WO2000007936A1

WO2000007936A1 - Method for preparing carbon material

Info

Publication number: WO2000007936A1
Application number: PCT/JP1999/004151
Authority: WO
Inventors: Ryoichi Nishida; Hiroaki Murase
Original assignee: Osaka Gas Company Limited
Priority date: 1998-08-03
Filing date: 1999-08-02
Publication date: 2000-02-17
Also published as: JP3521312B2

Abstract

A method for preparing a carbon material, characterized by reacting a polyolefin derivative represented by the following general formula: -(CX2-CX2)n- with Mg or an Mg alloy in an aprotic solvent in the presence of a Li salt and/or a metal halide, thereby forming a carbon material which has a polyyne structure represented by the following general formula: (-C C-)n and/or a cumulene structure represented by the following general formula: (=C=C=)n in at least a part of the main chain skeleton thereof.

Description

Specification

Manufacturing method of carbon material

Technical field

The present invention provides a method for producing a carbon material having a boron structure and / or a Z or cumulene structure in part or all of a main chain skeleton (a so-called carbine-based carbon material). About the method.

Conventional technology

Carbon materials that have a ruby structure in part or all of the main chain skeleton are electronic materials such as semiconductors for high-power high-temperature electronics, battery electrode materials, and conductive materials. Heat-resistant high-strength materials such as heat-resistant ultra-high-strength fibers for ultra-high-temperature composite materials for aerospace and nuclear fusion, precursors such as super-lubricating materials, brass or carbon nanotubes The application as a body is expected.

Methods for producing carbine-based carbon materials are broadly classified into physical methods and chemical methods.

The physical methods include (a) a method of producing carbon material containing carbin by ion sputtering or graphite discharge of graphite or arc discharge. (YP udryavtsey, et al., Carbon: 30 (1992) 213); (b) A method of irradiating a polychlorinated vinyl film with a laser in a vacuum to obtain a carbinic carbon material (M. Shimoyama, et al. al., Macromol. Chem., 193 (1992〉 569) ..

Reply

In addition, the following methods are known as ecological methods:

(c) a method of performing acetylene dehydrogenation in CuCl ₂ solution (VI Kastochikin, et al., Carbon, 11 (1973) 70);

(d) Chlorination (CHC1) of polyacetylene to produce halogeno-hyperbolic acetylene with excellent stereoregularity and dehydrohalogenation thereof (K. Akagi, et a 1., 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) The method of defluoridating a polytetrafluoroethylene film in a mercury amalgam of Li by the method of Ka Van, Synth. Metal, 58 (1993) 63);

(g) A PVDF single crystal film made from N, N-dimethylformamide solution of polyvinylidene fluoride (PVDF) mixed with acetonitrile. A method of dehydrofluorination by treating with a 40% strength ream uret solution at room temperature for 40 minutes (Y.P. Kudryavtsev, e1 al., Carbon, 30 (1992) 213);

(h) A method by electrode reduction of jodoacetylene in the presence of a Ni catalyst (H. Shirakawa, et al., Chem. Lett., 2011 (1994); ..

(i) A method in which a polyolefin derivative is subjected to an electrode reduction reaction using Mg, Zn, or an alloy mainly containing these metals or their metals 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, Ζη, Λ1 or an alloy containing these metals as a main component as an anode (JP-A-9-249405) Gazette).

However, the physical method requires that the reaction be carried out at a high temperature of, for example, 2700Κ or more, so that a variety of reactive species are generated and it is difficult to control the structure at a high level. There is a point. In addition, physical methods are not suitable for industrial mass production of carbine carbon materials in terms of yield, reaction scale, etc.ο

On the other hand, with regard to chemical methods, (c;), (e) and (f) are difficult to adopt as industrial processes in terms of safety and environmental pollution. In (d), (g) and (h), there are problems in terms of quality and yield due to reasons such as residual halogen. In addition, (i) and (j) can be used to produce high-quality carbine-based materials with a highly controlled structure in high yields without causing any safety and environmental pollution. Although it offers a new method of industrial production, it requires a special electrolytic cell for production, which increases production costs. In addition, if the olefin used as a raw material does not exist near the electrode, ..

