JP4214328B2 - Carbon material manufacturing method - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a carbon material having a polyin structure or cumulene structure in a part or all of a main chain skeleton (so-called calvin-based carbon material).
[0002]
[Prior art and its problems]
Carbon materials with a carbine structure in part or all of the main chain skeleton are heat-resistant materials such as semiconductor materials for high-power high-temperature electronics and heat-resistant ultra-high-strength fibers for aerospace and nuclear fusion ultra-high-temperature composite materials. Application as a precursor of materials, fullerenes or carbon nanotubes is expected.
[0003]
The manufacturing method of a carbine-type carbon material is divided roughly into a physical method and a chemical method.
Physical methods include (a) a method of producing a carbon material containing carbine by ion sputtering of graphite or arc discharge (YP Kudryavtsey, et al., Carbon, 30 (1992) 213, YP Kudryavtsev, et al., Carbon, 30 (1992) 213); (b) A method for obtaining a carbonaceous carbon material by irradiating a polyvinyl chloride film with a laser in vacuum (M. Shimoyama, et al., Makromol. Chem., 193 (1992) 569) is known.
[0004]
As chemical methods, the following methods are known.
(C) A method in which a dehydrogenation reaction of acetylene is carried out 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 a halogenated polyacetylene having excellent stereoregularity and dehydrohalogenation. (K. Akagi, et al., Synth. Metal, 17 (1987) 557);
(E) A method of synthesizing acetylene in the presence of oxygen using a catalyst comprising a cuprous salt and a tertiary amine as a ligand (Japanese Patent Publication No. 3-44582);
(F) A method of defluorinating a polytetrafluoroethylene film in a Li mercury amalgam (L. Kavan, Synth. Metal, 58 (1993) 63);
(G) PVDF single crystal film made from N, N-dimethylformamide solution of polyvinylidene fluoride (PVDF) is treated with 10% potassium ethylate solution of ethanol mixed with acetone for 40 minutes at room temperature to dehydrofluoride Method (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 (1994);
(I) A method of subjecting a polyolefin derivative to an electrode reduction reaction using Mg, Zn, Al or an alloy containing such a metal as a main component as an anode (Japanese Patent Laid-Open No. 9-249404);
(J) A method of subjecting an acetylene derivative to an electrode reduction reaction using Mg, Zn, Al, or an alloy containing such a metal as a main component as an anode (Japanese Patent Laid-Open No. 9-249405).
[0005]
However, the physical method has a problem that, for example, various reaction active species are generated because the reaction is performed at a high temperature of 2700 K or more, and it is difficult to control the structure at a high level. Also, the physical method is inappropriate for industrial mass production of carbyne carbon materials from the viewpoint of yield and reaction scale.
[0006]
On the other hand, regarding chemical methods, (c), (e) and (f) are difficult to adopt as industrial production methods in terms of safety and environmental pollution. Further, (d), (g) and (h) have problems in terms of quality and yield, such as halogen remaining. Furthermore, (i) and (j) provide a new method for industrially producing highly controlled and high-quality carbyne materials in high yield, safely and without causing environmental pollution. However, a special electrolytic cell is required for production. In addition, when the polyolefin or acetylene derivative used as a raw material does not exist in the vicinity of the electrode, the reaction does not proceed efficiently, so there is room for further improvement in terms of mass productivity.
[0007]
[Problems to be solved by the invention]
Therefore, the present invention provides a new method capable of industrially producing a high-quality calbin-based carbon material with a highly controlled structure in a high yield, safely and without causing environmental pollution. The main purpose is to provide.
[0008]
[Means for Solving the Problems]
As a result of intensive research in view of the current state of the prior art as described above, the present inventor has found that Mg or Mg alloy in the presence of a specific Li salt and / or a specific metal halide with respect to an acetylene derivative having a halogen. It has been found that the problems of the prior art are substantially eliminated or greatly reduced in the case of applying the function.
