JPH078910B2 - Conductive organic polymer composition - Google Patents

Description

The present invention relates to a novel conductive organic polymer composition, and more particularly to a novel high molecular weight organic polymer conductive composition obtained by oxidative polymerization of aniline.

Most organic materials are electrically insulating, but a group of electrically conductive organic polymers known as organic semiconductors have recently attracted attention. Generally, organic substances which are themselves conductive are classified into three types. The first is graphite. Graffite is not strictly regarded as an organic substance, but it can also be considered to have an organic conjugated ultimate structure. The graphite itself already has a fairly high conductivity, but by intercalating various compounds into it, it can be made even more conductive, and finally becomes a superconductor. However, since Graphite has a strong two-dimensionality and is difficult to mold,
It is an obstacle in its application.

The second is a charge transfer complex. For example, a crystalline substance obtained by using tetrathiafulvalene and tetracyanoquinodimethane as an electron donor and an electron acceptor, respectively, is
It has an extremely high conductivity of 400 to 500 S / cm, but since such a charge transfer complex is not a polymer, it has a molding processability problem similar to that of graphite for practical application.

The third is a π-electron conjugated organic polymer which is highly conductive by doping, as represented by polyacetylene. The electrical conductivity of polyacetylene before doping is 10 ⁻⁵ S / cm for the trans type and 10 ⁻⁹ S / cm for the cis type, and has properties close to those of a semiconductor or an insulator. However, by doping such polyacetylene with an electron-accepting compound such as arsenic pentafluoride, iodine, sulfur trioxide, ferric chloride or the like, or an electron-donating compound such as an alkali metal, a p-type semiconductor is obtained. It is also possible to form an n-type semiconductor, and further, it is possible to provide a high conductivity level of 10 ³ S / cm. The above-mentioned polyacetylene is a conductive organic polymer that is theoretically interesting, but on the other hand, polyacetylene is extremely susceptible to oxidation and is easily oxidized and deteriorated in the air to largely change its properties. In the doped state it is more sensitive to oxidation and even a small amount of moisture in the air causes a sharp decrease in conductivity. This tendency is particularly remarkable for n-type semiconductors.

In addition, the conductivity of poly (p-phenylene) and poly (p-phenylene sulfide) before the doping are respectively different.
Conductive organic polymer composition having a conductivity of 500 S / cm and 1 S / cm, for example, by doping with arsenic pentafluoride as described above, which is 10 ^-9 S / cm and 10 ^-16 S / cm, respectively. Can be The electrical properties of these doped organic polymer compositions are also more or less unstable.

The fact that the electrical properties of the conductive organic polymer composition thus doped are generally very unstable with respect to the environment is a phenomenon common to these types of conductive organic polymer compositions. These are obstacles to practical application.

As described above, various organic electroconductive substances have been heretofore known, but from the viewpoint of developing practical applications, polymer forms having excellent moldability are preferable.

On the other hand, research on aniline oxidation polymers as oxidative dyes has also been conducted for a long time in relation to aniline black. In particular, as an intermediate for the production of aniline black,
An octamer of aniline represented by the formula (I) has been confirmed as emeraldine (AGGreen e
t al., J. Chem. Soc., 97 , 2388 (1910); 101, 1117 (191
2)), which is soluble in 80% acetic acid, cold pyridine and N, N-dimethylformamide. Further, it is known that this emeraldine is oxidized in an ammonia medium to form a nigraniline represented by the formula (II), which also has solubility characteristics similar to those of emeraldine.

Furthermore, in recent years, it has been found by R. Buvet et al. That this sulfate salt of emeraldine has high conductivity (J. Polymer Sci., C, 16 , 2931; 2943 (1967); 22 ,
1187 (1969)).

Further, it is already known that an emeraldine-like organic substance can be obtained by the electrooxidative polymerization of aniline (DMMohilner et al., J. Amer. Chem. Soc., 84 , 3618).
(1962)). That is, according to this, an aqueous solution of aniline in sulfuric acid was used for a platinum electrode, and in order to avoid electrolysis of water, electrolytic oxidation polymerization was performed at an oxidation potential of +0.8 V with respect to a standard calomel electrode, and 80% acetic acid, pyridine And substances which are soluble in N, N-dimethylformamide are obtained.

