JP2013181002A - Fullerene derivative, process for producing the same and resin composition using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fullerene derivative and a resin composition which remarkably improve the properties of a resin material and do not cause bleeding over a long period.SOLUTION: As shown in reaction formula (A), a hydroxylated fullerene is allowed to react with acrylic acid chloride or methacrylic acid chloride to produce a fullerene derivative with part of hydroxyl groups being left. By so doing, a fullerene derivative having acryloyl groups or methacryloyl groups directly bonded to the part of the hydroxyl groups by ester bonds in the hydroxylated fullerene having hydroxyl groups directly bonded to the fullerene core is obtained. A resin composition is obtained by copolymerizing this fullerene derivative and a monomer having an unsaturated bond.

Description

  The present invention relates to a fullerene derivative capable of improving the chemical and physical properties of a resin, a method for producing the same, and a resin composition using the fullerene derivative.

  In recent years, many researches on nanocomposite materials of fullerenes, carbon nanotubes, graphenes and synthetic resin materials, which are nanomaterials, have been made. For example, fullerenes, which are nanomaterials, and a resin solution are mixed, fullerenes and a resin solution are melt-kneaded and mixed, and fullerenes are added and mixed during resin polymerization. On the other hand, in order to maximize the functions of fullerenes, which are nanomaterials, fullerenes need to be uniformly dispersed (ie, nanodispersed) to a nano-level size. However, there is almost no solvent that completely dissolves the fullerene, which is a nanoparticle, and the surface area of the nanoparticle is extremely large, and the distance between particles is small, so the aggregation of particles is prone to occur and industrially stable nanodispersion. It is difficult to create a system. Therefore, it is difficult to industrially produce a fullerene composite material in which the function (feature) of fullerene and the function of resin are expressed to the maximum.

  Japanese Patent Application Laid-Open No. 2004-75933 (Patent Document 1) discloses that a polyhydroxylated fullerene or polyhydroxylated fullerene hydrogensulfate and a thermoplastic resin are melt-kneaded to obtain a resin composition, and polyhydroxylated fullerene or It is disclosed that a resin composition is obtained by polymerizing a polyfullerene hydrogensulfate with a monomer or a thermoplastic resin precursor.

  In JP-A-2006-104417 (Patent Document 2), a spacer having a vinyl group is bonded to a fullerene via a connector, and the fullerene monomer and the film-forming polymer are dissolved in a solvent that can be dissolved or dispersed. And mixing to obtain a curable resin composition in which each component is uniformly dispersed.

JP 2004-75933 A JP 2006-104417 A

  In the resin composition disclosed in Patent Document 1, since fullerene is a derivative having a hydroxyl group, the dispersibility is better than that of fullerene itself, and the affinity with the resin is also good. However, since polyhydroxy fullerene or polyhydroxy fullerene hydrogen sulfate is only melt-kneaded and dispersed in the thermoplastic resin, there is a chemical reaction between the thermoplastic resin and poly fullerene hydrogen sulfate. There is no bond. Therefore, when the resin composition is used for a long period of time, there is a problem that the mixed polyhydroxyl fullerene hydrogensulfate bleeds out.

  In addition, polyhydroxyl fullerene or polyhydroxyl fullerene hydrogensulfate is a part of the hydroxylated fullerene that remains as an agglomerate during polymerization of a thermoplastic resin monomer or melt kneading with a thermoplastic resin. Cannot be used to the fullest. Further, when a film or a molded body is formed, aggregates are present on the surface, which causes various troubles.

    The fullerene monomer disclosed in Patent Document 2 is a fullerene having a complicated structure bonded to a vinyl group via a large number of linear or cyclic C (carbon) called spacers or connectors, and is specifically shown as an example. The fullerene monomer thus formed has a long alkyl group on both sides of the cyclic hydrocarbon via the cyclic hydrocarbon. For this reason, there is little contribution to the physical property peculiar to fullerene with respect to a thermoplastic resin. In addition, when a radically polymerizable monofunctional monomer or polyfunctional monomer and a fullerene monomer are mixed as necessary, steric hindrance occurs, the density of the polymer does not increase, and the physical properties of fullerene It is hard to get strength. Moreover, since the fullerene monomer of patent document 2 does not have a hydroxyl group, its chemical affinity for various resins is low, and therefore, interfacial strength is hardly produced.

