 8. An organic polymer comprising a quinonediimine structural unit represented by the general formula (II) and a phenylenediamine structural unit is dissolved in N-methyl-2-pyrrolidone to give 3 to
An organic compound which 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 be dissolved in N-methyl-2-pyrrolidone to form a 3-15 wt% strength solution, and
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 reducing half-cell based on a standard hydrogen electrode while maintaining the temperature of 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 standard hydrogen electrode as a reference. The standard electrode potential defined as the electromotive force in the reaction is 0.6
An aqueous solution of an oxidant of V or higher is added per mol of aniline
An aniline doped with the above-mentioned protic acid is added in an amount defined as the amount of 1 mol of the oxidant divided by the number of electrons required to reduce 1 molecule of the oxidant, and 2 to 2.5 equivalents are added. Of the general formula (II) embedded image which is then dedoped with a basic substance. (In the formula, m and n each represent a mole fraction of the quinonediimine structural unit and the phenylenediamine structural unit in the repeating unit, and 0 <m <1, 0 <n <1, m + n = 1). It is composed of a quinonediimine structural unit and a phenylenediamine structural unit, is soluble in an organic solvent in the undoped state, and has an intrinsic viscosity [η] of 0.40 dl measured at 30 ° C. in N-methyl-2-pyrrolidone.
Of the skeletal vibrations of para-substituted benzene in the laser Raman spectrum obtained by exciting with light having a wavelength of 457.9 nm, the Raman line of the skeletal stretching vibrations appearing at a wave number higher than 1600 cm ^-1 . Strength Ia and 1
An organic polymer having a Raman line intensity Ib ratio Ia / Ib of the skeleton stretching vibration appearing at a wave number lower than 600 cm ^-1 is 1.0 or more is obtained, and then the organic polymer is reduced with a reducing agent, General formula (I): Of the 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] measured at 30 ° C. in N-methyl-2-pyrrolidone of 0.40 dl / A method for producing a conductive organic polymer composition, which comprises obtaining an organic polymer having a weight of g or more, and then doping the organic polymer with an electron acceptor. 10. An organic polymer comprising a quinonediimine structural unit represented by the general formula (II) and a phenylenediamine structural unit is dissolved in N-methyl-2-pyrrolidone to give 3
A solution having a concentration of up to 30% by weight, an intrinsic viscosity [η] of 0.40 to 1.23 dl / g, and 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.