JP3506563B2 - Olefin polymerization catalyst, method for producing olefin polymer, and olefin polymer - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention is, Oh olefin polymerization catalyst, relates to a manufacturing method and an olefin polymer of an olefin polymer, more particularly, very high polymerization activity in a large molecular weight olefin (co) polymer is obtained And an olefin polymerization catalyst capable of obtaining an olefin copolymer having a high comonomer content even when the proportion of the comonomer used is small, an olefin (co) polymer having a very high polymerization activity and a large molecular weight, and The present invention relates to a method for producing an olefin polymer, which can obtain an olefin copolymer having a high comonomer content even when the proportion of the comonomer used is small, and an olefin polymer obtained by such a method.

[0002]

BACKGROUND OF THE INVENTION Conventionally, ethylene homopolymers,
As a method for producing an olefin (co) polymer such as an ethylene / α-olefin copolymer, a propylene homopolymer, and a propylene / α-olefin copolymer, a titanium-based catalyst comprising a titanium compound and an organoaluminum compound, Alternatively, a method is known in which an olefin is polymerized in the presence of a vanadium-based catalyst consisting of a vanadium compound and an organoaluminum compound.

Also known is a method of polymerizing an olefin in the presence of a metallocene catalyst comprising a transition metal compound such as zirconocene and an organoaluminumoxy compound (aluminoxane). It is known that an olefin (co) polymer having a high molecular weight distribution and a narrow compositional distribution can be obtained while being capable of polymerizing the above with high activity.

In recent years, there are various requirements for the physical properties of olefin (co) polymers, and olefin (co) polymers having various physical properties are required. Further, the appearance of a transition metal compound catalyst component capable of producing such an olefin (co) polymer is desired.

Under such circumstances, Japanese Unexamined Patent Publication No. 5-345
A transition metal compound having an indenyl group and a fluorenyl group as a ligand has been proposed as a new compound that can serve as a catalyst component for olefin polymerization in Japanese Patent No. 793. However, when an olefin is polymerized by using this transition metal compound as a catalyst component, there is a problem that only a polymer having a low activity and a small molecular weight can be obtained.

Also, in EP0707016A1, a transition metal compound having an indenyl group and a fluorenyl group is proposed, and a specific aryl group such as a phenyl group or a naphthyl group is introduced at a specific position (position 4) of the indenyl group. Such catalysts are disclosed. However,
Even if an olefin is polymerized using this transition metal compound as a catalyst component, there is a problem that a polymer having low activity and a small molecular weight is obtained.

The inventors of the present invention have conducted studies in view of such conventional techniques. As a result, a compound having a specific substituent at a specific position of an indenyl group in the transition metal compound has a very high polymerization activity and a high molecular weight. It has been found that a large olefin (co) polymer can be produced and an olefin copolymer having a high comonomer content can be obtained. Also,
By introducing a specific substituent at a specific position of a fluorenyl group of a transition metal compound having such characteristics, an olefin (co) polymer having a higher polymerization activity and a large molecular weight can be produced, and the comonomer content can be increased. It was found that an olefin copolymer having a high degree of polymerization can be obtained, and the present invention has been completed.

[0008]

SUMMARY OF THE INVENTION The present invention is greater olefin (co) polymer having a molecular weight in a very high polymerization activity is obtained, and an olefin polymerization catalyst and the catalyst such as higher olefin copolymer having comonomer content can be obtained It is an object of the present invention to provide a method for producing an olefin polymer used, and an olefin polymer obtained by such a method.

[0009]

The olefin polymerization catalyst according to the present invention comprises (A-1) a transition metal compound represented by the following general formula (I), (B ) an organoaluminum oxy compound, and / Or (B-2) reacts with the transition metal compound (A-1) to form an ion pair.
It is characterized in that it is composed of a compound to be formed and, if necessary, (C) an organoaluminum compound .

[0010]

[Chemical 3]

(Where M is titanium, zirconium or
Hafnium , R ^1's may be the same or different from each other, and have a hydrogen atom, a halogen atom, or a carbon number of 1
10 alkyl groups, and at least two adjacent groups of the groups represented by R ¹ together with the carbon atoms to which they are attached form an aromatic or aliphatic ring [wherein R 1 ^The ring formed by ¹ has a total of 4 to 20 carbon atoms including the carbon atom to which R ¹ is bound] , and R ² may be the same or different from each other,
Hydrogen atom, halogen atom, alkyl group having 1 to 10 carbon atoms, aryl group having 6 to 20 carbon atoms, alkenyl group having 2 to 10 carbon atoms, arylalkyl group having 7 to 40 carbon atoms An arylalkenyl group having 8 to 40 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group , R ¹ and R ² may be the same or different from each other, R ³ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 2 to 3 carbon atoms. An alkenyl group having 10 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, an arylalkenyl group having 8 to 40 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, a silicon-containing group, an oxygen-containing group, C-containing group, a nitrogen-containing group or a phosphorus-containing group, R ⁴ Is a methyl group, X ¹ and X
² may be the same or different from each other, a hydrogen atom,
A halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group or a nitrogen-containing group, and Y has a carbon atom number. 1-20 divalent hydrocarbon groups, 1 carbon atom
20 divalent halogenated hydrocarbon groups, divalent silicon-containing groups, divalent germanium-containing groups, divalent tin-containing groups,
-O -, - CO -, - S -, - SO -, - SO 2 -, -
NR ⁵ −, −P (R ⁵ ) −, −P (O) (R ⁵ ) −, −
BR ⁵ — or —AlR ⁵ — [wherein R ⁵ is a hydrogen atom,
A halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and a halogenated hydrocarbon group having 1 to 20 carbon atoms].

[0012]

The olefin polymerization catalyst according to the present invention includes:
An embodiment in which at least one of the above-mentioned component (A-1), component (B-1), component (B-2) and component (C) is a solid catalyst supported on a fine particle carrier, and Prepolymerization comprising a fine particle carrier, a component (A-1), a component (B-1) (or a component (B-2)) and an olefin polymer produced by the prepolymerization, and optionally a component (C). A mode that serves as a catalyst is also included.

The first method for producing an olefin polymer according to the present invention is characterized by homopolymerizing olefins or copolymerizing two or more kinds of olefins in the presence of the catalyst for olefin polymerization. .

The present invention is a homopolymerization of ethylene, a copolymerization of ethylene with an α-olefin having 3 to 20 carbon atoms,
It can be used for homopolymerization of propylene, copolymerization of propylene with an α-olefin other than propylene, and the like.

The first olefin polymer according to the present invention is
It is characterized by being manufactured by the above method. The first ethylene-based polymer and the first propylene-based polymer according to the present invention are characterized by being produced by the method as described above.

[0017]

[0018]

[0019]

[0020]

[0021]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the present invention engaging Luo olefin polymerization catalyst, specifically a method for manufacturing and olefin polymer of an olefin polymer.

In the present specification, the term "polymerization" may be used to mean not only homopolymerization but also copolymerization, and the term "polymer" means not only homopolymerization but also homopolymerization. In some cases, it is used in the sense of including a copolymer.

The novel transition metal compound according to the present invention is
It is a transition metal compound of Group 4 of the periodic table represented by the following general formula (I).

[0024]

[Chemical 5]

In the formula, M is a transition metal atom of Group 4 of the periodic table , specifically titanium, zirconium or hafnium, preferably zirconium. R
¹ may be the same as or different from each other, at least one of which is an aryl group having 11 to 20 carbon atoms, an arylalkyl group having 12 to 40 carbon atoms, and an arylalkenyl having 13 to 40 carbon atoms. A group, an alkylaryl group having 12 to 40 carbon atoms or a silicon-containing group, or at least two adjacent groups of the groups represented by R ¹ together with the carbon atoms to which they are bonded are singular or plural. Forming an aromatic ring or an aliphatic ring. In this case, the ring formed by R ¹ has 4 carbon atoms in all including carbon atoms to which R ¹ is attached
Twenty.

An example in which at least two groups adjacent to each other among the groups represented by R ¹ together with the carbon atoms to which they are bonded form one or more aromatic rings or aliphatic rings is a fused phenyl group. , Condensed cyclohexyl group, condensed cyclopentadienyl group, condensed dihydrocyclopentadienyl group, condensed indenyl group, condensed tetrahydroindenyl, condensed fluorenyl group, condensed tetrahydrofluorenyl group, condensed octa A hydrofluorenyl group etc. are mentioned. In addition, these groups may be substituted with a chain alkyl group, a cyclic alkyl group, a halogen atom, a halogen-substituted alkyl group, an aryl group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group or a phosphorus-containing group.

Aryl group, arylalkyl group, arylalkenyl group, alkylaryl group and aromatic ring,
R ¹ other than R ¹ to form an aliphatic ring is a hydrogen atom,
It is a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a silicon-containing group.

Examples of the aryl group having 11 to 20 carbon atoms include biphenylyl, anthryl and phenanthryl. Examples of the arylalkyl group having 12 to 40 carbon atoms include phenanthrylmethyl, phenanthrylethyl, Examples thereof include phenanthrylpropyl, and examples of the arylalkenyl group having 13 to 40 carbon atoms include vinylphenanthryl and the like, which has 12 carbon atoms.
Examples of the alkylaryl group of -40 include methylphenanthryl, ethylphenanthryl, propylphenanthryl, and the like, and halogen atoms include fluorine, chlorine, bromine, iodine, and the like, and the number of carbon atoms is 1. ~ 1
Examples of the alkyl group of 0 include methyl, ethyl, propyl,
Butyl, hexyl, cyclohexyl, octyl, nonyl and the like can be mentioned.

Examples of the silicon-containing group include methylsilyl, phenylsilyl, dimethylsilyl, diethylsilyl, diphenylsilyl, trimethylsilyl, triethylsilyl,
Examples include groups such as tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl, and trinaphthylsilyl.

The above alkyl group, aryl group, arylalkyl group, arylalkenyl group and alkylaryl group may be substituted with halogen. R
² may be the same or different from each other, a hydrogen atom,
Halogen atom, alkyl group having 1 to 10 carbon atoms, aryl group having 6 to 20 carbon atoms, 2-1 carbon atom
0 alkenyl group, C 7-40 arylalkyl group, C 8-40 arylalkenyl group, C 7-40 alkylaryl group, silicon-containing group, oxygen-containing group, sulfur-containing A group, a nitrogen-containing group or a phosphorus-containing group.

Further, at least two adjacent groups of the groups represented by R ² may form a single or plural aromatic ring or aliphatic ring together with the carbon atom to which they are bonded. In this case, the ring formed by R ² is R
R having a total of 4 to 20 carbon atoms including the carbon atom to which ² is bonded and forming an aromatic ring or an aliphatic ring.
R ² other than ² is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a silicon-containing group.

The group formed by the two groups represented by R ² forming one or more aromatic rings or aliphatic rings includes a mode in which the fluorenyl group has the following structure. Be done.

[0033]

[Chemical 6]

Examples of the alkyl group having 1 to 10 carbon atoms and the halogen atom include the same groups and atoms as described above. Examples of the aryl group having 6 to 20 carbon atoms include phenyl, biphenylyl, α- or β-naphthyl, anthryl and phenanthryl, and examples of the arylalkyl group having 7 to 40 carbon atoms include benzyl and phenylethyl. , Phenylpropyl, phenanthrylmethyl, phenanthrylethyl, phenanthrylpropyl, and the like. Examples of the arylalkenyl group having 8 to 40 carbon atoms include styryl, vinylphenanthryl, and the like. Examples of the alkylaryl group having 7 to 40 include tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, methylnaphthyl, methylphenanthryl, ethylphenanthryl, propylphenanthryl, and the like, and the number of carbon atoms. Is an alkenyl group of 2 to 10 Include vinyl, propenyl, cyclohexenyl, etc., the silicon-containing group includes the same groups as described above, the oxygen-containing group, a hydroxy group, an alkoxy group such as methoxy, ethoxy, propoxy, butoxy. , Phenoxy, methylphenoxy, dimethylphenoxy, aryloxy groups such as naphthoxy, phenylmethoxy, arylalkoxy groups such as phenylethoxy, and the like, the sulfur-containing group, a substituent in which oxygen of the oxygen-containing group is substituted with sulfur, And methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, trimethylbenzene sulfonate, triisobutylbenzene sulfonate, p-chlorobenzene sulfonate, petroleum sulfonate. Sulfonate groups such as pentafluorobenzene sulfonate, methylsulfinate, phenylsulfinate, benzenesulfinate, p-toluenesulfinate, trimethylbenzenesulfinate, pentafluorobenzenesulfinate and other sulfinate groups Examples of the nitrogen-containing group include amino groups, methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, alkylamino groups such as dicyclohexylamino, phenylamino, diphenylamino,
Examples thereof include arylamino groups such as ditolylamino, dinaphthylamino, and methylphenylamino, and alkylarylamino groups. Examples of the phosphorus-containing group include dimethylphosphino and diphenylphosphino.

