JP4953124B2 - Polymerization catalyst for olefins - Google Patents

Description

  The present invention relates to an olefin polymerization catalyst, and specifically to an olefin polymerization catalyst containing a fullerene derivative having a Group 4 transition metal.

  Since the establishment of a method for synthesizing carbon clusters (hereinafter also referred to as “fullerenes”) formed by arranging carbon atoms in a spherical or rugby ball shape, research on fullerenes has been vigorously developed. As a result, many fullerene derivatives have been synthesized.

In addition, research on the synthesis of fullerene metal complexes in which fullerenes are bonded to metals has also been vigorously conducted. Complexes in which the 5-membered ring part of fullerene is a cyclopentadienyl ligand and is coordinated to the metal in η ⁵ type, fullerene Transition metal complexes containing an organic ligand having a conjugated skeleton and a carbon cluster anion derived from benzene (JP-A-11-255508 (Patent Document 1), JP-A-2002-241389) (Patent Document 2)).

On the other hand, metallocene complexes in which cyclopentadienyl is coordinated to metal are attracting attention as polymerization catalysts for olefins such as ethylene and propylene by combining with specific aluminum compounds and boron compounds, and polymerization catalysts for olefins using metallocene complexes Many reports have been made on the production methods of (Japanese Patent Laid-Open No. 58-19309 (Patent Document 3), Japanese Patent Laid-Open No. 2003-292520 (Patent Document 4), Organomettalics, 10 , 840 (1991) (non- Patent Document 1)). It is known that the olefin polymerization activity and the properties of the obtained polyolefin differ greatly depending on the composition and properties of the polymerization catalyst, and more active research is being continued toward the development of new polymerization catalysts.
Japanese Patent Laid-Open No. 11-255508 JP 2002-241389 A JP-A-58-19309 JP 2003-292520 JP Organomettalics, 10, 840 (1991)

Under the above circumstances, for example, an olefin polymerization catalyst having high polymerization activity is desired. In particular, for example, there is a demand for an olefin polymerization catalyst in which the density of the metal that is the center of catalytic activity and the structure of the reaction field are controlled.
Further, for example, an olefin polymerization catalyst having an easily available ligand is desired.

  The present inventors have found that a fullerene derivative in which an organic group containing a transition metal is added to a fullerene skeleton is used for an olefin polymerization catalyst, and the present invention has been completed based on this finding. The present invention provides the following olefin polymerization catalyst and the like.

[1] General formula (1)
Cn (R ^A ) _m R ¹ (1)
(In the formula, Cn represents a fullerene having n carbon atoms, m represents an integer of 1 to 10, R ¹ represents a hydrogen atom or an organic group, and R ^A each independently represents a group 4 transition in the periodic table. Indicates an organic group containing a metal.)
The polymerization catalyst for olefins containing the fullerene derivative represented by these.
[2] Cn is a fullerene C _60, olefin for the polymerization catalyst according to [1].
[3] The polymerization catalyst for olefins according to [1] or [2], wherein m is an integer of 1 to 5.

（式中、Ｒ¹は水素原子または有機基を示し、Ｒ^Aはそれぞれ独立して周期律表の第４族遷移金属を含む有機基を示す。）
で表されるフラーレン誘導体を含むオレフィン用重合触媒。
［５］ Ｒ^Aが、一般式（２）

（式中、Ｒ²はそれぞれ独立して有機基を示し、ｐは０〜４の整数を示し、Ｍは周期律表の第４族の金属原子、Ｒ³は置換基を有してもよいシクロペンタジエニル基、Ｒ⁴はそれぞれ独立して有機基またはハロゲン原子を示す。）
で表される、［１］〜［４］のいずれかに記載のオレフィン用重合触媒。
［６］ Ｒ²が、それぞれ独立してＣ₁〜Ｃ₂₀アルキル基、Ｃ₂〜Ｃ₂₀アルケニル基またはＣ₂〜Ｃ₂₀アルキニル基であり、Ｐが０〜２の整数である、［５］に記載のオレフィン用重合触媒。
［７］ Ｒ³が、ペンタメチルシクロペンタジエニル基（Ｃｐ^*）である、［５］または［６］に記載のオレフィン用重合触媒。
［８］ Ｒ⁴がそれぞれ独立してＣ₁〜Ｃ₂₀アルキル基、Ｃ₂〜Ｃ₂₀アルケニル基、Ｃ₂〜Ｃ₂₀アルキニル基である、［５］〜［７］のいずれかに記載のオレフィン用重合触媒。
［９］ ［１］〜［８］のいずれかに記載のオレフィン用重合触媒を含むエチレン用重合触媒。 [4] General formula (10)

(In the formula, R ¹ represents a hydrogen atom or an organic group, and R ^A independently represents an organic group containing a Group 4 transition metal in the periodic table.)
The polymerization catalyst for olefins containing the fullerene derivative represented by these.
[5] R ^A is represented by the general formula (2)

(In the formula, each R ² independently represents an organic group, p represents an integer of 0 to 4, M represents a metal atom of Group 4 of the periodic table, and R ³ may have a substituent. (Cyclopentadienyl group and R ⁴ each independently represents an organic group or a halogen atom.)
The olefin polymerization catalyst according to any one of [1] to [4], which is represented by:
[6] R ² is each independently a C ₁ -C ₂₀ alkyl group, a C ₂ -C ₂₀ alkenyl group or a C ₂ -C ₂₀ alkynyl group, and P is an integer of 0-2. [5] The polymerization catalyst for olefins described in 1.
[7] The polymerization catalyst for olefins according to [5] or [6], wherein R ³ is a pentamethylcyclopentadienyl group (Cp ^* ).
[8] The olefin according to any one of [5] to [7], wherein each R ⁴ is independently a C _{1 to} C ₂₀ alkyl group, a C _{2 to} C ₂₀ alkenyl group, or a C _{2 to} C ₂₀ alkynyl group. Polymerization catalyst.
[9] An ethylene polymerization catalyst comprising the olefin polymerization catalyst according to any one of [1] to [8].

  The olefin polymerization catalyst according to a preferred embodiment of the present invention can increase the density of the metal that becomes the center of catalytic activity, for example. The olefin polymerization catalyst according to a preferred embodiment of the present invention has a high polymerization activity, for example. In the olefin polymerization catalyst according to a preferred embodiment of the present invention, for example, the structure of the reaction field of the polymerization reaction can be controlled. Furthermore, the olefin polymerization catalyst according to a preferred embodiment of the present invention can be synthesized at a low cost, for example.

The novel transition metal compound, olefin polymerization catalyst and olefin polymerization method using this catalyst in the present invention will be specifically described below.
In the present specification, the term “polymerization” is used in a meaning including not only homopolymerization but also copolymerization unless otherwise specified. In addition, the term “polymer” may be used in a sense including not only a homopolymer but also a copolymer unless otherwise specified.

1 Fullerene Derivative Used in the Catalyst of the Present Invention As described above, the fullerene derivative used in the catalyst of the present invention is represented by the general formula (1) Cn (R ^A ) _m R ¹ (1)
It is a fullerene derivative represented by these.
In formula (1), Cn represents a fullerene having n carbon atoms. Fullerene is a general term for carbon clusters formed by arranging carbon atoms in a spherical or rugby ball shape (June 2000 issue of Hyundai Kagaku). 46, see Chemical Reviews, 98 , 2527 (1998)), for example, fullerene C ₆₀ (so-called Buckminster fullerene), fullerene C ₇₀ , fullerene C ₇₆ , fullerene C ₇₈ , fullerene C ₈₂ , fullerene C ₈₄ , fullerene C ₉₀ , fullerene C ₉₄ , fullerene C _{96 and the} like.
In Formula (1), R ^A and R ¹ are groups added to the fullerene skeleton, and m is the number of R ^A added to the fullerene skeleton.
Here, R ¹ is a hydrogen atom or an organic group. Each R ^A is independently an organic group containing a Group 4 transition metal in the periodic table. Here, examples of the Group 4 transition metal in the periodic table include Ti, Zr, and Hf.

  In the fullerene derivative represented by the general formula (1), the fullerene derivative represented by the general formula (10) is more preferable.

In the present specification, the “organic group” is not particularly limited. For example, the C _{1 to} C ₂₀ hydrocarbon group which may have a substituent, or C which may have a substituent. _{1 to} C ₂₀ alkoxy group, C _{6 to} C ₂₀ aryloxy group which may have a substituent, amino group which may have a substituent, silyl group which may have a substituent, substituted alkylthio group which may have a group (-SY ^1, in the formula, Y ¹ is a good C ₁ -C ₂₀ alkyl group which may have a substituent.), which may have a substituent A good arylthio group (—SY ² , wherein Y ² represents an optionally substituted C ₆ -C ₁₈ aryl group), and an optionally substituted alkylsulfonyl group (—SO 2; ₂ Y ^3, in the formula, Y ³ represents a good C ₁ -C ₂₀ alkyl group which may have a substituent.) may have a substituent Reel sulfonyl group (-SO ₂ Y ^4,: in the formula, Y ⁴ is. Showing a good C ₆ -C ₁₈ aryl group which may have a substituent group),.

In the present specification, the hydrocarbon group of the “C ₁ -C ₂₀ hydrocarbon group” may be a saturated or unsaturated acyclic group, or a saturated or unsaturated cyclic group. When the C ₁ -C ₂₀ hydrocarbon group is acyclic, it may be linear or branched. The “C ₁ -C ₂₀ hydrocarbon group” includes a C ₁ -C ₂₀ alkyl group, a C ₂ -C ₂₀ alkenyl group, a C ₂ -C ₂₀ alkynyl group, a C ₄ -C ₂₀ alkyl dienyl group, a C _6- C ₁₈ aryl group, C ₇ -C ₂₀ alkylaryl group, C ₇ -C ₂₀ arylalkyl group, C ₄ -C ₂₀ cycloalkyl group, C ₄ -C ₂₀ cycloalkenyl group, (C ₃ ~C ₁₀ cycloalkyl) C ₁ -C ₁₀ alkyl groups and the like are included.

In the present specification, "C ₁ -C ₂₀ alkyl group" is preferably C ₁ -C ₁₀ alkyl group, more preferably a C ₁ -C ₆ alkyl group. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, dodecanyl and the like.

In the present specification, "C ₂ -C ₂₀ alkenyl group" is preferably C ₂ -C ₁₀ alkenyl group, more preferably a C ₂ -C ₆ alkenyl group. Examples of alkenyl groups include, but are not limited to, vinyl, allyl, propenyl, isopropenyl, 2-methyl-1-propenyl, 2-methylallyl, 2-butenyl and the like.

In the present specification, "C ₂ -C ₂₀ alkynyl group" is preferably C ₂ -C ₁₀ alkynyl group, more preferably a C ₂ -C ₆ alkynyl group. Examples of alkynyl groups include, but are not limited to, ethynyl, propynyl, butynyl, and the like.

In the present specification, "C ₄ -C ₂₀ alkyldienyl group" is preferably C ₄ -C ₁₀ alkadienyl group, more preferably a C ₄ -C ₆ alkadienyl group. Examples of alkyldienyl groups include, but are not limited to, 1,3-butadienyl and the like.

In the present specification, the “C ₆ -C ₁₈ aryl group” is preferably a C ₆ -C ₁₀ aryl group. Examples of the aryl group include, but are not limited to, phenyl, 1-naphthyl, 2-naphthyl, indenyl, biphenylyl, anthryl, phenanthryl and the like.

In the present specification, the “C ₇ -C ₂₀ alkylaryl group” is preferably a C ₇ -C ₁₂ alkylaryl group. Examples of alkylaryl groups include, but are not limited to, o-tolyl, m-tolyl, p-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, o-cumenyl, m -Cumenyl, p-cumenyl, mesityl and the like can be mentioned.

In the present specification, the “C ₇ -C ₂₀ arylalkyl group” is preferably a C ₇ -C ₁₂ arylalkyl group. Examples of arylalkyl groups include, but are not limited to, benzyl, phenethyl, diphenylmethyl, triphenylmethyl, 1-naphthylmethyl, 2-naphthylmethyl, 2,2-diphenylethyl, 3-phenylpropyl, 4-phenyl Examples include phenylbutyl and 5-phenylpentyl.

In the present specification, the “C ₄ -C ₂₀ cycloalkyl group” is preferably a C ₄ -C ₁₀ cycloalkyl group. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.

In the present specification, the “C ₄ -C ₂₀ cycloalkenyl group” is preferably a C ₄ -C ₁₀ cycloalkenyl group. Examples of cycloalkenyl groups include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl and the like.

In the present specification, the “C ₁ -C ₂₀ alkoxy group” is preferably a C ₁ -C ₁₀ alkoxy group, and more preferably a C ₁ -C ₆ alkoxy group. Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, pentyloxy and the like.

In the present specification, the “C ₆ -C ₂₀ aryloxy group” is preferably a C ₆ -C ₁₀ aryloxy group. Examples of aryloxy groups include, but are not limited to, phenyloxy, naphthyloxy, biphenyloxy, and the like.

In the present specification, “alkylthio group (—SY ¹ , wherein Y ¹ represents an optionally substituted C ₁ -C ₂₀ alkyl group)” and “alkylsulfonyl group (—SO ₂ Y ³ In the formula, Y ³ represents an optionally substituted C ₁ -C ₂₀ alkyl group.) ”, Y ¹ and Y ³ are preferably C ₁ -C ₁₀ alkyl groups, it is more preferably ₁ -C ₆ alkyl group. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, dodecanyl and the like.

In the present specification, “arylthio group (—SY ² , wherein Y ² represents an optionally substituted C ₆ -C ₁₈ aryl group)” and “arylsulfonyl group (—SO ₂ Y ⁴ In the formula, Y ⁴ represents an optionally substituted C ₆ -C ₁₈ aryl group.) ”, It is preferable that Y ² and Y ⁴ are C ₆ -C ₁₀ aryl groups. Examples of the aryl group include, but are not limited to, phenyl, 1-naphthyl, 2-naphthyl, indenyl, biphenylyl, anthryl, phenanthryl and the like.

“C ₁ -C ₂₀ hydrocarbon group”, “C ₁ -C ₂₀ alkoxy group”, “C ₆ -C ₂₀ aryloxy group”, “amino group”, “silyl group”, “alkylthio group”, “arylthio group” ”,“ Alkylsulfonyl group ”, and“ arylsulfonyl group ”may have a substituent introduced therein. Examples of the substituent include an ester group, a carboxyl group, an amide group, an alkyne group, a trimethylsilyl group, an amino group, a phosphonyl group, a thio group, a carbonyl group, a nitro group, a sulfo group, an imino group, a halogeno group, and an alkoxy group. Can be mentioned. In this case, one or more substituents may be introduced at the substitutable position up to the maximum number that can be substituted, and preferably 1 to 4 substituents may be introduced. When the number of substituents is 2 or more, each substituent may be the same or different.

  In the present specification, examples of the “amino group which may have a substituent” include, but are not limited to, amino, dimethylamino, methylamino, methylphenylamino, phenylamino and the like.

  In this specification, examples of “optionally substituted silyl group” include, but are not limited to, dimethylsilyl, diethylsilyl, trimethylsilyl, triethylsilyl, trimethoxysilyl, triethoxysilyl, diphenyl Examples include methylsilyl, triphenylsilyl, triphenoxysilyl, dimethylmethoxysilyl, dimethylphenoxysilyl, and methylmethoxyphenyl.

R ^A is preferably a group represented by the above formula (2). Here, in formula (2), R ² which is a substituent of the benzene ring is an organic group, preferably a C _{2 to} C ₁₀ alkyl group, a C _{2 to} C ₁₀ alkenyl group or a C _{2 to} C ₁₀ alkynyl group. is there. Among these, R ² is preferably isopropyl ( ⁱ Pr). The number p of R ² is 0-4. Here, p = 0 means that R ² is not substituted.

R ⁴ is independently an organic group, preferably a C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₀ alkenyl group, or a C ₁ -C ₁₀ alkynyl group. Among these, R ⁴ is independently preferably a C ₁ -C ₅ alkyl group, and most preferably methyl.

2. Method for Producing Fullerene Derivatives of the Present Invention The method for producing fullerene derivatives contained in the polymerization catalyst for olefins of the present invention can be produced by a known method and is not particularly limited.

The fullerene derivative contained in the olefin polymerization catalyst of the present invention can be synthesized, for example, through the following steps. In the present specification, “Me” represents methyl.
(1) Fullerene dissolved in an organic solvent such as orthodichlorobenzene solution contains a copper reagent (CuBr · Me ₂ S, etc.) or a polar substance (N, N-dimethylformamide, dimethyl sulfoxide, pyridine, etc.) and an additional group. A fullerene derivative A having -OMe at the terminal of the additional group is synthesized by adding a Grignard reagent and reacting.
(2) Lewis acid or the like (BBr ₃ · SMe ₂ or the like) is added to the organic solvent solution of the fullerene derivative A, the reaction is performed, and -OMe at the terminal of the addition group of the fullerene derivative 1 is converted to -OH. Derivative B is synthesized.
(3) A Group 4 transition metal (M) complex (for example, a cyclopentadienyl complex having a Group 4 transition metal) of the periodic table is added to an organic solvent solution of the fullerene derivative B, and the mixture is stirred. The fullerene derivative of the present invention having an organic group containing a transition metal is synthesized.

3 Olefin polymerization catalyst of the present invention 3.1 Olefin used for polymerization The olefin used as a raw material when the olefin polymerization catalyst of the present invention is used as a polymerization catalyst is not particularly limited, but has 2 to 20 carbon atoms. Olefins, diolefins having 2 to 20 carbon atoms, and the like can be used. In the polymerization reaction, one type of monomer can be used, or two or more types of monomers can be used.
Examples of olefins that can be used as the polymerization catalyst by the olefin polymerization catalyst of the present invention are shown below, but the present invention is not limited to the following olefins.

  Examples of the olefin that can be polymerized by the polymerization catalyst for olefin of the present invention include, for example, a linear or branched α-olefin having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1- Dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene; cyclic olefins having 3 to 30, preferably 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, Tetracyclododecene, 2-methyl 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a- Kutahydronaphthalene; polar monomers such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic anhydride Α, β-unsaturated carboxylic acids such as, and metal salts such as sodium, potassium, lithium, zinc, magnesium, calcium salts thereof; methyl acrylate, ethyl acrylate, n-propyl acrylate, Isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, Α, β-unsaturation such as isobutyl methacrylate Vinyl esters such as rubonic acid ester; vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate; glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconate And unsaturated glycidyl.

  In addition, vinylcyclohexane, diene, polyene, or the like can be used as the olefin that can be polymerized by the olefin polymerization catalyst of the present invention. As the diene or polyene, a cyclic or chain compound having 4 to 30, preferably 4 to 20 carbon atoms and having two or more double bonds is used. Specifically, butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1 , 3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidenenorbornene, vinylnorbornene, dicyclopentadiene; 7-methyl-1,6-octadiene, 4 -Ethylidene-8-methyl-1,7-nonadiene, 5,9-dimethyl-1,4,8-decatriene; further aromatic vinyl compounds such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene , O, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene Mono- or polyalkyl styrene such as methoxy styrene, ethoxy styrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxy styrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene, and other functional group-containing styrene derivatives; And 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene and the like.

3.2 Polymerization reaction The polymerization method using the polymerization catalyst for the olefin of the present invention is not particularly limited. For example, aliphatic hydrocarbons such as butane, pentane, hexane, heptane, and octane, benzene, Solvent polymerization using an aromatic hydrocarbon such as toluene and a halogenated hydrocarbon such as methylene dichloride as a solvent, slurry polymerization, gas phase polymerization in a gaseous monomer, and the like can be used. Both continuous polymerization and batch polymerization can be used.

Regarding the polymerization temperature, a preferable temperature range varies depending on the type of the target polymer, the type of the catalyst, and the like, but a range of −50 ° C. to 200 ° C. is usually preferable, and 0 ° C. to 100 ° C. is more preferable.
Similarly, with respect to the polymerization pressure, a preferable pressure range varies depending on the type of the target polymer, the type of the catalyst, and the like, but a range of normal pressure to 10 MPa is preferable.
The polymerization time varies depending on the type of the target polymer, the reaction apparatus, and the like, but is generally preferably 1 minute to 20 hours. It is also possible to add a chain transfer agent such as hydrogen in order to adjust the molecular weight of the produced polymer.

3.3 Cocatalyst that can be used in combination with polymerization catalyst for olefin of the present invention The polymerization catalyst for olefin of the present invention is an aluminum compound such as methylaluminoxane (MAO) used when a metallocene catalyst is used, non-coordinating property It is preferably used in combination with a promoter such as a boron compound containing an anion [B (C ₆ F ₅ ) ₄ ] ⁻ . Among these, boron compounds such as [Ph ₃ C] ⁺ [B (C ₆ F ₅ ) ₄ ] ⁻ and Li ⁺ [B (C ₆ F ₅ ) ₄ ] ⁻ are particularly preferably used as a co-catalyst. Can do.

When the olefin polymerization catalyst of the present invention is used in combination with a promoter of an aluminum compound, the molar ratio of the polymerization catalyst of the present invention to the promoter (promoter / polymerization catalyst of the present invention) is preferably 0.1 to 10,000. 1 to 2000 is more preferable.
When the olefin polymerization catalyst of the present invention is used in combination with a boron compound cocatalyst, the molar ratio of the polymerization catalyst of the present invention to the cocatalyst (cocatalyst / polymerization catalyst of the present invention) is 0.01-100. Is preferable, and 0.5 to 10 is more preferable.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples.

スキーム１に示すように、窒素雰囲気下室温にてフラーレンＣ₆₀(３００ｍｇ, ０．４１７ｍｍｏｌ)をオルトジクロロベンゼン(３０ｍＬ)に溶かした。ＣｕＢｒ・Ｍｅ₂ Ｓ（１．０３ｇ，５．００ｍｍｏｌ）のＴＨＦ（２０ｍＬ）懸濁液に（３，５−ｉＰｒ₂−４−ＯＭｅ）Ｃ₆Ｈ₂ＭｇＢｒのＴＨＦ溶液（０．８４３Ｍ，５．９３ｍＬ，５．００ｍｍｏｌ）を加え、室温で１０分間撹拌した。この溶液に上記のＣ₆₀オルトジクロロベンゼン溶液をカニュラーで移し、３５℃で２時間攪拌した。この溶液に脱気した飽和塩化アンモニウム水溶液１．０ｍＬを加え、反応を停止した。系を減圧にし、系中に存在するＴＨＦとジメチルスルフィドを除いた。濃縮された茶色の溶液にトルエン（５０ｍＬ）を加え、シリカゲルのカラムで濾過した。得られた濾液を減圧下、固体がわずかに析出するまで濃縮した。メタノール（５０ｍＬ）を加えて析出させ、濾取・乾燥により目的物であるフラーレン誘導体Ｃ₆₀（Ｃ₆Ｈ₂−ＯＭｅ−４−ｉ−Ｐｒ₂−３，５）₅Ｈが得られた(６３３ｍｇ、収率９５％）。 [Example _{1] C 60 (C 6 H} 2 -OMe-4-i-Pr 2 -3,5) preparation of ₅ H

As shown in Scheme 1, fullerene C ₆₀ (300 mg, 0.417 mmol) was dissolved in orthodichlorobenzene (30 mL) at room temperature under a nitrogen atmosphere. To a suspension of CuBr · Me ₂ S (1.03 g, 5.00 mmol) in THF (20 mL), (3,5-iPr ₂ -4-OMe) C ₆ H ₂ MgBr in THF (0.843 M, 5. 93 mL, 5.00 mmol) was added, and the mixture was stirred at room temperature for 10 minutes. The C ₆₀ orthodichlorobenzene solution was transferred to this solution with a cannula and stirred at 35 ° C. for 2 hours. 1.0 mL of deaerated saturated ammonium chloride aqueous solution was added to this solution to stop the reaction. The system was depressurized to remove THF and dimethyl sulfide present in the system. Toluene (50 mL) was added to the concentrated brown solution and filtered through a silica gel column. The obtained filtrate was concentrated under reduced pressure until a solid slightly precipitated. Methanol (50 mL) was added for precipitation, and the fullerene derivative C ₆₀ (C ₆ H ₂ -OMe-4-i-Pr ₂ -3,5) ₅ H, which was the target product, was obtained by filtering and drying (633 mg). Yield 95%).

Measurement of APCI-HRMS by IR, ¹ H-NMR, ¹³ C-NMR and TOF method for the obtained fullerene derivative C ₆₀ (C ₆ H ₂ -OMe-4-i-Pr ₂ -3,5) ₅ H Went. The results are shown below.

IR (powder, cm ^-1 ): 2960 (s), 2928 (s), 2869 (s), 2827 (m) (ν _CH ), 1479 (s), 1461 (s), 1428 (ν _CC );
¹ H-NMR (400 MHz, CDCl3): δ0.865 (d, 12H, ³ J = 7.3 Hz, CHCH ₃ ), 0.883 (d, 12H, ³ J = 7.3 Hz, CHCH ₃ ), 0.887 (d, 12H , ³ J = 6.9 Hz, CHCH ₃ ), 0.975 (d, 12H, ³ J = 6.9 Hz, CHCH ₃ ), 0.985 (d, 12H, ³ J = 7.32 Hz, CHCH ₃ ), 3.08-3.22 (m, 10H , CHCH ₃ ), 3.66 (s, 3H, OCH ₃ ), 3.67 (s, 6H, OCH ₃ ), 3.72 (s, 6H, OCH ₃ ), 5.70 (s, 1H, FCpH), 7.19 (s, 2H, Ph), 7.32 (s, 4H, Ph), 7.48 (s, 4H, Ph); ¹³ C-NMR (100 MHz, CDCl ₃ ): δ23.65 (4C, CHCH ₃ ), 23.65 (4C, CHCH ₃ ) , 23.73 (4C, CHCH ₃ ), 23.83 (4C, CHCH ₃ ), 23.89 (4C, CHCH ₃ ), 26.66 (2C, CHCH ₃ ), 26.83 (4C, CHCH ₃ ), 26.95 (4C, CHCH ₃ ), 58.65 (2C, C60), 59.05 (2C, C ₆₀ ), 61.02 (1C, OCH ₃ ), 61.80 (2C, OCH ₃ ), 61.82 (2C, OCH ₃ ), 61.98 (1C, C ₆₀ ), 63.69 (1C, FCpH), 122.72 (4C, Ph), 123.22 (2C, Ph), 123.31 (4C, Ph), 135.79 (2C, Ph), 136.57 (3C, Ph), 142.10 (4C + 2C, Ph, C ₆₀ ), 142.14 (2C, Ph), 142.28 (4C, Ph), 143.07 (2C, C ₆₀ ), 143.60 (2C, C ₆₀ ), 143.96 (2C, C ₆₀ ), 144.07 (2C, C ₆₀ ), 144.10 (2C, C ₆₀ ), 144.34 (2C, C ₆₀ ), 144.51 (2C , C ₆₀ ), 144.79 (2C, C ₆₀ ), 145.52 (3C, C ₆₀ ), 145.86 (2C, C ₆₀ ), 146.07 (2C, C ₆₀ ), 146.38 (2C, C ₆₀ ), 147.03 (1C, C ₆₀ ), 147.16 (2C, C ₆₀ ), 147.25 (2C, C ₆₀ ), 147.76 (2C, C ₆₀ ), 148.06 (2C, C ₆₀ ), 148.12 (2C, C ₆₀ ), 148.20 (2C, C ₆₀ ) , 148.33 (2C, C ₆₀ ), 148.64 (2C, C ₆₀ ), 148.66 (2C, C ₆₀ ), 151.67 (2C, C ₆₀ ), 153.08 (2C C ₆₀ ), 153.19 (2C, C ₆₀ ), 153.08 ( 1C, Ph-a), 154.34 (2C, Ph-a), 154.58 (2C, Ph-a), 155.56 (2C, C ₆₀ );
APCI-HRMS: m / z calcd.for C ₁₂₅ H ₉₅ O ₅ [MH ⁺ ], 1675.71795, found, 1675.71220.

スキーム２に示すように、実施例１で合成されたＣ₆₀（Ｃ₆Ｈ₂−ＯＭｅ−４−ｉ−Ｐｒ₂−３，５）₅Ｈ（２８０ｍｇ、０．１６７ｍｍｏｌ）をオルトジクロロベンゼン溶液（５０ｍＬ）に溶解し、ＢＢｒ₃・ＳＭｅ₂（５１５ｍｇ、２．５１ｍｍｏｌ）を加えた。得られた赤色の溶液を１２０℃で２４時間攪拌した後、水（２０ｍＬ）を加えて反応を停止した。酢酸エチルで有機層を３回抽出し、合わせた赤色の溶液にＭｇＳＯ₄を加えて乾燥させた。ＭｇＳＯ₄を濾過して除いた後、減圧下で溶媒を留去させた。高速液体クロマトグラフィ（カラム：Nakalai Tesque社製 Buckyprep, 20 mm×250 mm，溶離液：トルエン／2-プロパノール = 7／3）で精製を行った。精製後、メタノールを加えて析出させ、濾過・乾燥させて目的物であるＣ₆₀（Ｃ₆Ｈ₂−ＯＨ−４−ｉ−Ｐｒ₂−３，５）₅Ｈを得た（単離収率 ５７%）。 Example 2 Production of C ₆₀ (C ₆ H ₂ —OH-4-i-Pr ₂ -3,5) ₅ H

As shown in Scheme 2, C ₆₀ (C ₆ H ₂ -OMe-4-i-Pr ₂ -3,5) ₅ H (280 mg, 0.167 mmol) synthesized in Example 1 was added to an orthodichlorobenzene solution ( 50 mL) and BBr ₃ .SMe ₂ (515 mg, 2.51 mmol) was added. The resulting red solution was stirred at 120 ° C. for 24 hours, and then water (20 mL) was added to stop the reaction. The organic layer was extracted three times with ethyl acetate, and MgSO ₄ was added to the combined red solution and dried. After removing MgSO ₄ by filtration, the solvent was distilled off under reduced pressure. Purification was performed by high performance liquid chromatography (column: Buckyprep, 20 mm × 250 mm, manufactured by Nakalai Tesque, eluent: toluene / 2-propanol = 7/3). After purification, methanol was added for precipitation, followed by filtration and drying to obtain C ₆₀ (C ₆ H ₂ —OH-4-i-Pr ₂ -3,5) ₅ H (isolation yield). 57%).

Measurement of APCI-HRMS by IR, ¹ H-NMR, ¹³ C-NMR and TOF method for the obtained fullerene derivative C ₆₀ (C ₆ H ₂ —OH-4-i-Pr ₂ -3,5) ₅ H Went. The results are shown below.

IR (powder, cm ^-1 ): 3606 (m), 3593 (m), 3564 (m) (ν _OH ), 2958 (s), 2929 (s), 2867 (s) (ν _CH ), 1459 (s ), 1449 (s) (ν _CC );
¹ H-NMR (500 MHz, CDCl ₃ ): δ 0.892 (d, 12H, ³ J = 6.85 Hz, CHCH ₃ ), 0.916 (d, 24H, ³ J = 6.85 Hz, CHCH ₃ ), 1.00 (d, 12H , ³ J = 6.90 Hz, CHCH ₃ ), 1.01 (d, 12H, ³ J = 6.90 Hz, CHCH ₃ ), 2.84-3.03 (m, 10H, CHCH ₃ ), 4.68 (s, 2H, OH), 4.70 ( s, 1H, OH), 4.74 (s, 2H, OH), 5.55 (s, 1H, FCpH), 7.14 (s, 2H, Ph), 7.21 (s, 4H, Ph), 7.38 (s, 4H, Ph ); ¹³ C-NMR (125 MHz, CDCl ₃ ): δ22.02 (8C, CHCH ₃ ), 22.15 (4C, CHCH ₃ ), 22.17 (4C, CHCH ₃ ), 22.26 (4C, CHCH ₃ ), 27.37 ( 2C, CHCH ₃ ), 27.42 (4C, CHCH ₃ ), 27.57 (4C, CHCH ₃ ), 58.57 (1C, C (sp3)), 58.84 (2C, C (sp3)), 60.84 (2C, C (sp3) ), 63.62 (1C, FCpH), 122.65 (4C, Ph), 123.01 (2C, Ph), 123.28 (4C, Ph), 131.91 (2C, Ph), 132.40 (2C, Ph), 132.40 (2C, Ph) , 133.65 (4C, Ph), 133.93 (6C, Ph), 138.47 (2C, Ph), 143.01 (2C, C ₆₀ ), 143.84 (2C, C ₆₀ ), 144.04 (2C, C ₆₀ ), 144.12 (2C, C ₆₀ ), 144.27 (4C, C ₆₀ ), 144.86 (2C, C ₆₀ ), 145.70 (2C, C ₆₀ ), 146.05 (2C, C ₆₀ ), 146.25 (2C, C ₆₀ ), 146.47 (2C, C ₆₀ ), 146.94 (1C, C ₆₀ ), 147.09 (2C, C ₆₀ ), 147.1 7 (2C, C ₆₀ ), 147.69 (2C, C ₆₀ ), 147.99 (4C, C ₆₀ ), 148.14 (1C, C ₆₀ ), 148.30 (2C, C ₆₀ ), 148.38 (2C, C ₆₀ ), 148.59 ( 4C, C ₆₀ ), 148.62 (2C, C ₆₀ ), 149.41 (1C, Ph-a), 149.82 (2C, Ph-a), 149.93 (2C, Ph-a), 152.18 (2C, C ₆₀ ), 152.63 (2C, C ₆₀ ), 153.18 (2C, C ₆₀ ), 156.10 (2C, C ₆₀ );
. APCI-HRMS: m / z calcd for C 120 H 86 O 5 [M -], 1606.64752, found, 1606.64839.

スキーム３に示すようにＨｆ（Ｃ₅Ｍｅ₅）Ｍｅ₃(40.0mg, 0.115 mmol)のＴＨＦ(5.0 mL)溶液に、実施例２で合成されたＣ₆₀（Ｃ₆Ｈ₂−ＯＨ−４−ｉ−Ｐｒ₂−３，５）₅Ｈ (29.9 mg, 0.0186 mmol)のＴＨＦ溶液（５．０ｍＬ）をカニュラーで加えた。反応溶液を室温で３０分攪拌すると赤色の溶液が得られた。溶媒を減圧下で留去した後、得られた固体をアルゴン下でアセトニトリルにより３回洗浄し、減圧で乾燥させたところ、目的のフラーレン五核ハフニウム錯体が赤色の固体として得られた（収率９５％）。 [Example _{3] C 60 (C 6 H} 2 - [OHf (C 5 Me 5) Me 2] -4-i-Pr 2 -3,5) 5 H preparation of

As shown in Scheme 3, C ₆₀ (C ₆ H ₂ —OH-4-) synthesized in Example 2 was added to a solution of Hf (C ₅ Me ₅ ) Me ₃ (40.0 mg, 0.115 mmol) in THF (5.0 mL). A THF solution (5.0 mL) of i-Pr ₂ -3,5) ₅ H (29.9 mg, 0.0186 mmol) was added by cannula. The reaction solution was stirred at room temperature for 30 minutes to obtain a red solution. After the solvent was distilled off under reduced pressure, the obtained solid was washed with acetonitrile three times under argon and dried under reduced pressure to obtain the desired fullerene pentanuclear hafnium complex as a red solid (yield) 95%).

A part of the obtained solid was taken in an NMR sample tube, deuterated THF (0.5 mL) was added, and after deaeration and sealing, ¹ H-NMR and ¹³ C-NMR were measured. The results are shown below.

¹ H-NMR (500 MHz, THF-d ₈ ): δ-0.240 (s, 6H, HfCH ₃ ), -0.221 (s, 6H, HfCH ₃ ), -0.214 (s, 6H, HfCH ₃ ), -0.193 (s, 6H, HfCH ₃ ), -0.187 (s, 6H, HfCH ₃ ), 0.884 (d, 12H, J = 6.8 Hz, CHCH ₃ ), 0.909 (d, 24H, J = 6.8 Hz, CHCH ₃ ), 1.00 (d, 12H, J = 6.8 Hz, CHCH ₃ ), 1.01 (d, 12H, J = 6.8 Hz, CHCH ₃ ), 2.00 (s, 15H, Cp *), 2.01 (s, 30H, Cp *), 2.03 (s, 30 H, Cp *), 3.10 (m, 10H, CHCH ₃ ), 5.79 (s, 1H, FCpH), 7.24 (s, 2H, Ph), 7.37 (s, 4H, Ph), 7.53 ( s, 4H, Ph); ¹³ C-NMR (125 MHz, C ₄ D ₈ O): δ 11.05 (5C, CH ₃ (Cp *)). 11.10 (5C, CH ₃ (Cp *)), 11.15 (5C , CH ₃ (Cp *)), 23.776 (4C. CHCH ₃ ), 23.781 (4C. CHCH ₃ ), 23.83 (4C. CHCH ₃ ), 24.00 (4C. CHCH ₃ ), 24.11 (4C. CHCH ₃ ), 27.82 (4C, CHCH ₃ ), 27.85 (4C, CHCH ₃ ), 27.98 (4C, CHCH ₃ ), 46.20 (4C, HfCH ₃ ), 46.10 (4C, HfCH ₃ ), 46.18 (2C, HfCH ₃ ), 59.89 (1C , C ₆₀ ), 60.26 (2C, C ₆₀ ), 62.25 (2C, C ₆₀ ), 64.86 (1C, FCp), 119.77 (5C, C (Cp *)), 119.81 (10C, C (Cp *)), 119.84 (10C, C (Cp *)), 122.87 (4C, Ph), 123.26 (2C, Ph), 123.45 (4C, Ph), 132.26 (4C, Ph), 132.82 (4C, Ph), 138.44 (2C, Ph-b), 138.45 (4C, Ph), 138.75 (4C, Ph), 139.26 (2C, Ph), 143.84 (2C, C ₆₀ ), 144.75 ( 2C, C ₆₀ ), 144.86 (2C, C ₆₀ ), 144.87 (2C, C ₆₀ ), 144.91 (2C, C ₆₀ ), 145.16 (2C, C ₆₀ ), 145.71 (2C, C ₆₀ ), 146.02 (2C, C ₆₀ ), 146.74 (2C, C ₆₀ ), 147.02 (2C, C ₆₀ ), 147.32 (2C, C ₆₀ ), 147.86 (2C, C ₆₀ ), 147.91 (1C, C ₆₀ ), 148.06 (2C, C ₆₀ ), 148.16 (2C, C ₆₀ ), 148.61 (2C, C ₆₀ ), 148.86 (1C, C ₆₀ ), 148.90 (2C, C ₆₀ ), 149.05 (2C, C ₆₀ ), 149.20 (2C, C ₆₀ ), 149.41 (2C, C ₆₀ ), 149.45 (2C, C ₆₀ ), 149.50 (2C, C ₆₀ ), 149.64 (2C, C ₆₀ ), 153.36 (2C, C ₆₀ ), 154.01 (2C, C ₆₀ ), 154.67 ( 2C, C ₆₀ ), 156.78 (1C, Ph-a), 157.21 (2C, Ph-a), 157.27 (2C, C ₆₀ ), 157.48 (2C, Ph).

原料錯体としてＴｉ（Ｃ₅Ｍｅ₅）Ｍｅ₃を用いた以外は、実施例３と同じ条件でＣ₆₀（Ｃ₆Ｈ₂−［ＯＴｉ（Ｃ₅Ｍｅ₅）Ｍｅ₂］−４−ｉ−Ｐｒ₂−３，５）₅Ｈを合成した（収率９５％）。 [Example 4] Production of C ₆₀ (C ₆ H _2- [OTi (C ₅ Me ₅ ) Me ₂ ] -4-i-Pr ₂ -3,5) ₅ H

C ₆₀ (C ₆ H ₂ — [OTi (C ₅ Me ₅ ) Me ₂ ] -4-i-Pr under the same conditions as in Example 3 except that Ti (C ₅ Me ₅ ) Me ₃ was used as a raw material complex. ₂ -3,5) a ₅ H was synthesized (95% yield).

A part of the obtained solid was taken in an NMR sample tube, deuterated THF (0.5 mL) was added, and after deaeration and sealing, ¹ H-NMR and ¹³ C-NMR were measured. The results are shown below.

¹ H-NMR (500 MHz, THF-d ₈ ): δ0.382 (s, 6H, TiCH ₃ ), 0.391 (s, 6H, TiCH ₃ ), 0.397 (s, 6H, TiCH ₃ ), 0.426 (s, 6H, TiCH ₃ ), 0.428 (s, 6H, TiCH ₃ ), 0.964 (d, 12H, J = 6.85 Hz, CHCH ₃ ), 0.976 (d, 24H, J = 6.85 Hz, CHCH ₃ ), 1.05 (d, 12H, J = 6.85 Hz, CHCH ₃ ), 1.07 (d, 12H, J = 6.85 Hz, CHCH ₃ ), 1.91 (s, 15H, Cp *), 1.92 (s, 30H, Cp *), 1.94 (s, 30 H, Cp *), 3.05-3.18 (m, 10H, CHCH ₃ ), 5.99 (s, 1H, FCpH), 7.37 (s, 2H, Ph), 7.48 (s, 4H, Ph), 7.61 (s, 4H, Ph); ¹³ C-NMR (125 MHz, C ₄ D ₈ O): δ11.83 (5C, CH ₃ (Cp *)). 11.87 (5C, CH ₃ (Cp *)), 11.92 (5C, CH ₃ (Cp *)), 24.40 (4C. CHCH ₃ ), 24.41 (4C. CHCH ₃ ), 24.62 (4C. CHCH ₃ ), 24.70 (4C. CHCH ₃ ), 24.78 (4C. CHCH ₃ ), 27.46 ( 8C, CHCH ₃ ), 27.64 (4C, CHCH ₃ ), 54.57 (2C, TiCH ₃ ), 54.60 (2C, TiCH ₃ ), 54.61 (2C, TiCH ₃ ), 54.70 (2C, TiCH ₃ ), 54.85 (2C, TiCH ₃ ), 59.97 (1C, C ₆₀ ), 60.40 (2C, C ₆₀ ), 62.39 (2C, C ₆₀ ), 64.90 (1C, FCp), 122.85 (2C, Ph), 123.37-123.41 (33C, br, Ph and C (Cp *)), 133.20 (4C, Ph), 134.18 (4C, Ph), 139.42 (2C, Ph), 139.70 (2C, Ph), 139.83 (4C, Ph), 140.03 (4C, Ph), 143.83 (2C, C ₆₀ ), 144.72 (2C, C ₆₀ ), 144.84 (2C, C ₆₀ ), 144.86 ( 2C, C ₆₀ ), 144.87 (2C, C ₆₀ ), 145.14 (2C, C ₆₀ ), 145.83 (2C, C ₆₀ ), 146.05 (2C, C ₆₀ ), 146.73 (2C, C ₆₀ ), 147.08 (2C, C ₆₀ ), 147.38 (2C, C ₆₀ ), 147.88 (2C, C ₆₀ ), 147.91 (1C, C ₆₀ ), 148.07 (2C, C ₆₀ ), 148.18 (2C, C ₆₀ ), 148.61 (2C, C ₆₀ ), 148.86 (1C, C ₆₀ ), 148.90 (2C, C ₆₀ ), 149.05 (2C, C ₆₀ ), 149.19 (2C, C ₆₀ ), 149.39 (2C, C ₆₀ ), 149.42 (2C, C ₆₀ ), 149.50 (2C, C ₆₀ ), 149.64 (2C, C ₆₀ ), 153.27 (2C, C ₆₀ ), 154.40 (2C, C ₆₀ ), 154.71 (2C, C ₆₀ ), 157.01 (2C, C ₆₀ ), 159.06 ( 1C, Ph), 159.56 (2C, Ph), 159.72 (2C, Ph).

[Example 5] Ethylene polymerization reaction using C ₆₀ (C ₆ H _2- [OHf (C ₅ Me ₅ ) Me ₂ ] -4-i-Pr ₂ -3,5) ₅ H Schlenk tube (Pyrex ( C ₆₀ (C ₆ H ₂ — [OHf (C ₅ Me ₅ ) Me ₂ ] -4-i-Pr ₂ -3,5) ₅ synthesized in Example 3 in a registered trademark (made of glass, inner volume 25 mL) ₅ H (7.80 mg, 2.25 μmol) and toluene (3 mL) were added, a balloon containing ethylene was attached to the system, and the inside of the Schlenk tube was made an ethylene atmosphere. Toluene solution of commercially available trityltetrakis (pentafluorophenyl) borate Ph3C ⁺ B (C6F5) 4 ⁻ (Tosoh Finechem Co., Ltd .: trade name Tri-FABA) (10.4 mg, 11.25 μmol) as a co-catalyst (0.5 mL) was quickly added and stirred at room temperature for 30 minutes, whereupon a white solid gradually precipitated. A methanol solution (20 mL) of hydrochloric acid was added to stop the reaction, and the resulting white solid was collected by filtration. Washing with methanol three times and drying under reduced pressure gave 17.3 mg of polyethylene. The catalyst activity per hour per 1 mol of the catalyst was 3.09 × 10 ³ (g-PE / mol of Hf · h).

[Example 6] Ethylene polymerization reaction using C ₆₀ (C ₆ H _2- [OTi (C ₅ Me ₅ ) Me ₂ ] -4-i-Pr ₂ -3,5) ₅ H C ₆₀ (C ₆ Instead of H _2- [OHf (C ₅ Me ₅ ) Me ₂ ] -4-i-Pr ₂ -3,5) ₅ H, C ₆₀ (C ₆ H _2- [ The polymerization reaction was carried out under the same conditions as in Example 5 except that OTi (C ₅ Me ₅ ) Me ₂ ] -4-i-Pr ₂ -3,5) ₅ H (6.34 mg, 2.25 μmol) was used. And 88.1 mg of polyethylene was obtained. The catalytic activity was 1.57 × 10 ⁴ (g-PE / mol of Ti · h).

  Examples of the utilization method of the present invention include synthesis of a polymer such as polyethylene.

Claims (6)

General formula (1)
Cn (R ^A ) _m R ¹ (1)
(In the formula, Cn represents a fullerene having n carbon atoms, m represents an integer of 1 to 10, R ¹ represents a hydrogen atom or an organic group, and R ^A independently represents a general formula (2).

(In the formula, each R ² independently represents an organic group, p represents an integer of 0 to 4, M represents a metal atom of Group 4 of the periodic table, and R ³ may have a substituent. A cyclopentadienyl group and R ⁴ each independently represents an organic group or a halogen atom. )
The polymerization catalyst for olefins containing the fullerene derivative represented by these. General formula (10)

(In the formula, R ¹ represents a hydrogen atom or an organic group, and R ^A independently represents each of the general formula (2)

(In the formula, each R ² independently represents an organic group, p represents an integer of 0 to 4, M represents a metal atom of Group 4 of the periodic table, and R ³ may have a substituent. A cyclopentadienyl group and R ⁴ each independently represents an organic group or a halogen atom. )
The polymerization catalyst for olefins containing the fullerene derivative represented by these. The R ² is each independently a C _{1 to} C ₂₀ alkyl group, a C _{2 to} C ₂₀ alkenyl group or a C _{2 to} C ₂₀ alkynyl group, and P is an integer of 0 to 2 . The polymerization catalyst for olefins as described. The polymerization catalyst for olefins according to any one of claims 1 to ³ , wherein R ³ is a pentamethylcyclopentadienyl group (Cp ^* ). The polymerization catalyst for olefins according to any one of claims 1 to 4 , wherein each R ⁴ is independently a C _{1 to} C ₂₀ alkyl group, a C _{2 to} C ₂₀ alkenyl group, or a C _{2 to} C ₂₀ alkynyl group. The polymerization catalyst for ethylene containing the polymerization catalyst for olefins in any one of Claims 1-5 .