JPH0360344B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a novel organic conductive material. More specifically, the present invention provides an organic conductive material which is characterized in that it is made highly conductive by adding inorganic salts and organic salts to a diacetylene compound, polymerizing the mixture, and applying a voltage to the molded product. This provides a simple manufacturing method.

In recent years, with remarkable technological progress in the electronics industry, there has been an urgent need to develop materials for electronics parts that are suitable for various purposes. 1 of them
Due to their excellent flexibility, processability, and chemical resistance, conductive materials mainly made of organic materials are attracting attention as wiring materials, electrode materials, sensors, photoelectric conversion elements, memory elements, and molecular devices. There is.

Conventionally, organic conductive materials have been known, such as polyacetylene, poly(p-phenylene), polyphenylene sulfide, polypyrrole, etc., to which doping components are added, and these have 10 ^-1 to 10 It shows an electrical conductivity of about ³ Scm ^-1 , but
Compared to inorganic conductive materials, it is considerably lower and less stable, so it cannot be said to be sufficient for practical use.

The present inventors have repeatedly researched organic conductive materials that can be put to practical use, and first, as a method of adding a doping component to a diacetylene polymer compound as a main component, the diacetylene compound crystals were polymerized in a dopant atmosphere. Or a doped solid phase polymerization method in which a diacetylene compound is crystallized in the presence of a doping component and then the crystals are polymerized,
It was discovered that a polymer crystal with an electrical conductivity of about 10 ^-4 S/cm can be obtained, but it is also possible to add a doping component to the diacetylene compound, which is useful as a material for high-strength and organic conductive materials. Then, after polymerizing it, it can be molded and electrodes attached to both ends, or it can be molded before polymerization, electrodes can be attached to both ends, and then a voltage can be applied to make it highly conductive. A method for manufacturing an organic conductive material was discovered, and the present invention was accomplished.

That is, the present invention provides a specific diacetylene compound with a concentration of 10 ^-3 to 10 per mole of the diacetylene compound.
Adding at least one doping component selected from inorganic salts and organic salts in a molar ratio,
Next, after polymerizing this, it is molded, and electrodes are provided at both ends of the molded product, and a voltage is applied between them, or alternatively, it is first molded, electrodes are provided at both ends of the molded product, and a voltage is applied between them. The present invention provides a method for producing an organic conductive material, which is characterized in that it is made highly conductive by polymerizing while applying a voltage to the organic conductive material.

The diacetylene compound used in the present invention has the general formula R ₁ -C≡C-C≡C-R ₂ , even if substituents R ₁ and R ₂ are the same,
or may be different, including hydrogen, halogen, metal, alkyl, alkenyl, alkynyl, aryl, alkaryl, aralkyl group, or halogen, alcohol, carboxyl, amine, amide, urethane, ester, sulfonyl,
It is selected from sulfoxyl, sulfinyl, silyl, siloxyl, phosphoro, phosphate, keto, aldehyde groups, etc., and basically,
It is a general term for compounds having a conjugated diacetylene group, and includes various derivatives thereof. Typical examples thereof include, for example, 2,4-hexadiyne, 1,4-diphenylbutadiyne, 1,11,
Hydrocarbon compounds such as 13,23-tterracosatetrine and their derivatives; Alcohols such as 3,5-octadiyn-1,8-diol;
and esters of these carboxylic acids and sulfonic acids; heterocyclic compounds such as 1,4-dipyridyl-1,3-butadiine, 1,6-dipyridyl-2,4-hexadiine, and derivatives thereof;
Acids such as 1,3-butadiyn-1,4-dicarboxylic acid, hexadeca-13,15-deinoitsucic acid, and their esters, amides, urethanes, and salts; metal acetylides such as bis(1,3-pentadiynyl)mercury and cyclic acetylenes such as 0,0-bis-phenylglutaratoacetylene. These diacetylene compounds are usually used as a single component, but two or more types can be used in combination if necessary.

In addition, doping components such as inorganic salts and organic salts used in the method of the present invention are the general formula, M _r X _s , where M is Ag, Cu, Co, Fe, Mn, Cr, Li, Na, K ,
Mg, Ca, N( _CH3 ), N( _C2H5 ) ₄ , N _{( C3H7 ) 4} ,
N( _C4H9 ) ₄ , N-Ph4 _, etc., and X is Cl, Br, I, _ClO4 , _BF4 , _PF6 , _{NO3 , SbF6} ,
It is selected from SO ₃ , SO ₄ , SO ₃ -Ph, CO _3, etc., and r and s are 1 to 3 selected so that the ion valence of the positive and negative ions and the multipliers of r and s are equal. is an integer. for example,
AgClO ₄ , AgNO ₃ , CuCl ₂ , LiClO ₄ , Na ₂ SO ₄ ,
Inorganic salts such as MgCO ₃ , N(C ₂ H ₅ ) ₄ ClO ₄ , N
They are organic salts such as (C ₄ H ₉ ) ₄ AsF ₆ and LiSO ₃ -Ph, and these doping components may be used alone or in combination of two or more.

