JP2011079761A - Transition metal complex, process for producing the same and process for producing olefin polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transition metal complex useful in an olefin polymerization catalyst capable of producing a high molecular weight olefin polymer. <P>SOLUTION: The transition metal complex is represented by formula [1] (wherein M is a group 4 transition metal atom in the element periodic table; A is a group 16 atom in the element periodic table; J is a group 14 atom in the element periodic table; Cp is a group having a cyclopentadienyl type anionic skeleton; R<SP>6</SP>is a 3-20C alicyclic hydrocarbon group; R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>, R<SP>4</SP>, R<SP>5</SP>, X<SP>1</SP>, and X<SP>2</SP>are each an alkyl group, an alkoxy group, an aryloxy group, halogen, hydrogen or the like). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a transition metal complex, a method for producing the same, and a method for producing an olefin polymer.

  Among single-site polymerization catalysts, Group 4 transition metal complexes having a compound in which cyclopentadiene and phenol are bonded via Group 14 atoms have been proposed to be highly active olefin polymerization catalysts. A method for producing an olefin polymer using an olefin polymerization catalyst is disclosed in Patent Document 1. By the way, it is known that the olefin polymer can further improve characteristics such as impact resistance and rigidity by increasing its molecular weight.

JP-A-9-87313

  However, the olefin polymerization catalyst obtained from the transition metal complex described in Patent Document 1 may have insufficient polymerization activity in order to obtain a higher molecular weight olefin polymer. There was room for improvement.

（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族の原子を表し、Ｃｐはシクロペンタジエニル型アニオン骨格を有する基を表す。
Ｒ^６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３〜２０の脂環式炭化水素基を表す。
Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｘ^１及びＸ^２はそれぞれ独立に、
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（Ｒ¹⁰）_３（３つのＲ¹⁰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Ｒ¹⁰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（Ｒ²⁰）_２（２つのＲ²⁰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、２つのＲ²⁰のうち少なくとも１つは炭化水素基又はハロゲン化炭化水素基であり、２つのＲ²⁰にある炭素原子数の合計が２〜２０である。）で示される置換アミノ基、
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及び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からなる群より選ばれる置換基であるか、水素原子又はハロゲン原子を表し、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置換基同士は結合して、それらが結合する炭素原子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；
を提供する。 As a result of intensive studies to solve the above problems, the present inventors have reached the present invention.
That is, the present invention
<1> Formula [1]

(In the formula, M represents a transition metal atom of Group 4 of the Periodic Table of Elements, A represents an atom of Group 16 of the Periodic Table of Elements, and J represents an atom of Group 14 of the Periodic Table of Elements) , Cp represents a group having a cyclopentadienyl type anion skeleton.
R ⁶ represents an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a halogen atom as a substituent.
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , X ¹ and X ² are each independently
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 ¹⁰ ) ₃ (three R ^{10 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 ^{10 s} is 1-20. Substituted silyl groups represented by
—N (R ²⁰ ) ₂ (two R ²⁰ each independently represents a hydrogen atom, a hydrocarbon group or a halogenated hydrocarbon group, and at least one of the two R ²⁰ is a hydrocarbon group or a halogenated hydrocarbon. A total of 2 to 20 carbon atoms in two R ²⁰ groups).
An alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent;
Selected from the group consisting of an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent and an aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent Or represents a hydrogen atom or a halogen atom, and among R ¹ , R ² , R ³ and R ⁴ , the substituents bonded to two adjacent carbon atoms are bonded to each other and bonded to each other. A ring may be formed together with the carbon atom. )
A transition metal complex represented by:
I will provide a.

（式中、Ｃｐ、Ａ、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６は、前記式[１]と同じ意味を表し、
Ｒ^７は、−Ｓｉ（Ｒ¹¹）_３（３つのＲ¹¹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Ｒ¹⁰にある炭素原子数の合計が１〜２０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と、
塩基と、
を反応させる第１工程と、
前記第１工程で得られた反応物と、式［３］

（式中、Ｘ^１及びＸ^２は前記式[１]と同じ意味を表し、
Ｘ^３及びＸ^４はそれぞれ独立に、
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（Ｒ¹²）_３（３つのＲ¹²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Ｒ¹²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
及び−Ｎ（Ｒ²²）_２（２つのＲ²⁰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、２つのＲ²²にある炭素原子数の合計が１〜２０である。）で示される置換アミノ基からなる群より選ばれる置換基であるか、水素原子又はハロゲン原子を表す。）
で示される遷移金属化合物と、
を反応させる第２工程と、
を含む製造方法；
を提供する。 The present invention also provides:
<2> A method for producing the transition metal complex according to <1> above,
Formula [2]

(In the formula, Cp, A, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ represent the same meaning as in the formula [1],
R ⁷ represents —Si (R ¹¹ ) ₃ (three R ¹¹ each independently represents a hydrogen atom, a hydrocarbon group or a halogenated hydrocarbon group, and the total number of carbon atoms in three R ¹⁰ is 1 to 3; A trisubstituted silyl group represented by:
Alternatively, it represents an organic group having 1 to 20 carbon atoms. )
A substituted cyclopentadiene compound represented by:
With a base,
A first step of reacting
The reaction product obtained in the first step and the formula [3]

(Wherein, X ¹ and X ² represent the same meaning as in the above formula [1],
X ³ and X ⁴ are each independently
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. ) And -N (R ²² ) ₂ (wherein two R ^{20 s} each independently represent a hydrogen atom, a hydrocarbon group or a halogenated hydrocarbon group, the total number of carbon atoms in the two R ^{22 s)} Is a substituent selected from the group consisting of substituted amino groups represented by formula (1) to (20), or represents a hydrogen atom or a halogen atom. )
A transition metal compound represented by
A second step of reacting
A production method comprising:
I will provide a.

Moreover, this invention provides the manufacturing method of the olefin polymer using the catalyst for olefin polymerization of the following <3> and <4>, and the said catalyst for olefin polymerization.
<3> Olefin polymerization catalyst containing the transition metal complex of <1> above as an active ingredient;
<4> the transition metal complex of <1> above,
The following compound (A) and / or the following compound (B),
An olefin polymerization catalyst obtained by contacting the catalyst;
Compound (A): The following (A1), (A2) and (A3) [hereinafter sometimes referred to as “(A1) to (A3)”. 1 or more types of aluminum compounds (A1) selected from the group consisting of: an organoaluminum compound (A2) represented by the formula E ¹ _a AlZ _3-a : a formula {—Al (E ² ) —O—} _b Cyclic aluminoxane (A3) having a structure represented by the formula: E ³ {-Al (E ³ ) —O—} _c Linear aluminoxane having a structure represented by AlE ³ ₂ (wherein a is 0 < It represents an integer satisfying a ≦ 3, b represents an integer of 2 or more, and c represents an integer of 1 or more.
E ¹ , E ² and E ³ each independently represents a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms. When there are a plurality of E ^{1 in} (A1), they may be the same as or different from each other. When there are a plurality of E ^{2 in} (A2), they may be the same as or different from each other. When there are a plurality of E ^{3 in} (A3), they may be the same as or different from each other. Z represents a hydrogen atom or a halogen atom, and when there are a plurality of Z, they may be the same as or different from each other. )
Compound (B): The following (B1), (B2) and (B3) [hereinafter sometimes referred to as “(B1) to (B3)”. One or more boron compounds (B1) selected from the group consisting of: A boron compound (B2) represented by the formula BQ ¹ Q ² Q ³ : a formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ Boron compound (B3): Boron compound represented by the formula (L ¹ -H) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- (wherein B represents a trivalent valence state boron atom) , Q ¹ , Q ² , Q ³ and Q ⁴ are each independently a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms,
—Si (R ¹³ ) ₃ (Three R ^{13 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 ^{13 s} is 1-20. Substituted silyl groups represented by
An alkoxy group having 1 to 20 carbon atoms or —N (R ²³ ) ₂ (two R ²³ each independently represents a hydrocarbon group or a halogenated hydrocarbon group, and the total number of carbon atoms in two R ^{23 s)} Is a disubstituted amino group represented by formula (2) to (20)), G ⁺ represents an inorganic or organic cation, and L ¹ represents a neutral Lewis base. )

  <5> A method for producing an olefin polymer comprising a step of polymerizing an olefin in the presence of the catalyst for olefin polymerization according to <3> or <4>

  According to the catalyst for olefin polymerization containing the transition metal complex of the present invention as an active ingredient, a high molecular weight olefin polymer can be produced.

  Hereinafter, the present invention will be described in detail.

[Transition metal complexes]
In the transition metal complex represented by the formula [1] (hereinafter referred to as “transition metal complex [1]”) and the transition metal compound represented by the formula [3] (hereinafter referred to as “transition metal compound [3]”). Examples of the Group 4 element in the periodic table of the element represented by M include a titanium atom, a zirconium atom, and a hafnium atom. Among these, a titanium atom is preferable.

  In the transition metal complex [1], examples of the group 16 element in the periodic table of the element represented by A include an oxygen atom, a sulfur atom, and a selenium atom. Among these, an oxygen atom is preferable.