Of these, R ² is preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl or propyl.

A preferable example of the fluorenyl group having R ² as such a substituent is a 2,7-dialkyl-fluorenyl group. In this case, the alkyl group of 2,7-dialkyl includes a carbon atom. Examples thereof include alkyl groups having a number of 1 to 5.

Further, R ¹ and R ² described above may be the same or different from each other. R ³ and R ⁴ may be the same or different from each other, and are the same as the above hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon atom. Number is 2-10
An alkenyl group, an arylalkyl group having 7 to 40 carbon atoms, an arylalkenyl group having 8 to 40 carbon atoms,
It is an alkylaryl group having 7 to 40 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group.

Of these, at least one of R ³ and R ⁴ is preferably an alkyl group having 1 to 3 carbon atoms. X ¹ and X ² may be the same or different from each other, and each is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or an oxygen-containing group. A group, a sulfur-containing group or a nitrogen-containing group, or a conjugated diene residue formed from X ¹ and X ^2, and specifically, a halogen atom, an oxygen-containing group, a sulfur-containing group and a nitrogen-containing group, The same atom or group as described above can be exemplified.

As the hydrocarbon group having 1 to 20 carbon atoms, alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl, dodecyl, eicosyl, norbornyl and adamantyl; vinyl, propenyl, cyclo Alkenyl groups such as hexenyl; arylalkyl groups such as benzyl, phenylethyl, phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, α- or β-naphthyl, methylnaphthyl, anthryl, phenanthryl, benzyl. Phenyl,
Examples thereof include aryl groups such as pyrenyl, acenaphthyl, phenalenyl, aceanthrylenyl, tetrahydronaphthyl, indanyl and biphenylyl, and the like, and the number of carbon atoms is 1
Examples of the halogenated hydrocarbon group having 20 to 20 include groups obtained by substituting the above hydrocarbon group having 1 to 20 carbon atoms with halogen.

X¹And X²Conjugated diene residue formed from and
As a base, η^Four-1,4-diphenyl-1,3-butadiene, η^Four
-1,3-butadiene, η^Four-1,4-dibenzyl-1,3-butadier
, Η ^Four-1-phenyl-1,3-pentadiene, η^Four-3-methyl-
1,3-pentadiene, η^Four-1,4-bis (trimethylsilyl)
-1,3-butadiene, 2,3-dimethylbutadiene, η^Four-2,4-
Hexadiene, isoprene and the like can be mentioned.

The conjugated diene residue formed from X ¹ and X ² includes 1,3-butadiene, 2,4-hexadiene, 1-phenyl-1,3-pentadiene, and the remaining 1,4-diphenylbutadiene. A group is preferable, and these residues may be further substituted with a hydrocarbon group having 1 to 10 carbon atoms.

Of these, the number of halogen atoms and carbon atoms
Is a hydrocarbon group of 1 to 20 or a sulfur-containing group
Is preferred. Y is a divalent carbon having 1 to 20 carbon atoms
Hydrogen group, divalent halogenated carbonization having 1 to 20 carbon atoms
Hydrogen group, divalent silicon containing group, divalent germanium containing
Group, divalent tin-containing group, -O-, -CO-, -S-,-
SO-, -SO₂-, -NR ^Five-, -P (R^Five)-,-
P (O) (R^Five)-,-BR^Five-Or-AlR^Five−
[However, R^FiveIs the number of hydrogen atoms, halogen atoms, carbon atoms
Is a hydrocarbon group having 1 to 20 and halo having 1 to 20 carbon atoms.
Genated hydrocarbon group], specifically, methylene, di
Methylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene
1,1,3-trimethylene, 1,4-tetramethylene, 1,2-siku
Alkylene such as lohexylene and 1,4-cyclohexylene
Group, diphenylmethylene, diphenyl-1,2-ethylene
The number of carbon atoms of any arylalkylene group is 1 to 20
Divalent hydrocarbon group of; carbon source such as chloromethylene
A halogenated halogenated divalent hydrocarbon group having 1 to 20
Rogenated hydrocarbon group; methylsilylene, dimethylsilyle
N, diethyl silylene, di (n-propyl) silylene, di
(I-Propyl) silylene, di (cyclohexyl) silyle
Amine, methylphenylsilylene, diphenylsilylene, di
(P-Tolyl) silylene, di (p-chlorophenyl) silile
Alkylsilylene, alkylarylsilylene
Ane, arylsilylene group, tetramethyl-1,2-disilere
Alkyldiene such as tetraphenyl-1,2-disilylene
Silylene, alkylaryldisilirene, aryldisi
A divalent silicon-containing group such as a rylene group; the above divalent silicon
Bivalent germanium in which silicon in the containing group is replaced with germanium
Ni-containing group; tin of the above-mentioned divalent silicon-containing group is tin
And a divalent tin-containing group substituted with.

Among these divalent groups, those in which the shortest linking part of --Y-- represented by the general formula (I) is composed of 1 or 2 atoms are preferable. Also, R
⁵ is a halogen atom similar to the above, having 1 to 2 carbon atoms
It is a hydrocarbon group of 0 or a halogenated hydrocarbon group having 1 to 20 carbon atoms.

Of these, Y is preferably a divalent hydrocarbon group having 1 to 5 carbon atoms, a divalent silicon-containing group or a divalent germanium-containing group, and preferably a divalent silicon-containing group. More preferably, alkylsilylene,
Particularly preferred is alkylarylsilylene or arylsilylene.

Specific examples of the transition metal compound represented by the above general formula (I) are shown below. Ethylene {2-methyl-4
(9-phenanthryl) -1-indenyl} (9-fluorenyl) zirconium dichloride, ethylene {2-methyl-4
(9-phenanthryl) -1-indenyl} (2,7-dimethyl-
9-fluorenyl) zirconium dichloride, ethylene {2-methyl-4 (9-phenanthryl) -1-indenyl}
(2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, ethylene (2-methyl-4,5-benzo-1-indenyl) (9-fluorenyl) zirconium dichloride, ethylene (2-methyl-4, 5-benzo-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, ethylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di-t
-Butyl-9-fluorenyl) zirconium dichloride, ethylene (2-methyl-4,5-benzo-1-indenyl) (2,7-dibromo-9-fluorenyl) zirconium dichloride, ethylene (2,6-dimethyl-4, 5-benzo-1-indenyl) (2,
7-di-t-butyl-9-fluorenyl) zirconium dichloride, ethylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-dibromo-9-fluorenyl) zirconium dichloride, ethylene (2 -Methyl-α-acenaphtho-1-indenyl) (9-fluorenyl) zirconium dichloride,
Ethylene (2-methyl-α-acenaphtho-1-indenyl)
(2,7-Dimethyl-9-fluorenyl) zirconium dichloride, ethylene (2-methyl-α-acenaphtho-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, dimethylsilylene {2 -Methyl-4 (9-phenanthryl) -1-indenyl} (9-fluorenyl) zirconium dichloride, dimethylsilylene {2-n-propyl-4
(9-phenanthryl) -1-indenyl} (9-fluorenyl) zirconium dichloride, dimethylsilylene {2-methyl-4 (9-phenanthryl) -1-indenyl} (2,7-dimethyl-9-fluorenyl) zirconium dichloride, Dimethylsilylene {2-methyl-4 (9-phenanthryl) -1-
Indenyl} (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (2-methyl-4,5
-Benzo-1-indenyl) (9-fluorenyl) zirconium dichloride, dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (2 -Methyl-
4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (2-methyl-α-acenaphtho-1-indenyl) (9-fluorenyl) zirconium dichloride , Dimethylsilylene (2-methyl-α-acenaphth-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (2-methyl-α-acenaphth-1-indenyl) (2,7- Di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylsilylene {2-methyl-4 (9-phenanthryl) -1-indenyl} (9-fluorenyl) zirconium dichloride, diphenylsilylene {2-methyl-4
(9-phenanthryl) -1-indenyl} (2,7-dimethyl-
9-fluorenyl) zirconium dichloride, diphenylsilylene {2-methyl-4 (9-phenanthryl) -1-indenyl} (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylsilylene (2-methyl- 4,5-benzo-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenyl Silylene (2-methyl
-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylsilylene (2-methyl-α-acenaphtho-1-indenyl) (9-fluorenyl) zirconium Dichloride,

Diphenylsilylene (2-methyl-α-acenaphtho-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylsilylene (2-
Methyl-α-acenaphtho-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, methylphenylsilylene {2-methyl-4 (9-phenanthryl)
-1-Indenyl} (9-fluorenyl) zirconium dichloride, methylphenylsilylene {2-methyl-4 (9-phenanthryl) -1-indenyl} (2,7-dimethyl-9-fluorenyl) zirconium dichloride, methylphenylsilylene { 2-Methyl-4 (9-phenanthryl) -1-indenyl} (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, methylphenylsilylene (2-methyl-4,5-
Benzo-1-indenyl) (9-fluorenyl) zirconium dichloride, methylphenylsilylene (2-methyl-4,5
-Benzo-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, methylphenylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl- 9-fluorenyl) zirconium dichloride, methylphenylsilylene (2-methyl-α-acenaphtho-1-indenyl) (9-fluorenyl) zirconium dichloride,
Methylphenylsilylene (2-methyl-α-acenaphtho-1-
Indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, methylphenylsilylene (2-methyl
-α-acenaphtho-1-indenyl) (2,7-di-t-butyl-9-
Fluorenyl) zirconium dichloride, ethylene {3-
Methyl-4 (9-phenanthryl) -1-indenyl} (9-fluorenyl) zirconium dichloride, ethylene {3-methyl-4 (9-phenanthryl) -1-indenyl} (2,7-dimethyl-9-fluorenyl) zirconium Dichloride, ethylene {3-methyl-4 (9-phenanthryl) -1-indenyl} (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, ethylene (3-methyl-4,5-benzo-1) -Indenyl) (9-fluorenyl) zirconium dichloride, ethylene (3-methyl-4,5-benzo-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, ethylene (3-methyl-4,5 -Benzo-1-indenyl) (2,7-di
-t-butyl-9-fluorenyl) zirconium dichloride,
Ethylene (3-methyl-α-acenaphtho-1-indenyl)
(9-Fluorenyl) zirconium dichloride, ethylene (3-methyl-α-acenaphtho-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, ethylene (3-methyl-α-acenaphtho-1-indenyl) (2,7-
Di-t-butyl-9-fluorenyl) zirconium dichloride, dimethylsilylene {3-methyl-4 (9-phenanthryl) -1-indenyl} (9-fluorenyl) zirconium dichloride, dimethylsilylene {3-methyl-4 (9- Phenanthryl) -1-indenyl} (2,7-dimethyl-9-fluorenyl) zirconium dichloride, dimethylsilylene {3-
Methyl-4 (9-phenanthryl) -1-indenyl} (2,7-
Di-t-butyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (3-methyl-4,5-benzo-1-indenyl) (9-fluorenyl) zirconium dichloride, dimethylsilylene (3-methyl-4,5-benzo) -1-indenyl)
(2,7-Dimethyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (3-methyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, dimethyl Silylene (3-methyl-α-acenaphth-1-indenyl) (9-fluorenyl) zirconium dichloride, dimethylsilylene (3-methyl-α-acenaphth-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride ,

