JPH09249404A - Production of carbon material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To safely and industrially obtain a high quality carbyne-based carbon material having a highly controlled structure at a high yield by subjecting a specific polyolefin derivative to an electrode reaction in a nonaquenous system organic solvent dissolving a specific supporting electrolyte or both of the supporting electrolyte and an elector-conductive auxiliary and having a specific metal as an anode. SOLUTION: The objective carbon material has a polyyne structure of the formula: (-C≡C-)n ((n) is 2-1,000,000) or a cumlene structure of the formula: (=C=C=)m ((n) is 2-1,000,000) in a part or whole of the main chain skeleton, and is obtained by subjecting a polyolefin derivative of a general formula: -(CX2 -CX2 )n -(X is F, Cl, Br, I or H and may respectively be same or different; (n) is 2-1,000,000) to an electrode reducing reaction is a nonaqueous system organic solvent dissolving a dole supporting electrolyte or both of the supporting electrolyte and an elector-conductive auxiliary and having an anode composed of Mg, Zn, Al or an alloy containing the metal as main components, and in an inert gas atmosphere.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a carbon material having a polyyne structure or a cumulene structure in a part or all of the main chain skeleton (so-called carbine carbon material).

[0002]

2. Description of the Related Art Carbon materials having a carbine structure in part or all of the main chain skeleton are heat-resistant for electronic materials such as semiconductors for high-power high-temperature electronics, and ultra-high temperature composite materials for aerospace and nuclear fusion. It is expected to be applied to heat resistant materials such as super high strength fibers.

The method for producing a carbine carbon material is roughly classified into a physical method and a chemical method.

As a physical method, (a) a method of producing a carbon material containing carbine by ion sputtering of graphite or arc discharge (YP Kudryavts)
ey, et al., Carbon, 30 (1992) 213, YP Kudryavtse
v, et al., Carbon, 30 (1992) 213); (b) A method for obtaining a carbine-like carbon material by irradiating a polyvinyl chloride film with a laser in a vacuum (M. Shimoyama, et al., Makromol. Che.
m., 193 (1992) 569) and the like are known.

The following methods are known as chemical methods.

(C) A method of carrying out the dehydrogenation reaction of acetylene in a CuCl ₂ solution (VI Kasatochikin, et al., Carbon,
11 (1973) 70); (d) A method in which polyacetylene is chlorinated (CHCl) _x to produce halogenated polyacetylene having excellent stereoregularity, and dehydrohalogenation thereof is performed. (K. Akagi, et al., Synth. Me
tal, 17 (1987) 557); (e) A method for synthesizing acetylene in the presence of oxygen using a catalyst composed of a cuprous salt and a tertiary amine as a ligand (Japanese Patent Publication No. 3-44582). (F) Method of defluorinating polytetrafluoroethylene film in mercury amalgam of Li (L. Kavan, Synth. Meta
l, 58 (1993) 63); (g) N, N-dimethylfolm of polyvinylidene fluoride (PVDF)
PVDF single crystal film made from amide solution is treated with 10% potassium ethylate solution of ethanol mixed with acetone at room temperature for 40 minutes and dehydrofluorinated (YP Kudryavtsev,
et al., Carbon, 30 (1992) 213); (h) Method by electrode reduction of diiodoacetylene in the presence of Ni catalyst (H. Shirakawa, et al., Chem. Lett., 2011 (199)
Four).

However, the physical method is, for example, 27
Since the reaction is carried out at a high temperature of 00K or higher, various reactive species are generated, and there is a problem that it is difficult to control the structure at a high level.
Further, the physical method is unsuitable for industrially mass-producing the carbine-based carbon material in terms of yield and reaction scale.

On the other hand, regarding the chemical method, (c),
It is difficult to adopt (e) and (f) as an industrial manufacturing method in terms of safety and environmental pollution. Further, in (d), (g) and (h), there are problems in quality and yield such as halogen remaining, and it is necessary to develop a new reaction system for industrially producing carbine.

Further, attempts have been made to improve the adhesiveness of the film by chemically or electrochemically reducing the polytetrafluoroethylene film to form a carbon-like material on the surface thereof (US Patent. 3,967,018,
1976; US Patent 3,296,011, 1967; British Patent 7
65,284, 1957), this method uses only the film surface as a carbonaceous material, and there is a big problem that the yield is low as a method for obtaining a carbine-based carbon material.

[0010]

Therefore, the present invention provides a high-quality carbine-based carbon material having a highly controlled structure,
The main object of the present invention is to provide a new method which can be industrially produced with high yield, safety and without causing environmental pollution.

[0011]

Means for Solving the Problems As a result of intensive studies in view of the state of the art as described above, the present inventor has found that a polyolefin derivative having a functional group capable of leaving as an anion is used as a specific metal as an anode. By using an electrode reaction using a specific solvent, a specific supporting electrolyte or both a supporting electrolyte and a current-carrying auxiliary, the problems of the prior art can be substantially eliminated or significantly reduced. I found it.

