JP2012213765A - CATALYST FOR OLEFIN OLIGOMERIZATION AND METHOD FOR PRODUCING α-OLEFIN - Google Patents

Abstract

Olefin oligomerization capable of producing α-olefin such as 1-hexene by oligomerization reaction of ethylene while suppressing adhesion of by-product polymer to reactor walls and agitator even under high temperature conditions And a method for producing an α-olefin using the catalyst.
An olefin oligomerization catalyst obtained by contacting a support, an activation promoter component containing an element of Group 13 of the periodic table, and a specific transition metal complex. A catalyst for olefin oligomerization, in which an activation promoter component containing a specific transition metal complex and an element of Group 13 of the periodic table is supported on a carrier.
[Selection figure] None

Description

  The present invention relates to a catalyst for olefin oligomerization and a method for producing an α-olefin.

  The α-olefin is an industrially important raw material monomer produced by oligomerization of ethylene with a metal catalyst. However, since oligomerization of ethylene usually gives a mixture of α-olefins according to a Schulz-Flory distribution, development of a catalyst system capable of selectively producing one kind of α-olefin is very important industrially.

For example, Patent Document 1, by half metallocene titanium complex represented by formula _{(Cp-B (R) n} Ar) TiR 1 3 is activated with an activating co-catalyst component, optionally trimerization of ethylene It has been reported to act as a catalyst.
Among these selective ethylene trimerization catalysts, carbon atoms such as [1- (1-methyl-1- (3,5-dimethylphenyl) ethyl) -3-trimethylsilylcyclopentadienyl] titanium trichloride When a half metallocene titanium complex (carbon-bridged Cp-Ar complex) in which cyclopentadiene and a substituted aryl group are bonded uses MAO (methylaluminoxane) as an activation co-catalyst component, an efficient ethylene trioxide at 30 ° C. It has been reported that it works as a quantification catalyst (see, for example, Non-Patent Document 1). On the other hand, [dimethylphenylsilylcyclopentadienyl] titanium trichloride, which is one of the half metallocene titanium complexes (silicon-bridged Cp-Ar complexes) in which cyclopentadiene and substituted aryl group are bonded by a silicon atom, In US Pat. No. 6,057,096, it is reported that the catalyst activity of ethylene trimerization reaction is low and 1-hexene selectivity is low (see Non-Patent Document 1).

  Further, the catalyst system for ethylene trimerization using the carbon-bridged Cp-Ar complex and MAO has a catalytic activity for producing 1-hexene at a high temperature condition of 80 ° C. and a selectivity for producing 1-hexene at 30 ° C. Compared to this, it is reported that it is greatly reduced (see Non-Patent Document 2).

  By the way, in the ethylene oligomerization reaction, polyethylene is generally produced as a by-product. For this reason, in industrial production, the walls of the reactor, the stirrer and the like become dirty, and there is a problem that long-term operation cannot be performed. Patent Document 1 and Non-Patent Document 1 report a catalyst in which a half metallocene titanium complex in which a cyclopentadiene and a substituted aryl group are bonded to each other by a carbon atom is supported on a carrier. The reaction using the catalyst is 30. It is carried out under the condition of ° C., and industrial production is difficult.

Special table 2004-524959

Organometallics 2002, 21, 5122-5135. Chinese Journal of Chemistry 2006, 24, 1397-1401.

Under such circumstances, the problem to be solved by the present invention is that, even under high temperature conditions, 1-hexene or the like can be obtained by ethylene oligomerization reaction while suppressing the adhesion of by-product polymer to the reactor wall or stirrer. An object of the present invention is to provide a catalyst for olefin oligomerization capable of producing an α-olefin and a method for producing an α-olefin using the catalyst.

［式中、Ｍは元素周期律表の第４族の遷移金属原子を表し、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^１９、Ｒ^２０、Ｒ^２１、Ｒ^２４、Ｒ^２５、Ｒ^２６、Ｒ^２７、Ｘ^１、Ｘ^２及びＸ^３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^２２）_３（３つのＲ^２２はそれぞれ独立に、水素原子、ハイドロカルビル基またはハロゲン化ハイドロカルビル基を表し、３つのＲ^２２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、
または−Ｎ（Ｒ^２３）_２（２つのＲ^２３はそれぞれ独立にハイドロカルビル基またはハロゲン化ハイドロカルビル基を表し、２つのＲ^２３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、
Ｒ^１０及びＲ^１１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^２２）_３（３つのＲ^２２はそれぞれ独立に、水素原子、ハイドロカルビル基またはハロゲン化ハイドロカルビル基を表し、３つのＲ^２２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、
または−Ｎ（Ｒ^２３）_２（２つのＲ^２３はそれぞれ独立にハイドロカルビル基またはハロゲン化ハイドロカルビル基を表し、２つのＲ^２３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、
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２つの基は結合して、該２つの基が結合している２つの炭素原子と一緒になって環を形成していてもよく、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８及びＲ^９のうち、隣接した２つの炭素原子に結合する２つの基は結合して、該２つの基が結合している２つの炭素原子と一緒になって環を形成していてもよく、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５及びＲ^１６のうち、隣接した２つの炭素原子に結合する２つの基は結合して、該２つの基が結合している２つの炭素原子と一緒になって環を形成していてもよく、Ｒ^１７、Ｒ^１８、Ｒ^１９、Ｒ^２０及びＲ^２１のうち、隣接した２つの炭素原子に結合する２つの基は結合して、該２つの基が結合している２つの炭素原子と一緒になって環を形成していてもよく、Ｒ^５、Ｒ^２４、Ｒ^７、Ｒ^２５及びＲ^９のうち、隣接した２つの炭素原子に結合する２つの基は結合して、該２つの基が結合している２つの炭素原子と一緒になって環を形成していてもよく、Ｒ^１２、Ｒ^２６、Ｒ^１４、Ｒ^２７及びＲ^１６のうち、隣接した２つの炭素原子に結合する２つの基は結合して、該２つの基が結合している２つの炭素原子と一緒になって環を形成していてもよく、Ｒ^１０及びＲ^１１は結合してそれらが結合しているケイ素原子と一緒になって環を形成していてもよい。］ That is, the first of the present invention is a transition represented by any one of the following general formulas (1-1) to (1-3), a support, an activation promoter component containing a group 13 element of the periodic table. The present invention relates to an olefin oligomerization catalyst obtained by contacting a metal complex.

[Wherein, M represents a transition metal atom of Group 4 of the periodic table of elements, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ^12] , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , X ¹ , X ² and X ³ are Independently
Hydrogen atom, 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 ²² ) ₃ (three R ^{22 s} each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the three R ²² is 1 to 20; A substituted silyl group represented by:
Or —N (R ²³ ) ₂ (two R ²³ each independently represents a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the two R ²³ is 2 to 20). Represents a disubstituted amino group represented by:
R ¹⁰ and R ¹¹ 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 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 ²² ) ₃ (three R ^{22 s} each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the three R ²² is 1 to 20; A substituted silyl group represented by:
Or —N (R ²³ ) ₂ (two R ²³ each independently represents a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the two R ²³ is 2 to 20). Represents a disubstituted amino group represented by:
Of R ¹ , R ² , R ³ and R ⁴ , two groups bonded to two adjacent carbon atoms are bonded to form a ring together with the two carbon atoms to which the two groups are bonded. Of R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ , two groups bonded to two adjacent carbon atoms are bonded to each other, and the two groups are bonded to each other. Two carbon atoms may form a ring together with two carbon atoms out of R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ^16. Then, two carbon atoms to which the two groups are bonded may form a ring, and two of R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ that are adjacent to each other may be formed. Two groups bonded to one carbon atom are bonded together with the two carbon atoms to which the two groups are bonded. Is and may form a ^{ring, R 5, R 24, R} 7, of R ²⁵ and R ^9, the two groups bonded to two carbon atoms adjacent bonded, the two groups Two carbon atoms bonded to each other may form a ring, and two of R ¹² , R ²⁶ , R ¹⁴ , R ²⁷ and R ¹⁶ bonded to two adjacent carbon atoms The groups may be bonded together to form a ring together with the two carbon atoms to which the two groups are bonded, and R ¹⁰ and R ¹¹ are bonded to the silicon atom to which they are bonded. And may form a ring together. ]

［式中、Ｍは元素周期律表の第４族の遷移金属原子を表し、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、
Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^１９、Ｒ^２０、Ｒ^２１、Ｒ^２４、Ｒ^２５、Ｒ^２６、Ｒ^２７、Ｘ^１、Ｘ^２及びＸ^３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^２２）_３（３つのＲ^２２はそれぞれ独立に、水素原子、ハイドロカルビル基またはハロゲン化ハイドロカルビル基を表し、３つのＲ^２２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、
または−Ｎ（Ｒ^２３）_２（２つのＲ^２３はそれぞれ独立にハイドロカルビル基またはハロゲン化ハイドロカルビル基を表し、２つのＲ^２３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、
Ｒ^１０及びＲ^１１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^２２）_３（３つのＲ^２２はそれぞれ独立に、水素原子、ハイドロカルビル基またはハロゲン化ハイドロカルビル基を表し、３つのＲ^２２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、
または−Ｎ（Ｒ^２３）_２（２つのＲ^２３はそれぞれ独立にハイドロカルビル基またはハロゲン化ハイドロカルビル基を表し、２つのＲ^２３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、
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２つの基は結合して、該２つの基が結合している２つの炭素原子と一緒になって環を形成していてもよく、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８及びＲ^９のうち、隣接した２つの炭素原子に結合する２つの基は結合して、該２つの基が結合している２つの炭素原子と一緒になって環を形成していてもよく、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５及びＲ^１６のうち、隣接した２つの炭素原子に結合する２つの基は結合して、該２つの基が結合している２つの炭素原子と一緒になって環を形成していてもよく、Ｒ^１７、Ｒ^１８、Ｒ^１９、Ｒ^２０及びＲ^２１のうち、隣接した２つの炭素原子に結合する２つの基は結合して、該２つの基が結合している２つの炭素原子と一緒になって環を形成していてもよく、Ｒ^５、Ｒ^２４、Ｒ^７、Ｒ^２５及びＲ^９のうち、隣接した２つの炭素原子に結合する２つの基は結合して、該２つの基が結合している２つの炭素原子と一緒になって環を形成していてもよく、Ｒ^１２、Ｒ^２６、Ｒ^１４、Ｒ^２７及びＲ^１６のうち、隣接した２つの炭素原子に結合する２つの基は結合して、該２つの基が結合している２つの炭素原子と一緒になって環を形成していてもよく、Ｒ^１０及びＲ^１１は結合してそれらが結合しているケイ素原子と一緒になって環を形成していてもよい。］ The second aspect of the present invention is an activation assistant comprising a carrier containing a transition metal complex represented by any one of the following general formulas (1-1) to (1-3) and an element belonging to Group 13 of the periodic table. The present invention relates to an olefin oligomerization catalyst on which a catalyst component is supported.

[Wherein, M represents a transition metal atom of Group 4 of the periodic table of elements, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ ,
R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , X ¹ , X ² and X ³ Are independent of each other
Hydrogen atom, 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 ²² ) ₃ (three R ^{22 s} each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the three R ²² is 1 to 20; A substituted silyl group represented by:
Or —N (R ²³ ) ₂ (two R ²³ each independently represents a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the two R ²³ is 2 to 20). Represents a disubstituted amino group represented by:
R ¹⁰ and R ¹¹ 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 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 ²² ) ₃ (three R ^{22 s} each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the three R ²² is 1 to 20; A substituted silyl group represented by:
Or —N (R ²³ ) ₂ (two R ²³ each independently represents a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the two R ²³ is 2 to 20). Represents a disubstituted amino group represented by:
Of R ¹ , R ² , R ³ and R ⁴ , two groups bonded to two adjacent carbon atoms are bonded to form a ring together with the two carbon atoms to which the two groups are bonded. Of R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ , two groups bonded to two adjacent carbon atoms are bonded to each other, and the two groups are bonded to each other. Two carbon atoms may form a ring together with two carbon atoms out of R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ^16. Then, two carbon atoms to which the two groups are bonded may form a ring, and two of R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ that are adjacent to each other may be formed. Two groups bonded to one carbon atom are bonded together with the two carbon atoms to which the two groups are bonded. Is and may form a ^{ring, R 5, R 24, R} 7, of R ²⁵ and R ^9, the two groups bonded to two carbon atoms adjacent bonded, the two groups Two carbon atoms bonded to each other may form a ring, and two of R ¹² , R ²⁶ , R ¹⁴ , R ²⁷ and R ¹⁶ bonded to two adjacent carbon atoms The groups may be bonded together to form a ring together with the two carbon atoms to which the two groups are bonded, and R ¹⁰ and R ¹¹ are bonded to the silicon atom to which they are bonded. And may form a ring together. ]

  A third aspect of the present invention relates to a method for producing an α-olefin in which an olefin is oligomerized in the presence of the olefin oligomerization catalyst.

According to the present invention, an α-olefin such as 1-hexene can be produced by an oligomerization reaction of ethylene while suppressing adhesion of a by-product polymer to a reactor wall or a stirrer even under high temperature conditions.

  In the present invention, “oligomerization” refers to making an olefin into a 2 to 10 mer, preferably making an ethylene into a 3 to 4 mer, most preferably a trimer. In the present invention, the term “substituent” includes a halogen atom constituting a compound or group. Furthermore, in the present invention, the substituted cyclopentadiene compound represented by any one of the general formulas (5-1) to (5-3) includes isomers having different double bond positions on each cyclopentadienyl ring. Although present, in the present invention, the substituted cyclopentadienyl compound represents any of them or a mixture thereof.

<Transition metal complexes (1-1) to (1-3) (olefin oligomerization catalyst component)>
Hereinafter, the transition metal complex represented by any one of the general formulas (1-1) to (1-3) will be described in detail.
In the transition metal complexes (1-1) to (1-3), M represents a group 4 element in the periodic table, 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 complexes (1-1) to (1-3), the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , X ¹ , X ² and X ³ is defined in as described above, shows a specific example 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, the “optionally having a halogen atom as a substituent” in the “alkyl group optionally having a halogen atom as a substituent” means that part or all of the hydrogen atoms in the alkyl group are halogenated. It means that it may be replaced by an atom, and specific examples of the halogen atom 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 having 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, a dibromomethyl group, and a tribromomethyl group. , Fluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group and the like.

  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, preferred aryl groups are aryl groups having 6 to 10 carbon atoms, and more preferred are phenyl groups. In addition, “optionally having a halogen atom as a substituent” in “an aryl group optionally having a halogen atom as a substituent” means that a part or all of the hydrogen atoms in the aryl group are halogenated. It means that it may be replaced by an atom, and specific examples of the halogen atom 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. A particularly preferred aryl group having a halogen atom as a substituent is a fluorophenyl group, a difluorophenyl group, a trifluorophenyl group, a tetrafluorophenyl group, a pentafluorophenyl group, a chlorophenyl group, a bromophenyl group, or an iodophenyl group. Etc.

  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, (3,5-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-trimethylphenyl) 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-decylphenyl) methyl group, (n-dodecylphenyl) ) 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, “optionally having a halogen atom as a substituent” in “an aralkyl group optionally having a halogen atom as a substituent” means that a part or all of the hydrogen atoms in the aralkyl group are halogenated. It means that it may be replaced by an atom, and specific examples of the halogen atom 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-undecyloxy group, n-dodecyloxy group, tridecyloxy group, tetradecyloxy group, n-pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group, nonadecyloxy group, n -An eicosyloxy group etc. are mentioned. 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, “optionally having a halogen atom as a substituent” in “an alkoxy group optionally having a halogen atom as a substituent” means that some or all of the hydrogen atoms in the alkoxy group are halogenated. It means that it may be replaced by an atom, and specific examples of the halogen atom 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 more preferable.

