JP2005139073A - Transition metal complex, ligand, olefin polymerization catalyst, and method for producing olefin polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a transition metal complex and a polymerization catalyst, and to provide a method for producing a polymer. <P>SOLUTION: The transition metal complex is represented by formula(1) [wherein, M<SP>1</SP>is a group 4 transition metal atom; A is a group 16 element; B is a group 14 element; (n) is 0 or 1; Cp is a (substituted) cyclopentadienyl group either substituted with at least one (substituted) ferrocene or (substituted) ruthenocene or condensed therewith; R<SP>5</SP>, R<SP>6</SP>, R<SP>7</SP>, R<SP>8</SP>, R<SP>9</SP>and R<SP>10</SP>are each H, a halogen atom, (substituted) 1-20C alkyl, (substituted) 1-20C alkoxy, (substituted) 6-20C aryl, or the like; and X<SP>1</SP>and X<SP>2</SP>are each H, a halogen atom, (substituted) 1-20C alkyl, or the like]. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

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

Many reports have already been made on a method for producing an olefin polymer using a metallocene complex. For example, a method for producing an olefin polymer using a metallocene complex and an aluminoxane has been reported (see Patent Document 1). When olefin polymerization is carried out with a catalyst using bis (cyclopentadienyl) zirconium dichloride and methylaluminoxane, there is a problem that the molecular weight of the resulting olefin polymer is low. In order to improve this problem, a polymerization method using dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride has been reported (see Patent Document 2). However, although the activity of the catalyst is high, further improvement has been desired in terms of the molecular weight of the polymer obtained. In addition, ferrocene-substituted or condensed-ring metallocenes have been reported (see Patent Document 3). Here, ethylene polymerization, ethylene / propylene copolymerization, and ethylene / cyclic olefin copolymerization are carried out. Further improvements were desired in terms of molecular weight.
JP 58-19309 A JP-A-9-87313 JP-A-8-41088

  It is an object of the present invention to provide a transition metal complex that can be a catalyst component that exhibits good catalytic activity and gives a higher molecular weight polymer, and a method for producing an olefin polymer using the same.

  In order to solve the above-mentioned problems, the present inventors have continued intensive studies on transition metal complexes and olefin polymerization catalysts. As a result, they found a transition metal complex having a ligand in which a ferrocene or ruthenocene-substituted cyclopentadiene ring and a benzene ring having a substituent are connected by a covalent bond group, and the present invention has been completed.

［式中、Ｍ^１は第４族遷移金属を表し、Ａは第１６族元素を表し、Ｂは第１４族元素を表し、ｎは０または１を表し、
Ｃｐは置換もしくは無置換の少なくとも一つのフェロセンまたはルテノセンにより置換されているかまたはこれらと縮合している置換もしくは無置換のシクロペンタジエニル基を表し、
Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９およびＲ^１０は、同一または相異なり、水素原子、ハロゲン原子、置換もしくは無置換の炭素数１〜２０のアルキル基、
置換もしくは無置換の炭素数１〜２０のアルコキシ基、
置換もしくは無置換の炭素数６〜２０のアリール基、
置換もしくは無置換の炭素数６〜２０のアリールオキシ基、
置換もしくは無置換の炭素数７〜２０のアラルキル基、
置換もしくは無置換の炭素数７〜２０のアラルキルオキシ基、
置換もしくは無置換の炭素数１〜２０の炭化水素基で置換されたシリル基
または置換もしくは無置換の炭素数１〜２０の炭化水素基で置換されたアミノ基を表し、
また、前記Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０のうち隣接する２つの置換基は任意に結合して環を形成していてもよい。
Ｘ^１およびＸ^２は、同一または相異なり、水素原子、ハロゲン原子、置換もしくは無置換の炭素数１〜２０のアルキル基、
置換もしくは無置換の炭素数１〜２０のアルコキシ基、
置換もしくは無置換の炭素数６〜２０のアリール基、
置換もしくは無置換の炭素数６〜２０のアリールオキシ基、
置換もしくは無置換の炭素数７〜２０のアラルキル基、
置換もしくは無置換の炭素数７〜２０のアラルキルオキシ基または
置換もしくは無置換の炭素数１〜２０の炭化水素基で置換されたアミノ基を表す。］
で示される遷移金属錯体；
２．式（２）

［式中、Ａ、Ｂ、Ｃｐ、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９およびＲ^１０は、前記と同じ意味を表し、Ｒ^１１は、置換もしくは無置換の炭化水素基または炭化水素で三置換されたシリル基を表し、シクロペンタジエン環の二重結合の位置は任意であり、または二重結合の位置の異なったものの混合物であってもよい。］
で示されるシクロペンタジエン類と塩基を反応させた後、
式（３）、

［式中、Ｍ¹は第４族遷移金属を表し、ｎは０または１を表し、
Ｘ^１、Ｘ^２、Ｘ^３およびＸ^４は、同一または相異なり、水素原子、ハロゲン原子、置換もしくは無置換の炭素数１〜２０のアルキル基、置換もしくは無置換の炭素数１〜２０のアルコキシ基、置換もしくは無置換の炭素数６〜２０のアリール基、置換もしくは無置換の炭素数６〜２０のアリールオキシ基、置換もしくは無置換の炭素数７〜２０のアラルキル基、置換もしくは無置換の炭素数７〜２０のアラルキルオキシ基または置換もしくは無置換の炭素数１〜２０の炭化水素基で置換されたアミノ基を表す。］
で示される遷移金属化合物と反応させることを特徴とする請求項１記載の式（１）で示される遷移金属錯体の製造方法；
３．上記式（２）で示されるシクロペンタジエン類；
４．式（４）

［式中、Ｃｐは置換もしくは無置換の一つ以上のフェロセンまたはルテノセンにより置換されているかまたはこれらと縮合している置換もしくは無置換のシクロペンタジエニル基を表す。］
で示される置換もしくは無置換のシクロペンタジエンと塩基とを反応させた後、式（５）

［式中、Ａ、Ｂ、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０およびＲ^１１は、前記と同じ意味を表し、Ｘ^５はハロゲン原子を表す。］
で示される化合物を反応させることを特徴とする請求項10記載の式(２)で示されるシクロペンタジエン類の製造方法；
５．前記式（１）の遷移金属錯体、および下記化合物（Ａ）を組み合わせてなることを特徴とするオレフィン重合用触媒。
（Ａ）：下記化合物（Ａ１）〜（Ａ３）のいずれか、あるいはそれらの２種以上の混合物。
（Ａ１）：式 （Ｅ^１）_ａＡｌ（Ｚ）_{（３−ａ）}で示される有機アルミニウム化合物、
（Ａ２）：式｛−Ａｌ（Ｅ^２）−Ｏ−｝_b で示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−｝_ｃＡｌ（Ｅ^３）_２で示される構造を有する線状のアルミノキサン
［式中、Ｅ^１〜Ｅ^３は同一または相異なり、炭素原子数１〜８の炭化水素基であり、Ｚは同一または相異なり、水素原子またはハロゲン原子を表し、ａは１、２または３の整数を表し、ｂは２以上の整数を表し、ｃは１以上の整数を表す。］。
６．前記式（１）で示される遷移金属錯体、上記化合物（Ａ）および下記化合物（Ｂ）を組み合わせてなることを特徴とするオレフィン重合用触媒。
（Ｂ）：下記化合物（Ｂ１）〜（Ｂ３）のいずれか、あるいはそれらの２種以上の混合物。
（Ｂ１）：式ＢＱ^１Ｑ^２Ｑ^３で示されるホウ素化合物、
（Ｂ２）：式Ｚ^＋（ＢＱ^１Ｑ^２Ｑ^３Ｑ^４）⁻で示されるホウ素化合物、
（Ｂ３）：式（Ｌ−Ｈ）^＋（ＢＱ^１Ｑ^２Ｑ^３Ｑ^４）⁻で示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であり、Ｑ^１〜Ｑ^４は同一または相異なり、ハロゲン原子、炭素原子数１〜２０の炭化水素基、炭素原子数１〜２０のハロゲン化炭化水素基、炭素原子数１〜２０の炭化水素で置換されたシリル基、炭素原子数１〜２０のアルコキシ基または炭素原子数１〜２０の炭化水素で二置換されたアミノ基を表し、Ｌ−Ｈは、ブレンステッド酸を表す］。
および
７．上記５．または６．に記載のオレフィン重合用触媒の存在下にオレフィンを重合させることを特徴とするオレフィン重合体の製造方法
を提供するものである。 That is, the present invention
1. Formula (1),

[Wherein, M ¹ represents a Group 4 transition metal, A represents a Group 16 element, B represents a Group 14 element, n represents 0 or 1,
Cp represents a substituted or unsubstituted cyclopentadienyl group which is substituted by or condensed with at least one substituted or unsubstituted ferrocene or ruthenocene;
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are the same or different and are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms,
A substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms,
A substituted or unsubstituted aryl group having 6 to 20 carbon atoms,
A substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms,
A substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms,
A substituted or unsubstituted aralkyloxy group having 7 to 20 carbon atoms,
A silyl group substituted with a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms or an amino group substituted with a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms,
Further, two adjacent substituents among R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ may be optionally bonded to form a ring.
X ¹ and X ² are the same or different and are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms,
A substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms,
A substituted or unsubstituted aryl group having 6 to 20 carbon atoms,
A substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms,
A substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms,
It represents an amino group substituted with a substituted or unsubstituted aralkyloxy group having 7 to 20 carbon atoms or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. ]
A transition metal complex represented by:
2. Formula (2)

