JP2007217641A - Polymerizable fullerene and its production process - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photo and thermal polymerizable fullerene which can be industrially produced and capable to be formed into any arbitrary form. <P>SOLUTION: The polymerizable fullerene has a structure shown by the below mentioned general formula XÐC<SB>n</SB>[(SiR<SP>1</SP>R<SP>2</SP>O)<SB>m</SB>(SiR<SP>3</SP>R<SP>4</SP>O)<SB>j</SB>SiR<SP>5</SP>R<SP>6</SP>-Y-OC(O)-CR<SP>7</SP>=CH<SB>2</SB>]k (1) with the proviso that R<SP>1</SP>to R<SP>6</SP>each independently represents a hydrogen or a 1-12C alkyl group, an arylalkyl group or an aryl group, Y represents a 3-12C alkyl group, R<SP>7</SP>represents a hydrogen or a 1-12C alkyl group, X represents an inert gas or a metal atom, XÐC<SB>n</SB>represents a fullerene having a carbon number of n and including an inert gas and/or a metal atom, n represents an integer of 60 or over, m and j represent an integer of 1-100 expressing the polymerization degree and k represents an integer of 1-11. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  Fullerene is a compound that exhibits a nonlinear optical effect, and its application to various electronic devices is considered. Polymerizable fullerene is expected to be used as an optical switch material indispensable for a next-generation large-capacity optical communication system as a polymer raw material capable of forming a thin film and shaping.

Examples of fullerene derivatives and fullerene-containing polymers include photosensitive fullerene organosilane copolymers (see, for example, Patent Document 1), fullerene derivatives having anionized sites, hydroxyl group-containing fullerenes, and epoxy group-containing fullerene polymers. Production method (for example, see Patent Document 2), a method for polycondensing a dicarboxylated fullerene biscycloproponate adduct monomer with an aromatic diamine at a temperature of 110 ° C. for 3 hours to obtain a fullerene-containing polyamide (for example, Patent Document 3), fullerene derivatives having a (meth) acryloyl group, a polymer, and a method for producing a cured product (see Patent Document 4, for example). In addition, a method for producing a fullerene-containing polyurethane by polymerizing a hydroxyl group-containing fullerene, a polyalkylene oxide glycol, and a diisocyanate compound is disclosed (for example, see Patent Document 5). Furthermore, fullerene organosiloxane copolymers are disclosed (for example, see Patent Document 6). A method for obtaining a fullerene-containing polyimide after synthesizing a polyamic acid by introducing an alkoxy group, a hydroxyl group, or an acid anhydride group into fullerene (see, for example, Patent Document 7), and organoanilinofullerene-dimethylsiloxane triblock Polymer synthesis method (for example, see Non-patent Document 1), production method for buckminsterfullerene C _60- containing siloxane hybrid rod (for example, see Non-Patent Document 2), method for producing C ₆₀ -silica hybrid material by sol-gel method (For example, refer nonpatent literature 3) The manufacturing method etc. are disclosed.

JP-A-7-62105 Japanese Patent Laid-Open No. 2003-238692 Japanese Patent Laid-Open No. 10-45905 JP-A-8-283199 JP-A-8-183830 JP-A-9-157398 Japanese Patent Laid-Open No. 9-301943 Journal of Macromolecular Science, A40, No. 12, 1263, 2003 ACS Symposium Series, Volume 572, “Inorganic and Organometallic Polymers II”, Chapter 9, p. 92, 1994 Journal of Sol-Gel Science and Technology, Vol. 22, p. 219, 2001

  In order to use fullerene as a functional material, a fullerene molecule alone is difficult to form into a molded body having an arbitrary shape, and thus a method for forming a desired shape is required. On the other hand, fullerene has a strong cohesive force, and it is difficult to disperse fullerene not chemically modified in a resin. From such a point of view, chemical modification of fullerene has been studied. However, as described above, all of these require complicated reactions, and a method for obtaining a resin containing fullerene economically has been demanded. The present invention has been made to solve such a problem, and a molded product containing fullerene can be obtained in a short time compared to the conventional method.

  As a result of intensive studies to solve such problems, the present inventors have found that a fullerene-containing polymer can be obtained in a short time by a polymerizable fullerene having a specific reactive group that is polymerized by heat or light irradiation. As a result, the present invention has been completed.