  In the transition metal complex [1], examples of the group 14 element in the periodic table of the element represented by J include a carbon atom, a silicon atom, and a germanium atom. Among these, a silicon atom is preferable.

In the transition metal complex [1], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , X ¹ , X ² , X ³ and X ⁴ are a substituent selected from the group described above, or a halogen atom Or it is a hydrogen atom. R ¹ , R ² , R ³ and R ⁴ bonded to the benzene ring in the transition metal complex [1] may be referred to as “R ^{1 to} R ⁴ ”.
The halogen atom may be any of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, but is preferably a chlorine atom.

Hereinafter, specific examples of the substituent selected from the above group will be described.
Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, amyl Group, n-hexyl group, heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, Nonadecyl group and n-eicosyl group are exemplified, and among them, methyl group, ethyl group, isopropyl group, tert-butyl group and amyl group are preferable.
An alkyl group having a halogen atom as a substituent (halogenated alkyl group) means a group in which part or all of the hydrogen atoms in the alkyl group are substituted with a halogen atom, and the halogen atom is a fluorine atom. , An atom selected from the group consisting of a chlorine atom, a bromine atom and an iodine atom, and when they are substituted with a plurality of halogen atoms, they may be the same or different.

  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, and 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-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl N-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, naphthyl group, anthracenyl group, etc. Illustratively, among them, a phenyl group is preferable. An aryl group having a halogen atom as a substituent (halogenated aryl group) means a group in which part or all of the hydrogen atoms in the aryl group are substituted with halogen atoms. The same as those exemplified for the halogenated alkyl group.

  Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, (2,3-dimethylphenyl) Methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-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, 4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2,3,4,6-tetramethyl) (Phenyl) methyl group, ( 2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group, (isopropylphenyl) methyl group, (n-butyl) (Phenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group, (n-hexylphenyl) methyl group, Examples include n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-decylphenyl) methyl group, naphthylmethyl group and anthracenylmethyl group, and among them, benzyl group is preferable. An aralkyl group having a halogen atom as a substituent (halogenated aralkyl group) means a group in which some or all of the hydrogen atoms in the aralkyl group are substituted with halogen atoms. The same as those exemplified for the alkyl group.

R ¹⁰ in the substituted silyl group represented by -Si (R ¹⁰⁾ ₃ is a hydrogen atom, a hydrocarbon group or a halogenated hydrocarbon group, at least one is a hydrocarbon group or a halogenated of the three R ¹⁰ The total number of carbon atoms of the hydrocarbon group and / or halogenated hydrocarbon group which is a hydrocarbon group and is bonded to silicon is in the range of 1 to 20. In the following description, a group in which one hydrocarbon group or halogenated hydrocarbon group substituent is bonded to a silicon atom is selected from the group consisting of a monosubstituted silyl group and a silicon atom consisting of a hydrocarbon group and a halogenated atom. A group in which two substituents are bonded is a disubstituted silyl group, and a group in which three substituents selected from the group consisting of a hydrocarbon group and a halogen atom are bonded to a silicon atom is a trisubstituted silyl group. To do. In addition, examples of the hydrocarbon group herein include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, Alkyl groups having 1 to 10 carbon atoms such as n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, n-nonyl group and n-decyl group, and 6 to 10 carbon atoms such as phenyl group An aryl group etc. are illustrated. The halogenated hydrocarbon group means a group in which part or all of the hydrogen atoms in the alkyl group or aryl group shown here are substituted with a halogen atom (herein, the halogen atom means the halogenated alkyl). The same as those exemplified in the group). Specific examples of the substituted silyl group include monosubstituted silyl groups such as methylsilyl group, ethylsilyl group and phenylsilyl group, disubstituted silyl groups such as dimethylsilyl group, diethylsilyl group and diphenylsilyl group, trimethylsilyl group, and 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- Examples thereof include trisubstituted silyl groups such as -n-pentylsilyl group, tri-n-hexylsilyl group, tricyclohexylsilyl group, and triphenylsilyl group. Among these, trisubstituted silyl groups such as trimethylsilyl group, tert-butyldimethylsilyl group, and triphenylsilyl group are preferable.

  Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, and neopentyl. Oxy group, n-hexyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-dodecyloxy group, n-undecyloxy group, n-dodecyloxy group, tridecyloxy group, tetra Examples include decyloxy group, n-pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group, nonadecyloxy group, and n-eicosyloxy group, among which methoxy group, ethoxy group, and tert-butoxy group Is preferred. An alkoxy group having a halogen atom as a substituent (halogenated alkoxy group) means a group in which some or all of the hydrogen atoms in the alkoxy group are substituted with halogen atoms. The same as those exemplified for the alkyl group.

  Examples of the aryloxy group having 6 to 20 carbon atoms include phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy Group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-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, pentamethyl Enoxy group, ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decyl Examples include phenoxy group, n-tetradecylphenoxy group, naphthoxy group and anthracenoxy group, among which phenoxy group and naphthoxy group are preferable. An aryloxy group having a halogen atom as a substituent (halogenated aryloxy group) is a group in which part or all of the hydrogen atoms in the aryloxy group are substituted with halogen atoms. The same as those exemplified for the halogenated alkyl group.

  Examples of the aralkyloxy group having 7 to 20 carbon atoms include benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, (4-methylphenyl) methoxy group, (2,3-dimethyl). (Phenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy group, 3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group, 2,4,5-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (3,4,5-trimethylphenyl) methoxy group, (2,3,4,5-tetra (Methylphenyl) 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-hexyl) Phenyl) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, naphthylmethoxy group, anthracenylmethoxy group and the like are exemplified, and among them benzyloxy group is preferable. An aralkyloxy group having a halogen atom as a substituent (halogenated aralkyloxy group) means a group in which some or all of the hydrogen atoms in the aralkyloxy group are substituted with halogen atoms. The same as those exemplified for the halogenated alkyl group.

-N (R ²⁰⁾ R ²⁰ in the substituted amino group represented by ₂ is a hydrogen atom, a hydrocarbon group or a halogenated hydrocarbon group, at least one is a hydrocarbon group or a halogenated one of the two R ²⁰ It is a hydrocarbon group, and the total number of carbon atoms of the two R ²⁰ ranges from 1 to 20. In the following description, a group in which one substituent selected from the group consisting of a hydrocarbon group and a halogenated hydrocarbon group is bonded to a nitrogen atom is a monosubstituted amino group, and two substituents selected from the above group The group to which is bonded is called a disubstituted amino group. Examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, an n-pentyl group, and an n-hexyl group. And an alkyl group such as a cyclohexyl group and an aryl group such as a phenyl group, and the two hydrocarbon groups R ²⁰ may be bonded to each other to form a ring together with the nitrogen atom. The halogenated hydrocarbon group is a group in which some or all of the hydrogen atoms in the alkyl group or aryl group shown here are substituted with halogen atoms (the examples of the halogen atom here are the halogenated hydrocarbons described above). The same as those exemplified for the alkyl group). Examples of the substituted amino group include methylamino group, ethylamino group, n-propylamino group, isopropylamino group, n-butylamino group, sec-butylamino group, tert-butylamino group, isobutylamino group, n -Hexylamino group, n-octylamino group, n-decylamino group, phenylamino group, monosubstituted amino group such as trimethylsilylamino group and tert-butyldimethylsilylamino group, dimethylamino group, diethylamino group, di-n-propyl Amino group, diisopropylamino group, di-n-butylamino group, di-sec-butylamino group, di-tert-butylamino group, di-isobutylamino group, tert-butylisopropylamino group, di-n-hexylamino Group, di-n-octylamino group, di-n-decyl Disubstituted amino groups such as amino group, diphenylamino group, bistrimethylsilylamino group, bis-tert-butyldimethylsilylamino group, pyrrolyl group, pyrrolidinyl group, piperidinyl group, carbazolyl group, dihydroindolyl group and dihydroisoindolyl group Among them, a disubstituted amino group such as a dimethylamino group, a diethylamino group, a pyrrolidinyl group, or a piperidinyl group is preferable.

Substituents bonded to two adjacent carbon atoms among R ¹ , R ² , R ³ and R ⁴ may be arbitrarily bonded to form a ring together with the carbon atoms to which they are bonded. Examples of the ring formed include saturated or unsaturated hydrocarbon rings having 3 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.