  The present invention solves the conventional problems, and in fullerene derivatives having high hydrophilicity such as fullerene hydroxide, the characteristics of fullerenes (fullerene and its derivatives) (for example, ultraviolet absorption, radical scavenging, proton conductivity) , Fullerene derivatives that can be specifically demonstrated when synthetic resins are used to improve strength, elasticity, hardness, heat resistance, gas barrier properties, etc. An object is to provide a manufacturing method.

  It is another object of the present invention to provide a resin composition that greatly improves the properties of the base resin material and that does not bleed out the fullerene derivative from the resin composition over a long period of time.

  According to the present invention, the above object has been achieved by a fullerene derivative having a hydroxyl group directly bonded to a fullerene nucleus and having an acryloyl group or a methacryloyl group directly ester-bonded to some hydroxyl groups.

  The fullerene derivative of the present invention has the general formula Cp (OR) n (OH) m (p is an even number of 60 or more, R is an acryloyl group or a methacryloyl group, n is a number of 10 or less greater than 1, and m is greater than 2 44. It is expressed by the following number).

Fullerene core comprises a C _60, C ₇₀ or C _60, is preferably a mixture of C ₇₀ or more higher fullerenes.

  Further, according to the present invention, the fullerene derivative is produced by reacting hydroxylated fullerene with acrylic acid chloride or methacrylic acid chloride, and leaving a partial hydroxyl group, thereby producing the fullerene derivative. Achieved the purpose.

  According to the present invention, in a fullerene hydroxide having a hydroxyl group directly bonded to a fullerene nucleus, a copolymer of a fullerene derivative having an acryloyl group or a methacryloyl group directly ester-bonded to a part of hydroxyl groups and a monomer having an unsaturated bond. The above object was achieved by a resin composition obtained by polymerization.

  The monomer having an unsaturated bond may be an acrylic ester or a methacrylic ester.

  In the resin composition, the molar ratio of the fullerene derivative is preferably 0.0001 mol% or more and 50 mol% or less with respect to the monomer having an unsaturated bond.

  According to the present invention, the fullerene hydroxide having a hydroxyl group directly bonded to the fullerene nucleus is a fullerene derivative having an acryloyl group or a methacryloyl group directly ester-bonded to a part of the hydroxyl groups, and thus has no complicated structure. The characteristics of fullerenes can be exhibited.

  In addition, since the fullerene derivative of the present invention has a hydroxyl group, it has good affinity with a synthetic resin, and since the end of the acryloyl group or methacryloyl group is a double bond, a single monomer having an unsaturated bond Can be copolymerized with the body.

  The fullerene derivative of the present invention is copolymerized with various resin monomers according to properties such as ultraviolet absorption, gas barrier properties, proton conductivity, radical scavenging properties, etc., to modify resins and surface modification of molded products and films. The chemical and physical properties of the resin such as quality and surface protection function can be improved.

  In the resin composition of the present invention, since the fullerene hydroxide derivative is uniformly introduced into the synthetic resin at the molecular level and both are copolymerized, the fullerene derivative bleeds out from the resin composition even after a long period of time. There is nothing.

  According to the present invention, a resin composition in which the chemical and physical properties of a resin are improved is obtained by a resin composition obtained by copolymerizing a fullerene derivative and a monomer having an unsaturated bond. That is, by copolymerizing a monomer of a fullerene hydroxide derivative and a resin monomer, a composite exhibiting the characteristics of both can be obtained to the maximum, and it can be used as a composite material for any application.

  According to the production method of the present invention, by using a fullerene having a hydroxyl group, an acrylic acid chloride having a double bond at the end or without using a connector having a complicated chemical structure as in Patent Document 2 or By reacting methacrylic acid chloride with the hydroxyl group of fullerene, the acryloyl group or methacryloyl group can be easily bonded to the fullerene nucleus. Therefore, the fullerene derivative of the present invention can be easily produced.

