JP2009019035A - Transition metal complex, its ligand, catalyst for olefin polymerization and method for producing olefin polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transition metal complex etc. <P>SOLUTION: The transition metal complex is represented by formula (I) [wherein M represents a titanium atom or the like; A represents an oxygen atom or the like; X<SP>1</SP>and X<SP>2</SP>each represents a monoanionic ligand; R<SP>1</SP>to R<SP>10</SP>each represents a hydrogen atom, a halogen atom, a 1-20C alkyl group or the like; Ln represents a divalent crosslinking group (the divalent crosslinking group represents R<SP>11</SP>R<SP>12</SP>C, R<SP>11</SP>R<SP>12</SP>Si, R<SP>11</SP>R<SP>12</SP>Ge, R<SP>11</SP>R<SP>12</SP>Sn, R<SP>11</SP>B, R<SP>11</SP>P, R<SP>11</SP>P=O, SO<SB>2</SB>or S, wherein R<SP>11</SP>and R<SP>12</SP>may be same or different and they are each a 1-20C alkyl group or a 6-20C aryl group or the like)]. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to a transition metal complex, a ligand thereof, a catalyst for olefin polymerization, and a method for producing an olefin polymer.
More specifically, the present invention relates to a transition metal complex useful as an olefin polymerization catalyst, a substituted indenyl compound as a ligand thereof, an olefin polymerization catalyst comprising the transition metal complex as a component, and an olefin polymer using the same. A process for producing an olefin polymer having excellent characteristics of being able to produce an olefin polymer with high activity, a catalyst for olefin polymerization that can be used as a catalyst for the production process, and a transition metal complex that is a component thereof And its ligands.

Polyolefins are used in various fields such as various molding materials and film materials because they are lightweight and have excellent processability and mechanical properties. In recent years, demands for physical properties of polyolefins have been diversified, and olefin polymerization catalysts capable of producing polyolefins having various properties are desired. Therefore, the appearance of a new transition metal catalyst that can be a catalyst component for olefin polymerization is desired.
Japanese Patent No. 2535249 JP-A-9-87313

  In such a situation, the problem to be solved by the present invention is that a transition metal complex useful as an olefin polymerization catalyst, a substituted indenyl compound as a ligand thereof, an olefin polymerization catalyst comprising the transition metal complex as a component, and A method for producing an olefin polymer, a method for producing an olefin polymer having an excellent characteristic that an olefin polymer can be produced with high activity, a catalyst for olefin polymerization which can be used as a catalyst for the production method, and a method thereof By providing a transition metal complex as a component and its ligand, the selection range of a catalyst suitable for the purpose of olefin polymerization is expanded.

  In order to achieve the above-mentioned object, the present inventors have continued intensive studies on transition metal complexes and olefin polymerization catalysts. As a result, a ligand in which an aromatic ring of an indenyl ring and an aromatic ring having a group 16 atom as a substituent are connected by a divalent bridging group and a transition metal complex having the ligand have been found, and the present invention has been achieved. .

（式中、Ｍは、元素の周期律表の第４族遷移金属原子を表し、Ａは、元素の周期律表の第１６族の原子を表し、Ｘ¹、Ｘ²は、それぞれ独立にモノアニオン性配位子を表し、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９及びＲ^１０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２〜２０のアルケニル基、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す。
ここで、Ｒ^１〜Ｒ^６及びＲ^７〜Ｒ^１０において、アルキル基、アリール基、アラルキル基、炭素原子数２〜２０のアルケニル基、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、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８ 、Ｒ^９及びＲ^１０に於いて、置換部位が隣接する基はそれぞれ任意に結合して環を形成していてもよい。
Ｌｎは２価の架橋基を表す。
（２価の架橋基は、Ｒ^１１Ｒ^１２Ｃ、Ｒ^１１Ｒ^１２Ｓｉ、Ｒ^１１Ｒ^１２Ｇｅ、Ｒ^１１Ｒ^１２Ｓｎ、Ｒ^１１Ｂ、Ｒ^１１Ｐ、Ｒ^１１Ｐ＝Ｏ、ＳＯ_２又はＳを表し、式中、Ｒ^１１、Ｒ^１２は、同一又は相異なり、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２〜２０のアルケニル基又は炭素原子数１〜２０の炭化水素基で置換されたシリル基を表し、Ｒ^１１とＲ^１２は結合して環を形成していてもよい。））
で示される遷移金属錯体（以下化合物〔１〕と称する。）に関し、
第二の発明は、式（２）

（式中、Ｌｎ、Ａ、Ｒ¹、Ｒ² 、Ｒ³、Ｒ⁴、Ｒ⁵ 、Ｒ⁶ 、Ｒ⁷、Ｒ⁸、Ｒ⁹及びＲ¹⁰は前記と同じ意味を表わし、Ｒ¹³は水素原子、炭素原子数１〜２０のアルキル基、炭素原子数２〜２０のアルケニル基、炭素原子数７〜２０のアラルキル基、炭素原子数６〜２０のアリール基又は炭素原子数１〜２０の炭化水素置換シリル基を示す、但しシクロペンタジエン骨格をもつ置換基は含まない。また、Ｒ¹³とＲ^1０は互いに結合して環を形成していてもよく、シクロペンタジエンの二重結合の位置は任意、又は混合物であっても良い。）
で示される置換インデニル化合物（以下化合物〔２〕と称する。）に係わるものであり、
第三の発明は、上記遷移金属錯体を含有することを特徴とするオレフィン重合用触媒成分に関し、
第四の発明は、上記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）
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−｝_ｃＡｌ（Ｅ^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はそれぞれ炭素原子数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、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。）
とを接触させて得られるオレフィン重合用触媒に関し
第五の発明は、上記オレフィン重合触媒を用いることを特徴とするオレフィンの重合体の製造方法に関するものである。 That is, the first invention of the present invention is
Formula (I)

(In the formula, M represents a group 4 transition metal atom in the periodic table of elements, A represents a group 16 atom in the periodic table of elements, and X ¹ and X ² are each independently mono Represents an anionic ligand, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are the same or different and are a hydrogen atom, halogen atom, carbon An alkyl group having 1 to 20 atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and a hydrocarbon group having 1 to 20 carbon atoms. Substituted by a substituted silyl 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 hydrocarbon group having 1 to 20 carbon atoms Represents an amino group formed.
Here, in R ^{1 to} R ⁶ and R ^{7 to} R ¹⁰ , an alkyl group, an aryl group, an aralkyl group, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group, an aryloxy group, an aralkyloxy group, or a hydrocarbon group is May be substituted with a halogen atom.
In R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ , the groups adjacent to each other are bonded to each other to form a ring. It may be.
Ln represents a divalent crosslinking group.
(The divalent bridging group is R ¹¹ R ¹² C, R ¹¹ R ¹² Si, R ¹¹ R ¹² Ge, R ¹¹ R ¹² Sn, R ¹¹ B, R ¹¹ P, R ¹¹ P═O, SO ₂ or S In the formula, R ¹¹ and R ¹² are the same or different and are 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, and a carbon atom. This represents a silyl group substituted with an alkenyl group having 2 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms, and R ¹¹ and R ¹² may be bonded to form a ring.
A transition metal complex represented by the following (hereinafter referred to as compound [1]),
The second invention is the formula (2)

(In the formula, Ln, A, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ represent the same meaning as described above, and R ¹³ represents a hydrogen atom. , An alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a hydrocarbon having 1 to 20 carbon atoms A substituted silyl group, except for a substituent having a cyclopentadiene skeleton, wherein R ¹³ and R ¹⁰ may be bonded to each other to form a ring, and the position of the double bond of cyclopentadiene is arbitrary; Or it may be a mixture.)
In relation to a substituted indenyl compound (hereinafter referred to as Compound [2]),
A third invention relates to a catalyst component for olefin polymerization characterized by containing the above transition metal complex,
4th invention is the said catalyst component for olefin polymerization, 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 Al (E ³ ) ₂ (wherein a satisfies 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 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, 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, L ¹ represents a neutral Lewis base.)
The fifth invention relates to a method for producing an olefin polymer, characterized by using the above-mentioned olefin polymerization catalyst.

  According to the present invention, there are provided a transition metal complex useful as an olefin polymerization catalyst, a substituted indenyl compound as a ligand thereof, an olefin polymerization catalyst containing the transition metal complex as a component, and a method for producing an olefin polymer using the same. The production method of an olefin polymer having an excellent feature of being able to produce an olefin polymer with high activity, an olefin polymerization catalyst that can be used as a catalyst for the production method, and a transition metal complex and its ligand as its components Thus, the selection range of the catalyst suitable for the purpose of olefin polymerization can be expanded.

The present invention will be described in detail below.
[Transition metal complexes]
In the compound [1], in the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ , the halogen atom includes a fluorine atom, a chlorine atom, A bromine atom, an iodine atom, etc. are illustrated, Preferably a fluorine atom is mentioned.

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 , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² Examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, tert-amyl group, n-hexyl group. , Heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and n- An eicosyl group is exemplified, and preferred examples include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, and a tert-amyl group.
In the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² , halogen-substituted alkyl having 1 to 20 carbon atoms Specific examples of the group include those in which these alkyl groups are substituted with a halogen atom such as a fluorine atom, chlorine atom, bromine atom or iodine atom, preferably those substituted with a fluorine atom.

Specific examples of the aryl group having 6 to 20 carbon atoms in the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² Examples include phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 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, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethyl Phenyl group, pentamethylphenyl group, ethylphenyl group, n- Propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n Examples include -decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, naphthyl group, anthracenyl group, and the like, preferably phenyl group.
In the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² , halogen-substituted aryl having 6 to 20 carbon atoms Specific examples of the group include those in which these aryl groups are substituted with a halogen atom such as a fluorine atom, chlorine atom, bromine atom or iodine atom, preferably those substituted with a fluorine 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 , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² Examples include benzyl, (2-methylphenyl) methyl, (3-methylphenyl) methyl, (4-methylphenyl) methyl, (2,3-dimethylphenyl) methyl, (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, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl group, (3,4,5-trimethylphenyl) methyl Group (2,4,6-trime Ruphenyl) methyl group, (2,3,4,5-tetramethylphenyl) 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-decyl) Phenyl) methyl group, (n-decylphenyl) methyl group, naphthylmethyl group, anthracenylmethyl group, dimethylphenylmethyl group, etc., preferably benzyl group And dimethylphenylmethyl group.
In the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² , the halogen-substituted aralkyl having 7 to 20 carbon atoms Specific examples of the group include those in which these aralkyl groups are substituted with a halogen atom such as a fluorine atom, chlorine atom, bromine atom or iodine atom, preferably those substituted with a fluorine atom.

Specific examples of the alkenyl group having 2 to 20 carbon atoms in the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² Examples include vinyl, allyl, crotyl, methallyl, prenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, decenyl, dodecenyl, etc., preferably allyl, methallyl Groups.
In the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² , halogen-substituted alkenyl having 7 to 20 carbon atoms Specific examples of the group include those in which these alkenyl groups are substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably those substituted with a fluorine atom.

Carbonization of a silyl group substituted with a hydrocarbon group in the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² Examples of the hydrogen group include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, n-hexyl, and cyclohexyl. Examples thereof include alkyl groups having 1 to 10 carbon atoms such as a 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 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.

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 , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ include a 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, tridecyloxy group, tetradecyloxy group, n-pentadecyloxy group, hexadecyloxy group Group, heptadecyloxy group, octadecyloxy group, nonadecyloxy group, n-eicosyloxy group, etc., preferably methoxy group Ethoxy group, and a tert- butoxy group.

Specific examples of the aryloxy group having 6 to 20 carbon atoms in the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ 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 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-tetramethylphenoxy 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, n-decylphenoxy group, n-tetradecylphenoxy group, naphthoxy group, anthracenoxy group, etc. A phenoxy group is mentioned.

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 , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ include Benzyloxy group, (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- Limethylphenyl) 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) A methoxy group, a naphthyl methoxy group, an anthracenyl methoxy group etc. are illustrated, Preferably a benzyloxy group is mentioned.

In the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ , an amino group substituted with a hydrocarbon group having 1 to 20 carbon atoms; Is an amino group substituted by two hydrocarbon groups, and examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a sec-butyl group. , Tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group, cyclohexyl group and other alkyl groups having 1 to 20 carbon atoms, and aryl groups such as phenyl group. It may combine 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.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² may be optionally substituted with two adjacent substituents. It may combine to form a ring.

Two substituents adjacent to each other at the substitution position of the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are bonded. Examples of the ring thus formed include saturated or unsaturated hydrocarbon rings substituted with a 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.

Examples of the Group 4 transition metal in the periodic table represented by M include titanium, zirconium, and hafnium, with titanium being preferred.

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

Monoanionic ligands represented by X ¹ and X ² include hydride groups; halides such as chloride and bromide; hydrocarbon groups having no β hydrogen such as methyl, benzyl, neopentyl and phenyl groups; methoxy groups Alkoxy groups such as ethoxy group and phenoxy group; ester groups such as acetate and benzoate; hydrocarbon-substituted silyl groups such as methyltrimethylsilyl group; and hydrocarbon disubstituted amino groups such as dimethylamino group and diethylamino group.

