JP3161789B2 - Hydrogenated fullerene and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrogenated fullerene and a method for producing the same, and more particularly, to a hydrogenated fullerene C ₆₀ and a fullerene C ₇₀ known as spherical carbon cluster molecules having 60 and 70 carbon atoms. Closed shell structure (spherical carbon cluster structure)
The a, and a C ₆₀ system and the C ₇₀ series of hydrogenated fullerene is a novel substance having a specific H / C ratio, their suitable manufacturing method. The _C60- based and _C70- based hydrogenated fullerenes of the present invention have a special closed shell structure (spherical carbon cluster skeleton) and a spherical molecular structure having a high degree of hydrogenation (H / C ratio). Therefore, it has various characteristic physical properties and can be expected to be used for various applications based on the physical properties and the like, and is suitably used as a lubricating member such as a solid lubricant and a lubricating oil additive. can do.

[0002]

2. Description of the Related Art Recently, as a new substance having a spherical molecular structure, a carbon cluster having a closed shell structure having 60, 70, or 84 carbon atoms has been extracted or synthesized from graphite-like carbon (soot). [Nature, Vol. 347,35
4-358 (1990) etc.]. The carbon cluster having this special structure is also called fullerene, and is called fullerene C ₆₀ , C ₇₀ , C _84, etc., depending on the number of carbons constituting the molecular skeleton. Since these fullerenes are new carbon materials, and are expected to exhibit unique physical properties due to their special molecular structures, research on their properties and application development seems to be extremely important.

For example, since fullerenes are spherical molecules, they are expected to have excellent lubricity from the molecular level. Therefore, as an application of fullerenes, for example, utilization as a lubricating member such as a solid lubricant, a lubricating oil additive and the like can be considered.

[0004] By the way, solid lubricants are also suitably used in high-temperature, very low-temperature, high-pressure places where lubricating oil is difficult to use, or food processing equipment which does not like to absorb the odor of lubricating oil. . Conventionally, substances used as solid lubricants include inorganic compounds such as molybdenum disulfide, graphite, graphite fluoride and mica, and organic compounds such as fluororesin compounds such as Teflon powder. However, conventional solid lubricants may not be satisfactory in terms of use conditions, working environment, price, and the like. For example, many conventional inorganic compound-based solid lubricants such as graphite may have insufficient lubricating properties depending on use conditions and may be avoided from affecting the working environment. However, they are relatively clean and have excellent lubricity, but are extremely expensive.

On the other hand, in order to improve the lubricating properties of lubricating base oils such as lubricating oils, it has been widely practiced to add suitable lubricating oil additives to them and disperse or dissolve them. For example, the above-mentioned inorganic compound-based solid lubricant such as graphite is also commonly used as a dispersion-type lubricant additive. However, many of these conventional solid lubricant additives used in dispersion such as solid lubricants often have drawbacks such as insufficient dispersion stability when added to lubricating oils and greases. It is a problem. In addition, a soluble lubricating oil additive is not only excellent in improving lubricity, but also has various properties (for example, molecular weight,
It is also required to satisfy the overall performance as a lubricant including stability, etc.), and in some cases, conventional lubricating oil additives may be insufficient. That is, in any lubricating member, in recent years, the demand for its performance has become more and more severe, and therefore, the necessity has arisen to design the lubricating member more precisely, for example, at the molecular level. .

Under these circumstances, fullerenes are attracting attention as potential candidates for lubricating members such as novel solid lubricants and lubricating oil additives. This is because fullerenes are expected to exhibit excellent lubrication performance because they are spherical molecules having a carbon cluster skeleton having an appropriate number of carbon atoms as described above.

However, since fullerenes such as C ₆₀ and C ₇₀ are substantially carbon molecules, they are only slightly soluble in very limited solvents such as specific aromatic compounds such as benzene and toluene. And therefore
It has the disadvantage that its field of use is severely limited. In fact, when fullerene was added to a liquid oil or binder such as lubricating oil or grease in order to use it as a lubricating oil additive, the solubility was extremely low, and the affinity was insufficient and the dispersion stability was poor. There was found. That is, fullerene has a remarkably low solubility and affinity for organic solvents, so its use is limited, and even when intended for use as a lubricating member, its use as a solid lubricant can be expected. However, they have the disadvantage that they are unsuitable for use as lubricating oil additives.