In addition, Diaz et al. (J. Electroanal. Chem., 111, 111 (198
0), Koyama et al. (Proceedings of the Polymer Society of Japan, 30 ,) (7), 1524
(1981); J. Electroanal. Chem., 161, 399 (1984)) also attempted the electrolytic oxidative polymerization of aniline, both of which were aimed at polymer-coated chemically modified electrodes, and electrolysis was 1 V.
The following potential is used.

The present inventors have diligently studied oxidative polymerization of aniline in order to obtain a stable and highly conductive organic material, particularly a conductive organic polymer, and as a result, select reaction conditions for oxidative polymerization of aniline. As a result, it has a much higher molecular weight than the emeraldine described above, and since it is already doped at the oxidative polymerization stage, it does not require a new doping operation, and is stable and highly conductive. It was found that coalescence can be obtained (Japanese Patent Application Nos. 58-212280 and 58-212281). Then, as a result of further intensive studies by the present inventors, they found that the polymer was a substantially linear high molecular weight polymer having a repeating unit substantially composed of a quinonediimine structure, and arrived at the present invention. It is a thing.

Therefore, the present invention aims to provide a novel conductive organic polymer composition.

The conductive organic polymer composition according to the present invention has substantially the same general formula: It consists of a repeating unit consisting of a quinonediimine structure represented by the formula: 0.5g / dl concentrated sulfuric acid solution is 0.38dl / g at 30 ℃.
A substantially linear polymer having the above logarithmic viscosity, containing an electron acceptor as a dopant and having an electric conductivity of 10
^-6 S / cm or more.

Such a conductive organic polymer composition according to the present invention usually exhibits a green to black green color in a dry powder state, and generally, the higher the conductivity, the brighter the green color. However, pressure-molded moldings usually show a glossy blue color.

The conductive organic polymer composition according to the present invention is insoluble in water and most organic solvents, but usually contains a part that is slightly soluble or dissolved in concentrated sulfuric acid. Solubility in concentrated sulfuric acid varies depending on the reaction method and reaction conditions for producing a polymer, but as described later, a conductive organic polymer obtained by oxidative polymerization of aniline with a chemical oxidizing agent is usually 0.2
~ 10% by weight, in most cases 0.25-5% by weight
Is the range. However, this solubility should be understood as including a portion having a solubility in the above range, particularly in the case of a high molecular weight polymer. As mentioned above, emeraldine is 80% acetic acid, cold pyridine and N, N-
In sharp contrast to being soluble in dimethylformamide.

The conductive organic polymer composition according to the present invention comprises 97% concentrated sulfuric acid.
A 0.5 g / dl solution has an inherent viscosity in the range 0.38-1.0 dl / g at 30 ° C. Even in this case, it should be understood that the portion soluble in concentrated sulfuric acid has a logarithmic viscosity in the above range, particularly in the case of a high molecular weight composition. In contrast, the logarithmic viscosities of emeraldine and aniline black under the same conditions are 0.02 and 0.005, respectively, indicating that the composition according to the invention is a high molecular weight organic polymer composition. Further, the differential thermal analysis results also show that the organic polymer composition according to the present invention is a high molecular weight polymer composition.

As a representative example of the conductive organic polymer composition according to the present invention,
The infrared absorption spectrum of the conductive polymer composition obtained by the oxidative polymerization of aniline is shown in FIG. 1, and the infrared absorption spectra of emeraldine and aniline black (diamond black as a commercial pigment) are shown for comparison. They are shown in FIGS. 2 and 3, respectively.

The infrared absorption spectrum of the conductive organic polymer composition according to the present invention is similar to that of emeraldine, while on the other hand, in the conductive organic polymer composition according to the present invention, the monosubstitution clearly observed in emeraldine. Absorption due to C—H out-of-plane bending vibration of benzene is hardly observed, whereas absorption due to para-substituted benzene is relatively large. However, the spectrum of the conductive organic polymer composition according to the present invention is significantly different from that of aniline black. Therefore, the conductive organic polymer composition according to the present invention has a structure other than emeraldines containing a large number of para-substituted benzenes.