The divalent crosslinking group represented by Ln is R ¹¹ R ¹² C, R ¹¹ R ¹² Si, R ¹¹ R ¹² Ge, R ¹¹ R ¹² Sn, R ¹¹ B, R ¹¹ P, R ¹¹ P═O, SO ₂ or S, wherein R ¹¹ and R ¹² are as exemplified above, specifically methylene, dimethylsilylene, diethylsilylene, tert-butylmethylsilylene, phenylmethylsilylene, dimethylgermylene, diethylgermylene, Examples thereof include dimethylstannylene, dibutylstannylene, phenylborylene, phenylphosphinylene, phenylphosphonylene, sulfanylene, sulfonylene, and preferably dimethylsilylene, diethylsilylene, tert-butylmethylsilylene, and phenylmethylsilylene.

Examples of the compound [1] include methylene (4-indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (4-indenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene. (4-indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (4-indenyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, methylene (4 -Indenyl) (3,5-di-tert-amyl-2-phenoxy) titanium dichloride, methylene (4-indenyl) (3,5-bis [dimethylphenylmethyl] -2-phenoxy) titanium dichloride, methylene (4- Indenyl) (3-dimethylpentafluoro Phenylmethyl-5-methyl-2-phenoxy) titanium dichloride, methylene (4-indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, methylene (4-indenyl) (5-methyl-3-trimethylsilyl) -2-phenoxy) titanium dichloride, methylene (4-indenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (4-indenyl) (3-tert-butyl-5-methoxy) -2-phenoxy) titanium dichloride, methylene (4-indenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Dimethylsilylene (4-indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (4-indenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (4-indenyl) ( 3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (4-indenyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (4-indenyl) ( 3,5-di-tert-amyl-2-phenoxy) titanium dichloride, dimethylsilylene (4-indenyl) (3,5-bis [dimethylphenylmethyl] -2-phenoxy) titanium dichloride, dimethylsilylene (4-indenyl) (3 Dimethylpentafluorophenylmethyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (4-indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (4-indenyl) (5- Methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (4-indenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (4-indenyl) (3- tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (4-indenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diethylsilylene (4-indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diethylsilylene (4-indenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diethylsilylene (4-indenyl) ( 3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (4-indenyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, diethylsilylene (4-indenyl) ( 3,5-di-tert-amyl-2-phenoxy) titanium dichloride, diethylsilylene (4-indenyl) (3,5-bis [dimethylphenylmethyl] -2-phenoxy) titanium dichloride, diethylsilylene (4-indenyl) (3 Dimethylpentafluorophenylmethyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (4-indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, diethylsilylene (4-indenyl) (5- Methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, diethylsilylene (4-indenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (4-indenyl) (3- tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diethylsilylene (4-indenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Phenylphosphinylene (4-indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, phenylphosphinylene (4-indenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, phenylphosphinylene (4-indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, phenylphosphinylene (4-indenyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, Phenylphosphinylene (4-indenyl) (3,5-di-tert-amyl-2-phenoxy) titanium dichloride, phenylphosphinylene (4-indenyl) (3,5-bis [dimethylphenylmethyl] -2- Phenoxy) titanium dichloride, fu Nylphosphinylene (4-indenyl) (3-dimethylpentafluorophenylmethyl-5-methyl-2-phenoxy) titanium dichloride, phenylphosphinylene (4-indenyl) (5-methyl-3-phenyl-2-phenoxy) ) Titanium dichloride, phenylphosphinylene (4-indenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, phenylphosphinylene (4-indenyl) (3-tert-butyldimethylsilyl-5-methyl) -2-phenoxy) titanium dichloride, phenylphosphinylene (4-indenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, phenylphosphinylene (4-indenyl) (3-tert-butyl) -5-chloro-2-phenoxy) titanium dichloride,

Methylene (1-methyl-4-indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (1-methyl-4-indenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene ( 1-methyl-4-indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (1-methyl-4-indenyl) (3,5-di-tert-butyl-2-phenoxy) ) Titanium dichloride, methylene (1-methyl-4-indenyl) (3,5-di-tert-amyl-2-phenoxy) titanium dichloride, methylene (1-methyl-4-indenyl) (3,5-bis [dimethyl] Phenylmethyl] -2-phenoxy) titanium dichloride, methylene (1- Til-4-indenyl) (3-dimethylpentafluorophenylmethyl-5-methyl-2-phenoxy) titanium dichloride, methylene (1-methyl-4-indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium Dichloride, methylene (1-methyl-4-indenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, methylene (1-methyl-4-indenyl) (3-tert-butyldimethylsilyl-5-methyl -2-phenoxy) titanium dichloride, methylene (1-methyl-4-indenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (1-methyl-4-indenyl) (3-tert -Butyl-5-chloro-2-pheno Xyl) titanium dichloride,

Dimethylsilylene (1-methyl-4-indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (1-methyl-4-indenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, Dimethylsilylene (1-methyl-4-indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (1-methyl-4-indenyl) (3,5-di-tert-butyl -2-phenoxy) titanium dichloride, dimethylsilylene (1-methyl-4-indenyl) (3,5-di-tert-amyl-2-phenoxy) titanium dichloride, dimethylsilylene (1-methyl-4-indenyl) (3 , 5-Bis [dimethylphenylmethyl] -2-phenyl Noxy) titanium dichloride, dimethylsilylene (1-methyl-4-indenyl) (3-dimethylpentafluorophenylmethyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (1-methyl-4-indenyl) (5- Methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (1-methyl-4-indenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (1-methyl-4-indenyl) ) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (1-methyl-4-indenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride Dimethylsilylene (1-methyl-4-indenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diethylsilylene (1-methyl-4-indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diethylsilylene (1-methyl-4-indenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, Diethylsilylene (1-methyl-4-indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (1-methyl-4-indenyl) (3,5-di-tert-butyl -2-phenoxy) titanium dichloride, diethylsilylene (1-methyl-4-indenyl) (3,5-di-tert-amyl-2-phenoxy) titanium dichloride, diethylsilylene (1-methyl-4-indenyl) (3 , 5-Bis [dimethylphenylmethyl] -2-phenyl Noxy) titanium dichloride, diethylsilylene (1-methyl-4-indenyl) (3-dimethylpentafluorophenylmethyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (1-methyl-4-indenyl) (5- Methyl-3-phenyl-2-phenoxy) titanium dichloride, diethylsilylene (1-methyl-4-indenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, diethylsilylene (1-methyl-4-indenyl) ) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (1-methyl-4-indenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride , Diethylsilylene (1-methyl-4-indenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Phenylphosphinylene (1-methyl-4-indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, phenylphosphinylene (1-methyl-4-indenyl) (3-tert-butyl-2-phenoxy) ) Titanium dichloride, phenylphosphinylene (1-methyl-4-indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, phenylphosphinylene (1-methyl-4-indenyl) (3 , 5-Di-tert-butyl-2-phenoxy) titanium dichloride, phenylphosphinylene (1-methyl-4-indenyl) (3,5-di-tert-amyl-2-phenoxy) titanium dichloride, phenylphosphini Len (1-methyl-4-indenyl) (3,5- [Dimethylphenylmethyl] -2-phenoxy) titanium dichloride, phenylphosphinylene (1-methyl-4-indenyl) (3-dimethylpentafluorophenylmethyl-5-methyl-2-phenoxy) titanium dichloride, phenylphosphini Len (1-methyl-4-indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, phenylphosphinylene (1-methyl-4-indenyl) (5-methyl-3-trimethylsilyl-2- Phenoxy) titanium dichloride, phenylphosphinylene (1-methyl-4-indenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, phenylphosphinylene (1-methyl-4-indenyl) ) (3-t ert-butyl-5-methoxy-2-phenoxy) titanium dichloride, phenylphosphinylene (1-methyl-4-indenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Methylene (2-methyl-4-indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (2-methyl-4-indenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene ( 2-methyl-4-indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (2-methyl-4-indenyl) (3,5-di-tert-butyl-2-phenoxy) ) Titanium dichloride, methylene (2-methyl-4-indenyl) (3,5-di-tert-amyl-2-phenoxy) titanium dichloride, methylene (2-methyl-4-indenyl) (3,5-bis [dimethyl] Phenylmethyl] -2-phenoxy) titanium dichloride, methylene (2- Til-4-indenyl) (3-dimethylpentafluorophenylmethyl-5-methyl-2-phenoxy) titanium dichloride, methylene (2-methyl-4-indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium Dichloride, methylene (2-methyl-4-indenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, methylene (2-methyl-4-indenyl) (3-tert-butyldimethylsilyl-5-methyl -2-phenoxy) titanium dichloride, methylene (2-methyl-4-indenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (2-methyl-4-indenyl) (3-tert -Butyl-5-chloro-2-pheno Xyl) titanium dichloride,

Dimethylsilylene (2-methyl-4-indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (2-methyl-4-indenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, Dimethylsilylene (2-methyl-4-indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (2-methyl-4-indenyl) (3,5-di-tert-butyl -2-phenoxy) titanium dichloride, dimethylsilylene (2-methyl-4-indenyl) (3,5-di-tert-amyl-2-phenoxy) titanium dichloride, dimethylsilylene (2-methyl-4-indenyl) (3 , 5-Bis [dimethylphenylmethyl] -2-phenyl Noxy) titanium dichloride, dimethylsilylene (2-methyl-4-indenyl) (3-dimethylpentafluorophenylmethyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (2-methyl-4-indenyl) (5- Methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (2-methyl-4-indenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (2-methyl-4-indenyl) ) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (2-methyl-4-indenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride Dimethylsilylene (2-methyl-4-indenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diethylsilylene (2-methyl-4-indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diethylsilylene (2-methyl-4-indenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, Diethylsilylene (2-methyl-4-indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (2-methyl-4-indenyl) (3,5-di-tert-butyl -2-phenoxy) titanium dichloride, diethylsilylene (2-methyl-4-indenyl) (3,5-di-tert-amyl-2-phenoxy) titanium dichloride, diethylsilylene (2-methyl-4-indenyl) (3 , 5-Bis [dimethylphenylmethyl] -2-phenyl Noxy) titanium dichloride, diethylsilylene (2-methyl-4-indenyl) (3-dimethylpentafluorophenylmethyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (2-methyl-4-indenyl) (5- Methyl-3-phenyl-2-phenoxy) titanium dichloride, diethylsilylene (2-methyl-4-indenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, diethylsilylene (2-methyl-4-indenyl) ) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (2-methyl-4-indenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride , Diethylsilylene (2-methyl-4-indenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Phenylphosphinylene (2-methyl-4-indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, phenylphosphinylene (2-methyl-4-indenyl) (3-tert-butyl-2-phenoxy) ) Titanium dichloride, phenylphosphinylene (2-methyl-4-indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, phenylphosphinylene (2-methyl-4-indenyl) (3 , 5-Di-tert-butyl-2-phenoxy) titanium dichloride, phenylphosphinylene (2-methyl-4-indenyl) (3,5-di-tert-amyl-2-phenoxy) titanium dichloride, phenylphosphini Len (2-methyl-4-indenyl) (3,5- [Dimethylphenylmethyl] -2-phenoxy) titanium dichloride, phenylphosphinylene (2-methyl-4-indenyl) (3-dimethylpentafluorophenylmethyl-5-methyl-2-phenoxy) titanium dichloride, phenylphosphini Len (2-methyl-4-indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, phenylphosphinylene (2-methyl-4-indenyl) (5-methyl-3-trimethylsilyl-2- Phenoxy) titanium dichloride, phenylphosphinylene (2-methyl-4-indenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, phenylphosphinylene (2-methyl-4-indenyl) ) (3-t ert-butyl-5-methoxy-2-phenoxy) titanium dichloride, phenylphosphinylene (2-methyl-4-indenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Methylene (1-phenyl-4-indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (1-phenyl-4-indenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene ( 1-phenyl-4-indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (1-phenyl-4-indenyl) (3,5-di-tert-butyl-2-phenoxy) ) Titanium dichloride, methylene (1-phenyl-4-indenyl) (3,5-di-tert-amyl-2-phenoxy) titanium dichloride, methylene (1-phenyl-4-indenyl) (3,5-bis [dimethyl] Phenylmethyl] -2-phenoxy) titanium dichloride, Len (1-phenyl-4-indenyl) (3-dimethylpentafluorophenylmethyl-5-methyl-2-phenoxy) titanium dichloride, methylene (1-phenyl-4-indenyl) (5-methyl-3-phenyl-2) -Phenoxy) titanium dichloride, methylene (1-phenyl-4-indenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, methylene (1-phenyl-4-indenyl) (3-tert-butyldimethylsilyl) -5-methyl-2-phenoxy) titanium dichloride, methylene (1-phenyl-4-indenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (1-phenyl-4-indenyl) (3-tert-butyl -5-chloro-2-phenoxy) titanium dichloride,