  Further, in the production method of the present invention, not all hydroxyl groups are ester-reacted, but some hydroxyl groups remain, so the generated fullerene derivative is more dispersible than the characteristics of fullerene hydroxide (that is, more dispersible than fullerene itself). And good affinity with the resin).

A spectral diagram according to fullerene C ₆₀ (OH) ₁₀ Fourier transform infrared spectroscopy (FT-IR), the transmittance on the vertical axis, taking the wavenumber on the horizontal axis. It is a FT-IR spectrum of the acrylic acid fullerene ester _{C 60 (OH) 8 (OCOCH} = CH 2) 2. FIG. 2 is a spectrum diagram of acrylic acid fullerene ester C ₆₀ (OH) ₈ (OCOCH═CH ₂ ) ₂ by proton nuclear magnetic resonance spectroscopy ( ¹ HNMR), where the vertical axis represents intensity and the horizontal axis represents chemical shift (ppm). . Methacrylic acid fullerene ester _{C 60 (OH) 8 (OCO} (CH 3) C = CH 2) is a FT-IR spectrum of _2. ^{1 is} a ¹ HNMR spectrum diagram of methacrylic acid fullerene ester C ₆₀ (OH) ₈ (OCO (CH ₃ ) C═CH ₂ ) _2. FIG. It is the figure which measured Example 3, Comparative Example 1, Comparative Example 2, and Comparative Example 3 by the gel permeation chromatography, respectively, and took the time to elution (retention time) on the horizontal axis. 6 is a TGA chart of Example 3 and Comparative Example 1. FIG.

  Hereinafter, the present invention will be described in detail.

  The novel fullerene derivative according to the present invention is a fullerene hydroxide having a hydroxyl group directly bonded to a fullerene nucleus and having an acryloyl group or a methacryloyl group directly ester-bonded to a part of the hydroxyl groups.

  More specifically, the general formula Cp (OR) n (OH) m (p is an even number of 60 or more, R is an acryloyl group or a methacryloyl group, n is a number of 10 or more greater than 1, and m is 44 or less greater than 2. A fullerene derivative represented by the number of

The fullerene nucleus used in the production of the fullerene derivative of the present invention is not particularly limited as long as it is a spherical carbon molecule, but is preferably a mixture of C ₆₀ , C ₇₀ or C ₆₀ and higher fullerenes of C ₇₀ or higher. . Although fullerene examples are C _60, not only the fullerene C _60, mixed fullerene chemical and physical properties including or similar fullerene C ₇₀ or _{C 60, (C 60, C} 70, a mixture of higher fullerenes ) As a starting material, it is considered that a compound having a similar structure and similar properties can be obtained.

  In addition, the fullerene hydroxide itself having a hydroxyl group directly bonded to the fullerene nucleus, which is a starting material for the fullerene derivative of the present invention, is already known and may be produced by any method.

  To produce the fullerene derivative of the present invention, a fullerene hydroxide is reacted with acrylic acid chloride or methacrylic acid chloride. As a result, the acrylic acid chloride or methacrylic acid chloride and the hydroxyl group of the fullerene hydroxide undergo a condensation reaction to esterify the acryloyl group or methacryloyl group to the fullerene nucleus.

  In reacting the hydroxylated fullerene with acrylic acid chloride or methacrylic acid chloride, in order to leave a part of the hydroxyl group, it can be controlled by reaction conditions, time, reagent equivalent, and the like.

  Since the fullerene derivative obtained as described above has an acryloyl group or a methacryloyl group having a double bond at an end, it easily reacts with other substances. In the present invention, a composite material which is a resin composition capable of expressing various characteristics resulting from a hydroxylated fullerene derivative by copolymerizing the obtained fullerene derivative and a monomer having an unsaturated bond (monomer). I was able to get it.

  Examples of the monomer having an unsaturated bond that can be used for copolymerization in the present invention include the following.

  As ester monomers of acrylic acid or methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, iso-propyl acrylate, iso-methacrylic acid iso- Propyl, n-butyl acrylate, n-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, pentyl acrylate, pentyl methacrylate, hexyl acrylate, hexyl methacrylate, heptyl acrylate, methacryl Acid heptyl, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octadecyl acrylate, octadecyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, acrylic Benzyl, and methacrylic acid benzyl.