The conductive organic polymer composition according to the present invention is doped with an electron acceptor present in the reaction system at the stage of oxidative polymerization of aniline, and as a result, has high conductivity. That is, charge transfer occurs from the oxidized polymer of aniline to the electron acceptor, and a charge transfer complex is formed between the polymer of aniline and the electron acceptor. For example, when the conductive organic polymer composition according to the present invention is molded into a disk shape and a pair of electrodes is attached to this and a temperature difference is given between these electrodes to generate a thermoelectromotive force peculiar to the semiconductor, Since the electrode side gives a positive electromotive force and the high temperature electrode side gives a negative electromotive force, it is shown that the conductive organic polymer composition according to the present invention is a p-type semiconductor.

Further, the composition according to the present invention has a greatly reduced conductivity due to chemical compensation with ammonia or the like, and also has an appearance that changes from black-green to purple, which is again receptive to an electron acceptor such as sulfuric acid. By doping with the body, the color returns to blackish green and the initial high conductivity is restored. This change is reversible, and the same result can be obtained by repeating chemical compensation and doping.

FIG. 4 shows changes in the infrared absorption spectra of the composition and the polymer due to this chemical compensation and re-doping. A is the original composition, B is the chemically compensated polymer, and C is the re-doped composition. It is clear that the spectrum of C almost completely coincides with that of A. Therefore, the chemical compensation and re-doping are not the change of the skeleton structure of the polymer contained in the composition, but the polymer and the chemical compensation reagent or the electron. It is the exchange of electrons with the acceptor. Thus, according to the present invention, the oxidative polymer of aniline is doped with an electron acceptor at the stage of its oxidative polymerization, and thus the conductive organic polymer composition according to the present invention contains a dopant. Is understood.

Examples of the dopant contained in the conductive organic polymer composition according to the present invention include halogen such as chlorine, bromine and iodine,
Lewis acids such as ferric chloride, tin tetrachloride, copper dichloride, inorganic acids such as hydrogen chloride, hydrogen bromide, sulfuric acid, nitric acid and picric acid,
Examples thereof include organic acids such as p-toluenesulfonic acid, but are not limited thereto.

The chemical structure of the conductive organic polymer composition according to the present invention is confirmed by the above-mentioned infrared absorption spectrum and elemental analysis of the composition, and the polymer obtained by chemically compensating the composition according to the present invention with ammonia or the like. It was also confirmed by elemental analysis (hereinafter referred to as compensation polymer), and substantially consisted of a linear high molecular polymer composed of the repeating unit and a dopant, and the π-electron conjugated system contained a dopant, and thus it was It seems to have conductivity.

However, the conductive organic polymer composition according to the present invention has the following repeating unit (IV) which is its reducing structure together with the repeating unit having the above quinonediimine structure. May be included. A composition containing such a reduced structure can be easily obtained, for example, by partially reducing the composition according to the present invention.

As described above, the conductive organic polymer composition obtained by the oxidative polymerization of aniline according to the present invention preferably consists essentially of the repeating unit and is already doped with a protic acid at the polymerization stage. Therefore, it has high conductivity without requiring a new doping process, and
Even if it is left in the air for a long period of time, its conductivity does not change at all, and it has a uniquely high stability compared to the conventionally known doped conductive organic polymer. There is.

The conductive organic polymer composition according to the present invention can be obtained, for example, by oxidatively polymerizing aniline or a water-soluble salt thereof in a reaction medium containing a protic acid and an oxidizing agent. As the water-soluble salt of aniline, usually, mineral acid salts such as hydrochloric acid and sulfuric acid are suitable, but not limited thereto.

The oxidizing agent is also not particularly limited, but chromium oxide (IV) and dichromates such as potassium dichromate and sodium dichromate are preferable, and potassium dichromate is most preferable. is there. However, chromium-based oxidizing agents such as chromic acid, chromate salts and chromyl acetate, and manganese-based oxidizing agents such as potassium permanganate can also be used if necessary.

Further, as the protic acid, sulfuric acid, hydrochloric acid, hydrobromic acid,
Tetrafluoroboric acid (HBF ₄ ), hexafluorophosphoric acid (HPF ₆ ) and the like are used, and sulfuric acid is particularly preferable. When using a mineral acid to form a water-soluble salt of aniline,
This mineral acid may be the same as or different from the above-mentioned protonic acid.