[0009]
That is, this invention provides the manufacturing method of the following carbyne type carbon material.
1. A method for producing a carbon material, comprising:
General formula
CX≡CX (1)
(Wherein X represents F, Cl, Br or I; X may be the same or two or more may be different from each other.)
By reacting Mg or an Mg alloy in the presence of a Li salt and / or a metal halide in an aprotic solvent with an acetylene derivative represented by:
General formula
(-C≡C-) _n (2)
(Where n is 2 to 1000000)
Polyyne structure or general formula
(= C = C =) _n (3)
(Where n is 2 to 1000000)
A carbon material having a cumulene structure represented by the formula (1) in a part or all of the main chain skeleton is formed.
2. Item 2. The method according to Item 1, wherein a Li salt and a metal halide are used in combination.
3. Item 3. The method according to Item 1 or 2, wherein LiCl is used as the Li salt.
4). As the metal _{halide, FeCl 2, FeCl 3, FeBr} 2, FeBr 3, CuCl 2, AlCl 3, AlBr 3, ZnCl 2, SnCl 2, SnCl 4, CoCl 2, VCl 2, TiCl 4, PdCl 2, SmCl 2 and Item 4. The method according to any one of Items 1 to 3, wherein at least one selected from SmI ₂ is used.
5. Item 5. The method according to Item 4, wherein FeCl ₂ is used as the metal halide.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, the acetylene derivative having a halogen used as a starting material has a general formula:
CX≡CX (1)
(In the formula, X represents I, F, Cl or Br. X may be the same or two or more may be different.)
It is shown by. X is more preferably I.
[0011]
The reaction product in the present invention has the general formula
(-C≡C-) _n (2)
(Where n is 2 to 1000000)
Polyyne structure represented by or a general formula
(= C = C =) _n (3)
(Where n is 2 to 1000000)
The carbon material having a cumulene structure represented by the formula in part or all of the main chain skeleton. Such a carbon material has a polymer with highly developed multiple bonds and a cross-linked three-dimensional highly developed multiple bond.
[0012]
The raw material of General formula (1) may be used individually by 1 type, or may use 2 or more types together.
[0013]
In the reaction, the acetylene derivative represented by the general formula (1) is dissolved in a solvent, accommodated in a reaction vessel, and used for the reaction.
[0014]
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, Examples thereof include bis (2-methoxyethyl) ether, p-dioxane, tetrahydrofuran, and methylene chloride. These solvents can be used alone or as a mixture of two or more. Furthermore, 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 preferred.
[0015]
The concentration of the acetylene derivative in the solvent is usually about 0.01 to 20 mol / l, more preferably about 0.05 to 10 mol / l, and most preferably about 0.1 to 5 mol / l.
[0016]
Examples of the Li salt used in the present invention include LiCl, LiNO ₃ , Li ₂ CO ₃ , and LiClO ₄ . Li salts may be used alone or in combination of two or more. Of these Li salts, LiCl is most preferred.
[0017]
If the concentration of Li salt is too low, the reaction does not proceed well, whereas if it is too high, the amount of lithium ions that have been reduced and precipitated is too large, which hinders the reaction. Arise. Therefore, the concentration of the Li salt in the solvent is usually about 0.05 to 5 mol / l, more preferably about 0.1 to 4 mol / l, and particularly preferably about 0.15 to 3 mol / l.
[0018]
The metal halide used in the present _{invention, FeCl 2, FeCl 3, FeBr} 2, FeBr 3, CuCl 2, AlCl 3, AlBr 3, ZnCl 2, SnCl 2, SnCl 4, CoCl 2, VCl 2, TiCl 4, PdCl ₂ , SmCl ₂ , SmI _{2 and the} like are exemplified. Among these metal halides, FeCl ₂ , CuCl ₂ , ZnCl _{2 and the} like are more preferable, and FeCl ₂ is most preferable. These metal halides may be used alone or in combination of two or more. If the concentration of the metal halide in the solvent is too low, the reaction will not proceed sufficiently, while if too high, it will not participate in the reaction. Therefore, the concentration of the metal halide in the solvent is usually about 0.01 to 6 mol / l, more preferably about 0.02 to 4 mol / l, and particularly preferably about 0.03 to 3 mol / l.