Examples of the styrene monomer include styrene, α-methyl styrene, p-t-butyl styrene, and the like.
Examples of polyolefin monomers include butadiene hydroxide, isoprene, chloroprene and the like.

  Examples of the vinyl monomer include vinyl chloride and vinyl acetate.

  Examples of nitrile monomers include acrylonitrile and methacrylonitrile.

  Examples of the monomer having two unsaturated bonds include ethylene glycol diacrylate, ethylene glycol dimethacrylate, and diethylene glycol diacrylate.

  A monomer having three or more unsaturated bonds can also be used.

  These monomers having an unsaturated bond are not limited to the above examples as long as they are polymerized by heat or light irradiation, and these monomers having an unsaturated bond may be used alone or in two kinds. Use in combination.

As the polymerization initiator used in the present invention, a peroxide or an azo compound is used.
Peroxides include benzoyl peroxide, cumene hydroperoxide, dicumyl peroxide, diisopropylbenzene hydroperoxide, t-butyl hydroperoxide, t-butyl cumyl peroxide, 1,1, -bis (t-butyl Peroxy) 3,3,5, -trimethylcyclohexane, hydrogen peroxide and the like.
Examples of the azo compound include azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), dimethyl 2,2′-azobisisobutyrate, and the like.

  As the polymerization method, any polymerization method such as solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization may be used. Moreover, it is also possible to use redox polymerization, living polymerization, or the like.

  The compounding ratio of the fullerene hydroxide monomer in the present invention is preferably 0.0001 to 50 mol%, more preferably 0.0001 to 30 mol%, relative to the resin monomer.

  Hereinafter, the present invention will be described with reference to specific examples, but the present invention is not limited to these examples.

<Synthesis of Partially Acrylic Esterified Fullerene Hydroxide C ₆₀ (OH) ₈ (OCOCH═CH ₂ ) ₂ >
Hydroxyl fullerene C ₆₀ (OH) ₁₀ (nanom spectra D100, 100 mg, manufactured by Frontier Carbon Co., Ltd.) was dissolved in dehydrated tetrahydrofuran (50 mL) in a 50 mL eggplant-shaped flask, and sodium hydride (200 mg) was added, followed by septum ( A rubber seal plug) was attached, and the mixture was stirred at room temperature for 30 minutes in an air atmosphere. Acrylic acid chloride (500 μL) was added to the slightly brownish suspension of the red-brown suspension solution, and stirring was continued at room temperature for another 16 hours. A cloudy solution was obtained.

  Using a separatory funnel, adding saturated brine to this solution and washing it was repeated 5 times. The organic layer was sufficiently dehydrated with magnesium sulfate, and then the solvent was distilled off by an evaporator. Was dried. In order to remove impurities and unreacted fullerene hydroxide, the brown fraction was fractionated using silica gel column chromatography with tetrahydrofuran as the mobile phase, and the solvent was distilled off with an evaporator to obtain a crude product as a brown solid. . Furthermore, in order to remove a small amount of impurities, this solid is dissolved in a small amount of tetrahydrofuran, re-precipitated by gradually adding pentane, and the solid obtained by centrifugation is dried at room temperature under reduced pressure to produce a purified product. The product was obtained as a brown powder (yield 105 mg, yield 96%).

用いた水酸化フラーレンＣ₆₀（ＯＨ）₁₀および得られた生成物の赤外線吸収（ＩＲ）スペクトルをそれぞれ図１および図２に示す。生成物のＩＲスペクトルは、出発原料として用いた水酸化フラーレンのスペクトルとは大きく異なっており、ほぼ原料が消失したことを示唆するとともに、アクリル酸エステルのスペクトルに特徴的なＣ＝Ｏ伸縮に基づく１７３４ｃｍ^−１の吸収、脂肪族Ｃ−Ｈ伸縮に基づく２９００ｃｍ^−１付近の小さなブロードの吸収を示していた。また、水酸化フラーレンの特徴であるＯ−Ｈ伸縮に基づく３４００ｃｍ^−１付近の大きなブロードな吸収とともに、図１に見られる１６００、１３５０、１０５０ｃｍ^−１付近のそれぞれＣ＝Ｃ、Ｃ−Ｏ−Ｈ、Ｃ−Ｏ結合に特徴的な吸収も確認されたことから、部分アクリル酸エステル化水酸化フラーレンの生成を確認した
この生成物の元素分析の値はＣ；７０．５９％，Ｈ；２．８５％となり、Ｃ₆₀（ＯＨ）₈（ＯＣＯＣＨ＝ＣＨ₂）₂・７Ｈ₂Ｏの組成式からの計算値（Ｃ；７０．４７％，Ｈ；２．５１％）とよく一致した。