Dimethylsilylene (1-phenyl-4-indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (1-phenyl-4-indenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, Dimethylsilylene (1-phenyl-4-indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (1-phenyl-4-indenyl) (3,5-di-tert-butyl -2-phenoxy) titanium dichloride, dimethylsilylene (1-phenyl-4-indenyl) (3,5-di-tert-amyl-2-phenoxy) titanium dichloride, dimethylsilylene (1-phenyl-4-indenyl) (3 , 5-Bis [dimethylphenylmethyl Ru] -2-phenoxy) titanium dichloride, dimethylsilylene (1-phenyl-4-indenyl) (3-dimethylpentafluorophenylmethyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (1-phenyl-4-) Indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (1-phenyl-4-indenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (1- Phenyl-4-indenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (1-phenyl-4-indenyl) (3-tert-butyl-5-methoxy-2-) Phenoxy ) Titanium dichloride, dimethylsilylene (1-phenyl-4-indenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diethylsilylene (1-phenyl-4-indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diethylsilylene (1-phenyl-4-indenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, Diethylsilylene (1-phenyl-4-indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (1-phenyl-4-indenyl) (3,5-di-tert-butyl -2-phenoxy) titanium dichloride, diethylsilylene (1-phenyl-4-indenyl) (3,5-di-tert-amyl-2-phenoxy) titanium dichloride, diethylsilylene (1-phenyl-4-indenyl) (3 , 5-Bis [dimethylphenylmethyl Ru] -2-phenoxy) titanium dichloride, diethylsilylene (1-phenyl-4-indenyl) (3-dimethylpentafluorophenylmethyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (1-phenyl-4-) Indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, diethylsilylene (1-phenyl-4-indenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, diethylsilylene (1- Phenyl-4-indenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (1-phenyl-4-indenyl) (3-tert-butyl-5-methoxy-2-) Phenoxy ) Titanium dichloride, diethylsilylene (1-phenyl-4-indenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Phenylphosphinylene (1-phenyl-4-indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, phenylphosphinylene (1-phenyl-4-indenyl) (3-tert-butyl-2-phenoxy) ) Titanium dichloride, phenylphosphinylene (1-phenyl-4-indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, phenylphosphinylene (1-phenyl-4-indenyl) (3 , 5-Di-tert-butyl-2-phenoxy) titanium dichloride, phenylphosphinylene (1-phenyl-4-indenyl) (3,5-di-tert-amyl-2-phenoxy) titanium dichloride, phenylphosphini Len (1-phenyl-4-indenyl (3,5-bis [dimethylphenylmethyl] -2-phenoxy) titanium dichloride, phenylphosphinylene (1-phenyl-4-indenyl) (3-dimethylpentafluorophenylmethyl-5-methyl-2-phenoxy) titanium Dichloride, phenylphosphinylene (1-phenyl-4-indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, phenylphosphinylene (1-phenyl-4-indenyl) (5-methyl-3 -Trimethylsilyl-2-phenoxy) titanium dichloride, phenylphosphinylene (1-phenyl-4-indenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, phenylphosphinylene (1- Phenyl-4 -Indenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, phenylphosphinylene (1-phenyl-4-indenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium Dichloride,

Methylene (2-phenyl-4-indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (2-phenyl-4-indenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene ( 2-phenyl-4-indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (2-phenyl-4-indenyl) (3,5-di-tert-butyl-2-phenoxy) ) Titanium dichloride, methylene (2-phenyl-4-indenyl) (3,5-di-tert-amyl-2-phenoxy) titanium dichloride, methylene (2-phenyl-4-indenyl) (3,5-bis [dimethyl] Phenylmethyl] -2-phenoxy) titanium dichloride, Len (2-phenyl-4-indenyl) (3-dimethylpentafluorophenylmethyl-5-methyl-2-phenoxy) titanium dichloride, methylene (2-phenyl-4-indenyl) (5-methyl-3-phenyl-2) -Phenoxy) titanium dichloride, methylene (2-phenyl-4-indenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, methylene (2-phenyl-4-indenyl) (3-tert-butyldimethylsilyl) -5-methyl-2-phenoxy) titanium dichloride, methylene (2-phenyl-4-indenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (2-phenyl-4-indenyl) (3-tert-butyl -5-chloro-2-phenoxy) titanium dichloride,

Dimethylsilylene (2-phenyl-4-indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (2-phenyl-4-indenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, Dimethylsilylene (2-phenyl-4-indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (2-phenyl-4-indenyl) (3,5-di-tert-butyl -2-phenoxy) titanium dichloride, dimethylsilylene (2-phenyl-4-indenyl) (3,5-di-tert-amyl-2-phenoxy) titanium dichloride, dimethylsilylene (2-phenyl-4-indenyl) (3 , 5-Bis [dimethylphenylmethyl Ru] -2-phenoxy) titanium dichloride, dimethylsilylene (2-phenyl-4-indenyl) (3-dimethylpentafluorophenylmethyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (2-phenyl-4-) Indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (2-phenyl-4-indenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (2- Phenyl-4-indenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (2-phenyl-4-indenyl) (3-tert-butyl-5-methoxy-2-) Phenoxy ) Titanium dichloride, dimethylsilylene (2-phenyl-4-indenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diethylsilylene (2-phenyl-4-indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diethylsilylene (2-phenyl-4-indenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, Diethylsilylene (2-phenyl-4-indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (2-phenyl-4-indenyl) (3,5-di-tert-butyl -2-phenoxy) titanium dichloride, diethylsilylene (2-phenyl-4-indenyl) (3,5-di-tert-amyl-2-phenoxy) titanium dichloride, diethylsilylene (2-phenyl-4-indenyl) (3 , 5-Bis [dimethylphenylmethyl Ru] -2-phenoxy) titanium dichloride, diethylsilylene (2-phenyl-4-indenyl) (3-dimethylpentafluorophenylmethyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (2-phenyl-4-) Indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, diethylsilylene (2-phenyl-4-indenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, diethylsilylene (2- Phenyl-4-indenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (2-phenyl-4-indenyl) (3-tert-butyl-5-methoxy-2-) Phenoxy ) Titanium dichloride, diethylsilylene (2-phenyl-4-indenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Phenylphosphinylene (2-phenyl-4-indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, phenylphosphinylene (2-phenyl-4-indenyl) (3-tert-butyl-2-phenoxy) ) Titanium dichloride, phenylphosphinylene (2-phenyl-4-indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, phenylphosphinylene (2-phenyl-4-indenyl) (3 , 5-Di-tert-butyl-2-phenoxy) titanium dichloride, phenylphosphinylene (2-phenyl-4-indenyl) (3,5-di-tert-amyl-2-phenoxy) titanium dichloride, phenylphosphini Len (2-phenyl-4-indenyl (3,5-bis [dimethylphenylmethyl] -2-phenoxy) titanium dichloride, phenylphosphinylene (2-phenyl-4-indenyl) (3-dimethylpentafluorophenylmethyl-5-methyl-2-phenoxy) titanium Dichloride, phenylphosphinylene (2-phenyl-4-indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, phenylphosphinylene (2-phenyl-4-indenyl) (5-methyl-3 -Trimethylsilyl-2-phenoxy) titanium dichloride, phenylphosphinylene (2-phenyl-4-indenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, phenylphosphinylene (2- Phenyl-4 -Indenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, phenylphosphinylene (2-phenyl-4-indenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium Dichloride,

