JPS6197328A - Polyazophenylene film and display element - Google Patents

Abstract

PURPOSE:A polyazophenylene film having electric conductivity and being useful as an electrode-activating substance of cells or a material for display elements such as photoswitches for use in electronics, obtained by electrochemically oxidizing phenylenediamine. CONSTITUTION:Phenylenediamine and an electrolyte (e.g., lithium iodide or lithium bromide) dissolved in a solvent such as acetonitrile or dimethylformami de is poured into a reaction apparatus equipped with an anode 2 of, e.g., plati num and a cathode 3 of, e.g., nickel. The phenylenediamine is electrochemically oxidized by application of a current between anode 2 and cathode 3 to deposit polyazophenylene having repeating units of the formula on the surface of anode 2. Anode 2 is withdrawn, washed with, e.g., acetonitrile and vacuum-dried to obtain the purpose film polyazophenylene.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a film-like polyazophenylene having a structure represented by the following formula as a repeating unit, and a display element using the same as a color former.

[Conventional technology]

In recent years, with the advancement of science and technology, the demand for electronic display elements, efficient batteries, various sensors, etc. has increased, and the development of a wide variety of conductive polymers is required.

So far, various electronically conjugated polymers such as polyacetylene, polythio-7-thienylene (yt?+7-thienylene), and polyvirol have been developed, and applications utilizing their electrical conductivity are currently being considered.

For example, JP-A-58789640 discloses a linear poly(2,5-thennylene) polymer, a method for producing the same, and a semiconductor made of the polymer. In the publication, an electrically conductive acetylene high 1 polymer is disclosed.

In addition, it has been proposed that the absorption spectrum change caused by the one-shot chemical redox reaction of 4-it polymers can be used in display elements for electronics such as optical switches and memories.So far, polythiophene, polypyrrole, and Although applied research has been carried out on 17-/ltl, the wavelength of absorbed light and the conditions for electrochemical redox reaction are limited for each polymer, so it has not yet been put to practical use.

1. [Problems to be solved by the invention] Various magneto-conjugated polymers that have been developed so far and whose applications are being considered degrade significantly in the air, or are extremely difficult to mold. It has the following problems.

Therefore, the current situation is that the practical application of these t-conjugated polymers is far behind.

Regarding display elements, to date, display elements using polyaniline are being considered as display elements using conductive polymers that are stable even in water, but strong acids such as sulfuric acid have been used as electrolytes. However, there is a problem in that the types of magnetic poles or containers are limited. In view of the above, there is currently a need to develop display elements using new materials that solve the problems of existing materials such as polythiophene, polypyrrole, and polyaniline.

[Means for resolving problems]

In the present invention, we will address the above problems, namely, that the electronically conjugated polymers that have been developed so far are extremely susceptible to deterioration in the air, and that it is extremely difficult to mold them. As a result of various studies to determine t-m, a film-like polymer compound having the structure t-mp return unit represented by the following formula: phenylenethia ξnot'l1lt
We have all found that it can be produced by vapor chemical oxidation. The film-like polymer compound mentioned above has electrical conductivity unique to electronically conjugated polymers.
It has the characteristic that it can be easily obtained in a film state suitable for practical use.

The film-like electronically conjugated polymer (polyazophenylene) of the present invention is obtained by electrochemically oxidizing phenylene diylene over a specific electrolyte.

An example of a ninth reactor for the electrochemical oxidation of phenylenediamine is shown in FIG. In Figure 1, 1 is a solution containing phenylenediamine, 2 is an anode, and 5 is a solution containing phenylenediamine.
is coated at the cathode, and polyazophenylene 4 is deposited on the anode surface.
is generated.

Pi, Nesagarasuji, etc. are used as the anode, and N1, etc. are used as the cathode.

Examples of electrolytes that can be used in producing the film-like polyazophenylene of the present invention include Lit.
Ha, K Temple's Alkaline Bon Dance, Be, Mg.

Alkaline earth metals such as Ca, Sr, Ba, Ou
, zn.

Examples include halides of various cations of transition metals such as Ag, Cd, and Au, and tetraalkyl ammonium such as tetramethylammonium and tetraethylammonium, but alkali metal halide salts are often used due to ease of reaction, especially LiI. and Liar are preferably used.

Solvents in which the above electrolyte is dissolved include acetonitrile, dimethylformamide, benzonitrile, hexamethylphosphoamide, pyridine, tetrapyrene carbonate, tetrahydro7rane, dioxane, methanol, ethanol, and the usual polar solvents in this issue. However, from the viewpoint of ease of reaction, a solvent with a higher dielectric constant is preferable.