Dimethylsilylene (3-methyl-α-acenaphtho-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylsilylene {3-
Methyl-4 (9-phenanthryl) -1-indenyl} (9-fluorenyl) zirconium dichloride, diphenylsilylene {3-methyl-4 (9-phenanthryl) -1-indenyl} (2,7-dimethyl-9-fluorenyl) Zirconium dichloride, diphenylsilylene {3-methyl-4 (9-phenanthryl) -1-indenyl} (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylsilylene (3-methyl-4,5- Benzo-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylsilylene (3-methyl-4,5-benzo-1-indenyl) (2,7-dimethyl
-9-fluorenyl) zirconium dichloride, diphenylsilylene (3-methyl-4,5-benzo-1-indenyl) (2,
7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylsilylene (3-methyl-α-acenaphtho-1-
Indenyl) (9-fluorenyl) zirconium dichloride, diphenylsilylene (3-methyl-α-acenaphtho-1-
Indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylsilylene (3-methyl-α
-Acenaphtho-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, methylphenylsilylene {3-methyl-4 (9-phenanthryl) -1-indenyl} (9-fluorenyl) zirconium Dichloride, methylphenylsilylene {3-methyl-4 (9-phenanthryl) -1-indenyl} (2,7-dimethyl-9-fluorenyl)
Zirconium dichloride, methylphenylsilylene {3-
Methyl-4 (9-phenanthryl) -1-indenyl} (2,7-
Di-t-butyl-9-fluorenyl) zirconium dichloride, methylphenylsilylene (3-methyl-4,5-benzo-1-
Indenyl) (9-fluorenyl) zirconium dichloride, methylphenylsilylene (3-methyl-4,5-benzo-1-
Indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, methylphenylsilylene (3-methyl
-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, methylphenylsilylene (3-methyl-α-acenaphtho-1-indenyl) (9-
Fluorenyl) zirconium dichloride, methylphenylsilylene (3-methyl-α-acenaphtho-1-indenyl)
(2,7-Dimethyl-9-fluorenyl) zirconium dichloride, methylphenylsilylene (3-methyl-α-acenaphtho-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, ethylene ( 2-methyl-4,5
-Benzo-1-indenyl) (2,7-ditrimethylsilyl-9-
Fluorenyl) zirconium dichloride, ethylene (2,
6-Dimethyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, ethylene (2,7-dimethyl-4,5-benzo-1-indenyl) (2,7-
Di-t-butyl-9-fluorenyl) zirconium dichloride, ethylene (2,7-dimethyl-4,5- (2-methyl-benzo))
-1-indenyl) (2,7-di-t-butyl-9-fluorenyl)
Zirconium dichloride, dimethyl silylene (2-methyl
-4,5-benzo-1-indenyl) (2,7-ditrimethylsilyl
-9-Fluorenyl) zirconium dichloride, dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-
Di-t-butyl-9-fluorenyl) zirconium bis (methanesulfonato), dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) Zirconium bis (trifluoromethanesulfonato), dimethylsilylene (2,6-dimethyl-4,5-benzo-1-
Indenyl) (2,7-di (trimethylsilyl) -9-fluorenyl) zirconium dichloride, dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-di (trimethylsilyl) -9- Fluorenyl) zirconium bis (methanesulfonato), dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-di (trimethylsilyl) -9-fluorenyl) zirconium bis (trifluoromethanemethanesulfone) Nat),

Dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (2,7-
Dimethyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo)) -1
-Indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (2-methyl-
4,5-benzo-1-indenyl) (2,7-dibromo-9-fluorenyl) zirconium dichloride, dimethylsilylene (2,
6-Dimethyl-4,5-benzo-1-indenyl) (2,7-dibromo
-9-Fluorenyl) zirconium dichloride, dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-
Di-t-butoxy-9-fluorenyl) zirconium dichloride, dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-di-t-butoxy-9-fluorenyl) zirconium dichloride, Dimethyl silylene (2-methyl-4,5
-Benzo-1-indenyl) (2,7-diphenyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (2,
6-Dimethyl-4,5-benzo-1-indenyl) (2,7-diphenyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,
7-di-i-propyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (2,6-dimethyl-4,5-benzo-1-
Indenyl) (2,7-di-i-propyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-dimethyl-9-fluorenyl) Zirconium dichloride, dimethyl silylene (2,6-dimethyl-4,5- (1-methyl-benzo) -1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, dimethyl silylene (2 , 7-Dimethyl-4,5- (2
-Methyl-benzo) -1-indenyl) (2,7-di (trimethylsilyl) -9-fluorenyl) zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-
Benzo) -1-indenyl) (2,7-dibromo-9-fluorenyl) zirconium dichloride, dimethylsilylene (2,7-
Dimethyl-4,5- (2-methyl-benzo) -1-indenyl)
(2,7-di-t-butoxy-9-fluorenyl) zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5- (2-
Methyl-benzo) -1-indenyl) (2,7-diphenyl-9-
Fluorenyl) zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di-i-propyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (2,7-Dimethyl-
4,5- (2-Methyl-benzo) -1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5- (1-methyl-benzo)) -1
-Indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5- (1-methyl-benzo) -1-indenyl) (2,7 -Di (trimethylsilyl) -9-fluorenyl) zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5- (1
-Methyl-benzo) -1-indenyl) (2,7-dibromo-9-fluorenyl) zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5- (1-methyl-benzo) -1-indenyl) ( 2,7-Di-t-butoxy-9-fluorenyl) zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5
-(1-Methyl-benzo) -1-indenyl) (2,7-diphenyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5- (1-methyl-benzo) -1
-Indenyl) (2,7-di-i-propyl-9-fluorenyl)
Zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5- (1-methyl-benzo) -1-indenyl) (2,7-
Dimethyl-9-fluorenyl) zirconium dichloride,
Dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-dibromo-9-fluorenyl) zirconium bis (methanesulfonato), dimethylsilylene (2,6-dimethyl-4,5-benzo) -1-indenyl) (2,7-dibromo-9-fluorenyl) zirconium bis (methanesulfonato),

Dimethylsilylene (2-methyl-4,5-benzo-
1-indenyl) (2,7-di-t-butoxy-9-fluorenyl)
Zirconium bis (methanesulfonato), dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-
Di-t-butoxy-9-fluorenyl) zirconium bis (methanesulfonato), dimethylsilylene (2-methyl-4,5-
Benzo-1-indenyl) (2,7-diphenyl-9-fluorenyl) zirconium bis (methanesulfonato), dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl)
(2,7-Diphenyl-9-fluorenyl) zirconium bis (methanesulfonato), dimethylsilylene (2-methyl-
4,5-benzo-1-indenyl) (2,7-di-i-propyl-9-fluorenyl) zirconium bis (methanesulfonate),
Dimethyl silylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-di-i-propyl-9-fluorenyl) zirconium bis (methanesulfonato), dimethyl silylene (2,
6-Dimethyl-4,5-benzo-1-indenyl) (2,7-dimethyl
-9-Fluorenyl) zirconium bis (methanesulfonato), dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di (trimethylsilyl) -9- Fluorenyl) zirconium bis (methanesulfonato), dimethylsilylene (2,7-dimethyl-4,5- (2-
Methyl-benzo) -1-indenyl) (2,7-dibromo-9-fluorenyl) zirconium bis (methanesulfonato),
Dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di-t-butoxy-9-fluorenyl) zirconium bis (methanesulfonato), dimethylsilylene (2,7-Dimethyl-4,5- (2-methyl-benzo) -1
-Indenyl) (2,7-diphenyl-9-fluorenyl) zirconium bis (methanesulfonato), dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2, 7-di-i-propyl-9-fluorenyl) zirconium bis (methanesulfonato), dimethylsilylene (2,7-
Dimethyl-4,5- (2-methyl-benzo) -1-indenyl)
(2,7-Dimethyl-9-fluorenyl) zirconium bis (methanesulfonato), dimethylsilylene (2,7-dimethyl-4,5- (1-methyl-benzo) -1-indenyl) (2,7-di -
t-Butyl-9-fluorenyl) zirconium bis (methanesulfonato), dimethylsilylene (2,7-dimethyl-4,5-
(1-Methyl-benzo) -1-indenyl) (2,7-di (trimethylsilyl) -9-fluorenyl) zirconium bis (methanesulfonato), dimethylsilylene (2,7-dimethyl-
4,5- (1-Methyl-benzo) -1-indenyl) (2,7-dibromo-9-fluorenyl) zirconium bis (methanesulfonato), dimethylsilylene (2,7-dimethyl-4,5- (1 -Methyl-benzo) -1-indenyl) (2,7-di-t-butoxy-9-
Fluorenyl) zirconium bis (methanesulfonato), dimethylsilylene (2,7-dimethyl-4,5- (1-methyl-benzo) -1-indenyl) (2,7-diphenyl-9-fluorenyl) zirconium bis (methane Sulfonato), dimethylsilylene (2,7-dimethyl-4,5- (1-methyl-benzo) -1-indenyl) (2,7-di-i-propyl-9-fluorenyl) zirconium bis (methanesulfonato ), Dimethylsilylene (2,7-dimethyl-4,5- (1-methyl-benzo) -1)
-Indenyl) (2,7-dimethyl-9-fluorenyl) zirconium bis (methanesulfonato), dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-dibromo
-9- (4,5-Methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-dibromo-9- (4,5- Methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di
-t-Butoxy-9- (4,5-methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2,6-dimethyl
-4,5-benzo-1-indenyl) (2,7-di-t-butoxy-9-
(4,5-Methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-diphenyl-9- (4,5-methylenephenanthryl)) ) Zirconium dichloride, dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-diphenyl-9- (4,5-methylenephenanthryl)) zirconium dichloride,

Dimethylsilylene (2-methyl-4,5-benzo-
1-indenyl) (2,7-di-i-propyl-9- (4,5-methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl)
(2,7-di-i-propyl-9- (4,5-methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2,
6-Dimethyl-4,5-benzo-1-indenyl) (2,7-dimethyl
-9- (4,5-Methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5- (2-
Methyl-benzo) -1-indenyl) (2,7-di (trimethylsilyl) -9- (4,5-methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2,7-dimethyl-
4,5- (2-Methyl-benzo) -1-indenyl) (2,7-dibromo-9- (4,5-methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2,7-dimethyl-4, 5- (2
-Methyl-benzo) -1-indenyl) (2,7-di-t-butoxy
-9- (4,5-Methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5- (2-
Methyl-benzo) -1-indenyl) (2,7-diphenyl-9-
(4,5-Methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di-i-propyl- 9-
(4,5-Methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-dimethyl-9- (4 ,Five-
Methylenephenanthryl)) zirconium dichloride,
Dimethylsilylene (2,7-dimethyl-4,5- (1-methyl-benzo) -1-indenyl) (2,7-di-t-butyl-9- (4,5-methylenephenanthryl)) zirconium Dichloride, dimethylsilylene (2,7-dimethyl-4,5- (1-methyl-benzo)
-1-indenyl) (2,7-di (trimethylsilyl) -9- (4,
5-Methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5- (1-methyl-
Benzo) -1-indenyl) (2,7-dibromo-9- (4,5-methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5- (1-methyl-benzo))
-1-Indenyl) (2,7-di-t-butoxy-9- (4,5-methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5- (1-methyl- Benzo) -1
-Indenyl) (2,7-diphenyl-9- (4,5-methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5- (1-methyl-benzo) -1-indenyl ) (2,7-Di-i-propyl-9- (4,5-methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5- (1-methyl-benzo) -1 -Indenyl) (2,7-dimethyl-9- (4,5-methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2-
Methyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-
9- (4,5-Methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di (trimethylsilyl) -9- (4,5- Methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9- (4,5-methylenephenanthryl) )) Zirconium dichloride, dimethyl silylene (2,
6-Dimethyl-4,5-benzo-1-indenyl) (2,7-di (trimethylsilyl) -9- (4,5-methylenephenanthryl))
Zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-
Di-t-butyl-9- (4,5-methylenephenanthryl)) zirconium dichloride,