That is, the present invention provides the following method for producing a carbine carbon material.

1. A method for producing a carbon material, comprising: a general formula-(CX ₂ -CX ₂ ) _n- (1) (wherein X represents F, Cl, Br, I or H; X is the same or 2 One or more may be different; n is 2 to 100
The polyolefin derivative represented by
n, Al or an alloy containing these metals as the main component is used as an anode, and subjected to an electrode reduction reaction in a non-aqueous organic solvent in which a supporting electrolyte alone or a supporting electrolyte and an energization aid are dissolved in an inert gas atmosphere. Thus, the polyyne structure represented by the general formula (-C≡C-) _n (2) (where n is 2 to 1000000) or the general formula (= C = C =) _n (3) (formula In the formula, n is 2 to 1000000), and a carbon material having a cumulene structure represented by a part or all of the main chain skeleton is formed.

2. LiCl, Li ₂ SO ₄ , LiBF as supporting electrolyte
₄ , LiClO ₄ , LiPF ₆ , (C ₄ H ₉ ) ₄ NF, (C ₄ H ₉ ) ₄ NCl, (C ₄ H ₉ ) ₄ NB
r, (C ₄ H ₉ ) ₄ NI, (C ₄ H ₉ ) ₄ NSO ₄ , (C ₄ H ₉ ) ₄ NBF ₄ , (C4H9) ₄ NCl
The method according to item 1 above, wherein at least one member selected from the group consisting of O ₄ and (C ₄ H ₉ ) ₄ NPF ₆ is used.

3. As current carrying _{aid, AlCl 3, Al (OEt)} 3, F
eCl ₂ , FeCl ₃ , MgCl ₂ , ZnCl ₂ , SnCl ₂ , CoCl ₂ , PdCl ₂ , VC
Item 3. The method according to Item 1 or 2, wherein at least one selected from l ₃ , CuCl ₂ and CaCl ₂ is used.

4. As a non-aqueous organic solvent, propylene carbonate, acetonitrile, N, N-dimethylformamide, N-methylformamide, formamide, ethylenediamine, dimethylene sulfoxide, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, p-dioxane Item 4. The method according to any one of Items 1 to 3, wherein at least one selected from the group consisting of, tetrahydrofuran and methylene chloride or a mixed solvent containing 10% or more of at least one of them is used.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a polyolefin derivative having a functional group capable of leaving as an anion used as a starting material is represented by the general formula:-(CX ₂ -CX ₂ ) _n- (1) (wherein X is , F, Cl, Br, I or H (where X is
Unless all are H). X's may be the same or different in two or more. ; N is 2 to 1000000). As X, F is more preferable.

The reaction product in the present invention is a polyyne structure represented by the general formula (-C≡C-) _n (2) (where n is 2 to 1000000) or a general formula (= C = C =) _n (3) A carbon material having a cumulene structure represented by the formula (n is 2 to 1000000) in a part or all of the main chain skeleton. Such a carbon material has a structure in which a polyolefin derivative used as a raw material remains, and a polymer in which multiple bonds are highly developed and a three-dimensional highly multiple bond cross-linked with the polymer.

As the raw material of the general formula (1), one kind may be used alone, or two or more kinds may be used in combination.

In the electrode reaction, the polyolefin derivative represented by the general formula (1) is housed in a reaction vessel and used for the reaction. When the polyolefin derivative is soluble in a solvent, it is dissolved in the solvent before use. The material that does not dissolve in the solvent is not particularly limited as long as the reaction occurs, but for example, a sheet-shaped material is placed in the reactor, or a particulate material is dispersed in a solvent and stored in a reaction container. Alternatively, an embodiment in which a porous sheet or a mesh-shaped material is installed on the cathode can be given.

As the solvent, aprotic solvents can be widely used. Specifically, propylene carbonate, acetonitrile, N, N-dimethylformamide, N-methylformamide, formamide, ethylenediamine, dimethylene sulfoxide, 1,2- Dimethoxyethane, bis (2-
Examples include methoxyethyl) ether, p-dioxane, tetrahydrofuran, methylene chloride and the like. These solvents can be used alone or as a mixture of two or more kinds. Further, a mixed solvent containing 10% or more of at least one of these aprotic solvents may be used. Of these solvents, 1,2-dimethoxyethane and tetrahydrofuran are more preferable.