The film-like polyazophenylene of the present invention can be produced by dissolving phenylene cyabane, which is a deuteron-conjugated molecule, and an electrolyte in the above-mentioned biosolvent, and dipping the anode and cathode into a ty solvent to generate a direct current or an alternating current. By applying an applied pressure, oxidative synthesis is carried out electrochemically on the anode surface. The type of electrolyte and phenylenediamine used is not particularly limited. The reaction temperature is also not particularly limited, but is preferably 80° C. or lower in order to avoid reaction between the solvent and phenylenediamine.

The texture and color of the reaction product are influenced by the electrolyte used and the magnitude or type of voltage applied, and by controlling these tones, a product of any shape and color can be obtained.

Usually, the applied voltage is a constant voltage or a scanning voltage in the range of -0.5 to 40V.

The film-like polyazophenylene of the present invention has 10-8 to
It has an electrical conductivity of about 1023/cIs, and therefore can be used as display elements for electronics such as '-polar material optical switches for batteries, and various sensors.

On the other hand, in order to solve the problems with conventional display elements such as the previous JPI, the present invention aims to provide a display element with novel characteristics, and in particular, the present invention aims to provide a display element with novel characteristics. The purpose is to provide a new type of display element that utilizes absorption spectrum changes caused by redox reactions.

That is, the present invention has one electrode as one electrode on a flat plate on a coloring body made of a conductive polymer compound, the flat electrode itself constitutes a part of a container holding an electrolyte solution, and the other electrode is provided in the container. 1jtM by applying current to both electrodes.
In a display element in which 14 acts as a dopant to generate a color, the flat plate electrode is synthesized on Nesa glass and is made of film-like polyazophenylene, and the electrolyte that becomes the dopant is a halogen compound. We provide dope/de-dope display indicators.

Display element U of the present invention uses polyazophenylene as the 4% polymer t4! The j+ characteristic is that by fully utilizing the properties of this conductive polymer, for example, it can be used in a water bath liquid system, which is rare in display elements that utilize the electrochemical redox reaction of conventional conductive polymers. The reaction must be possible, and in conjunction with this, the operating voltage for display must be -0.5 to 1. It has unprecedented advantages, such as low Ov, and the electrolyte used is chemically relatively stable halogenated Kinjo salt, rather than strong acid or explosive LiCjO4 etc. It has certain characteristics.

The conductive polymer polyazophenylene used in the display element of the present invention is usually prepared in the form of a film by an electrochemical oxidation method using gold halide as an electrolyte, but it can also be obtained by other methods. In the case of film-like polyazophenylene, which has the same properties in principle,
The method is not limited to this method.

In the present invention, the chemical oxidation method is to dissolve the substance to be oxidized in a container holding the electrolyte sludge and an anode and a cathode, and to apply electricity to the anode and cathode. It oxidizes the target material at 1JL.

The electrolyte used in the electrochemical oxidation reaction is Li, N
a, K % alkali metal, Be, Mg, Oa,
Sr.

8% alkaline earth gold - 1Ou, zn, cd, ^g
, halides of various cations of transition metals, tetramethylammonium, tetraethylammonium, and tetramethylammonium are used, and include many compounds used in general electrochemical reactions, but L
iBF4. LiG104゜＾go104 Temples are excluded. The electrolyte described here also corresponds to the electrolyte used in the electrochemical redox reaction of display elements.

The display element of the present invention has polyazophenylene synthesized on Nesa glass as one of the flat plate electrodes, the flat plate electrode itself constitutes a part of the container holding the electrolytic It has polarization. An example is shown in FIG. In the figure, polyazo 7-denylene 2 is placed on Nesa glass 1, and 3 is the other electrode, which is a nickel mesh in this example. 4 is a spacer, 5 is an upper lid, and the inside is filled with an electrolyte bath liquid 6. 7.8 When a voltage is applied to both ends, the display cable 2 changes color and functions as a display element.

The display cable of the present invention uses polyazophenylene synthesized on Nesa glass using an electrochemical oxidation method, and its function is improved by immersing it in or contacting it with the above-mentioned Kame W4 solution and applying a voltage. Express. As an electrolyte,
Alkali metal halide salts are preferred. Electricity used w4
There are no particular limitations on the amount of the dielectric and tetraelectric polymers. Further, the temperature at which it is used is not particularly limited, but it is preferably 80° C. or lower in order to avoid reaction between the solvent and the tortosome-conducting polymer. #As the solvent, polar solvents used in ordinary electrochemical reactions are used, but the reaction is particularly easy when water is used. When water is used as a solvent, the operating voltage of the display element is usually applied below the I pressure at which electrolysis of water occurs; It is.