In the transition metal complex [1] of the present invention, R ⁶ is an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a halogen atom as a substituent. When the present inventors have such an alicyclic hydrocarbon group in an atom of Group 14 of the Periodic Table of the Elements bonded to a cyclopentadienyl type anion skeleton, a method for producing an olefin polymer described later Was found to give a high molecular weight olefin polymer. Specific examples of the alicyclic hydrocarbon group include a cyclopropyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantyl group, and a bicycloheptyl group. Preferable examples include cyclohexyl group and adamantyl group. In addition, a group in which part or all of the hydrogen atoms in the alicyclic hydrocarbon group exemplified herein are substituted with a halogen atom can be exemplified. Examples of the halogen atom are the same as the halogen atoms exemplified for the halogenated alkyl group.
Further, the alicyclic hydrocarbon group may have a substituent other than a halogen atom in the range having 20 or less carbon atoms. When the alicyclic hydrocarbon group has a substituent other than a halogen atom, examples of the substituent include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, an amyl group, a phenyl group, a benzyl group, Examples include trimethylsilyl group, tert-butyldimethylsilyl group, triphenylsilyl group, methoxy group, ethoxy group, tert-butoxy group, phenoxy group, naphthoxy group, benzyloxy group, dimethylamino group, diethylamino group, pyrrolidinyl group and piperidinyl group. More preferably, it is a methyl group or an ethyl group. For example, a methyl group is preferable as the substituent when R ⁶ is a cyclohexyl group.

  Examples of the transition metal complex [1] of the present invention include the following compounds.

  Cyclohexylmethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, cyclohexylmethylsilylene (2,3,4,5-tetra Methylcyclopentadienyl) (2-phenoxy) titanium dichloride, cyclohexylmethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (3,4-dimethyl-2-phenoxy) titanium dichloride, cyclohexylmethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, cyclohexylmethylsilylene (2,3,4,5-tetramethylcyclopenta Dienyl) (3-tert-butyl) Ru-5-dimethylamino-2-phenoxy) titanium dichloride, cyclohexylmethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, cyclohexylmethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, cyclohexylmethylsilylene (2,3,4,5-tetramethylcyclopenta Dienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, cyclohexylmethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (3-trimethylsilyl-5-methyl) -2-phenoxy) titani Mujikurorido, cyclohexylmethyl silylene (2,3,4,5-tetramethyl cyclopentadienyl) (2-naphthoxy) titanium dichloride

  Cyclohexylmethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, cyclohexylmethylsilylene (cyclopentadienyl) (2-phenoxy) titanium dichloride, cyclohexylmethylsilylene (cyclopenta Dienyl) (3,4-dimethyl-2-phenoxy) titanium dichloride, cyclohexylmethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, cyclohexylmethylsilylene (cyclopenta) Dienyl) (3-tert-butyl-5-dimethylamino-2-phenoxy) titanium dichloride, cyclohexylmethylsilylene (cyclopentadienyl) (3-tert-butyl- -Phenoxy) titanium dichloride, cyclohexylmethylsilylene (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, cyclohexylmethylsilylene (cyclopentadienyl) (3-tert-butyldimethylsilyl) -5-methyl-2-phenoxy) titanium dichloride, cyclohexylmethylsilylene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, cyclohexylmethylsilylene (cyclopentadienyl) (2-naphthoxy) ) Titanium dichloride

  Cyclohexylmethylsilylene (indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, cyclohexylmethylsilylene (indenyl) (2-phenoxy) titanium dichloride, cyclohexylmethylsilylene (indenyl) (3,4-dimethyl) -2-phenoxy) titanium dichloride, cyclohexylmethylsilylene (indenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, cyclohexylmethylsilylene (indenyl) (3-tert-butyl-5-dimethylamino- 2-phenoxy) titanium dichloride, cyclohexylmethylsilylene (indenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, cyclohexylmethyl chloride Len (indenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, cyclohexylmethylsilylene (indenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, cyclohexylmethyl Silylene (indenyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, cyclohexylmethylsilylene (indenyl) (2-naphthoxy) titanium dichloride

Cyclohexylmethylsilylene (fluorenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, cyclohexylmethylsilylene (fluorenyl) (2-phenoxy) titanium dichloride, cyclohexylmethylsilylene (fluorenyl) (3,4-dimethyl) -2-phenoxy) titanium dichloride, cyclohexylmethylsilylene (fluorenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, cyclohexylmethylsilylene (fluorenyl) (3-tert-butyl-5-dimethylamino- 2-phenoxy) titanium dichloride, cyclohexylmethylsilylene (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, cyclohex Rumethylsilylene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, cyclohexylmethylsilylene (fluorenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, Examples include cyclohexylmethylsilylene (fluorenyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, cyclohexylmethylsilylene (fluorenyl) (2-naphthoxy) titanium dichloride, and the like.
Further, the “cyclohexylmethylsilylene” of the transition metal complex [1] exemplified here is replaced with “cyclohexylethylsilylene”, “cyclopentylmethylsilylene”, “cycloheptylmethylsilylene”, “cyclooctylmethylsilylene”, “1-adamantyl”. (Methyl) silylene ”or“ 2- (bicycloheptyl) methylsilylene ”, or“ titanium ”of transition metal complex [1] exemplified here, replaced with“ zirconium ”or“ hafnium ”, Examples in which “dichloride” in the transition metal complex [1] exemplified in 1 above is replaced by “difluoride”, “dibromide” or “diiodide” are also exemplified.

（式中、Ｃｐ、Ａ、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６は、前記式[１]と同じ意味を表し、
Ｒ^７は、−Ｓｉ（Ｒ¹¹）_３（３つのＲ¹¹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Ｒ¹⁰にある炭素原子数の合計が１〜２０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（以下、「置換シクロペンタジエン化合物［２］」という。）と、
塩基と、
を反応させる第１工程と、
前記第１工程で得られた反応物と、遷移金属化合物［３］

（式中、Ｘ^１及びＸ^２は前記式[１]と同じ意味を表し、
Ｘ^３及びＸ^４はそれぞれ独立に、
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（Ｒ¹²）_３（３つのＲ¹²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Ｒ¹²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
及び−Ｎ（Ｒ²²）_２（２つのＲ²⁰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、２つのＲ²²にある炭素原子数の合計が１〜２０である。）で示される置換アミノ基からなる群より選ばれる置換基であるか、水素原子又はハロゲン原子を表す。）
と、
を反応させる第２工程を含む製造方法により製造することができる。 [Production Method of Transition Metal Complex]
The transition metal complex [1] of the present invention is represented, for example, by the formula [2]

(In the formula, Cp, A, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ represent the same meaning as in the formula [1],
R ⁷ represents —Si (R ¹¹ ) ₃ (three R ¹¹ each independently represents a hydrogen atom, a hydrocarbon group or a halogenated hydrocarbon group, and the total number of carbon atoms in three R ¹⁰ is 1 to 3; A trisubstituted silyl group represented by:
Alternatively, it represents an organic group having 1 to 20 carbon atoms. )
A substituted cyclopentadiene compound (hereinafter referred to as “substituted cyclopentadiene compound [2]”),
With a base,
A first step of reacting
The reaction product obtained in the first step and the transition metal compound [3]

(Wherein, X ¹ and X ² represent the same meaning as in the above formula [1],
X ³ and X ⁴ are each independently
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. ) And a substituted silyl group represented by the formula: —N (R ²² ) ₂ (two R ^{20 s} each independently represent a hydrogen atom, a hydrocarbon group or a halogenated hydrocarbon group, and the total number of carbon atoms in two R ^{22 s)} Is a substituent selected from the group consisting of substituted amino groups represented by formula (1) to (20), or represents a hydrogen atom or a halogen atom. )
When,
It can manufacture by the manufacturing method including the 2nd process of making this react.

Here, in X ¹ and X ² , an alkyl group optionally having a halogen atom as a substituent, an alkoxy group optionally having a halogen atom as a substituent, and a halogen atom as a substituent An aryloxy group which may have a halogen atom as a substituent, an aralkyl group which may have a halogen atom as a substituent, and an aralkyl which may have a halogen atom as a substituent Specific examples of the oxy group are the same as those of the transition metal complex [1], and examples of the substituted silyl group and the substituted amino group are also the same as those of the transition metal complex [1].

Examples of the organic group of R ^{7 in} the substituted cyclopentadiene compound [2] include carbon such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group. An alkyl group having 1 to 10 atoms; carbon 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 Alkenyl groups having 2 to 10 atoms; aralkyl groups having 7 to 12 carbon atoms such as benzyl, (4-methylphenyl) methyl and (2,4,6-trimethylphenyl) methyl; methoxymethyl and methoxy And alkoxyalkyl groups such as ethoxymethyl group. Any of these organic groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and examples thereof include a 2-chloro-2-propenyl group.

Examples of the trisubstituted silyl group in R ⁷ are the same as those exemplified as the trisubstituted silyl group of the transition metal complex [1].

R ⁷ is preferably an alkenyl group or an alkyl group, more preferably an alkyl group, more preferably a transition metal complex [1] from the substituted cyclopentadiene compound [2] and the transition metal compound [3]. An allyl group or a methyl group.