Dimethylsilylene (2,7-dimethyl-4,5- (2
-Methyl-benzo) -1-indenyl) (2,7-di (trimethylsilyl) -9- (4,5-methylenephenanthryl)) zirconium dichloride, dimethylmethylene (2-methyl-4,5)
-Benzo-1-indenyl) (2,7-dibromo-9-fluorenyl) zirconium dichloride, dimethylmethylene (2,6-
Dimethyl-4,5-benzo-1-indenyl) (2,7-dibromo-9
-Fluorenyl) zirconium dichloride, dimethylmethylene (2-methyl-4,5-benzo-1-indenyl) (2,7-dienyl)
-t-butoxy-9-fluorenyl) zirconium dichloride, dimethylmethylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-di-t-butoxy-9-fluorenyl) zirconium dichloride, dimethyl Methylene (2-methyl-4,5
-Benzo-1-indenyl) (2,7-diphenyl-9-fluorenyl) zirconium dichloride, dimethylmethylene (2,
6-Dimethyl-4,5-benzo-1-indenyl) (2,7-diphenyl-9-fluorenyl) zirconium dichloride, dimethylmethylene (2-methyl-4,5-benzo-1-indenyl) (2,
7-di-i-propyl-9-fluorenyl) zirconium dichloride, dimethylmethylene (2,6-dimethyl-4,5-benzo-1-
Indenyl) (2,7-di-i-propyl-9-fluorenyl) zirconium dichloride, dimethylmethylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-dimethyl-9-fluorenyl) Zirconium dichloride, dimethylmethylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di (trimethylsilyl) -9-fluorenyl)
Zirconium dichloride, dimethylmethylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-
Dibromo-9-fluorenyl) zirconium dichloride,
Dimethylmethylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di-t-butoxy-9-fluorenyl) zirconium dichloride, dimethylmethylene (2,
7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl)
(2,7-Diphenyl-9-fluorenyl) zirconium dichloride, dimethylmethylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di-i-propyl- 9-
Fluorenyl) zirconium dichloride, dimethylmethylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, dimethylmethylene (2,7 -Dimethyl-4,5-
(1-Methyl-benzo) -1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, dimethylmethylene (2,7-dimethyl-4,5- (1-methyl-benzo)) -1
-Indenyl) (2,7-di (trimethylsilyl) -9-fluorenyl) zirconium dichloride, dimethylmethylene (2,7-dimethyl-4,5- (1-methyl-benzo) -1-indenyl) (2,7- Dibromo-9-fluorenyl) zirconium dichloride, dimethylmethylene (2,7-dimethyl-4,5- (1-
Methyl-benzo) -1-indenyl) (2,7-di-t-butoxy-
9-fluorenyl) zirconium dichloride, dimethylmethylene (2,7-dimethyl-4,5- (1-methyl-benzo) -1-indenyl) (2,7-diphenyl-9-fluorenyl) zirconium dichloride, dimethylmethylene (2 , 7-dimethyl-
4,5- (1-Methyl-benzo) -1-indenyl) (2,7-di-i-
Propyl-9-fluorenyl) zirconium dichloride,
Dimethylmethylene (2,7-dimethyl-4,5- (1-methyl-benzo) -1-indenyl) (2,7-dimethyl-9-fluorenyl)
Zirconium dichloride, dimethylmethylene (2-methyl
-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, dimethylmethylene (2-methyl-4,5-benzo-1-indenyl) (2,7 -Di (trimethylsilyl) -9-fluorenyl) zirconium dichloride, dimethylmethylene (2,6-dimethyl-4,5-benzo-1-
Indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, dimethylmethylene (2,6-dimethyl
-4,5-benzo-1-indenyl) (2,7-di (trimethylsilyl) -9-fluorenyl) zirconium dichloride, dimethylmethylene (2,7-dimethyl-4,5- (2-methyl-benzo))
-1-indenyl) (2,7-di-t-butyl-9-fluorenyl)
Zirconium dichloride, dimethylmethylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-
Di (trimethylsilyl) -9-fluorenyl) zirconium dichloride, dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium η ⁴ -1- Phenyl-1,3-pentadiene,
Dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di (trimethylsilyl) -9-fluorenyl)
Zirconium eta ^{4-1,4-diphenyl} butadiene, dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7
Dibromo-9-fluorenyl) zirconium η ⁴ -2,4-hexadiene, dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium eta ^{4-1,4-diphenyl-1,3-butadiene,} dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-di (trimethylsilyl) -9-fluorenyl) zirconium eta ^{4-3-methyl-1,3-pentadiene,}
Dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-dibromo-9-fluorenyl) zirconium η ⁴ -2,4-hexadiene, diphenylsilylene (2-methyl
-4,5-benzo-1-indenyl) (2,7-ditrimethylsilyl
-9-Fluorenyl) zirconium dichloride, diphenylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl)
(2,7-Di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylsilylene (2,7-dimethyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9- Fluorenyl) zirconium dichloride, diphenylsilylene (2,
7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl)
(2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, methylphenylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di (trimethyl) silyl-9-fluorenyl ) Zirconium dichloride, methylphenylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl)
(2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, methylphenylsilylene (2,7-dimethyl-4,5-
Benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, methylphenylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, ethylene (2-methyl-7-trimethylsilyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9 -Fluorenyl) zirconium dichloride, dimethylsilylene (2-methyl-7-trimethylsilyl-4,5- (1-methyl-benzo) -1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride Such.

It is also possible to use a compound in which zirconium is replaced by titanium or hafnium in the zirconium compound as described above. Among the above-mentioned zirconium compounds, for example, dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di-t-butyl-9-fluorenyl) The structural formula of zirconium dichloride is shown below.

[0053]

[Chemical 7]

In addition, dimethylsilylene (2,6-dimethyl-
4,5- (1-Methyl-benzo) -1-indenyl) (2,7-di-t-
The structural formula of butyl-9-fluorenyl) zirconium dichloride is shown below.

[0055]

[Chemical 8]

When the transition metal compound according to the present invention is used as a catalyst for olefin polymerization in combination with, for example, an organoaluminum oxy compound, an olefin (co) polymer having a large molecular weight can be obtained, and the proportion of comonomer used is small. Even in this case, an olefin copolymer having a high comonomer content can be obtained.

The transition metal compound according to the present invention can be produced, for example, as follows. First, a substituted fluorenyl anion (compound (i)) represented by the following general formula (i) and a compound (compound (ii)) represented by the following general formula (ii) are reacted in a solvent. The following general formula (ii
The compound represented by i) is obtained.

[0058]

[Chemical 9]

In the general formula (i), R ² may be the same or different from each other and is the same as R ² in the general formula (I). In the general formula (ii), Y
Is the same as R ² in the general formula (I), and X ³
And X ⁴ may be the same or different from each other, and are a hydrogen atom, a halogen atom, an —OR group, an —OCOR group, or —S.
R group, -OSO ₂ R group, -SO ₂ R group, -NRR 'group (wherein, R and R', which may be the same or different from each other, a hydrogen atom, a halogen atom, carbon atoms 1-1
An alkyl group of 0, an aryl group having 6 to 20 carbon atoms,
It is an alkylaryl group having 7 to 30 carbon atoms. )
Indicates.

In the general formula (iii), R ² , Y and X ⁴ are the same as in the general formulas (i) and (ii).
Examples of the solvent used in the reaction include ethers such as diethyl ether, tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene, toluene and mesitylene; and aliphatic hydrocarbons such as pentane, hexane and heptane. Of these, diethyl ether, tetrahydrofuran, toluene and hexane are preferable.

In the reaction between the compound (i) and the compound (ii), the compound (ii) is used in an amount in the range of 0.5 to 200, preferably 1 to 60 in molar ratio with respect to the compound (i). The solvent is used in a weight ratio of 1 to 10 with respect to the compound (ii).
It is used in an amount of 0, preferably 1-20.

The reaction temperature between the compound (i) and the compound (ii) is -78 ° C to 150 ° C, preferably -78 ° C to 50 ° C.
And the reaction time is 0.1 to 50 hours, preferably 1 to 25 hours.

The compound (i) can be obtained by reacting a substituted fluorene with a base in a solvent or without a solvent. Here, examples of the base include elemental metals such as metal sodium, metal potassium, and metal lithium; hydrogenated compounds such as potassium hydride and sodium hydride; organolithium compounds such as methyllithium and n-butyllithium. Among these, sodium metal, sodium hydride and n-butyllithium are preferable, and n-butyllithium is particularly preferable.

Examples of the solvent used in the reaction between the substituted fluorene and the base include the same as those used in the reaction between the compound (i) and the compound (ii). Among these, diethyl ether, tetrahydrofuran, Toluene and hexane are preferable, and diethyl ether and toluene are particularly preferable.

In the reaction of a substituted fluorene with a base,
The base has a molar ratio of 0.5 to 2.
0, preferably 0.90 to 1.5, and the solvent is used in a weight ratio of 1 to 10 with respect to the substituted fluorene.
It is used in an amount of 0, preferably 1-20.

The reaction temperature between the substituted fluorene and the base is −
It is in the range of 78 ° C to 150 ° C, preferably -78 ° C to 50 ° C, and the reaction time is 0.1 to 50 hours, preferably 1
~ 25 hours.

Next, a compound represented by the general formula (iii) (compound (iii)) is reacted with a substituted indenyl anion (compound (iv)) represented by the following general formula (iv) to give the following compound. A compound represented by the general formula (v) is produced.

[0068]

[Chemical 10]

[0069] In the general formula (iv), R ^1, R ³ and R ⁴ are the same as R ^1, R ³ and R ⁴ in the general formula (I), Z is lithium, sodium, potassium, etc. Indicates an alkali metal of.

In the general formula (v), R ¹ , R ² ,
R ³ , R ⁴ and Y are the same as R ¹ , R ² , R ³ , R ⁴ and Y in the general formula (I). In the reaction between the compound (iii) and the compound (iv), the compound (i
ii) is 0.5 to 10 in molar ratio with respect to compound (iv),
It is preferably used in an amount in the range of 0.5 to 5, and the solvent is
It is used in a weight ratio to the compound (iv) of 1 to 100, preferably 1 to 20.

The reaction temperature between the compound (iii) and the compound (iv) is -78 ° C to 150 ° C, preferably -78 ° C to 5 ° C.
The temperature is in the range of 0 ° C., and the reaction time is 0.1 to 50 hours, preferably 1 to 25 hours.

By reacting the compound (iii) with the compound (iv) under such conditions, the above-mentioned general formula (v)
A crosslinked substituted indenyl-substituted fluorenyl compound represented by can be obtained.

The compound (iv) can be obtained by reacting a substituted indene with a base in a solvent or without a solvent. Examples of the base used in the reaction include the same bases as those used in producing the substituted fluorenyl anion, and among these, metal sodium, sodium hydride, and n-butyllithium are preferable, and particularly, n-Butyl lithium is preferred.

Examples of the solvent used in the reaction include the same solvents as those used in the reaction between the compound (i) and the compound (ii), and among these, diethyl ether, tetrahydrofuran, toluene and hexane are preferable. Particularly preferred are diethyl ether and toluene.

In the reaction of the substituted indene with the base, the base has a molar ratio of 0.5 to 2.0 with respect to the substituted indene,
It is preferably used in an amount in the range of 0.90 to 1.5, and the solvent is used in an amount of 1 to 100, preferably 1 to 20 in weight ratio to the substituted indene.

The reaction temperature between the substituted indene and the base is -7.
It is in the range of 8 ° C to 150 ° C, preferably -78 ° C to 50 ° C, and the reaction time is 0.1 to 50 hours, preferably 1 to
25 hours.

The transition metal compound represented by the general formula (I) includes the anion of the crosslinked substituted indenyl-substituted fluorenyl compound prepared as described above and the following general formula (vi)
It can be produced by reacting the compound represented by i) in a solvent.

[0078]

[Chemical 11]

In the general formula (vi), R ¹ , R ² ,
R ³ , R ⁴ and Y are the same as R ¹ , R ² , R ³ , R ⁴ and Y in the general formula (I). In the general formula (vii), M is the same as M in the general formula (I), X ⁵ may be the same or different from each other, and a hydrogen atom, a halogen atom, an —OR group, and —OC.
OR group, -SR group, -OSO ₂ R group, an -SO ₂ R group, X ⁶ is a hydrogen atom, a halogen atom, -OR group, -O
COR group, -SR group, -OSO ₂ R group, -SO ₂ R group,
-NRR 'group (provided that R and R'may be the same or different from each other, a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, Is an alkylaryl group having 7 to 30 carbon atoms), and n is 1 or 2. When n = 2, X ⁶ may be the same as or different from each other.

In the reaction of the crosslinked substituted indenyl-substituted fluorenyl compound anion represented by the general formula (vi) (compound (vi)) with the compound represented by the general formula (vii) (compound (vii)) The compound (vii) is used in an amount in the range of 0.1 to 200, preferably 0.5 to 5.0 with respect to the compound (vi) in a molar ratio, and the solvent is used with respect to the substituted indenyl anion. It is used in a weight ratio of 1 to 100, preferably 1 to 20.

The reaction temperature between the compound (vi) and the compound (vii) is -78 ° C to 150 ° C, preferably -78 ° C to 5 ° C.
The temperature is in the range of 0 ° C., and the reaction time is 0.1 to 50 hours, preferably 1 to 25 hours.

The compound (vi) can be obtained by reacting a crosslinked substituted indenyl-substituted fluorenyl compound (compound (v)) with a base in a solvent or without solvent.

Examples of the base used in the reaction include the same bases as those used in the production of the substituted fluorenyl anion, and among these, metallic sodium, sodium hydride and n-butyllithium can be mentioned. Preferably
Particularly preferred is n-butyllithium.

Examples of the solvent used in the reaction include the same solvents as those used in the reaction between the compound (i) and the compound (ii), and among these, diethyl ether, tetrahydrofuran, toluene and hexane are preferable. Particularly preferred are diethyl ether and toluene.

In the reaction of the compound (v) with the base, the base is used in a molar ratio of 1.0 to 10.
0, preferably used in an amount ranging from 1.5 to 3.0,
The solvent is used in a weight ratio to the compound (v) of 1 to 100, preferably 1 to 20.

The reaction temperature between the substituted indene and the base is -7.
It is in the range of 8 ° C to 150 ° C, preferably -78 ° C to 50 ° C, and the reaction time is 0.1 to 50 hours, preferably 1 to
25 hours.

The transition metal compound obtained as described above can be purified by crystallization after removing the inorganic salt by a usual operation. Moreover, the transition metal compound according to the present invention can also be produced by the following method. First, the compound (iv) is reacted with the compound (ii) to produce a compound represented by the following general formula (viii) (compound (viii)).

[0088]

[Chemical 12]

Next, the crosslinked substituted indenyl-substituted fluorenyl compound (compound (v)) is obtained by reacting the compound (viii) with the substituted fluorenyl anion (compound (i)). Subsequently, the compound (vi) obtained by anionizing the compound (v) is reacted with the compound (vii) to obtain a transition metal compound. In this production method, the same reaction conditions as described above can be adopted as each reaction condition.