Methylene (1,2-dimethyl-4-indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (1,2-dimethyl-4-indenyl) (3-tert-butyl-2-phenoxy) titanium Dichloride, methylene (1,2-dimethyl-4-indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (1,2-dimethyl-4-indenyl) (3,5-di- -Tert-butyl-2-phenoxy) titanium dichloride, methylene (1,2-dimethyl-4-indenyl) (3,5-di-tert-amyl-2-phenoxy) titanium dichloride, methylene (1,2-dimethyl- 4-indenyl) (3,5-bis [dimethylphenylmethyl] -2-phenoxy) thio Nium dichloride, methylene (1,2-dimethyl-4-indenyl) (3-dimethylpentafluorophenylmethyl-5-methyl-2-phenoxy) titanium dichloride, methylene (1,2-dimethyl-4-indenyl) (5- Methyl-3-phenyl-2-phenoxy) titanium dichloride, methylene (1,2-dimethyl-4-indenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, methylene (1,2-dimethyl-4 -Indenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (1,2-dimethyl-4-indenyl) (3-tert-butyl-5-methoxy-2-phenoxy) Titanium dichloride, methylene (1,2- Dimethyl-4-indenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Dimethylsilylene (1,2-dimethyl-4-indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (1,2-dimethyl-4-indenyl) (3-tert-butyl-2-phenoxy) ) Titanium dichloride, dimethylsilylene (1,2-dimethyl-4-indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (1,2-dimethyl-4-indenyl) (3 , 5-Di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (1,2-dimethyl-4-indenyl) (3,5-di-tert-amyl-2-phenoxy) titanium dichloride, dimethylsilylene ( 1,2-dimethyl-4-indenyl) (3,5- [Dimethylphenylmethyl] -2-phenoxy) titanium dichloride, dimethylsilylene (1,2-dimethyl-4-indenyl) (3-dimethylpentafluorophenylmethyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene ( 1,2-dimethyl-4-indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (1,2-dimethyl-4-indenyl) (5-methyl-3-trimethylsilyl-2- Phenoxy) titanium dichloride, dimethylsilylene (1,2-dimethyl-4-indenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (1,2-dimethyl-4-indenyl) ) (3-t ert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (1,2-dimethyl-4-indenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diethylsilylene (1,2-dimethyl-4-indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diethylsilylene (1,2-dimethyl-4-indenyl) (3-tert-butyl-2-phenoxy) ) Titanium dichloride, diethylsilylene (1,2-dimethyl-4-indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (1,2-dimethyl-4-indenyl) (3 , 5-Di-tert-butyl-2-phenoxy) titanium dichloride, diethylsilylene (1,2-dimethyl-4-indenyl) (3,5-di-tert-amyl-2-phenoxy) titanium dichloride, diethylsilylene ( 1,2-dimethyl-4-indenyl) (3,5- [Dimethylphenylmethyl] -2-phenoxy) titanium dichloride, diethylsilylene (1,2-dimethyl-4-indenyl) (3-dimethylpentafluorophenylmethyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene ( 1,2-dimethyl-4-indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, diethylsilylene (1,2-dimethyl-4-indenyl) (5-methyl-3-trimethylsilyl-2- Phenoxy) titanium dichloride, diethylsilylene (1,2-dimethyl-4-indenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (1,2-dimethyl-4-indenyl) ) (3-t ert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diethylsilylene (1,2-dimethyl-4-indenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Phenylphosphinylene (1,2-dimethyl-4-indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, phenylphosphinylene (1,2-dimethyl-4-indenyl) (3-tert-butyl) -2-phenoxy) titanium dichloride, phenylphosphinylene (1,2-dimethyl-4-indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, phenylphosphinylene (1,2- Dimethyl-4-indenyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, phenylphosphinylene (1,2-dimethyl-4-indenyl) (3,5-di-tert-amyl- 2-phenoxy) titanium dichloride, phenylphosphinylene (1,2- Methyl-4-indenyl) (3,5-bis [dimethylphenylmethyl] -2-phenoxy) titanium dichloride, phenylphosphinylene (1,2-dimethyl-4-indenyl) (3-dimethylpentafluorophenylmethyl-5 -Methyl-2-phenoxy) titanium dichloride, phenylphosphinylene (1,2-dimethyl-4-indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, phenylphosphinylene (1,2- Dimethyl-4-indenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, phenylphosphinylene (1,2-dimethyl-4-indenyl) (3-tert-butyldimethylsilyl-5-methyl-) 2-phenoxy) titanium dichloride, Phenylphosphinylene (1,2-dimethyl-4-indenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, phenylphosphinylene (1,2-dimethyl-4-indenyl) (3 -Tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Methylene (1,3-dimethyl-4-indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (1,3-dimethyl-4-indenyl) (3-tert-butyl-2-phenoxy) titanium Dichloride, methylene (1,3-dimethyl-4-indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (1,3-dimethyl-4-indenyl) (3,5-di- -Tert-butyl-2-phenoxy) titanium dichloride, methylene (1,3-dimethyl-4-indenyl) (3,5-di-tert-amyl-2-phenoxy) titanium dichloride, methylene (1,3-dimethyl- 4-indenyl) (3,5-bis [dimethylphenylmethyl] -2-phenoxy) thio Nium dichloride, methylene (1,3-dimethyl-4-indenyl) (3-dimethylpentafluorophenylmethyl-5-methyl-2-phenoxy) titanium dichloride, methylene (1,3-dimethyl-4-indenyl) (5- Methyl-3-phenyl-2-phenoxy) titanium dichloride, methylene (1,3-dimethyl-4-indenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, methylene (1,3-dimethyl-4 -Indenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (1,3-dimethyl-4-indenyl) (3-tert-butyl-5-methoxy-2-phenoxy) Titanium dichloride, methylene (1,3- Dimethyl-4-indenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Dimethylsilylene (1,3-dimethyl-4-indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (1,3-dimethyl-4-indenyl) (3-tert-butyl-2-phenoxy) ) Titanium dichloride, dimethylsilylene (1,3-dimethyl-4-indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (1,3-dimethyl-4-indenyl) (3) , 5-Di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (1,3-dimethyl-4-indenyl) (3,5-di-tert-amyl-2-phenoxy) titanium dichloride, dimethylsilylene ( 1,3-dimethyl-4-indenyl) (3,5- [Dimethylphenylmethyl] -2-phenoxy) titanium dichloride, dimethylsilylene (1,3-dimethyl-4-indenyl) (3-dimethylpentafluorophenylmethyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene ( 1,3-dimethyl-4-indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (1,3-dimethyl-4-indenyl) (5-methyl-3-trimethylsilyl-2- Phenoxy) titanium dichloride, dimethylsilylene (1,3-dimethyl-4-indenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (1,3-dimethyl-4-indenyl) ) (3-t ert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (1,3-dimethyl-4-indenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diethylsilylene (1,3-dimethyl-4-indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diethylsilylene (1,3-dimethyl-4-indenyl) (3-tert-butyl-2-phenoxy) ) Titanium dichloride, diethylsilylene (1,3-dimethyl-4-indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (1,3-dimethyl-4-indenyl) (3) , 5-Di-tert-butyl-2-phenoxy) titanium dichloride, diethylsilylene (1,3-dimethyl-4-indenyl) (3,5-di-tert-amyl-2-phenoxy) titanium dichloride, diethylsilylene ( 1,3-dimethyl-4-indenyl) (3,5- [Dimethylphenylmethyl] -2-phenoxy) titanium dichloride, diethylsilylene (1,3-dimethyl-4-indenyl) (3-dimethylpentafluorophenylmethyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene ( 1,3-dimethyl-4-indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, diethylsilylene (1,3-dimethyl-4-indenyl) (5-methyl-3-trimethylsilyl-2- Phenoxy) titanium dichloride, diethylsilylene (1,3-dimethyl-4-indenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (1,3-dimethyl-4-indenyl) ) (3-t ert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diethylsilylene (1,3-dimethyl-4-indenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Phenylphosphinylene (1,3-dimethyl-4-indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, phenylphosphinylene (1,3-dimethyl-4-indenyl) (3-tert-butyl) -2-phenoxy) titanium dichloride, phenylphosphinylene (1,3-dimethyl-4-indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, phenylphosphinylene (1,3- Dimethyl-4-indenyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, phenylphosphinylene (1,3-dimethyl-4-indenyl) (3,5-di-tert-amyl- 2-phenoxy) titanium dichloride, phenylphosphinylene (1,3- Methyl-4-indenyl) (3,5-bis [dimethylphenylmethyl] -2-phenoxy) titanium dichloride, phenylphosphinylene (1,3-dimethyl-4-indenyl) (3-dimethylpentafluorophenylmethyl-5 -Methyl-2-phenoxy) titanium dichloride, phenylphosphinylene (1,3-dimethyl-4-indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, phenylphosphinylene (1,3- Dimethyl-4-indenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, phenylphosphinylene (1,3-dimethyl-4-indenyl) (3-tert-butyldimethylsilyl-5-methyl-) 2-phenoxy) titanium dichloride, Phenylphosphinylene (1,3-dimethyl-4-indenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, phenylphosphinylene (1,3-dimethyl-4-indenyl) (3 -Tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Methylene (1,2,3-trimethyl-4-indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (1,2,3-trimethyl-4-indenyl) (3-tert-butyl-2 -Phenoxy) titanium dichloride, methylene (1,2,3-trimethyl-4-indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (1,2,3-trimethyl-4- Indenyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, methylene (1,2,3-trimethyl-4-indenyl) (3,5-di-tert-amyl-2-phenoxy) titanium Dichloride, methylene (1,2,3-trimethyl-4-indenyl) (3,5-bis [dimethyl Phenylmethyl] -2-phenoxy) titanium dichloride, methylene (1,2,3-trimethyl-4-indenyl) (3-dimethylpentafluorophenylmethyl-5-methyl-2-phenoxy) titanium dichloride, methylene (1,2 , 3-trimethyl-4-indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, methylene (1,2,3-trimethyl-4-indenyl) (5-methyl-3-trimethylsilyl-2- Phenoxy) titanium dichloride, methylene (1,2,3-trimethyl-4-indenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (1,2,3-trimethyl-4 -Indenyl) (3-tert-butyl-5-methyl) Toxi-2-phenoxy) titanium dichloride, methylene (1,2,3-trimethyl-4-indenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Dimethylsilylene (1,2,3-trimethyl-4-indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (1,2,3-trimethyl-4-indenyl) (3-tert-butyl -2-phenoxy) titanium dichloride, dimethylsilylene (1,2,3-trimethyl-4-indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (1,2,3- Trimethyl-4-indenyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (1,2,3-trimethyl-4-indenyl) (3,5-di-tert-amyl- 2-phenoxy) titanium dichloride, dimethylsilylene (1,2,3-to Methyl-4-indenyl) (3,5-bis [dimethylphenylmethyl] -2-phenoxy) titanium dichloride, dimethylsilylene (1,2,3-trimethyl-4-indenyl) (3-dimethylpentafluorophenylmethyl-5 -Methyl-2-phenoxy) titanium dichloride, dimethylsilylene (1,2,3-trimethyl-4-indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (1,2,3- Trimethyl-4-indenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (1,2,3-trimethyl-4-indenyl) (3-tert-butyldimethylsilyl-5-methyl-) 2-phenoxy) titanium dichloride, Dimethylsilylene (1,2,3-trimethyl-4-indenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (1,2,3-trimethyl-4-indenyl) (3 -Tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diethylsilylene (1,2,3-trimethyl-4-indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diethylsilylene (1,2,3-trimethyl-4-indenyl) (3-tert-butyl -2-phenoxy) titanium dichloride, diethylsilylene (1,2,3-trimethyl-4-indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (1,2,3- Trimethyl-4-indenyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, diethylsilylene (1,2,3-trimethyl-4-indenyl) (3,5-di-tert-amyl- 2-phenoxy) titanium dichloride, diethylsilylene (1,2,3-to Methyl-4-indenyl) (3,5-bis [dimethylphenylmethyl] -2-phenoxy) titanium dichloride, diethylsilylene (1,2,3-trimethyl-4-indenyl) (3-dimethylpentafluorophenylmethyl-5 -Methyl-2-phenoxy) titanium dichloride, diethylsilylene (1,2,3-trimethyl-4-indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, diethylsilylene (1,2,3- Trimethyl-4-indenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, diethylsilylene (1,2,3-trimethyl-4-indenyl) (3-tert-butyldimethylsilyl-5-methyl-) 2-phenoxy) titanium dichloride, Diethylsilylene (1,2,3-trimethyl-4-indenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diethylsilylene (1,2,3-trimethyl-4-indenyl) (3 -Tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Phenylphosphinylene (1,2,3-trimethyl-4-indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, phenylphosphinylene (1,2,3-trimethyl-4-indenyl) (3 -Tert-butyl-2-phenoxy) titanium dichloride, phenylphosphinylene (1,2,3-trimethyl-4-indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, phenylphosphini Len (1,2,3-trimethyl-4-indenyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, phenylphosphinylene (1,2,3-trimethyl-4-indenyl) ( 3,5-di-tert-amyl-2-phenoxy) titanium dichloride, fluorine Nylphosphinylene (1,2,3-trimethyl-4-indenyl) (3,5-bis [dimethylphenylmethyl] -2-phenoxy) titanium dichloride, phenylphosphinylene (1,2,3-trimethyl-4 -Indenyl) (3-dimethylpentafluorophenylmethyl-5-methyl-2-phenoxy) titanium dichloride, phenylphosphinylene (1,2,3-trimethyl-4-indenyl) (5-methyl-3-phenyl-2) -Phenoxy) titanium dichloride, phenylphosphinylene (1,2,3-trimethyl-4-indenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, phenylphosphinylene (1,2,3- Trimethyl-4-indenyl) (3-tert-butyldimethyl) Silyl-5-methyl-2-phenoxy) titanium dichloride, phenylphosphinylene (1,2,3-trimethyl-4-indenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, phenylphosphine Finylene (1,2,3-trimethyl-4-indenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Methylene (4-benzindenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (4-benzindenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (4-benzindenyl) (3-tert -Butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (4-benzindenyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, methylene (4-benzindenyl) (3,5-di -Tert-amyl-2-phenoxy) titanium dichloride, methylene (4-benzindenyl) (3,5-bis [dimethylphenylmethyl] -2-phenoxy) titanium dichloride, methylene (4-benzindenyl) (3-dimethylpen Fluorophenylmethyl-5-methyl-2-phenoxy) titanium dichloride, methylene (4-benzindenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, methylene (4-benzindenyl) (5-methyl-3- Trimethylsilyl-2-phenoxy) titanium dichloride, methylene (4-benzindenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (4-benzindenyl) (3-tert-butyl-5- Methoxy-2-phenoxy) titanium dichloride, methylene (4-benzindenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Dimethylsilylene (4-benzindenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (4-benzindenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (4-benzindenyl) ( 3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (4-benzindenyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (4-benzindenyl) ( 3,5-di-tert-amyl-2-phenoxy) titanium dichloride, dimethylsilylene (4-benzindenyl) (3,5-bis [dimethylphenylmethyl] -2-phenoxy) titanium dichloride, di Tylsilylene (4-benzindenyl) (3-dimethylpentafluorophenylmethyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (4-benzindenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethyl Silylene (4-benzindenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (4-benzindenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethyl Silylene (4-benzindenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (4-benzindenyl) (3-tert-butyl -5-chloro-2-phenoxy) titanium dichloride,

Diethylsilylene (4-benzindenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diethylsilylene (4-benzindenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diethylsilylene (4-benzindenyl) ( 3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (4-benzindenyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, diethylsilylene (4-benzindenyl) ( 3,5-di-tert-amyl-2-phenoxy) titanium dichloride, diethylsilylene (4-benzindenyl) (3,5-bis [dimethylphenylmethyl] -2-phenoxy) titanium dichloride, di Tylsilylene (4-benzindenyl) (3-dimethylpentafluorophenylmethyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (4-benzindenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, diethyl Silylene (4-benzindenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, diethylsilylene (4-benzindenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diethyl Silylene (4-benzindenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diethylsilylene (4-benzindenyl) (3-tert-butyl -5-chloro-2-phenoxy) titanium dichloride,

Phenylphosphinylene (4-benzindenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, phenylphosphinylene (4-benzindenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, phenylphosphinylene (4-benzindenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, phenylphosphinylene (4-benzindenyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, Phenylphosphinylene (4-benzindenyl) (3,5-di-tert-amyl-2-phenoxy) titanium dichloride, phenylphosphinylene (4-benzindenyl) (3,5-bis [dimethylphenylmethyl] -2- F Noxy) titanium dichloride, phenylphosphinylene (4-benzindenyl) (3-dimethylpentafluorophenylmethyl-5-methyl-2-phenoxy) titanium dichloride, phenylphosphinylene (4-benzindenyl) (5-methyl-3- Phenyl-2-phenoxy) titanium dichloride, phenylphosphinylene (4-benzindenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, phenylphosphinylene (4-benzindenyl) (3-tert-butyldimethyl) Silyl-5-methyl-2-phenoxy) titanium dichloride, phenylphosphinylene (4-benzindenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichlori , Phenylphosphinylene (4-benzindenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, etc., compounds in which the titanium of these compounds is changed to zirconium or hafnium, chloride bromide, methyl , Benzyl, methoxide, phenoxide, dimethylamide, a compound changed to diethylamide, a compound changed from a phenoxy group to a phenylthio group, and the like.

（式中、Ｘ^３，Ｘ^４はそれぞれ独立にモノアニオン性配位子を表す。Ｍ，Ｘ^１，Ｘ^２はそれぞれ前記と同じ意味を示す。）
で示される遷移金属化合物（以下化合物〔３〕と称する。）を反応させることにより得ることができる。 Compound [1] is obtained by reacting compound [2] with a base, if necessary, and then reacting with formula (3)

(In the formula, X ³ and X ⁴ each independently represent a monoanionic ligand. M, X ¹ and X ² each have the same meaning as described above.)
It can obtain by making the transition metal compound shown below (it is hereafter called compound [3]) react.

Substituents ^R 1 ^{to R 10} in the compound [2], the A and Ln include those similar to the substituents ^R 1 ^{to R 10,} A and Ln in the compound (1), the number of carbon atoms in the substituent group ^{R 13} Specific examples of the alkyl group having 1 to 20 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, tert -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 Group, nonadecyl group, and n-eicosyl group are exemplified, preferably methyl group, ethyl group, isopropyl group, tert-butyl group and the like are mentioned. It is.

Specific examples of the alkenyl group having 2 to 20 carbon atoms in the substituent R ¹³ include an allyl group, a crotyl group, a methallyl group, a cinnamyl group, a prenyl group, and an α-methylallyl group, preferably an allyl group. It is done.

In the substituent R ¹³ , 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, 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 2,3,4-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 Group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group , A naphthyl group, an anthracenyl group and the like, and a phenyl group is preferable.

Specific examples of the aralkyl group having 7 to 20 carbon atoms in the substituent R ¹³ include benzyl group, diphenylmethyl group, triphenylmethyl group, naphthylmethyl group, anthracenylmethyl group, dimethylphenylmethyl group, p- A methoxybenzyl group etc. are illustrated, Preferably a benzyl group is mentioned.