Accordingly, the present inventors have found that hydrogenation of fullerene to hydrogenated fullerene can significantly improve the solubility and affinity for many solvents, and can be used not only as a lubricant additive but also in a wider range. It is thought that it will be possible to use it for application fields.

By the way, as the hydrogenation technique of conventional fullerene, the fullerene C ₆₀ in liquid ammonia, and treated with a reducing agent (lithium metal + tert-butyl alcohol), is known a method of obtaining the C ₆₀ H ₃₆ [J. Ph
ys. Chem. , 94 , 8634-8636 (199).
0)]. However, this conventional method is a special reductive hydrogenation reaction, and has problems in terms of cost and the like for industrial implementation. In addition, the product hydrogenated fullerene is also C ₆₀ H
There is a disadvantage that it is limited to only those with ₃₆ structures.

That is, conventionally, only hydrogenated fullerenes having a structure of C ₆₀ H ₃₆ have been obtained. Therefore, for example, C ₆₀ -based hydrogenated fullerenes having a higher degree of hydrogenation or C ₇₀ -based hydrogenated hydrogenated fullerenes have been obtained. Fullerene chloride was not known. Also, the development of a method for efficiently and inexpensively producing these novel hydrogenated fullerenes having a large degree of hydrogenation (H / C ratio) is extremely important industrially, and such development is strongly desired. is there.

[0011]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances. An object of the present invention is to provide a hydrogenated fullerene having a spherical molecular structure in which a carbon skeleton has a fullerene-like closed shell structure and a relatively high degree of hydrogenation (H / C ratio), and which has an organic solvent compared to fullerene. It is remarkably excellent in solubility and affinity for water, and can be dissolved or stably dispersed in a wide variety of organic solvents (for example, paraffinic hydrocarbons such as cycloalkanes as well as aromatic hydrocarbons). And therefore,
For example, solid lubricants, C ₆₀ based use to a wide range of application fields is a novel substance where expected, including use as various types lubricating member such as lubricating oil additives, and C
An object of the present invention is to provide a hydrogenated fullerene of the ₇₀ series.

Another object of the present invention, a method for obtaining a good low cost efficiently C ₆₀ system and the C ₇₀ based hydrogenation fullerene of the present invention, i.e., is an industrially significantly useful methods, hydrogen To provide a method for producing fullerene chloride.

[0013]

Means for Solving the Problems As described above, if the fullerene is sufficiently hydrogenated as described above, it is possible to improve characteristics such as solubility in an organic solvent and to improve lubricity and other characteristics of spherical molecules. considered material exhibiting specific physical properties are obtained, the C ₆₀ further hydrogenation degree than H ₃₆ (H / C ratio) is greater C ₆₀ based hydrogenated fullerene is known C ₆₀ based hydrogenated fullerene conventionally I did intensive research to get it. As a result, for example, the conventional hydrogenated fullerene (C ₆₀ H ₃₆ ) is obtained by catalytically hydrogenating C ₆₀ -based fullerene or a mixed raw material containing the same with hydrogen gas using a hydrogenation catalyst.
Hydrogenation degree than has succeeded in obtaining the C ₆₀ based hydrogen fullerenes higher various H / C ratio. Similar studies were also conducted on C ₇₀ -based hydrogenated fullerenes, which had not been known in the past, and it was found that various H / C ratios having a large degree of hydrogenation were obtained by the same catalytic hydrogenation method using C ₇₀ -based fullerenes as a raw material. also succeeded in obtaining a C ₇₀ hydrogenated fullerenes. Incidentally, these novel C ₆₀ system and C ₇₀ system result of various studies on hydrogenation fullerene production method, catalytic hydrogenation reaction of the hydrogen gas in the presence of a hydrogenation catalyst above C ₆₀ system and C ₇₀ fullerene Act has reached the conclusion that the C ₆₀ system and the C ₇₀ based hydrogenation fullerene of interest is industrially significantly useful method which can be obtained inexpensively and efficiently.

The present inventors have completed the present invention based on these findings. That is, the present invention has a closed shell structure, and has the general formula C ₆₀ H _n (where n is 38
Indicates an even number of ~ 58. ) Is provided.