Further, the transition metal compound according to the present invention can be produced by the following method. First,
Substituted indene represented by the following general formula (ix) (compound (i
x)) and a substituted ketone (compound (x)) represented by the following formula (x) are reacted to produce a compound (compound (xi)) represented by the following general formula (xi).

[0091]

[Chemical 13]

In the reaction, the substituted indene is converted to the substituted indenyl anion using the above-mentioned base, and the substituted ketone is substituted with the substituted indenyl anion in a molar ratio of 0.1 to 1: 1.
00, preferably 0.1 to 20 is added.

Next, the obtained compound (xi) is reacted with a substituted fluorenylalunion (compound (i)) to obtain a crosslinked substituted indenyl-substituted fluorenyl compound (compound (v)). This compound (xi) and compound (i)
In the reaction with, the compound (i) has a molar ratio of 0.1 to 100, preferably 0.5 to 5.
Used in quantities in the range 0. Then, the anion of the crosslinked substituted indenyl-substituted fluorenyl compound and the compound (vii) are reacted in a solvent to obtain a transition metal compound. In this production method, the same reaction conditions as described above can be adopted as each reaction condition.

The olefin polymerization catalyst according to the present invention comprises (A-1) a transition metal compound of Group 4 of the periodic table represented by the general formula (I), and (B) (B-1) an organoaluminum oxy A compound, and / or (B-2) a compound that reacts with the transition metal compound (A-1) to form an ion pair, and, if necessary, (C) an organoaluminum compound.

First, each component forming the catalyst for olefin polymerization according to the present invention will be described. In the present invention, as the transition metal compound (A-1), the transition metal compound represented by the general formula (I) is used. Two or more kinds of (A-1) transition metal compounds can be used in combination.

The organoaluminum oxy compound (B-1) used in the present invention may be a conventionally known aluminoxane, or a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687. It may be a compound.

The conventionally known aluminoxane can be produced, for example, by the following method. (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. The method of adding an organoaluminum compound such as trialkylaluminum to the suspension of a hydrocarbon medium, and reacting adsorbed water or crystal water with the organoaluminum compound. (2) A method in which water, ice, or steam is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of organometallic component. Further, the solvent or unreacted organoaluminum compound may be removed by distillation from the recovered aluminoxane solution and then redissolved in the solvent.

Specific examples of the organoaluminum compound used in the preparation of aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum and triisopropylaluminum.
n-butyl aluminum, triisobutyl aluminum,
Trisec-butylaluminum, tritert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum and other trialkylaluminums, tricyclohexylaluminum, tricyclooctylaluminum and other tricycloalkylaluminums, dimethylaluminum Chloride, diethylaluminum chloride,
Dialkyl aluminum halides such as diethyl aluminum bromide and diisobutyl aluminum chloride,
Dialkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride, dialkyl aluminum alkoxides such as dimethyl aluminum methoxide and diethyl aluminum ethoxide, and dialkyl aluminum aryloxides such as diethyl aluminum phenoxide.

Among these, trialkylaluminum and tricycloalkylaluminum are particularly preferable.
Further, as an organoaluminum compound used in the preparation of aluminoxane, a compound represented by the formula (i-C ₄ H ₉ ) _x Al _y (C
₅ H ₁₀ ) _z (where x, y, and z are positive numbers, and z ≧ 2
x. It is also possible to use isoprenylaluminum represented by the formula (1).

The above organoaluminum compounds may be used in combination of two or more kinds. As the solvent used in the preparation of aluminoxane, for example, aromatic hydrocarbons such as benzene, toluene, xylene, cumene, cymene, etc., aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, octadecane, etc. , Cyclopentane, cyclohexane, cyclooctane, methylcyclopentane, and other alicyclic hydrocarbons, petroleum fractions such as gasoline, kerosene, and light oil, and halogens of the above aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons And hydrocarbon solvents such as chlorides, bromides and the like.

Further, ethers such as ethyl ether and tetrahydrofuran can be used. Of these solvents, aromatic hydrocarbons are particularly preferable. As the compound (B-2) (hereinafter sometimes referred to as “ionized ionic compound”) which reacts with the transition metal compound (A-1) to form an ion pair used in the present invention, it is described in Table 1- 5019
Japanese Patent Laid-Open No. 50, Japanese Patent Publication No. 1-502036, Japanese Patent Laid-Open No.
-179005, JP-A-3-179006, JP-A-3-207703, and JP-A-3-207
Examples thereof include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in Japanese Patent Publication No. 704, USP-5321106 and the like.

Examples of the Lewis acid include magnesium-containing Lewis acid, aluminum-containing Lewis acid, boron-containing Lewis acid and the like, and among these, boron-containing Lewis acid is preferable.

Specific examples of the Lewis acid containing a boron atom include compounds represented by the following formula (III). BR ¹¹ R ¹² R ¹³ (III) (In the formula, R ¹¹ , R ¹² and R ¹³ may be the same or different from each other and have a substituent such as a fluorine atom, a methyl group and a trifluoromethyl group. Optionally a phenyl group,
Alternatively, it represents a fluorine atom. ) Specific examples of the compound represented by the above formula (III) include trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoro). Methylphenyl) boron, tris (pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron, tris {3,5-di (trifluoro) Methylphenyl)} boron and the like. Of these, tris (pentafluorophenyl) boron is particularly preferable.

The ionic compound is a salt composed of a cationic compound and an anionic compound. The anion has a function of cationizing the transition metal compound (A) by reacting with the transition metal compound (A) and stabilizing the transition metal cation species by forming an ion pair. Examples of such anions include organic boron compound anions,
There are organic arsenic compound anions, organic aluminum compound anions, etc., and those which are relatively bulky and stabilize the transition metal cation species are preferable. Examples of the cation include a metal cation, an organometallic cation, a carbonium cation, a tripium cation, an oxonium cation, a sulfonium cation, a phosphonium cation, and an ammonium cation. More specifically, it includes a triphenylcarbenium cation, a tributylammonium cation, an N, N-dimethylammonium cation, and a ferrocenium cation.

Of these, ionic compounds containing a boron compound as an anion are preferable, and specifically,
For example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, trimethylammonium tetra (p-tolyl) boron, trimethylammonium tetra (o-tolyl) boron , Tributylammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (m, m-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron , Tri (n-butyl) ammonium tetra (o-tolyl) boron, tri (n-butyl) ammonium tetra (4-fluorophenyl) boron and other trialkyl-substituted ammonium salts; N, N-dimethyl N, N-dialkylanilinium salts such as nirinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N-2,4,6-pentamethylanilinium tetra (phenyl) boron; di Dialkyl ammonium salts such as (n-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron; triphenylphosphonium tetra (phenyl) boron, tri (methylphenyl) phosphonium tetra (phenyl) Examples thereof include triarylphosphonium salts such as boron and tri (dimethylphenyl) phosphonium tetra (phenyl) boron.

Further, as an ionic compound containing a boron atom, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate,
Ferrocenium tetra (pentafluorophenyl) borate may also be mentioned.

Further, the following compounds can be exemplified as the ionic compound containing a boron atom. (In the ionic compounds listed below, the counter ion is, but not limited to, tri (n-butyl) ammonium.) Anion salts such as bis [tri (n-butyl) ammonium] nonaborate and bis [tri] (N-Butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl)]
Ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate, tri (n-butyl) ammonium-1-carbadecaborate, tri (n-butyl) ammonium-1-carbaundecaborate , Tri (n-butyl) ammonium-1-carbadodecaborate, tri (n-butyl) ammonium-1-trimethylsilyl-1-carbadecaborate, tri (n-butyl) ammonium bromo-1-carbadodecaborate, etc.

Examples of salts of borane compounds, carborane complex compounds and carborane anions include decaborane (1
4), 7,8-Dicarbaundecaborane (13), 2,7-Dicarbaundecaborane (13), Undecahydride-7,8-
Dimethyl-7,8-dicarbaundecaborane, dodecahydride-11-methyl-2,7-dicarbaundecaborane, tri (n-butyl) ammonium 6-carbadecaborate (1
4), tri (n-butyl) ammonium 6-carbadecaborate (12), tri (n-butyl) ammonium 7-carbaundecaborate (13), tri (n-butyl) ammonium
7,8-Dicarbaundecaborate (12), Tri (n-butyl) ammonium 2,9-Dicarbaundecaborate (1
2), tri (n-butyl) ammonium dodecahydride-8-methyl 7,9-dicarbaundecaborate, tri (n-
Butyl) ammonium undeca hydride 8-ethyl-
7,9-Dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7, 9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7- Carbaundecaborate etc. are mentioned.

Examples of the carborane compound or carborane salt include 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecaborane (14) and dodecahydride-1-phenyl. -1,3-dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane and the like can be mentioned.

Further, as the ionic compound containing a boron atom, the following metal carborane salts, metal borane anions and the like can be exemplified. (Note that the counter ion in the ionic compounds listed below is tri (n-butyl))
It is, but not limited to, ammonium. ) For example, tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (I
II), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) ferrate (ferrate) (III), tri (n-butyl) ammonium bis (undecahydride-7, 8-dicarbaundecaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) nickelate (III), tri (n-butyl) ammonium bis (un) Deca hydride-7,8-dicarbaundecaborate) cubrate (cuprate) (II
I), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) aurate (metal salt) (III), tri (n-butyl) ammonium bis (nonahydride-7,8- Dimethyl-7,8-dicarbaundecaborate) Ferrate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) chromate (chromate) ( III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarbaundecaborate) cobaltate (III), tri (n-butyl)
Ammonium bis (dodecahydride dicarbadodecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) nickelate (III), tris [tri (n-butyl) ammonium] bis ( Undecahydride-7-carbaundecaborate) Chromate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) manganate (I
V), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-cal Bounce Decaborate) Nickelate (IV) etc.

Furthermore, examples of the ionic compound containing a boron atom include the following compounds. Triphenylcarbenium tetrakis {(2,3,5,6-tetrafluoro-4-triisopropylsilyl) phenyl} borate, N, N-dimethylanilinium tetrakis {(2,3,5,
6-Tetrafluoro-4-triisopropylsilyl) phenyl} borate, triphenylcarbenium tetrakis {(2,3,5,6-tetrafluoro-4-dimethyl-t-butylsilyl) phenyl} borate, N, N-dimethyl Anilinium tetrakis {(2,3,5,6-tetrafluoro-4-dimethyl-t-butylsilyl) phenyl} borate, triphenylcarbenium bis (octafluorobiphenylene) borate,
N, N-dimethylanilinium bis (octafluorobiphenylene) borate, triphenylcarbenium bis (octafluoro-1,1'-spiro) biboronol, N, N-dimethylanilinium bis (octafluoro-1,1'- Spiro) viboronols and the like.

The above-mentioned ionized ionic compound is
Two or more kinds can be mixed and used. The olefin polymerization catalyst according to the present invention may further contain the following (C) organoaluminum compound in addition to the above components, if necessary.

The organoaluminum compound (C) optionally used in the present invention can be represented by, for example, the following general formula (IV). R ^a _n AlX _3-n ... (IV) (In the formula, R ^a is a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, and n is 1 to 1).
It is 3. In the above formula (IV), R ^a is a hydrocarbon group having 1 to 12 carbon atoms, such as an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, n-propyl group, isopropyl group, isobutyl group,
Examples include a pentyl group, a hexyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group and a tolyl group.

Specific examples of such an organoaluminum compound include the following compounds. Trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum,
Trioctylaluminum, trialkylaluminums such as tri-2-ethylhexylaluminum, alkenylaluminums such as isoprenylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dialkylaluminum halides such as dimethylaluminum bromide, methyl Alkyl aluminum sesquihalides such as aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide, methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, ethyl aluminum Alkylaluminum dihalides such as dibromide, diethyl aluminum hydride, alkyl aluminum hydride such as diisobutyl aluminum hydride.