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The reaction is no proceed efficiently, in terms of mass productivity, Ru Oh things to improved the al _r,

SUMMARY OF THE INVENTION

Accordingly, the present invention provides a high-quality carbine-based carbon material having a highly controlled structure, in a high yield, without causing any safety and environmental pollution, and at an even higher cost. Its main purpose is to provide new ways of mass-producing and manufacturing industrially.

DISCLOSURE OF THE INVENTION

The present inventor has conducted intensive studies in view of the current state of the prior art as described above, and as a result, has identified a polyolefin derivative having a functional group capable of leaving as an anion. When the Mg or Mg alloy is acted upon in the presence of the Li salt and / or the specific metal halide, the problems of the prior art are substantially reduced. Found to be eliminated or significantly reduced.

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

1. A method for producing a carbon material,

General formula

-(CX ₂ -CX ₂ ) „-(1)

(In the formula, X represents F, C1, Br, I or H; X may be the same or two or more may be different. Except where X is all H; n is between 2 and 100 000 000 is there . )

Is reacted with Mg or Mg alloy in the presence of a salt and / or a metal halide in a non-proton solvent. By doing so,

General formula

(-Cyo C-) _n (2)

(Where η is 2 to 1000000)

The polyline structure indicated by, and

General formula

(= C = C =) _n (3)

(Where n is 2 to 1000000)

A method characterized by forming a carbon material having a cumulene structure represented by the formula (1) in a part or the whole of the main chain skeleton. 2. The method according to the above item 1, wherein a combination of a salt and a metal halide is used.

3. The method described in 1 or 2 above, wherein LiCl is used as the Li salt.

4. Metal c b as a gain down _{products, FeCl 2, FeCl 3, FeBr} 2, FeBr 3, CuCl 2, A1C1 3, AlBr 3, ZnCl 2, SnCl 2, SnCl 4, CoCl 2, VC1 2, TiCl 4 , PdCl ₂ , NiCl ₂ , SmCl ₂ : j¾ and

The method according to any one of Sml Item 1 Ru physicians use a ₂ or al least for the one also chosen 1-3. .

5. Metal c b as a gain down product, F e C 1 ₂ Contact and / or the method according to the claim 4 Ru physicians use the FeCl _3.

Detailed description of the invention

In the present invention, a polyolefin derivative having a functional group capable of leaving as an anion to be used as a starting material is represented by a general formula:

-(CX ₂ -CX ₂ ) „-(1)

(In the formula, X represents F, C1, Br, I, or H. X may be the same or two or more and may be different. Except when all are H; n is 2 to 1,000,000)

It is indicated by. As X, F is more preferred.

The reaction product according to the present invention has a general formula

(-C≡ C-) _n (2)

(Where η is 2 to 1000000)

And the general formula

(= C) _n (3)

(Where n is 2 to 1000000)

Is a carbon material having a cumulene structure represented by or in part or all of the main chain skeleton.

The carbon material obtained by the method of the present invention is highly versatile while retaining the structure of the polyolefin derivative used as a raw material. -

It is a polymer with heavy bonds. In addition, some of the polymers have a three-dimensional structure in which the polymers are cross-linked.

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

At the time of the reaction, the polyolefin derivative represented by the general formula (1) is accommodated in a reaction vessel and used for the reaction.

When the polyolefin derivative is soluble in a solvent, use it after dissolving it in the solvent.

There is no particular limitation on those that do not dissolve in the solvent, as long as the reaction takes place.For example, a sheet-like material is placed in the reactor, and a small piece or a particle-like material is used. Examples of such a method include dispersing the compound in a solvent and storing it in a reaction vessel, or installing a porous sheet or a mesh-like substance in the reaction vessel.