  Specific examples of the “alkoxy group having 2 to 20 carbon atoms” of the alkoxy group having 2 to 20 carbon atoms which may have a halogen atom as a substituent include an ethoxy group, an n-propoxy group, and an isopropoxy group. , N-butoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, neopentyloxy group, n-hexyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n -Undecyloxy group, n-dodecyloxy group, tridecyloxy group, tetradecyloxy group, n-pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group, nonadecyloxy group, n-eicosyl An oxy group etc. are mentioned. Among these, preferable alkoxy groups are those having 2 to 10 carbon atoms, and more preferable examples include an ethoxy group and a tert-butoxy group. In addition, “optionally having a halogen atom as a substituent” in “an alkoxy group optionally having a halogen atom as a substituent” means that some or all of the hydrogen atoms in the alkoxy group are halogenated. It means that it may be replaced by an atom, and specific examples of the halogen atom 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 C2-C20, and the range of 2-10 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. In addition, the “optionally having a halogen atom as a substituent” in the “aryloxy group optionally having a halogen atom as a substituent” means that part or all of the hydrogen atoms in the aryloxy group are partially or entirely. , May be replaced by a halogen atom, and specific examples of the halogen atom 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 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) methoxy group, (Methylphenyl) methoxy group, (3,4,5-trimethylphenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,4,6-tetramethylphenyl) methoxy group (2,3,5,6-tetramethylphenyl) methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n -Butylphenyl) methoxy group, (sec-butylphenyl) methoxy group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy Group, naphthylmethoxy group, anthracenylmethoxy group 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. In addition, in the “aralkyloxy group optionally having a halogen atom as a substituent”, the “optionally having a halogen atom as a substituent” means that part or all of the hydrogen atoms in the aralkyloxy group are partially or entirely. , May be replaced by a halogen atom, and specific examples of the halogen atom 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.

—Si (R ²² ) ₃ (three R ^{22 s} each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the three R ²² is 1 to 20; In the substituted silyl group represented by formula (1), each R ²² independently represents a hydrogen atom; an alkyl group having 1 to 10 carbon atoms (methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, etc.), aryl group Hydrocarbyl groups such as (phenyl groups); halogenated hydrocarbyl groups in which some or all of the hydrogen atoms in the hydrocarbyl group are replaced by halogen atoms Yes, the total number of carbon atoms of three R ²² is in the range of 1-20. The total number of carbon atoms of the three R ²² is preferably in the range of 3-18. Specific examples of the substituted silyl group include a methyl silyl group, an ethyl silyl group, a phenyl silyl group, a hydrocarbyl group such as a group in which some or all of the hydrogen atoms of the hydrocarbyl group are replaced with halogen atoms, or A monosubstituted silyl group having one halogenated hydrocarbyl group; a dimethylsilyl group, a diethylsilyl group, a diphenylsilyl group, or a group in which some or all of the hydrogen atoms of the hydrocarbyl group are replaced with halogen atoms. Disubstituted silyl groups having two hydrocarbyl groups and / or halogenated hydrocarbyl groups such as: trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri-n-butylsilyl group , Tri-sec-butylsilyl group, tri-tert-butylsilane Group, tri-isobutylsilyl group, tert-butyl-dimethylsilyl group, tri-n-pentylsilyl group, tri-n-hexylsilyl group, tricyclohexylsilyl group, triphenylsilyl group, hydrocarbyl in these groups Examples thereof include a hydrocarbyl group such as a group in which part or all of the hydrogen atoms in the group are replaced with a halogen atom and / or a trisubstituted silyl group having three halogenated hydrocarbyl groups. Of these, a trisubstituted silyl group is preferable, and a trimethylsilyl group, a tert-butyldimethylsilyl group, a triphenylsilyl group, and a group in which some or all of the hydrogen atoms of these groups are replaced with halogen atoms are more preferable. .

—N (R ²³ ) ₂ (two R ²³ each independently represents a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the two R ²³ is 2 to 20). In the disubstituted amino group shown, each R ²³ independently represents a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms of the two R ²³ is in the range of 2 to 20, A range of 10 is more preferred. Such hydrocarbyl group and halogenated hydrocarbyl group are the same as those described as the hydrocarbyl group and halogenated hydrocarbyl group of the substituted silyl group. Further, the two R ²³ 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- tert-Butyldimethylsilylamino group, pyrrolyl group, pyrrolidinyl group, piperidinyl group, carbazolyl group, dihydroindolyl group, dihydroisoindolyl group, groups in which some or all of the hydrogen atoms in these groups are replaced by halogen atoms, etc. Is mentioned. Of these, preferred are a dimethylamino group, a diethylamino group, a pyrrolidinyl group, a piperidinyl group, and a group in which some or all of the hydrogen atoms in these groups are replaced with halogen atoms.

Among R ¹ , R ² , R ³ and R ⁴ , groups bonded to two adjacent carbon atoms are bonded to each other, and may form a ring together with the carbon atoms to which they are bonded. R ¹⁰ and R ¹¹ may be bonded together to form a ring together with the silicon atoms to which they are bonded, and among R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ , Groups bonded to two adjacent carbon atoms may be bonded together to form a ring together with the carbon atoms to which they are bonded, and R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and Of R ¹⁶ , groups bonded to two adjacent carbon atoms may be bonded together to form a ring together with the carbon atoms to which they are bonded, and R ¹⁷ , R ¹⁸ , R ^19, of ^{R 20} and ^{R 21,} are bonded to two carbon atoms adjacent Motodo Bonded to may be taken together with the carbon atoms to which they are attached to form a ^{ring, R 5, R 24, R} 7, of R ²⁵ and R ^9, 2 carbon atoms adjacent Two groups bonded to each other may be bonded together to form a ring together with the two carbon atoms to which the two groups are bonded, and R ¹² , R ²⁶ , R ¹⁴ , R ²⁷ and Of R ¹⁶ , two groups bonded to two adjacent carbon atoms may be bonded to form a ring together with the two carbon atoms to which the two groups are bonded. The ring referred to here is a saturated or unsaturated hydrocarbyl ring substituted with a hydrocarbyl group having 1 to 20 carbon atoms, saturated with a hydrocarbyl group having 1 to 20 carbon atoms. Or an unsaturated silahydrocarbyl ring. Specific examples thereof include cyclopropane ring, cyclopropene ring, cyclobutane ring, cyclobutene ring, cyclopentane ring, cyclopentene ring, cyclohexane ring, cyclohexene ring, cycloheptane ring, cycloheptene ring, cyclooctane ring, cyclooctene ring, benzene ring. , Naphthalene ring, anthracene ring, silacyclopropane ring, silacyclobutane ring, silacyclopentane ring, and silacyclohexane ring.

In the transition metal complexes (1-1) to (1-3), R ¹ , R ² , R ³ and R ⁴ are preferably independently a hydrogen atom, a halogen atom, or an alkyl having 1 to 20 carbon atoms. Group, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and at least one of them is preferably a substituent other than hydrogen.

（式中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は前記と同じ意味を表す。）
において、例えば、次のような部分構造を挙げることができる。 Specific examples of R ¹ , R ² , R ³ and R ⁴ include the partial structural formula (2)

(In the formula, R ¹ , R ² , R ³ and R ⁴ represent the same meaning as described above.)
For example, the following partial structure can be given.

  Cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, n-propylcyclopentadienyl, isopropylcyclopentadienyl, n-butylcyclopentadienyl, sec-butylcyclopentadienyl, tert-butyl Cyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl, tetramethylcyclopentadienyl, phenylcyclopentadienyl, benzylcyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, methyltetrahydroindenyl, dimethyl Tetrahydroindenyl, octahydrofluorenyl

  Of the cyclopentadienyl partial structures exemplified herein, a preferred cyclopentadienyl partial structure is tetramethylcyclopentadienyl and the like.

^R 5 in the transition metal complex ^{(1-1) (1-3), R} 6, R 7, R 8, R 9, R 12, R 13, R 14, R 15, R 16, R 17, R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²⁴ , R ²⁵ , R ²⁶ , and R ²⁷ are each independently preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or a carbon atom. An aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms.

（式中、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８及びＲ^９は前記と同じ意味を表す。）
部分構造式（３−２）

（式中、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５及びＲ^１６は前記と同じ意味を表す。）
部分構造式（３−３）

（式中、Ｒ^１７、Ｒ^１８、Ｒ^１９、Ｒ^２０及びＲ^２１は前記と同じ意味を表す。）
部分構造式（３−４）

（式中、Ｒ^５、Ｒ^２４、Ｒ^７、Ｒ^２５及びＲ^９は前記と同じ意味を表す。）
部分構造式（３−５）

（式中、Ｒ^１２、Ｒ^２６、Ｒ^１４、Ｒ^２７及びＲ^１６は前記と同じ意味を表す。）
において、例えば、次のような部分構造を挙げることができる。 Preferred combinations of R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ , preferred combinations of R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ A preferred combination of R ⁵ , R ²⁴ , R ⁷ , R ²⁵ and R ^{9 and} a preferred combination of R ¹² , R ²⁶ , R ¹⁴ , R ²⁷ and R ¹⁶ are each a partial structural formula ( 3-1)

(In the formula, R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ represent the same meaning as described above.)
Partial structural formula (3-2)

(Wherein R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ represent the same meaning as described above.)
Partial structural formula (3-3)

(In the formula, R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ represent the same meaning as described above.)
Partial structural formula (3-4)

(In the formula, R ⁵ , R ²⁴ , R ⁷ , R ²⁵ and R ⁹ represent the same meaning as described above.)
Partial structural formula (3-5)

(Wherein R ¹² , R ²⁶ , R ¹⁴ , R ²⁷ and R ¹⁶ represent the same meaning as described above.)
For example, the following partial structure can be given.

  Phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, tetramethylphenyl, pentamethylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, tetraethylphenyl, pentaethylphenyl, tert-butylphenyl, di-tert-butylphenyl, tert-butyl Methylphenyl, di (tert-butyl) methylphenyl, phenylphenyl, diphenylphenyl, triphenylphenyl, tetraphenylphenyl, pentaphenylphenyl, benzylphenyl, dibenzylphenyl, tribenzylphenyl, tetrabenzylphenyl, pentabenzylphenyl, naphthyl , Anthracenyl, chlorophenyl, dichlorophenyl, fluorophenyl, pentafluorophenyl, bis (trifluoro Methyl) phenyl, methoxyphenyl

  Of the partial structures exemplified here, preferred partial structures are phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, diethylphenyl, di-tert-butylphenyl and the like.

In the transition metal complex (1-1), R ¹⁰ and R ¹¹ are preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. Examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, and benzyl group.

（式中、Ｒ^１０及びＲ^１１は前記と同じ意味を表す。）
において、次のような部分構造を挙げることができる。 A preferred combination of R ¹⁰ and R ¹¹ is the partial structural formula (4)

(Wherein R ¹⁰ and R ¹¹ represent the same meaning as described above.)
The following partial structure can be mentioned.

  Dimethylsilylene, diethylsilylene, ethylmethylsilylene, di (n-propyl) silylene, methyl (n-propyl) silylene, di (n-butyl) silylene, n-butylmethylsilylene, n-hexylmethylsilylene, methyl (n- Octyl) silylene, n-decylmethylsilylene, methyl (n-octadecyl) silylene, cyclohexylmethylsilylene, cyclotetramethylenesilylene

In the partial structural formula (4),
A partial structural formula, wherein R ¹⁰ is a methyl group, and R ¹¹ is an alkyl group having 2 to 20 carbon atoms which may have a halogen atom as a substituent, or
R ¹⁰ and R ¹¹ are the same,
An alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
Or a structural formula that is
R ¹⁰ and R ¹¹ are not identical,
An alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
Preferably, the structural formula is
Specific examples include dimethylsilylene, diethylsilylene, ethylmethylsilylene, n-butylmethylsilylene, cyclohexylmethylsilylene, cyclotetramethylenesilylene, and the like.

As the transition metal complex of the formula (1-1), preferably R ⁶ and R ⁸ are each independently
A transition metal complex which is an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, or an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent. Can be mentioned.

In the transition metal complex (1-2), R ¹¹ is preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. Specific examples thereof include a methyl group , Ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, and benzyl group.

As the transition metal complex of the formula (1-2), preferably R ⁶ , R ⁸ , R ¹³ , and R ¹⁵ are each independently
A transition metal complex which is an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, or an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent. Can be mentioned.

As the transition metal complex of the formula (1-3), preferably R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ¹⁸ and R ²⁰ are each independently
A transition metal complex which is an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, or an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent. Can be mentioned.

  Specific examples of the transition metal complexes (1-1) to (1-3) include the following complexes.

  [1-dimethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-diethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride Chloride, [1-cyclotetramethylene (phenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-ethylmethylphenylsilyl-2,3,4,5-tetramethyl Cyclopentadienyl] titanium trichloride, [1-n-butylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-methyldiphenylsilyl-2,3,4 , 5-tetramethylcyclopentadienyl] titanium trichloride, [ -Methylbis (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-cyclohexylmethylphenylsilyl-2,3,4,5-tetramethylcyclo Pentadienyl] titanium trichloride, [1-methyl (n-octadecyl) phenylsilyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-triphenylsilyl-2,3, 4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-tri (4-n-butylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1 -Tri (3-methylphenyl) silyl-2,3,4,5-tetramethylcyclope Tadienyl] titanium trichloride, [1-tri (3-isopropylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-dimethyl (3,5-dimethylphenyl) silyl -2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-dimethyl (3,5-di-n-hexylphenyl) silyl-2,3,4,5-tetramethylcyclopenta Dienyl] titanium trichloride, [1-n-butylmethyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-tris (3,5 -Dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium tri Chloride, [1-tris (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-tris (3,5-diisopropylphenyl) silyl-2 , 3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-tris (3,5-di-tert-butylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl ] Titanium trichloride, [1-Tris (3,5-di-n-hexylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-n-butylmethyl (2 , 4,6-trimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloro Id, [1-n-butylmethyl (pentamethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1- (3,5-di-tert-butylphenyl) bis (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1- (3,5-di-tert-butylphenyl) (3,5-diethyl Phenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride, [1-tris (3,5-diphenylphenyl) silyl-2,3,4 , 5-tetramethylcyclopentadienyl] titanium trichloride, [1-tris (3,5-dibenzylphenyl) silyl-2, , 4,5-tetramethyl-cyclopentadienyl] titanium trichloride,

And chlorinated titanium complexes. In the complexes exemplified here, “2,3,4,5-tetramethylcyclopentadienyl” is replaced with “cyclopentadienyl”, “2-methylcyclopentadienyl”, “3-methylcyclopentadienyl”. “Enyl”, “2,3-dimethylcyclopentadienyl”, “2,4-dimethylcyclopentadienyl”, “2,5-dimethylcyclopentadienyl”, “2,3,5-trimethylcyclopentadiene” “Enyl”, “2-ethylcyclopentadienyl”, “3-ethylcyclopentadienyl”, “2-n-propylcyclopentadienyl”, “3-n-propylcyclopentadienyl”, “2- “Isopropylcyclopentadienyl”, “3-isopropylcyclopentadienyl”, “2-n-butylcyclopentadienyl”, “3-n-butylcyclopente” “Dienyl”, “2-sec-butylcyclopentadienyl”, “3-sec-butylcyclopentadienyl”, “2-tert-butylcyclopentadienyl”, “3-tert-butylcyclopentadienyl” , “2-phenylcyclopentadienyl”, “3-phenylcyclopentadienyl”, “2-benzylcyclopentadienyl”, “3-benzylcyclopentadienyl”, “indenyl”, “2-methylindene” Similarly exemplified are chlorinated titanium complexes in which “nil”, “fluorenyl”, “tetrahydroindenyl”, “2-methyltetrahydroindenyl”, “octahydrofluorenyl” are substituted.

Further, in the complexes exemplified here, chlorinated transition metal complexes such as chlorinated zirconium complexes in which “titanium” is replaced with “zirconium”, or chlorinated hafnium complexes in which “hafnium” is replaced, and “chloride” as “fluoride” Fluorinated titanium complexes replaced with “bromide”, brominated titanium complexes replaced with “bromide”, titanium iodide complexes replaced with “iodide”, titanium hydride complexes replaced with “hydride”, “methyl” Alkylated titanium complexes such as methylated titanium complexes replaced with phenoxy, arylated titanium complexes such as phenylated titanium complexes replaced with “phenyl”, aralkylated titanium complexes such as benzylated titanium complexes replaced with “benzyl”, “methoxides” The titanium methoxylated complex replaced by Aryloxylation such as n-butoxytitanium complex replaced with “n-butoxide”, alkoxylated titanium complex such as isopropoxytitanium complex replaced with “isopropoxide”, phenoxytitanium complex replaced with “phenoxide” Titanium complexes, aralkyloxylated titanium complexes such as benzyloxylated titanium complexes replaced with “benzyloxide”, dimethylamidated titanium complexes replaced with “dimethylamide”, amidated titanium complexes such as diethylamidated titanium complexes replaced with “diethylamide” Are also exemplified.