As the supporting electrolyte used in the electrode reaction,
LiCl, Li ₂ SO ₄ , LiBF ₄ , LiClO ₄ , LiPF ₆ and other lithium salts, (C ₄ H ₉ ) ₄ NF, (C ₄ H ₉ ) ₄ NCl, (C ₄ H ₉ ) ₄ NBr, (C ₄ H ₉ ) ₄ N
I, (C ₄ H ₉ ) ₄ NSO ₄ , (C ₄ H ₉ ) ₄ NBF ₄ , (C ₄ H ₉ ) ₄ NClO ₄ , (C ₄ H ₉ ) ₄
Examples thereof include quaternary ammonium salts such as NPF ₆ . These supporting electrolytes may be used alone or 2
More than one species may be used in combination. Among these supporting electrolytes, lithium chloride and lithium perchlorate are most preferable. If the concentration of the supporting electrolyte is too low, the reaction does not proceed due to difficult or impossible current flow, whereas if it is too high, the current flows too much to ensure the potential required for the reaction. There is a problem that the metal ions of the supporting electrolyte are reduced at the cathode and are produced in a large amount to hinder the reaction. Therefore, the concentration of the supporting electrolyte in the solvent is usually about 0.05 to 5 mol / l, more preferably 0.1 to 3 mol.
It is about 1 / l, and particularly preferably about 0.15 to 2.0 mol / l.

In the electrode reaction of the present invention, in order to carry out the electrode reaction more efficiently, an energization aid may be used in combination with the supporting electrolyte to improve the electroconductivity. Al salt such as AlCl ₃ and Al (OEt) ₃ ; F as an energization aid
Fe salts such as eCl ₂ and FeCl ₃ ; Mg salts such as MgCl ₂ ; Zn salts such as ZnCl ₂ ; Sn salts such as SnCl ₂ ; Co salts such as CoCl ₂ ; Pd salts such as PdCl ₂ ; VCl such as VCl ₃ Salts; Cu salts such as CuCl ₂ ; Ca salts such as CaCl ₂ and the like are exemplified as preferable ones. These energization aids may be used alone or in combination of two or more. Among these energization aids, AlC
l ₃ , FeCl ₂ , FeCl ₃ , CoCl ₂ , CuCl _{2 and the} like are more preferable.
If the concentration of the current-carrying aid in the solvent is too low, improvement of the current-carrying property is not sufficiently achieved, while if it is too high,
The current-carrying aid is reduced and does not participate in the reaction. Therefore, the concentration of the energization aid in the solvent is usually about 0.01 to 6 mol / l, more preferably about 0.03 to 4 mol / l, and particularly preferably about 0.05 to 3 mol / l.

In the electrode reaction of the present invention, Mg, Zn, Al or an alloy containing them as a main component is used as the anode. As an alloy containing Mg as a main component, for example, Al is 3
Included are those containing about 10%. Also, JIS H 61
25-1961 (Type 1 (MGA1), Type 2 (MGA2,
Common name is AZ63), 3 types (MGA3) and so on. The cathode is not particularly limited as long as it can pass an electric current, but stainless steel such as SUS304 and 316; Mg, Cu, Zn, S
Examples include various metals such as n, Al, Ni, Co, and platinum; carbon materials and the like.

When the same kind of metal is used for both the negative and positive electrodes, the polarity of the negative and positive electrodes may be switched at regular time intervals. As a result, the metal salt or the like adhering to the cathode can be removed. The switching interval is preferably in the range of 1 second to 10 minutes.

The shape of the electrode is not particularly limited as long as the current can be stably applied. However, a rod, a plate, a cylinder, a cone, a disc, a sphere, or those in which they are accommodated in a basket or a plate is used. Those wound in a coil are preferred. If necessary, the oxide film on the electrode surface is removed beforehand.
Any method can be used to remove the oxide film from the electrodes.
For example, the electrode can be washed with an acid, then washed with ethanol and ether, and dried under reduced pressure, the electrode can be polished under a nitrogen atmosphere, or a combination of these methods can be used.

The electrode reaction of the present invention is carried out, for example, by (a) a polyolefin derivative represented by the general formula (1) and a supporting electrolyte in a hermetically sealed reaction vessel having an anode and a cathode, and optionally an energization aid. And a solvent, and a method of causing an electrode reaction by supplying a predetermined amount of current while preferably mechanically or magnetically stirring, (b) an electrolytic cell having an anode and a cathode, and a reaction solution Using a flow-type electrode reactor composed of a storage tank, a pump, piping, etc., a polyolefin derivative, a supporting electrolyte, a solvent and, if necessary, a current-carrying auxiliary agent are put into the reaction solution storage tank, and the reaction solution composed of these is introduced. By circulating a predetermined amount of current while circulating the inside of the electrode reactor by a pump,
It can be carried out by a method of causing an electrode reaction in the electrolytic cell.