As the reaction medium, water, a water-miscible organic solvent and a mixture of two or more water-immiscible organic solvents can be used. When a water-soluble salt of aniline is used, the reaction medium is usually , Water that dissolves these water-soluble salts, water-miscible organic solvents or mixtures thereof are used, and when aniline itself is used, the reaction medium is a water-miscible organic solvent or water-immiscible organic solvent that dissolves them. Miscible organic solvents are used. In addition, it is necessary that none of the above organic solvents is oxidized by the oxidizing agent used. For example, as the water-miscible organic solvent, acetone, tetrahydrofuran, ketones such as acetic acid, ethers or organic acids are used, and as the water-immiscible organic solvent, carbon tetrachloride,
Hydrocarbon or the like is used.

A particularly preferred method for producing a conductive organic polymer composition according to the present invention is a method for producing a conductive organic polymer by oxidatively polymerizing aniline or a water-soluble salt thereof with an oxidizing agent in a reaction medium containing a protonic acid. The molar ratio of protonic acid / potassium dichromate in the reaction medium containing an oxidizing agent is 1.2 or more. The upper limit is not particularly limited, but is usually about 50.

The reaction temperature is not particularly limited as long as it is equal to or lower than the boiling point of the solvent, but as the reaction temperature becomes higher, the conductivity of the resulting oxidized polymer tends to decrease, so from the viewpoint of obtaining a polymer having high conductivity. It is preferably at room temperature or lower.

A particularly preferable method is to add the oxidant aqueous solution of a protonic acid to the organic solution of aniline or the aqueous solution of aniline water-soluble salt while stirring or add them all at once to carry out the reaction. Usually, the composition precipitates immediately after an induction period of about several minutes. Thus, the reaction is completed immediately, but the mixture is usually stirred for a few minutes to several hours for aging. Then, the reaction mixture is poured into a large amount of water or an organic solvent, the composition is filtered off, washed with water until the filtrate becomes neutral, and then washed with an organic solvent such as acetone until it is no longer colored, and vacuum Dry to obtain the conductive organic polymer composition according to the present invention.

In the method as described above, the conductivity of the resulting conductive organic polymer composition is closely related to the composition of the reaction medium containing the protic acid and the oxidizing agent, in which the oxidative polymerization of aniline or a water-soluble salt thereof is carried out. In order to obtain a highly conductive composition, it is necessary to optimally select the composition of the above reaction medium, and the conductivity is 10 ⁻⁶ S / cm or more. In order to obtain it, it is necessary to set the molar ratio of protonic acid / potassium dichromate in the reaction medium in which the reaction is carried out to 1.2, preferably 2 to 50. Usually, a highly conductive composition having an electric conductivity of 10 ⁻³ to 10 ¹ S / cm can be obtained by oxidative polymerization under such conditions. As described above, when the reaction is carried out by adding a protic acid-acidic oxidant aqueous solution to an organic solution of aniline or an aqueous solution of a water-soluble salt thereof, the concentration of the protonic acid in the oxidant aqueous solution is particularly limited. But usually in the range of 1-10 N.

In the above-mentioned method, if the protonic acid / potassium dichromate molar ratio in the reaction medium in which the oxidative polymerization of aniline is performed is constant, the conductivity of the obtained polymer is substantially the same, According to the method as described above, a composition having a predetermined conductivity with good reproducibility can be obtained. On the other hand, the amount of potassium dichromate relative to aniline determines the yield of the resulting composition. However, the conductivity of the composition is substantially unaffected by the amount of potassium dichromate used. Therefore, an oxidant aqueous solution having a predetermined protonic acid / potassium dichromate molar ratio is used,
Moreover, when potassium dichromate is used in an equivalent amount or more with respect to aniline or a water-soluble salt thereof, an organic polymer composition having a predetermined conductivity can be obtained almost quantitatively.

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

Example 1 (1) Production of Conductive Organic Polymer Composition 45 g of water was placed in a 300-ml volumetric flask, 4 ml of concentrated hydrochloric acid was added, and 5 g (0.0537 mol) of aniline was dissolved to prepare an aqueous solution of aniline hydrochloride. The flask was cooled with ice water.

Separately, 4.61 g (0.047 mol) of concentrated sulfuric acid was added to 28.8 g of water to prepare an aqueous oxidant solution (protonic acid / potassium dichromate molar ratio of 7.5) in which 1.84 g (0.00625 mol) of potassium dichromate was dissolved. Then, it was added dropwise to the above aniline hydrochloride aqueous solution cooled with ice water while stirring for 30 minutes from the dropping attempt. After the start of dropping, the solution was only colored yellow for the first 2 to 3 minutes, but thereafter, a green solid was promptly precipitated, and the reaction solution exhibited a black green color.