［式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０及びＲ^１１は前記と同義である。］
（５−２）

［式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、及びＲ^１６は前記と同義である。］
（５−３）

［式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^７、Ｒ^９、Ｒ^１２、Ｒ^１４、Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^１９、Ｒ^２０、Ｒ^２１、Ｒ^２４、Ｒ^２５、Ｒ^２６、及びＲ^２７は前記と同義である。］
以下、遷移金属錯体（１−１）を例に説明する。遷移金属錯体（１−１）は例えば、式（５−１）

［式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０及びＲ^１１は前記と同義である。］
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（５−１）」という。）と、塩基とをアミン化合物の存在下に反応させる工程；
前記置換シクロペンタジエン化合物（５−１）と塩基との反応物に、
以下の一般式（６）

（式中、Ｍ、Ｘ^１、Ｘ^２及びＸ^３は前記と同義であり、Ｘ^４はＸ^１、Ｘ^２及びＸ^３と同じ定義である。ｍは、０または１である。）
で示される遷移金属化合物（以下、「遷移金属化合物（６）」という。）を反応させる工程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（５−１）と塩基とをアミン化合物の存在下に反応させる工程を「第１反応工程」、前記置換シクロペンタジエン化合物（５−１）と塩基との反応物に、遷移金属化合物（６）を反応させる工程を「第２反応工程」ということがある。 <Production Method of Transition Metal Complexes (1-1) to (1-3)>
The transition metal complex (1-1) is from a substituted cyclopentadiene compound represented by the formula (5-1), and the transition metal complex (1-2) is from a substituted cyclopentadiene compound represented by the formula (5-2). The transition metal complex (1-3) can be produced in the same manner from the substituted cyclopentadiene compound represented by the formula (5-3).
(5-1)

[Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are as defined above]. ]
(5-2)

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ are It is synonymous with the above. ]
(5-3)

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁹ , R ¹² , R ¹⁴ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ are as defined above. ]
Hereinafter, the transition metal complex (1-1) will be described as an example. The transition metal complex (1-1) is represented by, for example, the formula (5-1)

[Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are as defined above]. ]
A process of reacting a base with a substituted cyclopentadiene compound represented by the following (hereinafter referred to as “substituted cyclopentadiene compound (5-1)”);
In the reaction product of the substituted cyclopentadiene compound (5-1) and the base,
The following general formula (6)

(Wherein, ^M, X 1, ^{X 2} and ^{X 3} are as defined above, ^{X 4} is .m the same definitions as ^X 1, ^{X 2} and ^{X 3} is 0 or 1.)
It can manufacture by the manufacturing method which has the process of making the transition metal compound shown below (henceforth "transition metal compound (6)") react. Hereinafter, the step of reacting the substituted cyclopentadiene compound (5-1) and a base in the presence of an amine compound is referred to as “first reaction step”, and the reaction product of the substituted cyclopentadiene compound (5-1) and the base is referred to as a reaction product. The step of reacting the transition metal compound (6) may be referred to as a “second reaction step”.

一般式（５−１）で表される化合物には、各シクロペンタジエニル環の二重結合位置がそれぞれ異なる異性体が存在するが、本発明においてはそれらのうちのいずれか、またはそれらの混合物を表わす。 In the substituted cyclopentadiene compound (5-1), isomers different in the position of the double bond of the cyclopentadiene ring are the following structural isomers.

In the compound represented by the general formula (5-1), there are isomers having different double bond positions on each cyclopentadienyl ring. In the present invention, any of them, or those Represents a mixture.

In the transition metal compound (6), the substituent X ⁴ has the same definition as described above, and specific examples thereof include the same groups as those described for X ¹ , X ² and X ³ .

  Examples of the transition metal compound (6) include titanium halides such as titanium tetrachloride, titanium trichloride, titanium tetrabromide, titanium tetraiodide; tetrakis (dimethylamino) titanium, dichlorobis (dimethylamino) titanium, 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 (6) is titanium tetrachloride.

  Examples of the base to be reacted with the substituted cyclopentadiene compound (5-1) in the first reaction step include, for example, methyl lithium, ethyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, lithium trimethylsilyl acetylide, And organic alkali metal compounds represented by organic lithium compounds such as lithium acetylide, 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 (5-1).

  In the reaction of the substituted cyclopentadiene compound (5-1) and the base in the first reaction step, an amine compound is used. 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, diisopropylamine, di-n-butylamine, di-tert-butylamine, di-n-octylamine, di-n-decylamine, pyrrolidine, hexamethyldisilazane, diphenylamine, etc. Secondary amine compounds; trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, diisopropylethylamine, tri-n-octylamine, tri-n-decylamine, triphenylamine Emissions, 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 5 mol per 1 mol of the base.

  In the first reaction step, when the substituted cyclopentadiene compound (5-1) is reacted with a base, it is preferably reacted in the presence of a solvent. When a solvent is used, the substituted cyclopentadiene compound (5-1) and the base are reacted in the solvent, and then the transition metal compound (6) is added to the reaction mixture, whereby the substituted cyclopentadiene compound (5 The transition metal compound (6) can be further reacted with the reaction product of -1) and the base. In the reaction mixture obtained by reacting the substituted cyclopentadiene compound (5-1) and the base, a solid may precipitate. In this case, a solvent is added or precipitated until the precipitated solid is dissolved. The solid may be once separated by filtration or the like, and the transition metal compound (6) may be added after the separated solid is dissolved by adding a solvent or suspended. When a solvent is used, the first reaction step and the second reaction step are carried out substantially simultaneously by simultaneously adding the substituted cyclopentadiene compound (5-1), the base and the transition metal compound (6) to the solvent. You can also.

  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 hydrocarbyl solvents such as benzene and toluene; aliphatic hydrocarbyl solvents such as hexane and heptane; ether solvents such as diethyl ether, tetrahydrofuran and 1,4-dioxane; hexa Amide solvents such as methylphosphoric amide and dimethylformamide; polar solvents such as acetonitrile, propionitrile, acetone, diethyl ketone, methyl isobutyl ketone and cyclohexanone; non-protons such as halogen solvents such as dichloromethane, dichloroethane, chlorobenzene and dichlorobenzene Examples of the solvent are exemplified. These solvents can be used alone or in admixture of two or more. The amount used is preferably 1 to 200 parts by weight, and 3 to 50 parts by weight per 1 part by weight of the substituted cyclopentadiene compound (5-1). Further preferred.

  The amount of the transition metal compound (6) 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 (5-1).

  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 | generated transition metal complex (1-1) can be taken out from the reaction mixture obtained through the 1st reaction process and the 2nd reaction process by various well-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 ( 1-1) can be obtained.

In addition, a part of X ¹ , X ² and X ³ of the transition metal complexes (1-1) to (1-3) may have a hydrogen atom or a halogen atom as a substituent. 20 alkyl groups, alkoxy groups having 1 to 20 carbon atoms which may have halogen atoms as substituents, aryl groups having 6 to 20 carbon atoms which may have halogen atoms as substituents, halogens An aryloxy group having 6 to 20 carbon atoms which may have an atom as a substituent, an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent, and a halogen atom as a substituent In the compound which may have an aralkyloxy group having 7 to 20 carbon atoms, X ¹ , X ² and X ³ of the transition metal complexes (1-1) to (1-3) are halogen atoms. The compound and the corresponding al Group, an alkoxy group, an aryl group, an aryloxy group, a lithium compound having an aralkyl group or an aralkyl group, a sodium compound, can be obtained by reaction of a potassium compound or Maguneshikumu compound.

<Substituted cyclopentadiene compounds (5-1) to (5-3)>

In the substituted cyclopentadiene compounds (5-1) to (5-3), the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ are as defined above. is there.

  Specific examples of the substituted cyclopentadiene compound (5-1) include the following substituted cyclopentadiene compounds.

  1-dimethylphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1-diethylphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1-phenyldi (n-propyl) silyl-2, 3,4,5-tetramethylcyclopentadiene, 1-diisopropylphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1-di (n-butyl) phenylsilyl-2,3,4,5-tetra Methylcyclopentadiene, 1-di (isobutyl) phenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1-di (sec-butyl) phenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1-di (tert-butyl) phenylsilyl-2,3,4,5-tetramethylcyclopentadiene, -Ethylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1-methylphenyl (n-propyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methylphenyl (isopropyl) Silyl-2,3,4,5-tetramethylcyclopentadiene, 1-n-butylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1-isobutylmethylphenylsilyl-2,3,4, 5-tetramethylcyclopentadiene, 1-sec-butylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1-tert-butylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadiene 1-cyclohexylmethylphenylsilyl-2,3,4,5-teto Methyl cyclopentadiene, 1-methyl (n- octadecyl) phenyl silyl-2,3,4,5-tetramethyl-cyclopentadiene,

  1-dimethyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-diethyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclo Pentadiene, 1- (3,5-dimethylphenyl) di (n-propyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-diisopropyl (3,5-dimethylphenyl) silyl-2,3 4,5-tetramethylcyclopentadiene, 1-di (n-butyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-di (isobutyl) (3,5 -Dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-di (sec-butyl) (3,5-dimethylphenyl) silyl 2,3,4,5-tetramethylcyclopentadiene, 1-di (tert-butyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-ethylmethyl (3 , 5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methyl (3,5-dimethylphenyl) (n-propyl) silyl-2,3,4,5-tetramethylcyclo Pentadiene, 1-methyl (3,5-dimethylphenyl) (isopropyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-n-butylmethyl (3,5-dimethylphenyl) silyl-2,3 4,5-tetramethylcyclopentadiene, 1-isobutylmethyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethyl Cyclopentadiene, 1-sec-butylmethyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-tert-butylmethyl (3,5-dimethylphenyl) silyl-2,3 4,5-tetramethylcyclopentadiene, 1-cyclohexylmethyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methyl (n-octadecyl) (3,5-dimethyl Phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene,

  And substituted cyclopentadiene compounds. In the substituted cyclopentadiene compounds exemplified here, “2,3,4,5-tetramethylcyclopentadiene” is replaced with “cyclopentadiene”, “2-methylcyclopentadiene”, “3-methylcyclopentadiene”, “2, “3-dimethylcyclopentadiene”, “2,4-dimethylcyclopentadiene”, “2,5-dimethylcyclopentadiene”, “2,3,5-trimethylcyclopentadiene”, “2-ethylcyclopentadiene”, “3- “Ethylcyclopentadiene”, “2-n-propylcyclopentadiene”, “3-n-propylcyclopentadiene”, “2-isopropylcyclopentadiene”, “3-isopropylcyclopentadiene”, “2-n-butylcyclopentadiene” , “3-n-butylcyclopentadiene , “2-sec-butylcyclopentadiene”, “3-sec-butylcyclopentadiene”, “2-tert-butylcyclopentadiene”, “3-tert-butylcyclopentadiene”, “2-phenylcyclopentadiene”, “ “3-phenylcyclopentadiene”, “2-benzylcyclopentadiene”, “3-benzylcyclopentadiene”, “indene”, “2-methylindene”, “fluorene”, “tetrahydroindene”, “2-methyltetrahydroindene” A substituted cyclopentadiene compound substituted with “octahydrofluorene” is also exemplified.

  Specific examples of the substituted cyclopentadiene compound (5-2) include the following substituted cyclopentadiene compounds.

  1-methyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1-ethyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1-n-propyldiphenylsilyl-2,3 4,5-tetramethylcyclopentadiene, 1-isopropyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1-n-butyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1 -Isobutyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1-sec-butyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1-tert-butyldiphenylsilyl-2,3 , 4,5-tetramethylcyclopentadiene, 1-cyclohexyldi Phenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1-n-octadecyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1-methylphenyl (2-methylphenyl) silyl-2, 3,4,5-tetramethylcyclopentadiene, 1-methylphenyl (3-methylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methylphenyl (4-methylphenyl) silyl-2, 3,4,5-tetramethylcyclopentadiene, 1-methylphenyl (2,3-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methylphenyl (2,4-dimethylphenyl) Silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methylphenyl (2, -Dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methylphenyl (2,6-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methylphenyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methylphenyl (3,4,5-trimethylphenyl) silyl-2,3,4,5-tetramethylcyclo Pentadiene,

  1-ethylphenyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-n-propylphenyl (3,5-dimethylphenyl) silyl-2,3,4,5 -Tetramethylcyclopentadiene, 1-isopropylphenyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-n-butylphenyl (3,5-dimethylphenyl) silyl-2 , 3,4,5-tetramethylcyclopentadiene, 1-isobutylphenyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-sec-butylphenyl (3,5- Dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-tert-butylpheny (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-cyclohexylphenyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-n-octadecylphenyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methyl (2-methylphenyl) (3,5-dimethylphenyl) silyl-2, 3,4,5-tetramethylcyclopentadiene, 1-methyl (3-methylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methyl (4-methyl) Phenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methyl 2,3-dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methyl (2,4-dimethylphenyl) (3,5-dimethylphenyl) silyl -2,3,4,5-tetramethylcyclopentadiene, 1-methyl (2,5-dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1- Methylphenyl (2,6-dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-methylbis (3,5-dimethylphenyl) silyl-2,3 4,5-tetramethylcyclopentadiene, 1-methyl (3,5-dimethylphenyl) (3,4,5-trimethylphenyl) silyl-2, 3,4,5-tetramethylcyclopentadiene,

  And substituted cyclopentadiene compounds. In the substituted cyclopentadiene compounds exemplified here, “2,3,4,5-tetramethylcyclopentadiene” is replaced with “cyclopentadiene”, “2-methylcyclopentadiene”, “3-methylcyclopentadiene”, “2, “3-dimethylcyclopentadiene”, “2,4-dimethylcyclopentadiene”, “2,5-dimethylcyclopentadiene”, “2,3,5-trimethylcyclopentadiene”, “2-ethylcyclopentadiene”, “3- “Ethylcyclopentadiene”, “2-n-propylcyclopentadiene”, “3-n-propylcyclopentadiene”, “2-isopropylcyclopentadiene”, “3-isopropylcyclopentadiene”, “2-n-butylcyclopentadiene” , “3-n-butylcyclopentadiene , “2-sec-butylcyclopentadiene”, “3-sec-butylcyclopentadiene”, “2-tert-butylcyclopentadiene”, “3-tert-butylcyclopentadiene”, “2-phenylcyclopentadiene”, “ “3-phenylcyclopentadiene”, “2-benzylcyclopentadiene”, “3-benzylcyclopentadiene”, “indene”, “2-methylindene”, “fluorene”, “tetrahydroindene”, “2-methyltetrahydroindene” A substituted cyclopentadiene compound substituted with “octahydrofluorene” is also exemplified.

  Specific examples of the substituted cyclopentadiene compound (5-3) include the following substituted cyclopentadiene compounds.

  1-triphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1-phenyldi (2-methylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-phenyldi (3-methyl Phenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-phenyldi (4-methylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-phenylbis (2,3- Dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-phenylbis (2,4-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-phenylbis ( 2,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-phenylbis ( , 6-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-phenylbis (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, Phenylbis (3,4,5-trimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene,

  1-diphenyl (2-methylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-diphenyl (3-methylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, Diphenyl (4-methylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-diphenyl (2,3-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1- Diphenyl (2,4-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-diphenyl (2,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-diphenyl (2,6-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene 1-diphenyl (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-diphenyl (3,4,5-trimethylphenyl) silyl-2,3,4,5-tetra Methylcyclopentadiene,

  1-phenyl (2-methylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-phenyl (3-methylphenyl) (3,5-dimethylphenyl) silyl -2,3,4,5-tetramethylcyclopentadiene, 1-phenyl (4-methylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-phenyl ( 2,3-dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-phenyl (2,4-dimethylphenyl) (3,5-dimethylphenyl) silyl -2,3,4,5-tetramethylcyclopentadiene, 1-phenyl (2,5-dimethylphenyl) (3,5-dimethylpheny ) Silyl-2,3,4,5-tetramethylcyclopentadiene, 1-phenyl (2,6-dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-phenyl (3,5-dimethylphenyl) (3,4,5-trimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene,

  1-di (2-methylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-di (3-methylphenyl) (3,5-dimethylphenyl) silyl -2,3,4,5-tetramethylcyclopentadiene, 1-di (4-methylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-bis ( 2,3-dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-bis (2,4-dimethylphenyl) (3,5-dimethylphenyl) silyl -2,3,4,5-tetramethylcyclopentadiene, 1-bis (2,5-dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-the Lamethylcyclopentadiene, 1-bis (2,6-dimethylphenyl) (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene, 1-tris (3,5-dimethylphenyl) Silyl-2,3,4,5-tetramethylcyclopentadiene, 1- (3,5-dimethylphenyl) bis (3,4,5-trimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene ,

  And substituted cyclopentadiene compounds. In the substituted cyclopentadiene compounds exemplified here, “2,3,4,5-tetramethylcyclopentadiene” is replaced with “cyclopentadiene”, “2-methylcyclopentadiene”, “3-methylcyclopentadiene”, “2, “3-dimethylcyclopentadiene”, “2,4-dimethylcyclopentadiene”, “2,5-dimethylcyclopentadiene”, “2,3,5-trimethylcyclopentadiene”, “2-ethylcyclopentadiene”, “3- “Ethylcyclopentadiene”, “2-n-propylcyclopentadiene”, “3-n-propylcyclopentadiene”, “2-isopropylcyclopentadiene”, “3-isopropylcyclopentadiene”, “2-n-butylcyclopentadiene” , “3-n-butylcyclopentadiene , “2-sec-butylcyclopentadiene”, “3-sec-butylcyclopentadiene”, “2-tert-butylcyclopentadiene”, “3-tert-butylcyclopentadiene”, “2-phenylcyclopentadiene”, “ “3-phenylcyclopentadiene”, “2-benzylcyclopentadiene”, “3-benzylcyclopentadiene”, “indene”, “2-methylindene”, “fluorene”, “tetrahydroindene”, “2-methyltetrahydroindene” A substituted cyclopentadiene compound substituted with “octahydrofluorene” is also exemplified.