The reaction vessel or reaction apparatus at the time of the electrode reaction may be in a dry atmosphere, but a dry nitrogen or inert gas atmosphere is more preferred, and further deoxidized and dried in a nitrogen atmosphere or an inert atmosphere. A gas atmosphere is particularly preferable. The amount of electric current may be 1 F / mol or more based on the leaving group in the polyolefin derivative, and by controlling the amount of electric current, control of the structure of the target product (amount ratio of the carbine structure in the product, 3D structure, etc.) is possible. Further, it is also possible to take out the carbon material generated at an energization amount of about 0.1 F / mol or more to the outside of the system, collect the remaining raw material polyolefin derivative, and reuse it.

The reaction time may differ depending on the amount of the raw material polyolefin derivative, the resistance of the reaction solution, and the like, which are related to the amounts of the supporting electrolyte and the current-carrying aid, and therefore may be appropriately determined. The temperature during the reaction is usually in the temperature range from -20 ° C to the boiling point of the solvent used, more preferably in the range of -5 to 30 ° C, and most preferably in the range of 0 to 25 ° C. It is in. In the electrode reaction of the present invention, the diaphragm, which is indispensable in the usual electrode reduction reaction, may be used, but it is not indispensable, so the operation becomes simple and practically advantageous.

[0030]

According to the present invention, the following remarkable effects are achieved.

(A) A high-quality carbine-based carbon material having a highly controlled structure can be produced in high yield.

Since the method (b) itself is a chemical method using an electrode reaction, which has a proven record in industrial production, it is suitable for mass production of carbine carbon materials.

(C) Since no dangerous materials or metals are used and the reaction can be performed under mild conditions at room temperature or lower, it is possible to safely manufacture a carbine carbon material without risk of polluting the environment. .

[0034]

EXAMPLES Examples are shown below to further clarify the features of the present invention.

Example 1 A three-necked flask (hereinafter referred to as a reactor) having an inner volume of 30 ml equipped with a three-way cock, a Mg anode (diameter 1 cm × 5 cm) and a stainless steel (SUS304) cathode (1 cm × 1 mm × 5 cm). To
Contains 0.4 g of LiCl and 0.24 g of FeCl ₂ and 1 mmH at 50 ℃
After heating and reducing the pressure to g and drying the lithium chloride and ferrous chloride, 10 polytetrafluoroethylene (PTFE) films of 7 mm x 7 mm were charged therein together with a stirrer chip. Deoxygenated dry nitrogen was introduced into the reactor, and further 15 ml of tetrahydrofuran which had been previously dried with sodium-benzophenone ketyl was added. While stirring the reaction solution with a magnetic stirrer and keeping the reactor at room temperature with a water bath, electricity was supplied with a constant current power source (initial voltage of about 30 V).

After 8 hours, the PTFE film turned black and a carbon film was obtained. When analyzed by FT-IR, the C = C absorption band (1630 cm ^-1 ) and the C≡C absorption band (2100 cm ^-1 ) which were not found in the PTFE film were
Observed.

Further, the absorption of the CF absorption band (1400 cm ^-1 ) observed in the PTFE film was not observed.

From these facts, it is understood that the carbine-based carbon material was obtained in high yield by this example.

Example 2 An electrode reaction was carried out in the same manner as in Example 1 except that Al was used as the anode.

As a result, in the IR analysis of the product, C = C
The absorption band of C and the absorption band of C≡C were observed, while the absorption of the absorption band of CF was significantly reduced. These results indicate that a carbine-based carbon material was synthesized.

Example 3 An electrode reaction was carried out in the same manner as in Example 1 except that Zn was used as the anode. In the IR analysis of the product, an absorption band of C = C and an absorption band of C≡C were observed, and the absorption band of CF was significantly reduced. From this, it became clear that a carbine-based carbon material was synthesized.

Comparative Example 1 The electrode reaction of the PTFE film was carried out in the same manner as in Example 1 except that stainless steel (SUS304) was used as the anode.

The PTFE film did not change to black color, neither the C = C absorption band nor the C≡C absorption band was observed by IR analysis, and the absorption of the CF absorption band did not decrease.

From these facts, it is clear that in this comparative example, the carbine carbon material has not been synthesized.

Example 4 An electrode reaction was performed in the same manner as in Example 1 except that a Mg alloy (containing 5% Al in Mg) was used as the anode.

In the IR analysis of the product, an absorption band of C = C and an absorption band of C≡C were observed, while the absorption band of CF was remarkably reduced. These indicate that the carbine-based carbon material was synthesized.

Example 5 An electrode reaction was carried out in the same manner as in Example 1 except that a duralumin plate (Al alloy plate) was used as the anode. In the IR analysis of the product, the C = C absorption band and the C≡C absorption band were observed, while the absorption in the CF absorption band was significantly reduced, indicating that the carbine-based carbon material was synthesized. Is clear.