After completion of dropping, the mixture was stirred for another 30 minutes, then, the reaction mixture was poured into 400 ml of acetone and stirred for 2 hours, and then the conductive polymer composition was filtered off. The resulting composition was washed with stirring in distilled water, filtered, and washed in this manner until the filtrate became neutral. Then, the composition portion separated by filtration was repeatedly washed with acetone until the filtrate was not colored. The composition separated by filtration was vacuum dried on phosphorus pentoxide at room temperature for 10 hours to obtain a conductive organic polymer composition of the present invention as a green powder.

(2) Physical Properties of Conductive Organic Polymer Composition The conductive organic polymer composition obtained above has a concentration of 97 at room temperature.
% Of concentrated sulfuric acid, the mixture was stirred and the solubility was examined. As a result, the amount of dissolution was 1.2% by weight. The 97% concentrated sulfuric acid solution having a concentration of 0.5 g / dl had a logarithmic viscosity of 0.46 dl / g at a temperature of 30 ° C. For comparison, the viscosities of emeraldine and diamond black under the same conditions were 0.02 dl / g and 0.005 dl / g, respectively.

Further, the results of thermogravimetric analysis in air of the above conductive organic polymer composition and emeraldine according to the present invention are shown in FIG. The heating rate is 10 ° C / min.

Next, about 120 mg of the powder of the conductive organic polymer composition obtained above
Was crushed in an agate mortar, and then pressure-molded with a tablet press for an infrared spectrophotometer at a pressure of 6000 kg / cm ² into a disk having a diameter of 13 mm. Four copper foils with a width of about 1 mm were adhered to the four corners of the disk with silver paste or graphite paste, and the conductivity was 2.0 S / c when measured according to the Juan der Pauw method in air.
It was m. The molded product of this conductive organic polymer composition is 1
It showed almost the same conductivity when measured in a vacuum of 0 ^-2 Torr. The disk was left in the air for 4 months, but the conductivity did not substantially change.

(3) Infrared absorption spectrum of conductive organic polymer composition The infrared absorption spectrum of the conductive organic polymer composition obtained above is shown in FIG. For comparison, infrared absorption spectra of emeraldine and aniline black are shown in FIGS. 2 and 3, respectively. Emeraldine is AGGree
(AGGreen et al., J. Che.
m.Soc., 97 , 2388 (1910)).

The infrared absorption spectrum of the conductive organic polymer composition according to the present invention is similar to that of emeraldine, but at the same time there is a large difference. That is, emeraldine has 690 cm ^-1 and 7 due to C-H out-of-plane bending vibration based on monosubstituted benzene.
Although a clear absorption of 40 cm ^-1 is observed, in the composition according to the invention, these absorptions are hardly observed, and instead, an absorption of 800 cm ^-1 indicating para-substituted benzene is strongly recognized. This is because emeraldine is a low-molecular weight substance, so that absorption based on mono-substituted benzene at the molecular end is relatively strong, whereas the composition according to the present invention is a high-molecular weight substance, and thus the polymer chain is This is because the absorption based on the para-substituted benzene that forms the is relatively strong. On the other hand, the infrared absorption spectrum of aniline black is significantly different from that of both the composition according to the present invention and emeraldine, and in particular, the broad absorption around 3200 to 3400 cm ⁻¹ , 16
Absorption recognized as a quinonic carbonyl group at 80 cm ^-1 ,
C-N stretching vibration region of 1200~1300cm ^-1, differ in 600 cm ^-1 or less in the region and the like is obvious.

Assignment of infrared absorption spectrum in the conductive organic polymer composition according to the present invention is as follows.

1610 ^-1 (Shoulder, C = N stretching vibration) 1570, 1480cm ^-1 (benzene ring CC stretching vibration) 1300, 1240cm ^-1 (CN stretching vibration) 1120cm ^-1 (absorption based on dopant. Types of dopants 800cm ^-1 (para-substituted benzene C-H out-of-plane bending vibration) 740, 690cm ^-1 (mono-substituted benzene C-H out-of-plane bending vibration) The infrared absorption spectrum of the conductive organic polymer composition according to the invention when ammonia-compensated is shown in FIG. 4 (B), and the infrared absorption spectrum after re-doping with 5N sulfuric acid is shown in FIG. 4 (C). Show. The spectrum after this re-doping is almost completely the same as the original spectrum shown in FIG. 4 (A), and the conductivity is also the same as before ammonia compensation.