Carbonization of a silyl group substituted with a hydrocarbon group in the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² Examples of the hydrogen group include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, n-hexyl, and cyclohexyl. Examples thereof include alkyl groups having 1 to 10 carbon atoms such as a 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 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 compound [2] include (2-hydroxy-3,5-dimethylphenyl) (4-indenyl) dimethylsilane, (2-hydroxy-3-tert-butylphenyl) (4-indenyl) dimethylsilane, ( 2-hydroxy-3-tert-butyl-5-methylphenyl) (4-indenyl) dimethylsilane, (2-hydroxy-3,5-di-tert-butylphenyl) (4-indenyl) dimethylsilane, (2- Hydroxy-3,5-di-tert-amylphenyl) (4-indenyl) dimethylsilane, (2-hydroxy-3,5-bis [dimethylphenylmethyl] dimethylphenylphenyl) (4-indenyl) dimethylsilane, (2 -Hydroxy-3-dimethylpentafluorophenyl-5-methylphenyl) (4-yne Nyl) dimethylsilane, (2-hydroxy-3-phenyl-5-methylphenyl) (4-indenyl) dimethylsilane, (2-hydroxy-3-trimethylsilyl-5-methylphenyl) (4-indenyl) dimethylsilane, ( 2-hydroxy-3-tert-butyldimethylsilyl-5-methylphenyl) (4-indenyl) dimethylsilane, (2-hydroxy-3-tert-butyl-5-methoxyphenyl) (4-indenyl) dimethylsilane, ( 2-Hydroxy-3-tert-butyl-5-chlorophenyl) (4-indenyl) dimethylsilane

(2-hydroxy-3,5-dimethylphenyl) (4-indenyl) diethylsilane, (2-hydroxy-3-tert-butylphenyl) (4-indenyl) diethylsilane, (2-hydroxy-3-tert-butyl) -5-methylphenyl) (4-indenyl) diethylsilane, (2-hydroxy-3,5-di-tert-butylphenyl) (4-indenyl) diethylsilane, (2-hydroxy-3,5-di-tert) -Amylphenyl) (4-indenyl) diethylsilane, (2-hydroxy-3,5-bis [dimethylphenylmethyl] dimethylphenylphenyl) (4-indenyl) diethylsilane, (2-hydroxy-3-dimethylpentafluorophenyl) -5-methylphenyl) (4-indenyl) diethylsilane, (2-hydride) Xyl-3-phenyl-5-methylphenyl) (4-indenyl) diethylsilane, (2-hydroxy-3-trimethylsilyl-5-methylphenyl) (4-indenyl) diethylsilane, (2-hydroxy-3-tert- Butyldimethylsilyl-5-methylphenyl) (4-indenyl) diethylsilane, (2-hydroxy-3-tert-butyl-5-methoxyphenyl) (4-indenyl) diethylsilane, (2-hydroxy-3-tert- Butyl-5-chlorophenyl) (4-indenyl) diethylsilane

(2-methoxy-3,5-dimethylphenyl) (4-indenyl) dimethylsilane, (2-methoxy-3-tert-butylphenyl) (4-indenyl) dimethylsilane, (2-methoxy-3-tert-butyl) -5-methylphenyl) (4-indenyl) dimethylsilane, (2-methoxy-3,5-di-tert-butylphenyl) (4-indenyl) dimethylsilane, (2-methoxy-3,5-di-tert) -Amylphenyl) (4-indenyl) dimethylsilane, (2-methoxy-3,5-bis [dimethylphenylmethyl] dimethylphenylphenyl) (4-indenyl) dimethylsilane, (2-methoxy-3-dimethylpentafluorophenyl) -5-methylphenyl) (4-indenyl) dimethylsilane, (2-methoxy-3-phenyl) 5-methylphenyl) (4-indenyl) dimethylsilane, (2-methoxy-3-trimethylsilyl-5-methylphenyl) (4-indenyl) dimethylsilane, (2-methoxy-3-tert-butyldimethylsilyl-) 5-methylphenyl) (4-indenyl) dimethylsilane, (2-methoxy-3-tert-butyl-5-methoxyphenyl) (4-indenyl) dimethylsilane, (2-methoxy-3-tert-butyl-5- Chlorophenyl) (4-indenyl) dimethylsilane

(2-methoxy-3,5-dimethylphenyl) (4-indenyl) diethylsilane, (2-methoxy-3-tert-butylphenyl) (4-indenyl) diethylsilane, (2-methoxy-3-tert-butyl) -5-methylphenyl) (4-indenyl) diethylsilane, (2-methoxy-3,5-di-tert-butylphenyl) (4-indenyl) diethylsilane, (2-methoxy-3,5-di-tert) -Amylphenyl) (4-indenyl) diethylsilane, (2-methoxy-3,5-bis [dimethylphenylmethyl] dimethylphenylphenyl) (4-indenyl) diethylsilane, (2-methoxy-3-dimethylpentafluorophenyl) -5-methylphenyl) (4-indenyl) diethylsilane, (2-methoxy-3-phenyl) 5-methylphenyl) (4-indenyl) diethylsilane, (2-methoxy-3-trimethylsilyl-5-methylphenyl) (4-indenyl) diethylsilane, (2-methoxy-3-tert-butyldimethylsilyl-) 5-methylphenyl) (4-indenyl) diethylsilane, (2-methoxy-3-tert-butyl-5-methoxyphenyl) (4-indenyl) diethylsilane, (2-methoxy-3-tert-butyl-5- Chlorophenyl) (4-indenyl) diethylsilane

(2-allyloxy-3,5-dimethylphenyl) (4-indenyl) dimethylsilane, (2-allyloxy-3-tert-butylphenyl) (4-indenyl) dimethylsilane, (2-allyloxy-3-tert-butyl) -5-methylphenyl) (4-indenyl) dimethylsilane, (2-allyloxy-3,5-di-tert-butylphenyl) (4-indenyl) dimethylsilane, (2-allyloxy-3,5-di-tert) -Amylphenyl) (4-indenyl) dimethylsilane, (2-allyloxy-3,5-bis [dimethylphenylmethyl] dimethylphenylphenyl) (4-indenyl) dimethylsilane, (2-allyloxy-3-dimethylpentafluorophenyl) -5-methylphenyl) (4-indenyl) dimethylsilane, Xyl-3-phenyl-5-methylphenyl) (4-indenyl) dimethylsilane, (2-allyloxy-3-trimethylsilyl-5-methylphenyl) (4-indenyl) dimethylsilane, (2-allyloxy-3-tert- Butyldimethylsilyl-5-methylphenyl) (4-indenyl) dimethylsilane, (2-allyloxy-3-tert-butyl-5-methoxyphenyl) (4-indenyl) dimethylsilane, (2-allyloxy-3-tert- Butyl-5-chlorophenyl) (4-indenyl) dimethylsilane

(2-allyloxy-3,5-dimethylphenyl) (4-indenyl) diethylsilane, (2-allyloxy-3-tert-butylphenyl) (4-indenyl) diethylsilane, (2-allyloxy-3-tert-butyl) -5-methylphenyl) (4-indenyl) diethylsilane, (2-allyloxy-3,5-di-tert-butylphenyl) (4-indenyl) diethylsilane, (2-allyloxy-3,5-di-tert) -Amylphenyl) (4-indenyl) diethylsilane, (2-allyloxy-3,5-bis [dimethylphenylmethyl] dimethylphenylphenyl) (4-indenyl) diethylsilane, (2-allyloxy-3-dimethylpentafluorophenyl) -5-methylphenyl) (4-indenyl) diethylsilane, Xyl-3-phenyl-5-methylphenyl) (4-indenyl) diethylsilane, (2-allyloxy-3-trimethylsilyl-5-methylphenyl) (4-indenyl) diethylsilane, (2-allyloxy-3-tert- Butyldimethylsilyl-5-methylphenyl) (4-indenyl) diethylsilane, (2-allyloxy-3-tert-butyl-5-methoxyphenyl) (4-indenyl) diethylsilane, (2-allyloxy-3-tert- Butyl-5-chlorophenyl) (4-indenyl) diethylsilane

(2-trimethylsiloxy-3,5-dimethylphenyl) (4-indenyl) dimethylsilane, (2-trimethylsiloxy-3-tert-butylphenyl) (4-indenyl) dimethylsilane, (2-trimethylsiloxy-3- tert-butyl-5-methylphenyl) (4-indenyl) dimethylsilane, (2-trimethylsiloxy-3,5-di-tert-butylphenyl) (4-indenyl) dimethylsilane, (2-trimethylsiloxy-3, 5-di-tert-amylphenyl) (4-indenyl) dimethylsilane, (2-trimethylsiloxy-3,5-bis [dimethylphenylmethyl] dimethylphenylphenyl) (4-indenyl) dimethylsilane, (2-trimethylsiloxy) -3-Dimethylpentafluorophenyl-5-methyl Phenyl) (4-indenyl) dimethylsilane, (2-trimethylsiloxy-3-phenyl-5-methylphenyl) (4-indenyl) dimethylsilane, (2-trimethylsiloxy-3-trimethylsilyl-5-methylphenyl) (4 -Indenyl) dimethylsilane, (2-trimethylsiloxy-3-tert-butyldimethylsilyl-5-methylphenyl) (4-indenyl) dimethylsilane, (2-trimethylsiloxy-3-tert-butyl-5-methoxyphenyl) (4-indenyl) dimethylsilane, (2-trimethylsiloxy-3-tert-butyl-5-chlorophenyl) (4-indenyl) dimethylsilane

(2-trimethylsiloxy-3,5-dimethylphenyl) (4-indenyl) diethylsilane, (2-trimethylsiloxy-3-tert-butylphenyl) (4-indenyl) diethylsilane, (2-trimethylsiloxy-3- tert-butyl-5-methylphenyl) (4-indenyl) diethylsilane, (2-trimethylsiloxy-3,5-di-tert-butylphenyl) (4-indenyl) diethylsilane, (2-trimethylsiloxy-3, 5-di-tert-amylphenyl) (4-indenyl) diethylsilane, (2-trimethylsiloxy-3,5-bis [dimethylphenylmethyl] dimethylphenylphenyl) (4-indenyl) diethylsilane, (2-trimethylsiloxy) -3-Dimethylpentafluorophenyl-5-methyl Phenyl) (4-indenyl) diethylsilane, (2-trimethylsiloxy-3-phenyl-5-methylphenyl) (4-indenyl) diethylsilane, (2-trimethylsiloxy-3-trimethylsilyl-5-methylphenyl) (4 -Indenyl) diethylsilane, (2-trimethylsiloxy-3-tert-butyldimethylsilyl-5-methylphenyl) (4-indenyl) diethylsilane, (2-trimethylsiloxy-3-tert-butyl-5-methoxyphenyl) (4-indenyl) diethylsilane, (2-trimethylsiloxy-3-tert-butyl-5-chlorophenyl) (4-indenyl) diethylsilane

(2-Benzyloxy-3,5-dimethylphenyl) (4-indenyl) dimethylsilane, (2-benzyloxy-3-tert-butylphenyl) (4-indenyl) dimethylsilane, (2-benzyloxy-3-tert-butyl) -5-methylphenyl) (4-indenyl) dimethylsilane, (2-benzyloxy-3,5-di-tert-butylphenyl) (4-indenyl) dimethylsilane, (2-benzyloxy-3,5-di-tert) -Amylphenyl) (4-indenyl) dimethylsilane, (2-benzyloxy-3,5-bis [dimethylphenylmethyl] dimethylphenylphenyl) (4-indenyl) dimethylsilane, (2-benzyloxy-3-dimethylpentafluorophenyl) -5-methylphenyl) (4-indenyl) dimethylsila , (2-benzyloxy-3-phenyl-5-methylphenyl) (4-indenyl) dimethylsilane, (2-benzyloxy-3-trimethylsilyl-5-methylphenyl) (4-indenyl) dimethylsilane, (2-benzyloxy- 3-tert-butyldimethylsilyl-5-methylphenyl) (4-indenyl) dimethylsilane, (2-benzyloxy-3-tert-butyl-5-methoxyphenyl) (4-indenyl) dimethylsilane, (2-benzyloxy- 3-tert-butyl-5-chlorophenyl) (4-indenyl) dimethylsilane

(2-Benzyloxy-3,5-dimethylphenyl) (4-indenyl) diethylsilane, (2-benzyloxy-3-tert-butylphenyl) (4-indenyl) diethylsilane, (2-benzyloxy-3-tert-butyl) -5-methylphenyl) (4-indenyl) diethylsilane, (2-benzyloxy-3,5-di-tert-butylphenyl) (4-indenyl) diethylsilane, (2-benzyloxy-3,5-di-tert) -Amylphenyl) (4-indenyl) diethylsilane, (2-benzyloxy-3,5-bis [dimethylphenylmethyl] dimethylphenylphenyl) (4-indenyl) diethylsilane, (2-benzyloxy-3-dimethylpentafluorophenyl) -5-methylphenyl) (4-indenyl) diethylsila , (2-benzyloxy-3-phenyl-5-methylphenyl) (4-indenyl) diethylsilane, (2-benzyloxy-3-trimethylsilyl-5-methylphenyl) (4-indenyl) diethylsilane, (2-benzyloxy- 3-tert-butyldimethylsilyl-5-methylphenyl) (4-indenyl) diethylsilane, (2-benzyloxy-3-tert-butyl-5-methoxyphenyl) (4-indenyl) diethylsilane, (2-benzyloxy- 3-tert-butyl-5-chlorophenyl) (4-indenyl) diethylsilane