Example 6 An electrode reaction was carried out in the same manner as in Example 1 except that a Zn alloy plate (containing 3% of Al) was used as the anode. In the IR analysis of the product, the C = C absorption band and the C≡C absorption band are
Observed, the absorption of the CF absorption band was significantly reduced.
Such results indicate that a carbine-based carbon material was synthesized.

Example 7 An electrode reaction was carried out in the same manner as in Example 1 except that a platinum plate was used as the cathode. In the IR analysis of the product, an absorption band of C = C and an absorption band of C≡C were observed, and absorption of the absorption band of CF was not observed at all. From these, it is understood that the carbine-based carbon material was obtained in a high yield.

Example 8 An electrode reaction was carried out in the same manner as in Example 1 except that Ni was used as the cathode. In the IR analysis of the product, an absorption band of C = C and an absorption band of C≡C were observed, and absorption of the absorption band of CF was not observed at all. From these results, it can be seen that the carbine-based carbon material was obtained in high yield.

Example 9 An electrode reaction was carried out in the same manner as in Example 1 except that N, N-dimethylformamide was used as the solvent. As a result, a carbine carbon material similar to that in Example 1 was obtained.

Example 10 An electrode reaction was carried out in the same manner as in Example 1 except that N-methylformamide was used as the solvent. As a result, Example 1
Almost the same carbine-based carbon material was obtained.

Example 11 An electrode reaction was carried out in the same manner as in Example 1 except that formamide was used as the solvent. As a result, a carbine carbon material similar to that in Example 1 was obtained.

Example 12 An electrode reaction was carried out in the same manner as in Example 1 except that ethylenediamine was used as the solvent. As a result, a carbine carbon material similar to that in Example 1 was obtained.

Example 13 An electrode reaction was carried out in the same manner as in Example 1 except that 1,2-dimethoxyethane was used as the solvent. As a result, Example 1
Almost the same carbine-based carbon material was obtained in high yield.

Example 14 An electrode reaction was carried out in the same manner as in Example 1 except that dioxane was used as the solvent. As a result, a carbine carbon material similar to that in Example 1 was obtained.

Example 15 An electrode reaction was carried out in the same manner as in Example 1 except that a mixed solvent of tetrahydrofuran (50 vol%) and ethylene glycol diethyl ether (50 vol%) was used as the solvent. As a result, a carbine carbon material similar to that in Example 1 was obtained.

Example 16 An electrode reaction was carried out in the same manner as in Example 1 except that a mixed solvent of tetrahydrofuran (10 vol%) and ethylene glycol diethyl ether (90 vol%) was used as the solvent. As a result, a carbine-based carbon material was obtained.

Comparative Example 2 An electrode reaction was carried out in the same manner as in Example 1 except that ethyl alcohol was used as the solvent.

As a result, the PTFE film did not become black and neither the C = C absorption band nor the C≡C absorption band was observed in IR analysis, while the CF absorption band absorption did not decrease. .

From this, it is clear that when an ethyl alcohol solvent is used, the carbine carbon material cannot be synthesized by reducing PTFE.

Comparative Example 3 An electrode reaction was carried out in the same manner as in Example 1 except that ethyl acetate was used as the solvent. As a result, the PTFE film did not become black, and neither the C = C absorption band nor the C≡C absorption band was observed in IR analysis, while the CF absorption band absorption did not decrease.

From this, it is clear that when an ethyl acetate solvent is used, the carbine carbon material cannot be synthesized by reducing PTFE.

Comparative Example 4 An electrode reaction was carried out in the same manner as in Example 1 except that chloroform was used as the solvent.

As a result, even in the IR analysis of the object to be treated,
The C = C absorption band and the C≡C absorption band were not observed, and the absorption of the CF absorption band did not decrease.

If a chloroform solvent is used, PT
It is clear that the carbine-based carbon material cannot be synthesized by reducing FE.

Example 17 An electrode reaction was carried out in the same manner as in Example 1 except that Li ₂ SO ₄ was used as the supporting electrolyte.

As a result, a carbine carbon material similar to that in Example 1 was obtained.

Example 18 An electrode reaction was carried out in the same manner as in Example 1 except that LiBF ₄ was used as the supporting electrolyte. After 8 hours, the PTFE film turned black and a carbon-like film was obtained.

In the IR analysis of the product, the C = C absorption band and the C≡C absorption band were observed, and the absorption of the CF absorption band was significantly reduced. From these, it is clear that a carbine-based carbon material was synthesized.

Example 19 An electrode reaction was carried out in the same manner as in Example 1 except that LiClO ₄ was used as the supporting electrolyte. After 8 hours, the PTFE film turned black and a carbon-like film was obtained. In the IR analysis of the product, the C = C absorption band and the C≡C absorption band were observed, and the absorption band of CF was not observed at all. This confirmed that the carbine-based carbon material was obtained in high yield.

