JP2011084508A - Transition metal complex - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transition metal complex useful as a polymerization catalyst for an olefin polymer such as an ethylene/α-olefin copolymer having a high copolymerization ratio of a structural unit derived from an α-olefin. <P>SOLUTION: The transition metal complex is represented by formula [1] (wherein: M is a group 4 transition metal atom in the periodic table of the elements; A is a group 16 atom in the periodic table of the elements; and J is a group 14 atom in the periodic table of the elements) and the olefin polymerization catalyst is prepared from the transition metal complex. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a transition metal complex useful for an olefin polymerization catalyst.

  Olefin polymers are used in many fields as general-purpose resins. The olefin polymer may be required to have excellent mechanical properties such as rigidity and impact strength while maintaining practical moldability. As one of such olefin polymers, for example, an olefin polymer obtained by copolymerizing ethylene and an α-olefin such as 1-hexene in the presence of a polymerization catalyst (olefin polymerization catalyst) is known. As a polymerization catalyst for giving such an olefin polymer, Patent Document 1 discloses diethylsilylene (cyclopenta [1,2-b: 4,3-b ′] dithiophen-7-yl) (3-tert-butyl-5-methyl). -2-phenoxy) titanium dichloride and diethylsilylene (2,5-dimethylcyclopenta [1,2-b: 4,3-b ′] dithiophen-7-yl) (3-tert-butyl-5-methyl-2 Transition metal complexes having a ligand having a cyclopenta [1,2-b: 4,3-b ′] dithiophen-7-yl group, such as -phenoxy) titanium dichloride have been proposed, and from such transition metal complexes According to the prepared olefin polymerization catalyst, it is disclosed that a high molecular weight ethylene copolymer can be obtained.

JP 2004-238387 A

  However, in the olefin polymerization catalyst disclosed in Patent Document 1, when an olefin polymer having a high copolymerization ratio of structural units derived from an α-olefin is to be obtained, the α-olefin can be polymerized with respect to the polymerizability of ethylene. Since the polymerizability is low, the amount of α-olefin used relative to the amount of ethylene used in the raw material monomer used in the production of the olefin polymer must be used in a larger excess than the amount used calculated from the copolymerization ratio. There is a problem.

［式中、Ｍは元素周期律表の第４族の遷移金属原子を表し、Ａは元素周期律表の第１６族の原子を表し、Ｊは元素周期律表の第１４族の原子を表す。Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、Ｘ^１及びＸ^２はそれぞれ独立に、水素原子、ハロゲン原子、
ハロゲン原子を置換基として有していてもよい炭素原子数１〜２０のアルキル基、
ハロゲン原子を置換基として有していてもよい炭素原子数７〜２０のアラルキル基、
ハロゲン原子を置換基として有していてもよい炭素原子数６〜２０のアリール基、
−Ｓｉ（Ｒ^１２）_３（３つのＲ^１２はそれぞれ独立に、水素原子、炭化水素基又はハロゲン化炭化水素基を表し、３つのＲ^１２にある炭素原子数の合計が１〜２０である。）で示される置換シリル基、
−Ｎ（Ｒ^１３）_２（２つのＲ^１３はそれぞれ独立に、炭化水素基又はハロゲン化炭化水素基を表し、２つのＲ^１３にある炭素原子数の合計が２〜２０である。）で示される２置換アミノ基、
ハロゲン原子を置換基として有していてもよい炭素原子数１〜２０のアルコキシ基、
ハロゲン原子を置換基として有していてもよい炭素原子数７〜２０のアラルキルオキシ基又は
ハロゲン原子を置換基として有していてもよい炭素原子数６〜２０のアリールオキシ基
を表し、
Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４のうち、隣接した２つの炭素原子に結合する基同士は結合して、それらが結合している炭素原子とともに環を形成していてもよく、Ｒ^７及びＲ^８は結合して、それらが結合している炭素原子とともに環を形成していてもよく、Ｒ^９及びＲ^１０は結合して、それらが結合している炭素原子とともに環を形成していてもよく、Ｒ^５及びＲ^６は結合して、Ｊととともに環を形成していてもよい。］
で示される遷移金属錯体に係るものである。かかる遷移金属錯体から調製されるオレフィン重合用触媒によれば、エチレンの使用量に対するα−オレフィンの使用量を大過剰に用いなくとも、α−オレフィンから誘導される構造単位の共重合比が高いオレフィン重合体を得ることができる。 As a result of intensive studies to solve the above problems, the present inventors have reached the present invention.
That is, the present invention provides the following formula [1]

[In the formula, M represents a group 4 transition metal atom in the periodic table, A represents a group 16 atom in the periodic table, and J represents a group 14 atom in the periodic table.] . R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , X ¹ and X ² are each independently a hydrogen atom, a halogen atom,
An alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
An aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
An aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent;
—Si (R ¹² ) ₃ (three R ^{12 s} each independently represent a hydrogen atom, a hydrocarbon group, or a halogenated hydrocarbon group, and the total number of carbon atoms in the three R ^{12 s} is 1-20. Substituted silyl groups represented by
—N (R ¹³ ) ₂ (two R ¹³ each independently represents a hydrocarbon group or a halogenated hydrocarbon group, and the total number of carbon atoms in the two R ¹³ is 2 to 20). A disubstituted amino group,
An alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent;
An aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent or an aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent;
Of R ¹ , R ² , R ³ and R ⁴ , groups bonded to two adjacent carbon atoms may be bonded to each other to form a ring together with the carbon atoms to which they are bonded, and R ⁷ And R ⁸ may be bonded to form a ring with the carbon atom to which they are bonded, and R ⁹ and R ¹⁰ are bonded to form a ring with the carbon atom to which they are bonded. R ⁵ and R ⁶ may be bonded to form a ring with J. ]
It concerns the transition metal complex shown by. According to the catalyst for olefin polymerization prepared from such a transition metal complex, the copolymerization ratio of structural units derived from α-olefin is high without using a large excess of the amount of α-olefin used relative to the amount of ethylene used. An olefin polymer can be obtained.

［式中、Ａ、Ｊ、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９及びＲ^１０は前記式［１］と同義である。
Ｒ^１１は、−Ｓｉ（Ｒ^１４）_３（３つのＲ^１４はそれぞれ独立に、炭化水素基又はハロゲン化炭化水素基を表し、３つのＲ^１４にある炭素原子数の合計が３〜２０である。）で示される三置換シリル基又は炭素原子数１〜２０の有機基を表す。］
で示される置換シクロペンタジエン化合物及び塩基を反応させる工程と、
前記塩基と反応させた前記置換シクロペンタジエン化合物及び
下記式［３］

（式中、Ｍ、Ｘ^１及びＸ^２は前記式［１］と同義であり、Ｘ^３及びＸ^４はそれぞれ独立に、水素原子、ハロゲン原子、
ハロゲン原子を置換基として有していてもよい炭素原子数１〜２０のアルキル基、
ハロゲン原子を置換基として有していてもよい炭素原子数１〜２０のアルコキシ基、
ハロゲン原子を置換基として有していてもよい炭素原子数６〜２０のアリール基、
ハロゲン原子を置換基として有していてもよい炭素原子数６〜２０のアリールオキシ基、
ハロゲン原子を置換基として有していてもよい炭素原子数７〜２０のアラルキル基、
ハロゲン原子を置換基として有していてもよい炭素原子数７〜２０のアラルキルオキシ基、
−Ｓｉ（Ｒ^１２）_３（３つのＲ^１２はそれぞれ独立に、水素原子、炭化水素基またはハロゲン化炭化水素基を表し、３つのＲ^１２にある炭素原子数の合計が１〜２０である。）で示される置換シリル基、
又は−Ｎ（Ｒ^１３）_２（２つのＲ^１３はそれぞれ独立に炭化水素基またはハロゲン化炭化水素基を表し、２つのＲ^１３にある炭素原子数の合計が２〜２０である。）で示される２置換アミノ基を表し、ｎは０又は１を表す。）
で示される遷移金属化合物を反応させる工程と、
を有する製造方法により得ることができる。 Such transition metal complexes are for example
Following formula [2]

[Wherein, A, J, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ have the same meanings as the formula [1].
R ¹¹ represents —Si (R ¹⁴ ) ₃ (three R ¹⁴ each independently represents a hydrocarbon group or a halogenated hydrocarbon group, and the total number of carbon atoms in the three R ¹⁴ is 3 to 20). .) Represents a trisubstituted silyl group or an organic group having 1 to 20 carbon atoms. ]
A step of reacting a substituted cyclopentadiene compound and a base represented by the formula:
The substituted cyclopentadiene compound reacted with the base and the following formula [3]

(In the formula, M, X ¹ and X ² have the same meanings as those in the formula [1], and X ³ and X ⁴ each independently represent a hydrogen atom, a halogen atom,
An alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
An alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent;
An aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent;
An aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent;
An aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
An aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent;
—Si (R ¹² ) ₃ (three R ^{12 s} each independently represent a hydrogen atom, a hydrocarbon group, or a halogenated hydrocarbon group, and the total number of carbon atoms in the three R ^{12 s} is 1-20. Substituted silyl groups represented by
Or -N (R ¹³ ) ₂ (two R ¹³ each independently represents a hydrocarbon group or a halogenated hydrocarbon group, and the total number of carbon atoms in the two R ¹³ is 2 to 20). And n represents 0 or 1. )
A step of reacting a transition metal compound represented by:
It can obtain by the manufacturing method which has this.