That is, the present invention relates to a polymerizable fullerene represented by the following general formula (1) and a method for producing the same.
^{_{X @ C n [(SiR 1}} R 2 O) m (SiR 3 R 4 O) j SiR 5 R 6 -Y-OC (O) -CR 7 = CH 2] k (1)
(Wherein R ^{1 to} R ⁶ each independently represents hydrogen or an alkyl group having 1 to 12 carbon atoms, an arylalkyl group or an aryl group, Y represents an alkylene group having 3 to 12 carbon atoms, and R ⁷ represents hydrogen or Represents an alkyl group having 1 to 12 carbon atoms, X represents an inert gas or a metal atom, X @ C _n represents an inert gas or a fullerene composed of n carbon atoms including the metal atom, and n is 60 or more M, j represents the degree of polymerization, and represents a positive number from 1 to 100, and k represents a positive number from 1 to 11.)
Hereinafter, the present invention will be described in detail.

The polymerizable fullerene of the present invention has a structure represented by the general formula (1), wherein R ^{1 to} R ⁶ are each independently hydrogen, an alkyl group having 1 to 12 carbon atoms, or an arylalkyl group. Represents an aryl group, Y represents an alkylene group having 3 to 12 carbon atoms, R ⁷ represents hydrogen or an alkyl group having 1 to 12 carbon atoms, X represents an inert gas or a metal atom, and X @ C _n Represents a fullerene composed of an inert gas and a carbon atom containing a metal atom, where n is a positive number of 60 or more, m, j represents a degree of polymerization, a positive number of 1 to 100, and k is a number of 1 to 11. Represents a positive number.

R ^{1 to} R ⁶ constituting the polymerizable fullerene of the present invention each independently represent hydrogen or an alkyl group having 1 to 12 carbon atoms, an arylalkyl group, or an aryl group. Examples of the alkyl group having 1 to 12 carbon atoms include Methyl group, ethyl group, propyl group and the like; examples of the arylalkyl group having 1 to 12 carbon atoms include benzyl group; examples of the aryl group having 1 to 12 carbon atoms include phenyl group, tolyl group and naphthyl group Of these, hydrogen, a methyl group, and a phenyl group are preferable.

  Y constituting the polymerizable fullerene of the present invention represents an alkylene group having 3 to 12 carbon atoms. Examples of the alkylene group having 3 to 12 carbon atoms include a propylene group and a butylene group. preferable.

R ⁷ constituting the polymerizable fullerene of the present invention represents hydrogen or an alkyl group having 1 to 12 carbon atoms. Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, and a propyl group. Of these, hydrogen and a methyl group are preferable.

X constituting the polymerizable fullerene of the present invention represents an inert gas and a metal atom, and X @ Cn represents a fullerene composed of a positive number of 60 or more carbons including the inert gas and the metal atom. the fullerenes containing gas, a metal atom, for example, _{He @ C 60, Ar @ C} 60, Li @ C 60, Kr @ C 60, Xe @ C 60, Li @ C 70, Ca @ C 70, Yb @ C ₇₀ , Ca @ _C74 , Yb @ _C74 , Eu @ _C82 , La @ _C82 , Yb @ _C82 , Ca @ _C82 , Ce @ _C82 , Gd @ _C82 , Tm @ _C82 , Dy @ C ₈₂ , Pr @ _C82 , Tm @ _C82, etc. are exemplified. Of these inert gases and fullerenes containing metal atoms, Li @ C ₆₀ is preferably used. In addition, it is possible to enclose two or more inert gases or metal atoms in the fullerene.

  These metal-encapsulated fullerenes can be synthesized by, for example, the method described in “Journal of Macromolecular Science, A40, No. 12, 1263, 2003”.

  As the method for producing the polymerizable fullerene of the present invention, any method can be used as long as the polymerizable fullerene represented by the general formula (1) is obtained. Among them, the polymerization represented by the general formula (1) can be easily performed. Since a silane compound is reacted with an inert gas or a fullerene encapsulating metal atoms to obtain a silane-containing fullerene in which silane is introduced into the fullerene, a method of adding a polymerizable compound is preferably used. It is done.

