JPH0344582B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel organic conductive material and a method for producing the same. In more detail,
The present invention relates to a novel organic conductive material having as a basic component a polyyne composition chemically containing 0.8 to 1.2 copper atoms per 20 carbon atoms, to which a doping agent is added.

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
One of the most important aspects of conductive materials is that they have excellent flexibility, processability, and chemical resistance.
It is attracting attention as a wiring material, electrode material, sensor, and photoelectric conversion element.

By the way, so far, organic conductive materials have been
Polyacetylene, poly(p-phenylene), polyphenylene sulfide, polypyrrole, etc. with doping agents added are known.
Although it exhibits an electrical conductivity of about 10 ^-1 to 10 ² Scm ^-1 , it is considerably lower than inorganic conductive materials and is inferior in stability, so it cannot be said to be sufficient for practical use.

In view of such social demands and the current state of research, the present inventors have conducted extensive research to develop practical organic conductive materials with high electrical conductivity.As a result, many ethynyl compounds have (Hay et al.,
J.Org.Chem., vol.27, p.3320-3321), which contains 0.8-1.2 copper atoms per 20 carbon atoms in terms of chemical bonds, obtained by applying this method to the oxidative coupling of acetylene. It has been discovered that a polyyne composition containing a doping component as a main component has a high electrical conductivity, and based on this knowledge, the present invention has been completed.

That is, the present invention provides (a) 0.8 copper atoms per 20 carbon atoms obtained by oxidative coupling of acetylene in the presence of oxygen using a catalyst consisting of a cuprous salt and a tertiary amine as a ligand. The present invention provides an organic conductive material comprising a polyyne composition containing chemically bonded 1.2 polyynes, and (b) at least one doping component selected from electron-accepting compounds and electron-donating compounds. be.

The polyyne composition used as component (a) of the present invention is a polymer obtained by oxidative coupling of acetylene in the presence of oxygen using a catalyst consisting of a cuprous salt and a tertiary amine as a ligand. ,
The basic structure is represented by the formula (-C≡C) _-o , and the degree of polymerization n is usually about 3 to 20.
The copper ion used as an oxidation coupling catalyst forms a chemical bond with the terminal acetylene, such as forming an acetylide or coordinating to a triple bond, resulting in a structure containing 0.8 to 1.2 copper atoms per 20 carbon atoms. It is a substance.

In addition, as the doping component of component (b), for example, an electron-accepting compound such as iodine, bromine, chlorine, arsenic pentafluoride, antimony pentafluoride, sulfur trioxide, perchloric acid, silver perchlorate, or Electron donating compounds such as lithium, sodium, potassium, lithium naphthalide, sodium naphthalide, potassium naphthalide are used. These may be used alone or in combination of two or more.

The content of the doping component is suitably within a range not exceeding 70% by weight, and is appropriately selected within this range depending on the desired electrical conductivity.

The organic conductive material of the present invention has an electrical conductivity of 10 -4 to 10 ^-4 depending on the type and content of the doping component.
It can be controlled within a range of about 10 ^-1 .

The organic conductive material of the present invention is preferably produced by introducing acetylene into a solution containing cuprous chloride and the ligand tetramethylethylenediamine in the presence of oxygen.
A polyyne composition chemically containing 0.8 to 1.2 copper atoms per 20 carbon atoms is formed, and then an electron-accepting compound and an electron-donating compound selected from an electron-accepting compound and an electron-donating compound are added to the polyyne composition thus obtained. It can be manufactured by doping with at least one substance.

The acetylene used as a raw material in this case is
For example, a gas generated by adding water to calcium carbide and dried through a desiccant such as calcium chloride, or a gas stored in an acetylene gas cylinder can be used.

Further, a solution containing cuprous chloride and the ligand tetramethylethylenediamine is a suitable oxidation coupling catalyst known in the above-mentioned literature of Hay et al., and the solvent is methanol, ethanol, acetone, dimethylformamide, dimethyl Acetamide, acetonitrile, N-methylpyrrolilodone, benzene, toluene, etc. can be used. The concentration of the solution is 0.001mol/~
Approximately 0.3 mol/mole is preferable.