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

  (2-allyloxyphenyl) (2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl) cyclohexylmethylsilane, (2-allyloxy-3-methylphenyl) (2,3, 4,5-tetramethylcyclopenta-2,4-dien-1-yl) cyclohexylmethylsilane, (2-allyloxy-3,5-dimethylphenyl) (2,3,4,5-tetramethylcyclopenta-2 , 4-Dien-1-yl) cyclohexylmethylsilane, (2-allyloxy-3-tert-butylphenyl) (2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl) cyclohexyl Methylsilane, (2-allyloxy-3-tert-butyl-5-methylphenyl) (2,3,4,5-tetramethylcyclopenta-2,4-diene 1-yl) cyclohexylmethylsilane, (2-allyloxy-3,5-di-tert-butylphenyl) (2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl) cyclohexylmethyl Silane, (2-allyloxy-5-methyl-3-phenylphenyl) (2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl) cyclohexylmethylsilane, (2-allyloxy-5 -Methyl-3-trimethylsilylphenyl) (2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl) cyclohexylmethylsilane, (2-allyloxy-3-tert-butyldimethylsilyl-5) -Methylphenyl) (2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl) cyclohexylmethyl Lan, (2-allyloxy-3,5-diamylphenyl) (2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl) cyclohexylmethylsilane, (2-allyloxy-3- tert-butyl-5-methoxyphenyl) (2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl) cyclohexylmethylsilane, (2-allyloxy-5-tert-butyl-3- Chlorophenyl) (2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl) cyclohexylmethylsilane, (1-allyloxynaphthalen-2-yl) (2,3,4,5- Tetramethylcyclopenta-2,4-dien-1-yl) cyclohexylmethylsilane, (2-allyloxy-3-tert-butyl-5-methoxyphenyl) ( 2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl) cyclohexylmethylsilane,

  (2-allyloxyphenyl) (cyclopentadienyl) cyclohexylmethylsilane, (2-allyloxy-3-methylphenyl) (cyclopentadienyl) cyclohexylmethylsilane, (2-allyloxy-3,5-dimethylphenyl) ( Cyclopentadienyl) cyclohexylmethylsilane, (2-allyloxy-3-tert-butylphenyl) (cyclopentadienyl) cyclohexylmethylsilane, (2-allyloxy-3-tert-butyl-5-methylphenyl) (cyclopenta Dienyl) cyclohexylmethylsilane, (2-allyloxy-3,5-di-tert-butylphenyl) (cyclopentadienyl) cyclohexylmethylsilane, (2-allyloxy-5-methyl-3-phenylphenyl) (cyclopenta Dienyl) cyclo Xylmethylsilane, (2-allyloxy-5-methyl-3-trimethylsilylphenyl) (cyclopentadienyl) cyclohexylmethylsilane, (2-allyloxy-3-tert-butyldimethylsilyl-5-methylphenyl) (cyclopentadi) Enyl) cyclohexylmethylsilane, (2-allyloxy-3,5-diamilphenyl) (cyclopentadienyl) cyclohexylmethylsilane, (2-allyloxy-3-tert-butyl-5-methoxyphenyl) (cyclopentadienyl) ) Cyclohexylmethylsilane, (2-allyloxy-5-tert-butyl-3-chlorophenyl) (cyclopentadienyl) cyclohexylmethylsilane, (1-allyloxynaphthalen-2-yl) (cyclopentadienyl) cyclohexylmethylsilane Down, (2-allyloxy -3-tert-butyl-5-methoxyphenyl) (cyclopentadienyl) cyclohexylmethyl silane,

  (2-allyloxyphenyl) (indenyl) cyclohexylmethylsilane, (2-allyloxy-3-methylphenyl) (indenyl) cyclohexylmethylsilane, (2-allyloxy-3,5-dimethylphenyl) (indenyl) cyclohexylmethylsilane, (2-allyloxy-3-tert-butylphenyl) (indenyl) cyclohexylmethylsilane, (2-allyloxy-3-tert-butyl-5-methylphenyl) (indenyl) cyclohexylmethylsilane, (2-allyloxy-3,5 -Di-tert-butylphenyl) (indenyl) cyclohexylmethylsilane, (2-allyloxy-5-methyl-3-phenylphenyl) (indenyl) cyclohexylmethylsilane, (2-allyloxy-5-methyl-3-trimethylsilyl) Phenyl) (indenyl) cyclohexylmethylsilane, (2-allyloxy-3-tert-butyldimethylsilyl-5-methylphenyl) (indenyl) cyclohexylmethylsilane, (2-allyloxy-3,5-diamylphenyl) (indenyl) Cyclohexylmethylsilane, (2-allyloxy-3-tert-butyl-5-methoxyphenyl) (indenyl) cyclohexylmethylsilane, (2-allyloxy-5-tert-butyl-3-chlorophenyl) (indenyl) cyclohexylmethylsilane, ( 1-allyloxynaphthalen-2-yl) (indenyl) cyclohexylmethylsilane, (2-allyloxy-3-tert-butyl-5-methoxyphenyl) (indenyl) cyclohexylmethylsilane,

  (2-allyloxyphenyl) (fluorenyl) cyclohexylmethylsilane, (2-allyloxy-3-methylphenyl) (fluorenyl) cyclohexylmethylsilane, (2-allyloxy-3,5-dimethylphenyl) (fluorenyl) cyclohexylmethylsilane, (2-allyloxy-3-tert-butylphenyl) (fluorenyl) cyclohexylmethylsilane, (2-allyloxy-3-tert-butyl-5-methylphenyl) (fluorenyl) cyclohexylmethylsilane, (2-allyloxy-3,5 -Di-tert-butylphenyl) (fluorenyl) cyclohexylmethylsilane, (2-allyloxy-5-methyl-3-phenylphenyl) (fluorenyl) cyclohexylmethylsilane, (2-allyloxy-5-methyl-3-) Limethylsilylphenyl) (fluorenyl) cyclohexylmethylsilane, (2-allyloxy-3-tert-butyldimethylsilyl-5-methylphenyl) (fluorenyl) cyclohexylmethylsilane, (2-allyloxy-3,5-diamylphenyl) (Fluorenyl) cyclohexylmethylsilane, (2-allyloxy-3-tert-butyl-5-methoxyphenyl) (fluorenyl) cyclohexylmethylsilane, (2-allyloxy-5-tert-butyl-3-chlorophenyl) (fluorenyl) cyclohexylmethyl Silane, (1-allyloxynaphthalen-2-yl) (fluorenyl) cyclohexylmethylsilane, (2-allyloxy-3-tert-butyl-5-methoxyphenyl) (fluorenyl) cyclohexylmethyl Run,

  In the substituted cyclopentadiene compound [2] exemplified here, “cyclohexylmethylsilane” is replaced with “cyclohexylethylsilane”, “cyclopentylmethylsilane”, “cycloheptylmethylsilane”, “cyclooctylmethylsilane”, “1” An example in which “adamantyl (methyl) silane” or “2- (bicycloheptyl) methyl silane” is substituted can also be exemplified.

  Examples of the transition metal compound [3] include titanium halides such as titanium tetrachloride, titanium tetrabromide and titanium tetraiodide; tetrakis (dimethylamino) titanium, dichlorobis (dimethylamino) titanium, trichloro (dimethylamino) titanium. And amide titanium such as tetrakis (diethylamino) titanium; alkoxytitanium such as tetraisopropoxytitanium, tetra-n-butoxytitanium, dichlorodiisopropoxytitanium and trichloroisopropoxytitanium; Moreover, what replaced "titanium" of each of these compounds with "zirconium" or "hafnium" can also be illustrated. Since M of the transition metal complex [1] is preferably a titanium atom, a transition metal compound [3] containing a titanium atom is preferable, and among these, titanium tetrachloride is more preferable.

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

  The amount of the base used is preferably 0.5 to 5 mol per 1 mol of the substituted cyclopentadienyl compound [2].

  In the step of reacting the substituted cyclopentadiene compound [2] with a base, an amine compound can be used in combination with the above-mentioned 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; Amines, diethylamine, di-n-propylamine, di-n-propylamine, di-n-butylamine, di-tert-butylamine, di-n-octylamine, di-n-decylamine, pyrrolidine, hexamethyldisilazane and Secondary amine compounds such as diphenylamine; trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, diisopropylethylamine, tri-n-octylamine, tri-n-decylamine, triphenyl Triethanolamine, N, N- dimethylaniline, N, N, N ', N'-tetramethylethylenediamine, tertiary amine compounds such as N- methylpyrrolidine and 4-dimethylaminopyridine; and the like. When using such an amine compound, the amount 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 method for producing the transition metal compound [1] of the present invention including the first step and the second step described above, it is easy to perform the first step and the second step in the same solvent. preferable. In this case, the first step is performed by adding and mixing the substituted cyclopentadiene compound [2] and the base in a solvent, and then the second step is performed by adding the transition metal compound [3] to the reaction solution. Can do. In the first step, after adding the substituted cyclopentadiene compound [2] and the base, a solid may precipitate from the reaction solution. In this case, after the solid is once taken out from the reaction solution, a solvent is added to the taken-out solid to form a slurry or solution, and then the transition metal compound [3] is added to perform the second step. . Moreover, the 1st process and a 2nd process can also be performed substantially simultaneously by adding substituted cyclopentadiene compound [2], a base, and a transition metal compound [3] to a solvent simultaneously.

  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 is selected from −100 ° C. to the boiling point of the solvent, but is preferably in the range of −80 to 100 ° C.