The change in conductivity was 0.45 S / cm before compensation (A), 1.6 × 10 ^-8 S / cm after compensation (B), and 0.3 after re-doping (C).
It was 1 S / cm. Therefore, according to the invention, it is shown that the polymer from the oxidative polymerization of aniline is already doped with the protic acid used at that stage.

(4) Chemical Structure of Conductive Organic Polymer Composition The elemental analysis values of the conductive organic polymer composition according to the present invention obtained above are shown below. Even if the composition was purified by washing with water and washing with acetone, anhydrous chromium oxide (Cr ₂ O ₃ ) was obtained after elemental analysis.
Since it is recognized that the green powder of No. 2 remains as a residue, the respective conversion values when the total is taken as 100 are shown together with the measured elemental analysis values. It is recognized that the converted value matches the theoretical value. The results are also shown for polymers chemically compensated with ammonia.

(A) Composition containing sulfuric acid as a dopant C ₁₂ H ₈ N ₂ (H ₂ SO ₄ ) _0.58 Theoretical value Measured value Converted value C 60.79 58.11 60.99 H 3.89 4.05 4.25 N 11.81 10.80 11.34 S 7.84 7.45 7.82 O 15.66 (14.87) (15.61) The amount of sulfuric acid in the theoretical formula was calculated from the measured value of sulfur, and the oxygen amount in the theoretical value was calculated based on this amount of sulfuric acid. The amount of oxygen in the measured value was calculated from the amount of sulfuric acid obtained by calculating the amount of sulfuric acid from the measured value of sulfur.

(B) Compensating polymer C ₁₂ H ₈ N ₂ theoretical value Measured value Converted value C 79.98 73.24 79.77 H 4.48 4.34 4.73 N 15.54 14.23 15.50 Example 2 (1) In sulfuric acid acidic oxidant aqueous solution with constant concentrated sulfuric acid Effect of the sulfuric acid / potassium dichromate molar ratio on the conductivity of the composition In a 300 ml flask, 45 g of water was added, 4 ml of concentrated hydrochloric acid was added, and 5 g (0.0537 mol) of aniline was dissolved to give an aqueous solution of aniline hydrochloride. Was prepared.

Separately, 1.84 g (0.00625 mol) of potassium dichromate was dissolved in various amounts of 3N sulfuric acid to prepare aqueous oxidant solutions having different sulfuric acid / potassium dichromate molar ratios. This oxidizing agent aqueous solution was added dropwise to the above aniline hydrochloride aqueous solution while stirring at room temperature. After completion of dropping, the mixture was stirred for another 30 minutes, after which the reaction mixture was poured into 400 ml of acetone and 2
After stirring for an hour, the resulting conductive organic polymer composition was filtered off and dried.

The electrical conductivity (σ) of the thus obtained unpurified conductive organic polymer composition is shown by a circle in FIG. Further, the above composition was washed with distilled water, filtered, and washed repeatedly until the filtrate became neutral in this manner. The conductivity of the purified composition thus obtained is shown by a black circle in FIG. Similarly, in the following drawings, the unpurified composition as described above is indicated by a circle, and the purified composition is indicated by a ●.

From the results shown in FIG. 6, it is possible to obtain a conductive organic polymer composition having an electric conductivity of 10 ⁻⁶ S / cm or more by setting the protonic acid / potassium dichromate molar ratio to 1.2 or more in the oxidizing agent aqueous solution. It is understood that

(2) Effect of sulfuric acid / potassium dichromate molar ratio on composition conductivity and yield in acidic sulfuric acid aqueous solution with constant potassium dichromate concentration Different concentrations of sulfuric acid and potassium dichromate 1.84 g (0.00625 mol) was dissolved to prepare an aqueous solution having a potassium dichromate concentration of 5.2% by weight. This oxidizing agent aqueous solution was added dropwise to an aqueous solution containing 0.0537 mol of aniline hydrochloride at room temperature with stirring as in Example 1 to obtain a conductive organic polymer composition according to the present invention.