The present invention also provides a hydrogenated fullerene having a closed shell structure and represented by the general formula C ₇₀ H _m (where _m represents an even number from 30 to 70). It is.

Furthermore, as the present invention is the preparation of C ₆₀ based hydrogenation fullerene of the present invention, C ₆₀ having a closed shell structure
Of the fullerene provides a method characterized by reacting the hydrogen gas in the presence of a hydrogenation catalyst and, as a method for producing C ₇₀ based hydrogenation fullerene of the present invention, the C ₇₀ having a closed shell structure The present invention also provides a method characterized by reacting fullerene with hydrogen gas in the presence of a hydrogenation catalyst. According to this method, C ₆₀ H _{38 to} C ₆₀ H ₄₄
Or C ₇₀ H ₃₀ ~C ₇₀ H ₄₆ are obtained.

The present invention also provides a method for obtaining various hydrogenated fullerenes having a higher degree of hydrogenation by hydrogenating using a hydrogenation catalyst and contacting with a Lewis acid compound in the above method. It is. According to this method, C ₆₀ H _{38 to} C ₆₀ H ₆₀ or C ₇₀ H _{30 to} C ₇₀ H ₇₀
Is obtained.

[0018] C _60-based hydrogenation fullerene of the present invention (i.e., hydrogenated fullerene 60 carbon atoms) has a closed shell structure, the general formula is C ₆₀ H _n (where, n is an even number of 38 to 58 .)). On the other hand, the C ₇₀ hydrogenated fullerene of the present invention (that is, 70 carbon atoms)
Has a closed shell structure and the general formula is C
It is a hydrogenated fullerene represented by ₇₀ H _m (where m is an even number from 30 to 70). Here, in the C ₆₀ series and C ₇₀ based hydrogen fullerenes, and has a closed shell structure, the carbon skeleton of their respective molecules, a predetermined number of carbon atoms of the carbon cluster structure (i.e., C ₆₀ fullerene or C ₇₀ (A closed shell structure unique to fullerene or a similar closed shell structure based on them). Accordingly, the C ₆₀ -based and C ₇₀ -based hydrogenated fullerene of the present invention correspond to the hydrides of C ₆₀ fullerene and C ₇₀ fullerene, respectively, and have a spherical molecular structure.

Specific examples of the C ₆₀ hydrogenated fullerene of the present invention include C ₆₀ H ₃₈ , C ₆₀ H ₄₀ , C ₆₀ H ₄₂ , C ₆₀ H ₄₄ ,
_{C 60 H 46, C 60 H} 48, C 60 H 50, C 60 H 52, C 60 H 54,
C ₆₀ H ₅₆ and C ₆₀ H ₅₈ and one or two of them
Mixtures containing any number of species or more in any proportion can be mentioned. On the other hand, specific examples of the C ₇₀ hydrogenated fullerene of the present invention include C ₇₀ H ₃₀ , C ₇₀ H ₃₂ , C ₇₀ H ₃₄ , C ₇₀ H ₃₆ ,
_{C 70 H 38, C 70 H} 40, C 70 H 42, C 70 H 44, C 70 H 46,
_{C 70 H 48, C 70 H} 50, C 70 H 52, C 70 H 54, C 70 H 56,
_{C 70 H 58, C 70 H} 60, C 70 H 62, C 70 H 64, C 70 H 66,
C ₇₀ H ₆₈ and C ₇₀ H ₇₀ and one or two of them
Mixtures containing any number of species or more in any proportion can be mentioned. Of course, like the C ₆₀ based hydrogenated fullerene and mixtures C ₇₀ based hydrogenated fullerene, at least one C ₆₀
Mixtures of any composition containing a system hydrogenated fullerene at least one of the C ₇₀ based hydrogenated fullerenes simultaneously also considered hydrogenated fullerene or its use aspects of the present invention.