  The first step and the second step are performed in an inert solvent that does not significantly inhibit the progress of the reaction according to each step. The inert solvent is preferably an aprotic solvent, for example, aromatic hydrocarbon solvents such as benzene and toluene; aliphatic hydrocarbon solvents such as hexane and heptane; diethyl ether, tetrahydrofuran and 1,4-dioxane. Ether solvents; amide solvents such as hexamethylphosphoric amide and dimethylformamide; polar solvents such as acetonitrile, propionitrile, acetone, diethyl ketone, methyl isobutyl ketone and cyclohexanone; halogenated carbonization such as dichloromethane, dichloroethane, chlorobenzene and dichlorobenzene A hydrogen solvent; and the like. Each of these solvents is used alone or in admixture of two or more. 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 transition metal complex [1] can be extracted from the reaction mixture after production of the transition metal complex [1] of the present invention by various extraction methods. For example, the target transition metal complex [1] can be obtained by concentrating the reaction solution to precipitate the transition metal complex [1] and then collecting the transition metal complex [1] by filtration. In addition, before concentrating a reaction liquid in this way, a salt etc. may precipitate. In that case, the precipitated salt may be removed by filtration or the like, and then the filtrate may be concentrated.

[Olefin polymerization catalyst]
The transition metal complex [1] of the present invention is useful as an active ingredient of an olefin polymerization catalyst. The “effective component of the olefin polymerization catalyst” as used herein is not only the olefin polymerization catalyst containing the transition metal complex [1], but also the transition metal complex [1] and other compounds (cocatalyst components). And a catalyst for olefin polymerization prepared from the above. In particular, an olefin polymerization catalyst prepared from the transition metal complex [1] and a cocatalyst component is preferable in that the polymerization activity for producing the olefin polymer can be further increased.
Hereinafter, the olefin polymerization catalyst prepared from the transition metal complex [1] and the cocatalyst component will be described in detail. Preparation of such an olefin polymerization catalyst is carried out by mixing the transition metal complex [1] and a cocatalyst component. As the cocatalyst component, the following compound (A) or compound (B) or a mixture thereof is particularly preferable.
Compound (A): One or more aluminum compounds selected from the group consisting of the following (A1) to (A3) (A1): Organoaluminum compound represented by formula E ¹ _a AlZ _3-a (A2): Formula { —Al (E ² ) —O—} Cyclic aluminoxane (A3) having a structure represented by _b : Formula E ³ {—Al (E ³ ) —O—} _c having a structure represented by AlE ³ ₂ Linear aluminoxane (wherein, a represents an integer satisfying 0 <a ≦ 3, b represents an integer of 2 or more, and c represents an integer of 1 or more.
E ¹ , E ² and E ³ each independently represents a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms. When there are a plurality of E ^{1 in} (A1), they may be the same as or different from each other. When there are a plurality of E ^{2 in} (A2), they may be the same as or different from each other. When there are a plurality of E ^{3 in} (A3), they may be the same as or different from each other. Z represents a hydrogen atom or a halogen atom, and when there are a plurality of Z, they may be the same as or different from each other. )

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 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 having 1 to 20 carbon atoms, or a carbon atom having 1 to 20 carbon atoms. Halogenated hydrocarbon groups,
—Si (R ¹³ ) ₃ (Three R ^{13 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 ^{13 s} is 1-20. Substituted silyl groups represented by
An alkoxy group having 1 to 20 carbon atoms or —N (R ²³ ) ₂ (two R ²³ each independently represents a hydrocarbon group or a halogenated hydrocarbon group, and the total number of carbon atoms in two R ^{23 s)} Is a disubstituted amino group represented by formula (2) to (20)), G ⁺ represents an inorganic or organic cation, and L ¹ represents a neutral Lewis base. )

Examples of the substituted silyl group in Q ¹ , Q ² , Q ³ and Q ⁴ are the same as those exemplified as the substituted silyl group of the transition metal complex [1].

Examples of the disubstituted amino group in Q ¹ , Q ² , Q ³ and Q ⁴ are the same as those exemplified as the disubstituted amino group among those exemplified as the substituted amino group of the transition metal complex [1].

The aluminum compounds (A1) to (A3) will be described.
(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 groups such as a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, an isobutyl group, a normal pentyl group, and a neopentyl group. 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 cyclic or linear aluminoxane can be produced 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. In addition, a method of making a trialkylaluminum (for example, trimethylaluminum) by contacting with a metal salt (for example, copper sulfate hydrate) containing water of crystallization can be mentioned.

  As the compound (A), any one of an organoaluminum compound (A1), a cyclic aluminoxane (A2), or a linear aluminoxane (A3) may be used, or one or more may be used. .

Next, the boron compounds (B1) to (B3) will be described.
(B1): In the boron compound represented by the formula BQ ¹ Q ² Q ³ , Q ^{1 to} Q ³ are preferably each independently a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or 1 to carbon atoms. 20 halogenated hydrocarbon groups, substituted silyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms or disubstituted amino groups having 2 to 20 carbon atoms, more preferably halogen atoms, A hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms. Examples of the boron compound (B1) include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, and tris (2,3,4,5-tetrafluorophenyl) borane. , Tris (3,4,5-trifluorophenyl) borane, tris (2,3,4-trifluorophenyl) borane and phenylbis (pentafluorophenyl) borane. preferable.

(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 ⁺ that is an inorganic cation is, for example, a ferrocenium cation, an alkyl-substituted ferrocenium cation, and a silver ion Examples of G ⁺ that is an organic cation include a triphenylmethyl cation. Examples of the anion represented by (BQ ¹ Q ² Q ³ Q ⁴ ) ^— include 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 And tetrakis (3,5-bistrifluoromethylphenyl) borate.
Examples of the boron compound (B2) include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1′-dimethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, and triphenylmethyl. Examples thereof include tetrakis (pentafluorophenyl) borate and triphenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate, and triphenylmethyltetrakis (pentafluorophenyl) borate is preferable.

(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 specific examples and preferred examples of Q ^{1 to} Q ⁴ are the same as those of Q ^{1 to} Q ³ in (B1) above.
In the boron compound of (B3), (L ¹ -H) ⁺ includes, for example, trialkyl-substituted ammonium, N, N-dialkylanilinium, dialkylammonium, triarylphosphonium and the like (BQ ¹ Q ² Q ³ Q ^{4) -} would include the same as (B2) are exemplified.
Examples of the boron compound (B3) include triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (normal butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (normal butyl) Ammonium tetrakis (3,5-bistrifluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-2, 4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (3,5-bistrifluoromethylpheny ) Borate, diisopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate and tri ( Examples thereof include dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, and tri (normal butyl) ammonium tetrakis (pentafluorophenyl) borate and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate are preferable.

  As the compound (B), any one of a boron compound of (B1), a boron compound of (B2), or a boron compound of (B3) may be used, or one or more of them may be used.

  Transition metal complex [1] and a cocatalyst component in the production of an olefin polymerization catalyst (hereinafter, the transition metal complex [1] and the cocatalyst component may be collectively referred to as “two catalyst components”). The mixing method is not particularly limited. For example, as a cocatalyst component, an aluminum compound selected from (A1) to (A3) and a boron compound selected from (B1) to (B3) can be used together. Also in this case, the order of mixing the transition metal complex [1] and the two cocatalyst components is arbitrary.

  Preparation of the olefin polymerization catalyst from the transition metal complex [1] and the cocatalyst component can also be performed in a polymerization reactor. Before the introduction of olefin (monomer) such as ethylene in the polymerization reactor (in the absence of monomer), the transition metal complex [1] is contacted with the organoaluminum compound (A) in advance so that the polymerization takes place. An olefin polymerization catalyst can be preliminarily prepared in the reactor. In addition, the transition metal complex [1] and the cocatalyst component can be charged into a polymerization reactor in which a monomer has been charged in advance.

Among the olefin polymerization catalysts thus prepared, an olefin polymerization catalyst obtained by mixing the transition metal complex [1] and the organoaluminum compound of the compound (A) is preferable. In the olefin polymerization catalyst prepared from the transition metal complex [1] and the organoaluminum compound of the compound (A), the amount ratio of each catalyst component is a transition metal complex for the aluminum atom of the compound (A). The range of 0.1 to 10000 is preferable and the range of 5 to 2000 is more preferable in terms of the molar ratio of [1] used. Moreover, when it represents with the molar ratio of the transition metal complex [1] with respect to the organoaluminum compound of a compound (A), the range of 0.3-500 is preferable and the range of 0.5-100 is more preferable.
When the compound (B) is used as a cocatalyst component, the molar ratio of the transition metal complex [1] to the compound (B) is preferably in the range of 0.01 to 100, and more preferably in the range of 0.5 to 10. .

  When the preparation of the catalyst for olefin polymerization is carried out in an appropriate solvent, the concentration of the transition metal complex [1] is preferably in the range of 0.0001 to 5 mmol / L, and more preferably in the range of 0.001 to 1 mmol / L. On the other hand, the concentration of the compound (A) is preferably in the range of 0.01 to 500 mmol / L, more preferably in the range of 0.1 to 100 mmol / L in terms of aluminum atoms. When using compound (B), the concentration of compound (B) is preferably in the range of 0.0001 to 5 mmol / L, and more preferably in the range of 0.001 to 1 mmol / L.