FIG. 7 shows the relationship between the sulfuric acid / potassium dichromate molar ratio in the oxidizing agent aqueous solution and the yield and conductivity of the composition. When the molar ratio is 1.2 or more, it is possible to obtain a composition having an electrical conductivity of 10 ^-6 S / cm or more, while the amount of potassium dichromate relative to aniline is constant, the yield of the composition Is almost constant.

(3) Effect of potassium dichromate concentration on electrical conductivity and yield of composition Dissolving potassium dichromate in sulfuric acid aqueous solutions having different concentrations such that the sulfuric acid / potassium dichromate molar ratio is 7.5,
Various potassium dichromate aqueous solutions were prepared. This oxidant aqueous solution was added dropwise at room temperature to an aqueous solution containing aniline hydrochloride in a molar amount of about 9 times that of potassium dichromate to obtain a composition according to the present invention.

As shown in FIG. 8, the results show that the sulfuric acid / potassium dichromate molar ratio is constant and the amount of potassium dichromate relative to aniline is constant even if the potassium dichromate concentration in the oxidizing agent aqueous solution is different. It is then shown that the composition is obtained in a substantially constant yield and its conductivity is also substantially constant.

(4) Effect of the amount of potassium dichromate with respect to aniline on the conductivity and yield of the composition: Potassium dichromate was dissolved in 3N sulfuric acid to prepare an oxidizing agent aqueous solution having a sulfuric acid / potassium dichromate molar ratio of 7.5. .
The above oxidant aqueous solution was added in various amounts to the same aniline hydrochloride aqueous solution as in Example 1 to obtain a composition.

The effect of the amount of potassium dichromate on aniline on the conductivity and yield of the composition is shown in FIG. Incidentally, 1 mol of potassium dichromate in sulfuric acid is equivalent to 3 equivalents,
In the drawings, the equivalence of potassium dichromate means the equivalence of potassium dichromate to aniline as an oxidizing agent.

Since the aqueous oxidant solution used has a constant sulfuric acid / potassium dichromate molar ratio, the resulting composition has substantially constant conductivity, while the yield of the resulting composition is similar to that of the aniline in the aqueous oxidant solution. It is understood that it is almost proportional to the amount of potassium dichromate.

(5) Effect of aniline concentration on electrical conductivity and yield of composition Oxidizing agent aqueous solution in which potassium dichromate is dissolved in 3N sulfuric acid and sulfuric acid / potassium dichromate molar ratio is 7.5 and potassium dichromate concentration is 5.2% by weight. Was prepared. This aqueous oxidizing agent solution was added so that the equivalent number of potassium dichromate to aniline was 1/3 to obtain a composition according to the present invention. The tenth result
Shown in the figure.

When the sulfuric acid / potassium dichromate molar ratio in the oxidant aqueous solution is constant and the amount of potassium dichromate to aniline is constant, the conductivity is almost constant and the yield is almost constant regardless of the aniline concentration. It is possible to obtain a composition having

Example 3 6.48 g (0.050 mol) of aniline hydrochloride was added to 84 ml of 3N sulfuric acid (0.12
An aqueous solution of aniline dissolved in 6 mol) was prepared. The above aniline salt aqueous solution was added dropwise at room temperature to an aqueous solution in which 4.90 g (0.0167 mol) of potassium dichromate was dissolved, and after completion of the addition,
Aged for 30 minutes. The protonic acid / potassium dichromate molar ratio under the above conditions is 7.5.

The precipitated composition was filtered off, washed with water in the same manner as in Example 1, washed with acetone, and then vacuum dried to obtain a composition according to the present invention. The conductivity of this composition was measured in the same manner as in Example 1 and found to be 2.8 × 10 ^-2 S / cm.

Example 4 Tetrahydrofuran (45 g) was placed in a 300 ml flask,
Aniline 5g (0.0537mol) was dissolved in this.

Separately, 13.17 g (0.134 mol) of concentrated sulfuric acid was added to 82.2 g of water to prepare an aqueous oxidant solution (protonic acid / potassium dichromate molar ratio of 7.5) in which 5.27 g (0.0179 mol) of potassium dichromate was dissolved. Then, it was added dropwise to the above tetrahydrofuran solution of aniline at room temperature with stirring for 30 minutes. After the start of the dropwise addition, the solution was only colored yellow, but thereafter, a yellowish greenish brown powder was deposited, and after a while, the powder turned green.