The hydrogenated fullerene of the present invention has a molecular structure that is specific to a C ₆₀ or C ₇₀ fullerene molecule, or
It has features such as having a carbon skeleton having a similar closed shell structure (ie, a spherical carbon cluster structure), and a spherical molecule in which the predetermined number of hydrogen atoms are bonded to the carbon skeleton. Therefore, various unique properties and physical properties based on the carbon cluster structure and the spherical molecular structure peculiar to the fullerenes can be expected, and for example, excellent lubrication performance (particularly, lubrication performance at a molecular level) can be expected. . Further, the hydrogenated fullerene of the present invention,
As described above, since the degree of hydrogenation (H / C ratio) is large, it is remarkably excellent in solubility or affinity in an organic solvent as compared with the corresponding fullerene. In fact, C ₆₀ and C ₇₀ fullerenes are only slightly soluble in aromatic solvents such as benzene, toluene, xylene, mesitylene and the like, and are not soluble in most solvents, whereas the hydrogenation of the present invention Fullerene is not only those aromatic hydrocarbon solvents, but also, for example, cyclohexane, various cycloalkanes such as methylcyclohexane and alkylcycloalkanes,
Shows sufficiently high solubility in various hydrocarbon solvents such as various alkanes such as hexane.

As described above, the hydrogenated fullerene of the present invention has sufficiently high solubility in various organic solvents and the like.
It can be expected to be used for a wider range of applications both physically and chemically. For example, conventional fullerene is expected to be used as a solid lubricant because it is a spherical carbon cluster molecule having a closed shell structure, but as described above, the solubility in an organic solvent is extremely low, and It has the disadvantage that its stability is insufficient, so that it is not suitable for use as a so-called lubricating oil additive in a system in which it is added to a lubricating oil or the like. Fullerene exhibits high solubility or dispersion stability in, for example, lubricating oils and greases, and thus has the advantage that it can be suitably used in applications as a dissolving and / or dispersing lubricating oil additive. Also have.

The various hydrogenated fullerenes of the present invention can be used alone or as a mixture containing two or more kinds in an arbitrary ratio. Alternatively, two or more components can be used as a mixture with other components.

The hydrogenated fullerene of the present invention is not particularly limited as a general production method, and can be produced by various methods. Usually, it can be suitably produced by the following method.

That is, the C ₆₀ hydrogenated fullerene of the present invention is a fullerene C ₆₀ (ie, a C ₆₀ having a closed shell structure).
₆₀ fullerene), the method of the present invention that the reaction of hydrogen gas in the presence of a hydrogenation catalyst (hereinafter sometimes referred to as method I.) By can be obtained suitably, while, C ₇₀ of the present invention The system hydrogenated fullerene is a method of the present invention in which fullerene C ₇₀ (that is, C ₇₀ fullerene having a closed shell structure) is reacted with hydrogen gas in the presence of a hydrogenation catalyst (hereinafter sometimes referred to as method II). )). In the above method, the desired product can be more suitably obtained by hydrogenation using a hydrogenation catalyst and contact treatment with a Lewis acid compound.

In the method for producing a hydrogenated fullerene of the present invention, at least fullerene C ₆₀ is used as a raw material in the method I, and at least fullerene C ₇₀ is used in the method II. Of course, it may be used a mixture of fullerene C ₆₀ and fullerene C _70, in this case, it is also possible to achieve methods I and II simultaneously. Here, fullerene C ₆₀ and fullerene C ₇₀ to be subjected to the hydrogenation reaction
Respectively contain not only pure ones but also various purity ones, or a mixture of fullerene C ₆₀ and fullerene C _{70 at} an arbitrary ratio, and further contain at least fullerene C ₆₀ and / or fullerene C ₇₀ . It can also be used as a mixture.

The hydrogenation catalyst is not particularly limited.
Various known hydrogenation catalysts, such as those known or proposed or proposed as hydrogenation catalysts for hydrocarbons and the like, can be used. Such hydrogenation catalysts include, for example, Cr, F
e, Co, Ni, Mo, Ru, Rh, Pd, W, Re,
There are various forms of catalysts composed of various metals including transition metals such as Os, Ir, Pt and the like. Representative examples of these include, for example, Pt colloid, Raney nickel, Raney ruthenium, Raney cobalt Metal catalysts such as metal colloids represented by, for example, platinum black, palladium black, ruthenium black, rhodium black, rhenium black, chromium oxide, molybdenum oxide, etc .; molybdenum sulfide, rhenium sulfide, etc. Metal sulfide-based catalysts, various metal complex-based catalysts such as various metal complex-based catalysts, and various supported catalysts in which these metals or metal compounds are supported on various supports (for example, supported catalysts). Various things such as Pd / carbon, Ru / carbon, nickel / diatomaceous earth, Pd / silica, etc. Among these, Pd / carbon, Ru / carbon, etc. can be particularly preferably used, and these hydrogenation catalysts may be used alone. , 2
More than one species may be used in combination, such as by mixing or complexing.