[Olefin polymer production method]
An olefin polymer can be produced by polymerizing an olefin such as ethylene in the presence of an olefin polymerization catalyst comprising the transition metal complex [1] of the present invention as an active ingredient.

  The reason why the olefin polymerization catalyst comprising the transition metal complex [1] of the present invention as an active ingredient is effective for increasing the molecular weight of the olefin polymer is not necessarily clear, but the present inventors have found the following. ing. That is, 2,1-insertion of the α-olefin can be cited as a cause of a decrease in molecular weight in the coordination-insertion reaction of the α-olefin with respect to the olefin polymerization catalyst. The olefin polymerization catalyst obtained by the present invention can produce a high molecular weight olefin polymer by controlling the 2,1-insertion.

  As the olefin used for the polymerization, a chain olefin, a cyclic olefin, or the like can be used, but an olefin having 2 to 20 carbon atoms is preferable. The polymerization may be homopolymerization using one kind of olefin or copolymerization using two or more kinds of olefins.

  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 in the case of copolymerization include ethylene / propylene, ethylene / 1-butene, ethylene / 1-hexene, ethylene / propylene / 1-butene, ethylene / propylene / 1-hexene, propylene / 1-butene. , Combinations of chain olefins / chain olefins such as propylene / 1-hexene; ethylene / vinylcyclohexane, ethylene / norbornene, ethylene / tetracyclododecene, ethylene / 5-ethylidene-2-norbornene, propylene / vinylcyclohexane, propylene Of chain olefins / cyclic olefins such as / norbornene, propylene / tetracyclododecene, propylene / 5-ethylidene-2-norbornene, ethylene / propylene / 5-ethylidene-2-norbornene Etc. can be mentioned.

  The polymerization method is not particularly limited, and examples thereof include aliphatic hydrocarbons (such as butane, pentane, hexane, heptane, and octane), aromatic hydrocarbons (such as benzene and toluene), and / or halogenated hydrocarbons (such as Examples thereof include solvent polymerization or slurry polymerization using methylene dichloride as a solvent, and gas phase polymerization using a gaseous monomer. The polymerization can be performed by either continuous polymerization or batch polymerization.

  The polymerization temperature is in the range of −50 ° C. to 300 ° C., and can be appropriately adjusted depending on the type of olefin used, the type of olefin polymerization catalyst, and the amount of use thereof, but the range of −20 ° C. to 250 ° C. is particularly preferable. The polymerization pressure is preferably a pressure condition of normal pressure to 90 MPa or less. 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, according to the present invention, a high molecular weight olefin polymer can be produced. In order to obtain an olefin polymer having a desired molecular weight, a chain transfer agent (such as hydrogen) for adjusting the molecular weight may be added. it can.

  According to such a polymerization method, a high molecular weight olefin polymer (high molecular weight olefin polymer) can be produced. Such a high molecular weight olefin polymer is excellent in properties such as impact resistance and rigidity, and thus is useful for production of industrial parts having excellent mechanical strength.

  Hereinafter, the present invention will be described in more detail with reference to experimental 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.
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, EXMOD 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) Carbon nuclear magnetic resonance spectrum ( ^13C -NMR)
Apparatus: EX270 manufactured by JEOL Ltd.
Sample cell: 5 mmφ tube Measurement solvent: CDCl ₃
Sample concentration: 30 mg / 0.5 mL (CDCl ₃ )
Measurement temperature: room temperature (about 25 ° C)
Measurement parameters: 5 mmφ probe, EXMOD BCM, OBNUC ¹³ C, integration number 2560 times Repeat time: ACQTM 1.79 seconds, PD 1.21 seconds Internal standard: CDCl ₃ (77 ppm)

(3) Mass spectrum [electron ionization mass spectrometry (EI-HRMS)]
Device: JMS-T100GC manufactured by JEOL Ltd.
Ionization voltage: 70 eV
Ion source temperature: 230 ° C
Acceleration voltage: 7 kV
MASS RANGE: m / z 35-800

[Experimental Example 1]
Synthesis of “cyclohexylmethylsilylene (2,3,4,5-tetramethylcyclopentadien-1-yl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (hereinafter referred to as complex 1) "

“Synthesis of (2-allyloxy-3-tert-butyl-5-methylphenyl) chlorocyclohexylmethylsilane”
Under nitrogen, 2-allyloxy-1-bromo-3-tert-butyl-5-methylbenzene (25.00 g, 88.28 mmol) was dissolved in 289 mL of toluene. After cooling to −78 ° C., a 1.60 M hexane solution of n-butyllithium (71.72 mL, 114.76 mmol) was added dropwise, and the temperature was gradually raised to −15 ° C. The mixture was stirred at -15 ° C for 2 hours and then cooled to -78 ° C. Dichlorocyclohexylmethylsilane (34.81 g, 176.55 mmol) was added all at once, and the temperature was gradually raised to room temperature. After stirring at 50 ° C. for 1 hour, the solvent was concentrated under reduced pressure. Hexane was added, filtered through Celite, and the solvent was concentrated under reduced pressure. Further, concentration under reduced pressure was continued at 70 ° C. for 3 hours to obtain (2-allyloxy-3-tert-butyl-5-methylphenyl) chlorocyclohexylmethylsilane (yield 70%). The obtained (2-allyloxy-3-tert-butyl-5-methylphenyl) chlorocyclohexylmethylsilane was used in the next reaction without further purification.
¹ H-NMR (CDCl ₃ ): 0.66 (s, 3H, SiMe), 1.10-1.35 (br, 5H, SiCy), 1.37 (s, 9H, t-Bu), 1.63-1.80 (br, 6H, SiCy) , 2.32 (s, 3H, arMe ), 4.30 (ddt, J = 13.8,4.3,1.8 Hz, 1H, OCH 2), 4.42 (ddt, J = 13.8,4.1,2.1Hz, 1H, OCH 2), 5.30 ( dq, J = 10.7, 1.8Hz, 1H, OCH ₂ CH = CH ₂ ), 5.52 (dq, J = 17.3, 2.0 Hz, 1H, OCH ₂ CH = CH ₂ ), 6.03 (ddt, J = 17.1, 10.7, _{4.3Hz, 1H, OCH 2 CH =} CH 2), 7.24 (d, J = 2.1Hz, 1H, ArH), 7.30 (d, J = 2.1Hz, 1H, ArH)
¹³ C-NMR (CDCl ₃ ): -0.08 (SiMe), 21.11 (ArMe), 26.60 (SiCy), 26.69 (SiCy), 27.68 (SiCy), 29.33 (SiCy), 31.21 (ArCMe ₃ ), 35.16 (ArCMe ₃ ), 76.50 (OCH ₂ ), 116.08, 128.14, 131.70, 132.91, 133.56, 135.29, 142.04, 160.96.
EI-HRMS: m / z calcd 364.19892, found 364.19930

“Synthesis of (2-allyloxy-3-tert-butyl-5-methylphenyl) (2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl) cyclohexylmethylsilane”
To nitrogen hydride (60 wt%, 0.89 g, 22.32 mmol) under nitrogen was added 43 mL of THF. The sodium hydride THF slurry was heated to 50 ° C. Aniline (0.14 g, 1.49 mmol) was added, and the mixture was further stirred at 50 ° C. for 1 hour. A solution of 1,2,3,4-tetramethyl-1,3-cyclopentadiene (2.00 g, 16.37 mmol) dissolved in 11 mL of THF was slowly added dropwise. After completion of dropping, the mixture was further stirred at 50 ° C. for 2 hours until the generation of hydrogen gas was stopped. After cooling to 20 ° C., a solution of (2-allyloxy-3-tert-butyl-5-methylphenyl) chlorocyclohexylmethylsilane (5.43 g, 14.88 mmol) dissolved in 11 mL of toluene was added dropwise at room temperature. Stirring was continued for 3 hours. The reaction solution was dropped into a mixed solution in which 27 mL of a 10% aqueous sodium hydrogen carbonate solution and 27 mL of a 10% aqueous sodium carbonate solution were cooled to 0 ° C., and the reaction was stopped by adding 27 mL of toluene. After drying over sodium sulfate, the solvent is concentrated under reduced pressure to give (2-allyloxy-3-tert-butyl-5-methylphenyl) (2,3,4,5-tetramethylcyclopenta-2,4-diene. -1-yl) cyclohexylmethylsilane was obtained (yield 93%). The resulting (2-allyloxy-3-tert-butyl-5-methylphenyl) (2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl) cyclohexylmethylsilane is further purified. It was used for the next reaction without any problems.
¹ H-NMR (CDCl ₃ , major isomer): 0.37 (s, 3H, SiMe), 1.11-1.41 (m, 5H, SiCy), 1.40 (s, 9H, t-Bu), 1.58-2.02 (m, 6H) , SiCy), 1.62 (s, 3H, C ₅ Me ₄ ), 1.67 (s, 3H, C ₅ Me ₄ ), 1.79 (s, 3H, C ₅ Me ₄ ), 1.92 (s, 3H, C ₅ Me ₄₎ ), 2.32 (s, 3H, arMe), 3.40 (s, 1H, C 5 Me 4 H), 4.41 (dt, J = 3.1,2.0Hz, 2H, OCH 2 CH = CH 2), 5.32 (dq, J _{= 10.7,1.8Hz, 1H, OCH 2 CH} = CH 2), 5.57 (dq, J = 17.1,1.8Hz, 1H, OCH 2 CH = CH 2), 6.09 (ddt, J = 17.1,10.7,4.4Hz, 1H, OCH ₂ CH = CH ₂ ), 7.06 (d, J = 1.6Hz, 1H, ArH), 7.20 (d, J = 1.6Hz, 1H, ArH)
¹³ C-NMR (CDCl ₃ , major isomer):-6.69 (SiMe), -2.33 (SiCH), 11.03 (CpMe), 11.16 (CpMe), 14.10 (CpMe), 14.20 (CpMe), 21.13 (ArMe), 26.84 (SiCy), 27.91 (SiCy), 29.33 (SiCy), 31.20 (ArCMe ₃ ), 35.09 (ArCMe ₃ ), 52.74, 76.63 (OCH ₂ ), 116.34, 129.53, 130.41, 130.92, 131.27, 132.69, 133.88, 134.06, 134.92, 135.87, 141.98, 161.13
EI-MS: m / z 450 (M ⁺ ), 367, 245, 191, 162, 147
EI-HRMS: m / z calcd 450.33179, found 450.32764