[Wherein, A, B, Cp, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ represent the same meaning as described above, and R ¹¹ represents a substituted or unsubstituted hydrocarbon group or carbon It represents a silyl group trisubstituted with hydrogen, and the position of the double bond of the cyclopentadiene ring is arbitrary, or may be a mixture of those having different positions of the double bond. ]
After reacting the cyclopentadiene represented by the above with a base,
Formula (3),

[Wherein M ¹ represents a Group 4 transition metal, n represents 0 or 1,
X ¹ , X ² , X ³ and X ⁴ are the same or different and are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms. Group, substituted or unsubstituted aryl group having 6 to 20 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, substituted or unsubstituted It represents an amino group substituted with an aralkyloxy group having 7 to 20 carbon atoms or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. ]
A process for producing a transition metal complex represented by the formula (1) according to claim 1, which comprises reacting with a transition metal compound represented by the formula:
3. Cyclopentadiene represented by the above formula (2);
4). Formula (4)

[Wherein Cp represents a substituted or unsubstituted cyclopentadienyl group which is substituted by or condensed with one or more substituted or unsubstituted ferrocenes or ruthenocenes. ]
After reacting a substituted or unsubstituted cyclopentadiene represented by the formula (5) with a base,

[Wherein, A, B, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ represent the same meaning as described above, and X ⁵ represents a halogen atom. ]
A method for producing a cyclopentadiene represented by the formula (2) according to claim 10, wherein the compound represented by formula (2) is reacted.
5). A catalyst for olefin polymerization comprising a combination of the transition metal complex of the formula (1) and the following compound (A).
(A): Any of the following compounds (A1) to (A3), or a mixture of two or more thereof.
(A1): an organoaluminum compound represented by the formula (E ¹ ) _a Al (Z) _(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 Al (E ³ ) ₂ [wherein E ^{1 to} E ³ are the same or different, Is a hydrocarbon group having 1 to 8 carbon atoms, Z is the same or different and represents a hydrogen atom or a halogen atom, a represents an integer of 1, 2 or 3, b represents an integer of 2 or more, c Represents an integer of 1 or more. ].
6). An olefin polymerization catalyst comprising a combination of the transition metal complex represented by the formula (1), the compound (A), and the following compound (B).
(B): Any of the following compounds (B1) to (B3), or a mixture of two or more thereof.
(B1): a boron compound represented by the formula BQ ¹ Q ² Q ³ ,
(B2): a boron compound represented by the formula Z ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻
(B3): A boron compound represented by the formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^— [wherein B is a boron atom in a trivalent valence state, and Q ^{1 to} Q ⁴ Are the same or different, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silyl group substituted with a hydrocarbon having 1 to 20 carbon atoms, carbon Represents an alkoxy group having 1 to 20 atoms or an amino group disubstituted with a hydrocarbon having 1 to 20 carbon atoms, and LH represents a Bronsted acid].
And 7. 5. above. Or 6. An olefin polymer is produced in the presence of the olefin polymerization catalyst described in 1 above.

  According to the present invention, it is possible to provide a transition metal complex which is a catalyst component capable of providing a higher molecular weight polymer with better catalytic activity than conventional polymers, and an olefin having excellent characteristics by using this complex as a catalyst component. A polymer can be provided.

Hereinafter, the present invention will be described in detail.
In the transition metal complex represented by the formula (1), the transition metal atom represented by M ¹ is a group 4 transition metal atom in the periodic table of elements (IUPAC Inorganic Chemical Nomenclature Revision Edition 1989), for example, , A titanium atom, a zirconium atom, a hafnium atom, etc., and preferably a titanium atom.

Examples of the group 16 element in the periodic table of the element represented by A include an oxygen atom, a sulfur atom, and a selenium atom, and preferably an oxygen atom.

  Examples of the group 14 element in the periodic table of the element represented by B include a carbon atom, a silicon atom, a germanium atom and the like, and preferably a silicon atom.

  n is 0 or 1, preferably 1.

In the substituents R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , X ¹ or X ² , examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, preferably A chlorine atom is mentioned.

In the substituent R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , X ¹ or X ² , examples of the substituent in the substituted alkyl group having 1 to 20 carbon atoms include a halogen atom. Is done.
Specific examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, 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, n-eicosyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, tribromomethyl Group, iodomethyl group, diiodomethyl group, triiodomethyl group, fluoroethyl , Difluoroethyl group, trifluoroethyl group, tetrafluoroethyl group, pentafluoroethyl group, chloroethyl group, dichloroethyl group, trichloroethyl group, tetrachloroethyl group, pentachloroethyl group, bromoethyl group, dibromoethyl group, tribromoethyl Group, tetrabromoethyl group, pentabromoethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluorooctyl group, perfluorododecyl group, perfluoropentadecyl group, perfluoropentyl group Fluoroeicosyl group, perchloropropyl group, perchlorobutyl group, perchloropentyl group, perchlorohexyl group, perchlorooctyl group, perchlorododecyl group, perchloropentadecyl group, perchloroeicosyl group, Examples include bromopropyl group, perbromobutyl group, perbromopentyl group, perbromohexyl group, perbromooctyl group, perbromododecyl group, perbromopentadecyl group, perbromoeicosyl group, preferably methyl group , Ethyl group, isopropyl group, tert-butyl group, amyl group and the like.

In the substituent R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , X ¹ or X ² , examples of the substituent in the substituted aralkyl group having 7 to 20 carbon atoms include an alkyl group and a halogen atom. Etc.
Specific examples of the substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms include benzyl group, (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-dimethyl) Phenyl) methyl group, (4,6-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethyl) Phenyl) methyl group, (3,4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) Til 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 etc. are illustrated, Preferably a benzyl group is mentioned. Any of these aralkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

In the substituent R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , X ¹ or X ² , examples of the substituent in the substituted aryl group having 6 to 20 carbon atoms include an alkyl group and a halogen atom. Etc.
Specific examples of the substituted or unsubstituted aryl group having 6 to 20 carbon atoms include phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, and 2,4-xylyl group. 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, 2,3,4-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6 -Tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl Tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, naphthyl Group, anthracenyl group and the like are exemplified, and a phenyl group is preferable. Any of these aryl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

In the substituent R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ or R ¹⁰ , the silyl group substituted with a hydrocarbon is a silyl group substituted with a substituted or unsubstituted hydrocarbon group, 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, an n-pentyl group, and an n-hexyl group. Examples thereof include alkyl groups having 1 to 10 carbon atoms such as a group, cyclohexyl group, n-heptyl group, n-octyl group, n-nonyl group and n-decyl group, and aryl groups such as phenyl group. Specific examples of the substituted silyl group having 1 to 20 carbon atoms include a monosubstituted silyl group having 1 to 20 carbon atoms such as a methylsilyl group, an ethylsilyl group, and a phenylsilyl group, a dimethylsilyl group, a diethylsilyl group, and a diphenylsilyl group. A disubstituted silyl group substituted with a hydrocarbon group having 1 to 20 carbon atoms, such as trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, 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, tricyclohexylsilyl group, triphenylsilyl group A trisubstituted silyl group substituted with a hydrocarbon group having 1 to 20 carbon atoms such as Illustrated, is preferably exemplified by trimethylsilyl group, tert- butyldimethylsilyl group, a triphenylsilyl group. As the hydrocarbon group constituting these substituted silyl groups, in addition to the unsubstituted hydrocarbon group as described above, a substituted hydrocarbon group substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom Is exemplified.

In the substituent R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , X ¹ or X ² , examples of the substituent in the substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms include halogen An atom etc. are mentioned. Specific examples of the substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, n-propoxy group, 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 Group, tridecyloxy group, tetradecyloxy group, n-pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group, nonadecyloxy group, n-eicosyloxy group and the like, preferably methoxy Group, ethoxy group, and tert-butoxy group. Any of these alkoxy groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Examples of the substituent in the substituted or unsubstituted aralkyloxy group having 7 to 20 carbon atoms in the substituent R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , X ¹ or X ² include, for example, halogen An atom etc. are mentioned.
Specific examples of the substituted or unsubstituted aralkyloxy group having 7 to 20 carbon atoms include benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, and (4-methylphenyl) methoxy group. 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, 3,4,5-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, anthra Examples include a senylmethoxy group, and a benzyloxy group is preferable. Any of these aralkyloxy groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

In the substituent R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , X ¹ or X ² , examples of the substituent in the substituted aryloxy group having 6 to 20 carbon atoms include an alkyl group, halogen An atom etc. are illustrated. Specific examples of the substituted or unsubstituted 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, 2,4,6-trimethylphenoxy group, 3,4,5-trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2,3,5,6-tetramethyl Phenoxy group, pentamethylphenoxy group, ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group Examples thereof include unsubstituted aryloxy groups having 6 to 20 carbon atoms such as a group, n-decylphenoxy group, n-tetradecylphenoxy group, naphthoxy group and anthracenoxy group, and preferably a phenoxy group. Further, those in which these aryl sites are substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom are also included.

In the substituents R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , X ¹ or X ² , the amino group substituted with a hydrocarbon having 1 to 20 carbon atoms is two hydrocarbon groups The substituted amino group, where the hydrocarbon is, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, Examples thereof include alkyl groups having 1 to 20 carbon atoms such as n-pentyl group, n-hexyl group and cyclohexyl group, and aryl groups such as phenyl group, and these substituents may be bonded to each other to form a ring. Good.

  Examples of the amino group substituted with the 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, Examples include diphenylamino group, bistrimethylsilylamino group, bis-tert-butyldimethylsilylamino group, pyrrolyl group, pyrrolidinyl group, piperidyl group, carbazolyl group, dihydroindolyl group, dihydroisoindolyl group and the like, preferably dimethylamino Group, diethylamino group, pyrrolidinyl group, piperidyl group And the like.