(2-phenoxy-3,5-dimethylphenyl) (4-indenyl) dimethylsilane, (2-phenoxy-3-tert-butylphenyl) (4-indenyl) dimethylsilane, (2-phenoxy-3-tert-butyl) -5-methylphenyl) (4-indenyl) dimethylsilane, (2-phenoxy-3,5-di-tert-butylphenyl) (4-indenyl) dimethylsilane, (2-phenoxy-3,5-di-tert) -Amylphenyl) (4-indenyl) dimethylsilane, (2-phenoxy-3,5-bis [dimethylphenylmethyl] dimethylphenylphenyl) (4-indenyl) dimethylsilane, (2-phenoxy-3-dimethylpentafluorophenyl) -5-methylphenyl) (4-indenyl) dimethylsilane, (2-phenyl Xyl-3-phenyl-5-methylphenyl) (4-indenyl) dimethylsilane, (2-phenoxy-3-trimethylsilyl-5-methylphenyl) (4-indenyl) dimethylsilane, (2-phenoxy-3-tert- Butyldimethylsilyl-5-methylphenyl) (4-indenyl) dimethylsilane, (2-phenoxy-3-tert-butyl-5-methoxyphenyl) (4-indenyl) dimethylsilane, (2-phenoxy-3-tert- Butyl-5-chlorophenyl) (4-indenyl) dimethylsilane

(2-phenoxy-3,5-dimethylphenyl) (4-indenyl) diethylsilane, (2-phenoxy-3-tert-butylphenyl) (4-indenyl) diethylsilane, (2-phenoxy-3-tert-butyl) -5-methylphenyl) (4-indenyl) diethylsilane, (2-phenoxy-3,5-di-tert-butylphenyl) (4-indenyl) diethylsilane, (2-phenoxy-3,5-di-tert) -Amylphenyl) (4-indenyl) diethylsilane, (2-phenoxy-3,5-bis [dimethylphenylmethyl] dimethylphenylphenyl) (4-indenyl) diethylsilane, (2-phenoxy-3-dimethylpentafluorophenyl) -5-methylphenyl) (4-indenyl) diethylsilane, (2-phenyl Xyl-3-phenyl-5-methylphenyl) (4-indenyl) diethylsilane, (2-phenoxy-3-trimethylsilyl-5-methylphenyl) (4-indenyl) diethylsilane, (2-phenoxy-3-tert- Butyldimethylsilyl-5-methylphenyl) (4-indenyl) diethylsilane, (2-phenoxy-3-tert-butyl-5-methoxyphenyl) (4-indenyl) diethylsilane, (2-phenoxy-3-tert- Butyl-5-chlorophenyl) (4-indenyl) diethylsilane and the like, and dimethylsilane and diethylsilane of these compounds are methane, dimethylgermanium, diethylgermanium, dibutylstannane, phenylphosphine, phenylphosphine oxide, phenylborane, sulfi , A compound changed to sulfoxide, (4-indenyl) as (4- [1-methyl-indenyl]), (4- [2-methyl-indenyl]), (4- [1-phenyl-indenyl]), ( 4- [2-phenyl-indenyl]), (4- [1,2-dimethyl-indenyl]), (4- [1,3-dimethyl-indenyl]), (4- [1,2,3-trimethyl) -Indenyl]), a compound changed to (4-benzindenyl), a compound obtained by changing hydroxy, methoxy, allyloxy, benzyloxy, phenoxy, trimethylsiloxy to thio, methylthio, and the like.

In these compounds [2], there may be a plurality of isomers derived from the difference in the position of the substituent of the indenyl skeleton and the position of the double bond. All isomers are included.

Examples of the monoanionic ligand shown as the substituents X ³ and X ⁴ in the compound [3] include those similar to those described above as the substituents X ¹ and X ² in the compound [1].

Examples of the compound [3] include titanium halides such as titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide, tetrakis (dimethylamino) titanium, dichlorobis (dimethylamino) titanium, trichloro (dimethylamino) titanium, tetrakis. Amido titanium such as (diethylamino) titanium, tetraisopropoxy titanium, tetra-n-butoxy titanium, dichlorodiisopropoxy titanium, alkoxy titanium such as trichloroisopropoxy titanium, alkyl titanium such as tetrabenzyl titanium, and titanium of each of the above compounds The compound etc. which changed to zirconium and hafnium are mentioned, The usage-amount is the range of 0.5-3 mol times normally with respect to compound [2], Preferably it is the range of 0.7-1.5 mol times.

Examples of the base include organic alkalis such as organic lithium compounds such as methyl lithium, ethyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, lithium trimethylsilyl acetylide, lithium acetylide, trimethylsilylmethyl lithium, phenyl lithium, and allyl lithium. A metal compound etc. are mentioned, The usage-amount is the range of 0.5-5 mol times normally with respect to compound [2].

An amine compound can also be used together 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, ethylenediamine, and dimethylamine. , Secondary amine compounds such as diethylamine, di-n-propylamine, di-n-butylamine, di-tert-butylamine, di-n-octylamine, di-n-decylamine, pyrrolidine, hexamethyldisilazane, diphenylamine , Trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-decylamine, triphenylamine, N, N-dimethylaniline, N, N, N ′, N′-tetramethylethylenediamine , N- methylpyrrolidine, tertiary amine compounds such as 4-methyl-dimethylaminopyridine and the like. The amount of the amine compound used is usually 10 mol times or less, preferably 0.5 to 10 mol times, more preferably 1 to 3 mol times based on the base.

The above 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, hexamethylphosphoric. Amido solvents such as 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 Preferably, aromatic hydrocarbon solvents such as benzene and toluene, and aliphatic hydrocarbon solvents such as hexane and heptane are used. Each of these solvents may be used alone or in combination of two or more. Used Te, the amount used is generally 1 to 200 times by weight relative to compound (2), preferably in the range of 3 to 50 times by weight.

The above reaction can be usually carried out by adding compound [2] to a solvent, adding a base as necessary, and then adding compound [3].

The reaction temperature is usually in the range of from −100 ° C. to the boiling point of the solvent, preferably from about −80 to 120 ° C.

（式中Ｒ^７〜Ｒ^１０、Ｒ^１３及びＡは前記と同じ意味を示し、Ｘ^５はハロゲン原子を示す。）
をマグネシウム又はアルキルマグネシウムハライド、ジアルキルマグネシウム、アルキルリチウムなどと作用させＸ^５部位をメタル化させた後、式（５）
ＬｎＸ^６Ｘ^７ （５）
（式中Ｌｎは前記と同じ意味を表し、Ｘ^６、Ｘ^７は、それぞれ独立にハロゲン原子、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリールオキシ基、炭素数７〜２０のアラルキルオキシ基、トシル基、メシル基を示す。）
と反応させることにより式（６）

（式中Ｌｎ、Ｘ^６、Ｒ^７〜Ｒ^１０、Ｒ^１３及びＡは前記と同じ意味を示す。）
を形成させ、次いで式（７）

（式中Ｒ^１〜Ｒ^６は前記と同じ意味を示し、Ｒ^１４は炭素原子数１〜２０の炭化水素基で置換されたシリル基を示し、Ｍ^３はリチウム、マグネシウムクロライド、マグネシウムブロマイドを示す。）
と反応させて得られる式（８）

（式中Ｒ^１〜Ｒ^１０、Ｒ^１３、Ｒ^１４、Ａ、Ｌｎは前記と同じ意味を示す。）
を酸で処理することにより製造することができる。 Compound [2] has the formula (4)

(Wherein R ^{7 to} R ¹⁰ , R ¹³ and A represent the same meaning as described above, and X ⁵ represents a halogen atom.)
Is reacted with magnesium or alkylmagnesium halide, dialkylmagnesium, alkyllithium, etc. to metallize the X ⁵ site, and then the formula (5)
LnX ⁶ X ⁷ (5)
(In the formula, Ln represents the same meaning as described above, and X ⁶ and X ⁷ each independently represent a halogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or an alkyl group having 7 to 20 carbon atoms. (Indicates aralkyloxy, tosyl, and mesyl groups.)
By reacting with (6)

(In the formula, Ln, X ⁶ , R ^{7 to} R ¹⁰ , R ¹³ and A have the same meaning as described above.)
And then formula (7)

(Wherein R ^{1 to} R ⁶ represent the same meaning as described above, R ¹⁴ represents a silyl group substituted with a hydrocarbon group having 1 to 20 carbon atoms, and M ³ represents lithium, magnesium chloride or magnesium bromide. .)
(8) obtained by reacting with

(Wherein R ^{1 to} R ¹⁰ , R ¹³ , R ¹⁴ , A and Ln have the same meaning as described above.)
Can be produced by treating with acid.

[Olefin polymerization catalyst]
The olefin polymerization catalyst of the present invention is an olefin polymerization catalyst having the compound [1] as an olefin polymerization catalyst component, and is obtained by contacting the compound [1] with another cocatalyst component. Examples of the olefin polymerization catalyst include olefin polymerization catalysts obtained by contacting the compound [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): Organoaluminum compound (A2) represented by the formula E ¹ _a AlZ _(3-a ): Cyclic aluminoxane (A3) having a structure represented by the formula {—Al (E ² ) —O—} _b : Formula E ³ {—Al (E ³ ) —O—} _c Al (E ³ ) ₂ A linear aluminoxane having the structure (wherein a represents 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 represents a hydrocarbon group having 1 to 20 carbon atoms, and the plurality of E ¹ , the plurality of E ^2, and the plurality of E ³ may be the same or different, and Z is a hydrogen atom or halogen. Represents an atom, and when there are a plurality of Z, the plurality of Z may be the same or different from each other May be.)
Compound (B): One or more boron compounds (B1) selected from the group consisting of the following (B1) to (B3): Boron compound (B2) represented by formula BQ ¹ Q ² Q ³ : Formula G ⁺ ( Boron compound (B3) represented by BQ ¹ Q ² Q ³ Q ⁴ ) ^- : Boron compound represented by formula (L ¹ -H) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- Represents a trivalent boron atom, and Q ¹ , Q ² , Q ³ and Q ⁴ are each independently a halogen atom, hydrocarbon group, halogenated hydrocarbon group, substituted silyl group, alkoxy group or disubstituted Represents an amino group, G ⁺ represents an inorganic or organic cation, and L ¹ represents a neutral Lewis base.)

(A1): As the organoaluminum compound represented by the formula E ¹ _a AlZ _(3-a) , for example, trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum; dimethyl Dialkylaluminum chlorides such as aluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, dihexylaluminum chloride; alkylaluminum dichlorides such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, hexylaluminum dichloride ; Dimethyl aluminum Examples thereof include dialkylaluminum hydrides such as nium hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride, and dihexylaluminum hydride. Trialkylaluminum is preferable, and triethylaluminum or triisobutylaluminum is more preferable.

(A2): a cyclic aluminoxane having a structure represented by the formula {—Al (E ² ) —O—} _b or (A3): a formula E ³ {—Al (E ³ ) —O—} _c Al (E as E ² and E ³ in the linear aluminoxane having a structure represented by ³⁾ _2, for example, a methyl group, an ethyl group, normal propyl group, an isopropyl group, normal butyl group, isobutyl group, normal pentyl group, neopentyl And an alkyl group such as a group. 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 crystallization water, etc. 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, 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, and 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.

In the boron compound represented by (B2): G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ , G ⁺ which 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): Boron compounds represented by the formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ include, for example, ferrocenium tetrakis (pentafluorophenyl) borate and 1,1′-dimethylferrocenium tetrakis (Pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, triphenylmethyltetrakis (pentafluorophenyl) borate, triphenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate, etc. Is 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 Brene. It is a Sted acid, B is a boron atom in a trivalent valence 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, triarylphosphonium, and the like can be mentioned. Examples of (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ include the same ones 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 (penta Fluorophenyl) 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-dimethyl Anilinium 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), usually, (B1): a boron compound represented by the formula BQ ¹ Q ² Q ³ , (B2): a boron represented by the formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ Either a compound or a boron compound represented by the formula (B3): 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 charged into the polymerization reactor in any order, and any two or more catalyst components are contacted in advance. You may throw in something.

As a usage-amount of each catalyst component, the molar ratio of a compound (A) (aluminum atom conversion) / transition metal 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) / transition metal complex (1) is more preferably 0.3 to 500, and further preferably 0.5 to 100. . The molar ratio of compound (B) / transition metal 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 transition metal complex (1) is usually 0.0001 to 5 mmol / liter, preferably 0.001 to 1 mmol / liter. The concentration of A) is usually 0.01 to 500 mmol / liter, preferably 0.1 to 100 mmol / liter, in terms of aluminum atom, and the concentration of compound (B) is usually 0.0001 to 5 mmol. / Liter, preferably 0.001 to 1 mmol / liter.

[Olefin polymer production method]
The method for producing an olefin polymer of the present invention is a method in which an olefin is polymerized in the presence of an olefin polymerization catalyst having the compound [1] as an olefin polymerization catalyst component.

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 combinations 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 solvent, solvent polymerization or slurry polymerization, gas phase polymerization in gaseous monomer, etc. are possible, and either continuous polymerization or batch polymerization is possible.