“Synthesis of Complex 1”
Under nitrogen, (2-allyloxy-3-tert-butyl-5-methylphenyl) (2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl) cyclohexylmethylsilane (6.17 g) , 14.89 mmol) and a toluene solution (105 mL) of triethylamine (6.78 g, 6699 mmol) at −78 ° C. were added dropwise a 1.60 M hexane solution (20.93 mL, 33.49 mmol) of n-butyllithium. After gradually warming to room temperature, the mixture was stirred at room temperature for 2.5 hours. A solution obtained by dissolving titanium tetrachloride (4.24 g, 22.33 mmol) in toluene (22 mL) was added dropwise to the obtained mixture, and the temperature was gradually raised to room temperature. After heating up to 90 degreeC, it stirred at the same temperature for 2 hours. The solvent was concentrated under reduced pressure, heptane was added and filtered to remove insoluble matters, and the solvent was concentrated under reduced pressure. Pentane was added and the precipitated solid was filtered, washed with a small amount of pentane, and then dried under reduced pressure to obtain Complex 1 (1.00 g, 14% yield) as an orange solid.
Mp: 208-211 ° C (dec)
¹ H-NMR (CDCl ₃ ): 0.43 (s, 3H, SiMe), 1.08-1.42 (m, 6H, SiCy), 1.38 (s, 9H, t-Bu), 1.69-1.83 (m, 3H, SiCy) , 1.85-2.02 (m, 2H, SiCy), 1.93 (s, 3H, C ₅ Me ₄ ), 2.03 (s, 3H, C ₅ Me ₄ ), 2.31 (s, 6H, C ₅ Me ₄ ), 2.37 ( s, 3H, ArMe), 7.13 (d, J = 2.0Hz, 1H, ArH), 7.16 (d, J = 2.0Hz, 1H, ArH)
¹³ C-NMR (CDCl ₃ ): -1.95 (SiMe), 12.79 (C ₅ Me ₄ ), 13.61 (C ₅ Me ₄ ), 13.92 (C ₅ Me ₄ ), 16.18 (C ₅ Me ₄ ), 21.35 (Ar -Me), 24.79 (SiCy), 26.65 (SiCy), 27.90 (SiCy), 27.96 (SiCy), 28.08 (SiCy), 28.28 (SiCy), 29.86 (ArCMe ₃ ), 34.83 (ArCMe ₃ ), 118.14, 128.83, 129.02, 132.13, 133.45, 136.16, 138.57, 139.56, 139.97, 141.50, 167.04
Anal Calcd for C ₂₇ H ₄₀ Cl ₂ OSiTi: C, 61.48 H, 7.64 Found C, 61.36 H, 7.68

<Propylene polymerization>
The properties of the propylene polymer were measured by the following method.

(1) Molecular weight and molecular weight distribution It was measured by gel permeation chromatography (GPC) under the following conditions. 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
(2) Ratio of 2,1-insertion in propylene polymer The ratio of 2,1-insertion in the propylene polymer was measured by a carbon nuclear magnetic resonance spectrum ( ¹³ C-NMR) under the following measurement conditions.
The ratio of 2,1-insertion was calculated according to the methods described in known literatures (Macromol. Chem. 1977, 178, 791., Macromolecules 1979, 12, 248. and Macromolecules 1992, 25, 521.).
<Measurement conditions>
Apparatus: DPX-600 manufactured by Bruker
Sample cell: 5 mmφ tube Measurement solvent: 4: 1 (volume ratio) mixture of orthodichlorobenzene and orthodichlorobenzene-d ₄ Sample concentration: 10 mg / 0.5 mL (CDCl ₃ )
Measurement temperature: Room temperature (130 ° C)
Measurement parameters: 5 mmφ probe, EXMOD zigg, OBNUC ¹³ C, integration number 4096 times Internal standard: orthodichlorobenzene (132.43 ppm)
<Calculation formula>
Signal integrated integrated value Tαγ (38.7 ppm) of signal integrated integrated value Tαγ (35.7 ppm) of signal integrated integrated value Tαγ (35.7 ppm) of signal integrated integrated value Tαγ (38.7 ppm) 2, 1-insertion rate (%) = Tβγ / (Tββ + Tβγ + Tαβ + Tαγ)
× 100

[Experiment 2]
<Production of propylene polymer>
145 ml of dehydrated toluene was put into a 300 ml autoclave purged with nitrogen. After raising the temperature to 40 ° C., 0.2 MPa of propylene was charged. 1 mL (60 μmol) of a 0.06 M toluene solution of triisobutylaluminum [manufactured by Tosoh Finechem Co., Ltd.] was charged, and then 1 mL (0.05 μmol) of 0.05 mM toluene solution of Complex 1 was added. Next, 1 mL (0.5 μmol) of a 0.5 mM toluene solution of triphenylmethanetetrakis (pentafluorophenyl) borate was added to the autoclave to initiate polymerization. After stirring the reaction solution for 5 minutes, 5 mL of methanol was added to stop the polymerization. The reaction solution was added to 500 mL of methanol added with 1 mL of 5% hydrochloric acid to precipitate a polymer. The polymer was filtered, washed with methanol, and then dried under vacuum at 80 ° C. for 2 hours until a constant weight was obtained.

[Comparative Example 1]
Instead of complex 1, dimethylsilylene (2,3,4,5-tetramethylcyclopentadien-1-yl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (hereinafter referred to as “complex 2”) Polymerization was carried out in the same manner as in Experimental Example 2 except that a polymer was obtained.

[Comparative Example 2]
Instead of complex 1, diethylsilylene (2,3,4,5-tetramethylcyclopentadien-1-yl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (hereinafter referred to as “complex 3”) Polymerization was carried out in the same manner as in Experimental Example 2 except that a polymer was obtained.

[Comparative Example 3]
Instead of complex 1, cyclotetramethylenesilylene (2,3,4,5-tetramethylcyclopentadien-1-yl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (hereinafter referred to as “complex”) Polymerization was carried out in the same manner as in Experimental Example 2 except that 4) was used.

[Comparative Example 4]
Instead of complex 1, ethylmethylsilylene (2,3,4,5-tetramethylcyclopentadien-1-yl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (hereinafter referred to as “complex 5 The polymer was obtained in the same manner as in Experimental Example 2 except that the polymer was obtained.

[Comparative Example 5]
Instead of complex 1, methylphenylsilylene (2,3,4,5-tetramethylcyclopentadien-1-yl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (hereinafter referred to as “complex 6 The polymer was obtained in the same manner as in Experimental Example 2 except that the polymer was obtained.

Table 1 below collectively shows the molecular weight, ¹³ C-NMR results, and 2,1-insertion ratio results obtained from the polymer obtained in Experimental Example 2 and Comparative Examples 1 to 5, respectively.

In the results shown in Table 1, the polymerization activity was determined as follows.
Polymerization activity:
In the experimental example and the comparative example, the polymer production amount (kg) per 1 mmol of the transition metal complex in the polymerization time of 1 hour was calculated from the amount of the transition metal complex used and the polymerization time. Therefore, the unit of this polymerization activity is kg / mmol-cat · h (“mmol-cat” means per 1 mmol of the transition metal complex).
Molecular weight: Weight average molecular weight Mw × 10 ⁻³
2,1-%: Ratio of 2,1-insertion (%)

  In Table 1, “mm”, “mr”, and “rr” relate to the stereoregularity of the polymer (propylene polymer). The stereoregularity of the polymer is marked by the local chain configuration of the polymer chain. In the chain of monomer units (doublet, diad), those having the same configuration are called “meso”, and those having the opposite configuration are called “racemo”, which are represented by m and r, respectively. “Mm”, “mr”, and “rr” represent a chain composed of three monomer units (triplet, triad), isotacticity is expressed as a ratio of “mm”, and syndiotacticity is It is expressed as a ratio of “rr”.