Moreover, two adjacent substituents out of R ⁵ and R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ may be optionally bonded to form a ring.

［式中

は置換もしくは無置換のフェロセンまたはルテノセンを表し、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は、同一または相異なり、
水素原子、置換もしくは無置換の炭素数１〜２０のアルキル基、
置換もしくは無置換の炭素数６〜２０のアリール基、
置換もしくは無置換の炭素数７〜２０のアラルキル基、
置換もしくは無置換の炭素数１〜２０の炭化水素基で置換されたシリル基、
置換もしくは無置換の炭素数１〜２０のアルコキシ基、
置換もしくは無置換の炭素数６〜２０のアリールオキシ基、
置換もしくは無置換の炭素数７〜２０のアラルキルオキシ基、
置換もしくは無置換の炭素数１〜２０の炭化水素基で置換されたシリルオキシ基、
置換もしくは無置換の炭素数１〜２０の炭化水素基で置換されたアミノ基、
置換もしくは無置換の炭素数１〜２０の炭化水素基で置換されたホスフィノ基、
および置換もしくは無置換の炭素数１〜２０の炭化水素基で置換されたチオ基を表し、隣接する２つの置換基は任意に結合して環を形成していてもよい。］
で表されるシクロペンタジエニル基が例示され、好ましくはフェロセノ［２，３］インデン−１−イル、フェロセノ［２，３］シクロペンタジエン−１−イル、４，５−ジメチルフェロセノ［２，３］シクロペンタジエン−１−イル、ペンタメチルフェロセノ［２，３］インデン−１−イル、４−フェロセニルフェロセノ［２，３］シクロペンタジエン−１−イルなどや、これらのシクロペンタジエニル基のフェロセンをルテノセンに変更した基が例示され、より好ましくは、フェロセノ［２，３］インデン−１−イル、フェロセノ［２，３］シクロペンタジエン−１−イルが挙げられる。 In the substituted or unsubstituted cyclopentadienyl group which is substituted with or condensed with at least one substituted or unsubstituted ferrocene or ruthenocene represented by Cp, the ferrocene or ruthenocene is usually 1 to 4 As such cyclopentadienyl group, for example,

[In the formula

Represents substituted or unsubstituted ferrocene or ruthenocene, and R ¹ , R ² , R ³ and R ⁴ are the same or different;
A hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms,
A substituted or unsubstituted aryl group having 6 to 20 carbon atoms,
A substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms,
A silyl group substituted with a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms,
A substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms,
A substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms,
A substituted or unsubstituted aralkyloxy group having 7 to 20 carbon atoms,
A silyloxy group substituted with a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms,
An amino group substituted with a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms,
A phosphino group substituted with a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms,
And a thio group substituted with a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and two adjacent substituents may be optionally bonded to form a ring. ]
And ferroceno [2,3] inden-1-yl, ferroceno [2,3] cyclopentadien-1-yl, 4,5-dimethylferroceno [2, 3] cyclopentadien-1-yl, pentamethylferroceno [2,3] inden-1-yl, 4-ferrocenylferroceno [2,3] cyclopentadien-1-yl, and the like Examples include groups in which the ferrocene of the enyl group is changed to ruthenocene, more preferably ferroceno [2,3] inden-1-yl and ferroceno [2,3] cyclopentadien-1-yl.

A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted carbon number 7 in the substituent R ¹ , R ² , R ³ or R ⁴ -20 aralkyl group, silyl group substituted with a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, substituted or unsubstituted alkoxy group with 1 to 20 carbon atoms, substituted or unsubstituted 6 to 6 carbon atoms Examples of the amino group substituted with 20 aryloxy groups, substituted or unsubstituted aralkyloxy groups having 7 to 20 carbon atoms, and substituted or unsubstituted hydrocarbon groups having 1 to 20 carbon atoms include substituents R ⁵ and R ^6. , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , X ¹ or X ² are the same as those described above.

The silyloxy group substituted with a hydrocarbon group having 1 to 20 carbon atoms in the substituent R ¹ , R ² , R ³ or R ⁴ is a silyloxy group substituted with three hydrocarbon groups, Examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group, Examples thereof include an alkyl group having 1 to 20 carbon atoms, such as a cyclohexyl group, and an aryl group such as a phenyl group, and these substituents may be bonded to each other to form a ring.
Examples of the silyloxy group substituted with the hydrocarbon having 1 to 20 carbon atoms include, for example, a trimethylsilyloxy group, a triethylsilyloxy group, a tri-n-butylsilyloxy group, a triphenylsilyloxy group, a triisopropylsilyloxy group, Examples thereof include a tert-butyldimethylsilyloxy group, a dimethylphenylsilyloxy group, and a methyldiphenylsilyloxy group, and a trimethylsilyloxy group, a triphenylsilyloxy group, and a triisopropylsilyloxy group are preferable.

In the substituent R ¹ , R ² , R ³ or R ⁴ , the phosphino group substituted with a hydrocarbon group having 1 to 20 carbon atoms is a phosphino group substituted with two hydrocarbon groups, As the hydrocarbon group, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group Cyclohexyl 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, Examples thereof include alkyl groups having 1 to 20 carbon atoms such as n-eicosyl group, and aryl groups such as phenyl group. These substituents are bonded to each other to form a ring. It may form. Moreover, an alkylsilyl group is also exemplified. Specific examples of the phosphino group substituted with such a hydrocarbon group having 1 to 20 carbon atoms include dimethylphosphino group, diethylphosphino group, di-n-propylphosphino group, diisopropylphosphino group, di-n- Butylphosphino group, di-sec-butylphosphino group, di-tert-butylphosphino group, di-isobutylphosphino group, tert-butylisopropylphosphino group, di-n-hexylphosphino group, di-n -Octylphosphino group, di-n-decylphosphino group, diphenylphosphino group, bistrimethylsilylphosphino group, bis-tert-butyldimethylsilylphosphino group, etc. are exemplified, preferably dimethylphosphino group, diethylphosphino group And a diphenylphosphino group.

Examples of the hydrocarbon group in the thio group substituted with the hydrocarbon group having 1 to 20 carbon atoms in the substituent R ¹ , R ² , R ³ or R ⁴ include a methyl group, an ethyl group, an n-propyl group, C 1-20 alkyl groups such as isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group, cyclohexyl group, and aryl groups such as phenyl group These substituents may be bonded to each other to form a ring or a thienyl group. Specific examples of the thio group substituted with the hydrocarbon group having 1 to 20 carbon atoms include methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, sec-butylthio group, tert-butylthio group. Group, isobutylthio group, n-hexylthio group, n-octylthio group, n-decylthio group, phenylthio group and the like.

In the compound represented by formula (1) or formula (2), as a ring formed by combining two adjacent substituents among R ⁵ and R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ , And a saturated or unsaturated hydrocarbon ring substituted with a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. 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.

  Specific examples of the transition metal complex represented by the formula (1) include, for example, dimethylsilyl (ferroceno [2,3] inden-1-yl) (2-phenoxy) titanium dichloride, dimethylsilyl (ferroceno [2,3]). Inden-1-yl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (ferroceno [2,3] inden-1-yl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl ( Ferroceno [2,3] inden-1-yl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (ferroceno [2,3] inden-1-yl) (3-tert-butyl-5- Methyl-2-phenoxy) titanium dichloride, dimethylsilyl (ferroceno [2,3 Inden-1-yl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (ferroceno [2,3] inden-1-yl) (5-methyl-3-phenyl-2- Phenoxy) titanium dichloride, dimethylsilyl (ferroceno [2,3] inden-1-yl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (ferroceno [2,3] indene) -1-yl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (ferroceno [2,3] inden-1-yl) (3-tert-butyl-5-methoxy-2-phenoxy) ) Titanium dichloride, dimethylsilyl (ferroceno [2,3] Nden-1-yl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (ferroceno [2,3] inden-1-yl) (3,5-diamil-2-phenoxy) Titanium dichloride,

Dimethylsilyl (ferroceno [2,3] cyclopentadien-1-yl) (2-phenoxy) titanium dichloride, dimethylsilyl (ferroceno [2,3] cyclopentadien-1-yl) (3-methyl-2-phenoxy) titanium Dichloride, dimethylsilyl (ferroceno [2,3] cyclopentadien-1-yl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (ferroceno [2,3] cyclopentadien-1-yl) (3 -Tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (ferroceno [2,3] cyclopentadien-1-yl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (ferroceno) [2,3] Siku Pentadien-1-yl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (ferroceno [2,3] cyclopentadien-1-yl) (5-methyl-3-phenyl-2) -Phenoxy) titanium dichloride, dimethylsilyl (ferroceno [2,3] cyclopentadien-1-yl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (ferroceno [2,3 ] Cyclopentadien-1-yl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (ferroceno [2,3] cyclopentadien-1-yl) (3-tert-butyl-5-methoxy) -2-phenoxy) titanium dichrome Id, dimethylsilyl (ferroceno [2,3] cyclopentadien-1-yl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (ferroceno [2,3] cyclopentadiene-1- Yl) (3,5-diamil-2-phenoxy) titanium dichloride,