The polymerization temperature can range from −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 an Example demonstrates this invention in detail, this invention is not limited to these Examples.

<Production of transition metal complex>
The physical properties were measured by the following method.
(1) Proton nuclear magnetic resonance spectrum ( ¹ H-NMR)
Apparatus: EX270 manufactured by JEOL Ltd. or DPX-300 manufactured by Bruker
Sample cell: 5 mmφ tube Measurement solvent: CDCl ₃
Sample concentration: 10 mg / 0.5 mL (CDCl ₃ )
Measurement temperature: room temperature (about 25 ° C)
Measurement parameters: 5 mmφ probe, MENU NON, OBNUC ¹ H, integration number 16 times Pulse angle: 45 degrees Repeat time: ACQTM 3 seconds, PD 4 seconds Internal standard: CDCl ₃ (7.26 ppm)

(2) 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

Example 1
“Synthesis of (4- [1-tert-butyldimethylsilyloxyindanyl]) (2-allyloxy-3-tert-butyl-5-methylphenyl) dimethylsilane”
Under a nitrogen atmosphere, 5.0 g (15.3 mmol) of 4-bromo-1-tert-butyldimethylsiloxyindane was dissolved in 50 mL of dehydrated ether in a 200 mL four-necked flask equipped with a stir bar, followed by cooling to −40 ° C. or lower. did. After adding dropwise 10 mL (16.1 mmol) of a 1.60 M hexane solution of n-BuLi, the mixture was stirred at 0 ° C. for 2 hours. The reaction solution was cooled to −40 ° C. or less (5.9 g of 2-allyloxy-3-tert-butyl-5-methylphenyl) dimethylsilyl chloride (a mixture containing about 16 mmol; synthesized according to JP-A-9-87313). The mixture was slowly warmed to room temperature and stirred overnight. Water was added to the reaction mixture, and after liquid separation, the organic layer was washed with saturated brine, dried over sodium sulfate, and low-boiling substances were distilled off under reduced pressure to obtain a crude product. The obtained crude product was recrystallized from ethanol to obtain 4.55 g of the title compound as a white powder (yield 58.3%).
¹ H-NMR (CDCl ₃ , δ (ppm)): 7.40 (d, J = 6.9 Hz, 1H), 7.40 (d, J = 6.9 Hz, 1H), 7.31 (d, J = 7.3 Hz, 1H), 7.27-7.16 (m, 3H), 5.70-5.58 (m, 1H), 5.24-5.17 (m, 2H), 5. 09-5.05 (m, 1H), 4.05-4.03 (m, 2H), 2.94-2.85 (m, 1H), 2.66-2.56 (m, 1H), 2.38-2.30 (m, 1H), 2.30 (s, 3H), 1.87-1.75 (m, 1H), 1.35 (s, 9H), 0.94 (s, 9H), 0.55 (s, 6H), 0.16 (s, 3H), 0.14 (s, 3H)
MS (EI) m / z 508 (M +), 260, 245, 75, 57

(Example 2)
“Synthesis of (4-indenyl) (2-allyloxy-3-tert-butyl-5-methylphenyl) dimethylsilane”
0.81-g (1.6 mmol) of (4- [1-tert-butyldimethylsilyloxyindanyl]) (2-allyloxy-3-tert-butyl-5-methylphenyl) dimethylsilane obtained in Example 1 and 0.48 g (1.9 mmol) of pyridinium p-toluenesulfonate was dissolved in 8.1 ml of dioxane and stirred at 100 ° C. for 3 hours. The reaction mixture was concentrated with an evaporator, ether and saturated brine were added to the mixture, the organic layer was separated, dried over sodium sulfate, and concentrated again with an evaporator. The resulting crude product was purified by silica gel column chromatography to obtain 0.53 g of the title compound as a white solid (yield 88.0%).
¹ H-NMR (CDCl ₃ , δ (ppm)): 7.42-7.37 (m, 2H), 7.27-7.21 (m, 3H), 6.86 (d, J = 5. 5 Hz, 1H), 6.50 (d, J = 5.5 Hz, 1H), 5.63 (ddt, J = 17.2, 10.6, 4.0 Hz, 1H), 5.16 (ddd, J = 17.2, 3.7, 1.8 Hz, 1H), 5.16 (ddd, J = 10.6, 3.7, 1.8 Hz, 1H), 4.01 (ddd, J = 4.0). , 1.8, 1.8, 2H), 3.26 (s, 2H), 2.32 (s, 3H), 1.55 (s, 1H), 1.34 (s, 9H),. 62 (s, 6H)
MS (EI) m / z 376 (M +), 260, 245, 145

(Example 3)
“Synthesis of (4-indenyl) (3-tert-butyl-5-methyl-2-phenoxy) dimethylsilane”
Under a nitrogen atmosphere, 0.31 g (0.82 mmol) of (4-indenyl) (2-allyloxy-3-tert-butyl-5-methylphenyl) dimethylsilane obtained in Example 2 and 0.019 g of tetrakistriphenylphosphine palladium (0.016 mmol) was dissolved in 8.2 ml of tetrahydrofuran. At room temperature, 0.047 g (1.2 mmol) of sodium borohydride was added in small portions, and then 1N hydrochloric acid was added. The mixture was extracted with ether, dried over sodium sulfate, and concentrated by an evaporator. The resulting mixture was purified by silica gel column chromatography to obtain the title compound as a light yellow solid as a double bond isomer mixture (0.19 g, yield 70.6%).
MS (EI) m / z 336 (M +), 220, 206

Example 4
“Synthesis of dimethylsilylene (4-indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium bis (dimethylamide)”
Under a nitrogen atmosphere, a solution of 0.18 g (0.53 mmol) of (4-indenyl) (3-tert-butyl-5-methyl-2-phenoxy) dimethylsilane (isomer mixture) obtained in Example 3 in a 3 ml toluene solution. A solution of 0.12 g (0.53 mmol) of tetrakis (dimethylamido) titanium in 2.3 ml of toluene was added dropwise. The mixed solution was heated and stirred at 100 ° C. for 3 hours, and then the low boiling point compound was distilled off under reduced pressure to obtain 0.25 g of a red oily substance containing the title compound as a main component.
¹ H-NMR (CDCl ₃ , δ (ppm)): 7.54 (d, J = 8.4 Hz, 1H), 7.33 (d, J = 6.2 Hz, 1H), 7.25 (s, 1H), 7.11 (s, 1H), 7.00 (dd, J = 8.4, 6.2 Hz, 1H), 6.74-6.73 (m, 1H), 6.71-6. 69 (m, 1H), 6.42-6.41 (m, 1H), 3.27 (s, 6H), 2.52 (s, 6H), 2.32 (s, 3H), 1.27 (S, 9H), 0.64 (s, 3H), 0.58 (s, 3H)

(Example 5)
“Synthesis of Dimethylsilylene (4-indenyl) (3-tert-Butyl-5-methyl-2-phenoxy) Titanium Monochlorodimethylamide”
Under a nitrogen atmosphere, the red oily substance obtained in Example 4 was dissolved in 3.7 ml of pentane, and 0.67 ml (5.3 mmol) of trimethylsilyl chloride was added at room temperature. The mixed solution was reacted under reflux conditions for 1 hour, and the precipitated solid was collected by filtration and dried to obtain 0.079 g of the title compound as a brown powder (yield 32.5%).
¹ H-NMR (CDCl ₃ , δ (ppm)): 7.68 (d, J = 8.6 Hz, 1H), 7.42 (d, J = 6.4 Hz, 1H), 7.28 (s, 1H), 7.16 (s, 1H), 7.11 (dd, J = 8.6, 6.4 Hz, 1H), 6.81-6.79 (m, 1H), 6.74-6. 73 (m, 1H), 6.60-6.59 (m, 1H), 2.77 (s, 6H), 2.35 (s, 3H), 1.32 (s, 9H), 0.69 (S, 3H), 0.67 (s, 3H)
MS (EI) m / z 461 (M +), 418, 382, 197, 46

(Example 6)
“Synthesis of Dimethylsilylene (4-indenyl) (3-tert-Butyl-5-methyl-2-phenoxy) Titanium Dichloride”
The filtrate obtained in Example 5 was concentrated, and 5 ml of toluene and 0.67 ml (5.3 mmol) of trimethylsilyl chloride were added. The mixed solution was heated to 60 ° C., stirred for 3 hours, and then cooled to room temperature. Hexane was added and the precipitated solid was filtered and dried to obtain 0.067 g of the title compound as a brown powder [yield 28.0%: dimethylsilylene (4-indenyl) (3-tert-butyl-5-methyl- Based on 2-phenoxy) titanium bis (dimethylamide)].
¹ H-NMR (CDCl ₃ , δ (ppm)): 7.87 (d, J = 8.4 Hz, 1H), 7.50 (d, J = 6.6 Hz, 1H), 7.41 (dd, J = 8.4, 6.6 Hz, 1H), 7.24-7.21 (m, 2H), 7.16 (s, 1H), 7.06-7.04 (m, 1H), 7. 01-7.00 (m, 1H), 2.34 (s, 3H), 1.38 (s, 9H), 0.76 (s, 3H), 0.69 (s, 3H)
MS (EI) m / z 452, 454 (M +), 416, 418, 401, 350, 157, 128

(Example 7)
“Synthesis of (4-indenyl) (3-tert-butyl-5-methyl-2-phenoxy) diethylsilane”
Under a nitrogen atmosphere, 5.0 g (15.3 mmol) of 4-bromo-1-tert-butyldimethylsiloxyindane was dissolved in 160 mL of dehydrated ether in a 500 mL four-necked flask equipped with a stir bar, and then cooled to −40 ° C. or lower. did. After dropping 32.8 mL (52.5 mmol) of a 1.60 M hexane solution of n-BuLi, the mixture was stirred at 0 ° C. for 2 hours. The reaction solution was cooled to −40 ° C. or lower, 15.7 g (100 mmol) of diethyldichlorosilane was added, and the temperature was slowly raised to room temperature, followed by stirring overnight. Low boiling point substances were distilled off under reduced pressure, 100 mL of dehydrated hexane was added, and insoluble matters were removed by Celite filtration. The filtrate was concentrated to obtain a crude product containing (4- [1-tert-butyldimethylsilyloxyindanyl]) diethylchlorosilane. The obtained crude product was diluted with DMF (50 mL) without purification, and 12.2 g (50 mmol) of 2-bromo-6-tert-butyl-4-methylphenol and 6.8 g (100 mmol) of imidazole in 130 mL of DMF. At 0 ° C. The mixture was stirred at room temperature for 12 hours, water and ether were added, and the extracted organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated to obtain an oily compound. 26.5 g of a pale yellow oil mainly composed of (4- [1-tert-butyldimethylsilyloxyindanyl]) (2-bromo-6-tert-butyl-4-methylphenoxy) diethylsilane was purified by silica gel column purification. Obtained. 26. A pale yellow oil mainly composed of (4- [1-tert-butyldimethylsilyloxyindanyl]) (2-bromo-6-tert-butyl-4-methylphenoxy) diethylsilane obtained by the above reaction 5 g was dissolved in 150 mL of THF, 30 mL of a 1.62 M hexane solution of n-BuLi was added dropwise at −78 ° C., and 1.5 hours later, water was added to treat excess n-BuLi. Hexane was added, the organic layer was extracted, washed with saturated brine, dried over sodium sulfate, and concentrated to give (4- [1-tert-butyldimethylsilyloxyindanyl]) (2-hydroxy-3-tert -Butyl-5-methylphenyl) diethylsilane 23.1 g was obtained. 8. (4- [1-tert-butyldimethylsilyloxyindanyl]) (2-hydroxy-3-tert-butyl-5-methylphenyl) diethylsilane (21 g) obtained by the above reaction and pyridinium-p-toluenesulfonate Dioxane (500 mL) was added to a 1 L four-necked flask containing 04 g, and the mixture was stirred at 100 ° C. for 1 hour. After the reaction, ethyl acetate and saturated brine were added, and the organic layer was extracted, dried over sodium sulfate, and concentrated. The obtained oil was purified by silica gel column chromatography (hexane / ethyl acetate = 20/1) to obtain 16.0 g of oil mainly composed of the title compound.
MS (EI) m / z 364 (M +), 248

(Example 8)
“Synthesis of Diethylsilylene (4-indenyl) (3-tert-Butyl-5-methyl-2-phenoxy) Titanium Dichloride”
Under a nitrogen atmosphere, tetrakis (dimethylamide) was added to a solution of 2.37 g (6.50 mmol) of (4-indenyl) (3-tert-butyl-5-methyl-2-phenoxy) diethylsilane obtained in Example 7 in 65 ml of toluene. 3.57 g (15.93 mmol) of titanium was added dropwise. The mixed solution was heated and stirred at 100 ° C. for 5 hours, then cooled to room temperature, and 8.25 ml (65.0 mmol) of trimethylsilyl chloride was added. The mixed solution was heated to 60 ° C., stirred for 4 hours, and then cooled to room temperature. After the reaction solution was dark, hexane was added and the precipitated solid was filtered off. The filtrate was concentrated, cold pentane was added and the precipitated powder was filtered and dried to give 0.483 g of the title compound as a dark red powder. Rate 15.4%].
¹ H-NMR (CDCl ₃ , δ (ppm)): 7.84 (d, J = 7.8 Hz, 1H), 7.50-7.41 (m, 2H), 7.21 (s, 1H) 7.18 (s, 1H), 7.09-7.07 (m, 2H), 6.94-6.92 (m, 1H), 2.35 (s, 3H), 1.38 (s , 9H), 1.35 to 0.86 (m, 10H)
MS (EI) m / z 480, 482 (M +), 444