［式中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は前記と同義であり

［式中、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０及びＲ^１１は前記と同義であり、Ｘ^５はハロゲン原子である。］

［式中、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、及びＲ^１６は前記と同義であり、Ｘ^５はハロゲン原子である。］

［式中、Ｒ^５、Ｒ^７、Ｒ^９、Ｒ^１２、Ｒ^１４、Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^１９、Ｒ^２０、Ｒ^２１、Ｒ^２４、Ｒ^２５、Ｒ^２６、及びＲ^２７は前記と同義であり、Ｘ^５はハロゲン原子である。］
以下、置換シクロペンタジエン化合物（５−１）を例に説明する。 <Method for Producing Substituted Cyclopentadiene Compounds (5-1) to (5-3)>
The substituted cyclopentadiene compound (5-1) is a step of reacting a substituted cyclopentadiene compound represented by formula (7) (hereinafter abbreviated as “substituted cyclopentadiene compound (7)”) with a base;
By reacting the reaction product of the substituted cyclopentadiene compound (7) with a base with a silicon halide compound represented by the formula (8-1) (hereinafter abbreviated as “silicon halide compound (8-1)”). ,
The substituted cyclopentadiene compound (5-2) is a step of reacting the substituted cyclopentadiene compound (7) with a base;
By reacting a reaction product of the substituted cyclopentadiene compound (7) with a base with a halogenated silicon compound represented by the formula (8-2) (hereinafter abbreviated as “halogenated compound (8-2)”). ,
The substituted cyclopentadiene compound (5-3) is a step of reacting the substituted cyclopentadiene compound (7) with a base;
By reacting a reaction product of the substituted cyclopentadiene compound (7) with a base with a silicon halide compound represented by the formula (8-3) (hereinafter abbreviated as “silicon halide compound (8-3)”). ,
Each can be produced in the same manner.

[Wherein, R ¹ , R ² , R ³ and R ⁴ are as defined above.

[Wherein, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ have the same meaning as described above, and X ⁵ represents a halogen atom. ]

[Wherein R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are as defined above, and X ⁵ is a halogen atom. is there. ]

[Wherein R ⁵ , R ⁷ , R ⁹ , R ¹² , R ¹⁴ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²⁴ , R ²⁵ , R ²⁶ , and R ²⁷ are As defined above, X ⁵ is a halogen atom. ]
Hereinafter, the substituted cyclopentadiene compound (5-1) will be described as an example.

［式中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は前記と同義であり

The substituted cyclopentadiene compound (7) is as follows.

[Wherein, R ¹ , R ² , R ³ and R ⁴ are as defined above.

  Examples of the substituted cyclopentadiene compound (7) include the following compounds.

  Cyclopentadiene, methylcyclopentadiene, 1,2-dimethylcyclopentadiene, 1,3-dimethylcyclopentadiene, 1,2,3-trimethylcyclopentadiene, 1,2,4-trimethylcyclopentadiene, 1,2,3,4 -Tetramethylcyclopentadiene, ethylcyclopentadiene, 1,2-diethylcyclopentadiene, 1,3-diethylcyclopentadiene, 1,2,3-triethylcyclopentadiene, 1,2,4-triethylcyclopentadiene, 1,2, 3,4-tetraethylcyclopentadiene, n-propylcyclopentadiene, isopropylcyclopentadiene, n-butylcyclopentadiene, sec-butylcyclopentadiene, tert-butylcyclopentadiene, n-pentylcyclopent Diene, neopentylcyclopentadiene, n-hexylcyclopentadiene, n-octylcyclopentadiene, phenylcyclopentadiene, naphthylcyclopentadiene, trimethylsilylcyclopentadiene, triethylsilylcyclopentadiene, tert-butyldimethylsilylcyclopentadiene, indene, 2-methylindene Tetrahydroindene, 2-methyltetrahydroindene, 3-methyltetrahydroindene, 2,3-dimethyltetrahydroindene, 2-ethyltetrahydroindene, 2-n-propyltetrahydroindene, 2-isopropyltetrahydroindene, 2-n-butyltetrahydro Indene, 2-sec-butyltetrahydroindene, 2-tert-butyltetrahydroindene, 2 n-pentyltetrahydroindene, 2-neopentyltetrahydroindene, 2-amyltetrahydroindene, 2-n-hexyltetrahydroindene, 2-cyclohexyltetrahydroindene, 2-n-octyltetrahydroindene, 2-n-decyltetrahydroindene, 2 -Phenyltetrahydroindene, 2-benzyltetrahydroindene, 2-naphthyltetrahydroindene, 2-methoxytetrahydroindene, 2-phenoxytetrahydroindene, 2-benzyloxytetrahydroindene, 2-dimethylaminotetrahydroindene, 2-trimethylsilyltetrahydroindene, fluorene , Octahydrofluorene

  In the substituted cyclopentadiene compound (7) exemplified here, when there are isomers having different positions of the double bond of the cyclopentadiene ring, a mixture of these isomers may be used.

［式中、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０及びＲ^１１は前記と同義であり、Ｘ^５はハロゲン原子である。］ The silicon halide compound (8-1) is as follows.

[Wherein, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ have the same meaning as described above, and X ⁵ represents a halogen atom. ]

  Specific examples of the silicon halide compound (8-1) include the following silicon halide compounds.

  Chlorodimethylphenylsilane, chlorodiethylphenylsilane, chlorophenyldi (n-propyl) silane, chlorodiisopropylphenylsilane, di (n-butyl) chlorophenylsilane, di (isobutyl) chlorophenylsilane, di (sec-butyl) chlorophenylsilane, di (Tert-butyl) chlorophenylsilane, chloroethylmethylphenylsilane, chloromethylphenyl (n-propyl) silane, chloromethylphenyl (isopropyl) silane, n-butylchloromethylphenylsilane, isobutylchloromethylphenylsilane, sec-butylchloro Methylphenylsilane, tert-butylchloromethylphenylsilane, chlorocyclohexylmethylphenylsilane, chloromethyl (n-octadecyl) phenylsilane Down,

  Chlorodimethyl (3,5-dimethylphenyl) silane, chlorodiethyl (3,5-dimethylphenyl) silane, chloro (3,5-dimethylphenyl) di (n-propyl) silane, chlorodiisopropyl (3,5-dimethylphenyl) ) Silane, di (n-butyl) chloro (3,5-dimethylphenyl) silane, di (isobutyl) chloro (3,5-dimethylphenyl) silane, di (sec-butyl) chloro (3,5-dimethylphenyl) Silane, di (tert-butyl) chloro (3,5-dimethylphenyl) silane, chloroethylmethyl (3,5-dimethylphenyl) silane, chloromethyl (3,5-dimethylphenyl) (n-propyl) silane, chloro Methyl (3,5-dimethylphenyl) (isopropyl) silane, n-butylchloromethyl (3 5-dimethylphenyl) silane, isobutylchloromethyl (3,5-dimethylphenyl) silane, sec-butylchloromethyl (3,5-dimethylphenyl) silane, tert-butylchloromethyl (3,5-dimethylphenyl) silane, Chlorocyclohexylmethyl (3,5-dimethylphenyl) silane, chloromethyl (n-octadecyl) (3,5-dimethylphenyl) silane,

  In the compounds exemplified here, those in which “chloro” is replaced with “fluoro”, “bromo”, “iodo” are also exemplified.

  Specific examples of the silicon halide compound (8-2) include the following silicon halide compounds.

  Chloromethyldiphenylsilane, chloroethyldiphenylsilane, chloro-n-propyldiphenylsilane, chloroisopropyldiphenylsilane, n-butylchlorodiphenylsilane, isobutylchlorodiphenylsilane, sec-butylchlorodiphenylsilane, tert-butylchlorodiphenylsilane, chloro Cyclohexyldiphenylsilane, chloro-n-octadecyldiphenylsilane, chloromethylphenyl (2-methylphenyl) silane, chloromethylphenyl (3-methylphenyl) silane, chloromethylphenyl (4-methylphenyl) silane, chloromethylphenyl (2 , 3-dimethylphenyl) silane, chloromethylphenyl (2,4-dimethylphenyl) silane, chloromethylphenyl (2,5-dimethylpheny ) Silane, chloromethyl phenyl (2,6-dimethylphenyl) silane, chloromethyl phenyl (3,5-dimethylphenyl) silane, chloromethyl phenyl (3,4,5-trimethylphenyl) silane,

  Chloroethylphenyl (3,5-dimethylphenyl) silane, chloro-n-propylphenyl (3,5-dimethylphenyl) silane, chloroisopropylphenyl (3,5-dimethylphenyl) silane, n-butylchlorophenyl (3,5 -Dimethylphenyl) silane, isobutylchlorophenyl (3,5-dimethylphenyl) silane, sec-butylchlorophenyl (3,5-dimethylphenyl) silane, tert-butylchlorophenyl (3,5-dimethylphenyl) silane, chlorocyclohexylphenyl ( 3,5-dimethylphenyl) silane, chloro-n-octadecylphenyl (3,5-dimethylphenyl) silane, chloromethyl (2-methylphenyl) (3,5-dimethylphenyl) silane, chloromethyl (3-methylphenyl) (3,5-dimethylphenyl) silane, chloromethyl (4-methylphenyl) (3,5-dimethylphenyl) silane, chloromethyl (2,3-dimethylphenyl) (3,5-dimethylphenyl) silane, chloromethyl (2,4-dimethylphenyl) (3,5-dimethylphenyl) silane, chloromethyl (2,5-dimethylphenyl) (3,5-dimethylphenyl) silane, chloromethylphenyl (2,6-dimethylphenyl) ( 3,5-dimethylphenyl) silane, chloromethylbis (3,5-dimethylphenyl) silane, chloromethyl (3,5-dimethylphenyl) (3,4,5-trimethylphenyl) silane,

  In the compounds exemplified here, those in which “chloro” is replaced with “fluoro”, “bromo”, “iodo” are also exemplified.

  Specific examples of the silicon halide compound (8-3) include the following silicon halide compounds.

  Chlorotriphenylsilane, chlorophenyldi (2-methylphenyl) silane, chlorophenyldi (3-methylphenyl) silane, chlorophenyldi (4-methylphenyl) silane, chlorophenylbis (2,3-dimethylphenyl) silane, chlorophenylbis ( 2,4-dimethylphenyl) silane, chlorophenylbis (2,5-dimethylphenyl) silane, chlorophenylbis (2,6-dimethylphenyl) silane, chlorophenylbis (3,5-dimethylphenyl) silane, chlorophenylbis (3 4,5-trimethylphenyl) silane,

  Chlorodiphenyl (2-methylphenyl) silane, chlorodiphenyl (3-methylphenyl) silane, chlorodiphenyl (4-methylphenyl) silane, chlorodiphenyl (2,3-dimethylphenyl) silane, chlorodiphenyl (2,4-dimethyl) Phenyl) silane, chlorodiphenyl (2,5-dimethylphenyl) silane, chlorodiphenyl (2,6-dimethylphenyl) silane, chlorodiphenyl (3,5-dimethylphenyl) silane, chlorodiphenyl (3,4,5-trimethyl) Phenyl) silane,

  Chlorophenyl (2-methylphenyl) (3,5-dimethylphenyl) silane, chlorophenyl (3-methylphenyl) (3,5-dimethylphenyl) silane, chlorophenyl (4-methylphenyl) (3,5-dimethylphenyl) silane , Chlorophenyl (2,3-dimethylphenyl) (3,5-dimethylphenyl) silane, chlorophenyl (2,4-dimethylphenyl) (3,5-dimethylphenyl) silane, chlorophenyl (2,5-dimethylphenyl) (3 , 5-dimethylphenyl) silane, chlorophenyl (2,6-dimethylphenyl) (3,5-dimethylphenyl) silane, chlorophenyl (3,5-dimethylphenyl) (3,4,5-trimethylphenyl) silane,

  Chlorodi (2-methylphenyl) (3,5-dimethylphenyl) silane, chlorodi (3-methylphenyl) (3,5-dimethylphenyl) silane, chlorodi (4-methylphenyl) (3,5-dimethylphenyl) silane Chlorobis (2,3-dimethylphenyl) (3,5-dimethylphenyl) silane, chlorobis (2,4-dimethylphenyl) (3,5-dimethylphenyl) silane, chlorobis (2,5-dimethylphenyl) (3 , 5-dimethylphenyl) silane, chlorobis (2,6-dimethylphenyl) (3,5-dimethylphenyl) silane, chlorotris (3,5-dimethylphenyl) silane, chloro (3,5-dimethylphenyl) bis (3 , 4,5-trimethylphenyl) silane,

  In the compounds exemplified here, those in which “chloro” is replaced with “fluoro”, “bromo”, “iodo” are also exemplified.

  Examples of the base to be reacted with the substituted cyclopentadiene compound (7) include alkali metal hydrides such as lithium hydride, sodium hydride and potassium hydride, alkaline earth metal hydrides such as calcium hydride, methyl lithium, ethyl lithium, Examples include organic alkali metal compounds typified by organic lithium compounds such as n-butyllithium, sec-butyllithium, tert-butyllithium, lithium trimethylsilylacetylide, lithium acetylide, trimethylsilylmethyllithium, vinyllithium, phenyllithium and allyllithium. The amount used thereof is usually in the range of 0.5 to 3 moles, preferably 0.9 to 2 moles, relative to the substituted cyclopentadiene compound (7). As for sodium hydride and potassium hydride, commercially available mineral oil-containing products can be used as they are, but of course, the mineral oil may be used after washing and removing with a hydrocarbyl solvent such as hexane.