Infrared absorption (IR) spectra of the fullerene hydroxide C ₆₀ (OH) _{10 used} and the resulting product are shown in FIGS. 1 and 2, respectively. The IR spectrum of the product is significantly different from the spectrum of the fullerene hydroxide used as the starting material, suggesting that the raw material has almost disappeared, and based on the C = O stretching characteristic of the spectrum of the acrylate ester absorption of 1734 cm ^-1, showed an absorption of small broad around 2900 cm ^-1 based on aliphatic C-H stretching. Further, together with the large broad absorption around 3400 cm ⁻¹ based on the OH stretching characteristic of the fullerene hydroxide, C═C and C—O—H around 1600, 1350 and 1050 cm ⁻¹ as shown in FIG. Since the absorption characteristic of the C—O bond was also confirmed, the production of partially acrylated fullerene hydroxide was confirmed. The elemental analysis values of this product were C; 70.59%, H; It was 85% and agreed well with the calculated value from the composition formula of C ₆₀ (OH) ₈ (OCOCH═CH ₂ ) ₂ .7H ₂ O (C; 70.47%, H; 2.51%).

The ¹ HNMR spectrum of this product was measured, and the number of introduced acrylic groups was quantified from the peak area ratio with the internal standard substance (FIG. 3). In deuterated DMF, 0.88 mg of 1,2-dichloroethane was added as an internal standard substance to 5.31 mg of the product, and the measurement was performed. A singlet peak derived from 1,2-dichloroethane was observed near the peak and 4 ppm, respectively. The integration ratio is 1.61: 2.10, and considering that the proton number of the internal standard substance is 4, the number of vinyl groups introduced is estimated to be 1.9, which is estimated from elemental analysis. It was in good agreement with the composition formula consisting of C ₆₀ (OH) ₈ (OCOCH═CH ₂ ) ₂ .

<Synthesis of Partial Methacrylate Ester Hydroxide Fullerene C ₆₀ (OH) ₈ (OCO (CH ₃ ) C═CH ₂ ) ₂ >
Hydroxylene fullerene C ₆₀ (OH) ₁₀ (nanom spectra D100, 1000 mg, manufactured by Frontier Carbon Co., Ltd.) was dissolved in dehydrated tetrahydrofuran (50 mL) in an eggplant type flask, sodium hydride (1730 mg) was added, and room temperature was maintained under an argon atmosphere at room temperature. For 1 hour. Methacrylic acid chloride (5.43 mL) was added thereto, and the mixture was further stirred at 50 ° C. for 24 hours, and then quenched (stopped) with saturated brine. Using a separatory funnel, adding saturated brine to this solution and washing it was repeated 6 times. The organic layer was sufficiently dehydrated with magnesium sulfate, and then the solvent was removed by filtration. In order to purify the resulting crude product solid, the brown fraction was fractionated through silica gel column chromatography using tetrahydrofuran as the mobile phase, and the solvent was distilled off by an evaporator to obtain the product as a brown solid (yield) 990 mg, 86% yield).