Further, the present invention provides an olefin polymerization catalyst prepared from the transition metal complex represented by the formula [1], preferably contacting the transition metal complex with the following compound (A) and / or the following compound (B). The olefin polymerization catalyst obtained by the above is provided.
Compound (A): One or more aluminum compounds selected from the group consisting of the following (A1), (A2) and (A3) (A1): an organoaluminum compound represented by the formula E ¹ _a AlZ _3-a ( A2): cyclic aluminoxane (A3) having a structure represented by the formula {—Al (E ² ) —O—} _b : Formula E ³ {—Al (E ³ ) —O—} _c Table represented by AlE 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 Even if it is.)
Compound (B): One or more boron compounds (B1) selected from the group consisting of the following (B1), (B2) and (B3): Boron compound (B2) represented by the formula BQ ¹ Q ² Q ³ : Boron compound represented by formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- (B3): Boron compound represented by formula (L ¹ -H) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- (In the formula, B represents a boron atom in a trivalent valence state, and Q ¹ , Q ² , Q ³ and Q ⁴ are each independently a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a substituted silyl group, Represents an alkoxy group or a disubstituted amino group, G ⁺ represents an inorganic or organic cation, and L ¹ represents a neutral Lewis base.)

  Moreover, this invention provides the manufacturing method of the olefin polymer which superposes | polymerizes an olefin in presence of the catalyst for said any olefin polymerization.

  When the transition metal complex of the present invention is used as a catalyst for olefin polymerization, an olefin copolymer having a high copolymerization ratio of structural units derived from an α-olefin without using a large excess of the α-olefin relative to ethylene. A polymer can be obtained.

The C ¹ -Y-M angle of three-dimensional space around the central metal M (coordination field) is a diagram schematically showing. FIG. 4 is a diagram showing the result of X-ray crystal structure analysis of complex 2. It is a figure which shows the X-ray crystal structure analysis result of the complex 4.

  Hereinafter, the present invention will be described in detail.

<Transition metal complex>
First, the transition metal complex represented by the formula [1] (hereinafter referred to as “transition metal complex [1]”) will be described. The present inventors have a tendency that the polymerization activity of α-olefin tends to be lower than the polymerization activity of ethylene, and polymerization is carried out in the presence of a conventional catalyst for olefin polymerization using ethylene and α-olefin as raw material monomers. In this case, ethylene is easily preferentially polymerized, and the copolymerization ratio of structural units derived from α-olefin in the resulting ethylene copolymer (hereinafter, sometimes referred to as “α-olefin structural unit”). I found it difficult to increase Therefore, in the polymerization in the presence of the conventional catalyst for olefin polymerization, an ethylene copolymer having a high copolymerization ratio of structural units of α-olefin is obtained by using a large excess of α-olefin with respect to ethylene. As a result, unreacted α-olefin remains. Under such circumstances, when the present inventors used a transition metal complex [1] condensed in a specific direction having a thiophene ring on a cyclopentadiene ring as an olefin polymerization catalyst described later, an unreacted α-olefin. It has been found that there is an astonishing effect that an ethylene-based copolymer having a high copolymerization of the structural unit of α-olefin can be obtained while reducing the residual amount of.

Hereinafter, the transition metal complex [1], and particularly preferable transition metal complex [1] will be described in detail.
In the transition metal complex [1], M represents a Group 4 element in the Periodic Table of Elements, and examples thereof include a titanium atom, a zirconium atom, and a hafnium atom. Among these, a titanium atom is preferable.

  In the transition metal complex [1], A is a group 16 element of the periodic table of elements, and examples thereof include an oxygen atom, a sulfur atom, and a selenium atom, and preferably an oxygen atom.

  In the transition metal complex [1], J is a group 14 element of the periodic table of elements, and examples thereof include a carbon atom, a silicon atom, and a germanium atom, and preferably a silicon atom.

In the transition metal complex [1], the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , X ¹ and X ² are as described above. A specific example is shown below.

  The halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom.

  Specific examples of the “alkyl group having 1 to 20 carbon atoms” of the alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent include a methyl group, an ethyl group, an n-propyl group, Isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, amyl group, n-hexyl group, heptyl group, n-octyl group, n-nonyl group, n-decyl Group, n-dodecyl group, n-tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group and n-eicosyl group. Among these, preferable alkyl groups are those having 1 to 10 carbon atoms, and more preferable examples include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, and an amyl group. In addition, “may have a halogen atom as a substituent” means a group in which a part or all of the hydrogen atoms in the alkyl group exemplified here are replaced by a halogen atom, Specific examples are as described above. In addition, when it has a halogen atom as a substituent, it is preferable that it is the range of the C1-C20, and the range of the C1-C10 is further more preferable. Examples of the alkyl group which may have a suitable halogen atom as a substituent include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group and a dibromomethyl group. , Tribromomethyl group, fluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group and perfluorohexyl group.

  Specific examples of the “aryl group having 6 to 20 carbon atoms” of the aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent include a phenyl group, a 2-tolyl group, and 3-tolyl. Group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2 , 3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2 , 3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propyl Phenyl group, isopropyl Phenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, Examples include n-dodecylphenyl group, n-tetradecylphenyl group, naphthyl group and anthracenyl group. Among these, a preferable aryl group is an aryl group having 6 to 10 carbon atoms, more preferably a phenyl group. In addition, “may have a halogen atom as a substituent” means a group in which part or all of the hydrogen atoms in the aryl group exemplified herein are replaced with a halogen atom. Specific examples are as described above. In addition, when it has a halogen atom as a substituent, the carbon atom number is preferable in the range of 6-20, and the range of 6-10 is further more preferable. Specific preferred aryl groups having a halogen atom as a substituent are fluorophenyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl group, chlorophenyl group, bromophenyl group and iodophenyl group. And so on.

  Specific examples of the “aralkyl group having 7 to 20 carbon atoms” of the aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent include a benzyl group and a (2-methylphenyl) methyl group. , (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, (2,3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl Group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl group, (4,6-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2 , 3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl group, (3,4,5-trimethylphenyl) methyl group, (2,4,6-trimethyl) Enyl) 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 and the like. Among these, a preferable aralkyl group is an aralkyl group having 7 to 10 carbon atoms, and more preferably a benzyl group. In addition, “may have a halogen atom as a substituent” means a group in which part or all of the hydrogen atoms in the aralkyl group exemplified herein are replaced with a halogen atom. Specific examples are as described above. In addition, when it has a halogen atom as a substituent, the carbon atom number is preferable in the range of 7-20, and the range of 7-10 is further more preferable.

  Specific examples of the “alkoxy group having 1 to 20 carbon atoms” of the alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent include a methoxy group, an ethoxy group, an 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, heptadecyloxy group, octadecyloxy group Group, nonadecyloxy group, n-eicosyloxy group and the like. Among these, preferable alkoxy groups are those having 1 to 10 carbon atoms, and more preferable examples include a methoxy group, an ethoxy group, and a tert-butoxy group. In addition, “may have a halogen atom as a substituent” means a group in which part or all of the hydrogen atoms in the alkoxy group exemplified here are replaced by halogen atoms, Specific examples are as described above. In addition, when it has a halogen atom as a substituent, it is preferable in it being the range of the C1-C20, and the range of 1-10 is further more preferable.

  Specific examples of the “aryloxy group having 6 to 20 carbon atoms” of the aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent include a phenoxy group, a 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group 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, , 4,6-tetramethylphenoxy group, 2,3,5,6-tetramethylphenoxy group, pentamethylphenoxy group, ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, sec- Examples include butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, n-tetradecylphenoxy group, naphthoxy group and anthracenoxy group. Among these, preferable aryloxy groups are aryloxy groups having 6 to 10 carbon atoms, and more preferable examples include phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, and 4-methylphenoxy group. it can. Further, “may have a halogen atom as a substituent” means a group in which some or all of the hydrogen atoms in the aryloxy group exemplified herein are replaced with halogen atoms, and the halogen atoms The specific example is as described above. In addition, when it has a halogen atom as a substituent, the carbon atom number is preferable in the range of 6-20, and the range of 6-10 is further more preferable.

  Specific examples of the “aralkyloxy group having 7 to 20 carbon atoms” of the aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent include a 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-dimethyl) Phenyl) 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) Nyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (3,4,5-trimethylphenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2, 3,4,6-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl) methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) Methoxy group, (isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, (sec-butylphenyl) methoxy group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octyl) Phenyl) methoxy group, (n-decylphenyl) methoxy group, naphthylmethoxy group, anthracenylmethoxy And the like. Among these, a preferable aralkyloxy group is an aralkyloxy group having 7 to 10 carbon atoms, and more preferably a benzyloxy group. Further, “may have a halogen atom as a substituent” means a group in which some or all of the hydrogen atoms in the aryloxy group exemplified herein are replaced with halogen atoms, and the halogen atoms The specific example is as described above. In addition, when it has a halogen atom as a substituent, the carbon atom number is preferable in the range of 7-20, and the range of 7-10 is further more preferable.