Dimethylsilyl (4,5-dimethylferroceno [2,3] cyclopentadien-1-yl) (2-phenoxy) titanium dichloride, dimethylsilyl (4,5-dimethylferroceno [2,3] cyclopentadiene-1- Yl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (4,5-dimethylferroceno [2,3] cyclopentadien-1-yl) (3,5-dimethyl-2-phenoxy) titanium dichloride, Dimethylsilyl (4,5-dimethylferroceno [2,3] cyclopentadien-1-yl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (4,5-dimethylferroceno [2,3 ] Cyclopentadien-1-yl) (3-tert-butyl-5-methyl-) -Phenoxy) titanium dichloride, dimethylsilyl (4,5-dimethylferroceno [2,3] cyclopentadien-1-yl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (4 , 5-Dimethylferroceno [2,3] cyclopentadien-1-yl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (4,5-dimethylferroceno [2,3] cyclo Pentadien-1-yl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (4,5-dimethylferroceno [2,3] cyclopentadien-1-yl) (5 -Methyl-3-trimethylsilyl-2-phenoxy) titanium dichloro Id, dimethylsilyl (4,5-dimethylferroceno [2,3] cyclopentadien-1-yl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (4,5-dimethyl) Ferroceno [2,3] cyclopentadien-1-yl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (4,5-dimethylferroceno [2,3] cyclopentadiene- 1-yl) (3,5-diamil-2-phenoxy) titanium dichloride,

Dimethylsilyl (pentamethylferroceno [2,3] inden-1-yl) (2-phenoxy) titanium dichloride, dimethylsilyl (pentamethylferroceno [2,3] inden-1-yl) (3-methyl-2 -Phenoxy) titanium dichloride, dimethylsilyl (pentamethylferroceno [2,3] inden-1-yl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (pentamethylferroceno [2,3] Inden-1-yl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (pentamethylferroceno [2,3] inden-1-yl) (3-tert-butyl-5-methyl-2 -Phenoxy) titanium dichloride, dimethylsilyl (pentamethylphenol) Roseno [2,3] inden-1-yl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (pentamethylferroceno [2,3] inden-1-yl) (5 -Methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (pentamethylferroceno [2,3] inden-1-yl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium Dichloride, dimethylsilyl (pentamethylferroceno [2,3] inden-1-yl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (pentamethylferroceno [2,3] indene- 1-yl) (3-tert-butyl-5-methoxy-2-phenoxy ) Titanium dichloride, dimethylsilyl (pentamethylferroceno [2,3] inden-1-yl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (pentamethylferroceno [2, 3] Inden-1-yl) (3,5-diamil-2-phenoxy) titanium dichloride,

And compounds obtained by changing 3-tert-butyl-2-phenoxy of these compounds to 3-phenyl-2-phenoxy, 3-trimethylsilyl-2-phenoxy or 3-tert-butyldimethylsilyl-2-phenoxy, dimethyl Compounds in which silyl is changed to diethylsilyl, diphenylsilyl or dimethoxysilyl, titanium is changed to zirconium or hafnium, chloride is bromide, iodide, dimethylamide, diethylamide, methoxide, n-butoxide, isopropoxide, methyl or benzyl Illustrated are a modified compound, a compound in which ferrocene is changed to ruthenocene, and a transition metal complex in which B in the formula (1) is an atom belonging to Group 14 of the periodic table of elements other than silicon atoms. Seno [2,3] inden-1-yl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (ferroceno [2,3] cyclopentadien-1-yl) (3-tert -Butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (4,5-dimethylferroceno [2,3] cyclopentadien-1-yl) (3-tert-butyl-5-methyl-2-phenoxy) ) Titanium dichloride, dimethylsilyl (pentamethylferroceno [2,3] inden-1-yl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride.

  Such a transition metal complex (1) is produced, for example, by reacting a cyclopentadiene represented by the formula (2) with a base and then reacting a transition metal compound represented by the formula (3). .

In the cyclopentadiene represented by the formula (2), the unsubstituted hydrocarbon group among the substituted or unsubstituted hydrocarbon groups represented by the substituent R ¹¹ includes a methyl group, an ethyl group, a propyl group, and a butyl group. An alkyl group having 1 to 10 carbon atoms such as pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group; vinyl group, allyl group, propenyl group, 2-methyl-2-propenyl group, homoallyl group, C2-C10 alkenyl groups such as pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl; benzyl, (4-methylphenyl) methyl, (2,4,6-trimethylphenyl) Examples thereof include aralkyl groups having 7 to 12 carbon atoms such as a methyl group. Examples of the substituted hydrocarbon group include alkoxyalkyl groups such as a methoxymethyl group and a methoxyethoxymethyl group, and further include hydrocarbon groups in which the above unsubstituted hydrocarbon group is substituted with a halogen atom. Examples of the hydrocarbon group substituted with a halogen atom include a 2-chloro-2-propenyl group.

The trisubstituted silyl group in the hydrocarbon substituents R ^11, trimethylsilyl group, triethylsilyl group, tri -n- propyl silyl group, triisopropylsilyl group, tri -n- butylsilyl group, tri -sec- butylsilyl , Tri-tert-butylsilyl group, tri-isobutylsilyl group, tert-butyl-dimethylsilyl group, tri-n-pentylsilyl group, tri-n-hexylsilyl group, tricyclohexylsilyl group, triphenylsilyl group, etc. Is done. Among these substituents R ¹¹ , an alkenyl group, particularly an allyl group is preferable in that the transition metal complex represented by the formula (1) can be produced with high yield.

A hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon atom number represented by the substituent X ³ or X ⁴ of the transition metal compound represented by the formula (3) 7 to 20 aralkyl groups, substituted or unsubstituted aryl groups having 6 to 20 carbon atoms, silyl groups substituted with substituted or unsubstituted hydrocarbons having 1 to 20 carbon atoms, substituted or unsubstituted carbon atoms An alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyloxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 1 to 20 carbon atoms, and a hydrocarbon having 2 to 20 carbon atoms; Examples of the disubstituted amino group are the same as those described above as the substituent X ¹ or X ² in the transition metal complex represented by the formula (1).

  Examples of the base used for producing the transition metal complex represented by the formula (1) include methyl lithium, ethyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, lithium trimethylsilyl acetylide, lithium acetylide, and trimethylsilyl. Examples include organic alkali metal compounds such as organic lithium compounds such as methyl lithium, vinyl lithium, phenyl lithium, and allyl lithium. Among such bases, tert-butyllithium is preferable because the transition metal complex represented by the formula (1) can be produced with good yield. The amount used is usually in the range of about 0.5 to 5 moles with respect to 1 mole of the cyclopentadiene represented by the formula (2).

  Moreover, an amine compound can also be used with a 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, dimethyl 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, tertiary amine compounds such as 4-dimethylaminopyridine can be exemplified. What is the amount of amine compound used? The amount is usually 10 mol or less, preferably 0.5 to 10 mol, more preferably 1 to 3 mol with respect to 1 mol of the base.

  The reaction for obtaining the transition metal complex represented by the formula (1) 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, hexamethylphosphine, and the like. Amide solvents such as hollic amide and dimethylformamide, polar solvents such as acetonitrile, propionitrile, acetone, diethyl ketone, methyl isobutyl ketone and cyclohexanone, and aprotic solvents such as halogen solvents such as dichloromethane, dichloroethane, chlorobenzene and dichlorobenzene Etc. are exemplified. Each of these solvents is used alone or in admixture of two or more. The amount used is usually 1 to 200 parts by weight, preferably 3 to 1 part by weight based on 1 part by weight of the substituted cyclopentadiene represented by the formula (2). The range is 50 parts by weight.

  This reaction can be usually performed by adding a cyclopentadiene represented by the formula (2) and a base to a solvent and then adding a transition metal compound represented by the formula (3). A solid may precipitate after the addition of the cyclopentadiene represented by the formula (2) and the base. In this case, the solid taken out from the reaction system is added to the same solvent as described above, and then the formula (3 You may add the transition metal compound shown by this. Further, the cyclopentadiene represented by the formula (2), the base and the transition metal compound represented by the formula (3) may be added simultaneously to the solvent. The reaction temperature is usually in the range of −100 ° C. to the boiling point of the solvent, preferably about −80 to 100 ° C.

  The obtained reaction mixture is filtered by a conventional method, for example, by filtering off the produced precipitate, concentrating the filtrate to precipitate the transition metal complex represented by the formula (1), and then filtering it. A transition metal complex represented by the formula (1) can be obtained.

［式中、Ｃｐは置換もしくは無置換の少なくとも一つのフェロセンまたはルテノセンにより置換されているかまたはこれらと縮合している置換もしくは無置換のシクロペンタジエニル基を表す。］
で示されるシクロペンタジエンと塩基とを反応させた後、式（５）

［式中、Ａ、Ｂ、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１およびＸ^５は、前記と同じ意味を表す。］
で示される化合物を反応させることにより製造される。 The cyclopentadiene represented by the formula (2) is, for example, the formula (4)

[Wherein Cp represents a substituted or unsubstituted cyclopentadienyl group which is substituted with or condensed with at least one substituted or unsubstituted ferrocene or ruthenocene. ]
Is reacted with a cyclopentadiene represented by the formula (5)

[Wherein, A, B, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and X ⁵ represent the same meaning as described above. ]
It is manufactured by making the compound shown by react.

  This step is usually performed by adding cyclopentadiene (4) and a base to the solvent, and then adding compound (5). 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 40 ° C.

  The base is not particularly limited, and examples thereof include methyl lithium, ethyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, lithium trimethylsilyl acetylide, lithium acetylide, trimethylsilylmethyl lithium, vinyl lithium, and phenyl lithium. And organic alkali metal compounds such as organolithium compounds such as allyllithium, inorganic bases such as sodium hydride, potassium hydride, sodium methoxide, potassium butoxide and the like. On the other hand, it is usually in the range of about 0.5 to 5 mol.

  The obtained reaction mixture containing cyclopentadiene (2) may be used in the next step as a solution, or after adding water or an acidic aqueous solution, the organic layer is separated and dried, and then the solvent is distilled off. That's fine. Preferably, the filtrate obtained by distilling off the solvent from the obtained reaction mixture under reduced pressure and then filtering off insoluble matters using a hydrocarbon solvent can be used after being concentrated under reduced pressure. The cyclopentadiene thus obtained may be further purified by a method such as recrystallization, distillation, column chromatography or the like.