  In the step of reacting the substituted cyclopentadiene compound (7) with a base, an amine compound may be used. Examples of such amine compounds include aniline, chloroaniline, bromoaniline, fluoroaniline, dichloroaniline, dibromoaniline, difluoroaniline, trichloroaniline, tribromoaniline, trifluoroaniline, tetrachloroaniline, tetrabromoaniline, tetrafluoroaniline. , Pentachloroaniline, pentafluoroaniline, nitroaniline, dinitroaniline, hydroxyaniline, phenylenediamine, anisidine, dimethoxyaniline, trimethoxyaniline, ethoxyaniline, diethoxyaniline, triethoxyaniline, n-propoxyaniline, isopropoxyaniline, n-butoxyaniline, sec-butoxyaniline, isobutoxyaniline, t-butoxyaniline, phenoxy Niline, methylaniline, ethylaniline, n-propylaniline, isopropylaniline, n-butylaniline, sec-butylaniline, isobutylaniline, t-butylaniline, dimethylaniline, diethylaniline, di-n-propylaniline, diisopropylaniline, Di-n-butylaniline, di-sec-butylaniline, diisobutylaniline, di-t-butylaniline, trimethylaniline, triethylaniline, diisopropylaniline, phenylaniline, benzylaniline, aminobenzoic acid, aminobenzoic acid methyl ester, amino Benzoic acid ethyl ester, aminobenzoic acid n-propyl ester, aminobenzoic acid isopropyl ester, aminobenzoic acid n-butyl ester, aminobenzoic acid isobutyl ester , Primary anilines such as aminobenzoic acid sec-butyl ester and aminobenzoic acid t-butyl ester, naphthylamine, naphthylmethylamine, benzylamine, propylamine, butylamine, pentylamine, hexylamine, cyclohexylamine, heptylamine, Primary amines including octylamine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine and the like;

  N-methylaniline, N-ethylaniline, diphenylamine, N-methylchloroaniline, N-methylbromoaniline, N-methylfluoroaniline, N-methylanisidine, N-methylmethylaniline, N-methylethylaniline, N- Methyl-n-propylaniline, N-methylisopropylaniline, diethylamine, dipropylamine, diisopropylamine, dipentylamine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, morpholine, piperidine, 2,2,6,6- Secondary amines such as tetramethylpiperidine, pyrrolidine, 2-methylaminopyridine, 3-methylaminopyridine, 4-methylaminopyridine,

  N, N-dimethylaniline, N, N-dimethylchloroaniline, N, N-dimethylbromoaniline, N, N-dimethylfluoroaniline, N, N-dimethylanisidine, N, N-dimethylethylaniline, N, N -Dimethyl-n-propylaniline, N, N-dimethylisopropylaniline, 1,4-diazabicyclo [2.2.2] octane, 1,5-diazabicyclo [4.3.0] non-5-ene, 1, 8-diazabicyclo [5.4.0] undec-7-ene, 2-dimethylaminopyridine, 3-dimethylaminopyridine, 4-dimethylaminopyridine, trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine Diisopropylethylamine, tri-n-octylamine, tri-n-decylamine, Tertiary amines such as phenylamine the like, preferably a primary amine or a secondary amine, more preferably primary anilines are used.

  The amount of the amine compound used is usually in the range of 0.001 to 2 mol times, preferably 0.01 to 0.5 mol times with respect to the base. The reaction is usually performed in a solvent inert to the reaction. Examples of such solvents include aromatic hydrocarbyl solvents such as benzene, toluene and xylene, aliphatic hydrocarbyl solvents such as pentane, hexane, heptane, octane and cyclohexane, diethyl ether, methyl t-butyl ether, tetrahydrofuran, Examples include aprotic solvents such as ether solvents such as 1,4-dioxane, amide solvents such as hexamethylphosphoric amide, dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and halogen solvents such as chlorobenzene and dichlorobenzene. . These solvents are used singly or as a mixture of two or more, and the amount used is usually in the range of 1 to 200 times by weight, preferably 3 to 30 times by weight with respect to the cyclopentadiene compound.

  In the reaction, for example, the substituted cyclopentadiene compound (7), the base and the amine compound may be mixed simultaneously in a solvent, or the base and the amine compound may be mixed in advance and then the substituted cyclopentadiene compound (7) may be added. Good. Although there is no restriction | limiting in particular in reaction temperature, the temperature range which does not require a low-temperature installation is industrially good, for example, is 0-70 degreeC, Preferably it is the range of 10-60 degreeC. Such a reaction efficiently produces a metal salt of the substituted cyclopentadiene compound (7). The metal salt of the substituted cyclopentadiene compound (7) thus obtained may be used as it is in the reaction mixture or may be used after being taken out from the reaction mixture, but the former is usually sufficient.

  The reaction for obtaining the substituted cyclopentadiene compound (5-1) is usually performed in a solvent inert to the reaction. Examples of such solvents include aromatic hydrocarbyl solvents such as benzene, toluene and xylene, aliphatic hydrocarbyl solvents such as pentane, hexane, heptane, octane and cyclohexane, diethyl ether, methyl t-butyl ether, tetrahydrofuran, Examples include aprotic solvents such as ether solvents such as 1,4-dioxane, amide solvents such as hexamethylphosphoric amide, dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and halogen solvents such as chlorobenzene and dichlorobenzene. . These solvents are used singly or as a mixture of two or more thereof, and the amount used is usually 1 to 200 times by weight, preferably 3 to 30 times by weight with respect to the substituted cyclopentadiene compound (7). This reaction is usually performed by, for example, mixing a base, an amine compound and a substituted cyclopentadiene compound (7) in a solvent and then adding the silicon halide compound (8-1). Even if the method of mixing is employed, the desired substituted cyclopentadiene compound (5-1) is produced. Although there is no restriction | limiting in particular in reaction temperature, the temperature range which does not require a low-temperature installation is industrially advantageous, for example, is 0-70 degreeC, Preferably it is the range of 10-60 degreeC.

  The amount of the substituted cyclopentadiene compound (7) is usually 0.5 to 5 moles, preferably 0.8 to 3 moles, relative to the halogenated silicon compound (8-1).

  After completion of the reaction, water, an aqueous solution of sodium hydrogen carbonate, an aqueous solution of sodium carbonate, an aqueous solution of ammonium chloride, or an aqueous solution of hydrochloric acid, etc. are added to the resulting reaction mixture, and then separated into an organic layer and an aqueous layer. A solution of the substituted cyclopentadiene compound (5-1) is obtained. When a solvent compatible with water is used in the reaction or when the organic layer and the aqueous layer cannot be separated easily due to a small amount of solvent used in the reaction, toluene, ethyl acetate, Liquid separation may be performed after adding an organic solvent insoluble in water such as chlorobenzene. If the obtained organic layer is concentrated, a substituted cyclopentadiene compound (5-1) can be obtained, but if necessary, it may be purified by a method such as distillation or column chromatography.

<Activation promoter component>
The activation promoter component is an activation promoter component containing an element belonging to Group 13 of the periodic table, and can include the following compound (A), compound (B) or compound (C), which are used in combination. May be.
Compound (A): One or more aluminum compounds selected from the group consisting of the following compounds (A1), (A2) and (A3) (A1): General formula (E ¹ ) _a Al (G) _3-a organoaluminum compounds represented (A2): the general formula ^{-Al (E 2) _-O-} cyclic aluminoxane (A3) having the structure represented by _b: formula ^{E 3 {-Al (E 3)} - A linear aluminoxane having a structure represented by O—} _c Al (E ³ ) ₂ (wherein E ¹ represents a hydrocarbyl group having 1 to 8 carbon atoms, and E ² and E ³ are Each independently represents a hydrocarbyl group having 1 to 8 carbon atoms, an alkoxy group containing an electron withdrawing group or an aryloxy group containing an electron withdrawing group, G represents a hydrogen atom or a halogen atom, a Represents an integer from 1 to 3 , B represents an integer of 2 or more, when c have a plurality .E ¹ is representing an integer of 1 or more, when a plurality of E ¹ have a plurality good .G also is optionally substituted by one or more identical to each other, a plurality G may be the same as or different from each other, the plurality of E ² may be the same or different from each other, and the plurality of E ³ may be the same or different from each other.
Compound (B): at least one boron compound selected from the group consisting of the following compounds (B1), (B2) and (B3) (B1): a boron compound represented by the general formula BQ ¹ Q ² Q ³ B2): Borate compound represented by general formula T ⁺ (BQ ⁴ Q ⁵ Q ⁶ Q ⁷ ) ⁻ (B3): General formula (LH) ⁺ (BQ ⁸ Q ⁹ Q ¹⁰ Q ¹¹ ) ⁻ Borate compound (wherein B represents a boron atom in a trivalent state, Q ¹ , Q ² , Q ³ , Q ⁴ , Q ⁵ , Q ⁶ , Q ⁷ , Q ⁸ , Q ⁹ , Q ¹⁰ And Q ¹¹ are the same or different and each is a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms that may be substituted with a halogen atom, or 1 to 20 carbon atoms that may be substituted with a halogen atom. Hydrocarbylsilyl group of halo Represents a down atoms substituted by optionally substituted at alkoxy group or a halogen atom having 1 to 20 carbon atoms optionally good C2-20 dihydrocarbyl amino groups, T ⁺ is an inorganic or organic (LH) ⁺ represents a Bronsted acid.)
Compound (C): One or more borate compounds selected from the group consisting of the following compounds (C1) and (C2) (C1): represented by the general formula T ⁺ (BY ¹ Y ² Y ³ Y ⁴ ) ⁻ Borate compound (C2): a borate compound represented by the general formula (LH) ⁺ (BY ⁵ Y ⁶ Y ⁷ Y ⁸ ) ^— (wherein B represents a boron atom in a trivalent valence state, Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ and Y ⁸ are the same or different and are each a halogen atom or a hydro carbon having 1 to 100 carbon atoms which may be substituted with a halogen atom. Represents a carbyl group, a hydrocarbylsilyl group having 1 to 100 carbon atoms, an alkoxy group having 1 to 100 carbon atoms or a dihydrocarbylamino group having 2 to 100 carbon atoms, Y ¹ , Y ² , Y low of ³ and ^{Y 4} At least one and one ^{Kutomo, Y 5, Y 6, Y} 7 and ^{Y 8} are each general formula (U-H) (wherein, U is expressed O, S, and NR, or PR, R is hydro Carbyl group, trihydrocarbylsilyl group, trihydrocarbylgermyl group or hydrogen.) T ⁺ represents an inorganic or organic cation, and (LH) ⁺ Represents a Bronsted acid.)

In the compounds (A1) to (A3), examples of the hydrocarbyl group having 1 to 8 carbon atoms in E ¹ , E ² and E ³ include an alkyl group having 1 to 8 carbon atoms, Examples of the alkyl group having 1 to 8 atoms include 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.

E ² and E ³ may be an alkoxy group containing an electron withdrawing group or an aryloxy group containing an electron withdrawing group. As an index of electron withdrawing property, Hammett's rule substituent constant σ and the like are known. A functional group having a positive Hammett's substituent constant σ is exemplified as an electron-withdrawing group.

  Specific examples of the electron withdrawing group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a carbonyl group, a sulfone group, and a phenyl group.

Examples of the alkoxy group containing an electron-withdrawing group in E ² and E ³ include, for example, a fluoromethoxy group, a chloromethoxy group, a bromomethoxy group, an iodomethoxy group, a difluoromethoxy group, a dichloromethoxy group, a dibromomethoxy group, a di Iodomethoxy group, trifluoromethoxy group, trichloromethoxy group, tribromomethoxy group, triiodomethoxy group, 2,2,2-trifluoroethoxy group, 2,2,2-trichloroethoxy group, 2,2,2- Tribromoethoxy group, 2,2,2-triiodoethoxy group, pentafluoroethoxy group, pentachloroethoxy group, pentabromoethoxy group, pentaiodoethoxy group, 2,2,3,3,3-pentafluoropropoxy group 2,2,3,3,3-pentachloropropoxy group, 2,2,3, , 3-pentabromopropoxy group, 2,2,3,3,3-pentaiodopropoxy group, heptafluoropropoxy group, heptachloropropoxy group, heptabromopropoxy group, heptaiodopropoxy group, 2,2,2-tri Fluoro-1-trifluoromethylethoxy group, 2,2,2-trichloro-1-trichloromethylethoxy group, 2,2,2-tribromo-1-tribromomethylethoxy group, 2,2,2-triiodo-1 -Triiodomethylethoxy group, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethoxy group, 1,1-bis (trichloromethyl) -2,2,2-trichloroethoxy group, 1 , 1-bis (tribromomethyl) -2,2,2-tribromoethoxy group, 1,1-bis (triiodomethyl) -2,2,2-triiodo Butoxy group, 1H, 1H-perfluoro-butoxy group, 1H, 1H-perfluoro pentoxy group, 1H, 1H-perfluoro hexanoate alkoxy group, 1H, such as 1H-perfluoro octanoate alkoxy group. Preferably, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethoxy group and the like can be mentioned.

As the aryloxy group containing an electron-withdrawing group in E ² and E ³ , for example, 2-fluorophenoxy group, 3-fluorophenoxy group, 4-fluorophenoxy group, 2,3-difluorophenoxy group, 2,4 -Difluorophenoxy group, 2,5-difluorophenoxy group, 2,6-difluorophenoxy group, 3,4-difluorophenoxy group, 3,5-difluorophenoxy group, 2,3,4-trifluorophenoxy group, 2, 3,5-trifluorophenoxy group, 2,3,6-trifluorophenoxy group, 2,4,5-trifluorophenoxy group, 2,4,6-trifluorophenoxy group, 3,4,5-trifluoro Phenoxy group, 2,3,4,5-tetrafluorophenoxy group, 2,3,4,6-tetrafluorophenoxy group, , 3,5,6-tetrafluorophenoxy group, 2,3,4,5,6-pentafluorophenoxy group, 2,3,5,6-tetrafluoro-4-trifluoromethylphenoxy group, 2-chlorophenoxy group Group, 3-chlorophenoxy group, 4-chlorophenoxy group, 2,3-dichlorophenoxy group, 2,4-dichlorophenoxy group, 2,5-dichlorophenoxy group, 2,6-dichlorophenoxy group, 3,4- Dichlorophenoxy group, 3,5-dichlorophenoxy group, 2,3,4-trichlorophenoxy group, 2,3,5-trichlorophenoxy group, 2,3,6-trichlorophenoxy group, 2,4,5-trichlorophenoxy group Group, 2,4,6-trichlorophenoxy group, 3,4,5-trichlorophenoxy group, 2,3,4,5-tetrachlorophenoxy group 2,3,4,6-tetrachlorophenoxy group, 2,3,5,6-tetrachlorophenoxy group, 2,3,4,5,6-pentachlorophenoxy group, 2,3,5,6- Tetrachloro-4-trichloromethylphenoxy group, 2-bromophenoxy group, 3-bromophenoxy group, 4-bromophenoxy group, 2,3-dibromophenoxy group, 2,4-dibromophenoxy group, 2,5-dibromophenoxy group Group, 2,6-dibromophenoxy group, 3,4-dibromophenoxy group, 3,5-dibromophenoxy group, 2,3,4-tribromophenoxy group, 2,3,5-tribromophenoxy group, 2, 3,6-tribromophenoxy group, 2,4,5-tribromophenoxy group, 2,4,6-tribromophenoxy group, 3,4,5-tribromophenoxy group, 2 3,4,5-tetrabromophenoxy group, 2,3,4,6-tetrabromophenoxy group, 2,3,5,6-tetrabromophenoxy group, 2,3,4,5,6-pentabromophenoxy Group, 2,3,5,6-tetrabromo-4-tribromomethylphenoxy group, 2-iodophenoxy group, 3-iodophenoxy group, 4-iodophenoxy group, 2,3-diiodophenoxy group, 2,4 -Diiodophenoxy group, 2,5-diiodophenoxy group, 2,6-diiodophenoxy group, 3,4-diiodophenoxy group, 3,5-diiodophenoxy group, 2,3,4-triiodo Phenoxy group, 2,3,5-triiodophenoxy group, 2,3,6-triiodophenoxy group, 2,4,5-triiodophenoxy group, 2,4,6-triiodophenoxy group, , 4,5-triiodophenoxy group, 2,3,4,5-tetraiodophenoxy group, 2,3,4,6-tetraiodophenoxy group, 2,3,5,6-tetraiodophenoxy group, 2 , 3,4,5,6-pentaiodophenoxy group, 2,3,5,6-tetraiodo-4-tribromomethylphenoxy group, and the like. Preferably, 3,4,5-trifluorophenoxy group, 2,3,4,5,6-pentafluorophenoxy group and the like are mentioned.

Examples of the organoaluminum compound (A1) represented by the general formula (E ¹ ) _a Al (G) _3-a include trialkylaluminum, dialkylaluminum chloride, alkylaluminum dichloride, and dialkylaluminum hydride. Examples of the alkylaluminum include trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, and trihexylaluminum. Examples of the dialkylaluminum chloride include dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, Examples include diisobutylaluminum chloride and dihexylaluminum chloride. Examples of the nium dichloride include methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, and hexylaluminum dichloride. Examples of the dialkylaluminum hydride include dimethylaluminum hydride, diethylaluminum hydride, and dipropylaluminum. Examples include hydride, diisobutylaluminum hydride, and dihexylaluminum hydride.

Formula {-Al (E ² ) —O—} Cyclic aluminoxane (A2) having a structure represented by _b or a structure represented by formula E ³ {—Al (E ³ ) —O—} _c AlE ³ ₂ Examples of E ² and E ³ in the linear aluminoxane (A3) having an alkyl group 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 , Alkoxy groups containing electron withdrawing groups such as trifluoromethoxy group, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethoxy group, 4-fluorophenoxy group, 3,4,5 -An aryloxy group containing an electron-withdrawing group such as a trifluorophenoxy group or a 2,3,4,5,6-pentafluorophenoxy 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, an isobutyl group, or a 3,4,5-trifluorophenoxy group, b is 2 to 40, and c is 1 to 40.