—Si (R ¹² ) ₃ (three R ^{12 s} each independently represent a hydrogen atom, a hydrocarbon group, or a halogenated hydrocarbon group, and the total number of carbon atoms in the three R ^{12 s} is 1-20. In the substituted silyl group represented by), each R ¹² independently represents a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n- An alkyl group having 1 to 10 carbon atoms such as a pentyl group, an n-hexyl group, a cyclohexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group and an n-decyl group; an aryl group such as a phenyl group; And the total number of three R ¹² carbon atoms is in the range of 1-20. The total number of carbon atoms of the three R ¹² is preferably in the range of 3-18. Specific examples of the substituted silyl group include a monosubstituted silyl group having one hydrocarbon group such as a methylsilyl group, an ethylsilyl group and a phenylsilyl group; two hydrocarbons such as a dimethylsilyl group, a diethylsilyl group and a diphenylsilyl group. A disubstituted silyl group having a group: trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri-n-butylsilyl group, tri-sec-butylsilyl group, tri-tert-butylsilyl group, tri -Trisubstituted silyl having three hydrocarbon groups such as isobutylsilyl group, tert-butyl-dimethylsilyl group, tri-n-pentylsilyl group, tri-n-hexylsilyl group, tricyclohexylsilyl group and triphenylsilyl group Groups and the like. Of these, a trisubstituted silyl group is preferable, and a trimethylsilyl group, a tert-butyldimethylsilyl group, and a triphenylsilyl group are more preferable. The hydrocarbon group in the substituted silyl group may also be a halogenated hydrocarbon group in which a part or all of the hydrogen atoms in the already exemplified alkyl group or aryl group are replaced with a halogen atom.

—N (R ¹³ ) ₂ (two R ¹³ each independently represents a hydrocarbon group or a halogenated hydrocarbon group, and the total number of carbon atoms in the two R ¹³ is 2 to 20). In the disubstituted amino group, each R ¹³ independently represents a hydrocarbon group, and the total number of carbon atoms of the two R ¹³ is in the range of 2 to 20, more preferably in the range of 2 to 10. Such a hydrocarbon group is the same as that described as the hydrocarbon group of the substituted silyl group, and part or all of the hydrogen atoms in the hydrocarbon group are halogenated hydrocarbon groups in which halogen atoms are replaced. May be. The two Rs may be bonded to each other and form a ring together with the nitrogen atom to which they are bonded. Examples of the disubstituted amino group include dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, di-sec-butylamino group, di-tert-butyl. Amino group, di-isobutylamino group, tert-butylisopropylamino group, di-n-hexylamino group, di-n-octylamino group, di-n-decylamino group, diphenylamino group, bistrimethylsilylamino group, bis- Examples thereof include a tert-butyldimethylsilylamino group, a pyrrolyl group, a pyrrolidinyl group, a piperidinyl group, a carbazolyl group, a dihydroindolyl group, and a dihydroisoindolyl group. Of these, preferred are a dimethylamino group, a diethylamino group, a pyrrolidinyl group, and a piperidinyl group.

Two substituents bonded to adjacent carbon atoms of R ¹ , R ² , R ^3, and R ⁴ may be bonded to form a ring together with the carbon atoms to which they are bonded. Similarly, R ⁵ and R ⁶ may be bonded to form a ring with J, and R ⁷ and R ⁸ may be bonded to form a ring with the carbon atom to which they are bonded. R ⁹ and R ¹⁰ may be bonded together to form a ring together with the carbon atom to which they are bonded. The ring here is a saturated or unsaturated hydrocarbon ring substituted with a hydrocarbon group having 1 to 20 carbon atoms. Specific examples thereof include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a benzene ring, a naphthalene ring, and an anthracene ring.

  Specific examples of the transition metal complex [1] include the following complexes.

  Dimethylsilylene (cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopenta [2,1 -B: 3,4-b '] dithiophen-4-yl) (2-phenoxy) titanium dichloride, dimethylsilylene (cyclopenta [2,1-b: 3,4-b'] dithiophen-4-yl) (3 , 4-Dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) (3-tert-butyl-5-methoxy-2-phenoxy) ) Titanium dichloride, dimethylsilylene (cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) (3-t rt-butyl-5-dimethylamino-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) (3-tert-butyl-2-phenoxy) ) Titanium dichloride, dimethylsilylene (cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopenta [2,1-b: 3,4-b ′] Dithiophen-4-yl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titaniu Dichloride, dimethylsilylene (cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopenta [2,1 -B: 3,4-b '] dithiophen-4-yl) (2-naphthoxy) titanium dichloride

Dimethylsilylene (2,6-dimethylcyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (2,6-dimethylcyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) (2-phenoxy) titanium dichloride, dimethylsilylene (2,6-dimethylcyclopenta [2,1 -B: 3,4-b '] dithiophen-4-yl) (3,4-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (2,6-dimethylcyclopenta [2,1-b: 3,4) -B '] dithiophen-4-yl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (2,6- Methylcyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) (3-tert-butyl-5-dimethylamino-2-phenoxy) titanium dichloride, dimethylsilylene (2,6-dimethyl) Cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (2,6-dimethylcyclopenta [2,1 -B: 3,4-b '] dithiophen-4-yl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (2,6-dimethylcyclopenta [2,1-b : 3,4-b ′] dithiophen-4-yl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (2,6-di) Tilcyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (2,6- Dimethylcyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (2,6-dimethylcyclopenta [ 2,1-b: 3,4-b ′] dithiophen-4-yl) (2-naphthoxy) titanium dichloride

Diethylsilylene (cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (cyclopenta [2,1 -B: 3,4-b '] dithiophen-4-yl) (2-phenoxy) titanium dichloride, diethylsilylene (cyclopenta [2,1-b: 3,4-b'] dithiophen-4-yl) (3 , 4-Dimethyl-2-phenoxy) titanium dichloride, diethylsilylene (cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) (3-tert-butyl-5-methoxy-2-phenoxy) ) Titanium dichloride, diethylsilylene (cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) (3-t rt-butyl-5-dimethylamino-2-phenoxy) titanium dichloride, diethylsilylene (cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) (3-tert-butyl-2-phenoxy) ) Titanium dichloride, diethylsilylene (cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, diethylsilylene (cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) (3-phenyl-2-phenoxy) titanium dichloride, diethylsilylene (cyclopenta [2,1-b: 3,4-b ′] Dithiophen-4-yl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titaniu Dichloride, diethylsilylene (cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (cyclopenta [2,1 -B: 3,4-b '] dithiophen-4-yl) (2-naphthoxy) titanium dichloride

Diethylsilylene (2,6-dimethylcyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (2,6-dimethylcyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) (2-phenoxy) titanium dichloride, diethylsilylene (2,6-dimethylcyclopenta [2,1 -B: 3,4-b '] dithiophen-4-yl) (3,4-dimethyl-2-phenoxy) titanium dichloride, diethylsilylene (2,6-dimethylcyclopenta [2,1-b: 3,4) -B '] dithiophen-4-yl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diethylsilylene (2,6- Methylcyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) (3-tert-butyl-5-dimethylamino-2-phenoxy) titanium dichloride, diethylsilylene (2,6-dimethyl) Cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) (3-tert-butyl-2-phenoxy) titanium dichloride, diethylsilylene (2,6-dimethylcyclopenta [2,1 -B: 3,4-b '] dithiophen-4-yl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, diethylsilylene (2,6-dimethylcyclopenta [2,1-b : 3,4-b ′] dithiophen-4-yl) (3-phenyl-2-phenoxy) titanium dichloride, diethylsilylene (2,6-di) Tilcyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (2,6- Dimethylcyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (2,6-dimethylcyclopenta [ 2,1-b: 3,4-b ′] dithiophen-4-yl) (2-naphthoxy) titanium dichloride and the like. Further, in the complexes exemplified here, those in which “titanium” is replaced with “zirconium” or “hafnium”, and those in which “dichloride” is replaced with “difluoride”, “dibromide”, or “diiodide” are also exemplified. The

［式中、Ａ、Ｊ、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９及びＲ^１０は前記式［１］と同義である。
Ｒ^１１は、−Ｓｉ（Ｒ^１４）_３（３つのＲ^１４はそれぞれ独立に、炭化水素基又はハロゲン化炭化水素基を表し、３つのＲ^１４にある炭素原子数の合計が３〜２０である。）で示される三置換シリル基または炭素原子数１〜２０の有機基を表す。］
で示される置換シクロペンタジエン化合物（以下、「置換シクロペンタジエン化合物［２］」という。）及び塩基を反応させる工程と、
前記塩基と反応させた前記置換シクロペンタジエン化合物［２］及び
下記式［３］