As the organoaluminum compound (C), a compound represented by the following formula (V) can also be used. R ^a _n AlY _3-n (V) (In the formula, R ^a is the same as above, Y is an —OR ^b group,
OSiR ^c ₃ group, -OAlR ^d ₂ group, -NR ^e ₂ group, -S
iR ^f ₃ group or —N (R ^g ) AlR ^h ₂ group, n is 1 to 2, R ^b , R ^c , R ^d and R ^h are methyl group, ethyl group, isopropyl group, isobutyl group, A cyclohexyl group, a phenyl group, etc., R ^e is hydrogen, a methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group, etc., and R ^f and R ^g are a methyl group,
For example, an ethyl group. ) Specific examples of such an organoaluminum compound include the following compounds. (I) Compounds represented by R ^a _n Al (OR ^b ) _3-n , such as dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide and the like. (Ii) ^a compound represented by R ^a _n Al (OSiR ^c ₃ ) _3-n , such as (C ₂ H ₅ ) ₂ Al (OSi (C
_{H 3) 3), (iso} -C 4 H 9) 2 Al (OSi (C
_{H 3) 3), (iso} -C 4 H 9) 2 Al (OSi (C 2 H 5)
₃ ) etc. (Iii) ^a compound represented by R ^a _n Al (OAlR ^d ₂ ) _3-n , for example, (C ₂ H ₅ ) ₂ Al (OAl (C
₂ H ₅ ) ₂ ), (iso-C ₄ H ₉ ) ₂ Al (OAl (iso-C ₄ H
₉ ) ₂ ) etc. (Iv) ^a compound represented by R ^a _n Al (NR ^e ₂ ) _3-n ,
For example _{(CH 3) 2 Al (N} (C 2 H 5) 2), (C
₂ H ₅ ) ₂ Al (NH (CH ₃ )), (CH ₃ ) ₂ Al (N
H (C ₂ H ₅ )), (C ₂ H ₅ ) ₂ Al [N (Si (C
_{H 3) 3) 2],} (iso-C 4 H 9) 2 Al [N (Si (C
H ₃ ) ₃ ) ₂ ] etc. (V) A compound represented by R ^a _n Al (SiR ^f ₃ ) _3-n , for example, (iso-C ₄ H ₉ ) ₂ Al (Si (CH ₃ ) ₃ )
Such.

In the present invention, among these, R ^a ₃ A
l, R ^a _n Al (OR ^b ) _3-n , R ^a _n Al (OAl
A preferable example is an organoaluminum compound represented by R ^d ₂ ) _3-n , and a compound in which R ^a is an isoalkyl group and n = 2 is particularly preferable. These organoaluminum compounds may be used in combination of two or more.

In the olefin polymerization catalyst according to the present invention, at least one of the above-mentioned component (A-1), component (B-1), component (B-2) and component (C) is a particulate carrier. It may be a solid catalyst supported on.

The olefin polymerization catalyst is a fine particle carrier, the component (A-1), the component (B-1) (or the component (B-2)) and an olefin polymer produced by prepolymerization, if necessary. A prepolymerization catalyst composed of the component (C) may be used.

The fine particle carrier used for the solid catalyst and the prepolymerization catalyst is an inorganic or organic compound and has a particle size of 10 to 300 μm, preferably 20 to 200.
It is a solid in the form of granules or fine particles of μm.

Among these, porous oxide is used as the inorganic carrier.
Preferably, specifically, SiO₂, Al₂O₃, MgO, Z
rO₂, TiO₂, B₂O₃, CaO, ZnO, Ba
O, ThO₂Or a mixture thereof, such as Si
O₂-MgO, SiO₂-Al₂O₃ , SiO₂-TiO₂, S
iO₂-V₂O_Five, SiO₂-Cr₂O₃, SiO₂-TiO₂-
MgO etc. can be illustrated. Among these Si
O₂And Al₂O₃At least one selected from the group consisting of
Also, those having one kind of component as a main component are preferable.

The above inorganic oxide contains a small amount of Na ₂ C.
O 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
_It does not matter even if it contains a carbonate, sulfate, nitrate, or oxide component such as ₂ O.

The properties of such a fine-particle carrier differ depending on the type and manufacturing method, but the specific surface area is 50 to 1000.
m ² / g, preferably 100~700m ² / g,
The pore volume is preferably 0.3 to 2.5 cm ³ / g. The particulate carrier may be 100-100, if necessary.
It is used by firing at a temperature of 0 ° C, preferably 150 to 700 ° C.

Further, the fine particle carrier has a particle size of 1
A granular or fine particle solid of an organic compound having a particle size of 0 to 300 μm can be mentioned. As these organic compounds, ethylene, propylene, 1-butene, 4-methyl-1-
Examples thereof include a (co) polymer produced mainly from an α-olefin having 2 to 14 carbon atoms such as pentene, or a polymer produced from vinylcyclohexane or styrene as a main component.

FIG. 1 shows the steps for preparing the olefin polymerization catalyst according to the present invention. In the method for producing an olefin polymer according to the present invention, the transition metal compound (A-1), the organoaluminum oxy compound and / or the ionized ionic compound (B) as described above, and the organoaluminum compound (C In the presence of a catalyst for olefin polymerization formed from 1) and 2), the olefin is homopolymerized or two or more kinds of olefins are copolymerized.

As the olefin used in the present invention,
Ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-
Heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene,
Examples thereof include linear or branched α-olefins having 3 to 20 carbon atoms such as 1-octadecene.

Further, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5,8-dimethano-1,2,3,4,4
Also included are olefins having an aliphatic ring or an aromatic ring such as a, 5,8,8a-octahydronaphthalene, styrene and vinylcyclohexane.

In addition to olefins, butadiene, isoprene, 1,4-hexadiene, dicyclopentadiene,
5-ethylidene-2-norbornene, chain or cyclic dienes such as 7-methyl-1,6-octadiene, 6,10-dimethyl-1,5,
Chain or cyclic triene such as 9-undecatriene, 5,9-dimethyl-1,4,8-decatriene, 6,10,14-trimethyl
Copolymerization of various polyenes such as chain or cyclic tetraenes such as -1,5,9,13-pentadecateethraene and 5,9,13-trimethyl-1,4,8,12-tetradecatetraene It can also be done.

In the (co) polymerization of olefins, the transition metal compound (A-1) is usually converted into transition metal atoms per 1 liter of the polymerization volume and is usually about 0.00005 to 0.
It is used in an amount of 1 mmol, preferably about 0.0001 to 0.05 mmol.

The organoaluminum oxy compound (B-1) is
Aluminum atom is usually about 1 to 10,000 mol, preferably 10 to 5,0, relative to 1 mol of transition metal atom.
It is used in an amount such that it is 00 mol.

The ionizable ionic compound (B-2) is used in such an amount that the boron atom is usually about 0.5 to 20 mol, preferably 1 to 10 mol, based on 1 mol of the transition metal atom. Used.

Further, the organoaluminum compound (C) is
The organic aluminum oxy compound (B-1) is used, if necessary, in an amount of usually about 0-200 mol, preferably about 0-100 mol, relative to 1 mol of aluminum atom. Further, it is usually used in an amount such that it is 0 to 1000 mol, preferably about 0 to 500 mol, relative to 1 mol of boron in the ionized ionic compound (B-2).

The (co) polymerization of olefin can be carried out by any of liquid phase polymerization method such as suspension polymerization and solution polymerization, gas phase polymerization method or high pressure method. In the liquid phase polymerization method, propane, butane, pentane, hexane, heptane, octane, decane, dodecane, aliphatic hydrocarbons such as kerosene, cyclopentane, cyclohexane, alicyclic hydrocarbons such as methylcyclopentane, benzene, toluene, Inert hydrocarbon media such as aromatic hydrocarbons such as xylene, halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane can be used. Also, the olefin itself can be used as a solvent. These may be used in combination.

Polymerization temperature in (co) polymerization of olefins
Is usually -50 to 100 when carrying out the suspension polymerization method.
C, preferably in the range of 0-90C
When carrying out the solution polymerization method, usually 0 to 300 ° C.,
It is preferably in the range of 20 to 250 ° C.
When carrying out the gas phase polymerization method, the polymerization temperature is usually 0 to
120 ° C, preferably in the range of 20-100 ° C
Is desirable. Also, when carrying out the high pressure method, the polymerization temperature
Is usually 50 to 1000 ° C., preferably 100 to 500 ° C.
It is preferably in the range of. Polymerization pressure is usually atmospheric pressure
~ 100 kg / cm ², Preferably atmospheric pressure to 50 kg / c
m²In the case of the high pressure method under the conditions of
10,000 kg / cm², Preferably 500-5000
kg / cm²Is the condition. Polymerization reaction is batch type, semi-continuous
It can be performed by either continuous or continuous method.
It Furthermore, divide the copolymerization into two or more stages with different reaction conditions.
It is also possible to do so.

The molecular weight of the obtained olefin polymer can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature and the polymerization pressure. Since the present invention uses a transition metal compound (A-1) having a ligand having an indenyl group having a specific substituent at a specific position as a transition metal catalyst component, it does not have such a substituent. As compared with an olefin polymerization catalyst containing a transition metal compound as a catalyst component, an olefin (co) polymer having a large molecular weight and an olefin copolymer having a high comonomer content can be obtained.

The melt flow rate (MFR) of the first olefin polymer of the present invention obtained by the above production method is usually 0.01 to 200 g / 10 min, preferably 0.03 to 100 g / 10. Min, the intrinsic viscosity [η] is usually 0.5 to 6.0 dl / g, preferably 1.0 to 4.0 dl / g, and the density is usually 0.85 to 0. 95 g / cm ³ , preferably 0.86 to
It is in the range of 0.94 g / cm ³ .

The olefin polymer obtained by the above-mentioned production method is characterized by having a narrow molecular weight distribution and narrow composition distribution. In the present invention, the molecular weight distribution (Mw / Mn) is measured as follows using GPC-150C manufactured by Millipore.

The separation column was TSK GNH HT, the column size was 72 mm in diameter and 600 mm in length, the column temperature was 140 ° C., the mobile phase was o-dichlorobenzene (Wako Pure Chemical Industries) and an antioxidant. As BH
Using 0.025% by weight of T (Takeda Yakuhin), 1.0 ml /
The sample concentration is 0.1% by weight, the sample injection amount is 500 microliters, and a differential refractometer is used as a detector. Standard polystyrene has a molecular weight of Mw <1
000 and Mw> 4 × 10 ⁶ are manufactured by Tosoh Corporation, and 1000 <Mw <4 × 10 ⁶ are manufactured by Pressure Chemicals.

The first method for producing an olefin polymer according to the present invention is particularly preferably used for producing an ethylene polymer and a propylene polymer. In the case of producing an ethylene-based polymer, ethylene is homopolymerized in the presence of the olefin polymerization catalyst, or ethylene is copolymerized with an α-olefin having 3 to 20 carbon atoms.
In addition, in this specification, an ethylene-based polymer means an ethylene homopolymer and an ethylene / α-olefin copolymer.

The α-olefin having 3 to 20 carbon atoms has 2 to 2 carbon atoms other than ethylene.
0 α-olefins. Among these,
Propylene, 1-butene, 1-hexene, 1-octene and the like are preferably used.

Further, ethylene and the number of carbon atoms are 3 to 20.
The same polyenes as described above can be copolymerized with the α-olefin. The polymerization conditions for producing the ethylene polymer are the same as above.

The first ethylene polymer of the present invention obtained by the above method has an ethylene / α-olefin component ratio of usually 55/45 to 100/2, preferably 6
It is in the range of 0/40 to 100/5.

MFR is usually 0.01 to 200 g / 10
Min, preferably 0.03 to 100 g / 10 min, and the intrinsic viscosity [η] is usually 0.5 to 5.0 dl / g,
It is preferably in the range of 1.0 to 4.0 dl / g, and the density is usually in the range of 0.85 to 0.95 g / cm ³ , preferably 0.86 to 0.94 g / cm ³ .

In the case of producing a propylene-based polymer,
Propylene is homopolymerized in the presence of the olefin polymerization catalyst, or propylene and an α-olefin other than propylene are copolymerized. In the present specification, the propylene-based polymer means a propylene homopolymer and a propylene / α-olefin copolymer.

Examples of the α-olefin other than propylene include the α-olefins having 2 to 20 carbon atoms other than propylene. Among these, ethylene, 1-butene, 1-hexene, 1-octene and the like are preferably used.

In addition, propylene and α other than propylene
-It is also possible to copolymerize the same polyenes as described above with the olefin. The polymerization conditions for producing the propylene-based polymer are the same as above.

The first propylene-based polymer of the present invention obtained by the above method has a propylene / α-olefin component ratio of usually 55/45 to 100/2, preferably 60/40 to 100/5. Is the range.

MFR is usually 0.01 to 200 g / 10
Min, preferably 0.03 to 100 g / 10 min, and the intrinsic viscosity [η] is usually 0.5 to 6.0 dl / g,
It is preferably in the range of 1.0 to 4.0 dl / g, and the density is usually in the range of 0.85 to 0.95 g / cm ³ , preferably 0.86 to 0.94 g / cm ³ .

Of the propylene-based polymers, the propylene homopolymer usually has a value of mr / (mm + rr) of 0.7 in the diad distribution measured by ¹³ C-NMR.
˜1.3, preferably 0.8 to 1.2.