[0019]
The shape of the Mg or Mg-based alloy used in the present invention is not particularly limited as long as the reaction can be performed, but examples thereof include powders, granules, ribbons, cutting pieces, lumps, rods, flat plates, etc. Among these, powders having a large surface area, granules, ribbons, cut pieces, and the like are more preferable. The amount of Mg or Mg-based alloy used is usually equimolar (as Mg) or more with respect to the acetylene derivative, more preferably 3 times mol or more, and most preferably 5 times mol or more. The Mg or Mg-based alloy reduces the acetylene derivative represented by the general formula (1) to form a carbine-based carbon material represented by the general formula (2), and is itself oxidized to release halogen. And form a compound.
[0020]
The present invention accommodates, for example, an acetylene derivative represented by the general formula (1), a Li salt and / or a metal halide and Mg (or an Mg-based alloy) together with a solvent in a sealable reaction vessel, preferably mechanically. Or it can implement by the method of performing reaction, stirring magnetically. As long as the reaction vessel can be sealed, there is no particular limitation on the shape and structure.
[0021]
The inside of the reaction vessel may be a dry atmosphere, but is preferably a dry nitrogen or inert gas atmosphere, more preferably a deoxygenated and dried nitrogen atmosphere or an inert gas atmosphere.
[0022]
In the case of stirring, the reaction time is shortened as the stirring speed is increased, as in the case of a general reaction. The stirring state varies depending on the reaction apparatus.For example, when using a 100 ml eggplant flask, a stirring bar having a length of 10 mm or more is used, and the number of revolutions of the stirring bar is set to 20 times / minute or more. Proceeds more smoothly.
[0023]
The reaction time varies depending on the amount of the raw material acetylene derivative, Li salt, metal halide, Mg (and / or Mg-based alloy), the stirring speed performed as necessary, etc., but is about 10 minutes or more, usually 0.5 ~ About 100 hours. By adjusting the reaction time, the molecular weight of the carbyne carbon material can be controlled.
[0024]
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 about −10 to 50 ° C., most preferably in the range of about −5 to 35 ° C. Is in.
[0025]
【The invention's effect】
According to the present invention, the following remarkable effects are achieved.
(A) A high-quality calbin-based carbon material with a highly controlled structure can be produced in a high yield.
(B) Since the reaction method is a chemical method and does not require a special device, a carbyne carbon material can be produced at low cost and with high mass productivity.
(C) Since the reaction can be carried out under mild conditions of room temperature or less without using dangerous materials and metals, a carbyne carbon material can be produced safely and without the risk of polluting the environment.
[0026]
【Example】
Examples are shown below to further clarify the features of the present invention.
[0027]
Example 1
In a 100 ml eggplant flask equipped with a three-way cock (hereinafter referred to as a reactor), 10.0 g of granular Mg, 2.66 g of anhydrous lithium chloride (LiCl), 1.60 g of anhydrous ferrous chloride (FeCl ₂ ) and a stirrer chip are accommodated. After heating and depressurizing to 1 mmHg at 50 ° C. to dry LiCl and FeCl ₂ , dry argon gas was introduced into the reactor, and further 4.9 g (18 mmol) of diiodoacetylene and sodium-benzophenone ketyl were previously dried. Tetrahydrofuran (THF) (44 ml) was added, and the mixture was stirred at room temperature with a magnetic stirrer for about 3 hours.
[0028]
After the stirring was completed, a black precipitate was separated from the reaction product, washed twice with 20 ml of dry THF, and vacuum-dried.
[0029]
When the obtained black powder was tableted with KBr and analyzed using FT-IR, a C≡C absorption band (2100 cm ⁻¹ ) was clearly observed. In addition, absorption of CI absorption band (1200 cm ⁻¹ ) was not observed.