（式中、Ｍ、Ｘ^１及びＸ^２は前記式［１］と同義であり、Ｘ^３及びＸ^４はそれぞれ独立に、水素原子、ハロゲン原子、
ハロゲン原子を置換基として有していてもよい炭素原子数１〜２０のアルキル基、
ハロゲン原子を置換基として有していてもよい炭素原子数１〜２０のアルコキシ基、
ハロゲン原子を置換基として有していてもよい炭素原子数６〜２０のアリール基、
ハロゲン原子を置換基として有していてもよい炭素原子数６〜２０のアリールオキシ基、
ハロゲン原子を置換基として有していてもよい炭素原子数７〜２０のアラルキル基、
ハロゲン原子を置換基として有していてもよい炭素原子数７〜２０のアラルキルオキシ基、
−Ｓｉ（Ｒ^１２）_３（３つのＲ^１２はそれぞれ独立に、水素原子、炭化水素基またはハロゲン化炭化水素基を表し、３つのＲ^１２にある炭素原子数の合計が１〜２０である。）で示される置換シリル基、
又は−Ｎ（Ｒ^１３）_２（２つのＲ^１３はそれぞれ独立に炭化水素基またはハロゲン化炭化水素基を表し、２つのＲ^１３にある炭素原子数の合計が２〜２０である。）で示される２置換アミノ基を表し、ｎは０又は１を表す。）
で示される遷移金属化合物（以下、「遷移金属化合物［３］」という。）
を反応させる工程と、
を有する製造方法により製造することができる。以下、前記置換シクロペンタジエン化合物［２］と塩基とを反応させる工程を「第１反応工程」、前記置換シクロペンタジエン化合物［２］と塩基との反応物に、遷移金属化合物［３］を反応させる工程を「第２反応工程」ということがある。前記置換シクロペンタジエン化合物［２］及び前記遷移金属化合物［３］を用いる以外は、当該製造方法に係る反応条件は、特開２００４−２３８３８７号公報に記載されている反応に準拠すればよい。 <Method for producing transition metal complex [1]>
The transition metal complex [1] is, for example, the following formula [2]

[Wherein, A, J, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ have the same meanings as the formula [1].
R ¹¹ represents —Si (R ¹⁴ ) ₃ (three R ¹⁴ each independently represents a hydrocarbon group or a halogenated hydrocarbon group, and the total number of carbon atoms in the three R ¹⁴ is 3 to 20). .) Represents a trisubstituted silyl group or an organic group having 1 to 20 carbon atoms. ]
A step of reacting a substituted cyclopentadiene compound represented by the following (hereinafter referred to as “substituted cyclopentadiene compound [2]”) and a base;
The substituted cyclopentadiene compound [2] reacted with the base and the following formula [3]

(In the formula, M, X ¹ and X ² have the same meanings as those in the formula [1], and X ³ and X ⁴ each independently represent a hydrogen atom, a halogen atom,
An alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
An alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent;
An aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent;
An aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent;
An aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
An aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent;
—Si (R ¹² ) ₃ (three R ^{12 s} each independently represent a hydrogen atom, a hydrocarbon group, or a halogenated hydrocarbon group, and the total number of carbon atoms in the three R ^{12 s} is 1-20. Substituted silyl groups represented by
Or -N (R ¹³ ) ₂ (two R ¹³ each independently represents a hydrocarbon group or a halogenated hydrocarbon group, and the total number of carbon atoms in the two R ¹³ is 2 to 20). And n represents 0 or 1. )
(Hereinafter referred to as “transition metal compound [3]”)
Reacting with
It can manufacture with the manufacturing method which has this. Hereinafter, the step of reacting the substituted cyclopentadiene compound [2] with a base is referred to as “first reaction step”, and the reaction product of the substituted cyclopentadiene compound [2] and the base is reacted with a transition metal compound [3]. The process may be referred to as a “second reaction process”. Except for using the substituted cyclopentadiene compound [2] and the transition metal compound [3], the reaction conditions relating to the production method may be based on the reaction described in JP-A-2004-238387.

Examples of the hydrocarbon group in R ¹¹ of the substituted cyclopentadiene compound [2] include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. An alkyl group having 1 to 10 carbon atoms; such as vinyl group, allyl group, propenyl group, 2-methyl-2-propenyl group, homoallyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group and decenyl group An alkenyl group having 2 to 10 carbon atoms; an aralkyl group having 7 to 12 carbon atoms such as a benzyl group, (4-methylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group; a methoxymethyl group; Examples include alkoxyalkyl groups such as methoxyethoxymethyl group. Any of these hydrocarbon groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and examples thereof include a 2-chloro-2-propenyl group.

In addition, the definition of the trisubstituted silyl group of R ¹¹ is as already described in the substituted silyl group represented by —Si (R ¹² ) ₃ , for example, trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, Triisopropylsilyl group, tri-n-butylsilyl group, tri-sec-butylsilyl group, tri-tert-butylsilyl group, tri-isobutylsilyl group, tert-butyl-dimethylsilyl group, tri-n-pentylsilyl group, tri- Examples thereof include an n-hexylsilyl group, a tricyclohexylsilyl group, and a triphenylsilyl group.

Among R ¹¹ exemplified above, an alkenyl group or an alkyl group is preferable, and an allyl group or a methyl group is more preferable from the viewpoint that the transition metal complex [1] can be produced with high yield.

  Examples of the substituted cyclopentadiene compound [2] include the following compounds.

(2-allyloxyphenyl) (4H-cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) dimethylsilane, (2-allyloxy-3-methylphenyl) (4H-cyclopenta [2 , 1-b: 3,4-b ′] dithiophen-4-yl) dimethylsilane, (2-allyloxy-3,5-dimethylphenyl) (4H-cyclopenta [2,1-b: 3,4-b ′]. Dithiophen-4-yl) dimethylsilane, (2-allyloxy-3-tert-butylphenyl) (4H-cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) dimethylsilane, 2-allyloxy-3-tert-butyl-5-methylphenyl) (4H-cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) dimethylsilane, Xy-3,5-di-tert-butylphenyl) (4H-cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) dimethylsilane, (2-allyloxy-5-methyl-3) -Phenylphenyl) (4H-cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) dimethylsilane, (2-allyloxy-5-methyl-3-trimethylsilylphenyl) (4H-cyclopenta [ 2,1-b: 3,4-b ′] dithiophen-4-yl) dimethylsilane, (2-allyloxy-3-tert-butyldimethylsilyl-5-methylphenyl) (4H-cyclopenta [2,1-b : 3,4-b ′] dithiophen-4-yl) dimethylsilane, (2-allyloxy-3,5-diamilphenyl) (4H-cyclopenta [2,1-b: 3, -B '] dithiophen-4-yl) dimethylsilane, (2-allyloxy-3-tert-butyl-5-methoxyphenyl) (4H-cyclopenta [2,1-b: 3,4-b'] dithiophene-4 -Yl) dimethylsilane, (2-allyloxy-5-tert-butyl-3-chlorophenyl) (4H-cyclopenta [2,1-b: 3,4-b '] dithiophen-4-yl) dimethylsilane, (1 -Allyloxynaphthalen-2-yl) (4H-cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) dimethylsilane, (2-allyloxy-3-tert-butyl-5-methoxy) Phenyl) (4H-cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) dimethylsilane,

(2-allyloxyphenyl) (4H-cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) diethylsilane, (2-allyloxy-3-methylphenyl) (4H-cyclopenta [2 , 1-b: 3,4-b ′] dithiophen-4-yl) diethylsilane, (2-allyloxy-3,5-dimethylphenyl) (4H-cyclopenta [2,1-b: 3,4-b ′). Dithiophen-4-yl) diethylsilane, (2-allyloxy-3-tert-butylphenyl) (4H-cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) diethylsilane, 2-allyloxy-3-tert-butyl-5-methylphenyl) (4H-cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) diethylsilane, (2-ant Xy-3,5-di-tert-butylphenyl) (4H-cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) diethylsilane, (2-allyloxy-5-methyl-3) -Phenylphenyl) (4H-cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) diethylsilane, (2-allyloxy-5-methyl-3-trimethylsilylphenyl) (4H-cyclopenta [ 2,1-b: 3,4-b ′] dithiophen-4-yl) diethylsilane, (2-allyloxy-3-tert-butyldimethylsilyl-5-methylphenyl) (4H-cyclopenta [2,1-b : 3,4-b ′] dithiophen-4-yl) diethylsilane, (2-allyloxy-3,5-diamilphenyl) (4H-cyclopenta [2,1-b: 3, -B '] dithiophen-4-yl) diethylsilane, (2-allyloxy-3-tert-butyl-5-methoxyphenyl) (4H-cyclopenta [2,1-b: 3,4-b'] dithiophene-4 -Yl) diethylsilane, (2-allyloxy-5-tert-butyl-3-chlorophenyl) (4H-cyclopenta [2,1-b: 3,4-b '] dithiophen-4-yl) diethylsilane, (1 -Allyloxynaphthalen-2-yl) (4H-cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) diethylsilane, (2-allyloxy-3-tert-butyl-5-methoxy) Phenyl) (4H-cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) diethylsilane,