Here, the values of mr, mm and rr in the Dyad distribution measured by ¹³ C-NMR were determined as follows. That is, 50 to 70 mg of the sample is N
Completely in an MR sample tube (5 mmφ) in a solvent containing about 0.05 ml of hexachlorobutadiene, o-dichlorobenzene or 1,2,4-trichlorobenzene and about 0.05 ml of deuterated benzene as a lock solvent. After dissolving
It was measured at 120 ° C. by the complete proton decoupling method.
The measurement conditions are a flip angle of 45 ° and a pulse interval of 3.
4T ₁ or more (T ₁ is the longest value of the spin lattice relaxation time of the methyl group) is selected. Since T ₁ of methylene group and methine group is shorter than that of methyl group, the recovery of magnetization is 99% or more under this condition. The chemical shift was set to 21.59 ppm for the third methyl group in the propylene unit 5 chain having head-to-tail bonds and the same methyl branch direction.

In the spectrum of the methyl carbon region (19 to 23 ppm), the peak region is the first region (21.1 to 2).
1.9 ppm), second region (20.3 to 21.0 pp)
m) and the third region (19.5 to 20.3 ppm). Each peak in the spectrum is
lymer, 30 (1989) 1350).

In addition, mr, mm and rr are each a propylene unit 3 bonded by head-to-tail represented by the following formula.
Indicates a chain.

[0153]

[Chemical 14]

Further, the propylene-based polymer obtained by the above-mentioned production method is characterized by a narrow molecular weight distribution and narrow composition distribution. Next, the second method for producing an olefin polymer and the olefin polymer according to the present invention will be described.

A second method for producing an olefin polymer according to the present invention is (A-2) a transition metal compound of Group 4 of the periodic table represented by the following general formula (II), (B) (B- 1) an organoaluminum oxy compound, and / or (B-2) an olefin composed of a compound which reacts with the transition metal compound (A-2) to form an ion pair, and (C) an organoaluminum compound, if necessary. The olefin is homopolymerized or two or more kinds of olefins are copolymerized in the presence of a polymerization catalyst.

First, the olefin polymerization catalyst used in the present invention will be described. In the present invention, a transition metal compound represented by the following general formula (II) is used as the transition metal compound (A-2).

[0157]

[Chemical 15]

In the formula, M is a transition metal atom of Group 4 of the periodic table , specifically titanium, zirconium or hafnium, preferably zirconium. R
⁶ may be the same or different from each other, a hydrogen atom,
Halogen atom, alkyl group having 1 to 10 carbon atoms, aryl group having 6 to 10 carbon atoms, 2-1 carbon atom
0 is an alkenyl group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, and specifically, as the halogen atom and the alkyl group having 1 to 10 carbon atoms, the above-mentioned general Examples of R ¹ in the formula (I) include a silicon-containing group, an oxygen-containing group,
As the sulfur-containing group, the nitrogen-containing group and the phosphorus-containing group,
The same as R ² in the general formula (I) can be mentioned.

The aryl group having 6 to 10 carbon atoms includes phenyl, α- or β-naphthyl, and the alkenyl group having 2 to 10 carbon atoms includes vinyl, propenyl, cyclohexenyl and the like. Can be mentioned.

The above alkyl group and alkenyl group may be substituted with halogen. Of these, R ⁶ is preferably an alkyl group, an aryl group or a hydrogen atom, and particularly, a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl, n-propyl and i-propyl, phenyl, α- It is preferably an aryl group such as naphthyl or β-naphthyl or a hydrogen atom.

R ^7's may be the same as or different from each other, and each is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 2 to 2 carbon atoms. 10 alkenyl groups, 7 to 4 carbon atoms
An arylalkyl group having 0, an arylalkenyl group having 8 to 40 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group. Specific examples thereof include those similar to R ² in the general formula (I).

The above-mentioned alkyl group, aryl group, alkenyl group, arylalkyl group, arylalkenyl group and alkylaryl group may be substituted with halogen.

Of these, R ⁷ is preferably a hydrogen atom or an alkyl group, particularly a hydrogen atom or methyl, ethyl, n-propyl, i-propyl, n-butyl, tert.
-Butyl is preferably a hydrocarbon group having 1 to 4 carbon atoms.

Further, R ⁶ and R ⁷ may be the same or different from each other. One of R ⁸ and R ⁹ is an alkyl group having 1 to 5 carbon atoms, and the other is the same hydrogen atom, halogen atom, or 1 to 5 carbon atom as R ² in the general formula (I). 10 alkyl groups, alkenyl groups having 2 to 10 carbon atoms, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups or phosphorus-containing groups.

Examples of the alkyl group having 1 to 5 carbon atoms include methyl, ethyl, propyl, butyl, pentyl and the like. Of these, one of R ⁸ and R ⁹ is preferably an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl and propyl, and the other is preferably a hydrogen atom.

[0166] X ¹ and X ² may be the same or different from each other, X ¹ in the general formula (I) and X
² the same hydrogen atom, halogen atom, 1 to carbon atoms
20 hydrocarbon groups, halogenated hydrocarbon groups having 1 to 20 carbon atoms, oxygen-containing groups, sulfur-containing groups or nitrogen-containing groups, or conjugated diene residues formed from X ¹ and X ² .

Of these, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms is preferable. Y
Is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, or a divalent silicon-containing group similar to Y in the general formula (I). Base, 2
Valent germanium-containing group, divalent tin-containing group, -O-,
-CO -, - S -, - SO -, - SO 2 -, - NR
^{5 -, - P (R 5} ) -, - P (O) (R 5) -, - BR
⁵ -or -AlR ^5- [wherein R ⁵ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms].

Of these, Y is preferably a divalent hydrocarbon group having 1 to 5 carbon atoms, a divalent silicon-containing group or a divalent germanium-containing group, and preferably a divalent silicon-containing group. More preferably, alkylsilylene,
Particularly preferred is alkylarylsilylene or arylsilylene.

Specific examples of the transition metal compound represented by the above general formula (II) are shown below. Ethylene (2-methyl-1-
Indenyl) (9-fluorenyl) zirconium dichloride, dimethylsilylene (2-methyl-1-indenyl) (9-
Fluorenyl) zirconium dichloride, diphenylsilylene (2-methyl-1-indenyl) (9-fluorenyl)
Zirconium dichloride, methylphenylsilylene (2-
Methyl-1-indenyl) (9-fluorenyl) zirconium dichloride, ethylene (3-methyl-1-indenyl) (9
-Fluorenyl) zirconium dichloride, dimethylsilylene (3-methyl-1-indenyl) (9-fluorenyl)
Zirconium dichloride, diphenylsilylene (3-methyl-1-indenyl) (9-fluorenyl) zirconium dichloride, methylphenylsilylene (3-methyl-1-indenyl) (9-fluorenyl) zirconium dichloride,
Ethylene (2-methyl-1-indenyl) (2,7-di-tert-butyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (2-methyl-1-indenyl) (2,7-di-tert
-Butyl-9-fluorenyl) zirconium dichloride, diphenylsilylene (2-methyl-1-indenyl) (2,7-di-
tert-Butyl-9-fluorenyl) zirconium dichloride, methylphenylsilylene (2-methyl-1-indenyl) (2,7-di-tert-butyl-9-fluorenyl) zirconium dichloride, ethylene (2-methyl-4-phenyl) -1-Indenyl) (9-fluorenyl) zirconium dichloride, dimethylsilylene (2-methyl-4-phenyl-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylsilylene (2-methyl-4-phenyl-1-indenyl) ) (9-Fluorenyl) zirconium dichloride, methylphenylsilylene (2-methyl-4-phenyl-1-indenyl) (9-fluorenyl) zirconium dichloride, ethylene (2-methyl-4-phenyl-1-indenyl) (2, 7-the-t
ert-Butyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (2-methyl-4-phenyl-1-indenyl) (2,7-di-tert-butyl-9-fluorenyl) zirconium dichloride, diphenylsilylene (2-methyl) -Four-
Phenyl-1-indenyl) (2,7-di-tert-butyl-9-fluorenyl) zirconium dichloride, methylphenylsilylene (2-methyl-4-phenyl-1-indenyl) (2,7-di
-tert-butyl-9-fluorenyl) zirconium dichloride, ethylene (2-methyl-4-naphthyl-1-indenyl)
(9-Fluorenyl) zirconium dichloride, dimethylsilylene (2-methyl-4-naphthyl-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylsilylene (2-methyl-4-naphthyl-1-indenyl) (9-fluorenyl ) Zirconium dichloride, methylphenylsilylene (2-methyl-4-naphthyl-1-indenyl) (9-fluorenyl) zirconium dichloride, ethylene (2-methyl
-4-naphthyl-1-indenyl) (2,7-di-tert-butyl-9-
Fluorenyl) zirconium dichloride, dimethylsilylene (2-methyl-4-naphthyl-1-indenyl) (2,7-di-t
ert-Butyl-9-fluorenyl) zirconium dichloride, diphenylsilylene (2-methyl-4-naphthyl-1-indenyl) (2,7-di-tert-butyl-9-fluorenyl) zirconium dichloride, methylphenylsilylene (2- Methyl-4-naphthyl-1-indenyl) (2,7-di-tert-butyl-9
-Fluorenyl) zirconium dichloride etc.

Further, in the zirconium compound as described above, a compound in which zirconium is replaced by titanium or hafnium can be used. Two or more kinds of the above-mentioned (A-2) transition metal compounds can be used in combination.

Examples of the organoaluminum oxy compound (B-1) used in the present invention include those similar to the above organoaluminum oxy compound, which react with the transition metal compound (A-2) to form an ion pair. Examples of the compound (B-2) to be used include the same compounds as those that react with the transition metal compound (A-1) to form an ion pair.

As the organoaluminum compound (C) used as necessary, the same organoaluminum compounds as mentioned above can be mentioned. The olefin polymerization catalyst used in the second method for producing an olefin polymer according to the present invention is selected from the above-mentioned component (A-2), component (B-1), component (B-2) and component (C). It may be a solid catalyst in which at least one component is supported on a fine particle carrier.

Further, this olefin polymerization catalyst comprises a fine particle carrier, component (A-2), component (B-1) (or component (B-
It may be a prepolymerization catalyst comprising 2)) and an olefin polymer produced by the prepolymerization and, if necessary, the component (C).

Examples of the fine particle carrier used for the solid catalyst and the prepolymerization catalyst include the same as the above-mentioned fine particle carriers. FIG. 2 shows a process for preparing an olefin polymerization catalyst used in the second method for producing an olefin polymer according to the present invention.

In the second method for producing an olefin polymer according to the present invention, the transition metal compound (A-2), the organoaluminum oxy compound and / or the ionized ionic compound (B) as described above, and if necessary, In the presence of an olefin polymerization catalyst formed from the organoaluminum compound (C), the olefin is homopolymerized or two or more kinds of olefins are copolymerized.

As the olefin used in the present invention,
Examples thereof include the same chain or branched olefins and the olefins having an aliphatic ring or an aromatic ring used in the first method for producing an olefin polymer.

In addition to the olefin, polyenes similar to the polyene used in the method for producing the first olefin polymer may be copolymerized. When (co) polymerizing an olefin, the transition metal compound (A
-2) is generally used in an amount of about 0.00005 to 0.1 mmol, preferably about 0.0001 to 0.05 mmol, calculated as transition metal atoms, per liter of polymerization volume.

The organoaluminum oxy compound (B-1) is
Aluminum atom is usually about 1 to 10,000 mol, preferably 10 to 5,0, relative to 1 mol of transition metal atom.
It is used in an amount such that it is 00 mol.

The ionizable ionic compound (B-2) is used in such an amount that the boron atom is usually about 0.5 to 20 mol, preferably 1 to 10 mol, based on 1 mol of the transition metal atom. Used.

Further, the organoaluminum compound (C) is
The organic aluminum oxy compound (B-1) is used, if necessary, in an amount of usually about 0-200 mol, preferably about 0-100 mol, relative to 1 mol of aluminum atom. Further, it is usually used in an amount such that it is 0 to 1000 mol, preferably about 0 to 500 mol, relative to 1 mol of boron in the ionized ionic compound (B-2).

The (co) polymerization of olefin can be carried out by any of liquid phase polymerization method such as suspension polymerization and solution polymerization, gas phase polymerization method or high pressure method. In the liquid phase polymerization method, the first
The same as the inert hydrocarbon medium used in the method for producing an olefin polymer can be used as the polymerization medium. Also, the olefin itself can be used as a solvent. These may be used in combination.

The polymerization temperature in the (co) polymerization of olefins is usually -50 to 100 when carrying out the suspension polymerization method.
C, preferably in the range of 0 to 90 ° C., and when carrying out the solution polymerization method, usually 0 to 250 ° C.,
It is preferably in the range of 20 to 200 ° C., and when carrying out the gas phase polymerization method, the polymerization temperature is usually 0 to
It is desired to be in the range of 120 ° C, preferably 20 to 100 ° C. When carrying out the high pressure method, the polymerization temperature is usually 50 to 1000 ° C., preferably 100 to 500.
It is preferably in the range of ° C. The polymerization pressure is usually normal pressure to 100 kg / cm ² , preferably normal pressure to 50 kg / cm ² .
In the case of the high pressure method under the condition of cm ² , the polymerization pressure is
Usually, 100 to 10,000 kg / cm ² , preferably 5
The condition is from 00 to 5000 kg / cm ² . The polymerization reaction can be carried out by any of batch method, semi-continuous method and continuous method. It is also possible to carry out the copolymerization in two or more stages under different reaction conditions.