Example 20 An electrode reaction was carried out in the same manner as in Example 1 except that LiPF ₆ was used as the supporting electrolyte.

As a result, a carbine carbon material was obtained.

Example 21 An electrode reaction was carried out in the same manner as in Example 1 except that (C ₄ H ₉ ) ₄ NF was used as the supporting electrolyte. As a result, a carbine-based carbon material was obtained.

Example 22 An electrode reaction was carried out in the same manner as in Example 1 except that (C ₄ H ₉ ) ₄ NCl was used as the supporting electrolyte. As a result, a carbine-based carbon material was obtained.

Example 23 An electrode reaction was carried out in the same manner as in Example 1 except that (C ₄ H ₉ ) ₄ NBr was used as the supporting electrolyte. As a result, a carbine-based carbon material was obtained.

Example 24 An electrode reaction was carried out in the same manner as in Example 1 except that (C ₄ H ₉ ) ₄ NI was used as the supporting electrolyte. As a result, a carbine-based carbon material was obtained.

Example 25 Example 1 except that (C ₄ H ₉ ) ₄ NSO ₄ is used as the supporting electrolyte.
The electrode reaction was carried out in the same manner as in. As a result, a carbine-based carbon material was obtained.

Example 26 Example 1 except that (C ₄ H ₉ ) ₄ NBF ₄ was used as the supporting electrolyte.
The electrode reaction was carried out in the same manner as in. As a result, a carbine-based carbon material was obtained.

Example 27 Example 1 except using (C ₄ H ₉ ) ₄ NClO ₄ as the supporting electrolyte.
The electrode reaction was carried out in the same manner as in. As a result, a carbine-based carbon material was obtained.

Example 28 Example 1 except that (C ₄ H ₉ ) ₄ NPF ₆ is used as the supporting electrolyte.
The electrode reaction was carried out in the same manner as in. As a result, a carbine-based carbon material was obtained.

Example 29 An electrode reaction was carried out in the same manner as in Example 1 except that a 1: 2 mixture of LiCl and (C ₄ H ₉ ) ₄ NCl was used as a supporting electrolyte. As a result, a carbine-based carbon material was obtained.

Example 30 An electrode reaction was carried out in the same manner as in Example 1 except that a 2: 1 mixture of LiBF ₄ and (C ₄ H ₉ ) ₄ NBF ₄ was used as the supporting electrolyte.
As a result, a carbine-based carbon material was obtained.

Comparative Example 5 An electrode reaction was carried out in the same manner as in Example 1 except that the supporting electrolyte was not used. There was no change in the PTFE film even after 8 hours. In the IR analysis, neither the C = C absorption band nor the C≡C absorption band was observed, and a strong CF absorption band was observed.

This indicates that the carbine-based carbon material is not synthesized under the synthesis condition without using the indicator electrolyte.

Example 31 An electrode reaction was carried out in the same manner as in Example 1 except that AlCl ₃ was used as a current carrying aid. As a result, the PTFE film turned black after 8 hours and a carbon film was obtained.

In the IR analysis of the film, the C = C absorption band and the C≡C absorption band were observed, and the CF absorption band was not observed at all.

From these results, it was found that the carbine carbon material was obtained in high yield.

Example 32 An electrode reaction was carried out in the same manner as in Example 1 except that FeCl ₃ was used as a current carrying aid. As a result, the PTFE film turned black after 8 hours, and a carbon film was obtained.

In the IR analysis of the film, the C = C absorption band and the C≡C absorption band were observed, and the CF absorption band was not observed at all. From this, it was found that the carbine-based carbon material was obtained in high yield.

Example 33 An electrode reaction was carried out in the same manner as in Example 1 except that CoCl ₂ was used as a current carrying aid. As a result, the PTFE film turned black after 8 hours, and a carbon film was obtained.

In the IR analysis of the product, the C = C absorption band and the C≡C absorption band were observed, and the absorption band of CF was not observed at all. From this, it was found that the carbine-based carbon material was obtained in high yield.

Example 34 An electrode reaction was carried out in the same manner as in Example 1 except that CuCl ₂ was used as a current carrying aid. As a result, the PTFE film turned black after 8 hours, and a carbon film was obtained.

In the IR analysis of the produced film, the C = C absorption band and the C≡C absorption band were observed, and the absorption band of CF was not observed at all. From this, it was found that the carbine-based carbon material was obtained in high yield.

Example 35 An electrode reaction was carried out in the same manner as in Example 1 except that SnCl ₂ was used as a current carrying aid. As a result, the PTFE film turned black after 8 hours, and a carbon film was obtained.

In the IR analysis of the product, the C = C absorption band and the C≡C absorption band were observed, and the CF absorption band was not observed at all. From this, it was found that the carbine-based carbon material was obtained in high yield.