As a method for introducing silane into the fullerene at that time, for example, as described in “ACS Symposium Series, Volume 572,“ Inorganic and Organometallic Polymer II ”, Chapter 9, page 92, 1994”, an inert gas is used. A silane-containing fullerene in which a silane is introduced into the fullerene can be obtained by reacting a fullerene (X @ C _n ) encapsulating a metal atom with a silane compound represented by the following general formula (2).
^{_{H- (SiR 8 R 9 O)}} p - (SiR 10 R 11 O) r -SiR 12 R 13 H (2)
(Here, R ^{8 to} R ¹³ are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms, an arylalkyl group, or an aryl group, p and r are degrees of polymerization, and represent a positive number from 1 to 100.)
R ^{8 to} R ¹³ in the silane compound represented by the general formula (2) used for obtaining the silane-containing fullerene each independently represent hydrogen or an alkyl group having 1 to 12 carbon atoms, an arylalkyl group, or an aryl group, Examples of the alkyl group having 1 to 12 carbon atoms include, for example, a methyl group, an ethyl group, and a propyl group; examples of the arylalkyl group having 1 to 12 carbon atoms include a benzyl group; and examples of an aryl group having 1 to 12 carbon atoms include A phenyl group, a tolyl group, a naphthyl group, etc. are mentioned, Among these, hydrogen, a methyl group, and a phenyl group are preferable.

  As a more specific silane compound represented by the general formula (2), for example, a silane compound represented by the following structure is preferable.

(Here, R ^{16 to} R ²⁷ each independently represent hydrogen, a methyl group, or a phenyl group, and q represents the degree of polymerization and represents a positive number from 1 to 100.)
Among these silane compounds, trisiloxanes such as 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane and 1,1,3,5,5-pentamethyl-3-phenyltrisiloxane Is preferred.

  In the production of the polymerizable fullerene of the present invention, the solvent used for the reaction of the inert gas, the fullerene encapsulating the metal atom and the silane compound represented by the general formula (2) is the inert gas, the fullerene encapsulating the metal atom. Can be used without any limitation as long as it dissolves and does not react with the silane compound. Examples thereof include diethyl ether, toluene, benzene, xylene, tetrahydrofuran (THF), chloroform and the like. In addition, since a reaction can be accelerated | stimulated, it is preferable to use a catalyst, and as this catalyst, dicobalt octcarbonyl is used suitably. The reaction temperature can be carried out without any limitation as long as it is not higher than the boiling point of the solvent and not lower than the freezing point, and is preferably 0 ° C. to 100 ° C., particularly preferably room temperature to 80 ° C., and more preferably 40 ° C. ℃ -80 ℃.

  The reaction charge ratio of the inert gas and the fullerene encapsulating the metal atom and the silane compound is preferably 0.5 to 30 times the molar amount of the silane compound with respect to 1 mol of the fullerene encapsulating the inert gas and the metal atom. More preferably, it is 1 to 20 times mol.

The method for producing polymerizable fullerene of the present invention is obtained by producing a silane-containing fullerene and then adding a polymerizable compound. The polymerizable compound reacts with the silane-containing fullerene and is represented by the general formula (1 Any polymerizable compound can be used as long as the polymerizable fullerene represented by (2) is obtained, and among them, the polymerizable compound represented by the general formula (3) is particularly preferable.
^{_{CH 2 = CH-R 14 -OC}} (O) -CR 15 = CH 2 (3)
(Here, R ¹⁴ represents an alkylene group having 1 to 10 carbon atoms, and R ¹⁵ represents hydrogen or an alkyl group having 1 to 12 carbon atoms.)
R ¹⁴ in the polymerizable compound represented by the general formula (3) used for the production of the polymerizable fullerene of the present invention is an alkylene group having 1 to 10 carbon atoms, and examples of the alkylene group having 1 to 10 carbon atoms include a methylene group. And an ethylene group, among which a methylene group is preferred.

R ¹⁵ in the general formula (3) is hydrogen or an alkyl group having 1 to 12 carbon atoms, and examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, and a propyl group. Hydrogen and a methyl group are preferable.

  Specific examples of the polymerizable compound represented by the general formula (3) include allyl acrylate and allyl methacrylate.