得られた生成物のＩＲスペクトルを図４に示す。生成物のＩＲスペクトルは、出発原料として用いた水酸化フラーレンのスペクトルとは大きく異なっており、ほぼ原料が消失したことを示唆するとともに、メタクリル酸エステルのスペクトルに特徴的なＣ＝Ｏ伸縮に基づく１７２０ｃｍ^−１の吸収、脂肪族Ｃ−Ｈ伸縮に基づく２９００ｃｍ^−１付近の小さなブロードの吸収を示していた。また、水酸化フラーレンの特徴であるＯ−Ｈ伸縮に基づく３４００ｃｍ^−１付近の大きなブロードな吸収とともに、１６００、１３５０、１０５０ｃｍ^−１付近のそれぞれＣ＝Ｃ、Ｃ−Ｏ−Ｈ、Ｃ−Ｏ結合に特徴的な吸収も確認されたことから、部分メタクリル酸エステル化水酸化フラーレンの生成を確認した。

The IR spectrum of the obtained product is shown in FIG. The IR spectrum of the product is very different from that of the fullerene hydroxide used as the starting material, suggesting that the raw material has almost disappeared, and based on the C = O stretching characteristic of the spectrum of the methacrylate ester. absorption of 1720 cm ^-1, showed an absorption of small broad around 2900 cm ^-1 based on aliphatic C-H stretching. Moreover, together with a large broad absorption around 3400 cm ⁻¹ based on the OH stretching characteristic of hydroxylated fullerene, C═C, C—O—H and C—O bonds around 1600, 1350 and 1050 cm ⁻¹ respectively. Since the characteristic absorption was also confirmed, the formation of partially methacrylic esterified fullerene hydroxide was confirmed.

The ¹ HNMR spectrum of this product was measured, and the number of introduced methacrylic groups was determined from the peak area ratio with the internal standard substance (FIG. 5). Measurement was performed by adding 0.60 mg of 1,2-dichloroethane as an internal standard substance to 14.0 mg of the product in deuterated DMF, and found that the vinyl proton of the methacryloyl group was 5.5 to 6.5 ppm. A broad peak derived from and a singlet peak derived from the internal standard substance 1,2-dichloroethane were observed around 4 ppm. The integration ratio is 2.65: 1.00, and considering that the proton number of the internal standard substance is 4, the number of introduced vinyl groups is estimated to be 2.4, and C ₆₀ (OH) _The composition formula was estimated to be ₈ (OCO (CH ₃ ) C═CH ₂ ) ₂ .

<Synthesis of Resin Composition by Copolymerization of Partially Methacrylic Acid Esterified Fullerene Hydroxide C ₆₀ (OH) ₈ (OCO (CH ₃ ) C═CH ₂ ) ₂ and Methyl Methacrylate>
Toluene (8 mL) and dimethylformamide (2 mL) were added to an eggplant-shaped flask, and methacrylic acid fullerene ester (0.03 mg) and methyl methacrylate (3 mL) obtained in Example 2 were added thereto, and further dissolved in toluene. Azobisisobutyronitrile (AIBN, 0.01 mg) was added. Nitrogen was bubbled through this solution for 30 minutes to remove oxygen, and the temperature was raised to 80 ° C. to initiate polymerization. After stirring for 24 hours, the reaction solution was slowly dropped with a pipette into a large amount of diethyl ether stirred with a magnetic stirrer, and the precipitated solid was subjected to suction filtration to obtain a product as a fine brown solid.

[Comparative Example 1]
<Synthesis of resin composition by polymerization of methyl methacrylate>
Toluene (7 mL) was added to the eggplant-shaped flask, nitrogen was bubbled through the solution for 30 minutes to remove oxygen, and the temperature was raised to 80 ° C. When the temperature of the solvent became constant, AIBN (0.009 mg) was dissolved in methyl methacrylate (0.3 mL) and added dropwise. When the temperature began to rise, methyl methacrylate (3 mL) was further added dropwise over 2 hours, and stirring was continued for 10 hours. After the reaction, the reaction solution was slowly dropped with a pipette into a large amount of diethyl ether stirred with a magnetic stirrer, and the precipitated solid was subjected to suction filtration to obtain a product as a white solid.

[Comparative Example 2]
<Synthesis of a resin composition of fullerene C ₆₀ and methyl methacrylate>
Toluene (10 mL) was added to an eggplant-shaped flask, C ₆₀ (0.021 mg) and methyl methacrylate (3 mL) were added, and AIBN (0.01 mg) dissolved in toluene was further added. Nitrogen was bubbled through this solution for 30 minutes to remove oxygen, and the temperature was raised to 80 ° C. to initiate polymerization. After stirring for 24 hours, the reaction solution was slowly dropped with a pipette into a large amount of diethyl ether stirred with a magnetic stirrer, and the precipitated solid was subjected to suction filtration to obtain a product as a slightly black solid.