The amount of the hydrogenation catalyst varies depending on various conditions of hydrogenation, but is usually 0.01 to 1 with respect to 1 part by weight of fullerenes.
It is used in an amount of about 00 parts by weight, preferably 0.1 to 10 parts by weight.

Examples of the Lewis acid compound include various zeolites, alumina, aluminum trihalide compounds, tin tetrachloride, arsenic chloride, antimony chloride, bismuth chloride, zinc chloride, zinc fluoride, cadmium chloride, cadmium fluoride, and chlorinated chloride. Zirconium, zirconium fluoride, and the like can be given. One of these Lewis acid compounds may be used alone, or two or more thereof may be used in combination.

Although the amount of the Lewis acid compound varies depending on various reaction conditions, it is usually 0.01 to 1 part by weight of fullerenes.
About 100 parts by weight, preferably 0.1 to 10 parts by weight.
Used by weight.

As the hydrogen gas used in the hydrogenation reaction, not only a pure hydrogen gas but also various purity or grade materials such as various industrial ones can be used. Can be.

In the method of the present invention, fullerene C ₆₀
And / or fullerene C ₇₀ or a raw material containing the same is contacted with hydrogen gas in the presence of the hydrogenation catalyst to obtain the desired C ₆₀ -based hydrogenated fullerene, C ₇₀
To produce a hydrogenated fullerene or a mixture thereof.

The hydrogenation reaction is usually carried out at room temperature to 300 ° C.
Preferably, it can be suitably performed at a temperature in the range of 30 to 280 ° C. Since the reaction time varies depending on other conditions such as temperature and hydrogen gas pressure, it cannot be determined uniformly, but usually about 10 minutes to 100 hours is sufficient.
The pressure of the hydrogen gas in the hydrogenation reaction is not particularly limited, but it is usually appropriate to carry out the hydrogenation reaction under the condition that the hydrogen gas partial pressure is equal to or higher than the atmospheric pressure. If the hydrogen gas pressure is lower than the atmospheric pressure, the reaction rate is too low to be practical. In the case of hydrogenation of fullerene C ₆₀ ,
Usually, in the range of 10 to 200 / cm ^2, whereas, in the case of the hydrogenation of the fullerene C ₇₀ is usually 20～250Kg
/ Cm ² is preferably set. Of course, in both cases, if the hydrogen gas is made higher, the hydrogenation proceeds further, so that it is possible to carry out the operation at a higher hydrogen gas pressure if necessary. Here, the hydrogenation pressure of the fullerene C _{60 and} the hydrogenation of the fullerene C ₇₀ have different suitable hydrogen gas pressure ranges.
Only fullerene C ₆₀ from a mixed raw material containing ₆₀ and fullerene C ₇₀ selectively hydrogenated, it is also possible to obtain good selectivities to C ₆₀ based hydrogenation fullerene. Similarly, by appropriately controlling the hydrogen gas pressure, hydrogenation of components other than the target raw material fullerene (for example, an aromatic solvent or the like) is suppressed,
It is also possible to selectively hydrogenate only the desired fullerene, and it is also possible to hydrogenate the raw material fullerene together with the aromatic solvent as described later.