  The solvent used for the reaction of the silane-containing fullerene and the polymerizable compound can be used without any limitation as long as it is a solvent in which the silane-containing fullerene and the polymerizable compound are dissolved and does not react with these compounds. For example, diethyl ether, toluene, benzene , Xylene, THF, chloroform and the like. The reaction temperature can be carried out without any limitation as long as it is below the boiling point of the solvent and above the freezing point, preferably from 0 ° C to 100 ° C, particularly preferably from room temperature to 80 ° C, more preferably. 40 ° C to 80 ° C.

  The reaction charge ratio of the silane-containing fullerene and the polymerizable compound is preferably 0.8 to 2 moles, particularly preferably 1.0 to 1 mole of the silane compound of the silane compound added to the fullerene in a molar ratio. 1.2 moles.

  The polymerizable fullerene encapsulating the inert gas and metal atoms obtained by the present invention can be dissolved in various organic solvents such as aromatic compounds such as toluene and benzene, and the polymerizable fullerene solution is prepared and applied. After the coating and casting on the substrate film, the solvent can be evaporated at room temperature or at a temperature not higher than the boiling point of the solvent used to form a film. After the film is dried at room temperature so as not to generate bubbles, the solvent is volatilized by heating and then photopolymerized by ultraviolet irradiation to form a crosslinked film. In this case, the UV irradiation time is preferably 30 minutes to 8 hours.

  The present invention can provide a photo- and heat-polymerizable fullerene derivative that can be shaped into any shape and is industrially easy to produce.

  EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In addition, unless otherwise indicated, the reaction in the Example and comparative example of this invention was performed under nitrogen.

  Allyl acrylate, chloroplatinic acid, and toluene used in the examples were all purchased from Wako Pure Chemical as reagents. Siloxanes were purchased as reagents from Aldrich.

Example 1
200 ml of dehydrated toluene, 504 mg (0.694 mmol) of Li @ C ₆₀ fullerene and 1,1,5,5-tetramethyl-3,3-diphenyl in a 500 ml four-necked flask equipped with a stirrer and a nitrogen introducing tube 0.785 g (2.776 mmol) of trisiloxane was charged. Further, 0.001 g of dicobalt octcarbonyl was charged as a catalyst, and the reaction was continued at 80 ° C. for 3 hours. The reaction solution was charged with 0.263 g (2.082 mmol) of allyl methacrylate and further reacted for 3 hours. After cooling the reaction solution, the obtained reaction solution was concentrated with an evaporator, washed with hexane several times, and then dried under reduced pressure to obtain 1.2 g (yield 89%) of polymerizable fullerene. From the elemental analysis value, it was found that the content of Li @ C ₆₀ was 37%, and an average of 3 mol of the oligosiloxane chain of the terminal methacrylate was added to one molecule of Li @ C ₆₀ .
_{Li @ C 60 [(SiCH 3} CH 3 O) (SiC 6 H 5 C 6 H 5 O) SiCH 3 CH 3 -CH 2 CH 2 CH 2 -OC (O) -C (CH 3) = CH 2] 3
To 0.4 g of the obtained polymerizable fullerene, 0.6 g of toluene and 0.001 g of benzophenone as a polymerization initiator were added to obtain a uniform solution, and then nitrogen substitution was performed three times to remove dissolved oxygen, and on a polyethylene terephthalate (PET) film. It was cast into. The mixture was left standing overnight at room temperature in a nitrogen stream, and further heated from 40 ° C. to 100 ° C. and dried. Thereafter, UV irradiation was performed for 30 minutes to obtain a uniform cured film. When the obtained film was peeled off, it was a transparent yellow-brown flexible film.