  Specific examples of the cyclopentadiene represented by the formula (2) include, for example, (2-allyloxyphenyl) (ferroceno [2,3] inden-1-yl) dimethylsilane, (2-allyloxy-3-methylphenyl) ) (Ferroceno [2,3] inden-1-yl) dimethylsilane, (2-allyloxy-3,5-dimethylphenyl) (ferroceno [2,3] inden-1-yl) dimethylsilane, (2-allyloxy- 3-tert-Butylphenyl) (ferroceno [2,3] inden-1-yl) dimethylsilane, (2-allyloxy-3-tert-butyl-5-methylphenyl) (ferroceno [2,3] indene-1- Yl) dimethylsilane, (2-allyloxy-3,5-di-tert-butylphenyl) (ferroceno [2,3] inden-1-yl Dimethylsilane, (2-allyloxy-5-methyl-3-phenylphenyl) (ferroceno [2,3] inden-1-yl) dimethylsilane, (2-allyloxy-5-methyl-3-trimethylsilylphenyl) (ferroceno [ 2,3] Inden-1-yl) dimethylsilane, (2-allyloxy-3-tert-butyldimethylsilyl-5-methylphenyl) (ferroceno [2,3] inden-1-yl) dimethylsilane, (2- Allyloxy-3,5-diamilphenyl) (ferroceno [2,3] inden-1-yl) dimethylsilane, (2-allyloxy-3-tert-butyl-5-methoxyphenyl) (ferroceno [2,3] indene -1-yl) dimethylsilane, (6-allyloxy-5-tert-butyl-3-chlorophenyl) (phen Seno [2,3] inden-1-yl) dimethylsilane, (1-allyloxy-2-yl) (ferroceno [2,3] inden-1-yl) dimethylsilane,

(2-Allyloxyphenyl) (ferroceno [2,3] cyclopentadien-1-yl) dimethylsilane, (2-Allyloxy-3-methylphenyl) (ferroceno [2,3] cyclopentadien-1-yl) dimethylsilane , (2-allyloxy-3,5-dimethylphenyl) (ferroceno [2,3] cyclopentadien-1-yl) dimethylsilane, (2-allyloxy-3-tert-butylphenyl) (ferroceno [2,3] cyclo Pentadien-1-yl) dimethylsilane, (2-allyloxy-3-tert-butyl-5-methylphenyl) (ferroceno [2,3] cyclopentadien-1-yl) dimethylsilane, (2-allyloxy-3,5 -Di-tert-butylphenyl) (ferroceno [2,3] cyclopentadien-1-yl) di Tylsilane, (2-allyloxy-5-methyl-3-phenylphenyl) (ferroceno [2,3] cyclopentadien-1-yl) dimethylsilane, (2-allyloxy-5-methyl-3-trimethylsilylphenyl) (ferroceno [ 2,3] cyclopentadien-1-yl) dimethylsilane, (2-allyloxy-3-tert-butyldimethylsilyl-5-methylphenyl) (ferroceno [2,3] cyclopentadien-1-yl) dimethylsilane, 2-allyloxy-3,5-diamilphenyl) (ferroceno [2,3] cyclopentadien-1-yl) dimethylsilane, (2-allyloxy-3-tert-butyl-5-methoxyphenyl) (ferroceno [2, 3] cyclopentadien-1-yl) dimethylsilane, (6-allyloxy-5 tert-butyl-3-chlorophenyl) (ferroceno [2,3] cyclopentadien-1-yl) dimethylsilane, (1-allyloxynaphthalen-2-yl) (ferroceno [2,3] cyclopentadien-1-yl) Dimethylsilane,

(2-allyloxyphenyl) (4,5-dimethylferroceno [2,3] cyclopentadien-1-yl) dimethylsilane, (2-allyloxy-3-methylphenyl) (4,5-dimethylferroceno [2 , 3] cyclopentadien-1-yl) dimethylsilane, (2-allyloxy-3,5-dimethylphenyl) (4,5-dimethylferroceno [2,3] cyclopentadien-1-yl) dimethylsilane, (2 -Allyloxy-3-tert-butylphenyl) (4,5-dimethylferroceno [2,3] cyclopentadien-1-yl) dimethylsilane, (2-allyloxy-3-tert-butyl-5-methylphenyl) ( 4,5-dimethylferroceno [2,3] cyclopentadien-1-yl) dimethylsilane, (2-allyloxy-3,5-di tert-butylphenyl) (4,5-dimethylferroceno [2,3] cyclopentadien-1-yl) dimethylsilane, (2-allyloxy-5-methyl-3-phenylphenyl) (4,5-dimethylferroceno [2,3] cyclopentadien-1-yl) dimethylsilane, (2-allyloxy-5-methyl-3-trimethylsilylphenyl) (4,5-dimethylferroceno [2,3] cyclopentadien-1-yl) dimethyl Silane, (2-allyloxy-3-tert-butyldimethylsilyl-5-methylphenyl) (4,5-dimethylferroceno [2,3] cyclopentadien-1-yl) dimethylsilane, (2-allyloxy-3, 5-Diamylphenyl) (4,5-dimethylferroceno [2,3] cyclopentadien-1-yl) dimethyl Rusilane, (2-allyloxy-3-tert-butyl-5-methoxyphenyl) (4,5-dimethylferroceno [2,3] cyclopentadien-1-yl) dimethylsilane, (6-allyloxy-5-tert- Butyl-3-chlorophenyl) (4,5-dimethylferroceno [2,3] cyclopentadien-1-yl) dimethylsilane, (1-allyloxynaphthalen-2-yl) (4,5-dimethylferroceno [2 , 3] cyclopentadien-1-yl) dimethylsilane

(2-allyloxyphenyl) (pentamethylferroceno [2,3] inden-1-yl) dimethylsilane, (2-allyloxy-3-methylphenyl) (pentamethylferroceno [2,3] indene-1- Yl) dimethylsilane, (2-allyloxy-3,5-dimethylphenyl) (pentamethylferroceno [2,3] inden-1-yl) dimethylsilane, (2-allyloxy-3-tert-butylphenyl) (penta Methylferroceno [2,3] inden-1-yl) dimethylsilane, (2-allyloxy-3-tert-butyl-5-methylphenyl) (pentamethylferroceno [2,3] inden-1-yl) dimethyl Silane, (2-allyloxy-3,5-di-tert-butylphenyl) (pentamethylferroceno [2,3] indene- 1-yl) dimethylsilane, (2-allyloxy-5-methyl-3-phenylphenyl) (pentamethylferroceno [2,3] inden-1-yl) dimethylsilane, (2-allyloxy-5-methyl-3) -Trimethylsilylphenyl) (pentamethylferroceno [2,3] inden-1-yl) dimethylsilane, (2-allyloxy-3-tert-butyldimethylsilyl-5-methylphenyl) (pentamethylferroceno [2,3 Inden-1-yl) dimethylsilane, (2-allyloxy-3,5-diamilphenyl) (pentamethylferroceno [2,3] inden-1-yl) dimethylsilane, (2-allyloxy-3-tert) -Butyl-5-methoxyphenyl) (pentamethylferroceno [2,3] inden-1-yl) dimethylsilane , (6-allyloxy-5-tert-butyl-3-chlorophenyl) (pentamethylferroceno [2,3] inden-1-yl) dimethylsilane, (1-allyloxynaphthalen-2-yl) (pentamethylferro) Ceno [2,3] inden-1-yl) dimethylsilane

And compounds in which allyloxy of these compounds is changed to methoxy, benzyloxy, ethoxy, trimethylsilyloxy, tert-butyldimethylsilyloxy or methoxymethoxy, dimethylsilane is changed to diethylsilane, diphenylsilane or dimethoxysilane, 2 -Compounds in which allyloxyphenyl is changed to 3-phenyl-2-allyloxyphenyl, 3-trimethylsilyl-2-allyloxyphenyl or 3-tert-butyldimethylsilyl-2-allyloxyphenyl, and compounds in which ferrocene is changed to ruthenocene And cyclopentadienyls in which B in formula (2) is an atom of Group 14 of the periodic table of elements other than silicon atoms, preferably (2-allyloxy-3-tert-butyl-5- Methylphenyl) Ferroceno [2,3] inden-1-yl) dimethylsilane, (2-allyloxy-3-tert-butyl-5-methylphenyl) (ferroceno [2,3] cyclopentadien-1-yl) dimethylsilane, (2 -Allyloxy-3-tert-butyl-5-methylphenyl) (4,5-dimethylferroceno [2,3] cyclopentadien-1-yl) dimethylsilane, (2-allyloxy-3-tert-butyl-5- An example is methylphenyl) (pentamethylferroceno [2,3] inden-1-yl) dimethylsilane.

  Examples of the transition metal compound represented by the formula (3) include titanium halides such as titanium tetrachloride, titanium trichloride, titanium tetrabromide, titanium tetraiodide, tetrakis (dimethylamino) titanium, dichlorobis (dimethylamino). Of titanium, amide titanium such as trichloro (dimethylamino) titanium, tetrakis (diethylamino) titanium, alkoxy titanium such as tetraisopropoxy titanium, tetra-n-butoxy titanium, dichlorodiisopropoxy titanium, trichloroisopropoxy titanium, and the above compounds Examples include compounds in which titanium is changed to zirconium or hafnium, preferably titanium tetrachloride. The amount used is usually in the range of 0.5 to 3 mol, preferably about 0.7 to 1.5 mol, per 1 mol of the cyclopentadiene represented by the formula (2).