The amount of the polyolefin derivative to be subjected to one reaction is not particularly limited as long as the reaction can be efficiently performed depending on the form. When the array (or sheet-like PTF membrane (10 mm x 10 mm x 50 μm)) is used for the reaction, 500 sheets of solvent per 100 ml of solvent should be used. It can be used in about a percentage.

As the solvent, a wide range of non-protonic solvents can be used. Specifically, propylene carbonate, acetonitrile, -.-

N, N-dimethylformamide, N-methylformamide, formamide, ethylamine, dimethylenesulfide KISHID, 1,2-METHEXITHETAN, BIS (2-METHEXITCHILLE)

—Tell, p-dioxane, tetrahydrofuran, methylene chloride, etc. are exemplified. These solvents can be used alone or as a mixture of two or more. In these solvents, 1,2-dimethoxetane and -tetrahydrobranka S are preferred, and 1,2-dimethoxetane is preferred. Also, a mixed solvent containing at least 10% of at least one kind of tetrahydrofuran is preferable.

The Li salts used in the present invention include Li Cl, Li NO 3,

_{_{L i 2 CO 3, L i}} C 1 0 4 , etc. are exemplified. The Li salt may be used alone, or two or more kinds may be used in combination. Of these Li salts, LiC1 is the most preferred.

If the concentration of the Li salt is too low, the reaction does not proceed well, whereas if it is too high, the amount of lithium ion reduced and precipitated is small. If it becomes too large, problems such as inhibition of the reaction may occur. Therefore, the concentration of salt in the solvent is usually about 0.05 to 5 mo 1/1, more preferably 0.1 to 5 mo 1/1.

It is about 4 mo 1/1, particularly preferably about 0.135 to 3 m0 1/1.

Examples of the metal halide used in the present invention include FeC ₁₂ , _{_{_{FeCl 3, FeBr 2, FeBr 3}}} , CuCl 2, A1C1 3, AlBr 3, ZnCl 2, SnCl 2, SnCl 4, CoCl 2, VC1 2, TiCl 4, PdCl 2, NiCl 2, SmCl 2, Sml 2 , etc. are Is exemplified. Among these metal halides, FeCl ₂ , FeCl ₃ , CuCl ₂ , ZnCl _{2, and the} like are preferable, and FeCl ₂ and FeCl ₃ are 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, whereas if it is too high, it will not participate in the reaction. . Therefore, the concentration of the metal nitrogenide in the solvent is usually about 0.01 to 6 mo 1/1, more preferably about 0.02 to 4 mo 1/1, and particularly preferably. It is about 0.03 to 3 mo 1/1.

The shape of Mg or Mg-based alloy used in the present invention is not particularly limited as long as the reaction is performed, but it is not limited to powder, granules, rib-like bodies, cut pieces, lumps, A rod-shaped body, a flat plate, and the like are illustrated, and among these, a force S such as a powder having a large surface area, a granular body, a ribbon-shaped body, and a cut piece is preferred. The amount of Mg or alloy used is usually at least 0.5 times the mole (as Mg) of the functional group that is eliminated as an anion in the polyolefin derivative. It is more preferably equal to or greater than equimolar, and most preferably equal to or greater than 3 times. Mg or Mg-based alloys are generally The polyolefin derivative represented by the formula (1) is reduced to give a rubin-based carbon represented by the general formula (2) and the general formula (3). As the material is formed, it itself is oxidized to form a compound with the released anion.

The present invention provides, for example, a polyolefin derivative represented by the general formula (1), a Li salt, or a metal halide in a hermetically closeable reaction vessel. And Mg (or Mg-based alloy) together with a solvent, and the reaction is carried out while stirring, preferably mechanically or magnetically. be able to . There is no restriction on the shape and structure of the reaction vessel as long as it can be sealed.

