JPH0125509B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel conductive organic polymer compound and a method for producing the same.

More specifically, 1,2,4,5-tetrazine-
The present invention relates to doped tetrazine polymers formed from a conjugated polymer containing a 3,6-diyl group in the main chain and an electron-accepting compound, and a method for producing the same.

In recent years, when polyacetylene, which is an organic polymer compound, is doped with an electron-accepting substance (electron-accepting dopant) or an electron-donating substance (electron-donating dopant), a charge transfer complex formation reaction occurs between the polyacetylene and the dopant, and electron Since it was discovered that a conductive organic polymer compound exhibiting high electrical conductivity based on conduction can be obtained, such an organic polymer compound has attracted attention.

Typical examples of such organic polymer compounds include polyphenylene, polyphenylene sulfide, polypyrrole, polythienylene, and the like, in addition to the above-mentioned polyacetylene.

Conductive organic polymer compounds exhibiting high electrical conductivity are formed from these organic polymer compounds because the free charges (carriers) generated when these organic polymer compounds form a complex with the dopant. It is explained that this is because it becomes possible to move through a conjugated double bond or a conjugated system of a lone pair of electrons and a double bond in an organic polymer compound.

The present inventors focused on the electron-donating properties and conjugation properties of heterocyclic compounds, and as a result of intensive research, we found that 1,2,4,
The inventors have discovered that a 5-tetrazine polymer can be doped with an electron-accepting dopant to become a conductive organic polymer compound that exhibits high electrical conductivity, and have achieved the present invention.

That is, the present invention provides the following general formula [] [However, in the formula, R is a group represented by the following formula (a) or (b) (-CH=CH(-n...(a) -Q(-X-Q(-m...(b)) Yes, in formulas (a) and (b), n is 1 to
represents an integer of 5, m is 0 or 1, Q represents phenylene or naphthylene, and X represents a direct bond, -O- or -S-. ] A doped tetrazine polymer characterized in that it is formed from a tetrazine polymer mainly consisting of repeating units represented by the following and an electron-accepting compound, and a method for producing the same.

The tetrazine polymers of the present invention mainly consist of repeating units represented by the above formula [], but may contain small amounts of other repeating units as long as they do not substantially adversely affect conductivity. It's okay.

In formula [], -R- is the following formula (a) or (b) (-CH=CH)-n...(a) -Q(-X-Q)-m...(b) [However, n represents an integer from 1 to 5, and m is 0 or 1. Q represents phenylene or naphthylene, and X is a direct bond, -O- or -S-. ], particularly preferably n
is a bonding unit of formula (a) in which Q is 1 or 2 or a bonding unit of formula (b) in which Q is phenylene.

For the production of tetrazine polymers mainly composed of repeating units represented by the above formula [], known methods can be used as they are, for example,
34499, i.e., dinitrile and hydrazines are reacted in the presence of a sulfur-containing compound to form the corresponding dihydrotetrazine polymer, which is then oxidized with sodium nitrite, etc. There are several methods.

Electron-accepting compounds to be doped into the above-mentioned tetrazine polymers include halogens such as iodine, bromine, and bromine iodide; antimony pentafluoride, arsenic pentafluoride, titanium tetrachloride, tin tetrachloride, iron trichloride, etc. metal halides; and Lewis acids such as sulfur trioxide. These electron-accepting compounds are used in an amount of 5 to 100 parts by weight of the tetrazine polymer.
It is doped with 500 parts by weight, preferably 10-400 parts by weight. If the amount of doping is less than this, electrical conductivity will not be developed, and even if the amount of doping exceeds this, it is not only difficult to expect an improvement in electrical conductivity, but in some cases, it may even decrease. be.

In the present invention, doping means adding an electron-accepting compound to the tetrazine polymers so that the tetrazine polymers have higher conductivity than the original tetrazine polymers. The relationship between the tetrazine polymer and the electron-accepting compound may be a chemical bond, for example, a complex, or a simple mixed state.