(2-allyloxyphenyl) (2,6-dimethyl-4H-cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) dimethylsilane, (2-allyloxy-3-methylphenyl) (2,6-dimethyl-4H-cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) dimethylsilane, (2-allyloxy-3,5-dimethylphenyl) (2,6- Dimethyl-4H-cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) dimethylsilane, (2-allyloxy-3-tert-butylphenyl) (2,6-dimethyl-4H-cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) dimethylsilane, (2-allyloxy-3-tert-butyl-5-methylphenyl) (2,6-dimethyl-4H— Clopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) dimethylsilane, (2-allyloxy-3,5-di-tert-butylphenyl) (2,6-dimethyl-4H-cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) dimethylsilane, (2-allyloxy-5-methyl-3-phenylphenyl) (2,6-dimethyl-4H-cyclopenta [2, 1-b: 3,4-b ′] dithiophen-4-yl) dimethylsilane, (2-allyloxy-5-methyl-3-trimethylsilylphenyl) (2,6-dimethyl-4H-cyclopenta [2,1-b : 3,4-b ′] dithiophen-4-yl) dimethylsilane, (2-allyloxy-3-tert-butyldimethylsilyl-5-methylphenyl) (2,6-dimethyl-4H— Clopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) dimethylsilane, (2-allyloxy-3,5-diamilphenyl) (2,6-dimethyl-4H-cyclopenta [2, 1-b: 3,4-b ′] dithiophen-4-yl) dimethylsilane, (2-allyloxy-3-tert-butyl-5-methoxyphenyl) (2,6-dimethyl-4H-cyclopenta [2,1 -B: 3,4-b '] dithiophen-4-yl) dimethylsilane, (2-allyloxy-5-tert-butyl-3-chlorophenyl) (2,6-dimethyl-4H-cyclopenta [2,1-b : 3,4-b ′] dithiophen-4-yl) dimethylsilane, (1-allyloxynaphthalen-2-yl) (2,6-dimethyl-4H-cyclopenta [2,1-b: 3,4-b '] Dithiophen-4-yl) dimethylsilane, (2-allyloxy-3-tert-butyl-5-methoxyphenyl) (2,6-dimethyl-4H-cyclopenta [2,1-b: 3,4-b ′] dithiophene -4-yl) dimethylsilane,

(2-allyloxyphenyl) (2,6-dimethyl-4H-cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) diethylsilane, (2-allyloxy-3-methylphenyl) (2,6-Dimethyl-4H-cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) diethylsilane, (2-allyloxy-3,5-dimethylphenyl) (2,6- Dimethyl-4H-cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) diethylsilane, (2-allyloxy-3-tert-butylphenyl) (2,6-dimethyl-4H-cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) diethylsilane, (2-allyloxy-3-tert-butyl-5-methylphenyl) (2,6-dimethyl-4H— Clopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) diethylsilane, (2-allyloxy-3,5-di-tert-butylphenyl) (2,6-dimethyl-4H-cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) diethylsilane, (2-allyloxy-5-methyl-3-phenylphenyl) (2,6-dimethyl-4H-cyclopenta [2, 1-b: 3,4-b ′] dithiophen-4-yl) diethylsilane, (2-allyloxy-5-methyl-3-trimethylsilylphenyl) (2,6-dimethyl-4H-cyclopenta [2,1-b : 3,4-b ′] dithiophen-4-yl) diethylsilane, (2-allyloxy-3-tert-butyldimethylsilyl-5-methylphenyl) (2,6-dimethyl-4H— Clopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) diethylsilane, (2-allyloxy-3,5-diamilphenyl) (2,6-dimethyl-4H-cyclopenta [2, 1-b: 3,4-b ′] dithiophen-4-yl) diethylsilane, (2-allyloxy-3-tert-butyl-5-methoxyphenyl) (2,6-dimethyl-4H-cyclopenta [2,1 -B: 3,4-b '] dithiophen-4-yl) diethylsilane, (2-allyloxy-5-tert-butyl-3-chlorophenyl) (2,6-dimethyl-4H-cyclopenta [2,1-b : 3,4-b ′] dithiophen-4-yl) diethylsilane, (1-allyloxynaphthalen-2-yl) (2,6-dimethyl-4H-cyclopenta [2,1-b: 3,4-b '] Dithiophen-4-yl) diethylsilane, (2-allyloxy-3-tert-butyl-5-methoxyphenyl) (2,6-dimethyl-4H-cyclopenta [2,1-b: 3,4-b ′] dithiophene -4-yl) diethylsilane,

  In the substituted cyclopentadiene compound [2] exemplified here, “dimethylsilane”, “ethylmethylsilane”, “methylphenylsilane” or “dimethylgermanium” can be used.

（式中、Ｒ^７、Ｒ^８、Ｒ^９及びＲ^１０は前記と同じ意味を示し、Ｔはアルカリ金属原子を示す。）
に例示されるシクロペンタジエニルのアルカリ金属塩を用い、式［５］

（式中、Ａ、Ｊ、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６及びＲ^１１は前記と同じ意味を示し、Ｘ^５はハロゲン原子を示す。）
で示される化合物を反応させることにより製造される。 In addition, the substituted cyclopentadiene compound [2] exemplified here is represented by, for example, the following formula [4].

(In the formula, R ⁷ , R ⁸ , R ⁹ and R ¹⁰ have the same meaning as described above, and T represents an alkali metal atom.)
And an alkali metal salt of cyclopentadienyl exemplified in formula [5]

(In the formula, A, J, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ¹¹ have the same meaning as described above, and X ⁵ represents a halogen atom.)
It is manufactured by making the compound shown by react.

  T in the alkali metal salt of cyclopentadienyl represented by the formula [4] is, for example, a lithium atom, a sodium atom, or a potassium atom, preferably a lithium atom.

（式中、Ｒ^７、Ｒ^８、Ｒ^９及びＲ^１０は前記と同じ意味を示す。）
で示されるシクロペンタジエン化合物を用いて、特開２００４−２３８３８７号公報に記載されている反応に準拠して製造することができる。 The alkali metal salt of cyclopentadienyl represented by the formula [4] is, for example, the formula [6].

(Wherein R ⁷ , R ⁸ , R ⁹ and R ¹⁰ have the same meaning as described above.)
Can be produced according to the reaction described in JP-A No. 2004-238387.

  The cyclopentadiene compound represented by the formula [6] is, for example, Tetrahedron 1968, 24, 3381. Or it can manufacture according to the manufacturing method described in WO01 / 47939).

In the transition metal compound [3], the substituents X ³ and X ⁴ are as defined above, and specific examples thereof are the same as those defined for X ¹ and X ² .

  Examples of the transition metal compound [3] include titanium halides such as titanium tetrachloride, titanium trichloride, titanium tetrabromide, and titanium tetraiodide; tetrakis (dimethylamino) titanium, dichlorobis (dimethylamino) titanium, and trichloro. Amido titanium such as (dimethylamino) titanium and tetrakis (diethylamino) titanium; alkoxytitanium such as tetraisopropoxytitanium, tetra-n-butoxytitanium, dichlorodiisopropoxytitanium and trichloroisopropoxytitanium. Moreover, the compound etc. which replaced "titanium" of each of these compounds with "zirconium" or "hafnium" are mentioned. Of these, the preferred transition metal compound [3] is titanium tetrachloride.

  Examples of the base to be reacted with the substituted cyclopentadiene compound [2] in the first reaction step include methyl lithium, ethyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, lithium trimethylsilyl acetylide, and lithium acetylide. Organic alkali metal compounds represented by organic lithium compounds such as trimethylsilylmethyl lithium, vinyl lithium, phenyl lithium and allyl lithium.

  The usage-amount of a base should just be the range of 0.5-5 mol per 1 mol of substituted cyclopentadienyl compounds [2].

  In the reaction of the substituted cyclopentadiene compound [2] and the base in the first reaction step, an amine compound can be used together with the organic alkali metal compound. Examples of such amine compounds include primary amine compounds such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, tert-butylamine, n-octylamine, n-decylamine, aniline, and ethylenediamine; Amine, diethylamine, di-n-propylamine, di-n-propylamine, di-n-butylamine, di-tert-butylamine, di-n-octylamine, di-n-decylamine, pyrrolidine, hexamethyldisilazane, Secondary amine compounds such as diphenylamine; trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, diisopropylethylamine, tri-n-octylamine, tri-n-decylamine, triphenyl Min, N, N- dimethylaniline, N, N, N ', N'-tetramethylethylenediamine, N- methylpyrrolidine, 4-tertiary amine compounds such as dimethylaminopyridine; and the like. The amount of the amine compound used is preferably 10 mol or less, more preferably 0.5 to 10 mol, and even more preferably 1 to 3 mol per mol of the organic alkali metal compound. .

  In the first reaction step, when the substituted cyclopentadiene compound [2] is reacted with a base, it is preferably reacted in the presence of a solvent. When a solvent is used, after reacting the substituted cyclopentadiene compound [2] and the base in the solvent, the transition metal compound [3] is added to the reaction mixture, whereby the substituted cyclopentadiene compound [2] and The transition metal compound [3] can be further reacted with the base reactant. A solid may precipitate in the reaction mixture obtained by reacting the substituted cyclopentadiene compound [2] and the base. In this case, a solvent is added until the precipitated solid is dissolved, or the precipitated solid is removed. After separation by filtration or the like, the solvent is added to the separated solid and dissolved, so that the reaction mixture obtained by reacting the substituted cyclopentadiene compound [2] and the base is in the form of a solution. The transition metal compound [3] may be added to the solution. When a solvent is used, the first reaction step and the second reaction step can be carried out substantially simultaneously by simultaneously adding the substituted cyclopentadiene compound [2], the base and the transition metal compound [3] to the solvent. .

  As the solvent used in the first reaction step or the first reaction step and the second reaction step, an inert solvent that does not significantly disturb the progress of the reaction related to these steps is used. Examples of such solvents include aromatic hydrocarbon solvents such as benzene and toluene; aliphatic hydrocarbon solvents such as hexane and heptane; ether solvents such as diethyl ether, tetrahydrofuran and 1,4-dioxane; Amide solvents such as hollic amide and dimethylformamide; polar solvents such as acetonitrile, propionitrile, acetone, diethyl ketone, methyl isobutyl ketone and cyclohexanone; aprotic solvents such as halogen solvents such as dichloromethane, dichloroethane, chlorobenzene and dichlorobenzene Etc. are exemplified. Such solvents can be used alone or in admixture of two or more, and the amount used is preferably 1 to 200 parts by weight, more preferably 3 to 50 parts by weight per 1 part by weight of the substituted cyclopentadiene compound [2]. .