The cyclopentadiene represented by the formula (4) can be synthesized, for example, by reducing ferroceno [2,3] indenone synthesized from ferrocene and anthranilic acid (see, for example, Patent Document 3 and J. Am. Chem. Soc. 1965, 87, 5607, etc.). Such cyclopentadiene (4) includes ferroceno [2,3] indene, ferroceno [2,3] cyclopentadiene, 4,5-dimethylferroceno [2,3] cyclopentadiene, pentamethylferroceno [2,3]. Examples include indene, 4-ferrocenylferroceno [2,3] cyclopentadiene, and compounds obtained by changing ferrocene of these cyclopentadiene to ruthenocene, and more preferable examples include ferroceno [2,3] indene and ferroceno [2 , 3] cyclopentadiene and the like.

  The transition metal complex represented by the formula (1) thus produced can be used by adding the compound (A) or further the compound (B) in any order during the polymerization. It is also possible to use a reaction product obtained by previously contacting a combination of

[Compound (A)]
As the compound (A) used in the present invention, for example, a known organoaluminum compound can be used. Preferably, any one of the following compounds (A1) to (A3) or a mixture of two or more thereof are exemplified.
(A1): an organoaluminum compound represented by the formula (E ¹ ) _a Al (Z) _(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 Al (E ³ ) ₂ .

Specific examples of the organoaluminum compound (A1) represented by the formula (E ¹ ) _a Al (Z) _(3-a) include, for example, trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, and trihexylaluminum. Trialkylaluminum; Dimethylaluminum chloride such as dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, dihexylaluminum chloride; methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, hexylaluminum dichloride Alkyl aluminum dichlora such as De; dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, diisobutylaluminum hydride, and the like can be exemplified dialkylaluminum hydride such as dihexyl aluminum hydride. Trialkylaluminum is preferable, and triethylaluminum, triisobutylaluminum, and the like are more preferable.

Formula ^{-Al (E 2) -O-} cyclic aluminoxane having a structure represented by _b (A2), wherein Formula _{^{E 3 {-Al (E 3)}} -O-} c Al (E 3) 2 Specific examples of E ² and E ^{3 in} the linear aluminoxane (A3) having the following structure include methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, normal pentyl group, and neopentyl group. And alkyl groups such as b is an integer of 2 or more, and c is an integer of 1 or more. Preferably, E ² and E ³ are a methyl group and an isobutyl group, b is 2 to 40, and c is 1 to 40.

  Said aluminoxane is manufactured by various methods. There is no restriction | limiting in particular about the method, What is necessary is just to manufacture according to a well-known method. For example, a solution in which a trialkylaluminum (for example, trimethylaluminum) is dissolved in a suitable organic solvent (benzene, aliphatic hydrocarbon, etc.) is brought into contact with water. Moreover, the method of making a trialkylaluminum (for example, trimethylaluminum etc.) contact with the metal salt (for example, copper sulfate hydrate etc.) containing crystal water can be illustrated.

[Compound B]
In the present invention, as the compound (B), (B1): a boron compound represented by the formula BQ ¹ Q ² Q ³ , (B2): a formula Z ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ Or a boron compound represented by the formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ , or a mixture of two or more thereof.

In the boron compound (B1) 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 include a halogen atom and 1 to 20 carbon atoms. Hydrocarbon group, halogenated hydrocarbon group containing 1-20 carbon atoms, substituted silyl group containing 1-20 carbon atoms, alkoxy group containing 1-20 carbon atoms or 1-20 carbons A disubstituted amino group containing atoms, which may be the same or different; Preferred Q ^{1 to} Q ³ are a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms, and a halogenated hydrocarbon group containing 1 to 20 carbon atoms.

  Specific examples of (B1) include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, tris (2,3,4,5-tetrafluorophenyl) borane, and tris. (3,4,5-trifluorophenyl) borane, tris (2,3,4-trifluorophenyl) borane, phenylbis (pentafluorophenyl) borane and the like are exemplified, but preferably tris (pentafluorophenyl) ) Borane is exemplified.

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

Specific examples of the compound represented by the formula Z ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ include an inorganic cation Z ⁺ which includes a ferrocenium cation, an alkyl-substituted ferrocenium cation, and a silver cation. Examples of Z ⁺ , which is an organic cation, include a triphenylmethyl cation. (BQ ¹ Q ² Q ³ Q ⁴ ) ^— includes tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluoro). Phenyl) borate, tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,2,4-trifluorophenyl) borate, phenylbis (pentafluorophenyl) borate, tetrakis (3,5-bistrifluoromethyl) Phenyl) borate and the like are exemplified.

  Specific examples of these combinations include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1′-dimethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, and triphenylcarbenium. Examples thereof include tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (3,5-bistrifluoromethylphenyl) borate, and preferably triphenylcarbenium tetrakis (pentafluorophenyl) borate.

In the boron compound (B3) represented by the formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ , L is a neutral Lewis base, and (LH) ⁺ 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.

As a specific example of the compound represented by the formula (L-H) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ , (LH) ⁺ which is a Bronsted acid includes trialkyl-substituted ammonium, N, N-dialkylanilinium, dialkylammonium, triarylphosphonium and the like are exemplified, and (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ is exemplified by the same ones as described above.

  Specific combinations of these include, for example, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) 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-dimethylanilinium tetrakis (3,5-bistrifluoromethyl Phenyl) borate, diisopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, tri Examples thereof include (dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, and preferably tri (normal butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl). Borate is exemplified.

  The amount of each catalyst component used is such that the molar ratio of compound (A) / transition metal complex (1) is 0.1 to 10,000, preferably 5 to 2000, and the molar ratio of compound (B) / transition metal complex (1). It is desirable to use each component so that is in the range of 0.01 to 100, preferably 0.5 to 10.

  Regarding the concentration when each catalyst component is used in a solution state, the transition metal complex represented by the formula (1) is 0.0001 to 5 mmol / liter, preferably 0.001 to 1 mmol / liter, A) in terms of Al atom is 0.01 to 500 mmol / liter, preferably 0.1 to 100 mmol / liter, and compound (B) is 0.0001 to 5 mmol / liter, preferably It is desirable to use each component so that it is in the range of 0.001 to 1 mmol / liter.

  In the present invention, the monomer used for the polymerization may be any olefin or diolefin having 2 to 20 carbon atoms, and two or more types of monomers may be used at the same time. Such monomers are exemplified below, but the present invention is not limited to the following compounds. Specific examples of such olefins include, for example, ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1, decene-1, 5-methyl-2-pentene- Examples include 1, vinylcyclohexene, 2-norbornene, cyclohexene, dicyclopentadiene and the like. Examples of the diolefin compound include conjugated dienes and nonconjugated dienes of hydrocarbon compounds. Specific examples of such compounds include 1,5-hexadiene, 1,4-hexadiene, 1 , 4-pentadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6 -Octadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-methyl-2-norbornene, norbornadiene, 5-methylene-2-norbornene, 1,5-cyclooctadiene, 5 , 8-endomethylenehexahydronaphthalene and the like, and specific examples of the conjugated diene compound include 1, - butadiene, isoprene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclooctadiene, and the like can be exemplified 1,3-cyclohexadiene.

Specific examples of monomers constituting the copolymer include ethylene and propylene, ethylene and butene-1, ethylene and hexene-1, propylene and butene-1, and 5-ethylidene-2-norbornene. Examples include combinations, but the present invention is not limited to the above compounds.

  In the present invention, an aromatic vinyl compound can also be used as a monomer. Specific examples of the aromatic vinyl compound include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, o -Chlorostyrene, p-chlorostyrene, α-methylstyrene, divinylbenzene and the like are exemplified.

  The polymerization method is not particularly limited. For example, aliphatic hydrocarbons such as butane, pentane, hexane, heptane, and octane, aromatic hydrocarbons such as benzene and toluene, or halogenated hydrocarbons such as methylene dichloride. Can be used as a solvent, slurry polymerization, gas phase polymerization in a gaseous monomer, or any of continuous polymerization and batch polymerization.

The polymerization temperature can usually be in the range of −50 ° C. to 250 ° C., but in order to produce a high molecular weight polymer, the range of about −20 ° C. to 100 ° C. is particularly preferable. For example, about 0.1 MPa) to 10 MPa (100 kg / cm ² G) is preferable. From an industrial point of view, polymerization at a high temperature and high pressure of 100 ° C. or higher and / or 10 MPa or higher may be preferable, but the present invention can also be used for these high temperature and high pressure polymerizations. In general, the polymerization time is appropriately determined depending on the type of the target polymer and the reaction apparatus, but can usually be in the range of 1 minute to 20 hours. In the present invention, a chain transfer agent such as hydrogen may be added in order to adjust the molecular weight of the copolymer.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.
[Example 1]

フェロセノ［２，３］インデン（０．５０ｇ、１．８２ｍｍｏｌ）のテトラヒドロフラン溶液（１０ｍＬ）に−７８℃でｎ−ブチルリチウムの１．５８Ｍのヘキサン溶液（１．２１ｍｌ、１．９２ｍｍｏｌ）を滴下し１０分撹拌後、室温で１時間撹拌した。反応混合溶液に、−７８℃で（２−アリロキシ−３−ｔｅｒｔ−ブチル−５−メチルフェニル）クロロジメチルシラン（０．５４ｇ、１．８２ｍｍｏｌ）のトルエン溶液（２ｍＬ）を滴下した。得られた反応混合液を室温まで昇温し、１．５時間攪拌した。溶媒を減圧留去後、ヘキサンを加え、不溶物を濾別した濾液を減圧濃縮することにより、（２−アリロキシ−３−ｔｅｒｔ−ブチル−５−メチルフェニル）（フェロセノ［２，３］インデン−１−イル）ジメチルシランを定量的に得た。
^１Ｈ−ＮＭＲ（重ベンゼン、δ（ｐｐｍ））：０．２２（ｓ、３Ｈ）、０．３９（ｓ、３Ｈ）、１．５２（ｓ、９Ｈ）、２．１６（ｓ、３Ｈ）、３．８１（ｓ、５Ｈ）、３．９４−４．４７（ｍ、４Ｈ）、５．１５−５．１９（ｍ、１Ｈ）、５．６１−５．６７（ｍ、１Ｈ）、５．８２−５．８９（ｍ、１Ｈ）、７．０２−７．４７（ｍ、６Ｈ）
マススペクトル（ＧＣ、ｍ／ｚ）：５３４（Ｍ^＋）
［実施例２］ Synthesis of (2-allyloxy-3-tert-butyl-5-methylphenyl) (ferroceno [2,3] inden-1-yl) dimethylsilane