  The above aluminoxane can be made by various methods. There is no restriction | limiting in particular about the method, What is necessary is just to make according to a well-known method. For example, a solution obtained by dissolving a trialkylaluminum (for example, trimethylaluminum) in an appropriate organic solvent (benzene, aliphatic hydrocarbyl, etc.) is made to contact with water. In addition, a method of making a trialkylaluminum (for example, trimethylaluminum) by contacting with a metal salt containing water of crystallization (for example, copper sulfate hydrate), and an electron withdrawing compound thus obtained Examples thereof include a method in which an alcohol containing a functional group and a phenol containing an electron withdrawing group are brought into contact with each other.

In the compounds (B1) to (B3), Q ¹ , Q ² , Q ³ , Q ⁴ , Q ⁵ , Q ⁶ , Q ⁷ , Q ⁸ , Q ⁹ , Q ¹⁰ and Q ¹¹ are preferably halogen atoms or A hydrocarbyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom. Examples of the inorganic cation for T ⁺ include a ferrocenium cation, an alkyl-substituted ferrocenium cation, and a silver cation. Examples of the organic cation include a triphenylmethyl cation. ^{(BQ 4 Q 5 Q 6 Q} 7) - and ^{(BQ 8 Q 9 Q 10 Q} 11) - as, 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 (2,3,4-trifluorophenyl) borate, phenyltris (penta Fluorophenyl) borate, tetrakis (3,5-bistrifluoromethylphenyl) borate and the like. Examples of (L—H) ⁺ that is a Bronsted acid include trialkyl-substituted ammonium, N, N-dialkylanilinium, dialkylammonium, triarylphosphonium, and the like.

Examples of the boron compound (B1) represented by the general 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. Can be mentioned.

Examples of the borate compound (B2) represented by the general formula T ⁺ (BQ ⁴ Q ⁵ Q ⁶ Q ⁷ ) ⁻ include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1′-bis-trimethylsilylferrocete. Examples thereof include nium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, triphenylmethyltetrakis (pentafluorophenyl) borate, and triphenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate.

Examples of the borate compound (B3) represented by the general formula (LH) ⁺ (BQ ⁸ Q ⁹ Q ¹⁰ Q ¹¹ ) ⁻ include triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluoro). Phenyl) borate, tri (normal butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (normal butyl) ammonium tetrakis (3,5-bistrifluoromethylphenyl) borate, N, N-bis-trimethylsilylanilinium tetrakis (pentafluoro) Phenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-2, , 6-Pentamethylanilinium tetrakis (pentafluorophenyl) borate, N, N-bis-trimethylsilylanilinium tetrakis (3,5-bistrifluoromethylphenyl) borate, diisopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (Pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, tri (bis-trimethylsilylphenyl) phosphonium tetrakis (pentafluorophenyl) borate It is done.

In the compounds (C1) to (C2), Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ and Y ⁸ are preferably substituted with a halogen atom or a halogen atom. A hydrocarbyl group having 1 to 100 carbon atoms, wherein at least one of Y ¹ , Y ² , Y ³ and Y ⁴ and at least one of Y ⁵ , Y ⁶ , Y ⁷ and Y ⁸ are each represented by the general formula: (U—H) (wherein U represents O, S, NR or PR, and R represents a hydrocarbyl group, a trihydrocarbylsilyl group, a trihydrocarbylgermyl group or hydrogen). Have T ⁺ represents an inorganic or organic cation, and (L—H) ⁺ represents a Bronsted acid. ). Examples of the inorganic cation for T ⁺ include a ferrocenium cation, an alkyl-substituted ferrocenium cation, and a silver cation. Examples of the organic cation include a triphenylmethyl cation. ^{(BY 1 Y 2 Y 3 Y} 4) - and ^{(BY 5 Y 6 Y 7 Y} 8) - as, for example,
Triphenyl (hydroxyphenyl) borate, diphenyl-di (hydroxyphenyl) borate, triphenyl (2,4-dihydroxyphenyl) borate, tri (p-tolyl) (hydroxyphenyl) borate, tris (pentafluorophenyl) (hydroxyphenyl) ) Borate, tris (2,4-dimethylphenyl) (hydroxyphenyl) borate, tris (3,5-dimethylphenyl) (hydroxyphenyl) borate, tris (3,5-di-trifluoromethyl-phenyl) (hydroxyphenyl) ) Borate, Tris (pentafluorophenyl) (2-hydroxyethyl) borate, Tris (pentafluorophenyl) (4-hydroxybutyl) borate, Tris (pentafluorophenyl) (4-hydroxycyclohexyl) Examples include borate, tris (pentafluorophenyl) (4- (4′-hydroxyphenyl) phenyl) borate, tris (pentafluorophenyl) (6-hydroxy-2-naphthyl) borate, and preferably tris (pentafluoro Phenyl) (4-hydroxyphenyl) borate. Other preferred anions are borates as described above in which the hydroxy function is replaced by an amino NHR function. However, R is preferably methyl, ethyl or t-butyl.
Examples of (L—H) ⁺ that is a Bronsted acid include trialkyl-substituted ammonium, N, N-dialkylanilinium, dialkylammonium, triarylphosphonium, and the like.

Examples of the borate compound (C1) represented by the general formula T ⁺ (BY ¹ Y ² Y ³ Y ⁴ ) ⁻ include ferrocenium tris (pentafluorophenyl) (4-hydroxyphenyl) borate, silver tris (penta Fluorophenyl) (4-hydroxyphenyl) borate, triphenylmethyltris (pentafluorophenyl) (4-hydroxyphenyl) borate, and the like.

Examples of the borate compound (C2) represented by the general formula (L-H) ⁺ (BY ⁵ Y ⁶ Y ⁷ Y ⁸ ) ⁻ include triethylammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate, tri Propyl ammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate, tri (normal butyl) ammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate, N, N-diethylanilinium tris (pentafluorophenyl) ( 4-hydroxyphenyl) borate, N, N-2,4,6-pentamethylanilinium tris (pentafluorophenyl) (4-hydroxyphenyl) borate, diisopropylammonium tris (pentafluorophenyl) (4-hydroxy Enyl) borate, dicyclohexylammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate, triphenylphosphonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate, tri (methylphenyl) phosphonium tris (pentafluorophenyl) ( 4-hydroxyphenyl) borate, and the like.

Compound (C) can be synthesized in accordance with the method described in JP-T-11-503113.

(Carrier)
As the carrier, a porous material is preferably used, an inorganic material or an organic polymer is more preferably used, and an inorganic material is more preferably used.
Examples of inorganic substances used for the carrier include inorganic oxides, magnesium compounds, and the like, and clays, clay minerals, zeolites, and the like can also be used. These may be mixed and used.

Specific examples of the inorganic oxide used for the support include SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO _{2 and the} like, and mixtures thereof, for example may be exemplified _SiO 2 _-MgO, etc. _{SiO 2 -Al 2 O 3, SiO} 2 -TiO 2, SiO 2 -V 2 O 5, SiO 2 -Cr 2 O 3, SiO 2 -TiO 2 -MgO . Among these inorganic oxides, SiO ₂ and Al ₂ O ₃ are preferable, and SiO ₂ is more preferable. The inorganic oxide includes a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ) _2. , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O and other carbonates, sulfates, nitrates, and oxide components may be contained.

  Inorganic oxides usually have hydroxyl groups on the surface, but as inorganic oxides, modified inorganic oxides in which active hydrogens on the surface hydroxyl groups are substituted with various substituents may be used. As the substituent, the substituent is preferably a silyl group. Specific examples of the modified inorganic oxide include trialkylchlorosilanes such as trimethylchlorosilane and tert-butyldimethylchlorosilane, triarylchlorosilanes such as triphenylchlorosilane, dialkyldichlorosilanes such as dimethyldichlorosilane, and diaryldisilanes such as diphenyldichlorosilane. Dialkyldialkoxy such as chlorosilane, alkyltrichlorosilane such as methyltrichlorosilane, aryltrichlorosilane such as phenyltrichlorosilane, trialkylalkoxysilane such as trimethylmethoxysilane, triarylalkoxysilane such as triphenylmethoxysilane, and dimethyldimethoxysilane Diaryl dialkoxysilanes such as silane, diphenyldimethoxysilane, and alkyltria such as methyltrimethoxysilane Contact treatment with aryltrialkoxysilane such as coxisilane, phenyltrimethoxysilane, tetraalkoxysilane such as tetramethoxysilane, alkyldisilazane such as 1,1,1,3,3,3-hexamethyldisilazane, tetrachlorosilane, etc. Inorganic oxides.

  Magnesium compounds used as carriers include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, magnesium fluoride; methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, octoxy magnesium chloride, etc. An alkoxy magnesium halide such as phenoxy magnesium chloride and methylphenoxy magnesium chloride; an alkoxy magnesium halide such as ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium and 2-ethylhexoxy magnesium; phenoxy magnesium; Allyloxymagnesium such as dimethylphenoxymagnesium Magnesium laurate, and the like can be exemplified carboxylates of magnesium such as magnesium stearate. Among these, magnesium halide or alkoxymagnesium is preferable, and magnesium chloride or butoxymagnesium is more preferable.

  Examples of the clay or clay mineral used for the carrier include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysingelite, bayophilite, talc, ummo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, Examples include naclite, dickite and halloysite. Among these, smectite, montmorillonite, hectorite, laponite or saponite is preferable, and montmorillonite or hectorite is more preferable.

As the zeolite used for the carrier, CFI, AFI, MAZ, AET, DON, FAU, CLO, VFI, ABW, ACO, AEI, AEL, AEN, AFG, AFN, AFO, AFR, AFS, AFT, AFX, Afy, Examples include AHT, ANA, APC, APD, AST, ASV, ATN, ATO, ATS, ATT, ATV, AWO, and AWW type zeolite.

  As the inorganic substance used for the carrier, an inorganic oxide is preferable.

  As these inorganic substances used for the carrier, those dried by heat treatment are preferably used. The temperature of the heat treatment is usually 100 to 1500 ° C, preferably 100 to 1000 ° C, more preferably 200 to 800 ° C. The time for the heat treatment is not particularly limited, but is preferably 10 minutes to 50 hours, more preferably 1 hour to 30 hours. As the heat treatment method, after heating an inorganic substance, for example, a dried inert gas (for example, nitrogen or argon) is circulated at a constant flow rate for several hours or more, or the pressure is reduced for several hours. Examples of the method include, but are not limited to.

The average particle size of the carrier made of an inorganic substance is preferably 5 to 1000 μm, more preferably 10 to 500 μm, and still more preferably 10 to 100 μm. The pore volume of the carrier made of an inorganic substance is preferably 0.1 ml / g or more, more preferably 0.3 to 10 ml / g. The specific surface area of the support made of an inorganic material is preferably 10 to 1000 m ² / g, more preferably 100 to 500 m ² / g.

  There is no restriction | limiting in particular as an organic polymer used for a support | carrier, You may use 2 or more types of organic polymers as a mixture. Polymers having a group having active hydrogen and / or a non-proton donating Lewis basic group are preferred.

  The group having active hydrogen is not particularly limited as long as it has active hydrogen. Specific examples include primary amino group, secondary amino group, imino group, amide group, hydrazide group, amidino group, hydroxy group, Examples include hydroperoxy group, carboxyl group, formyl group, carbamoyl group, sulfonic acid group, sulfinic acid group, sulfenic acid group, thiol group, thioformyl group, pyrrolyl group, imidazolyl group, piperidyl group, indazolyl group, carbazolyl group and the like. A primary amino group, secondary amino group, imino group, amide group, imide group, hydroxy group, formyl group, carboxyl group, sulfonic acid group or thiol group is preferred. Particularly preferred are a primary amino group, a secondary amino group, an amide group or a hydroxy group. These groups may be substituted with a halogen atom or a hydrocarbyl group having 1 to 20 carbon atoms.

  The non-proton-donating Lewis basic group is not particularly limited as long as it has a Lewis base portion having no active hydrogen atom, and specific examples include pyridyl group, N-substituted imidazolyl group, and N-substituted indazolyl group. , Nitrile group, azide group, N-substituted imino group, N, N-substituted amino group, N, N-substituted aminooxy group, N, N, N-substituted hydrazino group, nitroso group, nitro group, nitrooxy group, furyl Group, carbonyl group, thiocarbonyl group, alkoxy group, alkyloxycarbonyl group, N, N-substituted carbamoyl group, thioalkoxy group, substituted sulfinyl group, substituted sulfonyl group, substituted sulfonic acid group and the like. Preferred is a heterocyclic group, more preferred is an aromatic heterocyclic group having an oxygen atom and / or a nitrogen atom in the ring, and particularly preferred is a pyridyl group, an N-substituted imidazolyl group or an N-substituted indazolyl. Group, most preferably a pyridyl group. These groups may be substituted with a halogen atom or a hydrocarbyl group having 1 to 20 carbon atoms.

  As the amount of the group having such active hydrogen and the non-proton-donating Lewis basic group in the polymer, the molar amount of the group per gram of polymer unit is preferably 0.01 to 50 mmol / g, More preferably, it is 0.1-20 mmol / g.

  A polymer having such a group is obtained by, for example, homopolymerizing a monomer having a group having active hydrogen and / or a non-proton-donating Lewis basic group and one or more polymerizable unsaturated groups, or the like. And other monomers having one or more polymerizable unsaturated groups. Moreover, it is preferable to use a crosslinkable polymerizable monomer having two or more polymerizable unsaturated groups as at least one of the other monomers.

  Examples of the monomer having a group having active hydrogen and / or a non-proton-donating Lewis basic group and one or more polymerizable unsaturated groups include the group having active hydrogen and one or more polymerizable groups. Examples thereof include a monomer having a saturated group, and a monomer having a Lewis base part having no active hydrogen atom and one or more polymerizable unsaturated groups. Examples of such polymerizable unsaturated groups include alkenyl groups such as vinyl groups and allyl groups; alkynyl groups such as ethyne groups.

  Examples of monomers having groups having active hydrogen and one or more polymerizable unsaturated groups include vinyl group-containing primary amines, vinyl group-containing secondary amines, vinyl group-containing amide compounds, vinyl group-containing hydroxy compounds, etc. Can be mentioned. Specific examples include N- (1-ethenyl) amine, N- (2-propenyl) amine, N- (1-ethenyl) -N-methylamine, N- (2-propenyl) -N-methylamine, 1 -Ethenylamide, 2-propenylamide, N-methyl- (1-ethenyl) amide, N-methyl- (2-propenyl) amide, vinyl alcohol, 2-propen-1-ol, 3-buten-1-ol, etc. Can be mentioned.

  Specific examples of the monomer having a non-proton-donating Lewis basic group and one or more polymerizable unsaturated groups include vinylpyridine, vinyl (N-substituted) imidazole, vinyl (N-substituted) indazole and the like. be able to.

  Examples of other monomers having one or more polymerizable unsaturated groups include olefins and aromatic vinyl compounds. Specific examples include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1- Examples include pentene and styrene. Preferred is ethylene or styrene. Two or more of these monomers may be used. Specific examples of the crosslinkable monomer having two or more polymerizable unsaturated groups include divinylbenzene.

The average particle size of the support made of an organic polymer is preferably 5 to 1000 μm, more preferably 10 to 500 μm. The pore volume of the support made of an organic polymer is preferably 0.1 ml / g or more, more preferably 0.3 to 10 ml / g. The specific surface area of the support made of an organic polymer is preferably 10 to 1000 m ² / g, more preferably 50 to 500 m ² / g.

  As these organic polymers used for the carrier, those dried by heat treatment are preferably used. The temperature of the heat treatment is usually 30 to 400 ° C, preferably 50 to 200 ° C, and more preferably 70 to 150 ° C. The time for the heat treatment is not particularly limited, but is preferably 10 minutes to 50 hours, more preferably 1 hour to 30 hours. As the heat treatment method, the organic polymer is heated and then, for example, a dried inert gas (for example, nitrogen or argon) is circulated at a constant flow rate for several hours or more, or the pressure is reduced for several hours. Examples of the method include, but are not limited to.