  The amount of the transition metal compound [3] used is preferably in the range of 0.5 to 3 mol, more preferably in the range of 0.7 to 1.5 mol, per mol of the substituted cyclopentadiene compound [2].

  The reaction temperature in the first reaction step and the second reaction step may be −100 ° C. or more and not more than the boiling point of the solvent, and is preferably in the range of −80 to 100 ° C.

  Thus, the produced transition metal complex [1] can be extracted from the reaction mixture obtained through the first reaction step and the second reaction step by various known purification methods. For example, after the first reaction step and the second reaction step, after the generated precipitate is filtered, the filtrate is concentrated to precipitate a transition metal complex, and then the target transition metal complex [ 1] can be obtained.

<Olefin polymerization catalyst>
The transition metal complex [1] of the present invention can be suitably used as an olefin polymerization catalyst. In particular, the olefin polymerization catalyst obtained by bringing the transition metal complex [1] into contact with another cocatalyst component can be suitably used for the polymerization of a vinyl compound having a bulky substituent described later and ethylene. . Examples of the cocatalyst component include the following compound (A) and the following compound (B), and the compound (A) and the compound (B) may be used in combination.
Compound (A): One or more aluminum compounds selected from the group consisting of the following (A1), (A2) and (A3) (A1): an organoaluminum compound represented by the formula E ¹ _a AlZ _3-a ( A2): cyclic aluminoxane (A3) having a structure represented by the formula {—Al (E ² ) —O—} _b : Formula E ³ {—Al (E ³ ) —O—} _c Table represented by AlE 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 Even if it is.)
Compound (B): One or more boron compounds (B1) selected from the group consisting of the following (B1), (B2) and (B3): Boron compound (B2) represented by the formula BQ ¹ Q ² Q ³ : Boron compound represented by formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- (B3): Boron compound represented by formula (L ¹ -H) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- (In the formula, B represents a boron atom in a trivalent valence state, and Q ¹ , Q ² , Q ³ and Q ⁴ are each independently a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a substituted silyl group, Represents an alkoxy group or a disubstituted amino group, G ⁺ represents an inorganic or organic cation, and L ¹ represents a neutral Lewis base.)

Specific examples of the compound (A) are shown below.
(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; dimethylaluminum chloride Dialkylaluminum chlorides such as diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, dihexylaluminum chloride; alkylaluminum dichlorides such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, hexylaluminum dichloride; Examples thereof include dialkylaluminum hydrides such as 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) formula E ³ {—Al (E ³ ) —O—} _c AlE ³ ₂ Examples of E ² and E ³ in the linear aluminoxane having the structure represented include alkyl such as methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, normal pentyl group, and neopentyl group. 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-mentioned aluminoxane can be produced by various methods. The method is not particularly limited and may be produced according to a known method. For example, the aluminoxane can be produced by bringing a solution obtained by dissolving a trialkylaluminum (such as trimethylaluminum) into an appropriate organic solvent (such as benzene or aliphatic hydrocarbon) into contact with water. The aluminoxane can also be produced by bringing a trialkylaluminum (eg, trimethylaluminum) into contact with a metal salt containing crystal water (eg, copper sulfate hydrate).

Next, specific examples of the compound (B) are shown.
(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.

(B2): In the boron compound represented by the formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ , G ⁺ which is an inorganic cation includes, for example, a ferrocenium cation, an alkyl-substituted ferrocenium cation, Examples of G ⁺ in which a silver cation or the like is an organic cation include 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.

  The method for contacting each catalyst component in the preparation of the catalyst for olefin polymerization is not particularly limited. Moreover, the catalyst for olefin polymerization can also be prepared in this polymerization reaction apparatus by making each catalyst component contact in the polymerization reaction apparatus which bears manufacture of the olefin polymer mentioned later. In this case, the order in which the catalyst components are introduced into the polymerization reaction apparatus is arbitrary. Needless to say, an olefin polymerization catalyst can be prepared by bringing the catalyst components into contact with each other in advance before introducing them into the polymerization reaction apparatus.

The amount ratio used when preparing the catalyst for olefin polymerization by bringing the transition metal complex [1] into contact with the cocatalyst component will be described. When the compound (A) is used as a cocatalyst component, the usage ratio can be determined based on the aluminum atom in the compound (A). Specifically, the molar ratio of the aluminum atom in the compound (A) to the transition metal complex [1] is preferably in the range of 0.1 to 10,000, and more preferably in the range of 5 to 2000. When (A1) organoaluminum compound is used as compound (A), the molar ratio of compound (A1) / transition metal complex (1) is more preferably in the range of 0.3 to 500, and still more preferably 0.5 to 100. Range.
Moreover, when using a compound (B) as a cocatalyst component, the molar ratio of a compound (B) / transition metal complex (1) is the range of 0.01-100, Preferably it is the range of 0.5-10.

  In the preparation of the catalyst for olefin polymerization, the transition metal complex [1] and the cocatalyst component can be brought into contact with each other in an appropriate solvent. As the solvent at this time, a solvent capable of dissolving the transition metal complex [1] is preferably used. In preparing the olefin polymerization catalyst, the concentration of the transition metal complex [1] may be in the range of 0.0001 to 5 mmol / L, and preferably in the range of 0.001 to 1 mmol / L. When the compound (A) is used as a cocatalyst component, the concentration of the compound (A) may be in the range of 0.01 to 500 mmol / L in terms of aluminum atom, preferably 0.1 to 100 mmol / L. It is a range. When the compound (B) is used as a cocatalyst component, the concentration of the compound (B) may be in the range of 0.0001 to 5 mmol / L, and preferably in the range of 0.001 to 1 mmol / L.

  As the cocatalyst component, compound (A) is preferable, and among the compounds (A), (A1) organoaluminum compound is preferable. Further, when (A1) an organoaluminum compound is used as a cocatalyst component, the transition metal complex [1] and (A1) an organoaluminum compound are brought into contact with each other in advance before being introduced into the polymerization reaction apparatus, so that an olefin polymerization catalyst is prepared. It is preferable to prepare, and it is more preferable to contact the transition metal complex [1] and the (A1) organoaluminum compound in the absence of a monomer.

<Olefin polymer production method>
In the present invention, the monomer used for polymerization is ethylene; propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 3-methyl-1-pentene. An α-olefin having 3 to 20 carbon atoms, such as 4-methyl-1-pentene, 3,3-dimethyl-1-butene, 5-methyl-1-hexene, and 3,3-dimethyl-1-pentene; , 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-me 1,4-hexadiene, 7-methyl-1,6-octadiene, 3-methyl-1,4-hexadiene, 3-methyl-1,5-hexadiene, 3-ethyl-1,4-hexadiene, 3- Non-conjugated dienes such as ethyl-1,5-hexadiene, 3,3-dimethyl-1,4-hexadiene, 3,3-dimethyl-1,5-hexadiene; 1,3-butadiene, isoprene, 1,3-hexadiene Conjugated dienes such as 1,3-octadiene; norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, tetracyclododecene, tricyclodecene, tricycloundecene , Pentacyclopentadecene, pentacyclohexadecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene Monoolefins such as 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, norbornadiene, 5-methylene-2-norbornene, 1,5-cyclooctadiene, 7-methyl-2,5 -Norbornadiene, 7-ethyl-2,5-norbornadiene, 7-propyl-2,5-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-norbornadi 1-methyl-2,5-norbornadiene, 1-ethyl-2,5-norbornadiene, 1-propyl-2,5-norbornadiene, 1-butyl-2,5-norbornadiene, 1-chloro-2,5- Non-conjugated dienes such as norbornadiene, 1-bromo-2,5-norbornadiene, 5,8-endomethylenehexahydronaphthalene and vinylcyclohexene; conjugated dienes such as 1,3-cyclooctadiene and 1,3-cyclohexadiene; styrene , O-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, α-methylstyrene, divinylbenzene, and other aromatic compounds Can be mentioned.

  Among the olefin polymers, a copolymer composed of two or more olefins is a suitable combination of monomers for production, for example, a copolymer composed of two olefins is a suitable combination of monomers for production. Are ethylene / propylene, ethylene / butene-1, ethylene / 1-hexene, ethylene / vinylcyclohexane, propylene / 1-butene and the like. Further, a combination of 5-ethylidene-2-norbornene and the like is exemplified.