To a tetrahydrofuran solution (10 mL) of ferroceno [2,3] indene (0.50 g, 1.82 mmol) was added dropwise a 1.58 M hexane solution (1.21 ml, 1.92 mmol) of n-butyllithium at −78 ° C. After stirring for 10 minutes, the mixture was stirred at room temperature for 1 hour. A toluene solution (2 mL) of (2-allyloxy-3-tert-butyl-5-methylphenyl) chlorodimethylsilane (0.54 g, 1.82 mmol) was added dropwise to the reaction mixture at −78 ° C. The resulting reaction mixture was warmed to room temperature and stirred for 1.5 hours. The solvent was distilled off under reduced pressure, hexane was added, and the filtrate obtained by filtering insolubles was concentrated under reduced pressure to give (2-allyloxy-3-tert-butyl-5-methylphenyl) (ferroceno [2,3] indene- 1-yl) dimethylsilane was obtained quantitatively.
¹ H-NMR (heavy benzene, δ (ppm)): 0.22 (s, 3H), 0.39 (s, 3H), 1.52 (s, 9H), 2.16 (s, 3H), 3.81 (s, 5H), 3.94-4.47 (m, 4H), 5.15-5.19 (m, 1H), 5.61-5.67 (m, 1H), 5. 82-5.89 (m, 1H), 7.02-7.47 (m, 6H)
Mass spectrum (GC, m / z): 534 (M ⁺ )
[Example 2]

（２−アリロキシ−３−ｔｅｒｔ−ブチル−５−メチルフェニル）（フェロセノ［２，３］インデン−１−イル）ジメチルシラン（１．０９ｇ、２．０４ｍｍｏｌ）、トリエチルアミン（０．９３ｇ、９．１８ｍｍｏｌ）のトルエン溶液（１５ｍＬ）に、−７８℃でｔ−ブチルリチウムの１．４８Ｍペンタン溶液（３．１０ｍＬ、４．５９ｍｍｏｌ）を滴下し１０分攪拌後、室温で２時間攪拌した。反応混合溶液に、−７８℃で四塩化チタン（０．５８ｇ、３．０６ｍｍｏｌ）のトルエン溶液（６ｍＬ）を滴下し、９０℃で３時間攪拌した。濃縮し熱ヘキサンで濾過することで不溶物を除去し、溶媒を減圧留去後、ペンタンで洗浄することで、ジメチルシリル（フェロセノ［２，３］インデン−１−イル）（３−ｔｅｒｔ−ブチル−５−メチル−２−フェノキシ）チタニウムジクロライド（０．０９６ｇ、７．７％）を橙色固体として得た。
^１Ｈ−ＮＭＲ（重ベンゼン、δ（ｐｐｍ））：０．１８（ｓ、３Ｈ）、０．２１（ｓ、３Ｈ）、１．３５（ｓ、９Ｈ）、２．１８（ｓ、３Ｈ）、３．７７（ｓ、５Ｈ）、３．９０−４．４７（ｍ、４Ｈ）、７．０３−７．４６（ｍ、６Ｈ）
マススペクトル（ＥＩ、ｍ／ｚ）：６１１（Ｍ^＋） Synthesis of dimethylsilyl (ferroceno [2,3] inden-1-yl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride [complex 1]

(2-Allyloxy-3-tert-butyl-5-methylphenyl) (ferroceno [2,3] inden-1-yl) dimethylsilane (1.09 g, 2.04 mmol), triethylamine (0.93 g, 9.18 mmol) ) Was added dropwise to a toluene solution (15 mL) at −78 ° C. with a 1.48M pentane solution of t-butyllithium (3.10 mL, 4.59 mmol), stirred for 10 minutes, and then stirred at room temperature for 2 hours. A toluene solution (6 mL) of titanium tetrachloride (0.58 g, 3.06 mmol) was added dropwise to the reaction mixture solution at −78 ° C., and the mixture was stirred at 90 ° C. for 3 hours. Insoluble matter was removed by concentration and filtration with hot hexane, and the solvent was distilled off under reduced pressure, followed by washing with pentane, whereby dimethylsilyl (ferroceno [2,3] inden-1-yl) (3-tert-butyl) was removed. -5-Methyl-2-phenoxy) titanium dichloride (0.096 g, 7.7%) was obtained as an orange solid.
¹ H-NMR (heavy benzene, δ (ppm)): 0.18 (s, 3H), 0.21 (s, 3H), 1.35 (s, 9H), 2.18 (s, 3H), 3.77 (s, 5H), 3.90-4.47 (m, 4H), 7.03-7.46 (m, 6H)
Mass spectrum (EI, m / z): 611 (M ⁺ )

<Ethylene homopolymerization>
[Example 3]
In an autoclave, 5.0 mL of toluene was charged under nitrogen and stabilized at 40 ° C. Then, ethylene was pressurized to 0.60 MPa and stabilized. To this, MMAO (5.8 wt% Al, Tosoh Akzo Co.) (100 μmol) and Complex 1 (0.10 μmol) obtained in Example 2 were added and polymerized for 30 minutes. As a result of polymerization, 1.7 × 10 ⁶ g of polymer was produced per hour per 1 mole of titanium.

[Example 4]
Polymerization was performed in the same manner as in Example 3 except that hexane solution of triisobutylaluminum (40 μL, 1.0 M, Kanto Chemical) and pentafluorophenylborane (0.30 μmol) were used instead of MMAO. As a result of the polymerization, 1.0 × 10 ⁵ g of polymer was produced per hour per 1 mole of titanium.

[Example 5]
Example 3 was used except that hexane solution of triisobutylaluminum (40 μL, 1.0 M, Kanto Chemical) and dimethylanilinium tetrakis (pentafluorophenyl) borate (0.30 μmol) were used instead of MMAO. Polymerization was performed. As a result of the polymerization, 7.8 × 10 ⁶ g of polymer was produced per hour per 1 mole of titanium.

[Example 6]
Example 3 was used except that hexane solution of triisobutylaluminum (40 μL, 1.0 M, Kanto Chemical) and triphenylmethyltetrakis (pentafluorophenyl) borate (0.30 μmol) were used instead of MMAO. Polymerization was performed. As a result of the polymerization, 11.5 × 10 ⁶ g of polymer was produced per hour per 1 mole of titanium.

<Ethylene 1-hexene copolymerization>
[Example 7]
An autoclave was charged with 5.0 mL of toluene and 60 μL of 1-hexene under nitrogen and stabilized at 40 ° C., and then ethylene was pressurized to 0.60 MPa and stabilized. To this, MMAO (5.8 wt% Al, Tosoh Akzo) (100 μmol) and Complex 1 (0.10 μmol) were added and polymerized for 30 minutes. As a result of the polymerization, a polymer having a molecular weight (Mw) = 1,599,000, a molecular weight distribution (Mw / Mn) = 2.4, Tm = 115.0 ° C., and a methyl branching number of 28 per 1000 carbons of the polymer was converted to 1 mol of titanium. Per 1 hour, and manufactured 1.0 * 10 < ⁶ > g.

[Example 8]
Polymerization was carried out in the same manner as in Example 7 except that the amount of 1-hexene charged was 50 μL and the polymerization temperature was 70 ° C. As a result of the polymerization, a polymer having a molecular weight (Mw) = 665,000, a molecular weight distribution (Mw / Mn) = 2.1, Tm = 114.5 ° C., and a methyl branching number of 11 per 1000 carbons of the polymer is obtained per 1 mole of titanium. 3.2 × 10 ⁶ g was produced per hour.

[Example 9]
An autoclave was charged with 5.0 mL of toluene and 60 μL of 1-hexene under nitrogen and stabilized at 40 ° C., and then ethylene was pressurized to 0.60 MPa and stabilized. To this, a hexane solution of triisobutylaluminum (40 μL, 1.0 M, Kanto Chemical), dimethylanilinium tetrakis (pentafluorophenyl) borate (0.30 μmol), and complex 1 (0.10 μmol) were added and polymerized for 30 minutes. did. As a result of the polymerization, a polymer having a molecular weight (Mw) = 2,091,000, a molecular weight distribution (Mw / Mn) = 1.7, Tm = 113.9 ° C., and a methyl branch number of 20 per 1000 carbons of a polymer was converted to 1 mol of titanium. Per hour, 8.8 × 10 ⁶ g was produced.

[Example 10]
Polymerization was carried out in the same manner as in Example 9 except that the amount of 1-hexene charged was 50 μL and the polymerization temperature was 70 ° C. As a result of the polymerization, a polymer having a molecular weight (Mw) = 740,000, a molecular weight distribution (Mw / Mn) = 1.9, Tm = 107.9 ° C., and a methyl branching number of 3 per 1000 carbons of polymer is obtained per 1 mole of titanium. 16.4 × 10 ⁶ g was produced per hour.