  The volume-based geometric standard deviation of the particle size of the carrier is preferably 2.5 or less, more preferably 2.0 or less, and even more preferably 1.7 or less.

The carrier, inorganic materials are preferred, the inorganic oxide is preferable, and SiO ₂ is most preferable.

(Catalyst for olefin oligomerization)
The catalyst for olefin oligomerization of the present invention is an activation containing a carrier, a transition metal complex represented by any one of the general formulas (1-1) to (1-3), and an element belonging to Group 13 of the periodic table. The catalyst is obtained by contacting a cocatalyst component, and is a catalyst capable of producing an α-olefin from an olefin by oligomerization, preferably 1-hexene can be selectively produced from ethylene.

In the present invention, the catalyst for olefin oligomerization in which a transition metal complex and an activation promoter component are supported on a carrier is contacted with the carrier, transition metal complex, and activation promoter component in a solvent, followed by filtration. It refers to a catalyst obtained as a solid state by removing the solvent by performing an appropriate treatment such as decantation or distillation under reduced pressure of the solvent.

  In order to suppress adhesion of by-product polymers to the walls of the reactor and the stirrer, it is preferable to use an olefin oligomerization catalyst in which a transition metal complex and an activation promoter component are supported on a carrier. Furthermore, in order to increase the catalytic activity of 1-hexene synthesis, the solid component having an activation promoter component supported on a support and a transition metal complex are brought into contact with each other in a solvent, and then the solvent is removed. It is more preferable to use a supported catalyst for olefin oligomerization.

  Hereinafter, the case where the activation promoter component (A) and / or the activation promoter component (B) is used as the activation promoter component will be described.

The catalyst for olefin oligomerization of the present invention comprises a carrier, a transition metal complex represented by any one of the general formulas (1-1) to (1-3), an activation promoter component (A) and / or a compound ( Although it can be obtained by bringing B) into contact, the contacting method is not particularly limited. At this time, a plurality of components (A1) to (A3) may be used as the activation promoter component (A).
For example, the following contact methods can be mentioned, and method 2 is preferable.
Method 1: Method of contacting a carrier with a contact product obtained by contacting a transition metal complex and an activation promoter component (A) and / or (B) Method 2: Activation promoter component (A) and / or A method of contacting the transition metal complex with the contact product obtained by contacting (B) with the support. Method 3: activating promoter component (A) and / or the contact product obtained by contacting the transition metal complex with the support. Method 4 for contacting (B): Method for contacting three components at the same time Further, some or all of these contacts may be carried out in the reactor, and the charging sequence is not particularly limited. Absent.

  It is preferable to contact the support, the transition metal complex, and the activation promoter component in a solvent. Examples of the solvent include aliphatic hydrocarbyl such as butane, pentane, hexane, heptane, and octane, aromatic hydrocarbyl such as benzene and toluene, and halogenated hydrocarbyl such as methylene dichloride. 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 carrier.

  The temperature at which the support, the transition metal complex, and the activation promoter component are contacted is usually from −30 ° C. to the boiling point of the solvent, preferably from −10 ° C. to 120 ° C. The reaction time is not particularly limited.

  When the support, the transition metal complex, and the activation promoter component (A) are contacted, the ratio of each component is 0.01 to 20 parts by weight of the transition metal complex, the activation promoter component ( A) 10 to 300 parts by weight, preferably 0.05 to 10 parts by weight of the transition metal complex and 20 to 200 parts by weight of the activation promoter component (A) per 100 parts by weight of the support.

  When the support, the transition metal complex, and the activation promoter component (B) are contacted, the ratio of each component is 0.01 to 20 parts by weight of the transition metal complex and 100% by weight of the activation assistant. The catalyst component (B) is 0.1 to 60 parts by weight, preferably 0.05 to 10 parts by weight of the transition metal complex, and the activation promoter component (B) is 0.2 to 30 parts by weight.

Next, the case where the activation promoter component (C) is used as the activation promoter component will be described.
The olefin oligomerization catalyst is obtained by bringing the carrier, the transition metal complex, and the activation promoter component (C) into contact with each other, and a method in which the activation promoter component (A) is further used is preferable. This contact method is not particularly limited. At this time, a plurality of components (A1) to (A3) may be used as the activation promoter component (A). The support, the transition metal complex, the activation promoter component (C) and the activation promoter component (A) may be contacted at the same time, any two of them may be pre-contacted, and then the remaining The two components may be contacted in any order or pre-contact and then any three of them may be pre-contacted and then another component contacted; Each of them may be contacted in any order.
For example, the following contact methods are mentioned.
Method 5: Method of bringing the activation promoter component (C) into contact with the contact product obtained by bringing the activation promoter component (A) and the carrier into contact with each other, and further contacting the transition metal complex. Method 7: Contacting the support and the activation promoter component (A) with the support in contact with (A) and the activation promoter component (C) Method 8: Contacting the transition metal complex with the contacted material and further contacting the activation promoter component (C) Method 8: Activation of the contact material with the contact between the support and the activation promoter component (A) A method of contacting the transition metal complex after contacting the promoter component (C), preferably method 6, method 7 and method 8, more preferably method 6 and method 8.
Moreover, you may perform some or all of these contacts in a reactor, and the order of injection in that case is not specifically limited.

  It is preferable to contact the support, the transition metal complex, the activation promoter component (A), and the activation promoter component (C) in a solvent. Examples of the solvent include aliphatic hydrocarbyl such as butane, pentane, hexane, heptane, and octane, aromatic hydrocarbyl such as benzene and toluene, and halogenated hydrocarbyl such as methylene dichloride. 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 carrier.

  The temperature at which the support, transition metal complex, activation promoter component (A), and activation promoter component (C) are contacted is usually from −30 ° C. to the boiling point of the solvent, preferably from −10 ° C. to 120 ° C. The reaction time is not particularly limited.

  When the support, the transition metal complex, the activation promoter component (A), and the activation promoter component (C) are contacted, the ratio of each component is 100 parts by weight of the support, and the transition metal complex is 0.01-20. Parts by weight, 10 to 300 parts by weight of activation promoter component (A), 1 to 30 parts by weight of activation promoter component (C), preferably 0.05 to 10 parts by weight of a transition metal complex, A) 20 to 200 parts by weight, activation promoter component (C) 2 to 15 parts by weight.

<Method for producing α-olefin>
The α-olefin production method of the present invention is a method of producing a 2 to 10 mer by oligomerization of an olefin in the presence of an olefin oligomerization catalyst, preferably a 3 to 4 mer is produced from ethylene. Most preferred is a method of trimerizing ethylene to produce 1-hexene.

  The oligomerization reaction of ethylene is not particularly limited. For example, aliphatic hydrocarbyl such as butane, pentane, hexane, heptane and octane, aromatic hydrocarbyl such as benzene and toluene, or methylene dichloride, An oligomerization reaction using a halogenated hydrocarbyl such as chlorobenzene as a solvent, an oligomerization reaction in a slurry state, an oligomerization reaction in gaseous ethylene, or the like is possible.

  The oligomerization reaction of ethylene can be carried out in any of batch, semi-continuous and continuous methods.

  The pressure of ethylene is usually from normal pressure to 10 MPa, preferably from normal pressure to 5 MPa.

  The temperature of the ethylene oligomerization reaction can usually range from -50 ° C to 220 ° C. Preferably it is the range of 0 degreeC-170 degreeC, More preferably, it is the range of 50 degreeC-120 degreeC.

  The time for the ethylene oligomerization reaction is generally appropriately determined depending on the intended reaction apparatus, and is usually 1 minute to 20 hours.

  When the oligomerization reaction is carried out in a solvent, the concentration of the transition metal complex used as the catalyst component is usually 0.0001 to 5 mmol / liter, preferably 0.001 to 1 mmol / liter. The concentration of the activation promoter component (A) is usually 0.01 to 500 mmol / liter, preferably 0.1 to 100 mmol / liter, in terms of aluminum atoms. The concentration of the activation promoter component (B) is usually 0.0001 to 5 mmol / liter, and preferably 0.001 to 1 mmol / liter. The concentration of the activation promoter component (C) is usually 0.0001 to 5 mmol / liter, and preferably 0.001 to 1 mmol / liter.

<Olefin polymerization catalyst component>
By using the oligomerization catalyst of the present invention in combination with an olefin polymerization catalyst component, a branched olefin polymer can be produced. The catalyst component for olefin polymerization may be anything as long as it does not poison the catalyst for oligomerization, and many polymerization catalyst components can be used. For example, Ziegler-Natta type solid catalyst components, metallocene complexes, and the like can be mentioned. Among metallocene complexes, a metallocene complex having one cyclopentadiene ring and a geometrically constrained structure, and a metallocene having two cyclopentadiene rings And a metallocene complex having three cyclopentadiene rings. A metallocene complex having one cyclopentadiene ring and a geometrically constrained structure or a metallocene complex having two cyclopentadiene rings, which have a high α-olefin copolymerization property, can be mentioned as preferred polymer complexes. More preferable examples of the polymerization complex include a metallocene complex having one cyclopentadiene ring and a geometrically constrained structure and a metallocene complex in which two cyclopentadiene rings are bridged.
In addition, olefin polymerization is changing an olefin into a polymer, The molecular weight of the said polymer is larger than the molecular weight of an oligomer, and is generally 10,000 or more.

Specific examples of the polymerization catalyst component include, for example, methylene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3,5-dimethyl- 2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadiene) Enyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene ( ert-Butylamide) (cyclopentadienyl) titanium dichloride, diphenylmethylene (tert-butylamide) (cyclopentadienyl) titanium dichloride, dimethylsilylene (tert-butylamide) (cyclopentadienyl) titanium dichloride, diphenylmethylene (cyclopenta Dienyl) (fluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, methylenebis (cyclopentadienyl) zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, methylenebis (indenyl) hafnium dichloride, bis ( Cyclopentadienyl) zirconium dichloride, bis (indenyl) zirconi And methylene chloride, bis (fluorenyl) zirconium dichloride, and the like. Preferred are methylene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3 , 5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene ( Tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl-5-methyl-2) -Phenoxy) titanium dichloride, methylene (tert-butylamide) (cyclopentadienyl) titanium dichloride, diphenylmethylene (tert-butylamide) (cyclopentadienyl) titanium dichloride, dimethylsilylene (tert-butylamide) (cyclopentadienyl) Titanium dichloride, diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, methylene bis (cyclopentadienyl) zirconium dichloride, ethylene bis (indenyl) zirconium dichloride, methylene bis (Indenyl) hafnium dichloride, more preferably methylene Cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene ( tert-Butylamide) (cyclopentadienyl) titanium dichloride, ethylenebis (indenyl) zirconium dichloride.

  The polymerization catalyst component can be used in combination with the activation promoter component (A) and the activation promoter component (B).

  An ethylene polymer can be produced by polymerizing ethylene in the presence of the catalyst used in combination with the catalyst component for olefin oligomerization and the catalyst component for olefin polymerization. In the polymerization, polymerization may be performed by supplying only ethylene as a raw material monomer, or polymerization may be performed by supplying a monomer copolymerizable with ethylene and ethylene.

Hereinafter, the present invention will be described by reference examples, examples and comparative 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 times 16 times or more Repeat time: ACQTM 6 seconds, PD 1 second Internal standard: CDCl ₃ (7.26 ppm)

(2) Carbon nuclear magnetic resonance spectrum ( ¹³ C-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 256 times or more Repeat time: ACQTM 1.79 seconds, PD 1.21 seconds Internal standard: CDCl ₃ (77.0 ppm)

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

[Reference Example 1]
“Synthesis of [1-tris (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride (hereinafter referred to as“ complex 1 ”)”

“Synthesis of 1-tris (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene”
Under a nitrogen atmosphere, sodium hydride (0.49 g, 20.45 mmol as sodium hydride) dispersed in mineral oil and tetrahydrofuran (23 mL) were added. The mixture was warmed to 50 ° C., aniline (0.13 g, 1.36 mmol) was added, and the mixture was stirred at 50 ° C. for 1 hour. A solution prepared by dissolving 1,2,3,4-tetramethylcyclopenta-1,3-diene (1.83 g, 15.00 mmol) in tetrahydrofuran (6 mL) was added dropwise thereto, and the mixture was stirred at 50 ° C. for 3 hours and a half. did. The solution was cooled to 0 ° C., and a solution of chlorotris (3,5-dimethylphenyl) silane (5.17 g, 13.64 mmol) dissolved in toluene (6 mL) was added dropwise to the solution, followed by stirring at room temperature for 3 hours. Then, it stirred at 50 degreeC for 22 hours. The resulting mixture was added dropwise at 0 ° C. to a 10% aqueous sodium carbonate solution (40 mL). Toluene (50 mL) was added for liquid separation, and the oil phase was washed twice with water (50 mL), and further with saturated brine (50 mL). The oil phase was dried over sodium sulfate, filtered and the solvent was concentrated under reduced pressure. After purification by silica gel column chromatography, 50 ° C. hexane was added to the obtained solid and filtered to remove insoluble matters, and the solvent was concentrated from the filtrate under reduced pressure. The obtained solid was washed with a small amount of hexane and then dried under reduced pressure to obtain 1-tris (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene (1. 49 g, yield 23.4%).
¹ H-NMR (CDCl ₃ , δ ppm): 1.54 (s, 6H), 1.60 (s, 6H), 2.27 (s, 18H), 3.73 (s, 1H), 6.98 (S, 3H), 7.17 (s, 6H)
Mass spectrum (EI-MS, m / z): 464 (M ⁺ )

“Synthesis of Complex 1”
Under a nitrogen atmosphere, 1-tris (3,5-dimethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadiene (0.93 g, 2.00 mmol), triethylamine (1.01 g, 10.00 mmol) To a toluene solution (20 mL) was added dropwise a 1.67 M hexane solution (1.32 mL, 2.20 mmol) of n-butyllithium at −78 ° C., and the mixture was gradually warmed to room temperature and then stirred at room temperature for 5 hours. . The obtained mixture was cooled to −78 ° C., and a solution of titanium tetrachloride (0.42 g, 2.20 mmol) in toluene (2 mL) was added dropwise at the same temperature. The mixture was gradually warmed to room temperature and stirred at room temperature overnight. After the reaction, the solvent was concentrated under reduced pressure, heptane was added to the residue and filtered to remove insoluble matters, and the solvent was concentrated from the filtrate under reduced pressure. Furthermore, diethyl ether was added to the obtained residue and filtered to remove insoluble matters, and the solvent was concentrated from the filtrate under reduced pressure. After adding pentane and cooling to −20 ° C., the obtained solid was filtered, washed with a small amount of pentane, and then dried under reduced pressure to obtain Complex 1 (0.03 g, yield 2.7%) as an orange solid. Got as.
¹ H-NMR (CDCl ₃ , δ ppm): 2.03 (s, 6H), 2.27 (s, 18H), 2.36 (s, 6H), 7.06 (s, 3H), 7.20 (S, 6H)
¹³ C-NMR (CDCl ₃ , δ ppm): 14.52, 17.83, 21.41, 131.63, 132.93, 134.60, 137.03, 142.26, 146.34
Mass spectrum (EI-MS, m / z): 616 (M ⁺ )

<Production of 1-hexene>
(1) The analysis was performed using 1-hexene active gas chromatography (Shimadzu GC-2010, DB-1 column).
(2) Evaluation of the fouling state The evaluation of the fouling state was judged from the amount of unfixed solid adhering to the stirring blade after opening the autoclave after the reaction. Amorphous solid adhered to the entire surface of the stirring blade (×), Amorphous solid adhered to a part (more than half) of the stirring blade (△), Amorphous to a part of the stirring blade (less than half) It was judged by dividing into the state where the solid was attached (◯) and the state where the amorphous blade was hardly attached to the stirring blade (◎). The results are shown in Table 1.

[Reference Example (SiO ₂ / MAO Preparation Example)]
Under a nitrogen atmosphere, 1 g of dried silica (Sypolol 948 manufactured by Devison; 50% volume average particle size = 55 μm; pore volume = 1.67 ml / g; specific surface area = 325 m 2 / g) was weighed into a 200 mL flask, and dehydrated into this. Toluene 15 mL was added. After cooling to 0 ° C. with an ice bath, 5.0 mL (17.5 mmol) of 3.5 mol / L MAO (manufactured by Tosoh Corporation) diluted with toluene was slowly added over 30 minutes using a dropping funnel. After dropping, the temperature was raised to 95 ° C. and stirred for 4 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and the supernatant was removed by decantation. Further, 15 mL of toluene was added thereto and stirred, and then allowed to stand to remove the supernatant again by decantation. This washing operation was performed three times, and finally, the target solid (sometimes referred to as SiO ₂ / MAO) was obtained by drying under reduced pressure at 100 ° C. for 1 hour. The yield was 1.2 g. As a result of elemental analysis (% by weight), Si was 24% and Al was 19%.