The hydrogenation reaction can be carried out without solvent, but it is usually preferable to carry out the reaction in a suitable solvent (or dispersion solvent) from the viewpoint of improving the reactivity.
The solvent for dissolving the fullerene C ₆₀ and fullerene C ₇₀ (e.g., benzene, toluene, xylene, aromatic solvent mesitylene) is carried out in preferred. Depending on the conditions, the above-mentioned aromatic hydrocarbon used as a solvent may be hydrogenated and converted into corresponding cycloalkanes (eg, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, etc.). . Although these cycloalkanes sufficiently dissolve the hydrogenated fullerene as the target product, they do not dissolve the raw material fullerene and carbons such as graphite contained in the raw material in some cases. Alternatively, even when graphite or other insoluble components in the raw material remain in the reaction mixture (product), they are decomposed when a soluble catalyst such as a complex catalyst is used. A solution containing the desired hydrogenated fullerene at a high purity can be obtained by a very simple separation operation of separating by filtration or the like together with a solid residue). The recovery of hydrogenated fullerene from this solution can be easily performed by a usual method of distilling off the solvent. Therefore, the reactivity is improved by using the above-mentioned aromatic hydrocarbon (single solvent or mixed solvent) as a solvent, and the reaction conditions (for example, hydrogen gas pressure, reaction temperature, etc.) are appropriately controlled to convert the raw material fullerene into water. A reaction method in which the aromatic hydrocarbon is sufficiently hydrogenated to convert it into the corresponding cycloalkane can be suitably employed as a preferred embodiment of the method of the present invention.

Of course, it is also possible to carry out the reaction under the reaction conditions in which the aromatic hydrocarbon used as the solvent is not substantially hydrogenated. Further, the separation / purification of the target hydrogenated fullerene from a product (reaction mixture) is not limited to the above method. For example, if the raw material fullerene is sufficiently added to the intended hydrogenated fullerene, even if the aromatic hydrocarbons of the solvent are not necessarily sufficiently hydrogenated, high-purity can be obtained by removing a solid residue such as a solid catalyst by filtration or the like. A solution containing the hydrogenated fullerene can be obtained. Also, when unreacted fullerene and the target hydrogenated fullerene are dissolved in the aromatic solution in the product,
After removing a solid residue such as a solid catalyst from the solution by filtration or the like, at least a solvent component that dissolves the raw material fullerene is sufficiently removed from the solution, and then, for example, a target hydrogenated fullerene such as cycloalkane is sufficiently removed. A method of extracting and separating the hydrogenated fullerene with a solvent that dissolves in water can also be suitably employed.

[0035] As described above, it is possible to obtain a mixture of any ratio C ₆₀ based hydrogenated fullerene or C ₇₀ based hydrogen fullerenes or their hydrogenated fullerene of the present invention suitably. The target hydrogenated fullerene thus obtained can be obtained by various methods such as a known separation / purification method (for example, a method combining a solvent extraction method such as the separation method described above, a filtration method, a solvent distillation method and the like, and the like). ) Can be separated and recovered from the reaction mixture. Usually, when fullerene C ₆₀ is used as a raw material, the desired C ₆₀ H
_{n (n} = _38~58) hydrogenated fullerene hydride fullerene containing a high purity obtained in the case where the fullerene C ₇₀ as a raw material _{is, C 70 H m (m =} 30~7 of interest
0) hydrogenated fullerene containing high purity hydrogenated fullerene is obtained, and fullerene C ₆₀ and fullerene C
_When a mixture of ₇₀ is used as a raw material, a mixture thereof is obtained. The composition of each of these mixed hydrogenated fullerenes can be easily adjusted by selecting reaction conditions such as hydrogen gas pressure as described above. In addition, each single hydrogenated fullerene can be separated from these mixed hydrogenated fullerenes, if necessary.

As described above, the C ₆₀ -based and C ₇₀ -based hydrogenated fullerene of the present invention has a special closed shell structure (spherical carbon cluster skeleton) and a hydrogenation degree (H / C ratio).
Has a highly spherical molecular structure, so it has excellent lubricating properties and has various characteristic physical properties such as easy dissolution in various organic solvents. It can be expected to be used for applications, either as a single compound or as a mixture, such as a solid lubricant,
It can be suitably used as a lubricating member such as a lubricating oil additive.