〔Example〕

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

Example 1 Lithium iodide (0, IS Ii, 0.
0017), paraphenylenecyamine (0,54#,
After completely dissolving lithium iodide and para-phenylenediamine, a platinum plate was immersed as an anode and a nickel plate was immersed as a cathode in an argon gas atmosphere. When a constant pressure of .5V was applied, a red precipitate was immediately formed on the platinum plate.After 15 minutes of reaction, the 1!L electrode was taken out, washed with acetonitrile, and then dried under reduced pressure to form a film. The transmitted light of this film-like polyazophenylene is blue in color and the reflected light is red in color.Also, the electrical conductivity of this film-like polyazophenylene is It was '''5S/-.

The film-like polyazophenylene obtained as described above was analyzed using an infrared absorption spectrum, and the results are shown in FIG. -N=N- specific peak is 2250.1
600 and around 1520 to 1550 ra, and the production of polyazophenylene was confirmed.

Further, the elemental analysis results of this film-like polyazophenylene are as shown in the following table, and it can be seen that the target substance was obtained.

Example 2 Lithium iodide (0,151), paraphenylenediamine (0,54,9), and benzonitrile (50 ml) were charged in the same pot as in Example 1, and a platinum plate was used as an anode under an argon gas atmosphere. , a nickel plate was immersed as the IiA electrode, and 4.0 to 5. When one scanning pressure was applied at a scanning speed of 10 V/sec in the range of Ov, a blue precipitate was formed on the platinum plate. The electrical conductivity of the film obtained by taking it out, washing it with benzonitrile, and drying it is 2X1.
There were 6 o-'s/rn.

The result of analysis using the infrared absorption spectrum of the film-like polyazophenylene gold obtained by filtration as above δ ft
It is shown in Figure 5. -N=N- specific peak is 2250.
1600 and around 1520 to 1530011-', and the production of polyazophenylene was confirmed.

Further, the elemental analysis results of this film-like polyazophenylene are as shown in the table below, which shows that the target substance was obtained.

Example 3 Lithium chloride (0.04 I!, 0.001 solu), halapenylene diamine (0.541), and acetonitrile (50 rnt) were all charged into a reaction vessel, and a constant voltage of 4.5 V was applied in the same manner as in Example 1. When the voltage was applied, a green precipitate was immediately formed on the platinum electrode plate.The electrical conductivity of the film obtained after washing and drying was 1.1 x 10 s/square. The electrical conductivity increased to 2.0×10 S/city when fused and processed.

Example 4 Lithium iodide (0,049, 0,001 mol) and para-phenylenediamine (0,541) were charged into a reaction vessel, and t-t of ion-exchanged water (5011Lt) was added to completely dissolve, and then used as an anode. When a platinum plate and a nickel plate were immersed as a cathode and a constant voltage of 2.0V was applied, a dark blue film was immediately deposited on the platinum electrode plate. After 5 minutes of reaction, the electrode was removed and the pressure was reduced. A film was obtained by drying.

The electrical conductivity of this film is 2 x 10”2S at room temperature.
/ (To) I got it. From the results of the IR spectrum of this film, the existence of -N=N- bonds was confirmed. In addition, the results of elemental analysis of this film were H: 4.12%, a
: 69.08%, N: 26.80%, and it was confirmed that the desired shed was produced.

Example 5 Lithium iodide (0.04Ji!, 0.04Ji!) was placed in a reaction vessel.
001 mol゛], orthophenylenediamine (0.54
. When a constant pressure of Ov was applied, a dark green film was immediately deposited on the platinum shield plate. The electrical conductivity of the film obtained after washing and drying was 5 x 10-3 s/(to) at room temperature.

Example 6 Lithium iodide (0.04y, 0.001
Example 4
4. in the same way as 4. When a constant voltage of Ov was applied, a yellow-green film was deposited.

Example 7 Lithium iodide (0.04 g, 0.001 mol) and metaphenylene diamine (0.54 Ii) were placed in a reaction vessel, and ion-exchanged water (50 iJ) was added. In addition, 6. in the same manner as in Example 4. When a constant pressure of Ov was applied, a dark blue film was immediately deposited.

Example 8 A film of polyorthoazophenyl was synthesized on Nesa glass by magnetochemical polymerization, and a cell as shown in FIG. 4 was prepared using this film.

This cell was filled with a Q, I MLiBr aqueous solution, and with a nickel mesh as a counter electrode,
When a voltage of 2V was applied, the hue of the light transmitted through the cell quickly changed from blue to red.