  The form of the production method of the olefin polymer is not particularly limited, and solution polymerization or slurry polymerization using a solvent, and a vinyl compound having a bulky substituent and another olefin are both in a gaseous state in a standard state. In some cases, gas phase polymerization may be used. Examples of the solvent used for solution polymerization or slurry polymerization include aliphatic hydrocarbons (butane, pentane, hexane, cyclohexane, heptane, octane, etc.), aromatic hydrocarbons (benzene, toluene, etc.), or halogenated hydrocarbons (methylene dichloride). And the like, and a solvent for olefin polymerization (especially an olefin polymerization catalyst comprising the transition metal complex [1] and the cocatalyst component) containing the transition metal complex [1] in the solvent is dissolved or dispersed. In addition, an olefin polymer can be produced by mixing a bulky group-containing olefin and another olefin in this solution or dispersion. In the case of gas phase polymerization, for example, a reactor charged with an olefin polymerization catalyst containing the transition metal complex [1] (in particular, an olefin polymerization catalyst comprising the transition metal complex [1] and the cocatalyst component). The bulky group-containing olefin and other olefin gas can be used for polymerization. The solution polymerization, slurry polymerization, or gas phase polymerization shown here can be either continuous polymerization or batch polymerization.

  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 in the range from normal pressure (atmospheric pressure) to 90 MPa. The polymerization time is appropriately determined depending on the type of the target olefin polymer and the reaction apparatus, but can be in the range of 1 minute to 20 hours. In addition, a chain transfer agent such as hydrogen can be added to adjust the molecular weight of the olefin polymer.

  According to the olefin polymerization catalyst containing the transition metal complex [1] of the present invention, when an olefin polymer is produced by copolymerization using the α-olefin and the other olefin as described above, an excess α-olefin is removed. Even if it is not used, an olefin polymer having a high α-olefin copolymerization ratio can be produced.

  In order to increase the copolymerization ratio of the α-olefin, a sterically appropriate space is required around the central metal M in the transition metal complex [1] for allowing the α-olefin to undergo a coordination-insertion reaction. The three-dimensional space (coordination field) around the central metal M in the transition metal complex [1] can be confirmed by X-ray crystal structure analysis of the transition metal complex [1].

（式中、Ｍ、Ｒ^７、Ｒ^８、Ｒ^９及びＲ^１０は前記と同じ意味を示し、Ｃ^１、Ｃ^２、Ｃ^３、Ｃ^４及びＣ^５はシクロペンタジエン環の炭素原子を示し、右肩の数字はこれらを区別するために付したものである。Ｙは、Ｃ^１、Ｃ^２、Ｃ^３、Ｃ^４及びＣ^５で形成されるシクロペンタジエン環と遷移金属原子Ｍとの結合点を模式的に表すものであり、該シクロペンタジエン環の中心点である。）
で示される部分構造において、Ｃ^１−Ｙ−Ｍの角度（以下、Ｃ^１−Ｙ−Ｍの角度をβとする）の大きさで中心金属Ｍの周辺の立体的な空間を表すことができる。すなわち、βが小さい場合、図１（Ａ）に示すとおり、相対的に、α−オレフィンが配位−挿入反応を起こすために接近する配位場が広くなり、α−オレフィンの接近がより有利となり、α−オレフィンの共重合比を高めることができる。逆に、βが大きい場合、図１（Ｂ）に示すとおり、相対的に、α−オレフィンが配位−挿入反応を起こすために接近する配位場が狭くなり、α−オレフィンの接近がより不利となる。βは８１°以下であると好ましい。 For example, in the transition metal complex [1], the formula [7]

(In the formula, M, R ⁷ , R ⁸ , R ⁹ and R ¹⁰ have the same meaning as described above, C ¹ , C ² , C ³ , C ⁴ and C ⁵ represent carbon atoms of the cyclopentadiene ring, The number on the shoulder is attached to distinguish them from each other Y represents the point of attachment between the cyclopentadiene ring formed by C ¹ , C ² , C ³ , C ⁴ and C ⁵ and the transition metal atom M. (It is schematically represented and is the center point of the cyclopentadiene ring.)
In the partial structure represented in, it can be represented C 1 ^-Y-M angle (hereinafter, the angle of the C 1 ^-Y-M and beta) three-dimensional space around the central metal M in the size of the . That is, when β is small, as shown in FIG. 1 (A), the coordinating field in which the α-olefin is relatively approached to cause the coordination-insertion reaction becomes relatively wide, and the approach of the α-olefin is more advantageous. Thus, the α-olefin copolymerization ratio can be increased. On the other hand, when β is large, as shown in FIG. 1 (B), the coordinating field that the α-olefin relatively approaches to cause the coordination-insertion reaction is narrowed, and the α-olefin is more approached. Disadvantageous. β is preferably 81 ° or less.

Similarly to β, the C ¹ , C ² , C ³ , C ^4, and the bond length between C ⁵ and M can be mentioned as a three-dimensional space around the central metal M. That is, as compared with the C 1 ^-M bond length, C 3 when ^-M bond lengths and C ⁴ -M bond length is long, if β is small as well as α- olefin coordination - to cause insertion reaction The approaching coordinating field becomes wider, the approach of the α-olefin becomes more advantageous, and the copolymerization ratio of the α-olefin can be increased. The C ³ -M bond length and the C ⁴ -M bond length are preferably 2.52 mm or more.

  The three-dimensional space around the central metal M in the transition metal complex [1] can be confirmed by various molecular orbital calculations of the transition metal complex [1].

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

<Manufacture of 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: JEOL Ltd. JMS-AX505W
Ionization voltage: 70 eV
Ion source temperature: 230 ° C
Data processing device: MS-MP8020D
MASS RANGE: m / z 35-1000

[Experimental Example 1]
“Diethylsilylene (cyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (hereinafter referred to as“ complex 1 ”) .)) "
4H-cyclopenta [2,1-b: 3,4-b ′] dithiophene was synthesized according to methods described in the known art (see, for example, Tetrahedron 1968, 24, 3381.).
Under a nitrogen atmosphere, 4H-cyclopenta [2,1-b: 3,4-b ′] dithiophene (0.83 g, 4.68 mmol) was dissolved in toluene (17 mL), and this was cooled to −78 ° C. To this solution, a 1.56 M hexane solution (3.00 mL, 4.68 mmol) of n-butyllithium was added dropwise. The temperature was gradually raised to room temperature, and the mixture was further stirred at room temperature for 3 hours. After the reaction, the solvent was concentrated under reduced pressure, and the precipitate obtained by adding pentane was filtered and vacuum dried to obtain 1.54 g of a white solid. 0.86 g of the obtained white solid was dissolved in tetrahydrofuran (17 mL), and this was cooled to -78 ° C. A solution prepared by dissolving (2-allyloxy-3-tert-butyl-5-methylphenyl) diethylsilane (1.52 g, 4.67 mmol) in toluene (2 mL) was added dropwise to this solution. The temperature was gradually raised to room temperature, and the mixture was stirred at room temperature for 3 hours. The solvent was concentrated under reduced pressure, hexane was added to remove insoluble matters by filtration, and the filtrate was concentrated to give (2-allyloxy-3-tert-butyl-5-methylphenyl) (4H-cyclopenta [2,1 -B: 3,4-b '] dithiophen-4-yl) diethylsilane was obtained as a brown oil (1.96 g).

A toluene solution (24 mL) of triethylamine (1.15 g, 11.41 mmol) was prepared, and the brown oil (1.96 g) obtained above was added thereto under a nitrogen atmosphere. After cooling to −78 ° C., a 1.56M hexane solution (3.66 mL, 5.71 mmol) of n-butyllithium was added dropwise. The mixture was gradually warmed to room temperature and then stirred at room temperature for 3 hours. The obtained mixture was cooled to −78 ° C., and a solution of titanium tetrachloride (0.72 g, 3.80 mmol) in toluene (4 mL) was added dropwise at the same temperature. Again, the temperature was raised to room temperature and stirred for 2 hours. Hexane was added and filtered to remove insoluble matters, and the solvent was concentrated from the filtrate under reduced pressure. Pentane was added to the residue, the precipitated solid was filtered, washed with a small amount of pentane, and then dried under reduced pressure to obtain Complex 1 (45 mg, yield 4%) as a brown solid.
¹ H-NMR (CDCl ₃ , δ ppm): 0.99-1.08 (m, 6H), 1.16-1.26 (m, 4H), 1.26 (s, 9H), 2.41 ( s, 3H), 6.91 (d, J = 5.4 Hz, 2H), 7.20 (s, 1H), 7.21 (s, 1H), 7.57 (d, J = 5.4 Hz, 2H)
¹³ C-NMR (CDCl ₃ , δ ppm): 4.88, 7.39, 21.34, 29.84, 34.78, 101.93, 122.18, 126.93, 129.58, 132.37 133.66, 133.70, 135.73, 136.47, 146.98, 168.79
Mass spectrum (EI-HRMS, m / z): calcd 542.02073, found 542.01882.

[Experiment 2]
“Diethylsilylene (2,6-dimethylcyclopenta [2,1-b: 3,4-b ′] dithiophen-4-yl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride "Synthesis of" Complex 2 ")
2,6-Dimethyl-4H-cyclopenta [2,1-b: 3,4-b ′] dithiophene was synthesized according to a method described in the known art (for example, see WO 01/47939).
Except for using 2,6-dimethyl-4H-cyclopenta [2,1-b: 3,4-b ′] dithiophene instead of 4H-cyclopenta [2,1-b: 3,4-b ′] dithiophene Synthesis was performed in the same manner as in Experimental Example 1 to obtain Complex 2 (450 mg, 33% yield) as a brown solid.
¹ H-NMR (CDCl ₃ , δ ppm): 0.99-1.07 (m, 6H), 1.14-1.23 (m, 4H), 1.26 (s, 9H), 2.41 ( s, 3H), 2.53 (d, J = 1.2 Hz, 6H), 6.55 (d, J = 1.2 Hz, 2H), 7.19 (s, 2H)
¹³ C-NMR (CDCl ₃ , δ ppm): 4.83, 7.40, 16.96, 21.35, 29.74, 34.78, 101.55, 119.27, 126.87, 129.44 131.59, 133.25, 133.71, 136.38, 147.34, 151.15, 168.65
Mass spectrum (EI-HRMS, m / z): calcd 570.05203, found 570.05015.