[0037]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples of the present invention, but the present invention is not limited to these Examples. Example 1 100 mg of fullerene C ₆₀ was dissolved in 300 ml of toluene, and 5.16 g of 5% ruthenium carbon (50% by weight) was dissolved.
Was added as a catalyst, the hydrogen pressure was set to 70 kg / cm ² , and the temperature was raised. At a temperature of about 50 ° C., the hydrogen pressure began to drop, and when the pressure became 10 kg / cm ² or less, hydrogen gas was injected to return the hydrogen pressure to 70 kg / cm ² . This operation was repeated until the hydrogen pressure did not decrease. The internal temperature at that time was about 180 ° C. Thereafter, the reaction was carried out at a temperature of 180 ° C. and a pressure of 80 kg / cm ² for 2 hours, and the reaction was terminated by cooling. After completion of the reaction, the catalyst was filtered, measured to concentrating the filtrate mass spectrum, as shown in FIG. 1, C ₆₀ H ₃₈ fullerene C ₆₀ was obtained it is hydrogenated with C ₆₀ H ₄₀ And a peak of these isotopes were observed, and it was confirmed that the mixture was a mixture thereof. This mixture is obtained as a white powder with a yield of 52
mg. FIG. 2 shows the infrared absorption spectrum of the obtained compound. When the solubility of the obtained hydrogenated fullerene was examined, 100 mg of hydrogenated fullerene was completely dissolved in 100 ml of cyclohexane. Incidentally, fullerene C ₆₀ of the raw materials was completely insoluble in cyclohexane.

Example 2 100 mg of fullerene C ₇₀ was dissolved in 300 ml of toluene, and 5.16 g of 5% ruthenium carbon (50% by weight) was dissolved.
Was added as a catalyst, the hydrogen pressure was set to 80 kg / cm ² , and the temperature was raised. At a temperature of about 50 ° C., the hydrogen pressure began to drop, and when the pressure became 10 kg / cm ² or less, hydrogen gas was injected to return the hydrogen pressure to 80 kg / cm ² . This operation was repeated until the hydrogen pressure did not decrease. Then. Temperature 240 ° C, pressure 120kg / cm ²
For 2 hours and cooled to complete the reaction. After completion of the reaction, the catalyst was filtered off, the filtrate was concentrated, and the mass spectrometry spectrum was measured. As shown in FIG. 3, fullerene C ₇₀ was hydrogenated to obtain C ₇₀ H ₃₀ to C ₇₀ H _46. Compound peaks and peaks of these isotopes were observed, and it was confirmed that they were a mixture thereof. This mixture was obtained as a white powder, and the yield was 45 mg.

Example 3 A raw material mixture containing 90 mg of fullerene C ₆₀ and 10 mg of fullerene C ₇₀ was operated in the same manner as in Example 1 to obtain a final temperature of 2%.
The same processing as in Example 1 was performed except that the reaction was performed at 40 ° C. and a pressure of 110 kg / cm ² . The mass spectrum after hydrogenation is shown in FIG. From this mass spectrum, C ₆₀ H ₃₈ fullerene C ₆₀ was obtained is hydrogenated, C ₆₀ H _40,
The peaks of C ₆₀ H ₄₂ and C ₆₀ H ₄₄ and their isotopes, and C ₇₀ H ₃₀ to C ₇₀ H obtained by hydrogenating fullerene C _70
46 peaks and peaks of these isotopes were observed, and it was confirmed that the mixture was a mixture of these compounds.

Example 4 500 mg of fullerene C ₆₀ was used as a raw material, and this was dissolved in 500 ml of toluene.
5 g of ruthenium carbon and 5 g of Y-type zeolite as a Lewis acid compound were added, hydrogen gas was further introduced, and a pressure of 7 g was added.
The pressure was increased to 0 kg / cm ² G, and the temperature was raised. Reaction temperature 50
When the temperature reaches ℃, the hydrogen pressure starts to decrease and 10 kg / cm
^{When the} pressure drops to ² G, hydrogen gas is injected to reduce the hydrogen pressure to 7.
It was 0 kg / cm ² G. This operation was repeated until the hydrogen pressure did not decrease. The reaction temperature at that time is about 1
It was about 80 ° C.

After replacing the solvent with dodecane, the temperature of the reactor was increased to 280 ° C. and the pressure was increased to 180 kg / cm ² G.
After performing the reaction for 4 hours, the reaction was stopped by cooling. After completion of the reaction, the catalyst and the Y-type zeolite were removed from the obtained product by filtration, and the filtrate was concentrated by an evaporator to precipitate crystals. The yield of the final product, obtained as a white powder, was 100 mg. FIG. 5 shows a mass spectrometry spectrum of the obtained final product, and FIG. 6 shows an infrared absorption spectrum thereof. From these analytical results, the product obtained fullerene C ₆₀ was obtained is hydrogenated, has a closed-shell structure, it is confirmed to be hydrogenated fullerene represented by C ₆₀ H ₃₆ ~C ₆₀ H ₆₀ Was.