In order to dope tetrazine polymers with an electron-accepting compound, (i) In the case of an electron-accepting compound that is itself a gas or has a vapor pressure, such as halogens, antimony pentafluoride, or sulfur trioxide, (ii) So-called wet doping method, in which tetrazine polymers are immersed in a solution of an electron-accepting compound dissolved in an inert solvent, etc. can be adopted.

In the vapor phase doping method, the doping amount can be adjusted by controlling the temperature of the dopant atmosphere, the dopant partial pressure, and the doping time, and thereby the electrical conductivity to be developed can also be adjusted. .

At this time, the temperature of the dopant atmosphere is generally -
The temperature is 30 to 250°C, preferably 0 to 200°C. If it is less than that, the doping rate will be slow, and if it is more than that, it will be difficult to control or cause deterioration of the polymer, which is not preferable.

The dopant partial pressure is 1 mmHg to 10 atm,
Preferably, the pressure is in the range of 10 mmHg to 5 atm.
Below that, doping is generally slow, and above that there is no effect of pressure increase.

Doping time is generally 1 minute to 1000 hours,
Preferably it is 5 minutes to 500 hours.

Inert solvents used in wet doping are those that react with electron-accepting compounds or tetrazine polymers, deactivating their ability as electron-accepting compounds, or modifying the tetrazine polymers to restore their original properties. A solvent that does not impair functionality. Examples of such inert solvents include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; hydrocarbons such as hexane, heptane, petroleum ether, and cyclohexane; aromatic solvents such as benzene, toluene, xylene, nitrobenzene, and anisole; Ethers such as ether, tetrahydrofuran, and dioxane,
Esters such as ethyl acetate, butyl acetate, Celsolve acetate, isoamyl acetate, alcohols such as methanol, ethanol, isopropanol, butanol, aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, etc. Examples include solvents such as nitromethane and acetonitrile.

Of course, these solvents are appropriately selected depending on the solubility of the dopant. The dopant concentration in the solvent, immersion temperature, and time in the wet doping method are not particularly limited, but generally 0.1 g/~ saturation concentration, preferably 1 g/~ saturation concentration, -30 ° C ~ 100 ° C.
℃ Preferably 0 to 80℃, time is 1 minute to 100 hours,
It is preferably carried out for a period of 5 minutes to 80 hours.

High conductivity can be imparted to the tetrazine polymers by forming them into a disk shape or by doping them with an electron-accepting compound while in powder form.

The doped tetrazine polymers of the present invention not only exhibit high electrical conductivity, but can also be easily formed into various molded products, such as battery electrodes, solar cells, or electromagnetic shielding casings. It is a useful material and is widely used in the electrical, electronic, and communications fields.

Hereinafter, the present invention will be explained in detail with reference to Examples. however,
The present invention is not limited to this. In the examples, all "parts" refer to "parts by weight." Note that the doping amount (%) is expressed as the weight part of the doped dopant relative to the weight part of the polymer before doping.

Synthesis example 1 In a three-necked flask, add 25.4 terephthalonitrile.
135 parts, dimethylacetamide containing 5% LiCl
1.1 parts of sulfur powder, 5.3 parts of β-mercaptoethanol, and 2.6 parts of hydrazine hydrate (100%).
Stirring was carried out at 80°C for 5 hours. After the reaction is complete, pour into water from step 3 and filter the produced orange solid.
It was washed three times with warm water, once with ethanol, and once with acetone, and air-dried to obtain poly(p-phenylene-S-tetrazine dihydride). Yield: 29 parts, Yield: 89
%, ηinh=0.30 dl/g (30°C, H ₂ SO ₄ ).

20 parts of this poly(p-phenylene-S-tetrazine dihydride) was suspended in 300 parts of acetic acid, and 30 parts of sodium nitrite was slowly added. After addition,
The mixture was heated and stirred at ~80°C for 5 hours. Thereafter, the bright red solid was filtered off, washed three times with water and once with ethanol, and dried at 130°C.

Yield 16.8 parts Yield 85% ηinh=0.17dl/g (H ₂ SO ₄ , 30°C) Synthesis example 2 Fumaronitrile instead of terephthalonitrile
A synthesis reaction was carried out in the same manner as in Synthesis Example 1 except that 15.6 parts were used, and 8 parts (yield 37%) of poly(vinylene-S-tetrazine dihydride) was obtained.