In a more advantageous implementation, oxygen is introduced into the solution containing cuprous chloride and the ligand tetramethylethylenediamine, and acetylene gas is also introduced into this solution. At this time, the color of the solution changes from blue to dark blue, and a black precipitate gradually forms. This black precipitate is repeatedly washed with water and diluted hydrochloric acid, further washed with acetone, and then vacuum dried to obtain a polyyne composition as an insoluble and intangible black solid. This material was stable in air, and as a result of analysis by photoelectron spectroscopy, the abundance ratio of carbon and copper elements was 20:1. The copper element content of this polyyne composition is carbon element: copper element = 20: 0.8 ~
20:1.2.

The polyyne composition thus obtained is 10 ^-12 S
It has an electrical conductivity of cm ⁻¹ , but it can be made to have an even higher electrical conductivity by doping.

That is, the polyyne composition is formed into a powder or a pellet, and then exposed to a gas atmosphere containing an electron-accepting compound, an electron-donating compound, or a mixture thereof, or immersed in a solution containing the same. dope the ingredients. In this way, the electrical conductivity is 10 ^-4 ~
It can be increased up to 10 ^-1 Scm ^-1 .

The polyyne composition used in the present invention is preferably thoroughly washed to remove impurities, but it can be used even if it contains a certain amount of copper ions from the catalyst remaining during manufacturing, water by-products, or organic solvents. can do.

The organic conductive material of the present invention has constant high electrical conductivity over a wide temperature range and is stable in the air, so it is suitable as a material for various electronic components, electrodes, sensors, photoelectric conversion elements, etc. It is.

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

Reference example 1 1 g (0.01 mol) of cuprous chloride in 100 ml of acetone
1.2g of tetramethylethylenediamine dissolved in
Add to make a catalyst solution. Bubble oxygen into this.

32g (0.5mol) of calcium carbide and 20g of water
ml of the acetylene gas generated is dried through a trap in a dry ice methanol bath and a calcium chloride tube and introduced into the catalyst solution prepared as described above. The catalyst solution changes from blue to dark blue, and a black precipitate gradually forms. This precipitate was filtered, washed repeatedly with water and diluted hydrochloric acid, and further washed with acetone, and then dried under reduced pressure to obtain 3.8 g of a black solid polyyne composition.

The physical properties of this material are shown below.

Abundance ratio of carbon and copper elements Actual value C:Cu=20:0.96 (photoelectron spectroscopy) Infrared absorption based on C≡C bond 2130cm ^-1 Electrical conductivity 10 ^-12 Scm ^-1 Reference example 2 Previous inventors The method involves doping an electron-accepting compound or an electron-donating compound to a butadiinyl copper coordination polymer compound having a structure in which a plurality of basic units expressed by the formula H-C≡C-C≡C-Cu are bonded. We are proposing an organic conductive material obtained by this method. This basic component, the butadiinyl copper coordination polymer compound, undergoes explosive denaturation when subjected to external stimulation, such as impact, thermal stimulation, electrical stimulation, etc. Specifically, a butadiinyl copper coordination polymer compound is placed in a vacuum degassed glass ampoule,
When heated from the outside with a gas burner to around 200℃, it instantly undergoes explosive metamorphosis.

The polyyne compositions of the present invention are quite stable and do not undergo denaturation even when heated for more than 10 minutes under the same conditions.

Example 1 50 mg of the polyyne composition obtained in Reference Example 1 was pressure-molded into a disk shape to form pellets with a diameter of 13 mm and a thickness of 0.50 mm. Four platinum wire electrodes are fixed on the circumference of this pellet with gold paste and suspended in a container containing solid iodine. The interior of the container is evacuated to cause iodine deposition to occur and to advance doping into the pellets of the polyyne composition. After 5 days, the iodine content of the pellets was approximately 56% by weight.
The electrical conductivity measured by the van der Pauw method is
It was 0.13Scm ^-1 .

Example 2 Sample pellets were formed in the same manner as in Example 1 and doped with antimony pentafluoride under the same conditions. After 3 days, the antimony pentafluoride content was approximately 30% by weight, and the electrical conductivity was 5×10 ⁻² Scm ⁻¹ .

Claims (1)

[Claims] 1 (a) Chemical coupling of 0.8 to 1.2 copper atoms per 20 carbon atoms obtained by oxidative coupling of acetylene in the presence of oxygen using a catalyst consisting of a cuprous salt and a tertiary amine as a ligand. An organic conductive material comprising a polyyne composition containing a bond and (b) at least one doping component selected from electron-accepting compounds and electron-donating compounds.