Methods for adding these doping components to the diacetylene compound include simply mixing them, mixing and dissolving them in a solvent in which both are soluble, and crystallizing the diacetylene.
Any method is acceptable.

In addition, the content of the doping component depends on the required electrical conductivity, and the content of the doping component is determined per mole of diacetylene compound.
The proportion is selected between 10 ⁻³ and 10 mol.

It can be easily inferred that the polymerization of a diacetylene compound to which a doping component has been added can be carried out in the same way as the polymerization of a normal diacetylene compound. A solid sample is made into a polymer by exposing it to radiation such as X-rays and gamma rays, and high pressure of several thousand to hundreds of thousands of atmospheres below the decomposition temperature of the sample, for a period of several minutes to several tens of hours. be able to. Generally, the degree of polymerization of the polymer is between several tens and several thousand.

In the first method of the present invention, a diacetylene compound to which a doping component has been added is polymerized and then molded, and electrodes are provided at both ends of the molded product.
A voltage is applied between them.

Further, in the second method of the present invention, after molding the diacetylene compound to which a doping component has been added, electrodes are provided at both ends of the molded body,
Polymerization is carried out while applying a voltage during this time.

For molding a sample containing a diacetylene compound with a doping component added, there are several possible molding methods, such as making it into a pellet using an ordinary tablet molding machine, or using the molded product as it is during high-pressure polymerization, but which method is best? But it doesn't matter.

Methods of providing electrodes at both ends of the molded product include applying a conductive paste such as gold paste, silver paste, or carbon paste, vapor-depositing metal such as gold, silver, or aluminum, or depositing a gold plate, platinum plate, etc.
There is a method such as sandwiching it between silver plates.

Methods for applying voltage to such a product with electrodes attached at both ends include batteries, stabilized power sources, and the like, and either direct current or alternating current may be used. The voltage is appropriately selected from several millivolts to several tens of volts. As the conductivity of the sample gradually increases, the amount of current that flows increases even when a small voltage is applied, so the applied voltage becomes smaller.

The organic conductive material thus obtained by the production method of the present invention has a conductivity of about 10 ^-4 to 10 S/cm, is not only stable in general environments such as air, but also has diacetylene It also has a large elastic modulus, which is a characteristic of polymer compounds, so it can be used for various electronic parts,
It is suitable as a material for electrodes, sensors, photoelectric conversion elements, etc.

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 418 mg (1 mmol) of 2,4-hexadiyne-1,6-diol p-toluenesulfonic acid ester (PTS) synthesized and purified by a conventional method and 207 mg (1 mmol) of silver perchlorate (AgClO ₄ ) were added. acetone 20
ml, and a PTS crystal containing AgClO ₄ as a doping component is prepared by slow evaporation. It is clear that AgClO ₄ is added to this crystal at a ratio of approximately 5 mol% to 1 mol of PTS.
Confirmed by quantitative titration of Ag ⁺ ions. The crystals were sufficiently ground in an agate mortar, vacuum-sealed in a glass ampoule, and irradiated with 10MR gamma rays to form a polymer. Take about 150 mg of polymer sample,
It was molded into circular pellets with a diameter of 1.3 cm and a thickness of about 0.06 cm using a tablet molding machine. Silver paste is applied to an area of approximately 0.5 cm ² on both sides of the pellet, and a voltage is applied by connecting an ammeter and a stabilized power source using a platinum wire as a lead wire, as shown in FIG. The current-voltage relationship at that time is shown in FIG. in the beginning,
When the voltage is gradually increased, a few μA flows at a few V, so the resistance is measured to be about 10 ⁶ Ω, but at a certain voltage, a sudden decrease in resistance occurs, and the voltage required to flow the same current descends. If the voltage is further applied, 1mA will flow at 0.05V, the resistance will be 50Ω, and the conductivity will be 2.4 _X 10 ^-3 S/cm.
It became. The conductivity increased 10 ³ times by applying voltage. This conductivity did not change even after being left in air for more than one month.

Example 2 50 mg of the PTS AgClO ₄ doped monomer sample obtained in Example 1 was packed into a Teflon capsule, incorporated into pyroferite, and subjected to a high pressure of about 50,000 atmospheres in a link pressurizer. High pressure polymerization was carried out for 30 minutes. This polymer sample had already been taken out in the form of a circular pellet with a thickness of 0.2 cm and a diameter of 0.3 cm, so gold paste electrodes were attached to both sides of the pellet and a voltage was applied in the same manner as in Example 1. After applying 0.1V for one day, I measured the current and found that it was flowing 67mA, and the resistance was 1.5Ω.
The electrical conductivity was 1.9S/cm.