The structure of the complex 2 obtained here was performed by X-ray crystal structure analysis. A single crystal suitable for X-ray crystal structure analysis was obtained by gradually evaporating a toluene solution of Complex 2 at room temperature. Β of Complex 2 was 80.9 °. The X-ray crystal structure of Complex 2 is shown in FIG. The C ¹ -M bond length, C ² -M bond length, C ³ -M bond length, C ⁴ -M bond length and C ⁵ -M bond length are shown in Table 2 below.

[Experiment 3]
<Ethylene / 1-hexene copolymerization>
After the atmosphere in the 400 mL autoclave was replaced with argon, 15 mL of 1-hexene and 185 mL of dehydrated toluene were added. After raising the temperature to 180 ° C., 2.5 MPa of ethylene was charged. A toluene solution of triisobutylaluminum (0.3 mmol) [concentration of Al atom equivalent to 20.3 wt% manufactured by Tosoh Finechem Co., Ltd.] is charged, and then a solution of complex 1 (0.5 μmol) dissolved in dehydrated toluene is added. did. Next, a toluene solution of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (hereinafter referred to as AB) (3.0 μmol) was charged into an autoclave to initiate polymerization. After stirring the reaction solution for 2 minutes, 5 mL of ethanol / methanol (9/1) was added to stop the polymerization. The reaction solution was poured into a solution obtained by adding 5% hydrochloric acid (1 mL) to ethanol / methanol (9/1) (500 mL), and an ethylene / 1-hexene copolymer was obtained by filtration. The obtained ethylene / 1-hexene copolymer was washed with methanol and dried under reduced pressure at 80 ° C. for 2 hours. As a result, 0.45 g of ethylene / 1-hexene copolymer was obtained.
The obtained ethylene / 1-hexene copolymer had a weight average molecular weight (Mw) of 79,000 and a molecular weight distribution (Mw / Mn) of 1.9. The 1-hexene content was determined as SCB (number of short chain branches per 1000 carbons of polymer) by FT-IR, and SCB = 34.

[Comparative Example 1]
Instead of complex 1, diethylsilylene (cyclopenta [1,2-b: 4,3-b ′] dithiophen-7-yl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (hereinafter, Except for using “Complex 3”), ethylene / 1-hexene copolymerization was carried out in the same manner as in Experimental Example 3 to obtain 0.81 g of an ethylene / 1-hexene copolymer.
The obtained ethylene / 1-hexene copolymer had a weight average molecular weight (Mw) of 94,000 and a molecular weight distribution (Mw / Mn) of 1.9. The 1-hexene content was determined as SCB (number of short chain branches per 1000 carbons of polymer) in FT-IR, and SCB = 27.

重合活性：単位：ｋｇ／（ｍｍｏｌ−ｃａｔ・ｈｒ）
ＳＣＢ：ポリマー１０００炭素あたりの短鎖分岐数

Polymerization activity: Unit: kg / (mmol-cat · hr)
SCB: number of short chain branches per 1000 carbons of polymer

[Reference Example 1]
Diethylsilylene (2,5-dimethylcyclopenta [1,2-b: 4,3-b ′] dithiophen-7-yl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (hereinafter, X-ray crystal structure analysis of “Complex 4”) was conducted in the same manner as in Experimental Example 2, and β of Complex 4 was 81.6 °. The X-ray crystal structure of Complex 4 is shown in FIG. Complexes 4 ^{shows C} 1 -M bond ^{length, C} 2 -M bond ^{lengths, C} 3 -M bond ^lengths, in Table 2 below ^C 4 -M bond lengths and ^C 5 -M bond length.

Ｃ^１−Ｍ：Ｃ^１−Ｍ結合長：単位Å
Ｃ^２−Ｍ：Ｃ^２−Ｍ結合長：単位Å
Ｃ^３−Ｍ：Ｃ^３−Ｍ結合長：単位Å
Ｃ^４−Ｍ：Ｃ^４−Ｍ結合長：単位Å
Ｃ^５−Ｍ：Ｃ^５−Ｍ結合長：単位Å

C ¹ -M: C ¹ -M bond length: unit Å
C ² -M: C ² -M bond length: unit Å
C ³ -M: C ³ -M bond length: unit Å
C ⁴ -M: C ⁴ -M bond length: unit Å
C ⁵ -M: C ⁵ -M bond length: unit Å

  The transition metal complex of the present invention is particularly useful as a catalyst for olefin polymerization of a copolymer of ethylene and α-olefin.

Claims (8)

Following formula [1]

[In the formula, M represents a group 4 transition metal atom in the periodic table, A represents a group 16 atom in the periodic table, and J represents a group 14 atom in the periodic table.] . R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , X ¹ and X ² are each independently a hydrogen atom, a halogen atom,
An alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
An aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
An aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent;
—Si (R ¹² ) ₃ (three R ^{12 s} each independently represent a hydrogen atom, a hydrocarbon group, or a halogenated hydrocarbon group, and the total number of carbon atoms in the three R ^{12 s} is 1-20. Substituted silyl groups represented by
—N (R ¹³ ) ₂ (two R ¹³ each independently represents a hydrocarbon group or a halogenated hydrocarbon group, and the total number of carbon atoms in the two R ¹³ is 2 to 20). A disubstituted amino group,
An alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent;
An aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent or an aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent;
Of R ¹ , R ² , R ³ and R ⁴ , groups bonded to two adjacent carbon atoms may be bonded to each other to form a ring together with the carbon atoms to which they are bonded, and R ⁷ And R ⁸ may be bonded to form a ring with the carbon atom to which they are bonded, and R ⁹ and R ¹⁰ are bonded to form a ring with the carbon atom to which they are bonded. R ⁵ and R ⁶ may be bonded to form a ring with J. ]
A transition metal complex represented by   The transition metal complex according to claim 1, wherein M is a titanium atom.   The transition metal complex according to claim 1 or 2, wherein A is an oxygen atom.   The transition metal complex according to any one of claims 1 to 3, wherein J is a silicon atom. A method for producing the transition metal complex according to any one of claims 1 to 4,
Following formula [2]

[Wherein, A, J, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ have the same meanings as the formula [1].
R ¹¹ represents —Si (R ¹⁴ ) ₃ (three R ¹⁴ each independently represents a hydrocarbon group or a halogenated hydrocarbon group, and the total number of carbon atoms in the three R ¹⁴ is 3 to 20). .) Represents a trisubstituted silyl group or an organic group having 1 to 20 carbon atoms. ]
A step of reacting a substituted cyclopentadiene compound and a base represented by the formula:
The substituted cyclopentadiene compound reacted with the base and the following formula [3]

(In the formula, M, X ¹ and X ² have the same meanings as those in the formula [1], and X ³ and X ⁴ each independently represent a hydrogen atom, a halogen atom,
An alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
An alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent;
An aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent;
An aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent;
An aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
An aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent;
—Si (R ¹² ) ₃ (three R ^{12 s} each independently represent a hydrogen atom, a hydrocarbon group, or a halogenated hydrocarbon group, and the total number of carbon atoms in the three R ^{12 s} is 1-20. Substituted silyl groups represented by
Or -N (R ¹³ ) ₂ (two R ¹³ each independently represents a hydrocarbon group or a halogenated hydrocarbon group, and the total number of carbon atoms in the two R ¹³ is 2 to 20). And n represents 0 or 1. )
A step of reacting a transition metal compound represented by:
A manufacturing method comprising:   An olefin polymerization catalyst prepared from the transition metal complex according to claim 1. The transition metal complex according to any one of claims 1 to 4,
The following compound (A) and / or the following compound (B),
Olefin polymerization catalyst obtained by mixing.
Compound (A): One or more aluminum compounds selected from the group consisting of the following (A1), (A2) and (A3) (A1): an organoaluminum compound represented by the formula E ¹ _a AlZ _3-a ( A2): cyclic aluminoxane (A3) having a structure represented by the formula {—Al (E ² ) —O—} _b : Formula E ³ {—Al (E ³ ) —O—} _c Table represented by AlE 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 Even if it is.)
Compound (B): One or more boron compounds (B1) selected from the group consisting of the following (B1), (B2) and (B3): Boron compound (B2) represented by the formula BQ ¹ Q ² Q ³ : Boron compound represented by formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- (B3): Boron compound represented by formula (L ¹ -H) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- (In the formula, B represents a boron atom in a trivalent valence state, and Q ¹ , Q ² , Q ³ and Q ⁴ are each independently a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a substituted silyl group, Represents an alkoxy group or a disubstituted amino group, G ⁺ represents an inorganic or organic cation, and L ¹ represents a neutral Lewis base.)   The manufacturing method of the olefin polymer which has the process of superposing | polymerizing an olefin in presence of the catalyst for olefin polymerization described in Claim 6 or 7.

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