The reaction vessel may be in a dry atmosphere, but more preferably in a dry nitrogen or inert gas atmosphere.In addition, there is a deoxygenated and dried nitrogen atmosphere. Or an inert gas atmosphere is particularly preferred.

In the case of stirring, as in the case of a general reaction, the higher the stirring speed, the shorter the reaction time. The state of stirring varies depending on the shape and dimensions of the reactor.For example, when using a 100 ml eggplant flask, use a stirrer with a length of 10 mm or more. By setting the rotation speed of the stirrer to 20 times / minute or more, the reaction proceeds more smoothly.

The reaction time depends on the amount of the starting polyolefin derivative, Li salt, Although it depends on the amount of metal halide, Mg (or Mg-based alloy), and the agitation speed as required, it is usually about 10 minutes or more. It is about 0.5 to 100 hours. By adjusting the reaction time, it is possible to control the structure of the target product (such as the ratio of rubbing structures in the product and the number of three-dimensional structures): Reaction When the time is increased, the ratio of the carbine structure becomes large, and a structure suitable for using carbine itself as a heat-resistant material is obtained.

Also, if a carbine structure is formed on a polyrefin substrate and used as an electronic material or super lubricating material, the reaction time should be shortened. What is necessary is to reduce the amount ratio of the carbine structure _c

Temperature of the reaction is usually - 2 0 ° Ri Ah in the temperature range of the boiling point or the C or al to use a solvent, is rather to good or - Ri 1 0 to 5 0 ^e C about range near, Most preferably, it is in the range of -5 to 35 ° C.

The invention's effect

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

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

(b) The reaction method is a chemical method and special equipment ..

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Since such a method is not required, it is possible to produce a carbon-based carbon material at low cost and with high mass productivity.

(c) The reaction proceeds without the use of hazardous materials or metals, and under mild conditions at room temperature or lower, so that rubin-based carbon materials can be safely and without risk of polluting the environment. The force S can be manufactured.

Example

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

Example 1

A 100 ml Nas flask (hereinafter referred to as a “reactor”) equipped with a three-way cock was charged with 0.0 g of granular Mgl, 2.66 g of anhydrous lithium chloride (iCl), and anhydrous sodium chloride. 1.60 g of dani ferrous iron (FeCl ₂ ) 20 pieces of polytetrafluoroethylene (PTFE) film (8mmX8mmX50m) (total weight about 0.2g) After receiving the stacker, heating and reducing the pressure to 1 mmHg at 50 ° C to dry the raw materials, dry argon gas is introduced into the reactor, and then Apply 44 ml of tetrahydrofuran (THF) dried with Trim-Venzofen enketone to a magnetic stacker at room temperature. The mixture was stirred for about 3 hours.

After completion of the stirring, the PTFE film that turned black in the reaction mixture and became a force-bon-like state was recovered, and washed twice with 20 ml of dry THF. And dried under vacuum.

When this force-like film was analyzed using a Raman spectrometer, it was found that the peak from C = C, which was not found in the raw PTFE film, was used. 1500cm- ¹ ) and a peak from C3C

(2100cm- ¹ ) mosquito was clearly observed.

Conversely, the peak (732 cm- ¹ ) derived from CF found in the raw PTFE film was no longer observed in the bonbon film after the reaction.

From these facts, it can be seen that a carbine-based carbon material was obtained in high yield according to this example.

Example 2

The reaction was carried out in the same manner as in Example 1 except that a Mg alloy (containing A1 at 5 ° /.) Was used instead of Mg.

In the Raman analysis of the product, peaks derived from C = C and peaks derived from C-C were observed, and peaks derived from C-F were significantly reduced. These facts indicate that a carbine-based carbon material was synthesized.

Example 3

The reaction was carried out in the same manner as in Example 1 except that 1,2-dimethoxetane was used as a solvent. As a result, a carbine-based carbon material substantially similar to that of Example 1 was obtained.

Example 4 ..