When the voltage was further changed from 10.2V to +1.5V, the hue of the transmitted light changed from red to blue again. This color change can be repeated. Changes in the absorption spectrum accompanying this reaction are shown in FIG.

Example 9 When polyorthoazophenylene in the form of a film synthesized on Nesa glass in the same manner as in Example 8 is immersed in total ammonia water, the transmitted light of the film changes from blue to red. Using this product, the cell kfIr shown in FIG. 4 was manufactured in the same manner as in Example 8. Fill the cell with 0.1M lithium iodide aqueous solution,
When a voltage of 1.2 V was applied to the Nesa glass side, the transmitted light from the cell quickly changed to black. The change in absorption spectrum accompanying this reaction is shown in FIG.

Example 10 Polyparaazophenylene in the form of a "C" film was synthesized on Nesa glass by magnetochemical polymerization, and the cell shown in FIG. 1M
l, iBr water 1615. When a pressure of 10.2 V was applied to the Nesa glass side with ', c light filling, the hue of the transmitted light of the cell changed from green to red. Furthermore, the voltage (+″-0,2
When v-0,2v is applied, the hue of the cell transmitted light immediately changes to green and L again. The change in the absorption spectrum accompanying this reaction is shown in FIG. 7, and this reaction is reversible and can be repeated over and over again.

Example 11 A cell as shown in FIG. 4 was prepared using polymethazophenylene synthesized on Nesa glass.

0 for this. I MLiI Aqueous solution is filled with light, -0,2
When a voltage of V was applied, the hue of the light transmitted through the cell changed from yellow-green to yellow to red. Furthermore, the voltage 'i-0,2
When the voltage was changed from V to 1.2V, the hue of the cell transmitted light became yellow-green again.

Example 12 A cell as shown in FIG. 4 was prepared using polyvarazophenylene synthesized on Nesa glass, and a cell with 0. I MLi
Next, fill with O/water bath liquid. When a voltage from 10.2 V to 1.2 V was applied to the Nesa glass, the hue of the cell-transmitted light changed reversibly from red to green.

〔Effect of the invention〕

In the present invention, the phenylene diamine monomer is oxidized using a specific electrolyte, and a film-like phenylene diamine polymer is deposited on the hexode plate. The film-form polyazophenylene of the present invention not only has the electrical conductivity unique to electronically conjugated polymers, but also has the special feature that it can be obtained in a film form suitable for practical use.
1. The film-like polyazophenylene of the present invention can be used as an electric display element and various sensors, usually having a density of about 10-8 to 10-''8/f)1.

The display element of the present invention uses boriazophenylene/ as a conductive polymer. The reaction can be carried out in a small amount of aqueous solution. 9. Along with this, the operating pressure for display is -0.5 to 1. Something as low as Ov is fine, and furthermore,
LifJO uses strong acids and may be exposed to light.
There is an advantage that a chemically relatively stable halogenated metal salt can be used instead of a 4-hydrogen salt.

[Brief explanation of the drawing]

Figure 1 is a schematic diagram of an example of a reaction apparatus used in the production method of the present invention, Figure 2 is an IR spectrum of the polyazophenylene obtained in Example 1, and Figure 5 is the IR spectrum of the polyazophenylene obtained in Example 2. It is an XR spectrum of polyazophenylene. FIG. 4 is a schematic perspective view and a sectional view of one example of the display element of the present invention. Fifth
The figure shows the change in the absorption spectrum due to voltage of the polyorthoazophenylene of Example 8, Figure 6 ti, the change in the return spectrum due to one pressure of the polyorthoazophenylene of Example 9, and Figure 7 shows the change in the absorption spectrum due to voltage of the polyorthoazophenylene of Example 10. 7 shows changes in absorption spectrum due to voltage. Applicant's Agent Kaoru Furuya 1 Figure 4 Polymer Figure 2 Wave number (il) Wave number (m') Figure 4 Figure 5 Wavelength (nm) Figure 6 Wavelength (nm)

Claims (1)

[Claims] 1. A film-like polyazophenylene having a structure represented by the following formula: ▲Mathematical formula, chemical formula, table, etc.▼ as a repeating unit. 2. Having a color forming body made of a conductive polymer compound as one of the flat plate electrodes, the flat plate electrode itself forming a part of a container for holding an electrolyte solution, having the other electrode in the container, and having both electrodes. In a display element in which an electrolyte becomes a dopant and a coloring body develops color when electricity is applied to the electrode, the flat plate electrode is a film-like polyazophenylene synthesized on Nesa glass, and the electrolyte that becomes the dopant is a halogen compound. A doped/undoped display element characterized by: 3. The display element according to claim 2, wherein the halogen compound is an alkali metal halide salt.