Example 2
200 ml of dehydrated toluene, 0.5 g (0.694 mmol) of Li @ C ₆₀ fullerene and 1,1,5,5-tetramethyl-3,3 in a 500 ml four-necked flask equipped with a stirrer and a nitrogen introducing tube -0.588 g (2.082 mmol) of diphenyltrisiloxane was charged. Further, 0.001 g of dicobalt octcarbonyl was charged as a catalyst, and the reaction was continued at 80 ° C. for 3 hours. The reaction solution was charged with 0.263 g (2.082 mmol) of allyl methacrylate and further reacted for 3 hours. After cooling the reaction solution, the obtained reaction solution was concentrated with an evaporator, washed with hexane several times, and then dried under reduced pressure to obtain 1.08 g (yield 80%) of polymerizable fullerene. From the elemental analysis value, it was found that the content of Li @ C ₆₀ was 37%, and an average of 3 mol of the oligosiloxane chain of the terminal methacrylate was added to one molecule of Li @ C ₆₀ .
_{Li @ C 60 [(SiCH 3} CH 3 O) (SiC 6 H 5 C 6 H 5 O) SiCH 3 CH 3 -CH 2 CH 2 CH 2 -OC (O) -C (CH 3) = CH 2] 3
To 0.4 g of the obtained polymerizable fullerene, 0.6 g of toluene and 0.001 g of benzophenone as a polymerization initiator were added to obtain a uniform solution, and then nitrogen substitution was performed three times to remove dissolved oxygen and cast onto a PET film. . The mixture was left standing overnight at room temperature in a nitrogen stream, and further heated from 40 ° C. to 100 ° C. and dried. Thereafter, UV irradiation was performed for 30 minutes to obtain a uniform cured film. When the obtained film was peeled off, it was a transparent and flexible film.

Example 3
200 ml of dehydrated toluene, 0.5 g (0.694 mmol) of Li @ C ₆₀ fullerene and 1,1,5,5-tetramethyl-3,3 in a 500 ml four-necked flask equipped with a stirrer and a nitrogen introducing tube -0.196 g (0.694 mmol) of diphenyltrisiloxane was charged. Further, 0.001 g of dicobalt octcarbonyl was charged as a catalyst, and the reaction was continued at 80 ° C. for 3 hours. To this reaction solution, 0.088 g (0.694 mmol) of allyl methacrylate was charged, and the reaction was further performed for 3 hours. After cooling the reaction solution, the obtained reaction solution was concentrated with an evaporator, washed with hexane several times, and then dried under reduced pressure to obtain 0.61 g (yield 83%) of polymerizable fullerene. From the elemental analysis value, it was found that the Li @ C ₆₀ content was 64%, and an average of 1 mol of the oligosiloxane chain of the terminal methacrylate was added to one molecule of Li @ C ₆₀ .
_{Li @ C 60 [(SiCH 3} CH 3 O) (SiC 6 H 5 C 6 H 5 O) SiCH 3 CH 3 -CH 2 CH 2 CH 2 -OC (O) -C (CH 3) = CH 2]
To 0.2 g of the polymerizable fullerene obtained was added 0.3 g of toluene and 0.001 g of benzophenone as a polymerization initiator to obtain a homogeneous solution, followed by nitrogen substitution three times to remove dissolved oxygen and cast onto a PET film. . The mixture was left standing overnight at room temperature in a nitrogen stream, and further heated from 40 ° C. to 100 ° C. and dried. Thereafter, UV irradiation was performed for 30 minutes to obtain a uniform cured film. When the obtained film was peeled, it was a flexible film.

Example 4
200 ml of dehydrated toluene, 0.5 g (0.694 mmol) of Li @ C ₆₀ fullerene and 1,1,5,5-tetramethyl-3,3 in a 500 ml four-necked flask equipped with a stirrer and a nitrogen introducing tube -1.129 g (2.776 mmol) of diphenyltrisiloxane were charged. Further, 0.001 g of dicobalt octcarbonyl was charged as a catalyst, and the reaction was continued at 80 ° C. for 3 hours. This reaction solution was charged with 0.263 g (2.082 mmol) of allyl methacrylate and 0.5 mg of chloroplatinic acid, and further reacted for 3 hours. After cooling the reaction solution, the obtained reaction solution was concentrated with an evaporator, washed with hexane several times, and then dried under reduced pressure to obtain 1.5 g (yield 89%) of polymerizable fullerene. From the elemental analysis values, the C ₆₀ content was 37%, and it was found that 3 mol of silane was added on average per 1 molecule of C ₆₀ .
_{Li @ C 60 [(SiCH 3} CH 3 O) (SiC 6 H 5 C 6 H 5 O) SiCH 3 CH 3 -CH 2 CH 2 CH 2 -OC (O) -C (CH 3) = CH 2] 3
To 0.4 g of the obtained polymerizable fullerene, 0.6 g of toluene and 0.001 g of benzophenone as a polymerization initiator were added to obtain a uniform solution, and then nitrogen substitution was performed three times to remove dissolved oxygen and cast onto a PET film. . The mixture was left standing overnight at room temperature in a nitrogen stream, and further heated from 40 ° C. to 100 ° C. and dried. Thereafter, UV irradiation was performed for 30 minutes to obtain a uniform cured film. When the obtained film was peeled off, it was a transparent yellow-brown flexible film.