Example 36 An electrode reaction was carried out in the same manner as in Example 1 except that PdCl ₂ was used as a current carrying aid. As a result, the PTFE film turned black after 8 hours, and a carbon film was obtained.

In the IR analysis of the product, the C = C absorption band and the C≡C absorption band were observed, and the CF absorption band was not observed at all. From this, it was found that the carbine-based carbon material was obtained in high yield.

Example 37 An electrode reaction was carried out in the same manner as in Example 1 except that VCl ₃ was used as a current carrying aid. As a result, the PTFE film turned black after 8 hours, and a carbon film was obtained. In the IR analysis of the product, the C = C absorption band and the C≡C absorption band were observed, and the CF absorption band was not observed at all. From this, it was found that the carbine-based carbon material was obtained in high yield.

Example 38 An electrode reaction was carried out in the same manner as in Example 1 except that ZnCl ₂ was used as a current carrying aid. As a result, the PTFE film turned black after 8 hours, and a carbon film was obtained. In the IR analysis of the product, the C = C absorption band and the C≡C absorption band were observed, and the absorption band of CF was not observed at all. From this, it was found that the carbine-based carbon material was obtained in high yield.

Example 39 An electrode reaction was carried out in the same manner as in Example 1 except that a 1: 1 mixture of AlCl ₃ and FeCl ₂ was used as a current carrying aid. As a result, the PTFE film turned black after 8 hours, and a carbon film was obtained. In the IR analysis of the product,
C = C absorption band and C≡C absorption band are observed, and CF
No absorption band was observed. From this, it was found that the carbine-based carbon material was obtained in high yield.

Example 40 An electrode reaction was carried out in the same manner as in Example 1 except that a 1: 1 mixture of CuCl ₂ and FeCl ₃ was used as a current carrying aid. As a result, the PTFE film turned black after 8 hours and a carbon-like film was obtained. In IR analysis of the product, C = C absorption band and C≡C absorption band were observed,
No absorption of the CF absorption band was observed. From this, it was found that the carbine-based carbon material was obtained in high yield.

Example 41 Synthesis was carried out in the same manner as in Example 1 except that the energization aid was not used. After 8 hours, the PTFE film turned black,
A carbon-like film was obtained. In the IR analysis of the product, an absorption band of C = C and an absorption band of C≡C were observed, and the absorption band of CF was significantly reduced. As a result, it was shown that a carbine-based carbon material was synthesized.

However, the absorption band of CF is clearly seen and the absorption band of C≡C is observed, but the absorption is not large. From this, it is clear that although the carbine-based carbon material was obtained in the product of this example in which the current-carrying aid was not used, the unreacted component remained.

Comparative Example 6 A synthesis was carried out in the same manner as in Example 1 except that the supporting electrolyte and the current-carrying aid were not used, and even after 8 hours, P
The TFE film did not turn black.

In the IR analysis of the object to be treated, neither the C═C absorption band nor the C≡C absorption band was observed, and strong absorption of the CF absorption band was observed. From this, it was shown that a carbine-based carbon material cannot be obtained by this method.

Example 42 An electrode reaction was carried out in the same manner as in Example 1 except that a porous PTFE film was used as a starting material and was placed near the cathode.

As a result, the PTFE porous film turned black after 8 hours, and a carbon film was obtained.

In the IR analysis of the product, C = C absorption band and C≡C absorption band were observed, and CF absorption band was not observed at all. From this, it was found that the carbine-based carbon material was obtained in high yield.

Example 43 An electrode reaction was carried out in the same manner as in Example 1 except that PTFE powder was used as a starting material by dispersing it in a reaction solution.

As a result, the PTFE powder turned black and became carbon-like after 8 hours. In the IR analysis of the obtained carbonaceous powder, the C = C absorption band and the C≡C absorption band were observed, while the absorption of the CF absorption band was not observed at all. From this, it was found that the carbine-based carbon material was obtained in high yield.

Example 44 An electrode reaction was carried out in the same manner as in Example 1 except that PTFE was dissolved in tetrahydrofuran as a starting material and used as a 10% solution thereof.

In the IR analysis of the product, the C = C absorption band and the C≡C absorption band were observed, and the CF absorption band was not observed at all. From this, it was found that the carbine-based carbon material was obtained in high yield.

Example 45 An electrode reaction was carried out in the same manner as in Example 1 except that a-(CH ₂ -CF ₂ ) _n -film was used as a starting material. As a result, after 8 hours, the film turned black and became carbon-like. In the IR analysis of the obtained carbonaceous material, a C = C absorption band was observed, but a C≡C absorption band was not observed. From this, it is considered that a polyacetylene-like substance was synthesized.