Seven parts of this poly(vinylene-S-tetrazine dihydride) were suspended in 150 parts of acetic acid, and 15 parts of sodium nitrite were slowly added. After addition, 80
The mixture was heated and stirred at ℃ for 2 hours. Filter off the solid;
Washed with water and ethanol.

Yield: 6.6 parts Yield: 96% Example 1 The powder of tetrazine polymer A obtained in Synthesis Example 1 was dissolved in antimony pentafluoride saturated steam at 40°C.
After being left for a while, the disk-shaped product was doped with 148% by weight of antimony pentafluoride.
It exhibited a conductivity of 2.1×10 ^-2 S/cm. The conductivity of the powder disc molded before doping is
10 ^-12 S/cm or less, and by doping
An improvement of more than an order of magnitude in electrical conductivity was observed.

Example 2 The powder of Tetrazine Polymer A obtained in Synthesis Example 1 was molded into a disc and then left in fuming sulfuric acid at 40°C for 9 minutes, and the powder exhibited a conductivity of 5.0×10 ^-5 S/cm.

Example 3 The powder of Tetrazine Polymer B obtained in Synthesis Example 2 was left in iodine saturated steam at 40°C for 74.5 hours and then molded into a disk shape. The powder was doped with 53% by weight of iodine and was 1.1×10 ^- It exhibited a conductivity of ⁶ S/cm.

Example 4 The powder of tetrazine polymer B obtained in Synthesis Example 2 was molded into a disc and then placed in bromine-saturated steam at 40°C.
After being left for a minute, the conductivity was 1.0×10 ⁻⁵ S/cm.

Example 5 The powder of Tetrazine Polymer B obtained in Synthesis Example 2 was molded into a disk and left in fuming sulfuric acid at 40°C for 3 minutes, and the conductivity was 3.5×10 ^-4 S/cm.
It was doped with 25 wt% _SO3 .

Example 6 The powder of tetrazine polymer B obtained in Synthesis Example 2 was molded into a disc and left in antimony pentafluoride vapor at 40°C for 20 minutes, and the conductivity was 1.4×10 ^-3
It was S/cm. It was doped with 41% by weight of antimony pentafluoride.

Comparative Example 1 The powder of Tetrazine Polymer A obtained in Synthesis Example 1 was molded into a disc shape in air at room temperature.
It exhibited a conductivity of 1.5×10 ^-12 S/cm.

Comparative Example 2 The powder of Tetrazine Polymer B obtained in Synthesis Example 2 was molded into a disc shape in air at room temperature.
It exhibited a conductivity of 1.7×10 ^-12 S/cm.

Example 7 Tetrazine polymer A obtained by Synthesis Example 1
The powder was molded into a disc shape at 40℃.
4.5 for those left in iodine saturated steam for 22 hours.
It exhibited a conductivity of ×10 ^-6 S/cm.

Claims (1)

[Claims] 1. The following general formula [] [However, in the formula, R is a group represented by the following formula (a) or (b) (-CH=CH)-n...(a) -Q(-X-Q)-m...(b) Yes, in formulas (a) and (b), n is 1 to
represents an integer of 5, m is 0 or 1, Q represents phenylene or naphthylene, and X represents a direct bond, -O- or -S-. ] A doped tetrazine polymer characterized in that it is formed from a tetrazine polymer mainly consisting of repeating units represented by the above formula and an electron-accepting compound. 2 General formula below [] [However, in the formula, R is a group represented by the following formula (a) or (b) (-CH=CH)-n...(a) -Q(-X-Q)-m...(b) Yes, in formulas (a) and (b), n is 1 to
represents an integer of 5, m is 0 or 1, Q represents phenylene or naphthylene, and X represents a direct bond, -O- or -S-. ] A method for producing doped tetrazine polymers, which comprises doping a tetrazine polymer mainly consisting of repeating units represented by the following with an electron-accepting compound.