JPH0125507B2 - - 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, it relates to doped dihydrotetrazine polymers formed from a main polymer containing a 1,8-dihydro-1,2,4,5-tetrazine-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 property and conjugation property of heterocyclic compounds, and as a result of intensive research, we found that a 1,2-dihydro-1,2,4,5-tetrazine polymer in which dihydrotetrazine is bonded at the 3.6-position, which is the conjugated position, has an electron The present invention was achieved by discovering that a conductive organic polymer compound can be doped with a receptive dopant and exhibit high electrical conductivity.

That is, the present invention has the following general formula [] [However, R in the formula is a group represented by the following formula (a) or (b) (-CH=CH)-n...(a) -Q(-x-Q)-m...(b) , in formulas (a) and (b), n is 1 to
represents an integer of 5, m is 0 or 1, Q represents phenylene or naphthylene, × is a direct bond,
-O- or -S-. ] Doped dihydrotetrazine polymers characterized by being formed from dihydrotetrazine polymers mainly consisting of repeating units represented by the following and an electron-accepting compound, and a method for producing the same.

The dihydrotetrazine polymers in the present invention are
Although it mainly consists of the repeating unit represented by the above formula [], it may contain a small amount of other repeating units as long as it does not substantially adversely affect the conductivity.

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

For the production of dihydrotetrazine polymers mainly composed of repeating units represented by the above formula [], known methods can be used as they are; Examples include a method of reacting hydrazines in the presence of a sulfur-containing compound to produce the corresponding dihydrotetrazine polymer.

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

In the present invention, doping or doping refers to the addition of an electron-accepting compound to the dihydrotetrazine polymers, resulting in improved conductivity compared to that of the original dihydrotetrazine polymers. The relationship between the dihydrotetrazine polymer and the electron-accepting compound may be a chemical bond, for example, a complex, or a simple mixed state.

To dope dihydrotetrazine polymers with electron-accepting compounds: (i) In the case of electron-accepting compounds that are themselves gases or have vapor pressure, such as halogens, antimony pentafluoride, or sulfur trioxide, , a so-called gas phase doping method in which tetrazine polymers are exposed to the vapor atmosphere.

(ii) A so-called wet doping method in which tetrazine polymers are immersed in an inert solution containing an electron-accepting compound.

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. can.

At this time, the temperature of the dodopant atmosphere is generally in the range of -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 dihydrotetrazine polymers to deactivate their ability as electron-accepting compounds or modify dihydrotetrazine polymers. means a solvent that does not impair its original function.

Such inert solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, hexane, heptane,
Hydrocarbons such as petroleum ether and cyclohexane,
Aromatic solvents such as benzene, toluene, xylene, nitrobenzene, anisole, ethers such as ether, tetrahydrofuran, dioxane, esters such as ethyl acetate, butyl acetate, cellosolve acetate, isoamyl acetate, methanol, ethanol, isopropanol, butanol, etc. Examples include alcohols, aprotic polar solvents such as dimethylformamide, dimethylacetonamide, dimethylsulfoxide, and N-methylpyrrolidone, and other solvents such as nitromethane and acetonitrile.

Of course, these solvents are appropriately selected depending on the solubility of the dopant. There are no particular limitations on the dopant concentration in the solvent or the immersion temperature and time in the wet doping method, but generally 0.1 g/~ saturation concentration,
The concentration is preferably 1 g/~saturation, -30°C to 100°C, preferably 0 to 80°C, and the time is 1 minute to 100 hours, preferably 5 minutes to 80 hours.

The dihydrotetrazine polymers are formed into a disk shape, a sheet shape, etc., or by doping with an electron-accepting compound while in powder form.
It is possible to impart high conductivity.

The doped dihydrotetrazine polymers of the present invention not only exhibit high electrical conductivity, but also can be easily formed into various molded products, such as battery electrodes, solar cells, or electromagnetic shielding casings. It is a useful material for the body and is widely used in the electrical, electronic, and communication 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% iCl
1.1 parts of sulfur powder, 5.3 parts of β-mercaptoethanol, and 26 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.
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 ).

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.

Example 1 The powder of dihydrotetrazine polymer A obtained in Synthesis Example 1 was left in iodine saturated steam at 40°C for 20 hours and molded into a disk shape.The powder was doped with 170% by weight of iodine and had a density of 4.8×10 It showed a conductivity of ^-5 S/cm.

Example 2 The powder of dihydrotetrazine polymer A obtained in Synthesis Example 1 was molded into a disk and then left in fuming sulfuric acid at 40°C for 1 minute, and the conductivity was 1.4 × 10 ^-2 S/cm.
It was hot.

Example 3 The powder of dihydrotetrazine polymer A obtained in Synthesis Example 1 was molded into a disk and then left in antimony pentafluoride vapor at 40°C for 9 minutes, and the electrical conductivity was
It was 2.3×10 ^-5 S/cm.

Example 4 A disk molded product of the powder of dihydrotetrazine polymer A obtained in Synthesis Example 1 was immersed in a 5% nitromethane solution of iron trichloride for 1 hour and then dried, and the conductivity was 1.5×10 ^-2 S. It was /cm.

Example 5 The powder of dihydrotetrazine polymer B obtained in Synthesis Example 2 was left in iodine saturated steam at 40°C for 16 hours, and then molded into a disc shape with a concentration of 282% by weight.
of iodine and exhibited an electrical conductivity of 2.4×10 ⁻² S/cm.

Comparative Example 1 The powder of dihydrotetrazine polymer A obtained in Synthesis Example 1 was molded into a disc at room temperature,
It exhibited conductivity of 1.0×10 ^-12 S/cm or less in air.

Comparative Example 2 The powder of dihydrotetrazine polymer B obtained in Synthesis Example 2 was molded into a disc at room temperature,
It exhibited conductivity of 1.0×10 ^-12 S/cm or less in air.

Claims (1)

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