Example 9
“Synthesis of [4- (2-methylindenyl)] (3-tert-butyl-5-methyl-2-phenoxy) diethylsilane”
Under a nitrogen atmosphere, 4.80 g (14.1 mmol) of 4-bromo-1-tert-butyldimethylsiloxy-2-methylindane was dissolved in 48 mL of dehydrated ether in a 300 mL four-necked flask equipped with a stir bar, followed by −40 Cooled below ℃. After adding 11.9 mL (19.7 mmol) of a 1.65 M hexane solution of n-BuLi dropwise, the mixture was warmed to room temperature and stirred for 2 hours. The reaction solution was cooled to −40 ° C. or lower, and 5.7 g (17.6 mmol) of diethylsilyl chloride (2-allyloxy-3-tert-butyl-5-methylphenyl) was added, and the mixture was slowly warmed to room temperature and stirred overnight. . Water was added to the reaction mixture, and after liquid separation, the organic layer was washed with saturated brine, dried over sodium sulfate, and the low boiling point product was distilled off under reduced pressure to obtain 9.10 g of a crude product. MS (EI) m / z 550 (M +), 288 7.74 g of the resulting crude product was diluted with 230 mL of dioxane without purification, and 3.53 g (14.1 mmol) of pyridinium-p-toluenesulfonate at room temperature. And stirred at 100 ° C. for 5 hours. After the reaction, ethyl acetate and saturated brine were added, and the organic layer was extracted, dried over sodium sulfate, and concentrated to obtain 9.38 g of a crude product. MS (EI) m / z 418 (M +), 333,288 Without purification, the resulting crude product was diluted with 97 mL of THF under a nitrogen atmosphere and 1.12 g (0.96 mmol) of tetrakistriphenylphosphine palladium, Sodium borohydride 0.55 g (14.5 mmol) was added, and the mixture was stirred at room temperature for 3 hours. Thereafter, 1N hydrochloric acid was added, and the mixture was extracted with ether, dried over sodium sulfate, and concentrated by an evaporator. The obtained mixture was purified by silica gel column chromatography to obtain a mixture containing the title compound as a main component as a pale yellow solid (3.10 g).
MS (EI) m / z 378 (M +), 349, 321, 248

(Example 10)
"Synthesis of diethylsilylene [4- (2-methylindenyl)] (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride"
Under a nitrogen atmosphere, [4- (2-methylindenyl)] (3-tert-butyl-5-methyl-2-phenoxy) diethylsilane 2.60 g (pure content 4.0 mmol) of toluene obtained in Example 9 Tetrakis (dimethylamido) titanium (1.79 g, 8.0 mmol) was added dropwise to the 40 ml solution. The mixed solution was heated and stirred at 100 ° C. for 5 hours, and then cooled to room temperature, and 5.08 ml (40.0 mmol) of trimethylsilyl chloride was added. The mixed solution was heated to 60 ° C., stirred for 4 hours, and then cooled to room temperature. After darkening the reaction mixture, hexane was added and the precipitated solid was filtered off. The filtrate was concentrated, cold pentane was added and the precipitated powder was filtered and dried to give 0.67 g of the title compound as a brown powder [Yield 33.8%].
¹ H-NMR (CDCl ₃ , δ (ppm)): 7.77 (d, J = 7.0 Hz, 1H), 7.41-7.39 (m, 2H), 7.23 (s, 1H) 7.20 (s, 1H), 6.91 (s, 2H), 6.67 (s, 1H), 2.49 (s, 3H), 2.37 (s, 3H), 1.39 ( s, 9H), 1.34 to 0.83 (m, 10H)
MS (EI) m / z 494, 496 (M +), 458, 460

Example 11
“Synthesis of [4- (2-phenylindenyl)] (3-tert-butyl-5-methyl-2-phenoxy) diethylsilane”
In a 300 mL four-necked flask equipped with a stir bar under a nitrogen atmosphere, 5.66 g (14.1 mmol) of 4-bromo-1-tert-butyldimethylsiloxy-2-phenylindane was dissolved in 48 mL of dehydrated ether, followed by −40 Cooled below ℃. After adding 13.6 mL (22.5 mmol) of a 1.65M hexane solution of n-BuLi dropwise, the mixture was warmed to room temperature and stirred for 2 hours. The reaction solution was cooled to −40 ° C. or lower, and 5.7 g (17.6 mmol) of diethylsilyl chloride (2-allyloxy-3-tert-butyl-5-methylphenyl) was added, and the mixture was slowly warmed to room temperature and stirred overnight. . Water was added to the reaction mixture, and after liquid separation, the organic layer was washed with saturated brine, dried over sodium sulfate, and the low boiling point product was distilled off under reduced pressure to obtain 9.10 g of a crude product. The obtained crude product (10.54 g) was diluted with 86.1 mL of dioxane without purification, and 2.83 g (11.2 mmol) of pyridinium-p-toluenesulfonate was added at room temperature, followed by stirring at 100 ° C. for 8 hours. . After the reaction, ethyl acetate and saturated brine were added, and the organic layer was extracted, dried over sodium sulfate, and concentrated to obtain 6.04 g of a crude product. MS (EI) m / z 480 (M +), 451, 288 Without purification, the resulting crude product was diluted with 100 mL of THF under a nitrogen atmosphere, and 1.45 g (1.25 mmol) of tetrakistriphenylphosphine palladium, Sodium borohydride 0.71g (18.8mmol) was added, and it stirred at room temperature for 3 hours. Thereafter, 1N hydrochloric acid was added, and the mixture was extracted with ether, dried over sodium sulfate, and concentrated by an evaporator. The resulting mixture was purified by silica gel column chromatography to obtain a mixture containing the title compound as a main component (1.88 g).
MS (EI) m / z 440 (M +), 411, 355, 248, 219

Example 12
“Synthesis of Diethylsilylene [4- (2-Phenylindenyl)] (3-tert-butyl-5-methyl-2-phenoxy) titanium Dichloride”
1.70 g (pure content 2.4 mmol) toluene of [4- (2-phenylindenyl)] (3-tert-butyl-5-methyl-2-phenoxy) diethylsilane obtained in Example 11 under nitrogen atmosphere Tetrakis (dimethylamido) titanium 1.18 g (5.3 mmol) was added dropwise to the 24 ml solution. The mixed solution was heated and stirred at 100 ° C. for 5 hours, then cooled to room temperature, and 3.05 ml (24.0 mmol) of trimethylsilyl chloride was added. The mixed solution was heated to 60 ° C., stirred for 5 hours, and then cooled to room temperature. After the reaction liquid was dark, hexane was added and the precipitated solid was filtered off. The filtrate was concentrated, cold pentane was added and the precipitated powder was filtered and dried to give 0.31 g of the title compound as a brown powder [Yield 23.1%].
¹ H-NMR (CDCl ₃ , δ (ppm)): 7.90-7.84 (m, 1H), 7.71 (d, J = 5.7 Hzm, 2H), 7.45-7.36 ( m, 6H), 7.28 (s, 1H), 7.20 (s, 1H), 7.17 (s, 1H), 2.40 (s, 3H), 1.28 (s, 9H), 1.45-0.84 (m, 10H)
MS (EI) m / z 556, 558 (M +), 520, 522

<Manufacture of olefin polymer>

The transition metal complex obtained in the above Example was used as a catalyst component for olefin polymerization, and olefin polymerization was performed under the following polymerization conditions using Symyx PPR (48 series autoclave).

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

(Example 13)
Under nitrogen, 5.0 mL of toluene was charged in an autoclave and stabilized at 40 ° C., and then propylene was pressurized to 0.20 MPa and stabilized. Here, 40 μL of TIBA in hexane (manufactured by Kanto Chemical Co., Inc., TIBA concentration 1.0 mol / L), dimethylanilinium tetrakis (pentafluorophenyl) borate 0.30 μmol, and dimethylsilylene (4-indenyl) (3-tert- Butyl-5-methyl-2-phenoxy) titanium dichloride (0.10 μmol) was added and polymerized for 20 minutes. As a result of the polymerization, 2.5 × 10 ⁶ g of a polymer having a molecular weight (Mw) = 24,000 and a molecular weight distribution (Mw / Mn) = 1.6 was produced per 1 mol of the catalyst per hour.

(Example 14)
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. Here, 40 μL of TIBA hexane solution (manufactured by Kanto Chemical Co., Inc., TIBA concentration 1.0 mol / L), trityltetrakis (pentafluorophenyl) borate 0.30 μmol, and dimethylsilylene (4-indenyl) (3-tert-butyl- 0.10 μmol of 5-methyl-2-phenoxy) titanium dichloride was added and polymerized for 20 minutes. As a result of the polymerization, 5.5 × 10 ⁶ g of polymer was produced per hour per 1 mol of the catalyst.

(Example 15)
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. Here, 40 μL of TIBA hexane solution (manufactured by Kanto Chemical Co., Inc., TIBA concentration 1.0 mol / L), trityltetrakis (pentafluorophenyl) borate 0.30 μmol, and dimethylsilylene (4-indenyl) (3-tert-butyl- 0.10 μmol of 5-methyl-2-phenoxy) titanium dichloride was added and polymerized for 1.5 minutes. As a result of the polymerization, a polymer having a molecular weight (Mw) = 156,800, a molecular weight distribution (Mw / Mn) = 1.8, and a 1-hexene unit content (SCB) = 14 in the copolymer was converted to 1 hour per 1 mol of the catalyst. 131.1 × 10 ⁶ g per unit was produced.

(Example 16)
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. Here, 40 μL of TIBA hexane solution (manufactured by Kanto Chemical Co., Inc., TIBA concentration 1.0 mol / L), dimethylanilinium tetrakis (pentafluorophenyl) borate 0.30 μmol, and diethylsilylene (4-indenyl) (3-tert- (Butyl-5-methyl-2-phenoxy) titanium dichloride (0.10 μmol) was added and polymerized for 5 minutes. As a result of the polymerization, a polymer having a molecular weight (Mw) = 301,400, a molecular weight distribution (Mw / Mn) = 1.7, and a 1-hexene unit content (SCB) = 16 in the copolymer per 1 mol of the catalyst is 1 hour. 43.3 × 10 ⁶ g was produced.

Claims (8)

Formula (I)

(In the formula, M represents a group 4 transition metal atom in the periodic table of elements, A represents a group 16 atom in the periodic table of elements, and X ¹ and X ² are each independently mono Represents an anionic ligand, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are the same or different and are a hydrogen atom, halogen atom, carbon An alkyl group having 1 to 20 atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and a hydrocarbon group having 1 to 20 carbon atoms. Substituted by a substituted silyl 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 hydrocarbon group having 1 to 20 carbon atoms Represents an amino group formed.
Here, in R ^{1 to} R ⁶ and R ^{7 to} R ¹⁰ , an alkyl group, an aryl group, an aralkyl group, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group, an aryloxy group, an aralkyloxy group, or a hydrocarbon group is May be substituted with a halogen atom.
In R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ , the groups adjacent to each other are bonded to each other to form a ring. It may be.
Ln represents a divalent crosslinking group.
(The divalent bridging group is R ¹¹ R ¹² C, R ¹¹ R ¹² Si, R ¹¹ R ¹² Ge, R ¹¹ R ¹² Sn, R ¹¹ B, R ¹¹ P, R ¹¹ P═O, SO ₂ or S In the formula, R ¹¹ and R ¹² are the same or different and are 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, and a carbon atom. This represents a silyl group substituted with an alkenyl group having 2 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms, and R ¹¹ and R ¹² may be bonded to form a ring.
A transition metal complex represented by The transition metal complex according to claim 1, wherein Ln in the transition metal complex represented by the formula (1) according to claim 1 is R ¹¹ R ¹² Si. The transition metal complex according to claim 1 or 2, wherein A in the transition metal complex represented by the formula (1) according to claim 1 is an oxygen atom. Formula (2)

(In the formula, Ln, A, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ represent the same meaning as described above, and R ¹³ represents a hydrogen atom. , An alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a hydrocarbon having 1 to 20 carbon atoms Represents a substituted silyl group, but does not include a substituent having a cyclopentadiene skeleton, and R ¹³ and R ¹⁰ may be bonded to each other to form a ring, and the position of the double bond of cyclopentadiene is arbitrary; Or it may be a mixture.)
A substituted indenyl compound represented by: The substituted indenyl compound according to claim 4, wherein R ¹³ in the substituted indenyl compound represented by the formula (2) according to claim 4 is hydrogen, an allyl group or a trimethylsilyl group. A catalyst component for olefin polymerization comprising the transition metal complex according to any one of claims 1 to 3. An olefin polymerization catalyst obtained by contacting the catalyst component for olefin polymerization according to claim 6 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 Al (E ³ ) ₂ (wherein a satisfies 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 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, 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, L ¹ represents a neutral Lewis base.) A method for producing an olefin polymer, wherein the olefin is polymerized using the olefin polymerization catalyst according to claim 7.