Example 46 An electrode reaction was carried out in the same manner as in Example 1 except that a-(CF ₂ -CFCl) _n -film was used as a starting material. As a result, 8
After a lapse of time, the film turned black and became carbon-like. In the IR analysis of the product, C = C absorption band and C≡C
The absorption band of was observed. From this, it was confirmed that a carbine-based carbon material was synthesized.

Example 47 An electrode reaction was carried out in the same manner as in Example 1 except that a-(CCl ₂ -CCl ₂ ) _n -film was used as a starting material. As a result, 8
After a lapse of time, the film turned black and became carbon-like. In the IR analysis of this carbon-like film, a C = C absorption band and a C≡C absorption band were observed. From this, it was confirmed that a carbine-based carbon material was synthesized.

Example 48 An electrode reaction was carried out in the same manner as in Example 1 except that a-(CH ₂ -CCl ₂ ) _n -film was used as a starting material. As a result, 8
After a lapse of time, the film turned black and became carbon-like. In the IR analysis of the carbon-like film, a C = C absorption band was observed, but a C≡C absorption band was not observed. From this, it is considered that a polyacetylene-like substance was synthesized. From this, it was confirmed that a carbine-based carbon material was synthesized.

Example 49 An electrode reaction was carried out in the same manner as in Example 1 except that a-(CBr ₂ -CBr ₂ ) _n -film was used as a starting material. As a result, 8
After a lapse of time, the film turned black and became carbon-like. In the IR analysis of the product, C = C absorption band and C≡C
The absorption band of was observed. As a result, it was shown that a carbine-based carbon material was synthesized.

Example 50 An electrode reaction was carried out in the same manner as in Example 1 except that-(CI ₂ -CI ₂ ) _n -film was used as a starting material. As a result, after 8 hours, the film turned black and became carbon-like. In the IR analysis of the product, C = C absorption band and C≡C
Was observed. As a result, it was shown that a carbine-based carbon material was synthesized.

Comparative Example 7 When a starting material was replaced with a-(CH2-CH2) n-film and synthesis was carried out in the same manner as in Example 1, even after 8 hours,
The film did not turn black.

In the IR analysis of the object to be treated, the C = C absorption band and the C≡C absorption band were not observed, and the carbine carbon material was not synthesized.

Comparative Example 8 A starting material was replaced with a — (CH ₂ —CH (CH ₃ )) _n — film and synthesis was carried out in the same manner as in Example 1. Even after 8 hours, the film turned black. It did not discolor.

In the IR analysis of the object to be treated, the C = C absorption band and the C≡C absorption band were not observed, and the carbine carbon material was not synthesized.

Claims (4)

[Claims] 1. A method for producing a carbon material, comprising: a general formula-(CX ₂ -CX ₂ ) _n- (1) (wherein X represents F, Cl, Br, I or H; X represents , Each may be the same or two or more may be different;
n is 2 to 1000000. ) Is used as a positive electrode in a non-aqueous organic solvent in which Mg, Zn, Al or an alloy containing these metals as a main component is used as an anode and a supporting electrolyte alone or both a supporting electrolyte and a current-carrying aid are dissolved. By subjecting it to an electrode reduction reaction carried out in an active gas atmosphere, a polyyne structure represented by the general formula (-C≡C-) _n (2) (where n is 2 to 1000000) or a general formula (= C = C =) _n (3) A method comprising forming a carbon material having a cumulene structure represented by the formula (wherein n is 2 to 1000000) in a part or all of the main chain skeleton. 2. LiCl, Li ₂ SO ₄ , LiBF ₄ , L as a supporting electrolyte
iClO ₄ , LiPF ₆ , (C ₄ H ₉ ) ₄ NF, (C ₄ H ₉ ) ₄ NCl, (C ₄ H ₉ ) ₄ NBr,
(C ₄ H ₉ ) ₄ NI, (C ₄ H ₉ ) ₄ NSO ₄ , (C ₄ H ₉ ) ₄ NBF ₄ , (C ₄ H ₉ ) ₄ NClO ₄
The method according to claim 1, wherein at least one member selected from the group consisting of and (C ₄ H ₉ ) ₄ NPF ₆ is used. 3. AlCl ₃ , Al (OEt) ₃ , FeC as an energization aid
l ₂ , FeCl ₃ , MgCl ₂ , ZnCl ₂ , SnCl ₂ , CoCl ₂ , PdCl ₂ , VC
The method according to claim 1 or 2, wherein at least one selected from l ₃ , CuCl ₂ and CaCl ₂ is used. 4. A non-aqueous organic solvent such as propylene carbonate, acetonitrile, N, N-dimethylformamide,
At least one selected from N-methylformamide, formamide, ethylenediamine, dimethylene sulfoxide, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, p-dioxane, tetrahydrofuran and methylene chloride or at least one of them. A 10
The method according to any one of claims 1 to 3, wherein a mixed solvent containing at least% is used.