After completion of the dropping, the mixture was stirred for another 30 minutes, after which the reaction mixture was poured into 600 ml of acetone and stirred for 2 hours, and then the composition was filtered off. After the composition was washed and dried in the same manner as in Example 1, the electric conductivity was measured and found to be 0.25 S / cm. The logarithmic viscosity of the concentrated sulfuric acid solution was 0.38 dl / g.

Example 5 A black-green powdery composition was obtained in exactly the same manner as in Example 4 except that 45 g of carbon tetrachloride was used instead of 45 g of tetrahydrofuran. This composition has an electrical conductivity
It was 0.21 S / cm, and the logarithmic viscosity of the concentrated sulfuric acid solution was 0.41 dl / g.

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum of the conductive organic polymer composition according to the present invention, FIGS. 2 and 3 are infrared absorption spectra of emeraldine and aniline black, respectively.
FIG. 4 (A) is a conductive organic polymer composition according to the present invention,
(B) is a polymer obtained by ammonia compensation of this conductive organic polymer composition, and (C) is a conductive organic polymer composition obtained by re-doping the polymer of (B) with sulfuric acid. It is each infrared absorption spectrum. FIG. 5 is a graph showing the weight residual ratio of the electrically conductive organic polymer composition and emeraldine according to the present invention upon heating. FIG. 6 is a graph showing the relationship between the sulfuric acid / potassium dichromate molar ratio of an aqueous oxidant solution having a constant sulfuric acid concentration and the electrical conductivity of the resulting conductive organic polymer composition in the method of the present invention. Fig. 7 shows the sulfuric acid / potassium dichromate molar ratio of an acidic sulfuric acid aqueous solution containing a constant concentration of potassium dichromate,
FIG. 8 is a graph showing the relationship between the yield of the obtained conductive organic polymer composition and the electric conductivity, and FIG. 8 shows the potassium dichromate concentration of the sulfuric acid acidic oxidant aqueous solution having a constant sulfuric acid / potassium dichromate molar ratio. FIG. 9 is a graph showing the effect of the obtained conductive organic polymer composition on the yield and the electric conductivity, and FIG. 9 shows the equivalence to aniline of a sulfuric acid acidic oxidizer aqueous solution having a constant sulfuric acid / potassium dichromate molar ratio. FIG. 10 is a graph showing the relationship between the yield and the conductivity of the obtained conductive organic polymer composition, and FIG. 10 is a graph showing the use of a fixed amount of an aqueous oxidant solution having a constant sulfuric acid / potassium dichromate molar ratio. 3 is a graph showing the relationship between the concentration of aniline hydrochloride and the yield and conductivity of the resulting conductive organic polymer composition.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masao Abe 1-2-1, Shimohozumi, Ibaraki City, Osaka Prefecture Nitto Electric Industry Co., Ltd. (72) Inventor Jun 1-2, 1-2-1, Shimohozumi, Ibaraki City, Osaka Prefecture No. Nitto Electric Industry Co., Ltd. (72) Inventor Takashi Ichise 1-2-2 Shimohozumi, Ibaraki City, Osaka Prefecture Nitto Electric Industry Co., Ltd. (72) Inventor Keiji Nakamoto 1-1-1, Shimohozumi, Ibaraki City, Osaka Prefecture No. 2 Nitto Electric Industry Co., Ltd. (72) Inventor, Keiji Yumoto 1-2 1-2 Shimohozumi, Ibaraki City, Osaka Prefecture Nitto Electric Industry Co., Ltd. (56) References JP-A-60-197728 (JP, A) British Patent 1216549 (GB, A) "Bulletin of the Chemical Society of Japan" 57 [8] (1984-8) P. 2254-2257.

Claims (1)

[Claims] 1. Substantially the general formula It consists of a repeating unit consisting of a quinonediimine structure represented by the formula: 0.5g / dl concentrated sulfuric acid solution is 0.38dl / g at 30 ℃.
A substantially linear polymer having the above logarithmic viscosity, containing an electron acceptor as a dopant and having an electric conductivity of 10
^-6 S / cm or more, a conductive organic polymer composition characterized by the above.