Example 3 1,6-dicarbazoyl-2,4 according to a conventional method
-Synthesize and refine hexadiyne (DCHD) into diacetylene monomer crystal powder. To this, 30% by weight of copper perchlorate (CuClO ₄ ) is added as a doping component, and the mixture is thoroughly ground and mixed in an agate mortar. 50 mg of this sample was packed in a Teflon tube in the same manner as in Example 2, platinum plates were attached to both ends as electrodes, leads were taken with gold foil, and the sample was incorporated into pyroferrite, and a pressure of 83,000 atmospheres was applied while applying a voltage of 1 V for 12 hours. High-pressure polymerization was carried out over time. The sample was obtained as a polymer molded into a circular pellet with a thickness of 0.3 cm and a diameter of 0.3 cm, and its electrical conductivity was measured by the two-terminal method to be 5 S/cm.

Example 4 DCHD monomer prepared in Example 3 and CuClO ₄
150mg of the mixed powder was made into a tablet with a diameter of 1.3
The pellet was molded into a circular pellet with a size of 0.1 cm and a thickness of 0.1 cm, electrodes with an area of 0.5 cm ² were attached to both sides of the pellet using silver paste, and a voltage of 3 V was applied while thermal polymerization was performed at 120° C. for 24 hours to obtain a polymer. When the conductivity was measured using the two-probe method with this electrode configuration, it was 2 _x 10 ^-2 S/cm.

Example 5 A metal acetylide type diacetylene compound, bis(1,3-petadiynyl)mercury (BPM), was synthesized and purified according to a conventional method, and 326 mg (1
196 mg (1 mmol) of lithium hexafluoroarsenite (LiAsF ₆ ) is added to the solution (1 mmol), and then 30 ml of THF is added. This suspension is evaporated to form a mixture of diacetylene compound and doping component, which is then sealed in a vacuum tube and heated to 120°C.
A polymer was obtained by heating for 10 hours. This sample was molded and electrodes were attached in the same manner as in Example 1, and a voltage was applied by a method of flowing a constant current. The relationship between the current and conductivity is shown in FIG. This figure shows that in a region with high resistance, a jump in conductivity can be seen with the application of 1.1V, and as the resistance decreases and a large current flows, a similar change can be seen with the application of 0.08V. It shows. The final conductivity of this sample was 8 _X 10 ^-3 S/cm.

Example 6 Hexadeca synthesized and purified according to conventional methods
Add 50% by weight of iron chloride (FeCl ₃ ) to 13,15-deinoscinic acid (HDDA) and dissolve it in methanol.
This is used as evaporation to remove doping components.
A diacetylene monomer to which FeCl ₃ was uniformly added was polymerized by irradiating it with ultraviolet light for 60 hours.
The following treatments were carried out in the same manner as in Example 1, and the electrical conductivity of the obtained material was 3 _X 10 ^-4 S/cm.

Example 7 AgClO ₄ was added as a doping component to bis(2,5-ditrifluoromethylphenyl)butadiin (FDA) synthesized and purified according to a conventional method.
10% by weight was added, once dissolved in methanol, and then evaporated to obtain thoroughly mixed powder diacetylene crystals. Put this in a vacuum sealed tube and emit gamma rays.
Polymerization was performed by 5MR irradiation. The following operations were carried out in the same manner as in Example 1, and the electrical conductivity of the obtained material was 10 S/cm.

Example 8 The same operation as in Example 7 was carried out using tetrabutylammonium hexafluorophosphate ((C ₄ H ₉ ) ₄ N PF ₆ ) as the doping component.
The electrical conductivity of the material obtained was _{1.times.10.sup.} ^-4 S/cm.

Example 9 Di(m-acetylaminophenyl)butadiin (m-AAPB) synthesized and purified according to a conventional method
To this, 10% by weight of tetraethylammonium perchlorate ((C ₂ H ₅ ) ₄ N ClO ₄ ) was added as a doping component, dissolved in acetone, and evaporated to obtain a diacetylene monomer powder to which the doping component was added sufficiently uniformly. . This was sealed in a vacuum tube and irradiated with 600MR of gamma rays to form a polymer. When a voltage was applied to this sample in the same manner as in Example 1, it exhibited a conductivity of 3 _x 10 ^-4 S/cm.