Example 5
200 ml of dehydrated toluene, 0.5 g (0.694 mmol) of Li @ C ₆₀ fullerene and 1,1,3,5,5-pentamethyl-3-liter in a 500 ml four-necked flask equipped with a stirrer and a nitrogen introducing tube 0.975 g (2.776 mmol) of phenyltrisiloxane was charged. Further, 0.001 g of dicobalt octcarbonyl was charged as a catalyst, and the reaction was continued at 80 ° C. for 3 hours. This reaction solution was charged with 0.232 g (2.082 mmol) of allyl acrylate and 0.5 mg of chloroplatinic acid, and further reacted for 3 hours. After cooling the reaction solution, the obtained reaction solution was concentrated with an evaporator, washed with hexane several times, and then dried under reduced pressure to obtain 1.4 g (yield 90%) of polymerizable fullerene. From the elemental analysis values, the C ₆₀ content was 37%, and it was found that 3 mol of silane was added on average per 1 molecule of C ₆₀ .
_{Li @ C 60 [(SiCH 3} CH 3 O) (SiC 6 H 5 CH 3 O) SiCH 3 CH 3 -CH 2 CH 2 CH 2 -OC (O) -CH 2 = CH 2] 3
To 0.4 g of the obtained polymerizable fullerene, 0.6 g of toluene and 0.001 g of benzophenone as a polymerization initiator were added to obtain a uniform solution, and then nitrogen substitution was performed three times to remove dissolved oxygen and cast onto a PET film. . The mixture was left standing overnight at room temperature in a nitrogen stream, and further heated from 40 ° C. to 100 ° C. and dried. Thereafter, UV irradiation was performed for 30 minutes to obtain a uniform cured film. When the obtained film was peeled off, it was a transparent yellow-brown flexible film.

Claims (2)

A polymerizable fullerene represented by the following general formula (1):
^{_{X @ C n [(SiR 1}} R 2 O) m (SiR 3 R 4 O) j SiR 5 R 6 -Y-OC (O) -CR 7 = CH 2] k (1)
(Wherein R ^{1 to} R ⁶ each independently represents hydrogen or an alkyl group having 1 to 12 carbon atoms, an arylalkyl group or an aryl group, Y represents an alkylene group having 3 to 12 carbon atoms, and R ⁷ represents hydrogen or Represents an alkyl group having 1 to 12 carbon atoms, X represents an inert gas or a metal atom, X @ C _n represents an inert gas or a fullerene composed of n carbon atoms including the metal atom, and n is 60 or more M, j represents the degree of polymerization, and represents a positive number from 1 to 100, and k represents a positive number from 1 to 11.) X @ C _n (where X is an inert gas or a metal atom, X @ C _n is an inert gas or a fullerene composed of n carbon atoms enclosing the metal atom, and n is a positive number of 60 or more. Fullerene and the following general formula (2)
^{_{H- (SiR 8 R 9 O)}} p - (SiR 10 R 11 O) r -SiR 12 R 13 H (2)
(Here, R ^{8 to} R ¹³ each independently represent hydrogen or an alkyl group having 1 to 12 carbon atoms, an arylalkyl group, or an aryl group, and p and r represent the degree of polymerization and represent a positive number from 1 to 100, respectively. ) Represented by the following general formula (3)
^{_{CH 2 = CH-R 14 -OC}} (O) -CR 15 = CH 2 (3)
(Here, R ¹⁴ represents an alkylene group having 1 to 10 carbon atoms, and R ¹⁵ represents hydrogen or an alkyl group having 1 to 12 carbon atoms.)
The method for producing a polymerizable fullerene according to claim 1, wherein a polymerizable compound represented by the formula: