JP2008201709A - Vanadium complex, olefin polymerization catalyst and method for producing olefin polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new vanadium complex usable as a component of an olefin polymerization catalyst. <P>SOLUTION: The invention provides a vanadium complex expressed by formula (1) (in the formula, A is a group 14 element of the periodic table of elements; Cp is a group having a cyclopentadienyl-type anion skeleton; V is a 4-valent vanadium atom; R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>, R<SP>4</SP>, R<SP>5</SP>and R<SP>6</SP>are each independently a hydrogen atom, a halogen atom, a 1-20C alkyl group or the like; X<SP>1</SP>and X<SP>2</SP>are each independently a hydrogen atom, a halogen atom, a 1-20C alkyl group or the like; Y<SP>1</SP>is a neutral ligand; and k is an integer of ≥0), a method for producing the complex, an olefin polymerization catalyst component composed of the vanadium complex expressed by formula (1), and a method for producing an olefin polymer. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention relates to a vanadium complex, a catalyst for olefin polymerization, and a method for producing an olefin polymer.

As a polymerization catalyst using a metallocene compound having vanadium as a central metal, examples relating to polymerization of ethylene, propylene, or α-olefin using bis (cyclopentadienyl) vanadium dichloride are known (for example, patents). Reference 1). As a conjugated diene polymerization catalyst, a vanadium trihalide complex having a cyclopentadienyl derivative as a ligand is known (for example, see Patent Document 2). On the other hand, as a metal complex having a ligand in which cyclopentadiene and phenol are cross-linked, a Group 4 transition metal complex is known as an olefin polymerization catalyst (see, for example, Patent Document 3). There are no known vanadium complexes of the present invention having a ligand in which cyclopentadiene and phenol are crosslinked, and examples using this complex as a catalyst for olefin polymerization.
JP 4-41166 JP-A-10-298230 JP-A-9-87313

The present invention is intended to provide a novel vanadium complex that can be used as a catalyst component for olefin polymerization.

（式中、Ａは元素の周期律表の第１４族元素を表し、Ｃｐはシクロペンタジエニル型アニオン骨格を有する基を表し、Ｖは４価のバナジウム原子を表し、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６は同一又は相異なり、水素原子、ハロゲン原子、炭素原子数１〜２０のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアラルキル基、炭素原子数１〜２０の炭化水素基で置換されたシリル基、炭素原子数１〜２０のアルコキシ基、炭素原子数６〜２０のアリールオキシ基、炭素原子数７〜２０のアラルキルオキシ基又は炭素原子数１〜２０の炭化水素基で置換されたアミノ基を表し、
ここで、Ｒ^１〜Ｒ^６において、アルキル基、アリール基、アラルキル基、アルコキシ基、アリールオキシ基、アラルキルオキシ基又は炭化水素基は、ハロゲン原子で置換されていてもよい、
Ｒ^１とＲ^２は結合して環を形成していてもよく、Ｒ^３とＲ^４、Ｒ^４とＲ^５、Ｒ^５とＲ^６は、それぞれ任意に結合して環を形成していてもよく、
Ｘ^１及びＸ^２は、同一又は相異なり、水素原子、ハロゲン原子、炭素原子数１〜２０のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアラルキル基、炭素原子数１〜２０の炭化水素基で置換されたシリル基、炭素原子数１〜２０のアルコキシ基、炭素原子数６〜２０のアリールオキシ基、炭素原子数７〜２０のアラルキルオキシ基又は炭素原子数１〜２０の炭化水素基で置換されたアミノ基を表し、
ここで、Ｘ^１及びＸ^２において、アルキル基、アリール基、アラルキル基、アルコキシ基、アリールオキシ基、アラルキルオキシ基又は炭化水素基は、それぞれハロゲン原子で置換されていてもよい、
Ｙ^１は中性配位子を表し、ｋは０以上の整数を表す。）
で示されるバナジウム錯体；
［２］：式（２）

（式中、Ａ、Ｃｐ、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６は、前記と同じ意味を表し、Ｒ^７は炭化水素基又は炭化水素三置換シリル基を表す）
で示されるシクロペンタジエン化合物と塩基とを反応させた後、式（３）

（式中、Ｘ^３は水素原子、ハロゲン原子、炭素原子数１〜２０のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアラルキル基、炭素原子数１〜２０の炭化水素基で置換されたシリル基、炭素原子数１〜２０のアルコキシ基、炭素原子数６〜２０のアリールオキシ基、炭素原子数７〜２０のアラルキルオキシ基又は炭素原子数１〜２０の炭化水素基で置換されたアミノ基を表し、
ここで、Ｘ^３において、アルキル基、アリール基、アラルキル基、アルコキシ基、アリールオキシ基、アラルキルオキシ基又は炭化水素基は、ハロゲン原子で置換されていてもよい、
Ｙ^２は中性配位子を表し、ｍは２〜５までの整数を表し、ｎは０以上の整数を表す。）
で示されるバナジウム化合物を反応させることを特徴とする上記［１］に記載の式（１）で示されるバナジウム錯体の製造方法；
［３］：式（１）で示されるバナジウム錯体からなるオレフィン重合用触媒成分；
［４］：該オレフィン重合用触媒成分と、下記化合物（Ａ）及び／又は下記化合物（Ｂ）とを接触させて得られるオレフィン重合用触媒。
化合物（Ａ）：下記（Ａ１）〜（Ａ３）からなる群から選ばれる１種以上のアルミニウム化合物
（Ａ１）式Ｅ^１ _ａＡｌＺ_３−ａで表される有機アルミニウム化合物；
（Ａ２）式｛−Ａｌ（Ｅ^２）−Ｏ−｝_ｂで表される構造を有する環状のアルミノキサン；
（Ａ３）式Ｅ^３｛−Ａｌ（Ｅ^３）−Ｏ−｝_ｃＡｌＥ^３ _２で表される構造を有する線状のアルミノキサン
（式中、ａは０＜ａ≦３を満足する数を表し、ｂは２以上の整数を表し、ｃは１以上の整数を表す。Ｅ^１、Ｅ^２及びＥ^３は炭素原子数１〜２０の炭化水素基を表し、複数のＥ^１、複数のＥ^２及び複数のＥ^３はそれぞれ同じであっても異なっていてもよい。Ｚは水素原子又はハロゲン原子を表し、Ｚが複数ある場合、複数のＺは互いに同じであっても異なっていてもよい。）
化合物（Ｂ）：下記（Ｂ１）〜（Ｂ３）からなる群から選ばれる１種以上のホウ素化合物
（Ｂ１）式 ＢＱ^１Ｑ^２Ｑ^３で表されるホウ素化合物。
（Ｂ２）式 Ｇ^＋（ＢＱ^１Ｑ^２Ｑ^３Ｑ^４）⁻で表されるホウ素化合物
（Ｂ３）式 （Ｌ^１−Ｈ）^＋（ＢＱ^１Ｑ^２Ｑ^３Ｑ^４）⁻で表されるホウ素化合物
（式中、Ｂは３価の原子価状態のホウ素原子を表し、Ｑ^１、Ｑ^２、Ｑ^３及びＱ^４はそれぞれ独立にハロゲン原子、炭化水素基、ハロゲン化炭化水素基、置換シリル基、アルコキシ基又は２置換アミノ基を表し、Ｇ^＋は無機又は有機のカチオンを表し、Ｌ^１は中性ルイス塩基を表す。）；
及び、
［５］：該オレフィン重合用触媒の存在下、オレフィンを重合させるオレフィン重合体の製造方法を提供するものである。 As a result of intensive studies in order to solve the above problems, the present inventors have found a vanadium complex useful as a catalyst component capable of polymerizing olefins, and have reached the present invention.
That is, the present invention
[1]: Formula (1)

(In the formula, A represents a group 14 element in the periodic table of elements, Cp represents a group having a cyclopentadienyl type anion skeleton, V represents a tetravalent vanadium atom, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a 7 to 20 carbon atom. Aralkyl group, silyl group substituted with hydrocarbon group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, aralkyloxy having 7 to 20 carbon atoms Represents an amino group substituted with a group or a hydrocarbon group having 1 to 20 carbon atoms,
Here, in R ^{1 to} R ⁶ , the alkyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, aralkyloxy group or hydrocarbon group may be substituted with a halogen atom.
R ¹ and R ² may be bonded to form a ring, and R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ may be bonded together to form a ring, respectively. Often,
X ¹ and X ² are the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a carbon atom. A silyl group substituted by a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, or the number of carbon atoms Represents an amino group substituted with 1-20 hydrocarbon groups,
Here, in X ¹ and X ² , each of the alkyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, aralkyloxy group or hydrocarbon group may be substituted with a halogen atom.
Y ¹ represents a neutral ligand, and k represents an integer of 0 or more. )
A vanadium complex represented by:
[2]: Formula (2)

(In the formula, A, Cp, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ represent the same meaning as described above, and R ⁷ represents a hydrocarbon group or a hydrocarbon trisubstituted silyl group)
After reacting the cyclopentadiene compound represented by formula (3) with a base,

(In the formula, X ³ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. A silyl group substituted with a hydrocarbon group, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, or a carbonization having 1 to 20 carbon atoms Represents an amino group substituted with a hydrogen group,
Here, in X ³ , the alkyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, aralkyloxy group or hydrocarbon group may be substituted with a halogen atom.
Y ² represents a neutral ligand, m represents an integer of 2 to 5, and n represents an integer of 0 or more. )
A process for producing a vanadium complex represented by the formula (1) according to the above [1], wherein the vanadium compound represented by formula (1) is reacted;
[3]: Olefin polymerization catalyst component comprising a vanadium complex represented by the formula (1);
[4] An olefin polymerization catalyst obtained by contacting the olefin polymerization catalyst component with the following compound (A) and / or the following compound (B).
Compound (A): one or more aluminum compounds selected from the group consisting of the following (A1) to (A3) (A1) an organoaluminum compound represented by the formula E ¹ _a AlZ _3-a ;
(A2) a cyclic aluminoxane having a structure represented by the formula {—Al (E ² ) —O—} _b ;
(A3) a linear aluminoxane having a structure represented by the formula E ³ {-Al (E ³ ) —O—} _c AlE ³ ₂ (wherein, a represents a number satisfying 0 <a ≦ 3, b represents an integer of 2 or more, c represents an integer of 1 or more, E ¹ , E ² and E ³ represent a hydrocarbon group having 1 to 20 carbon atoms, and a plurality of E ¹ , a plurality of E ² and The plurality of E ³ may be the same or different, Z represents a hydrogen atom or a halogen atom, and when there are a plurality of Z, the plurality of Z may be the same or different.
Compound (B): One or more boron compounds selected from the group consisting of the following (B1) to (B3) (B1) A boron compound represented by the formula BQ ¹ Q ² Q ³ .
(B2) Boron compound represented by formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ (B3) Boron represented by formula (L ¹ -H) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ Compound (wherein B represents a boron atom in a trivalent valence state, and Q ¹ , Q ² , Q ³ and Q ⁴ are each independently a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, or a substituted silyl group. Represents an alkoxy group or a disubstituted amino group, G ⁺ represents an inorganic or organic cation, and L ¹ represents a neutral Lewis base).
as well as,
[5]: Provided is a method for producing an olefin polymer in which an olefin is polymerized in the presence of the olefin polymerization catalyst.

The novel vanadium complex obtained by the present invention is useful, for example, as a catalyst for olefin polymerization reaction.

Hereinafter, the present invention will be described in detail.

In the vanadium complex represented by the formula (1) (hereinafter abbreviated as vanadium complex (1)), the group having a cyclopentadienyl type anion skeleton represented by Cp is substituted with an alkyl group, an aryl group, or the like. Also good. Examples of the vanadium complex (1) include a substituted or unsubstituted cyclopentadienyl group, indenyl group, and fluorenyl group.
Specifically, cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, ethylcyclopentadienyl group, n-propylcyclopentadienyl Enyl, isopropylcyclopentadienyl, n-butylcyclopentadienyl, sec-butylcyclopentadienyl, tert-butylcyclopentadienyl, tetrahydroindenyl, octahydrofluorenyl, phenylcyclopentyl Substituted or unsubstituted cyclopentadienyl groups, such as tantadienyl group, trimethylsilylcyclopentadienyl group, tert-butyldimethylsilylcyclopentadienyl group,
Indenyl group, methyl indenyl group, dimethyl indenyl group, ethyl indenyl group, n-propyl indenyl group, isopropyl indenyl group, n-butyl indenyl group, sec-butyl indenyl group, tert-butyl indenyl group A substituted or unsubstituted indenyl group such as a phenylindenyl group,
Fluorenyl group, 2-methylfluorenyl group, 2,7-dimethylfluorenyl group, 2-ethylfluorenyl group, 2,7-diethylfluorenyl group, 2-n-propylfluorenyl group, 2 , 7-di-n-propylfluorenyl group, 2-isopropylfluorenyl group, 2,7-diisopropylfluorenyl group, 2-n-butylfluorenyl group, 2-sec-butylfluorenyl group 2-tert-butylfluorenyl group, 2,7-di-n-butylfluorenyl group, 2,7-di-sec-butylfluorenyl group, 2,7-di-tert-butylfluorene Nyl group, 3,6-di-tert-butylfluorenyl group, 2-phenylfluorenyl group, 2,7-di-phenylfluorenyl group, 2-methylphenylfluorenyl group, etc. Replacement Oreniru group, and the like,
Preferred examples include a cyclopentadienyl group, a methylcyclopentadienyl group, a dimethylcyclopentadienyl group, a trimethylcyclopentadienyl group, a tetramethylcyclopentadienyl group, and a tert-butylcyclopentadienyl group.

In the cyclopentadiene compound represented by the vanadium complex (1) and the formula (2) (hereinafter abbreviated as cyclopentadiene compound (2)), the group 14 element of the periodic table of the element represented by A is, for example, carbon An atom, a silicon atom, a germanium atom, etc. are illustrated, Preferably a carbon atom and a silicon atom are illustrated.

In the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ , examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable.

Specific examples of the alkyl group having 1 to 20 carbon atoms in the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, amyl group, n-hexyl group, heptyl group, n-octyl group, n-nonyl group, n-decyl group, n -Dodecyl group, n-tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group and n-eicosyl group are exemplified, preferably methyl group, ethyl group, isopropyl group, tert-butyl Group, amyl group and the like.
Specific examples of the halogen-substituted alkyl group having 1 to 20 carbon atoms in the substituents R ¹ , R ² , R ³ , R ⁴ , R ^5, and R ⁶ include a fluorine atom and a chlorine atom. And those substituted with a halogen atom such as a bromine atom or an iodine atom.

In the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ , specific examples of the aryl group having 6 to 20 carbon atoms include phenyl group, 2-tolyl group, 3-tolyl group, 4 -Tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3 4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,6 4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, Isopropylphenyl group, n-butyl Tilphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, An n-tetradecylphenyl group, a naphthyl group, an anthracenyl group and the like are exemplified, and a phenyl group is preferable.
Specific examples of the halogen-substituted aryl group having 6 to 20 carbon atoms in the substituents R ¹ , R ² , R ³ , R ⁴ , R ^5, and R ⁶ include a fluorine atom, a chlorine atom, and the like. And those substituted with a halogen atom such as a bromine atom or an iodine atom.

Specific examples of the aralkyl group having 7 to 20 carbon atoms in the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ include a benzyl group, a (2-methylphenyl) methyl group, (3 -Methylphenyl) methyl group, (4-methylphenyl) methyl group, (2,3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, 2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl group, (4,6-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, 5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl group, (3,4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, 3,4,5-tetramethyl Phenyl) methyl group, (2,3,4,6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl Group, (n-propylphenyl) methyl group, (isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n-pentylphenyl) ) Methyl group, (neopentylphenyl) methyl group, (n-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-decylphenyl) methyl group, naphthylmethyl Group, anthracenylmethyl group and the like are exemplified, and a benzyl group is preferable.
Specific examples of the halogen-substituted aralkyl group having 7 to 20 carbon atoms in the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ include those aralkyl groups represented by fluorine atom, chlorine Examples thereof include those substituted with a halogen atom such as an atom, bromine atom or iodine atom.

In the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ , examples of the hydrocarbon group of the silyl group substituted with a hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, Isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n -C1-C10 alkyl groups, such as a decyl group, aryl groups, such as a phenyl group, etc. are illustrated. Specific examples of the silyl group substituted with a hydrocarbon having 1 to 20 carbon atoms include monosubstituted silyl groups having 1 to 20 carbon atoms such as methylsilyl group, ethylsilyl group, and phenylsilyl group, dimethylsilyl group, and diethyl. A disubstituted silyl group substituted with a hydrocarbon group having 1 to 20 carbon atoms such as a silyl group and a diphenylsilyl group, a trimethylsilyl group, a triethylsilyl group, a tri-n-propylsilyl group, a triisopropylsilyl group, a tri-n -Butylsilyl group, tri-sec-butylsilyl group, tri-tert-butylsilyl group, tri-isobutylsilyl group, tert-butyl-dimethylsilyl group, tri-n-pentylsilyl group, tri-n-hexylsilyl group, tricyclohexyl A hydrocarbon group having 1 to 20 carbon atoms such as silyl group and triphenylsilyl group. Such conversion has been trisubstituted silyl groups and the like, preferably trimethylsilyl group, tert- butyldimethylsilyl group, and triphenylsilyl group.
Examples of the hydrocarbon group constituting these substituted silyl groups include hydrocarbon groups substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom in addition to the hydrocarbon group as described above. .

Specific examples of the alkoxy group having 1 to 20 carbon atoms in the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ include a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group. , N-butoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, neopentyloxy group, n-hexyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n -Dodecyloxy group, n-undecyloxy group, n-dodecyloxy group, tridecyloxy group, tetradecyloxy group, n-pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group, nonadecyloxy group Group, n-eicosyloxy group, etc., preferably methoxy group, ethoxy group, tert-butoxy Groups.
Specific examples of the halogen-substituted alkoxy group having 1 to 20 carbon atoms include those in which these alkoxy groups are substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

In the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ , specific examples of the aryloxy group having 6 to 20 carbon atoms include phenoxy group, 2-methylphenoxy group, 3-methylphenoxy Group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3, 5-dimethylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,4 6-trimethylphenoxy group, 3,4,5-trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group, 2,3,4,6-tetramethyl group Enoxy group, 2,3,5,6-tetramethylphenoxy group, pentamethylphenoxy group, ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butyl Examples thereof include aryloxy groups having 6 to 20 carbon atoms such as phenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, n-tetradecylphenoxy group, naphthoxy group and anthracenoxy group. . As specific examples of the halogen-substituted aryloxy group having 6 to 20 carbon atoms, the aryloxy group having 6 to 20 carbon atoms is substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Are illustrated.

Specific examples of the aralkyloxy group having 7 to 20 carbon atoms in the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ include a benzyloxy group and a (2-methylphenyl) methoxy group. , (3-methylphenyl) methoxy group, (4-methylphenyl) methoxy group, (2,3-dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy Group, (2,6-dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2 , 3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group, (2,4,5-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, ( , 4,5-trimethylphenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,4,6-tetramethylphenyl) methoxy group, (2,3,5, 6-tetramethylphenyl) methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, sec-butylphenyl) methoxy group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, naphthylmethoxy group, anthracene Examples include a nylmethoxy group, and a benzyloxy group is preferable.
Specific examples of the halogen-substituted aralkyloxy group having 7 to 20 carbon atoms include those in which these aralkyloxy groups are substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

In the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ , an amino group substituted with a hydrocarbon group having 1 to 20 carbon atoms is an amino group substituted with two hydrocarbon groups. Here, examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, and an n-pentyl group. Group, an alkyl group having 1 to 20 carbon atoms such as an n-hexyl group and a cyclohexyl group, and an aryl group such as a phenyl group. These substituents may be bonded to each other to form a ring. Examples of the amino group substituted with a hydrocarbon group having 1 to 20 carbon atoms include, for example, a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-n-butylamino group, a di- -Sec-butylamino group, di-tert-butylamino group, di-isobutylamino group, tert-butylisopropylamino group, di-n-hexylamino group, di-n-octylamino group, di-n-decylamino group , Diphenylamino group, bistrimethylsilylamino group, bis-tert-butyldimethylsilylamino group, pyrrolyl group, pyrrolidinyl group, piperidinyl group, carbazolyl group, dihydroindolyl group, dihydroisoindolyl group, etc. Amino group, diethylamino group, pyrrolidinyl group, piperi Group and the like.
Examples of the hydrocarbon group constituting these substituted amino groups include hydrocarbon groups substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom in addition to the hydrocarbon group as described above. .

R ¹ and R ² may be bonded to form a ring, R ³ and R ⁴ , R ⁴ and R ⁵ , and R ⁵ and R ⁶ are optionally bonded to form a ring. Also good.

The ring formed by combining R ¹ and R ² and the ring formed by arbitrarily combining R ³ and R ⁴ , R ⁴ and R ⁵ , and R ⁵ and R ⁶ are carbon atoms. Examples thereof include saturated or unsaturated hydrocarbon rings substituted with a hydrocarbon group of 1 to 20. Specific examples thereof include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, benzene ring, naphthalene ring, anthracene ring and the like.

Examples of the vanadium complex (1) of the present invention include isopropylidene (cyclopentadienyl) (2-phenoxy) dichlorovanadium, isopropylidene (cyclopentadienyl) (3,4-dimethyl-2-phenoxy) dichlorovanadium. Isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) dichlorovanadium, isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) Dichlorovanadium, isopropylidene (cyclopentadienyl) (3-tert-butyl-5-dimethylamino-2-phenoxy) dichlorovanadium, isopropylidene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) dichloro vanadium, Sopropylidene (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) dichlorovanadium, isopropylidene (cyclopentadienyl) (3-phenyl-2-phenoxy) dichlorovanadium, isopropylidene (cyclopenta Dienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) dichlorovanadium, isopropylidene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) dichlorovanadium, isopropylidene ( Cyclopentadienyl) (2-naphthoxy) dichlorovanadium,

Isopropylidene (2,3,4,5-tetramethylcyclopentadienyl) (2-phenoxy) dichlorovanadium, isopropylidene (2,3,4,5-tetramethylcyclopentadienyl) (3,4-dimethyl) -2-phenoxy) dichlorovanadium, isopropylidene (2,3,4,5-tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) dichlorovanadium, isopropylidene (2,3 , 4,5-tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) dichlorovanadium, isopropylidene (2,3,4,5-tetramethylcyclopentadienyl) (3 -Tert-butyl-5-dimethylamino-2-phenoxy) dichlorovanadium, isop Pyridene (2,3,4,5-tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) dichlorovanadium, isopropylidene (2,3,4,5-tetramethylcyclopentadienyl) ( 3-tert-butyl-5-chloro-2-phenoxy) dichlorovanadium, isopropylidene (2,3,4,5-tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) dichlorovanadium, isopropylidene ( 2,3,4,5-tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) dichlorovanadium, isopropylidene (2,3,4,5-tetramethylcyclopenta Dienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) dichloroba Indium, isopropylidene (2,3,4,5-tetramethyl cyclopentadienyl) (2-naphthoxy) dichloro vanadium,

Isopropylidene (indenyl) (2-phenoxy) dichlorovanadium, isopropylidene (indenyl) (3,4-dimethyl-2-phenoxy) dichlorovanadium, isopropylidene (indenyl) (3-tert-butyl-5-methyl-2- Phenoxy) dichlorovanadium, isopropylidene (indenyl) (3-tert-butyl-5-methoxy-2-phenoxy) dichlorovanadium, isopropylidene (indenyl) (3-tert-butyl-5-dimethylamino-2-phenoxy) dichloro Vanadium, isopropylidene (indenyl) (3-tert-butyl-2-phenoxy) dichlorovanadium, isopropylidene (indenyl) (3-tert-butyl-5-chloro-2-phenoxy) dichlorovanadium, iso Ropyridene (indenyl) (3-phenyl-2-phenoxy) dichlorovanadium, isopropylidene (indenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) dichlorovanadium, isopropylidene (indenyl) (3-trimethylsilyl) -5-methyl-2-phenoxy) dichlorovanadium, isopropylidene (indenyl) (2-naphthoxy) dichlorovanadium,

Isopropylidene (2,7-di-tert-butylfluoren-9-yl) (2-phenoxy) dichlorovanadium, isopropylidene (2,7-di-tert-butylfluoren-9-yl) (3,4-dimethyl) -2-phenoxy) dichlorovanadium, isopropylidene (2,7-di-tert-butylfluoren-9-yl) (3-tert-butyl-5-methyl-2-phenoxy) dichlorovanadium, isopropylidene (2,7 -Di-tert-butylfluoren-9-yl) (3-tert-butyl-5-methoxy-2-phenoxy) dichlorovanadium, isopropylidene (2,7-di-tert-butylfluoren-9-yl) (3 -Tert-butyl-5-dimethylamino-2-phenoxy) dichlorovanadium, isop Pyridene (2,7-di-tert-butylfluoren-9-yl) (3-tert-butyl-2-phenoxy) dichlorovanadium, isopropylidene (2,7-di-tert-butylfluoren-9-yl) ( 3-tert-butyl-5-chloro-2-phenoxy) dichlorovanadium, isopropylidene (2,7-di-tert-butylfluoren-9-yl) (3-phenyl-2-phenoxy) dichlorovanadium, isopropylidene ( 2,7-di-tert-butylfluoren-9-yl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) dichlorovanadium, isopropylidene (2,7-di-tert-butylfluorene-9 -Yl) (3-trimethylsilyl-5-methyl-2-phenoxy) dichloroba Indium, isopropylidene (2,7-di -tert- butyl fluoren-9-yl) (2-naphthoxy) dichloro vanadium

Isopropylidene (3,6-di-tert-butylfluoren-9-yl) (2-phenoxy) dichlorovanadium, isopropylidene (3,6-di-tert-butylfluoren-9-yl) (3,4-dimethyl) -2-phenoxy) dichlorovanadium, isopropylidene (3,6-di-tert-butylfluoren-9-yl) (3-tert-butyl-5-methyl-2-phenoxy) dichlorovanadium, isopropylidene (3,6 -Di-tert-butylfluoren-9-yl) (3-tert-butyl-5-methoxy-2-phenoxy) dichlorovanadium, isopropylidene (3,6-di-tert-butylfluoren-9-yl) (3 -Tert-butyl-5-dimethylamino-2-phenoxy) dichlorovanadium, isop Pyridene (3,6-di-tert-butylfluoren-9-yl) (3-tert-butyl-2-phenoxy) dichlorovanadium, isopropylidene (3,6-di-tert-butylfluoren-9-yl) ( 3-tert-butyl-5-chloro-2-phenoxy) dichlorovanadium, isopropylidene (3,6-di-tert-butylfluoren-9-yl) (3-phenyl-2-phenoxy) dichlorovanadium, isopropylidene ( 3,6-di-tert-butylfluoren-9-yl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) dichlorovanadium, isopropylidene (3,6-di-tert-butylfluorene-9 -Yl) (3-trimethylsilyl-5-methyl-2-phenoxy) dichloroba Indium, isopropylidene (3,6-di -tert- butyl fluoren-9-yl) (2-naphthoxy) dichloro vanadium

Diethylmethylene (cyclopentadienyl) (2-phenoxy) dichlorovanadium, diethylmethylene (cyclopentadienyl) (3,4-dimethyl-2-phenoxy) dichlorovanadium, diethylmethylene (cyclopentadienyl) (3-tert -Butyl-5-methyl-2-phenoxy) dichlorovanadium, diethylmethylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) dichlorovanadium, diethylmethylene (cyclopentadienyl) (3 -Tert-butyl-5-dimethylamino-2-phenoxy) dichlorovanadium, diethylmethylene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) dichlorovanadium, diethylmethylene (cyclopentadienyl) (3- ert-butyl-5-chloro-2-phenoxy) dichlorovanadium, diethylmethylene (cyclopentadienyl) (3-phenyl-2-phenoxy) dichlorovanadium, diethylmethylene (cyclopentadienyl) (3-tert-butyldimethyl) Silyl-5-methyl-2-phenoxy) dichlorovanadium, diethylmethylene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) dichlorovanadium, diethylmethylene (cyclopentadienyl) (2-naphthoxy) Dichlorovanadium,

Diethylmethylene (2,3,4,5-tetramethylcyclopentadienyl) (2-phenoxy) dichlorovanadium, diethylmethylene (2,3,4,5-tetramethylcyclopentadienyl) (3,4-dimethyl -2-phenoxy) dichlorovanadium, diethylmethylene (2,3,4,5-tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) dichlorovanadium, diethylmethylene (2,3 , 4,5-tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) dichlorovanadium, diethylmethylene (2,3,4,5-tetramethylcyclopentadienyl) (3 -Tert-butyl-5-dimethylamino-2-phenoxy) dichlorovanadium, diethyl Methylene (2,3,4,5-tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) dichlorovanadium, diethylmethylene (2,3,4,5-tetramethylcyclopentadienyl) ( 3-tert-butyl-5-chloro-2-phenoxy) dichlorovanadium, diethylmethylene (2,3,4,5-tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) dichlorovanadium, diethylmethylene ( 2,3,4,5-tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) dichlorovanadium, diethylmethylene (2,3,4,5-tetramethylcyclopenta Dienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) dichloroba Indium, diethylmethylene (2,3,4,5-tetramethyl cyclopentadienyl) (2-naphthoxy) dichloro vanadium,

Diethylmethylene (indenyl) (2-phenoxy) dichlorovanadium, diethylmethylene (indenyl) (3,4-dimethyl-2-phenoxy) dichlorovanadium, diethylmethylene (indenyl) (3-tert-butyl-5-methyl-2- Phenoxy) dichlorovanadium, diethylmethylene (indenyl) (3-tert-butyl-5-methoxy-2-phenoxy) dichlorovanadium, diethylmethylene (indenyl) (3-tert-butyl-5-dimethylamino-2-phenoxy) dichloro Vanadium, diethylmethylene (indenyl) (3-tert-butyl-2-phenoxy) dichlorovanadium, diethylmethylene (indenyl) (3-tert-butyl-5-chloro-2-phenoxy) dichlorovanadium, die Rumethylene (indenyl) (3-phenyl-2-phenoxy) dichlorovanadium, diethylmethylene (indenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) dichlorovanadium, diethylmethylene (indenyl) (3-trimethylsilyl) -5-methyl-2-phenoxy) dichlorovanadium, diethylmethylene (indenyl) (2-naphthoxy) dichlorovanadium,

Diethylmethylene (2,7-di-tert-butylfluoren-9-yl) (2-phenoxy) dichlorovanadium, diethylmethylene (2,7-di-tert-butylfluoren-9-yl) (3,4-dimethyl -2-phenoxy) dichlorovanadium, diethylmethylene (2,7-di-tert-butylfluoren-9-yl) (3-tert-butyl-5-methyl-2-phenoxy) dichlorovanadium, diethylmethylene (2,7 -Di-tert-butylfluoren-9-yl) (3-tert-butyl-5-methoxy-2-phenoxy) dichlorovanadium, diethylmethylene (2,7-di-tert-butylfluoren-9-yl) (3 -Tert-butyl-5-dimethylamino-2-phenoxy) dichlorovanadium, diethyl Methylene (2,7-di-tert-butylfluoren-9-yl) (3-tert-butyl-2-phenoxy) dichlorovanadium, diethylmethylene (2,7-di-tert-butylfluoren-9-yl) ( 3-tert-butyl-5-chloro-2-phenoxy) dichlorovanadium, diethylmethylene (2,7-di-tert-butylfluoren-9-yl) (3-phenyl-2-phenoxy) dichlorovanadium, diethylmethylene ( 2,7-di-tert-butylfluoren-9-yl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) dichlorovanadium, diethylmethylene (2,7-di-tert-butylfluorene-9 -Yl) (3-trimethylsilyl-5-methyl-2-phenoxy) dichloroba Indium, diethylmethylene (2,7-di -tert- butyl fluoren-9-yl) (2-naphthoxy) dichloro vanadium

Diethylmethylene (3,6-di-tert-butylfluoren-9-yl) (2-phenoxy) dichlorovanadium, diethylmethylene (3,6-di-tert-butylfluoren-9-yl) (3,4-dimethyl -2-phenoxy) dichlorovanadium, diethylmethylene (3,6-di-tert-butylfluoren-9-yl) (3-tert-butyl-5-methyl-2-phenoxy) dichlorovanadium, diethylmethylene (3,6 -Di-tert-butylfluoren-9-yl) (3-tert-butyl-5-methoxy-2-phenoxy) dichlorovanadium, diethylmethylene (3,6-di-tert-butylfluoren-9-yl) (3 -Tert-butyl-5-dimethylamino-2-phenoxy) dichlorovanadium, diethyl Methylene (3,6-di-tert-butylfluoren-9-yl) (3-tert-butyl-2-phenoxy) dichlorovanadium, diethylmethylene (3,6-di-tert-butylfluoren-9-yl) ( 3-tert-butyl-5-chloro-2-phenoxy) dichlorovanadium, diethylmethylene (3,6-di-tert-butylfluoren-9-yl) (3-phenyl-2-phenoxy) dichlorovanadium, diethylmethylene ( 3,6-di-tert-butylfluoren-9-yl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) dichlorovanadium, diethylmethylene (3,6-di-tert-butylfluorene-9 -Yl) (3-trimethylsilyl-5-methyl-2-phenoxy) dichloroba Indium, diethylmethylene (3,6-di -tert- butyl fluoren-9-yl) (2-naphthoxy) dichloro vanadium

Diphenylmethylene (cyclopentadienyl) (2-phenoxy) dichlorovanadium, diphenylmethylene (cyclopentadienyl) (3,4-dimethyl-2-phenoxy) dichlorovanadium, diphenylmethylene (cyclopentadienyl) (3-tert -Butyl-5-methyl-2-phenoxy) dichlorovanadium, diphenylmethylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) dichlorovanadium, diphenylmethylene (cyclopentadienyl) (3 -Tert-butyl-5-dimethylamino-2-phenoxy) dichlorovanadium, diphenylmethylene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) dichlorovanadium, diphenylmethylene (cyclopentadi) Nyl) (3-tert-butyl-5-chloro-2-phenoxy) dichlorovanadium, diphenylmethylene (cyclopentadienyl) (3-phenyl-2-phenoxy) dichlorovanadium, diphenylmethylene (cyclopentadienyl) (3 -Tert-butyldimethylsilyl-5-methyl-2-phenoxy) dichlorovanadium, diphenylmethylene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) dichlorovanadium, diphenylmethylene (cyclopentadienyl) (2-naphthoxy) dichlorovanadium,

Diphenylmethylene (2,3,4,5-tetramethylcyclopentadienyl) (2-phenoxy) dichlorovanadium, diphenylmethylene (2,3,4,5-tetramethylcyclopentadienyl) (3,4-dimethyl -2-phenoxy) dichlorovanadium, diphenylmethylene (2,3,4,5-tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) dichlorovanadium, diphenylmethylene (2,3 , 4,5-tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) dichlorovanadium, diphenylmethylene (2,3,4,5-tetramethylcyclopentadienyl) (3 -Tert-butyl-5-dimethylamino-2-phenoxy) dichlorovanadiu Diphenylmethylene (2,3,4,5-tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) dichlorovanadium, diphenylmethylene (2,3,4,5-tetramethylcyclopentadienyl) ) (3-tert-butyl-5-chloro-2-phenoxy) dichlorovanadium, diphenylmethylene (2,3,4,5-tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) dichlorovanadium, diphenyl Methylene (2,3,4,5-tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) dichlorovanadium, diphenylmethylene (2,3,4,5-tetramethyl) Cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenyl) Phenoxy) dichloro vanadium, diphenylmethylene (2,3,4,5-tetramethylcyclopentadienyl) (2-naphthoxy) dichloro vanadium,

Diphenylmethylene (indenyl) (2-phenoxy) dichlorovanadium, diphenylmethylene (indenyl) (3,4-dimethyl-2-phenoxy) dichlorovanadium, diphenylmethylene (indenyl) (3-tert-butyl-5-methyl-2- Phenoxy) dichlorovanadium, diphenylmethylene (indenyl) (3-tert-butyl-5-methoxy-2-phenoxy) dichlorovanadium, diphenylmethylene (indenyl) (3-tert-butyl-5-dimethylamino-2-phenoxy) dichloro Vanadium, diphenylmethylene (indenyl) (3-tert-butyl-2-phenoxy) dichlorovanadium, diphenylmethylene (indenyl) (3-tert-butyl-5-chloro-2-phenoxy) dichlorova Palladium, diphenylmethylene (indenyl) (3-phenyl-2-phenoxy) dichlorovanadium, diphenylmethylene (indenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) dichlorovanadium, diphenylmethylene (indenyl) ( 3-trimethylsilyl-5-methyl-2-phenoxy) dichlorovanadium, diphenylmethylene (indenyl) (2-naphthoxy) dichlorovanadium,

Diphenylmethylene (2,7-di-tert-butylfluoren-9-yl) (2-phenoxy) dichlorovanadium, diphenylmethylene (2,7-di-tert-butylfluoren-9-yl) (3,4-dimethyl) -2-phenoxy) dichlorovanadium, diphenylmethylene (2,7-di-tert-butylfluoren-9-yl) (3-tert-butyl-5-methyl-2-phenoxy) dichlorovanadium, diphenylmethylene (2,7 -Di-tert-butylfluoren-9-yl) (3-tert-butyl-5-methoxy-2-phenoxy) dichlorovanadium, diphenylmethylene (2,7-di-tert-butylfluoren-9-yl) (3 -Tert-butyl-5-dimethylamino-2-phenoxy) dichlorovanadiu Diphenylmethylene (2,7-di-tert-butylfluoren-9-yl) (3-tert-butyl-2-phenoxy) dichlorovanadium, diphenylmethylene (2,7-di-tert-butylfluoren-9-yl) ) (3-tert-butyl-5-chloro-2-phenoxy) dichlorovanadium, diphenylmethylene (2,7-di-tert-butylfluoren-9-yl) (3-phenyl-2-phenoxy) dichlorovanadium, diphenyl Methylene (2,7-di-tert-butylfluoren-9-yl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) dichlorovanadium, diphenylmethylene (2,7-di-tert-butylfluorene) -9-yl) (3-trimethylsilyl-5-methyl-2-phenyl) Phenoxy) dichloro vanadium, diphenylmethylene (2,7-di -tert- butyl fluoren-9-yl) (2-naphthoxy) dichloro vanadium

Diphenylmethylene (3,6-di-tert-butylfluoren-9-yl) (2-phenoxy) dichlorovanadium, diphenylmethylene (3,6-di-tert-butylfluoren-9-yl) (3,4-dimethyl -2-phenoxy) dichlorovanadium, diphenylmethylene (3,6-di-tert-butylfluoren-9-yl) (3-tert-butyl-5-methyl-2-phenoxy) dichlorovanadium, diphenylmethylene (3,6 -Di-tert-butylfluoren-9-yl) (3-tert-butyl-5-methoxy-2-phenoxy) dichlorovanadium, diphenylmethylene (3,6-di-tert-butylfluoren-9-yl) (3 -Tert-butyl-5-dimethylamino-2-phenoxy) dichlorovanadiu Diphenylmethylene (3,6-di-tert-butylfluoren-9-yl) (3-tert-butyl-2-phenoxy) dichlorovanadium, diphenylmethylene (3,6-di-tert-butylfluoren-9-yl) ) (3-tert-butyl-5-chloro-2-phenoxy) dichlorovanadium, diphenylmethylene (3,6-di-tert-butylfluoren-9-yl) (3-phenyl-2-phenoxy) dichlorovanadium, diphenyl Methylene (3,6-di-tert-butylfluoren-9-yl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) dichlorovanadium, diphenylmethylene (3,6-di-tert-butylfluorene) -9-yl) (3-trimethylsilyl-5-methyl-2-phenyl) Phenoxy) dichloro vanadium, diphenylmethylene (3,6-di -tert- butyl fluoren-9-yl) (2-naphthoxy) dichloro vanadium

Dimethylsilylene (cyclopentadienyl) (2-phenoxy) dichlorovanadium, dimethylsilylene (cyclopentadienyl) (3,4-dimethyl-2-phenoxy) dichlorovanadium, dimethylsilylene (cyclopentadienyl) (3-tert -Butyl-5-methyl-2-phenoxy) dichlorovanadium, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) dichlorovanadium, dimethylsilylene (cyclopentadienyl) (3 -Tert-butyl-5-dimethylamino-2-phenoxy) dichlorovanadium, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) dichlorovanadium, dimethylsilylene (cyclopentadienyl) (3- ert-butyl-5-chloro-2-phenoxy) dichlorovanadium, dimethylsilylene (cyclopentadienyl) (3-phenyl-2-phenoxy) dichlorovanadium, dimethylsilylene (cyclopentadienyl) (3-tert-butyldimethyl) Silyl-5-methyl-2-phenoxy) dichlorovanadium, dimethylsilylene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) dichlorovanadium, dimethylsilylene (cyclopentadienyl) (2-naphthoxy) Dichlorovanadium,

Dimethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (2-phenoxy) dichlorovanadium, dimethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (3,4-dimethyl -2-phenoxy) dichlorovanadium, dimethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) dichlorovanadium, dimethylsilylene (2,3 , 4,5-tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) dichlorovanadium, dimethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (3 -Tert-butyl-5-dimethylamino-2-phenoxy) dichlorovanadium, dimethyl Silylene (2,3,4,5-tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) dichlorovanadium, dimethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) ( 3-tert-butyl-5-chloro-2-phenoxy) dichlorovanadium, dimethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) dichlorovanadium, dimethylsilylene ( 2,3,4,5-tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) dichlorovanadium, dimethylsilylene (2,3,4,5-tetramethylcyclopenta Dienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) dichloroba Indium, dimethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (2-naphthoxy) dichloro vanadium,

Dimethylsilylene (indenyl) (2-phenoxy) dichlorovanadium, dimethylsilylene (indenyl) (3,4-dimethyl-2-phenoxy) dichlorovanadium, dimethylsilylene (indenyl) (3-tert-butyl-5-methyl-2- Phenoxy) dichlorovanadium, dimethylsilylene (indenyl) (3-tert-butyl-5-methoxy-2-phenoxy) dichlorovanadium, dimethylsilylene (indenyl) (3-tert-butyl-5-dimethylamino-2-phenoxy) dichloro Vanadium, dimethylsilylene (indenyl) (3-tert-butyl-2-phenoxy) dichlorovanadium, dimethylsilylene (indenyl) (3-tert-butyl-5-chloro-2-phenoxy) dichlorovanadium, dimethyl Lucylylene (indenyl) (3-phenyl-2-phenoxy) dichlorovanadium, dimethylsilylene (indenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) dichlorovanadium, dimethylsilylene (indenyl) (3-trimethylsilyl) -5-methyl-2-phenoxy) dichlorovanadium, dimethylsilylene (indenyl) (2-naphthoxy) dichlorovanadium,

Dimethylsilylene (2,7-di-tert-butylfluoren-9-yl) (2-phenoxy) dichlorovanadium, dimethylsilylene (2,7-di-tert-butylfluoren-9-yl) (3,4-dimethyl -2-phenoxy) dichlorovanadium, dimethylsilylene (2,7-di-tert-butylfluoren-9-yl) (3-tert-butyl-5-methyl-2-phenoxy) dichlorovanadium, dimethylsilylene (2,7 -Di-tert-butylfluoren-9-yl) (3-tert-butyl-5-methoxy-2-phenoxy) dichlorovanadium, dimethylsilylene (2,7-di-tert-butylfluoren-9-yl) (3 -Tert-butyl-5-dimethylamino-2-phenoxy) dichlorovanadium, dimethyl Silylene (2,7-di-tert-butylfluoren-9-yl) (3-tert-butyl-2-phenoxy) dichlorovanadium, dimethylsilylene (2,7-di-tert-butylfluoren-9-yl) ( 3-tert-butyl-5-chloro-2-phenoxy) dichlorovanadium, dimethylsilylene (2,7-di-tert-butylfluoren-9-yl) (3-phenyl-2-phenoxy) dichlorovanadium, dimethylsilylene ( 2,7-di-tert-butylfluoren-9-yl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) dichlorovanadium, dimethylsilylene (2,7-di-tert-butylfluorene-9 -Yl) (3-trimethylsilyl-5-methyl-2-phenoxy) dichloroba Indium, dimethylsilylene (2,7-di -tert- butyl fluoren-9-yl) (2-naphthoxy) dichloro vanadium

Dimethylsilylene (3,6-di-tert-butylfluoren-9-yl) (2-phenoxy) dichlorovanadium, dimethylsilylene (3,6-di-tert-butylfluoren-9-yl) (3,4-dimethyl -2-phenoxy) dichlorovanadium, dimethylsilylene (3,6-di-tert-butylfluoren-9-yl) (3-tert-butyl-5-methyl-2-phenoxy) dichlorovanadium, dimethylsilylene (3,6 -Di-tert-butylfluoren-9-yl) (3-tert-butyl-5-methoxy-2-phenoxy) dichlorovanadium, dimethylsilylene (3,6-di-tert-butylfluoren-9-yl) (3 -Tert-butyl-5-dimethylamino-2-phenoxy) dichlorovanadium, dimethyl Silylene (3,6-di-tert-butylfluoren-9-yl) (3-tert-butyl-2-phenoxy) dichlorovanadium, dimethylsilylene (3,6-di-tert-butylfluoren-9-yl) ( 3-tert-butyl-5-chloro-2-phenoxy) dichlorovanadium, dimethylsilylene (3,6-di-tert-butylfluoren-9-yl) (3-phenyl-2-phenoxy) dichlorovanadium, dimethylsilylene ( 3,6-di-tert-butylfluoren-9-yl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) dichlorovanadium, dimethylsilylene (3,6-di-tert-butylfluorene-9 -Yl) (3-trimethylsilyl-5-methyl-2-phenoxy) dichloroba Indium, dimethylsilylene (3,6-di -tert- butyl fluoren-9-yl) (2-naphthoxy) dichloro vanadium

Diethylsilylene (cyclopentadienyl) (2-phenoxy) dichlorovanadium, diethylsilylene (cyclopentadienyl) (3,4-dimethyl-2-phenoxy) dichlorovanadium, diethylsilylene (cyclopentadienyl) (3-tert -Butyl-5-methyl-2-phenoxy) dichlorovanadium, diethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) dichlorovanadium, diethylsilylene (cyclopentadienyl) (3 -Tert-butyl-5-dimethylamino-2-phenoxy) dichlorovanadium, diethylsilylene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) dichlorovanadium, diethylsilylene (cyclopentadienyl) (3- ert-butyl-5-chloro-2-phenoxy) dichlorovanadium, diethylsilylene (cyclopentadienyl) (3-phenyl-2-phenoxy) dichlorovanadium, diethylsilylene (cyclopentadienyl) (3-tert-butyldimethyl) Silyl-5-methyl-2-phenoxy) dichlorovanadium, diethylsilylene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) dichlorovanadium, diethylsilylene (cyclopentadienyl) (2-naphthoxy) Dichlorovanadium,

Diethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (2-phenoxy) dichlorovanadium, diethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (3,4-dimethyl -2-phenoxy) dichlorovanadium, diethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) dichlorovanadium, diethylsilylene (2,3 , 4,5-tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) dichlorovanadium, diethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (3 -Tert-butyl-5-dimethylamino-2-phenoxy) dichlorovanadium, diethyl Silylene (2,3,4,5-tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) dichlorovanadium, diethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) ( 3-tert-butyl-5-chloro-2-phenoxy) dichlorovanadium, diethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) dichlorovanadium, diethylsilylene ( 2,3,4,5-tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) dichlorovanadium, diethylsilylene (2,3,4,5-tetramethylcyclopenta Dienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) dichloroba Indium, diethyl silylene (2,3,4,5-tetramethyl cyclopentadienyl) (2-naphthoxy) dichloro vanadium,

Diethylsilylene (indenyl) (2-phenoxy) dichlorovanadium, diethylsilylene (indenyl) (3,4-dimethyl-2-phenoxy) dichlorovanadium, diethylsilylene (indenyl) (3-tert-butyl-5-methyl-2- Phenoxy) dichlorovanadium, diethylsilylene (indenyl) (3-tert-butyl-5-methoxy-2-phenoxy) dichlorovanadium, diethylsilylene (indenyl) (3-tert-butyl-5-dimethylamino-2-phenoxy) dichloro Vanadium, diethylsilylene (indenyl) (3-tert-butyl-2-phenoxy) dichlorovanadium, diethylsilylene (indenyl) (3-tert-butyl-5-chloro-2-phenoxy) dichlorovanadium, die Lucylylene (indenyl) (3-phenyl-2-phenoxy) dichlorovanadium, diethylsilylene (indenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) dichlorovanadium, diethylsilylene (indenyl) (3-trimethylsilyl) -5-methyl-2-phenoxy) dichlorovanadium, diethylsilylene (indenyl) (2-naphthoxy) dichlorovanadium,

Diethylsilylene (2,7-di-tert-butylfluoren-9-yl) (2-phenoxy) dichlorovanadium, diethylsilylene (2,7-di-tert-butylfluoren-9-yl) (3,4-dimethyl -2-phenoxy) dichlorovanadium, diethylsilylene (2,7-di-tert-butylfluoren-9-yl) (3-tert-butyl-5-methyl-2-phenoxy) dichlorovanadium, diethylsilylene (2,7 -Di-tert-butylfluoren-9-yl) (3-tert-butyl-5-methoxy-2-phenoxy) dichlorovanadium, diethylsilylene (2,7-di-tert-butylfluoren-9-yl) (3 -Tert-butyl-5-dimethylamino-2-phenoxy) dichlorovanadium, diethyl Silylene (2,7-di-tert-butylfluoren-9-yl) (3-tert-butyl-2-phenoxy) dichlorovanadium, diethylsilylene (2,7-di-tert-butylfluoren-9-yl) ( 3-tert-butyl-5-chloro-2-phenoxy) dichlorovanadium, diethylsilylene (2,7-di-tert-butylfluoren-9-yl) (3-phenyl-2-phenoxy) dichlorovanadium, diethylsilylene ( 2,7-di-tert-butylfluoren-9-yl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) dichlorovanadium, diethylsilylene (2,7-di-tert-butylfluorene-9 -Yl) (3-trimethylsilyl-5-methyl-2-phenoxy) dichloroba Indium, diethyl silylene (2,7-di -tert- butyl fluoren-9-yl) (2-naphthoxy) dichloro vanadium

Diethylsilylene (3,6-di-tert-butylfluoren-9-yl) (2-phenoxy) dichlorovanadium, diethylsilylene (3,6-di-tert-butylfluoren-9-yl) (3,4-dimethyl) -2-phenoxy) dichlorovanadium, diethylsilylene (3,6-di-tert-butylfluoren-9-yl) (3-tert-butyl-5-methyl-2-phenoxy) dichlorovanadium, diethylsilylene (3,6 -Di-tert-butylfluoren-9-yl) (3-tert-butyl-5-methoxy-2-phenoxy) dichlorovanadium, diethylsilylene (3,6-di-tert-butylfluoren-9-yl) (3 -Tert-butyl-5-dimethylamino-2-phenoxy) dichlorovanadium, diethyl Silylene (3,6-di-tert-butylfluoren-9-yl) (3-tert-butyl-2-phenoxy) dichlorovanadium, diethylsilylene (3,6-di-tert-butylfluoren-9-yl) ( 3-tert-butyl-5-chloro-2-phenoxy) dichlorovanadium, diethylsilylene (3,6-di-tert-butylfluoren-9-yl) (3-phenyl-2-phenoxy) dichlorovanadium, diethylsilylene ( 3,6-di-tert-butylfluoren-9-yl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) dichlorovanadium, diethylsilylene (3,6-di-tert-butylfluorene-9 -Yl) (3-trimethylsilyl-5-methyl-2-phenoxy) dichloroba Indium, diethylsilylene (3,6-di-tert-butylfluoren-9-yl) (2-naphthoxy) dichlorovanadium, and the like can be mentioned. Examples in which redene, diethylmethylene and trichloro are replaced by trifluoro, tribromo and triiodo are also exemplified.

The vanadium complex (1) is produced by a method in which a cyclopentadiene compound (2) and a base are reacted and then a vanadium compound represented by the formula (3) (hereinafter abbreviated as vanadium compound (3)) is allowed to act. be able to.

Examples of the hydrocarbon group in the substituent R ⁷ include 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. An alkyl group of 2 to 10 carbon atoms such as vinyl, allyl, propenyl, 2-methyl-2-propenyl, homoallyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl Aralkyl groups having 7 to 12 carbon atoms such as benzyl group, (4-methylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group; methoxymethyl group, methoxyethoxymethyl group, etc. An alkoxyalkyl group etc. are mentioned. Any of these hydrocarbon groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and examples thereof include a 2-chloro-2-propenyl group.

Examples of the trisubstituted silyl group in the substituent R ⁷ include trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri-n-butylsilyl group, tri-sec-butylsilyl group, tri- Examples thereof include a tert-butylsilyl group, a tri-isobutylsilyl group, a tert-butyl-dimethylsilyl group, a tri-n-pentylsilyl group, a tri-n-hexylsilyl group, a tricyclohexylsilyl group, and a triphenylsilyl group.

The substituent R ⁷ is preferably an alkenyl group, more preferably an allyl group, from the viewpoint of producing the vanadium complex (1) with good yield.

The cyclopentadiene compound (2) can be produced, for example, according to a known technique (for example, see Patent Document 3).

Examples of the cyclopentadiene compound (2) include (2-allyloxyphenyl) (cyclopentadienyl) diethylsilane, (2-allyloxy-3-methylphenyl) (cyclopentadienyl) diethylsilane, (2- Allyloxy-3,5-dimethylphenyl) (cyclopentadienyl) diethylsilane, (2-allyloxy-3-tert-butylphenyl) (cyclopentadienyl) diethylsilane, (2-allyloxy-3-tert-butyl- 5-methylphenyl) (cyclopentadienyl) diethylsilane, (2-allyloxy-3,5-di-tert-butylphenyl) (cyclopentadienyl) diethylsilane, (2-allyloxy-5-methyl-3- Phenylphenyl) (cyclopentadienyl) diethylsilane, (2-a Loxy-5-methyl-3-trimethylsilylphenyl) (cyclopentadienyl) diethylsilane, (2-allyloxy-3-tert-butyldimethylsilyl-5-methylphenyl) (cyclopentadienyl) diethylsilane, (2- Allyloxy-3,5-diamylphenyl) (cyclopentadienyl) diethylsilane, (2-allyloxy-3-tert-butyl-5-methoxyphenyl) (cyclopentadienyl) diethylsilane, (2-allyloxy-5) -Tert-butyl-3-chlorophenyl) (cyclopentadienyl) diethylsilane, (1-allyloxynaphthalen-2-yl) (cyclopentadienyl) diethylsilane, (2-allyloxy-3-tert-butyl-5 -Methoxyphenyl) (cyclopentadienyl) diethyl Down.

(2-allyloxyphenyl) (2,3,4,5-tetramethylcyclopentadienyl) diethylsilane, (2-allyloxy-3-methylphenyl) (2,3,4,5-tetramethylcyclopentadiene) Enyl) diethylsilane, (2-allyloxy-3,5-dimethylphenyl) (2,3,4,5-tetramethylcyclopentadienyl) diethylsilane, (2-allyloxy-3-tert-butylphenyl) (2 , 3,4,5-tetramethylcyclopentadienyl) diethylsilane, (2-allyloxy-3-tert-butyl-5-methylphenyl) (2,3,4,5-tetramethylcyclopentadienyl) diethyl Silane, (2-allyloxy-3,5-di-tert-butylphenyl) (2,3,4,5-tetramethylcyclopentadienyl) di Tylsilane, (2-allyloxy-5-methyl-3-phenylphenyl) (2,3,4,5-tetramethylcyclopentadienyl) diethylsilane, (2-allyloxy-5-methyl-3-trimethylsilylphenyl) ( 2,3,4,5-tetramethylcyclopentadienyl) diethylsilane, (2-allyloxy-3-tert-butyldimethylsilyl-5-methylphenyl) (2,3,4,5-tetramethylcyclopentadiene) Enyl) diethylsilane, (2-allyloxy-3,5-diamilphenyl) (2,3,4,5-tetramethylcyclopentadienyl) diethylsilane, (2-allyloxy-3-tert-butyl-5- Methoxyphenyl) (2,3,4,5-tetramethylcyclopentadienyl) diethylsilane, (2-allyloxy-5 tert-butyl-3-chlorophenyl) (2,3,4,5-tetramethylcyclopentadienyl) diethylsilane, (1-allyloxynaphthalen-2-yl) (2,3,4,5-tetramethylcyclo) Pentadienyl) diethylsilane, (2-allyloxy-3-tert-butyl-5-methoxyphenyl) (2,3,4,5-tetramethylcyclopentadienyl) diethylsilane.

(2-allyloxyphenyl) (indenyl) diethylsilane, (2-allyloxy-3-methylphenyl) (indenyl) diethylsilane, (2-allyloxy-3,5-dimethylphenyl) (indenyl) diethylsilane, (2- Allyloxy-3-tert-butylphenyl) (indenyl) diethylsilane, (2-allyloxy-3-tert-butyl-5-methylphenyl) (indenyl) diethylsilane, (2-allyloxy-3,5-di-tert- Butylphenyl) (indenyl) diethylsilane, (2-allyloxy-5-methyl-3-phenylphenyl) (indenyl) diethylsilane, (2-allyloxy-5-methyl-3-trimethylsilylphenyl) (indenyl) diethylsilane, ( 2-Allyloxy-3-tert-butyldimethyl Rusilyl-5-methylphenyl) (indenyl) diethylsilane, (2-allyloxy-3,5-diamilphenyl) (indenyl) diethylsilane, (2-allyloxy-3-tert-butyl-5-methoxyphenyl) (indenyl) ) Diethylsilane, (2-allyloxy-5-tert-butyl-3-chlorophenyl) (indenyl) diethylsilane, (1-allyloxynaphthalen-2-yl) (indenyl) diethylsilane, (2-allyloxy-3-tert) -Butyl-5-methoxyphenyl) (indenyl) diethylsilane.

(2-Allyloxyphenyl) (2,7-di-tert-butylfluoren-9-yl) diethylsilane, (2-allyloxy-3-methylphenyl) (2,7-di-tert-butylfluorene-9- Yl) diethylsilane, (2-allyloxy-3,5-dimethylphenyl) (2,7-di-tert-butylfluoren-9-yl) diethylsilane, (2-allyloxy-3-tert-butylphenyl) (2 , 7-Di-tert-butylfluoren-9-yl) diethylsilane, (2-allyloxy-3-tert-butyl-5-methylphenyl) (2,7-di-tert-butylfluoren-9-yl) diethyl Silane, (2-allyloxy-3,5-di-tert-butylphenyl) (2,7-di-tert-butylfluoren-9-yl) di Tylsilane, (2-allyloxy-5-methyl-3-phenylphenyl) (2,7-di-tert-butylfluoren-9-yl) diethylsilane, (2-allyloxy-5-methyl-3-trimethylsilylphenyl) ( 2,7-di-tert-butylfluoren-9-yl) diethylsilane, (2-allyloxy-3-tert-butyldimethylsilyl-5-methylphenyl) (2,7-di-tert-butylfluorene-9- Yl) diethylsilane, (2-allyloxy-3,5-diamilphenyl) (2,7-di-tert-butylfluoren-9-yl) diethylsilane, (2-allyloxy-3-tert-butyl-5- Methoxyphenyl) (2,7-di-tert-butylfluoren-9-yl) diethylsilane, (2-allyloxy-5 tert-butyl-3-chlorophenyl) (2,7-di-tert-butylfluoren-9-yl) diethylsilane, (1-allyloxynaphthalen-2-yl) (2,7-di-tert-butylfluorene- 9-yl) diethylsilane, (2-allyloxy-3-tert-butyl-5-methoxyphenyl) (2,7-di-tert-butylfluoren-9-yl) diethylsilane.

(2-allyloxyphenyl) (3,6-di-tert-butylfluoren-9-yl) diethylsilane, (2-allyloxy-3-methylphenyl) (3,6-di-tert-butylfluorene-9- Yl) diethylsilane, (2-allyloxy-3,5-dimethylphenyl) (3,6-di-tert-butylfluoren-9-yl) diethylsilane, (2-allyloxy-3-tert-butylphenyl) (3 , 6-Di-tert-butylfluoren-9-yl) diethylsilane, (2-allyloxy-3-tert-butyl-5-methylphenyl) (3,6-di-tert-butylfluoren-9-yl) diethyl Silane, (2-allyloxy-3,5-di-tert-butylphenyl) (3,6-di-tert-butylfluoren-9-yl) di Tylsilane, (2-allyloxy-5-methyl-3-phenylphenyl) (3,6-di-tert-butylfluoren-9-yl) diethylsilane, (2-allyloxy-5-methyl-3-trimethylsilylphenyl) ( 3,6-di-tert-butylfluoren-9-yl) diethylsilane, (2-allyloxy-3-tert-butyldimethylsilyl-5-methylphenyl) (3,6-di-tert-butylfluorene-9- Yl) diethylsilane, (2-allyloxy-3,5-diamylphenyl) (3,6-di-tert-butylfluoren-9-yl) diethylsilane, (2-allyloxy-3-tert-butyl-5- Methoxyphenyl) (3,6-di-tert-butylfluoren-9-yl) diethylsilane, (2-allyloxy-5 tert-butyl-3-chlorophenyl) (3,6-di-tert-butylfluoren-9-yl) diethylsilane, (1-allyloxynaphthalen-2-yl) (3,6-di-tert-butylfluorene- 9-yl) diethylsilane, (2-allyloxy-3-tert-butyl-5-methoxyphenyl) (3,6-di-tert-butylfluoren-9-yl) diethylsilane, and the like. Examples of silane, diphenylsilane, ethylmethylsilane, methylphenylsilane, dimethylmethane, and diethylmethane are also exemplified.

In the vanadium complex (1) and the vanadium compound (3), examples of the halogen of the substituent X ¹ , X ² or X ³ include fluorine, chlorine, bromine, iodine and the like, and preferably a chlorine atom.

In the vanadium complex (1) and the vanadium compound (3), examples of the neutral ligand represented by the substituents Y ¹ and Y ² include olefins, aromatic compounds, ethers, sulfides, amines, and nitriles. , Phosphines or phosphine oxides.
Specific examples of the neutral coordination represented by Z include ethylene, propylene, 1-butene, 2-butene, isobutene, 1,3-butadiene, 1-pentene, 2-pentene, 1-hexene and 2-hexene. 3-hexene, 4,4-dimethyl-1-pentene, 1-octene, 1-decene, cyclopentene, cyclohexene, cyclooctadiene, styrene, α-methylstyrene, β-methylstyrene, stilbene, 1-vinylnaphthalene, 2-vinylnaphthalene, benzene, toluene, xylene, mesitylene, naphthalene, anthracene, diethyl ether, diisopropyl ether, diisopentyl ether, methyl-tert-butyl ether, furan, tetrahydrofuran, pyran, benzofuran, 1,2-dimethoxyethane, 1 , 3-Dimethoxyp Lopane, dimethyl sulfide, diethyl sulfide, 1- (methylthio) propane, diphenyl sulfide, 1,2-bis (methylthio) ethane, 3,6-dithiaoctane, thiophene, tetrahydrothiophene, thiacyclohexane, thiacyclooctane, trimethylamine, triethylamine, Ethyldiisopropylamine, triphenylamine, tri (p-tolylamine), N, N-dimethylaniline, N, N, N ′, N′-tetramethylethylenediamine, N-methylpyrrole, N-methylimidazole, pyridine, N, N-dimethylaminopyridine, acetonitrile, ethyl cyanide, propionitrile, benzonitrile, trimethylphosphine, triethylphosphine, tri-n-butylphosphine, tri-tert-butylphosphine Tri-n-hexylphosphine, tricyclohexylphosphine, dimethylphenylphosphine, methyldiphenylphosphine, triphenylphosphine, tribenzylphosphine, trimethylphosphine oxide, triethylphosphine oxide, tri-n-butylphosphine oxide, tri-tert-butylphosphine oxide , Tri-n-hexylphosphine oxide, tricyclohexylphosphine oxide, dimethylphenylphosphine oxide, methyldiphenylphosphine oxide, triphenylphosphine oxide or tribenzylphosphine oxide, preferably olefins, aromatic compounds, sulfides , Ethers or amines, more preferably ethers It can be mentioned amines.

k represents an integer of 0 or more, preferably 0 to 2, and more preferably 0 or 1. m represents an integer of 2 to 5, preferably 2 to 4, and more preferably 3 or 4. n represents an integer of 0 or more, preferably 0 to 3, and more preferably 0 or 3.

Examples of the vanadium compound (3) include a halogenated vanadium compound and a halogenated alkyl vanadium compound. More specifically, vanadium dichloride, vanadium trichloride, vanadium tetrachloride, and vanadium dibromide. , Vanadium tribromide, vanadium tetrabromide, vanadium diiodide, vanadium triiodide, vanadium tetraiodide, bis (dimethylamino) vanadium, tris (dimethylamino) vanadium, tetrakis (dimethylamino) vanadium, bis (diethylamino) ) Vanadium, tris (diethylamino) vanadium, tetrakis (diethylamino) vanadium, etc., and these compounds are ethylene, propylene, 1-butene, 2-butene, isobutene, 1,3-butadiene, 1-pentene, -Pentene, 1-hexene, 2-hexene, 3-hexene, 4,4-dimethyl-1-pentene, 1-octene, 1-decene, cyclopentene, cyclohexene, cyclooctadiene, styrene, α-methylstyrene, β- Methyl styrene, stilbene, 1-vinyl naphthalene, 2-vinyl naphthalene, benzene, toluene, xylene, mesitylene, naphthalene, anthracene, diethyl ether, diisopropyl ether, diisopentyl ether, methyl-tert-butyl ether, furan, tetrahydrofuran, pyran, Benzofuran, 1,2-dimethoxyethane, 1,3-dimethoxypropane, dimethyl sulfide, diethyl sulfide, 1- (methylthio) propane, diphenyl sulfide, 1,2-bis (methylthio) ethane, 3 6-dithiaoctane, thiophene, tetrahydrothiophene, thiacyclohexane, thiacyclooctane, trimethylamine, triethylamine, ethyldiisopropylamine, triphenylamine, tri (p-tolylamine), N, N-dimethylaniline, N, N, N ′, N It may be an adduct of '-tetramethylethylenediamine, N-methylpyrrole, N-methylimidazole, pyridine or N, N-dimethylaminopyridine.

Of these, a tetrahydrofuran complex of vanadium trichloride is particularly preferable.

Examples of the base to be reacted with the cyclopentadiene compound (2) include methyl lithium, ethyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, lithium trimethylsilyl acetylide, lithium acetylide, trimethylsilylmethyl lithium, vinyl lithium, Organic alkali metal compounds such as organolithium compounds such as phenyl lithium and allyl lithium; metal hydrides such as sodium hydride and potassium hydride; metal alkoxides such as sodium methoxide and potassium butoxide. The usage-amount of this base is 0.5-5 mol normally with respect to 1 mol of cyclopentadiene compounds (2).

In the reaction of the cyclopentadiene compound (2) and the base, an amine compound can be used together with the base. Examples of such amine compounds include primary amine compounds such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, tert-butylamine, n-octylamine, n-decylamine, aniline, and ethylenediamine; Amine, diethylamine, di-n-propylamine, di-n-propylamine, di-n-butylamine, di-tert-butylamine, di-n-octylamine, di-n-decylamine, pyrrolidine, hexamethyldisilazane, Secondary amine compounds such as diphenylamine; trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, diisopropylethylamine, tri-n-octylamine, tri-n-decylamine, triphenyl Min, N, N- dimethylaniline, N, N, N ', N'-tetramethylethylenediamine, N- methylpyrrolidine, 4-tertiary amine compounds such as dimethyl amino pyridine. The amount of the amine compound used is usually 10 mol or less, preferably 0.5 to 10 mol, more preferably 1 to 3 mol per mol of the base.

In the method of reacting the cyclopentadiene compound (2) and the base and then reacting the vanadium compound (3), the cyclopentadiene compound (2) and the base are usually added to the solvent, and then the vanadium compound (3) is added. Can be done by adding. A solid may precipitate after the cyclopentadiene compound (2) and the base are added. In this case, the solid taken out from the reaction system is added to the same solvent as described above, and then the vanadium compound (3) is added. May be.

The usage-amount of a vanadium compound (3) is 0.5-5 mol normally with respect to 1 mol of cyclopentadiene compounds (2), Preferably it is 1.5-2.5 mol.

The reaction temperature is usually from −100 ° C. to the boiling point of the solvent, and when an organic alkali metal compound is used as the base, it is preferably in the range of −80 ° C. to 60 ° C.

The reaction is usually performed in a solvent inert to the reaction. Examples of such solvents include aromatic hydrocarbon solvents such as benzene and toluene; aliphatic hydrocarbon solvents such as hexane and heptane; ether solvents such as diethyl ether, tetrahydrofuran and 1,4-dioxane; Amide solvents such as hollic amide and dimethylformamide; polar solvents such as acetonitrile, propionitrile, acetone, diethyl ketone, methyl isobutyl ketone and cyclohexanone; aprotic solvents such as halogen solvents such as dichloromethane, dichloroethane, chlorobenzene and dichlorobenzene Etc. are exemplified. These solvents are used alone or in admixture of two or more, and the amount used is usually 1 to 200 parts by weight, preferably 3 to 50 parts by weight per part by weight of the cyclopentadiene compound (2).

The desired transition metal complex can be obtained from the resulting reaction mixture by a usual method, for example, by filtering off the formed precipitate, concentrating the filtrate to precipitate a vanadium complex, and then collecting this by filtration. it can.

[Olefin polymerization catalyst]
The catalyst for olefin polymerization of the present invention is an olefin polymerization catalyst having the vanadium complex (1) as a catalyst component for olefin polymerization, and is obtained by bringing the vanadium complex (1) into contact with another cocatalyst component. Examples of the olefin polymerization catalyst include olefin polymerization catalysts obtained by contacting the vanadium complex (1) with the following compound (A) and / or the following compound (B).
Compound (A): One or more aluminum compounds selected from the group consisting of the following (A1) to (A3).
(A1) an organoaluminum compound represented by the formula E ¹ _a AlZ _3-a ;
(A2) a cyclic aluminoxane having a structure represented by the formula {—Al (E ² ) —O—} _b ;
(A3) Linear aluminoxane having a structure represented by the formula E ³ {-Al (E ³ ) —O—} _c Al (E ³ ) ₂ (wherein a is a number satisfying 0 <a ≦ 3) B represents an integer of 2 or more, c represents an integer of 1 or more, E ¹ , E ² and E ³ represent a hydrocarbon group having 1 to 20 carbon atoms, a plurality of E ¹ , a plurality of E ² and a plurality of E ³ may be the same or different, Z represents a hydrogen atom or a halogen atom, and when there are a plurality of Z, the plurality of Z may be the same or different from each other Good.)
Compound (B): One or more boron compounds selected from the group consisting of the following (B1) to (B3).
(B1) a boron compound represented by the formula BQ ¹ Q ² Q ³ ;
(B2) A boron compound represented by the formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ ;
(B3) A boron compound represented by the formula (L ¹ -H) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- (wherein B represents a boron atom in a trivalent valence state, and Q ¹ , Q ² , Q ³ and Q ⁴ each independently represent a halogen atom, hydrocarbon group, halogenated hydrocarbon group, substituted silyl group, alkoxy group or disubstituted amino group, G ⁺ represents an inorganic or organic cation, L ¹ represents a neutral Lewis base.)

(A1) Examples of the organoaluminum compound represented by the formula E ¹ _a AlZ _3-a include trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum; dimethylaluminum chloride, Dialkylaluminum chlorides such as diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, dihexylaluminum chloride; alkylaluminum dichlorides such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, hexylaluminum dichloride; dimethylaluminum Examples thereof include dialkylaluminum hydrides such as hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride and dihexylaluminum hydride; and alkylaluminum sesquichloride such as ethylaluminum sesquichloride. Trialkylaluminum and trialkylaluminum chloride are preferable, and triethylaluminum, triisobutylaluminum, and ethylaluminum sesquichloride are more preferable.

(A2) Cyclic aluminoxane having a structure represented by the formula {-Al (E ² ) —O—} _b or (A3) Formula E ³ {—Al (E ³ ) —O—} _c AlE ³ ₂ Examples of E ² and E ³ in the linear aluminoxane having the above structure include alkyl groups such as a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, an isobutyl group, a normal pentyl group, and a neopentyl group. Is mentioned. b is an integer of 2 or more, and c is an integer of 1 or more. Preferably, E ² and E ³ are each independently a methyl group or an isobutyl group, b is 2 to 40, and c is 1 to 40.

The above aluminoxane can be made by various methods. The method is not particularly limited, and may be made according to a known method. For example, a solution in which a trialkylaluminum (for example, trimethylaluminum) is dissolved in a suitable organic solvent (such as benzene or an aliphatic hydrocarbon) is contacted with water. Moreover, the method etc. which make trialkylaluminum (for example, trimethylaluminum etc.) contact the metal salt (for example, copper sulfate hydrate etc.) containing crystal water are mentioned.

(B1) In the boron compound represented by the formula BQ ¹ Q ² Q ³ , B is a boron atom in a trivalent valence state. Q ^{1 to} Q ³ are preferably each independently a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or a substituted silyl group having 1 to 20 carbon atoms. , An alkoxy group having 1 to 20 carbon atoms or a disubstituted amino group having 2 to 20 carbon atoms, more preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a 1 to 20 carbon atom. A halogenated hydrocarbon group;

(B1) Examples of the boron compound represented by the formula BQ ¹ Q ² Q ³ include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, and tris (2,3 , 4,5-tetrafluorophenyl) borane, tris (3,4,5-trifluorophenyl) borane, tris (2,3,4-trifluorophenyl) borane, phenylbis (pentafluorophenyl) borane, etc. Preferred is tris (pentafluorophenyl) borane.

(B2) In the boron compound represented by the formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ , G ⁺ is an inorganic or organic cation, B is a boron atom in a trivalent valence state, Q ^{1 to} Q ⁴ are the same as Q ^{1 to} Q ³ in (B1) above.

(B2) In the boron compound represented by the formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ , G ⁺ that is an inorganic cation includes, for example, ferrocenium cation, alkyl-substituted ferrocenium cation, silver Examples of G ⁺ whose cation is an organic cation include, for example, a triphenylmethyl cation. Examples of (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ include, for example, tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4, 5-tetrafluorophenyl) borate, tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,2,4-trifluorophenyl) borate, phenylbis (pentafluorophenyl) borate, tetrakis (3 , 5-bistrifluoromethylphenyl) borate and the like.

(B2) Examples of the boron compound represented by the formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1′-dimethylferrocenium tetrakis ( Pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, triphenylmethyltetrakis (pentafluorophenyl) borate, triphenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate and the like, preferably , Triphenylmethyltetrakis (pentafluorophenyl) borate.

(B3) In the boron compound represented by the formula (L ¹ -H) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ , L ¹ is a neutral Lewis base, and (L ¹ -H) ⁺ is Bronsted. It is an acid, B is a boron atom in a trivalent state, and Q ^{1 to} Q ⁴ are the same as Q ^{1 to} Q ³ in (B1) above.

(B3) In the boron compound represented by the formula (L ¹ -H) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ , (L ¹ -H) ⁺ includes, for example, trialkyl-substituted ammonium, N, N - dialkylanilinium, dialkylammonium and triarylphosphonium ^{mentioned, (BQ 1 Q 2 Q 3} Q 4) - to include the same as described above.

(B3) Examples of the boron compound represented by the formula (L ¹ —H) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^— include triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluoro). Phenyl) borate, tri (normal butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (normal butyl) ammonium tetrakis (3,5-bistrifluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) Borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethyla Nilinium tetrakis (3,5-bistrifluoromethylphenyl) borate, diisopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (methylphenyl) ) Phosphonium tetrakis (pentafluorophenyl) borate, tri (dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, etc., preferably tri (normal butyl) ammonium tetrakis (pentafluorophenyl) borate or N, N -Dimethylanilinium tetrakis (pentafluorophenyl) borate.

As the compound (B), (B1) a boron compound represented by the formula BQ ¹ Q ² Q ³ , (B2) a boron compound represented by the formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ or (B3) ^{One of} boron compounds represented by the formula (L ¹ -H) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ is used.

In the method of contacting each catalyst component in the production of an olefin polymerization catalyst, any two catalyst components may be contacted in advance, and then another catalyst component may be contacted. In addition, each catalyst component may be contacted in the polymerization reactor, each catalyst component may be separately introduced into the polymerization reactor in any order, and any two or more catalyst components are contacted in advance. You may throw in something. It is preferable to contact the vanadium complex (1) and the (A1) organoaluminum compound in advance, and it is preferable to contact the vanadium complex (1) and the (A1) organoaluminum compound in advance in the absence of the monomer.

As usage-amount of each catalyst component, the molar ratio of a compound (A) (aluminum atom conversion) / vanadium complex (1) is 0.1-10000 normally, Preferably it is 5-2000. When (A1) organoaluminum compound is used as compound (A), the molar ratio of compound (A) / vanadium complex (1) is more preferably 0.3 to 500, and still more preferably 0.5 to 100. The molar ratio of compound (B) / vanadium complex (1) is usually 0.01 to 100, preferably 0.5 to 10.

Regarding the concentration when each catalyst component is used in a solution state, the concentration of the vanadium complex (1) is usually 0.0001 to 5 mmol / liter, preferably 0.001 to 1 mmol / liter, and the compound (A ) In terms of aluminum atoms is usually 0.01 to 500 mmol / liter, preferably 0.1 to 100 mmol / liter, and the concentration of compound (B) is usually 0.0001 to 5 mmol / liter. Liter, preferably 0.001-1 mmol / liter.

[Olefin polymer production method]
The method for producing an olefin polymer of the present invention is to polymerize an olefin in the presence of an olefin polymerization catalyst having the vanadium complex (1) as a catalyst component for olefin polymerization.

As the olefin used for the polymerization, a chain olefin, a cyclic olefin or the like can be used, and homopolymerization may be performed using one type of olefin, or copolymerization may be performed using two or more types of olefins. Good. Usually, an olefin having 2 to 20 carbon atoms is used as the olefin.

Examples of chain olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 3-methyl-1-pentene, 4-methyl- An α-olefin having 3 to 20 carbon atoms such as 1-pentene, 3,3-dimethyl-1-butene, 5-methyl-1-hexene, 3,3-dimethyl-1-pentene; 1,5-hexadiene, 1,4-hexadiene, 1,4-pentadiene, 1,5-heptadiene, 1,6-heptadiene, 1,6-octadiene, 1,7-octadiene, 1,7-nonadiene, 1,8-nonadiene, 1, 8-decadiene, 1,9-decadiene, 1,12-tetradecadiene, 1,13-tetradecadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hex Diene, 7-methyl-1,6-octadiene, 3-methyl-1,4-hexadiene, 3-methyl-1,5-hexadiene, 3-ethyl-1,4-hexadiene, 3-ethyl-1,5- Non-conjugated dienes such as hexadiene, 3,3-dimethyl-1,4-hexadiene, 3,3-dimethyl-1,5-hexadiene; 1,3-butadiene, isoprene, 1,3-hexadiene, 1,3-octadiene And conjugated dienes.

Cyclic olefins include alicyclic compounds such as vinylcyclopentane, vinylcyclohexane, vinylcycloheptane, norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, tetracyclo Monoolefins such as dodecene, tricyclodecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene; 5-ethylidene-2-norbornene, di Cyclopentadiene, 5-vinyl-2-norbornene, norbornadiene, 5-methylene-2-norbornene, 1,5-cyclooctadiene, 7-methyl-2,5-norbornadiene, 7-ethyl-2,5-norbornadiene, 7 -Propyl- , 5-norbornadiene, 7-butyl-2,5-norbornadiene, 7-pentyl-2,5-norbornadiene, 7-hexyl-2,5-norbornadiene, 7,7-dimethyl-2,5-norbornadiene, 7,7 -Methylethyl-2,5-norbornadiene, 7-chloro-2,5-norbornadiene, 7-bromo-2,5-norbornadiene, 7-fluoro-2,5-norbornadiene, 7,7-dichloro-2,5- Norbornadiene, 1-methyl-2,5-norbornadiene, 1-ethyl-2,5-norbornadiene, 1-propyl-2,5-norbornadiene, 1-butyl-2,5-norbornadiene, 1-chloro-2,5- Norbornadiene, 1-bromo-2,5-norbornadiene, 5,8-endomethylenehexahydronaphtha Down, non-conjugated dienes such as vinylcyclohexene; 1,3-cyclooctadiene, etc. conjugated dienes such as 1,3-cyclohexadiene and the like. As aromatic compounds, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, α-methylstyrene And divinylbenzene.

Examples of the combination of olefins when copolymerizing olefins include, for example, ethylene / propylene, ethylene / 1-butene, ethylene / 1-hexene, ethylene / propylene / 1-butene, ethylene / propylene / 1-hexene, propylene / Combinations of chain olefins / chain olefins such as 1-butene and propylene / 1-hexene; ethylene / vinylcyclohexane, ethylene / norbornene, ethylene / tetracyclododecene, ethylene / 5-ethylidene-2-norbornene, propylene / vinyl Chain olefins / cyclic olefins such as cyclohexane, propylene / norbornene, propylene / tetracyclododecene, propylene / 5-ethylidene-2-norbornene, ethylene / propylene / 5-ethylidene-2-norbornene Or the like can be mentioned a combination of.

The polymerization method is not particularly limited. For example, aliphatic hydrocarbons (butane, pentane, hexane, heptane, octane, etc.), aromatic hydrocarbons (benzene, toluene, etc.) or halogenated hydrocarbons (methylene dichloride). Etc.) as a solvent, solvent polymerization or slurry polymerization, gas phase polymerization in a gaseous monomer, and the like are possible, and either continuous polymerization or batch polymerization is possible.

The polymerization temperature can be in the range of −50 ° C. to 300 ° C., but the range of −20 ° C. to 250 ° C. is particularly preferable. The polymerization pressure is preferably normal pressure to 90 MPa. In general, the polymerization time is appropriately determined depending on the type of the target polymer and the reaction apparatus, but can be in the range of 1 minute to 20 hours. In the present invention, a chain transfer agent such as hydrogen may be added to adjust the molecular weight of the polymer.

  EXAMPLES Hereinafter, although this invention is demonstrated in more detail by an experiment example, this invention is not limited to these experiment examples.

<Manufacture of vanadium complex>
The physical properties were measured by the following method.

(1) Mass spectrum [electron ionization mass spectrometry (EI-MS)]
Device: JMS-T100GC manufactured by JEOL Ltd.
Ionization voltage: 70 eV
Ion source temperature: 230 ° C
Acceleration voltage: 7 kV
MASS RANGE: m / z 35-1000

[Experimental Example 1]
Synthesis of “diethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) dichlorovanadium (hereinafter referred to as vanadium complex (A))” "
Under nitrogen, (2-allyloxy-3-tert-butyl-5-methylphenyl) (2,3,4,5-tetramethylcyclopentadienyl) diethylsilane (1.50 g, 3.65 mmol), triethylamine (1 To a toluene solution (23 mL) of .66 g, 16.43 mmol), a 1.59 M hexane solution (5.17 mL, 8.22 mmol) of n-butyllithium was added dropwise at −78 ° C., and the temperature was gradually raised to room temperature. Thereafter, the mixture was stirred at room temperature for 4 hours. After concentrating the solvent under reduced pressure, 23 mL of tetrahydrofuran was added and the mixture was cooled to -30 ° C. To this mixture was added a mixture of VCl ₃ (thf) ₃ (3.07 g, 8.22 mmol) suspended in tetrahydrofuran (8 mL), and the mixture was gradually warmed to room temperature and then stirred at room temperature for 17 hours. . The solvent was concentrated under reduced pressure, toluene was added and filtered to remove insoluble matters, and the solvent was concentrated under reduced pressure. Pentane was added and the precipitated solid was filtered, washed with a small amount of pentane, and then dried under reduced pressure to obtain vanadium complex (A) (1.13 g, yield 63%) as a brown solid.
Mass spectrum (EI-MS, m / z): 489 (M ⁺ ), 438, 397, 368, 343, 294, 226, 177, 149, 91

[Experiment 2]
"Synthesis of vanadium complex (A)"
Under nitrogen, (2-allyloxy-3-tert-butyl-5-methylphenyl) (2,3,4,5-tetramethylcyclopentadienyl) diethylsilane (3.00 g, 7.30 mmol), triethylamine (3 To a toluene solution (47 mL) of .33 g, 32.87 mmol), a 1.59 M hexane solution (10.34 mL, 16.43 mmol) of n-butyllithium was added dropwise at −78 ° C., and the temperature was gradually raised to room temperature. Thereafter, the mixture was stirred at room temperature for 4 hours. The solvent was concentrated under reduced pressure to obtain diethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) dilithium.
The resulting diethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) dilithium (1.02 g, 2.68 mmol) was added to a tetrahydrofuran solution ( 4 mL) was mixed at −30 ° C. with a mixture of VCl ₃ (thf) ₃ (1.00 g, 2.68 mmol) suspended in tetrahydrofuran (4 mL). After gradually raising the temperature to room temperature, the mixture was stirred at room temperature for 3 hours. The solvent was concentrated under reduced pressure, diethyl ether was added and filtered to remove insoluble matters, and the solvent was concentrated under reduced pressure. Pentane was added and the precipitated solid was filtered, washed with a small amount of pentane, and then dried under reduced pressure to obtain vanadium complex (A) (0.19 g, yield 15%) as a brown solid.

[Experiment 3]
Synthesis of “diethylsilylene (2,7-di-tert-butylfluoren-9-yl) (3-tert-butyl-5-methyl-2-phenoxy) dichlorovanadium (hereinafter referred to as vanadium complex (B))” "
Under nitrogen, (2-allyloxy-3-tert-butyl-5-methylphenyl) (2,7-di-tert-butylfluoren-9-yl) diethylsilane (1.69 g, 2.98 mmol), triethylamine (1 To a toluene solution (24 mL) of .36 g, 13.41 mmol), a 1.58 M hexane solution (4.25 mL, 6.71 mmol) of n-butyllithium was added dropwise at −78 ° C., and the temperature was gradually raised to room temperature. Thereafter, the mixture was stirred at room temperature for 18 hours. After concentrating the solvent under reduced pressure, 25 mL of tetrahydrofuran was added and the mixture was cooled to -30 ° C. To this mixture was added a mixture of VCl ₃ (thf) ₃ (2.51 g, 6.71 mmol) suspended in tetrahydrofuran (7 mL), and the mixture was gradually warmed to room temperature and then stirred at room temperature for 18 hours. . The solvent was concentrated under reduced pressure, toluene was added and filtered to remove insoluble matters, and the solvent was concentrated under reduced pressure. Pentane was added and the precipitated solid was filtered, washed with a small amount of pentane, and then dried under reduced pressure to obtain vanadium complex (B) (0.72 g, yield 38%) as a brown solid.

[Experimental Example 4]
"Synthesis of dimethylsilylene (indenyl) (3-tert-butyl-5-methyl-2-phenoxy) dichlorovanadium (hereinafter referred to as vanadium complex (C))"
Under nitrogen, (2-allyloxy-3-tert-butyl-5-methylphenyl) (indenyl) diethylsilane (1.12 g, 2.97 mmol), triethylamine (1.35 g, 13.38 mmol) in toluene (18 mL) To the mixture, 1.58 M hexane solution (4.23 mL, 6.69 mmol) of n-butyllithium was added dropwise at −78 ° C., and the mixture was gradually warmed to room temperature and stirred at room temperature for 18 hours. The solvent was concentrated under reduced pressure, 17 mL of tetrahydrofuran was added, and the mixture was cooled to -30 ° C. To this mixture was added a mixture of VCl ₃ (thf) ₃ (2.50 g, 6.69 mmol) suspended in tetrahydrofuran (7 mL), and the mixture was gradually warmed to room temperature and then stirred at room temperature for 18 hours. . The solvent was concentrated under reduced pressure, toluene was added and filtered to remove insoluble matters, and the solvent was concentrated under reduced pressure. Pentane was added and the precipitated solid was filtered, washed with a small amount of pentane, and then dried under reduced pressure to obtain vanadium complex (C) (0.65 g, yield 48%) as a brown solid.

<Manufacture of ethylene homopolymer>
Using the vanadium complex (A) obtained in Experimental Example 1 as a catalyst component for olefin polymerization, homopolymerization of ethylene was carried out under the following polymerization conditions using PPR (48 autoclave) manufactured by Symyx.

“Experimental Example 5”
Toluene (5.0 mL) was charged into an autoclave under nitrogen and stabilized at 40 ° C., and then ethylene (0.60 MPa) was pressurized and stabilized. To this was added aluminoxane (MMAO, 5.8 wt% Al, manufactured by Tosoh Finechem) (100 μmol) (Al atom conversion value), vanadium complex (A) (0.10 μmol), and polymerized for 20 minutes. As a result of the polymerization, 6.5 × 10 ⁶ g of polymer was produced per hour per 1 mol of the catalyst.

"Experimental example 6"
Similar to Experimental Example 5 except that TIBA hexane solution (manufactured by Kanto Chemical Co., Inc., TIBA concentration 1.0 mol / L) (40 μmol) and tris (pentafluorophenyl) borane (0.30 μmol) were used instead of methylaluminoxane. Polymerization was carried out. As a result of the polymerization, 1.7 × 10 ⁶ g of polymer was produced per hour per 1 mol of the catalyst.

"Experimental example 7"
Experimental example, except that hexane solution of TIBA (manufactured by Kanto Chemical Co., TIBA concentration 1.0 mol / L) (40 μmol), dimethylanilinium tetrakis (pentafluorophenyl) borate (0.30 μmol) was used instead of methylaluminoxane Polymerization was carried out in the same manner as in Example 5. As a result of the polymerization, 10.1 × 10 ⁶ g of polymer was produced per hour per 1 mol of the catalyst.

"Experimental example 8"
Experimental example, except that hexane solution of TIBA (manufactured by Kanto Chemical Co., TIBA concentration 1.0 mol / L) (40 μmol), triphenylmethyltetrakis (pentafluorophenyl) borate (0.30 μmol) was used instead of methylaluminoxane Polymerization was carried out in the same manner as in Example 5. As a result of the polymerization, 7.0 × 10 ⁶ g of polymer was produced per hour per 1 mol of the catalyst.

"Experimental example 9"
Polymerization was carried out in the same manner as in Experimental Example 5, except that a toluene solution of ethylaluminum sesquichloride (manufactured by Aldrich, concentration 25 wt%) (4 μmol) was used instead of methylaluminoxane. As a result of the polymerization, 2.9 × 10 ⁶ g of polymer was produced per hour per 1 mol of the catalyst.

"Experimental example 10"
Polymerization was carried out in the same manner as in Experimental Example 5 except that a toluene solution of ethylaluminum sesquichloride (manufactured by Aldrich, concentration 25 wt%) (40 μmol) was used instead of methylaluminoxane. As a result of the polymerization, 6.0 × 10 ⁶ g of polymer was produced per hour per 1 mol of the catalyst.

<Production of ethylene-α-olefin copolymer>

The physical properties were measured by the following method.

(1) 1-hexene unit content in the copolymer (SCB, unit: 1 / 1000C)
It calculated | required by the infrared spectroscopy using the infrared spectrophotometer (Equinox55 by Bruker). The characteristic absorption of butyl ^branches, using a peak of 1378cm ^-1 ~1303cm -1, 1- hexene unit content was expressed as the ethylene-1-hexene copolymer 1000 number of butyl branches per carbon.

(2) Molecular weight and molecular weight distribution It was measured under the following conditions by gel permeation chromatography (GPC). The molecular weight distribution was evaluated by the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn).
Apparatus: Liquid feeding apparatus (LC pump) Model 305 (pump head 25.SC) manufactured by Gilson
Column: Polymer Laboratories PLgel Mixed-B 10 μm (7.5 mmφ × 300 mm)
Measurement temperature: 160 ° C
Mobile phase: Orthodichlorobenzene Sample concentration: 1 mg of copolymer / 1 mL of 1,2,4-trichlorobenzene
Flow rate: 2 mL / min Standard substance: (standard PS molecular weight) 5,000, 10,050, 28,500, 65,500, 185,400, 483,000, 1,013,000, 3,390,000

"Experimental example 11"
The vanadium complex (A) obtained in Experimental Example 1 was used as a catalyst component for olefin polymerization, and copolymerization of ethylene and 1-hexene was carried out under the following polymerization conditions using PPR (48 autoclave) manufactured by Symyx.
Under nitrogen, toluene (5.0 mL) and 1-hexene (50 μL) were charged in an autoclave and stabilized at 70 ° C., and then ethylene (0.60 MPa) was pressurized and stabilized. To this, aluminoxane (MMAO, 5.8 wt% Al manufactured by Tosoh Finechem) (100 μmol, Al atom conversion value) and vanadium complex (A) (0.10 μmol) were added and polymerized for 20 minutes. As a result of the polymerization, a polymer having a molecular weight (Mw) = 14,000,000, a molecular weight distribution (Mw / Mn) = 2.1, and a 1-hexene unit content (SCB) = 3 in the copolymer per mol of catalyst, 7.7 × 10 ⁶ g was produced per hour.

"Experimental example 12"
Under nitrogen, toluene (5.0 mL) and 1-hexene (50 μL) were charged in an autoclave and stabilized at 70 ° C., and then ethylene (0.60 MPa) was pressurized and stabilized. Here, a hexane solution of TIBA (manufactured by Kanto Chemical Co., Inc., TIBA concentration 1.0 mol / L) (40 μmol), dimethylanilinium tetrakis (pentafluorophenyl) borate (0.30 μmol), and vanadium complex (A) (0. 10 μmol) was added and polymerized for 20 minutes. As a result of the polymerization, a polymer having a molecular weight (Mw) = 2,060,000, a molecular weight distribution (Mw / Mn) = 1.5, and a 1-hexene unit content (SCB) = 13 in the copolymer per mol of the catalyst. 5.7 × 10 ⁶ g was produced per hour.

"Experimental example 13"
Under nitrogen, toluene (5.0 mL) and 1-hexene (50 μL) were charged in an autoclave and stabilized at 70 ° C., and then ethylene (0.60 MPa) was pressurized and stabilized. Here, a hexane solution of TIBA (manufactured by Kanto Chemical Co., TIBA concentration 1.0 mol / L) (40 μmol), triphenylmethyltetrakis (pentafluorophenyl) borate (0.30 μmol), and vanadium complex (A) (0. 10 μmol) was added and polymerized for 20 minutes. As a result of the polymerization, a polymer having a molecular weight (Mw) = 1,920,000, a molecular weight distribution (Mw / Mn) = 1.4, and a 1-hexene unit content (SCB) = 5 in the copolymer per mol of the catalyst, 2.0 × 10 ⁶ g was produced per hour.

<Production of ethylene-α-olefin-cyclic olefin copolymer>

The physical properties were measured by the following method.

(1) Propylene and 5-ethylidene-2-norbornene unit content (unit:%) in the copolymer was measured by NMR in the following manner.
Apparatus: EX270 manufactured by JEOL Ltd. or DPX-300 manufactured by Bruker
Sample cell: 5 mmΦ tube Measurement solvent: Heavy dichlorobenzene sample concentration; 30-40 mg / 0.6 mL
Measurement temperature: 135 ° C. or room temperature (about 25 ° C.)
Measurement parameters: 5 mmΦ probe, MENU NON, OBNUC ¹ H, integration number 2000 times Pulse angle: 45 degrees Repeat time: ACQTM 3 seconds, PD 4 seconds Internal standard: heavy dichlorobenzene (7.40 ppm: 3,6-position low) Magnetic field peak)
Composition ratio calculation method: Peak derived from 5-ethylidene-2-norbornene unit (double bond peak near 5.10 to 5.70 ppm) and peak derived from proton bonded to other saturated carbon (0.60 to 3) .05 ppm).

(2) Molecular weight and molecular weight distribution It was measured under the following conditions by gel permeation chromatography (GPC). The molecular weight distribution was evaluated by the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn).
Apparatus: Liquid feeding apparatus (LC pump) Model 305 (pump head 25.SC) manufactured by Gilson
Column: Polymer Laboratories PLgel Mixed-B 10 μm (7.5 mmφ × 300 mm)
Measurement temperature: 160 ° C
Mobile phase: Orthodichlorobenzene Sample concentration: 1 mg of copolymer / 1 mL of 1,2,4-trichlorobenzene
Flow rate: 2 mL / min Standard substance: (standard PS molecular weight) 5,000, 10,050, 28,500, 65,500, 185,400, 483,000, 1,013,000, 3,390,000

"Experimental example 14"
Copolymerization of ethylene, propylene, and 5-ethylidene-2-norbornene under the following polymerization conditions using Symyx PPR (48-series autoclave) with the vanadium complex (A) obtained in Experimental Example 1 as a catalyst component for olefin polymerization. Went.
Under nitrogen, hexane (5.0 mL) and 5-ethylidene-2-norbornene (0.5 mmol) were charged in an autoclave and stabilized at 80 ° C., and then ethylene (0.55 MPa) and propylene (0.35 MPa) were added. Pressurized and stabilized. To this, aluminoxane (MMAO, 5.8 wt% Al manufactured by Tosoh Finechem) (100 μmol, Al atom conversion value) and vanadium complex (A) (0.10 μmol) were added and polymerized for 20 minutes. As a result of polymerization, molecular weight (Mw) = 201,000, molecular weight distribution (Mw / Mn) = 3.3, ratio of ethylene, propylene and 5-ethylidene-2-norbornene in the copolymer (96/3/1) Of the polymer was produced at 2.1 × 10 ⁶ g per hour per 1 mol of the catalyst.

"Experimental Example 15"
Under nitrogen, toluene (5.0 mL) and 5-ethylidene-2-norbornene (0.5 mmol) were charged in an autoclave and stabilized at 80 ° C., and then ethylene (0.55 MPa) and propylene (0.35 MPa) were added. Pressurized and stabilized. Here, a hexane solution of TIBA (manufactured by Kanto Chemical Co., TIBA concentration 1.0 mol / L) (40 μmol), triphenylmethyltetrakis (pentafluorophenyl) borate (0.30 μmol), and vanadium complex (A) (0. 10 μmol) was added and polymerized for 20 minutes. As a result of the polymerization, molecular weight (Mw) = 1,220,000, molecular weight distribution (Mw / Mn) = 1.4, ratio of ethylene, propylene and 5-ethylidene-2-norbornene in the copolymer (97/2 / The polymer of 1) was produced at 2.0 × 10 ⁶ g per hour per 1 mol of the catalyst.

Claims (8)

Formula (1)

(In the formula, A represents a group 14 element in the periodic table of elements, Cp represents a group having a cyclopentadienyl type anion skeleton, V represents a tetravalent vanadium atom, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a 7 to 20 carbon atom. Aralkyl group, silyl group substituted with hydrocarbon group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, aralkyloxy having 7 to 20 carbon atoms Represents an amino group substituted with a group or a hydrocarbon group having 1 to 20 carbon atoms,
Here, in R ^{1 to} R ⁶ , the alkyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, aralkyloxy group or hydrocarbon group may be substituted with a halogen atom.
R ¹ and R ² may be bonded to form a ring, and R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ may be bonded together to form a ring, respectively. Often,
X ¹ and X ² are the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a carbon atom. A silyl group substituted by a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, or the number of carbon atoms Represents an amino group substituted with 1-20 hydrocarbon groups,
Here, in X ¹ and X ² , each of the alkyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, aralkyloxy group or hydrocarbon group may be substituted with a halogen atom.
Y ¹ represents a neutral ligand, and k represents an integer of 0 or more. )
A vanadium complex represented by The vanadium complex according to claim 1, wherein A is a silicon atom. Formula (2)

(In the formula, A, Cp, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ represent the same meaning as defined in claim 1, and R ⁷ is a hydrocarbon group or a hydrocarbon trisubstituted silyl. Represents a group.)
After reacting the cyclopentadiene compound represented by formula (3) with a base,

(In the formula, X ³ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. A silyl group substituted with a hydrocarbon group, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, or a carbonization having 1 to 20 carbon atoms Represents an amino group substituted with a hydrogen group,
Here, in X ³ , the alkyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, aralkyloxy group or hydrocarbon group may be substituted with a halogen atom.
Y ² represents a neutral ligand, m represents an integer of 2 to 5, and n represents an integer of 0 or more. )
A method for producing a vanadium complex represented by the formula (1) according to claim 1, wherein the vanadium compound represented by formula (1) is reacted. A catalyst component for olefin polymerization comprising a vanadium complex represented by the formula (1) according to claim 1. The catalyst for olefin polymerization obtained by making the catalyst component for olefin polymerization of Claim 4 and the following compound (A) and / or the following compound (B) contact.
Compound (A): One or more aluminum compounds selected from the group consisting of the following (A1) to (A3).
(A1) an organoaluminum compound represented by the formula E ¹ _a AlZ _3-a ;
(A2) a cyclic aluminoxane having a structure represented by the formula {—Al (E ² ) —O—} _b ;
(A3) Linear aluminoxane having a structure represented by the formula E ³ {—Al (E ³ ) —O—} _c Al (E ³ ) ₂ (wherein a is a number satisfying 0 <a ≦ 3) B represents an integer of 2 or more, and c represents an integer of 1 or more, E ¹ , E ² and E ³ each represent a hydrocarbon group having 1 to 20 carbon atoms, and a plurality of E ¹ The plurality of E ² and the plurality of E ³ may be the same or different from each other, Z represents a hydrogen atom or a halogen atom, and the plurality of Z may be the same or different from each other.
Compound (B): One or more boron compounds selected from the group consisting of the following (B1) to (B3).
(B1) a boron compound represented by the formula BQ ¹ Q ² Q ³ ;
(B2) A boron compound represented by the formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ ;
(B3) A boron compound represented by the formula (L ¹ -H) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- (wherein B represents a boron atom in a trivalent valence state, and Q ¹ , Q ² , Q ³ and Q ⁴ each independently represent a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a substituted silyl group, an alkoxy group or a disubstituted amino group, G ⁺ represents an inorganic or organic cation, and L ¹ represents a neutral Lewis base.) An olefin polymer production method comprising polymerizing an olefin in the presence of the olefin polymerization catalyst according to claim 5. A method for producing an ethylene-α-olefin copolymer, wherein ethylene and an α-olefin are copolymerized in the presence of the olefin polymerization catalyst according to claim 5. A method for producing an ethylene-α-olefin copolymer, comprising copolymerizing ethylene, an α-olefin, and a cyclic olefin in the presence of the olefin polymerization catalyst according to claim 5.