[Example 11]
Polymerization was carried out in the same manner as in Example 9 except that the amount of 1-hexene charged was 40 μL, the polymerization temperature was 130 ° C., and the hexane solution of triisobutylaluminum was 4 μL. As a result of the polymerization, 2.2 × 10 ⁶ g of polymer was produced per hour per 1 mole of titanium.

[Example 12]
An autoclave was charged with 5.0 mL of toluene and 60 μL of 1-hexene under nitrogen and stabilized at 40 ° C., and then ethylene was pressurized to 0.60 MPa and stabilized. To this was added a hexane solution of triisobutylaluminum (40 μL, 1.0 M, Kanto Chemical), triphenylmethyltetrakis (pentafluorophenyl) borate (0.30 μmol), and complex 1 (0.10 μmol), and polymerized for 30 minutes. did. As a result of the polymerization, a polymer having a molecular weight (Mw) = 1,852,000, a molecular weight distribution (Mw / Mn) = 2.1, Tm = 111.2 ° C., and a methyl branching number of 22 per 1000 carbons of polymer was converted to 1 mol of titanium. 6.9 × 10 ⁶ g per hour was produced.

[Example 13]
Polymerization was carried out in the same manner as in Example 12 except that the amount of 1-hexene charged was 50 μL and the polymerization temperature was 70 ° C. As a result of the polymerization, a polymer having a molecular weight (Mw) = 1,233,000, a molecular weight distribution (Mw / Mn) = 1.9, Tm = 110.6 ° C., and a methyl branching number of 0 per 1000 carbons of the polymer was converted to 1 mol of titanium. Per hour, 8.2 × 10 ⁶ g was produced.

[Example 14]
Polymerization was carried out in the same manner as in Example 12 except that the amount of 1-hexene charged was 40 μL, the polymerization temperature was 130 ° C., and the hexane solution of triisobutylaluminum was 4 μL. As a result of the polymerization, 1.9 × 10 ⁶ g of polymer was produced per hour per 1 mole of titanium.

[Comparative Example 1]
An autoclave was charged with 5.0 mL of toluene and 50 μL of 1-hexene under nitrogen and stabilized at 40 ° C., and then ethylene was pressurized to 0.60 MPa and stabilized. Here, a hexane solution of triisobutylaluminum (50 μL, 1.0 M, Kanto Chemical), triphenylmethyltetrakis (pentafluorophenyl) borate (0.30 μmol), and dimethylsilyl (tetramethylcyclopentadienyl) (3- tert-Butyl-5-methyl-2-phenoxy) titanium dichloride (0.10 μmol) was added and polymerized for 30 minutes. As a result of the polymerization, a polymer having a molecular weight (Mw) = 654,000, a molecular weight distribution (Mw / Mn) = 2.6, Tm = 98.2 ° C., and a methyl branching number of 19 per 1000 carbons of the polymer is obtained per 1 mole of titanium. 26.3 × 10 ⁶ g was produced per hour.

[Comparative Example 2]
Polymerization was carried out in the same manner as in Comparative Example 1 except that the polymerization temperature was 70 ° C. As a result of the polymerization, a polymer having a molecular weight (Mw) = 260,000, a molecular weight distribution (Mw / Mn) = 2.5, Tm = 88.0 ° C., and a methyl branching number of 28 per 1000 carbons of the polymer, 152.3 × 10 ⁶ g was produced per hour.

[Comparative Example 3]
Polymerization was carried out in the same manner as in Comparative Example 1 except that the polymerization temperature was 130 ° C. and the hexane solution of triisobutylaluminum was 4 μL. As a result of the polymerization, a polymer having a molecular weight (Mw) = 169,000, a molecular weight distribution (Mw / Mn) = 2.1, Tm = 90.3 ° C., and a methyl branching number of 24 per 1000 carbons of the polymer, 30.8 × 10 ⁶ g was produced per hour.

Claims (18)

Formula (1)

[Wherein, M ¹ represents a Group 4 transition metal, A represents a Group 16 element, B represents a Group 14 element, n represents 0 or 1,
Cp represents a substituted or unsubstituted cyclopentadienyl group which is substituted by or condensed with at least one substituted or unsubstituted ferrocene or ruthenocene;
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are the same or different and are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms,
A substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms,
A substituted or unsubstituted aryl group having 6 to 20 carbon atoms,
A substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms,
A substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms,
A substituted or unsubstituted aralkyloxy group having 7 to 20 carbon atoms,
A silyl group substituted with a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms or an amino group substituted with a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms,
Further, two adjacent substituents among R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ may be optionally bonded to form a ring.
X ¹ and X ² are the same or different and are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms,
A substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms,
A substituted or unsubstituted aryl group having 6 to 20 carbon atoms,
A substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms,
A substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms,
It represents an amino group substituted with a substituted or unsubstituted aralkyloxy group having 7 to 20 carbon atoms or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. ]
A transition metal complex represented by The transition metal complex according to claim 1, wherein Cp is a substituted or unsubstituted cyclopentadienyl group condensed with at least one substituted or unsubstituted ferrocene or ruthenocene. The transition metal complex according to claim 1, wherein Cp is a substituted or unsubstituted cyclopentadienyl group condensed with at least one substituted or unsubstituted ferrocene. The transition metal complex according to any one of claims 1 to 3, wherein A is an oxygen atom. The transition metal complex according to any one of claims 1 to 4, wherein B is a silicon atom. R ¹⁰ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, The transition metal complex according to any one of claims 1 to 5, which is an unsubstituted C1-C20 substituted silyl group. The transition metal complex according to any one of claims 1 to 6, wherein n is 1. The transition metal complex according to any one of claims 1 to 7, wherein M ¹ is titanium. The transition metal complex according to claim 1, wherein X ¹ and X ² are chlorine atoms. Formula (2)

[Wherein, A, B, Cp, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ represent the same meaning as described above, and R ¹¹ represents a substituted or unsubstituted hydrocarbon group or carbon It represents a silyl group trisubstituted with hydrogen, and the position of the double bond of the cyclopentadiene ring is arbitrary, or may be a mixture of those having different positions of the double bond. ]
After reacting the cyclopentadiene represented by the above with a base,
Formula (3),

[Wherein M ¹ represents a Group 4 transition metal, n represents 0 or 1,
X ¹ , X ² , X ³ and X ⁴ are the same or different and are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms. Group, substituted or unsubstituted aryl group having 6 to 20 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, substituted or unsubstituted It represents an amino group substituted with an aralkyloxy group having 7 to 20 carbon atoms or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. ]
A process for producing a transition metal complex represented by the formula (1) according to claim 1, which comprises reacting with a transition metal compound represented by the formula: The method for producing a transition metal complex according to claim 10, wherein the base is an organolithium compound. The method for producing a transition metal complex according to claim 11, wherein the organolithium compound is t-butyllithium. The cyclopentadiene represented by the formula (2) according to claim 10. Formula (4)

[Wherein Cp represents a substituted or unsubstituted cyclopentadienyl group which is substituted by or condensed with one or more substituted or unsubstituted ferrocenes or ruthenocenes. ]
After reacting a substituted or unsubstituted cyclopentadiene represented by the formula (5) with a base,

[Wherein, A, B, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ represent the same meaning as described above, and X ⁵ represents a halogen atom. ]
11. The process for producing a cyclopentadiene represented by the formula (2) according to claim 10, wherein the compound represented by the formula (2) is reacted. An olefin polymerization catalyst comprising the transition metal complex according to any one of claims 1 to 9 and the following compound (A) in combination.
(A): Any one of the following compounds (A1) to (A3), or a mixture of two or more thereof (A1): an organoaluminum compound represented by the formula (E ¹ ) _a Al (Z) _(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 Al (E ³ ) ₂ [wherein E ^{1 to} E ³ are the same or different, Is a hydrocarbon group having 1 to 8 carbon atoms, Z is the same or different and represents a hydrogen atom or a halogen atom, a represents an integer of 1, 2 or 3, b represents an integer of 2 or more, c Represents an integer of 1 or more. ]. An olefin polymerization catalyst comprising a combination of the transition metal complex according to any one of claims 1 to 9 and the following compounds (A) and (B).
(A): Any of the following compounds (A1) to (A3), or a mixture of two or more thereof.
(A1): an organoaluminum compound represented by the formula (E ¹ ) _a Al (Z) _(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 Al (E ³ ) ₂ [wherein E ^{1 to} E ³ are the same or different, Is a hydrocarbon group having 1 to 8 carbon atoms, Z is the same or different and represents a hydrogen atom or a halogen atom, a represents an integer of 1, 2 or 3, b represents an integer of 2 or more, c Represents an integer of 1 or more. ];
(B): Any of the following compounds (B1) to (B3), or a mixture of two or more thereof.
(B1): a boron compound represented by the formula BQ ¹ Q ² Q ³ ,
(B2): a boron compound represented by the formula Z ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻
(B3): A boron compound represented by the formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^— [wherein B is a boron atom in a trivalent valence state, and Q ^{1 to} Q ⁴ Are the same or different, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silyl group substituted with a hydrocarbon having 1 to 20 carbon atoms, carbon It represents an amino group disubstituted by an alkoxy group having 1 to 20 atoms or a hydrocarbon having 1 to 20 carbon atoms, and LH represents a Bronsted acid. ]. A method for producing an olefin polymer, comprising polymerizing an olefin in the presence of the olefin polymerization catalyst according to claim 15 or 16. The method for producing an olefin polymer according to claim 17, wherein the polymerization reaction of olefin is carried out in a polymerization temperature range of -50 ° C to 250 ° C under a polymerization pressure of normal pressure to 10 MPa.