[0042]

According to the present invention, a hydrogenated fullerene having a spherical molecular structure in which the carbon skeleton has a fullerene-like closed shell structure and a relatively high degree of hydrogenation (H / C ratio), Compared to organic solvents, the solubility and affinity are remarkably superior, and the dissolution or stable dispersion in a wide variety of organic solvents (for example, paraffinic hydrocarbons such as cycloalkanes as well as aromatic hydrocarbons) can be achieved. A novel substance that has advantages such as being possible and therefore can be expected to be used in a wide range of application fields including use as various types of lubricating members such as solid lubricants and lubricating oil additives. _C60- based and _C70- based hydrogenated fullerenes can be provided. According to the present invention, also a method for obtaining a good low cost efficiently C ₆₀ system and the C ₇₀ based hydrogenation fullerene of the present invention, i.e., industrially also significantly useful method, the production of hydrogenated fullerene A method can be provided.

[Brief description of the drawings]

FIG. 1 is a chart showing an example of the measurement results of the mass spectrometry spectrum of the product obtained in Example 1, which is an example of the method of the present invention, that is, the hydrogenated fullerene of the present invention (an example of a mixture). The inset in the figure is an enlarged spectrum chart of the main part.

FIG. 2 is a chart showing an example of a measurement result of an infrared absorption spectrum of the product obtained in Example 1, which is an example of the method of the present invention, that is, a hydrogenated fullerene of the present invention (an example of a mixture).

FIG. 3 is a chart showing an example of a measurement result of a mass spectrometry spectrum of a product obtained in Example 2, which is an example of the method of the present invention, that is, a hydrogenated fullerene of the present invention (an example of a mixture).

FIG. 4 is a chart showing an example of a measurement result of a mass spectrometry spectrum of the product obtained in Example 3, which is an example of the method of the present invention, that is, the hydrogenated fullerene of the present invention (an example of a mixture). The inset in the figure is an enlarged spectrum chart of the main part.

FIG. 5 is a chart showing an example of a measurement result of a mass spectrometry spectrum of the product obtained in Example 4, which is an example of the method of the present invention, that is, the hydrogenated fullerene of the present invention (an example of a mixture).

FIG. 6 is a chart showing an example of a measurement result of an infrared absorption spectrum of a product obtained in Example 4 which is an example of the method of the present invention, that is, a hydrogenated fullerene of the present invention (an example of a mixture).

──────────────────────────────────────────────────続 き Continuation of the front page (56) References Chemical Physics Letters, Vol. 176, No. 5 (25 January 1991) p. 427 (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 13/62 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (6)

(57) [Claims] 1. A hydrogenated fullerene having a closed shell structure and represented by a general formula C ₆₀ H _n (where _n represents an even number of 38 to 58). 2. A hydrogenated fullerene having a closed shell structure and represented by a general formula C ₇₀ H _m (where _m represents an even number from 30 to 70). 3. A C ₆₀ fullerene having a closed shell structure,
The method for producing hydrogenated fullerene according to claim 1, wherein hydrogen gas is reacted in the presence of a hydrogenation catalyst. 4. A C ₇₀ fullerene having a closed shell structure,
The method for producing hydrogenated fullerene according to claim 2, wherein hydrogen gas is reacted in the presence of a hydrogenation catalyst. 5. A C ₆₀ fullerene having a closed shell structure,
2. The method for producing hydrogenated fullerene according to claim 1, wherein hydrogen gas is reacted and hydrogenated in the presence of a hydrogenation catalyst, and is subjected to a contact treatment with a Lewis acid compound. 6. A C ₇₀ fullerene having a closed shell structure,
3. The method for producing hydrogenated fullerene according to claim 2, wherein hydrogen gas is reacted and hydrogenated in the presence of a hydrogenation catalyst, and is subjected to a contact treatment with a Lewis acid compound.