[Comparative Example 3]
<Synthesis of Resin Composition of Fullerene Hydroxide C ₆₀ (OH) ₁₀ and Methyl Methacrylate>
Toluene (6 mL) and dimethylformamide (4 mL) were added to an eggplant type flask, C ₆₀ (OH) ₁₀ (0.026 mg) and methyl methacrylate (3 mL) were added, and AIBN (0.01 mg) dissolved in toluene was further added. Was added. Nitrogen was bubbled through this solution for 30 minutes to remove oxygen, and the temperature was raised to 80 ° C. to initiate polymerization. After stirring for 24 hours, the reaction solution was slowly dropped with a pipette into a large amount of diethyl ether stirred with a magnetic stirrer, and the precipitated solid was subjected to suction filtration to obtain a product as a slightly yellow solid.

(Molecular weight measurement of resin composition)
The molecular weights of the resin compositions obtained in Example 3 and Comparative Examples 1 to 3 were measured using gel permeation chromatography. The results are shown in FIG. In Comparative Example 1, one broad peak having a weight average molecular weight (Mw) of 34,000 and a polydispersity of Mw / Mn = 1.7 was observed. On the other hand, in Example 3, a similar broad peak appeared at substantially the same retention time, but a peak having a small molecular weight of 869,000 was also observed before the retention time. From this, in Example 3, a resin composition containing a component having a molecular weight increased by copolymerization of partially methacrylic esterified fullerene hydroxide with methyl methacrylate and further crosslinking via a fullerene skeleton was obtained. It was confirmed.

  Further, in Comparative Examples 2 and 3, only one similar broad peak appeared at substantially the same holding time as in Comparative Example 1, and the peak as seen in Example 3 was observed at the holding time before that. Was not. Therefore, in order to cause copolymerization with methyl methacrylate, it is effective to use a fullerene derivative having a group having a double bond at the end, such as partially methacrylated fullerene hydroxide. I understood.

[Measurement of thermal stability of resin composition]
Regarding the weight loss change when the resin composition obtained in Example 3 and Comparative Example 1 was heated from room temperature to 500 ° C. using a thermogravimetric analyzer (TGA), the temperature rising rate was 5 ° C. under nitrogen flow. Measurement was performed at / min. As a result, it was found that the resin composition containing the fullerene hydroxide moiety obtained in Example 3 was greatly improved in thermal stability as compared with polymethyl methacrylate (PMMA) obtained in Comparative Example 1. .

Claims (9)

  A fullerene derivative having a hydroxyl group directly bonded to a fullerene nucleus and having an acryloyl group or a methacryloyl group directly ester-bonded to a part of the hydroxyl groups.   Represented by the general formula Cp (OR) n (OH) m (p is an even number of 60 or more, R is an acryloyl group or a methacryloyl group, n is a number of 10 or more greater than 1 and m is a number of 44 or less greater than 2) The fullerene derivative according to claim 1. The fullerene derivative according to claim 1, wherein the fullerene nucleus is C ₆₀ . Fullerene derivative according to claim 1 or claim 2, wherein the fullerene core is C _70. The fullerene derivative according to claim 1, wherein the fullerene nucleus is a mixture with a higher-order fullerene having C ₇₀ or higher, including C ₆₀ .   A method for producing a fullerene derivative, comprising reacting a fullerene hydroxide with acrylic acid chloride or methacrylic acid chloride to produce a fullerene derivative while leaving a part of the hydroxyl groups.   A resin composition obtained by copolymerization of the fullerene derivative according to any one of claims 1 to 5 and a monomer having an unsaturated bond.   8. The resin composition according to claim 7, wherein the monomer having an unsaturated bond is an acrylic ester or a methacrylic ester.   The resin composition according to claim 7 or 8, wherein the molar ratio of the fullerene derivative is 0.0001 mol% or more and 50 mol% or less with respect to the monomer having an unsaturated bond.

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