[Example 1]
After drying under reduced pressure, 90 mL of toluene and 2.2 mL of hexane solution of triisobutylaluminum (TIBA) having a concentration of 0.93 mmol / mL were charged into a 0.4 liter autoclave equipped with nitrogen and purged with nitrogen. After raising the temperature to 80 ° C., ethylene was introduced to 2.0 MPa to stabilize the system. To this, 1.0 mL of a toluene solution of Complex 1 (1 μmol / mL) was added, and subsequently 95.3 mg of SiO ₂ / MAO obtained in Reference Example was added. During the reaction, while continuously supplying ethylene gas so as to keep the total pressure constant, the reaction was performed at 80 ° C. for 30 minutes, and 2.0 mL of ethanol was added to stop the reaction. Thereafter, ethylene was purged, and the contents in the autoclave were deashed with ethanol-hydrochloric acid and filtered. 1-hexene was obtained with an activity of 1.8 × 10 ⁶ g / mol complex / h, and a polymer was obtained with an activity of 0.21 × 10 ⁶ g / mol complex / h.

[Example 2]
Under a nitrogen atmosphere, 5 mL of toluene was added to the flask, 2.5 μmol of Complex 1 and 247 mg of SiO ₂ / MAO obtained in Reference Example were added, and the mixture was stirred for 5 minutes. The solvent toluene was distilled off under reduced pressure to obtain a supported catalyst for olefin oligomerization.
After drying under reduced pressure, 90 mL of toluene and 2.2 mL of hexane solution of triisobutylaluminum (TIBA) having a concentration of 0.93 mmol / mL were charged into a 0.4 liter autoclave equipped with nitrogen and purged with nitrogen. After raising the temperature to 80 ° C., ethylene was introduced to 2.0 MPa to stabilize the system. To this, 152 mg of the supported catalyst for olefin oligomerization obtained above was charged. During the reaction, while continuously supplying ethylene gas so as to keep the total pressure constant, the reaction was performed at 80 ° C. for 30 minutes, and 2.0 mL of ethanol was added to stop the reaction. Thereafter, ethylene was purged, and the contents in the autoclave were deashed with ethanol-hydrochloric acid and filtered. 1-hexene was obtained with an activity of 2.01 × 10 ⁶ g / mol complex / h, and a polymer was obtained with an activity of 0.34 × 10 ⁶ g / mol complex / h.

[Example 3]
Under a nitrogen atmosphere, 5 mL of toluene was added to the flask, and [1-tris (3,5-diethylphenyl) silyl-2,3,4,5-tetramethylcyclopentadienyl] titanium trichloride (hereinafter referred to as “complex 2”). 2 μmol and 183 mg of SiO ₂ / MAO obtained in Reference Example were added and stirred for 5 minutes. The solvent toluene was distilled off under reduced pressure to obtain a supported catalyst for olefin oligomerization.
After drying under reduced pressure, 90 mL of toluene and 2.2 mL of hexane solution of triisobutylaluminum (TIBA) having a concentration of 0.93 mmol / mL were charged into a 0.4 liter autoclave equipped with nitrogen and purged with nitrogen. After raising the temperature to 80 ° C., ethylene was introduced to 2.0 MPa to stabilize the system. To this, 120 mg of the supported catalyst for olefin oligomerization obtained above was charged. During the reaction, while continuously supplying ethylene gas so as to keep the total pressure constant, the reaction was performed at 80 ° C. for 30 minutes, and 2.0 mL of ethanol was added to stop the reaction. Thereafter, ethylene was purged, and the contents in the autoclave were deashed with ethanol-hydrochloric acid and filtered. 1-hexene was obtained with an activity of 2.02 × 10 ⁶ g / mol complex / h, and a polymer was obtained with an activity of 0.48 × 10 ⁶ g / mol complex / h.

[Example 4]
Under a nitrogen atmosphere, 5 mL of toluene was added to the flask, 0.2 μmol of Complex 2 and 210 mg of SiO ₂ / MAO obtained in Reference Example were added, and the mixture was stirred for 5 minutes. The solvent toluene was distilled off under reduced pressure to obtain a supported catalyst for olefin oligomerization.
After drying under reduced pressure, 90 mL of toluene and 2.2 mL of a hexane solution of triisobutylaluminum (TIBA) having a concentration of 0.93 mmol / mL were charged into a 0.4 liter autoclave substituted with nitrogen and the temperature inside the system. After raising the temperature to 40 ° C., ethylene was introduced to 2.0 MPa to stabilize the system. To this, 132 mg of the supported catalyst for olefin oligomerization obtained above was charged. During the reaction, while continuously supplying ethylene gas so as to keep the total pressure constant, the reaction was carried out at 40 ° C. for 60 minutes, and 2.0 mL of ethanol was added to stop the reaction. Thereafter, ethylene was purged, and the contents in the autoclave were deashed with ethanol-hydrochloric acid and filtered. 1-hexene was obtained with an activity of 27.9 × 10 ⁶ g / mol complex / h, and a polymer was obtained with an activity of 2.46 × 10 ⁶ g / mol complex / h.

[Example 5]
Under a nitrogen atmosphere, 5 mL of toluene was added to the flask, 0.2 μmol of Complex 1 and 194 mg of SiO ₂ / MAO obtained in Reference Example were added, and the mixture was stirred for 5 minutes. The solvent toluene was distilled off under reduced pressure to obtain a supported catalyst for olefin oligomerization.
After drying under reduced pressure, 90 mL of toluene and 2.2 mL of a hexane solution of triisobutylaluminum (TIBA) having a concentration of 0.93 mmol / mL were charged into a 0.4 liter autoclave substituted with nitrogen and the temperature inside the system. After raising the temperature to 40 ° C., ethylene was introduced to 2.0 MPa to stabilize the system. To this, 106 mg of the supported catalyst for olefin oligomerization obtained above was charged. During the reaction, while continuously supplying ethylene gas so as to keep the total pressure constant, the reaction was carried out at 40 ° C. for 60 minutes, and 2.0 mL of ethanol was added to stop the reaction. Thereafter, ethylene was purged, and the contents in the autoclave were deashed with ethanol-hydrochloric acid and filtered. 1-hexene was obtained with an activity of 38.1 × 10 ⁶ g / mol complex / h, and a polymer was obtained with an activity of 2.56 × 10 ⁶ g / mol complex / h.

[Example 6]
Under a nitrogen atmosphere, 5 mL of toluene was added to the flask, and 12 μmol of Complex 12 and 220 mg of SiO ₂ / MAO obtained in Reference Example were added and stirred for 5 minutes. The solvent toluene was distilled off under reduced pressure to obtain a supported catalyst for olefin oligomerization.
After drying under reduced pressure, 90 mL of heptane and 2.2 mL of hexane solution of triisobutylaluminum (TIBA) having a concentration of 0.93 mmol / mL were charged into a 0.4 liter autoclave purged with nitrogen, and the temperature inside the system. After raising the temperature to 80 ° C., ethylene was introduced to 2.0 MPa to stabilize the system. To this was added 123 mg of the supported catalyst for olefin oligomerization obtained above. During the reaction, while continuously supplying ethylene gas so as to keep the total pressure constant, the reaction was performed at 80 ° C. for 30 minutes, and 2.0 mL of ethanol was added to stop the reaction. Thereafter, ethylene was purged, and the contents in the autoclave were deashed with ethanol-hydrochloric acid and filtered. 1-hexene was obtained with an activity of 2.28 × 10 ⁶ g / mol complex / h, and a polymer was obtained with an activity of 1.45 × 10 ⁶ g / mol complex / h.

[Example 7]
Under a nitrogen atmosphere, 5 mL of toluene was added to the flask, and 12 μmol of Complex 12 and 220 mg of SiO ₂ / MAO obtained in Reference Example were added and stirred for 5 minutes. The solvent toluene was distilled off under reduced pressure to obtain a supported catalyst for olefin oligomerization.
50 g of dried NaCl was placed in a 5 L autoclave, and the inside of the autoclave was replaced with argon. The internal temperature was adjusted to 40 ° C., and ethylene was supplied into the autoclave so that the ethylene pressure was 2 MPa. Next, 1 mmol of triisobutylaluminum was added to the autoclave, 118 mg of the supported catalyst for olefin oligomerization obtained above was added, and gas phase polymerization was performed at 40 ° C. for 60 minutes. After the reaction, ethanol was added to the autoclave to stop the reaction, the temperature in the autoclave was cooled to room temperature, and 60 mL of toluene was further charged under pressure. After depressurization, the autoclave was opened, and the toluene solution remaining in the system was analyzed by gas chromatography. Further, a mixture of NaCl and polymer was taken out, water was added to the mixture to remove NaCl, and the obtained solid was dried by heating, and then the solid yield was measured. As a result, 1-hexene was obtained with an activity of 3.6 × 10 ⁶ g / mol complex / h, and a polymer was obtained with an activity of 0.18 × 10 ⁶ g / mol complex / h.

[Comparative Example 1]
After drying under reduced pressure, in a 0.4 liter autoclave equipped with a stirrer substituted with nitrogen, 90 mL of toluene and 0.35 mL of a toluene solution of methylaluminoxane having a Al concentration of 3.6 mmol / mL (TMAO-s manufactured by Tosoh Finechem) After the temperature in the system was raised to 80 ° C., ethylene was introduced up to 2.0 MPa to stabilize the system. To this, 0.25 mL of a toluene solution of Complex 1 (1 μmol / mL) was added. During the reaction, while continuously supplying ethylene gas so as to keep the total pressure constant, the reaction was performed at 80 ° C. for 60 minutes, and 2.0 mL of ethanol was added to stop the reaction. Thereafter, ethylene was purged, and the contents in the autoclave were deashed with ethanol-hydrochloric acid and filtered. 1-hexene was obtained with an activity of 16.9 × 10 ⁶ g / mol complex / h, and a polymer was obtained with an activity of 0.65 × 10 ⁶ g / mol complex / h.

Claims (8)

Olefin obtained by contacting a support, an activation promoter component containing an element of Group 13 of the periodic table, and a transition metal complex represented by any of the following general formulas (1-1) to (1-3) Catalyst for oligomerization.

[Wherein, M represents a transition metal atom of Group 4 of the periodic table of elements, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ^12] , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , X ¹ , X ² and X ³ are Independently
Hydrogen atom, 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 ²² ) ₃ (three R ^{22 s} each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the three R ²² is 1 to 20; A substituted silyl group represented by:
Or —N (R ²³ ) ₂ (two R ²³ each independently represents a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the two R ²³ is 2 to 20). Represents a disubstituted amino group represented by:
R ¹⁰ and R ¹¹ 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 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 ²² ) ₃ (three R ^{22 s} each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the three R ²² is 1 to 20; A substituted silyl group represented by:
Or —N (R ²³ ) ₂ (two R ²³ each independently represents a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the two R ²³ is 2 to 20). Represents a disubstituted amino group represented by:
Or, among R ¹ , R ² , R ³ and R ⁴ , two groups bonded to two adjacent carbon atoms are bonded to each other together with the two carbon atoms to which the two groups are bonded. A ring may be formed, and among R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ , two groups bonded to two adjacent carbon atoms are bonded to each other, and the two groups are bonded. Two carbon atoms may form a ring together, and two groups out of R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ that are bonded to two adjacent carbon atoms are May be bonded together to form a ring together with two carbon atoms to which the two groups are bonded, and are adjacent to each other among R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ . Two groups bonded to two carbon atoms are bonded together to form two carbon atoms to which the two groups are bonded May form a ring ^{together, R 5, R 24, R} 7, of R ²⁵ and R ^9, the two groups bonded to two carbon atoms adjacent bonded, the two It may combine with two carbon atoms to which the group is bonded to form a ring, and is bonded to two adjacent carbon atoms among R ¹² , R ²⁶ , R ¹⁴ , R ²⁷ and R ^16. Two groups may be bonded together to form a ring together with two carbon atoms to which the two groups are bonded, and R ¹⁰ and R ¹¹ are bonded and they are bonded. A ring may be formed together with a silicon atom. ] Olefin oligomer in which an activation promoter component containing a transition metal complex represented by any one of the following general formulas (1-1) to (1-3) and an element belonging to Group 13 of the periodic table is supported on a carrier Catalyst.

[Wherein, M represents a transition metal atom of Group 4 of the periodic table of elements, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ^12] , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , X ¹ , X ² and X ³ are Independently
Hydrogen atom, 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 ²² ) ₃ (three R ^{22 s} each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the three R ²² is 1 to 20; A substituted silyl group represented by:
Or —N (R ²³ ) ₂ (two R ²³ each independently represents a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the two R ²³ is 2 to 20). Represents a disubstituted amino group represented by:
R ¹⁰ and R ¹¹ 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 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 ²² ) ₃ (three R ^{22 s} each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the three R ²² is 1 to 20; A substituted silyl group represented by:
Or —N (R ²³ ) ₂ (two R ²³ each independently represents a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in the two R ²³ is 2 to 20). Represents a disubstituted amino group represented by:
Or, among R ¹ , R ² , R ³ and R ⁴ , two groups bonded to two adjacent carbon atoms are bonded to each other together with the two carbon atoms to which the two groups are bonded. A ring may be formed, and among R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ , two groups bonded to two adjacent carbon atoms are bonded to each other, and the two groups are bonded. Two carbon atoms may form a ring together, and two groups out of R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ that are bonded to two adjacent carbon atoms are May be bonded together to form a ring together with two carbon atoms to which the two groups are bonded, and are adjacent to each other among R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ . Two groups bonded to two carbon atoms are bonded together to form two carbon atoms to which the two groups are bonded May form a ring ^{together, R 5, R 24, R} 7, of R ²⁵ and R ^9, the two groups bonded to two carbon atoms adjacent bonded, the two It may combine with two carbon atoms to which the group is bonded to form a ring, and is bonded to two adjacent carbon atoms among R ¹² , R ²⁶ , R ¹⁴ , R ²⁷ and R ^16. Two groups may be bonded together to form a ring together with two carbon atoms to which the two groups are bonded, and R ¹⁰ and R ¹¹ are bonded and they are bonded. A ring may be formed together with a silicon atom. ] The catalyst for olefin oligomerization according to claim 1 or 2, wherein the activation promoter component is the following compound (A).
Compound (A): One or more aluminum compounds selected from the group consisting of the following compounds (A1), (A2) and (A3) (A1): General formula (E ¹ ) _a Al (G) _3-a organoaluminum compounds represented (A2): the general formula ^{-Al (E 2) _-O-} cyclic aluminoxane (A3) having the structure represented by _b: formula ^{E 3 {-Al (E 3)} - A linear aluminoxane having a structure represented by O—} _c Al (E ³ ) ₂ (wherein E ¹ represents a hydrocarbyl group having 1 to 8 carbon atoms, and E ² and E ³ are Each independently represents a hydrocarbyl group having 1 to 8 carbon atoms, an alkoxy group containing an electron withdrawing group or an aryloxy group containing an electron withdrawing group, G represents a hydrogen atom or a halogen atom, a Represents an integer from 1 to 3 , B represents an integer of 2 or more, when c have a plurality .E ¹ is representing an integer of 1 or more, when a plurality of E ¹ have a plurality good .G also is optionally substituted by one or more identical to each other, a plurality G may be the same as or different from each other, the plurality of E ² may be the same or different from each other, and the plurality of E ³ may be the same or different from each other.   The catalyst for olefin oligomerization according to any one of claims 1 to 3, wherein M in the general formulas (1-1) to (1-3) is a titanium atom. The catalyst for olefin oligomerization according to any one of claims 1 to 4, wherein R ¹ , R ² , R ³ and R ^{4 in the} general formulas (1-1) to (1-3) are methyl groups.   The catalyst for olefin oligomerization according to any one of claims 1 to 5, wherein the transition metal complex is represented by the general formula (1-3). R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ¹⁸ and R ²⁰ in the general formula (1-3) are each independently
The alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, or the aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent. The catalyst for olefin oligomerization as described.   The manufacturing method of the alpha olefin which oligomerizes an olefin in presence of the catalyst for olefin oligomerization in any one of Claims 1-7.