Example 10 The same operations as in Example 1 were carried out using n-butoxycarbonylmethylurethane of 4,6-decadiine-1,10-diol, which was synthesized and purified according to a conventional method, as a diacetylene compound. . The material obtained exhibited a conductivity of 2 _X 10 ^-2 S/cm.

Example 11 1, 11, 13, 15, 23 synthesized and purified by conventional methods
- 322 mg (1 mmol) of tetracosatetrine and 207 mg (1 mmol) of silver perchlorate (AgClO ₄ ) were dissolved in 20 ml of acetone, and the mixture was dissolved by slow evaporation.
A diacetylene crystal containing AgClO ₄ as a doping component is created. This crystal has
AgClO ₄ is about 1 mole of cyacetylene monomer
It was confirmed by quantitative titration of Ag ⁺ ions that it was added at a ratio of 20 mol%. This crystal,
After thoroughly pulverizing the mixture in an agate mortar, it was vacuum sealed in a glass ampoule and irradiated with 50MR gamma rays to obtain a polymer. Approximately 100 mg of the polymer sample was taken and molded into a circular pellet with a diameter of 1.3 cm and a thickness of approximately 0.15 cm using a tablet molding machine. Silver paste was applied to an area of about 0.5 cm ² on both sides of the pellet, and a stabilized AC power source was connected to it using a platinum wire as a lead wire, and a voltage of 3 V was applied at a frequency of 0.003 Hz. 10 after voltage application
When removing the sample in time and measuring the conductivity
It became 50S/cm.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram showing an example of a method of applying a voltage to a sample in the method for producing an organic conductive material according to the present invention, in which reference numeral 1 is an electrode, and 2 is a doping component added to diacetylene. Added sample, 3
is a stabilized power supply, and 4 is an ammeter. FIG. 2 is a graph showing the relationship with the current when voltage V is applied to the sample in the method for producing an organic conductive material of the present invention. Further, FIG. 3 is a graph showing the change in conductivity with respect to current when the voltage application method is performed at a constant current in the method for producing an organic conductive material of the present invention, and the numbers in the figure are It shows the potential when the conductivity increases rapidly.

Claims (1)

[Claims] 1 General formula R ₁ -C≡C-C≡C-R ₂ (substituents R ₁ and R ₂ may be the same or different, hydrogen, halogen, Metal, alkyl, alkenyl, alkynyl, aryl, alkaryl, aralkyl group, or halogen, alcohol, carboxyl, amine, amide, urethane, ester, sulfonyl, sulfoxyl, sulfinyl, silyl, siloxyl, keto, aldehyde, phosphoro, A diacetylene compound ^represented by the general _formula M _r Ag, Cu, Co, Fe, Mn, Cr, Li, Na,
K, Mg, Ca, N(CH ₃ ) ₄ , N(C ₂ H ₅ ) ₄ , N
( _C3H7 ) ₄ , N( _{C4H9 ) 4 ,} N- _Ph4 , and X is Cl, Br, I, _ClO4 ,
BF ₄ , PF ₆ , AsF ₆ , NO ₃ , SbF ₆ , SO ₃ , SO ₄ ,
An anion selected from SO ₃ -Ph, CO ₃ , and r and s are integers of 1 to 3), at least one doping component selected from inorganic salts and organic salts. Add,
A method for producing an organic conductive material, which is characterized in that the product is then polymerized and then molded, electrodes are provided at both ends of the molded product, and a voltage is applied between them to make the material highly conductive. 2 General formula R ₁ -C≡C-C≡C-R ₂ (substituents R ₁ and R ₂ may be the same or different, hydrogen, halogen, metal, alkyl, alkenyl, Alkynyl, aryl, alkaryl, aralkyl groups, or substituents thereof, including halogen, alcohol, carboxyl, amine, amide, urethane, ester, sulfonyl, sulfoxyl, sulfinyl, silyl, siloxyl, keto, aldehyde, phosphoro, phosphonate group A diacetylene compound represented by ^the general formula M _r X _s (M is Ag, Cu, Co, Fe, Mn, Cr, Li, Na,
K, Mg, Ca, N(CH ₃ ) ₄ , N(C ₂ H ₅ ) ₄ , N
( _C3H7 ) ₄ , N( _{C4H9 ) 4 ,} N- _Ph4 , and X is Cl, Br, I, _ClO4 ,
BF ₄ , PF ₅ , AsF ₆ , NO ₃ , SbF ₆ , SO ₃ , SO ₄ ,
An anion selected from SO ₃ -Ph, CO ₃ , and r and s are integers of 1 to 3), at least one doping component selected from inorganic salts and organic salts. Add,
Next, after molding this, electrodes were provided at both ends of the molded body, and while applying a voltage between them,
A method for producing an organic conductive material characterized by polymerizing it to make it highly conductive.