<Ethylene / 1-hexene copolymerization>
The properties of the ethylene / 1-hexene copolymer were measured by the following method.

(1) Molecular weight and molecular weight distribution It measured on the following conditions by the 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

(2) Content of 1-hexene unit in ethylene / 1-hexene copolymer The content of vinylcyclohexane unit in the ethylene / 1-hexene copolymer is determined by proton nuclear magnetic resonance spectrum ( ¹ H -NMR) and carbon nuclear magnetic resonance spectra ( ^13C -NMR).
The 1-hexene unit content was calculated according to a method described in known literature (J. Polym. Sci., Polym. Phys. Ed. 1973, 11, 275).
<Measurement conditions>
Apparatus: EX270 manufactured by JEOL Ltd.
Sample cell: 10 mmφ tube Measurement solvent: 4: 1 (volume ratio) mixture of orthodichlorobenzene and orthodichlorobenzene-d ₄ Sample concentration: 10 mg / 3 mL
Measurement temperature: Room temperature (135 ° C)
(2-1) Proton nuclear magnetic resonance spectrum ( ¹ H-NMR)
Measurement parameters: 10 mmφ probe, MENU NON, OBNUC ¹ H, integration count 1000 times Pulse angle: 45 degrees Repeat time: ACQTM + PD 7 seconds Internal standard: 3,6-position peak of orthodichlorobenzene (7.40 ppm)
(2-2) Carbon nuclear magnetic resonance spectrum ( ¹³ C-NMR)
Measurement parameters: 10 mmφ probe, MENU BCM, OBNUC ¹³ C, integration number 30000 times Pulse angle: 45 degrees Repeat time: ACQTM + PD 3 seconds Internal standard: 4,5-position peak of orthodichlorobenzene (127.68 ppm)

[Experiment 3]
<Production of ethylene / 1-hexene copolymer>
In a 300 ml autoclave purged with nitrogen, 1.5 ml of 1-hexene and 144 ml of dehydrated toluene were charged. After raising the temperature to 70 ° C., 0.6 MPa of ethylene was charged. 1 mL (60 μmol) of a 0.06M toluene solution of triisobutylaluminum [manufactured by Tosoh Finechem Co., Ltd.] was charged, and then 1 mL (0.02 μmol) of a 0.02 mM toluene solution of Complex 1 was charged. Next, 1 mL (0.1 μmol) of a 0.1 mM toluene solution of triphenylmethanetetrakis (pentafluorophenyl) borate was added to the autoclave to initiate polymerization. After stirring the reaction solution for 2 minutes, the polymerization was stopped with 5 mL of methanol. The reaction solution was added to 500 mL of methanol added with 1 mL of 5% hydrochloric acid to precipitate a polymer. The polymer was filtered and washed with methanol, and then dried at 80 ° C. for 2 hours under vacuum until a constant weight was reached.

[Comparative Example 6]
Polymerization was carried out in the same manner as in Experimental Example 3 except that Complex 2 was used instead of Complex 1 to obtain a polymer.

[Comparative Example 7]
Polymerization was carried out in the same manner as in Experimental Example 3 except that Complex 3 was used instead of Complex 1 to obtain a polymer.

[Comparative Example 8]
Polymerization was performed in the same manner as in Experimental Example 3 except that Complex 4 was used instead of Complex 1 to obtain a polymer.

[Comparative Example 9]
Polymerization was carried out in the same manner as in Experimental Example 3 except that Complex 5 was used instead of Complex 1 to obtain a polymer.

  Table 2 below lists the results obtained in Experimental Example 3 and Comparative Examples 6-9.

In the results shown in Table 2, the polymerization activity was determined as follows.
Polymerization activity:
In the examples and comparative examples, from the amount of the transition metal complex used and the polymerization time, the polymer production amount (kg) per 1 mmol of the transition metal complex at a polymerization time of 1 hour was calculated. Therefore, the unit of this polymerization activity is kg / mmol-cat · h (“mmol-cat” means per 1 mmol of the transition metal complex).
Molecular weight:
Weight average molecular weight Mw × 10 ⁻³

  When the transition metal complex of the present invention is used as an olefin polymerization catalyst, a high molecular weight olefin polymer having excellent characteristics such as impact resistance and rigidity can be produced.

Claims (8)

Formula [1]

(In the formula, M represents a transition metal atom of Group 4 of the Periodic Table of Elements, A represents an atom of Group 16 of the Periodic Table of Elements, and J represents an atom of Group 14 of the Periodic Table of Elements) , Cp represents a group having a cyclopentadienyl type anion skeleton.
R ⁶ represents an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a halogen atom as a substituent.
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , X ¹ and X ² are each independently
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 ¹⁰ ) ₃ (three R ^{10 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 ^{10 s} is 1-20. Substituted silyl groups represented by
—N (R ²⁰ ) ₂ (two R ²⁰ each independently represents a hydrogen atom, a hydrocarbon group or a halogenated hydrocarbon group, and at least one of the two R ²⁰ is a hydrocarbon group or a halogenated hydrocarbon. A total of 2 to 20 carbon atoms in two R ²⁰ groups).
An alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent;
Selected from the group consisting of an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent and an aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent Or represents a hydrogen atom or a halogen atom, and among R ¹ , R ² , R ³ and R ⁴ , the substituents bonded to two adjacent carbon atoms are bonded to each other and bonded to each other. A ring may be formed together with the carbon atom. )
A transition metal complex represented by   The transition metal complex according to claim 1, wherein M in the formula [1] is a titanium atom.   The transition metal complex according to claim 1 or 2, wherein A in the formula [1] is an oxygen atom.   The transition metal complex according to any one of claims 1 to 3, wherein J in the formula [1] is a silicon atom. A method for producing the transition metal complex according to any one of claims 1 to 4,
Formula [2]

(In the formula, Cp, A, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ represent the same meaning as in the formula [1],
R ⁷ represents —Si (R ¹¹ ) ₃ (three R ¹¹ each independently represents a hydrogen atom, a hydrocarbon group or a halogenated hydrocarbon group, and the total number of carbon atoms in three R ¹⁰ is 1 to 3; A trisubstituted silyl group represented by:
Alternatively, it represents an organic group having 1 to 20 carbon atoms. )
A substituted cyclopentadiene compound represented by:
With a base,
A first step of reacting
The reaction product obtained in the first step and the formula [3]

(Wherein, X ¹ and X ² represent the same meaning as in the above formula [1],
X ³ and X ⁴ are each independently
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. ) And a substituted silyl group represented by the formula: —N (R ²² ) ₂ (two R ^{20 s} each independently represent a hydrogen atom, a hydrocarbon group or a halogenated hydrocarbon group, and the total number of carbon atoms in two R ^{22 s)} Is a substituent selected from the group consisting of substituted amino groups represented by formula (1) to (20), or represents a hydrogen atom or a halogen atom. )
A transition metal compound represented by
A second step of reacting
Manufacturing method.   The catalyst for olefin polymerization which uses the transition metal complex in any one of Claims 1-4 as an active ingredient. 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): a cyclic aluminoxane having a structure represented by the formula {-Al (E ² ) —O—} _b (A3): represented by the formula E ³ {—Al (E ³ ) —O—} _c AlE ³ ₂ A linear aluminoxane having the structure (wherein, a represents an integer satisfying 0 <a ≦ 3, b represents an integer of 2 or more, and c represents an integer of 1 or more.
E ¹ , E ² and E ³ each independently represents a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms. When there are a plurality of E ^{1 in} (A1), they may be the same as or different from each other. When there are a plurality of E ^{2 in} (A2), they may be the same as or different from each other. When there are a plurality of E ^{3 in} (A3), they may be the same as or different from each other. Z represents a hydrogen atom or a halogen atom, and when there are a plurality of Z, they may be the same as or different from each other. )
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 (B3) represented by formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- : Boron compound represented by formula (L ¹ -H) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- In the formula, B represents a trivalent boron atom, and Q ¹ , Q ² , Q ³ and Q ⁴ are each independently a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or the number of carbon atoms. 1 to 20 halogenated hydrocarbon groups,
—Si (R ¹³ ) ₃ (Three R ^{13 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 ^{13 s} is 1-20. Substituted silyl groups represented by
An alkoxy group having 1 to 20 carbon atoms or —N (R ²³ ) ₂ (two R ²³ each independently represents a hydrocarbon group or a halogenated hydrocarbon group, and the total number of carbon atoms in two R ^{23 s)} Is a disubstituted amino group represented by formula (2) to (20)), G ⁺ represents an inorganic or organic cation, and L ¹ represents a neutral Lewis base. )   The manufacturing method of the olefin polymer including the process of superposing | polymerizing an olefin in presence of the catalyst for olefin polymerization described in Claim 6 or 7.