[0030]
From these results, it can be seen that the present example obtained a carbyne carbon material with high yield.
[0031]
Example 2
The reaction was performed in the same manner as in Example 1 except that Mg alloy (containing 5% Al in Mg) was used instead of Mg.
[0032]
In the FT-IR analysis of the product, a C≡C absorption band was observed, while the CI absorption band was significantly reduced. These facts indicate that a calvin-based carbon material has been synthesized.
[0033]
Example 3
The reaction was performed in the same manner as in Example 1 except that 1,2-dimethoxyethane was used as a solvent. As a result, a carbyne carbon material substantially similar to that of Example 1 was obtained.
[0034]
Example 4
The reaction was performed in the same manner as in Example 1 except that dioxane was used as the solvent. As a result, a carbyne carbon material substantially similar to that of Example 1 was obtained.
[0035]
Example 5
The reaction was performed in the same manner as in Example 1 except that an equal volume mixture of THF and ethylene glycol diethyl ether was used as a solvent. As a result, a carbyne carbon material substantially similar to that of Example 1 was obtained.
[0036]
Example 6
The reaction was performed in the same manner as in Example 1 except that a mixture of THF (10 vol%) and ethylene glycol diethyl ether (90 vol%) was used as a solvent. As a result, a carbyne carbon material substantially similar to that of Example 1 was obtained.
[0037]
Example 7
The reaction was performed in the same manner as in Example 1 except that LiNO ₃ was used as the Li salt. As a result, a carbyne carbon material substantially similar to that of Example 1 was obtained.
[0038]
Example 8
The reaction was performed in the same manner as in Example 1 except that LiClO ₄ was used as the Li salt. As a result, a carbyne carbon material substantially similar to that of Example 1 was obtained.
[0039]
Example 9
The reaction was carried out in the same manner as in Example 1 except that the metal halide FeCl ₃ was used. As a result, a carbine-based carbon material substantially the same as that of Example 1 was obtained.
[0040]
Example 10
The reaction was conducted in the same manner as in Example 1 except that AlCl ₃ was used as the metal halide. As a result, a carbyne carbon material substantially similar to that of Example 1 was obtained.
[0041]
Example 11
The reaction was performed in the same manner as in Example 1 except that PdCl ₂ was used as the metal halide. As a result, a carbyne carbon material substantially similar to that of Example 1 was obtained.
[0042]
Example 12
The reaction was conducted in the same manner as in Example 1 except that acetylene dichloride was used as a starting material. As a result, a carbyne carbon material similar to that in Example 1 was obtained.
[0043]
Example 13
The reaction was carried out in the same manner as in Example 1 except that acetylene dibromide was used as a starting material. As a result, a carbyne carbon material similar to that in Example 1 was obtained.

Claims (4)

A method for producing a carbon material, comprising:
General formula
CX≡CX (1)
(Wherein X represents F, Cl, Br or I; X may be the same or two or more may be different from each other.)
Is reacted with Mg or an Mg alloy in the presence of a Li salt and a metal halide in an aprotic solvent while stirring .
General formula
(-C≡C-) n (2)
(Where n is 2 to 1000000)
Polyyne structure or general formula
(= C = C =) n (3)
(Where n is 2 to 1000000)
A carbon material having a cumulene structure represented by the formula (1) in a part or all of the main chain skeleton is formed. The process according to claim 1 , wherein LiCl is used as the Li salt. As the metal _{halide, FeCl 2, FeCl 3, FeBr} 2, FeBr 3, CuCl 2, AlCl 3, AlBr 3, ZnCl 2, SnCl 2, SnCl 4, CoCl 2, VCl 2, TiCl 4, PdCl 2, SmCl 2 and The method according to claim 1 or 2 , wherein at least one selected from SmI ₂ is used. The method according to claim 3 , wherein FeCl ₂ is used as the metal halide.