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The 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-based carbon material substantially similar to that of Example 1 was obtained.

Example 5

The reaction was carried out in the same manner as in Example 1 except that an equal-volume mixture of THF and ethyl glycol ethyl ester was used as the solvent. As a result, a carbine-based carbon material almost similar to that of Example 1 was obtained.

Example 6

As in Example 1 except that a mixture of THF (10 V 0 1%) and ethylene glycol methyl ether (90 \ '0 1%) was used as the solvent. The reaction was performed. As a result, a carbine-based carbon material almost similar to that of Example 1 was obtained.

Example 7

The reaction was carried out in the same manner as in Example 1 except that Li NO ₃ was used as the Li salt. As a result, a carbine-based carbon material almost similar to that of Example 1 was obtained.

Example 8

Except that as the L i salt Ru have use the L i C 1 0 ₄ was Tsu rows reaction in the same manner as in Example 1. As a result, a carbine-based carbon material almost similar to that of Example 1 was obtained.

Example 9 .

Fifteen

Except that Ru with metal c b gain down halide FeC 1 ₃ was Tsu rows reaction in the same manner as in Example 1. As a result, almost the same rubin-based carbon material as in Example 1 was obtained.

Example 10

Except while creating use the A 1 C 1 ₃ and the metal C B gain down product was Tsu rows reaction in the same manner as in Example 1. As a result, a carbine-based carbon material substantially similar to that of Example 1 was obtained.

Example 1 1

The reaction was carried out in the same manner as in Example 1 except that PdCl ₂ was used as the metal halide. As a result, a carbine-based carbon material almost similar to that of Example 1 was obtained.

Example 1 2

Except while creating use a N i C 1 ₂ as the metal C B gain down product Reaction was carried out in the same manner as in Example 1. As a result, a carbine-based carbon material substantially similar to that of Example 1 was obtained.

Example 13

The reaction was carried out in the same manner as in Example 1 except that granular PTFE was used as the polyolefin derivative. As a result, a granular carbine-based carbon material was obtained.

Example 14

The reaction was carried out in the same manner as in Example 1 except that a porous PTFE film was used as the polyolefin derivative. That As a result, a porous film-like carbin-based carbon material was obtained.

Example 15

The reaction was carried out in the same manner as in Example 1 except that-(CF ₂ -CFC1) „-film was used as the starting material, and as a result, the reaction was carried out in the same manner as in Example 1. A ruby-based carbon material was obtained.

Claims

The scope of the claims

1. A method for producing a carbon material,

General formula

_{_{_{- (CX 2 -CX 2) u}}} - (1)

(Wherein X represents F, CI, Br, I or H; X may be the same or two or more different, provided that X is H N is from 2 to 1,000,000 ₂ )

Is converted to a Mg or Mg alloy in the presence of Li salt Z or metal halide in a non-proton solvent. By acting

General formula

(-C≡ C-) _n (2)

(Where n is 2 to 1000000)

, And Z or Z

General formula

(= C = C =) _n (3)

(Where n is 2 to 1000000)

A method characterized by forming a carbon material having a cumulene structure represented by the formula (1) in a part or the whole of the main chain skeleton.

2. The method according to claim 1, wherein a Li salt and a metal halide are used in combination.

3. The method according to claim 1 or 2, wherein L i C 1 is used as the salt.

4. As metal nodogenides, Fe Fe 1, FeCl 3 FeBr.,,

_{_{_{FeBr, s CuCl 2, A1C1 3}}} , AlBr 3, ZnCl 2, SnCl SnCl CoCl 2, VC1 2, TiCl 4, PdCl 2, NiCl 2, SmCl 2 your good beauty Sml ₂ forceゝet al selected small name rather than the also The method according to any one of claims 1 to 3, wherein one type is used.

5. Metal Nono b gate as a down product, F e C 1 ₂ Contact good beauty Z or the method of claim 4 Ru physicians use the FeCl _3.