The molecular weight of the obtained olefin polymer can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature and the polymerization pressure. The present invention uses the (A-2) transition metal compound having an indenyl group having a specific substituent at a specific position as a ligand, as a transition metal catalyst component, and therefore, it does not have such a substituent. As compared with an olefin polymerization catalyst containing a transition metal compound as a catalyst component, an olefin (co) polymer having a large molecular weight and an olefin copolymer having a high comonomer content can be obtained.

The present invention obtained by the manufacturing method as described above
The light second olefin polymer has an MFR of usually 0.0.
1 to 200 g / 10 minutes, preferably 0.03 to 100 g /
It is in the range of 10 minutes, and the intrinsic viscosity [η] is usually 0.5 to
6.0 dl / g, preferably 1.0-4.0 dl / g
Range, density usually 0.85-0.95 g / cm
³, Preferably 0.86-0.94 g / cm³In the range of
is there.

The olefin polymer obtained by the above-mentioned production method is characterized by having a narrow molecular weight distribution and narrow composition distribution. The second method for producing an olefin polymer according to the present invention is particularly preferably used for producing an ethylene polymer and a propylene polymer.

In the case of producing an ethylene polymer, ethylene is homopolymerized in the presence of the olefin polymerization catalyst, or ethylene is copolymerized with an α-olefin having 3 to 20 carbon atoms.

Here, the α-olefin having 3 to 20 carbon atoms has 2 to 2 carbon atoms other than ethylene.
0 α-olefins. Among these,
Propylene, 1-butene, 1-hexene, 1-octene and the like are preferably used.

Further, ethylene and the number of carbon atoms are 3 to 20.
The same polyenes as described above can be copolymerized with the α-olefin. The polymerization conditions for producing the ethylene polymer are the same as above.

The second ethylene polymer of the present invention obtained by the above method has an ethylene / α-olefin component ratio of usually 55/45 to 100/2, preferably 6
It is in the range of 0/40 to 100/5.

MFR is usually 0.01 to 200 g / 10
Min, preferably 0.03 to 100 g / 10 min, and the intrinsic viscosity [η] is usually 0.5 to 5.0 dl / g,
It is preferably in the range of 1.0 to 4.0 dl / g, and the density is usually in the range of 0.85 to 0.95 g / cm ³ , preferably 0.86 to 0.94 g / cm ³ .

When a propylene-based polymer is produced,
Propylene is homopolymerized in the presence of the olefin polymerization catalyst, or propylene and an α-olefin other than propylene are copolymerized.

Examples of α-olefins other than propylene include α-olefins having 2 to 20 carbon atoms other than propylene. Among these, ethylene, 1-butene, 1-hexene, 1-octene and the like are preferably used.

In addition, propylene and α other than propylene
-It is also possible to copolymerize the same polyenes as described above with the olefin. The polymerization conditions for producing the propylene-based polymer are the same as above.

The second propylene polymer of the present invention obtained by the above method has a propylene / α-olefin component ratio of usually 55/45 to 100/2, preferably 60/40 to 100/5. Is the range.

MFR is usually 0.01 to 200 g / 10
Min, preferably 0.03 to 100 g / 10 min, and the intrinsic viscosity [η] is usually 0.5 to 6.0 dl / g,
It is preferably in the range of 1.0 to 4.0 dl / g, and the density is usually in the range of 0.85 to 0.95 g / cm ³ , preferably 0.86 to 0.94 g / cm ³ .

Of the propylene-based polymers, the propylene homopolymer usually has a value of mr / (mm + rr) of 0.7 in the diad distribution measured by ¹³ C-NMR.
˜1.3, preferably 0.8 to 1.2.

Further, the propylene-based polymer obtained by the above-mentioned production method is characterized by having a narrow molecular weight distribution and narrow composition distribution.

[0198]

INDUSTRIAL APPLICABILITY When the transition metal compound according to the present invention is used as a catalyst component for olefin polymerization, an olefin (co) polymer having a large molecular weight can be obtained, and the comonomer content can be reduced even when the comonomer content is small. A high olefin copolymer is obtained.

Since the olefin polymerization catalyst according to the present invention uses a specific transition metal compound as the olefin polymerization catalyst component, when an olefin (co) polymer having a large molecular weight is obtained and the comonomer usage ratio is small. Even in this case, an olefin copolymer having a high comonomer content can be obtained. Further, in the polymerization using polyene together with olefin, an olefin copolymer having a high polyene content can be obtained even when the proportion of polyene used is small.

Since the first method for producing an olefin polymer according to the present invention uses a specific transition metal compound as a catalyst component for olefin polymerization, an olefin (co) polymer having a large molecular weight can be obtained and a comonomer can be obtained. An olefin polymer having a high comonomer content can be obtained even when the usage ratio is low. Further, in the polymerization using a polyene together with an olefin, an olefin polymer having a high polyene content can be obtained even when the proportion of the polyene used is small.

The first olefin polymer according to the present invention is
The molecular weight distribution is narrow, and when the olefin polymer is a copolymer, the molecular weight distribution and the composition distribution are narrow. In the second method for producing an olefin polymer according to the present invention, since a specific transition metal compound is used as a catalyst component for olefin polymerization, an olefin (co) polymer having a large molecular weight is obtained, and the proportion of the comonomer used is Even when the content is small, an olefin polymer having a high comonomer content can be obtained. Further, in the polymerization using a polyene together with an olefin, an olefin polymer having a high polyene content can be obtained even when the proportion of the polyene used is small.

The second olefin polymer according to the present invention is
The molecular weight distribution is narrow, and when the olefin polymer is a copolymer, the molecular weight distribution and the composition distribution are narrow.

[0203]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples.

[0204]

[Production Example 1] [Synthesis of dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride] Reactor having an internal volume of 100 ml Then, 50 ml of diethyl ether and 5.57 g (20 mmol) of 2,7-di-t-butyl-9-fluorene were charged into the flask, and the mixture was cooled with ice.
Hexane solution of n-butyllithium (1.67 mmol /
(ml) 12.0 ml was added dropwise over 10 minutes, and the mixture was stirred at room temperature for 10 hours to obtain a mixed solution A.

40 ml of diethyl ether and 41.2 g of dimethyldichlorosilane were placed in a reactor having an internal volume of 200 ml.
(320 mmol), and then the above mixture A under ice cooling.
Was added dropwise over 1 hour, and the mixture was further stirred at room temperature for 1 hour. After diethyl ether and dimethyldichlorosilane were distilled off under reduced pressure, 100 ml of methylene chloride was added and stirred, and solids were removed using a glass filter. From the obtained methylene chloride solution, methylene chloride was distilled off under reduced pressure, the pressure was reduced with a vacuum pump, and the solvent was further distilled off to obtain an orange viscous oil.

50 ml of diethyl ether and 3.6 ml of 2-methyl-4,5-benzoindene were added to a reactor having an internal volume of 100 ml.
After adding 0 g (20 mmol), n-butyllithium hexane solution (1.67 mmol / ml) under ice-cooling 1
2.0 ml was added dropwise over 10 minutes, and the mixture was stirred at room temperature for another 13 hours to obtain a mixed solution B.

[0207] 40 ml of a diethyl ether solution of orange viscous oil obtained in the above reaction was placed in a reactor having an internal volume of 200 ml, and then the mixed solution B was added dropwise under ice cooling for 30 minutes, and then at room temperature. It was stirred for another day. The obtained reaction solution was poured into a saturated aqueous solution of ammonium chloride, the ether layer was washed with water, and dried over anhydrous magnesium sulfate. After concentrating the ether layer, it was separated and purified by silica gel column chromatography (developing solution; n-hexane) to give the desired product [dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7 -Di-t-butyl-9-fluorene)] 4.0 g (yield; 40%) was obtained as a slightly yellow amorphous solid.

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (δ value, CDCl ₃ , 90 MHz) -0.4 (s, 3H), -0.3 (d, J = 3.6H)
z, 3H), 1.23 to 1.60 (m, 18H), 2.
29-2.40 (br.s, 3H), 3.80-3.9
4 (m, 1H), 4.17 to 4.31 (m, 1H),
7.29-8.34 (m, 13H).

In a reactor having an inner volume of 100 ml, 50 ml of diethyl ether and dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-
Fluorene) (1.50 g, 3.2 mmol) was added thereto, and then n-butyllithium hexane solution (1.6
(7 mmol / ml) (3.8 ml) was added dropwise over 10 minutes, and the reaction was further continued at room temperature for 1 hour and under reflux for 30 minutes.
The obtained dark yellow slurry solution was cooled to −60 ° C., and 0.75 g (3.2 mmol) of zirconium tetrachloride was added little by little. The temperature was raised naturally to room temperature, and the mixture was further stirred at room temperature for 12 hours.

The solid formed was filtered through a glass filter. After 10 ml of diethyl ether was added to the obtained solid to wash it, it was filtered under reduced pressure. The obtained solid was washed with 40 ml of methylene chloride, filtered through a glass filter, and the solid precipitated by concentrating the methylene chloride solution was separated with a glass filter to obtain the desired product [dimethylsilylene (2-methyl-4,5- Benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride] 0.
84 g were obtained as an orange powder.

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (δ value, CDCl ₃ , 90 MHz) 1.26 (s, 9H), 1.35 (s, 9H), 1.4
4 (s, 3H), 1.54 (s, 3H), 2.37
(S, 3H), 7.01 to 8.02 (m, 13H).

[0212]

[Production Example 2] [Synthesis of dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (9-fluorenyl) zirconium dichloride] In a reactor having an internal volume of 100 ml, 50 ml of diethyl ether and 3.32 g of fluorene. After charging (20 mmol), 12.0 ml of a hexane solution of n-butyllithium (1.67 mmol / ml) was added dropwise over 10 minutes under ice cooling, and the mixture was stirred at room temperature for another 10 hours to prepare a mixed solution C. Got

40 ml of diethyl ether and 41.2 g of dimethyldichlorosilane were placed in a reactor having an internal volume of 200 ml.
(320 mmol), and then the mixture C under ice cooling.
Was added dropwise over 1 hour, and the mixture was further stirred at room temperature for 1 hour. After diethyl ether and dimethyldichlorosilane were distilled off under reduced pressure, 100 ml of methylene chloride was added and stirred, and solids were removed using a glass filter. From the obtained methylene chloride solution, methylene chloride was distilled off under reduced pressure, the pressure was reduced with a vacuum pump, and the solvent was further distilled off to obtain an orange viscous oil.

In a reactor having an internal volume of 100 ml, 50 ml of diethyl ether and 3.8 of 2-methyl-4,5-benzoindene were added.
After adding 9 g (20 mmol), n-butyllithium hexane solution (1.67 mmol / ml) under ice-cooling 1
2.0 ml was added dropwise over 10 minutes, and the mixture was stirred at room temperature for another 13 hours to obtain a mixed solution D.

40 ml of a viscous oily diethyl ether solution obtained in the above reaction was placed in a reactor having an internal volume of 200 ml, and the mixed solution D was added dropwise to the mixture under ice cooling for 30 minutes. It was stirred for another day. The obtained reaction solution was poured into a saturated aqueous solution of ammonium chloride, the ether layer was washed with water, and dried over anhydrous magnesium sulfate. After concentrating the ether layer, it was separated and purified by silica gel column chromatography (developing solution; n-hexane) to obtain the desired product [dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (9-fluorene). )] 3.88 g (yield; 48%) was obtained as a pale yellow amorphous solid.

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (δ value, CDCl ₃ , 90 MHz) -0.4 (s, 3H), -0.3 (d, J = 3.6H)
z, 3H), 2.29 to 2.40 (br.s, 3H),
3.94 (br.s, 1H), 4.26 (br.s, 1
H), 7.09 to 8.31 (m, 15H) 50 mL of diethyl ether was added to a reactor having an internal volume of 100 ml.
ml, 1.30 g of dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (9-fluorene) obtained above
(3.2 mmol), and then n-butyllithium hexane solution (1.67 mmol / ml) 3.8 under ice cooling.
ml dropwise over 10 minutes, at room temperature for 1 hour, under reflux at 30
The reaction was continued for another minute. The resulting dark yellow slurry solution was cooled to -60 ° C and zirconium tetrachloride 0.75g
(3.2 mmol) was added in small portions. The temperature was raised naturally to room temperature, and the mixture was further stirred at room temperature for 12 hours.

The solid formed was filtered through a glass filter. After 10 ml of diethyl ether was added to the obtained solid to wash it, it was filtered under reduced pressure. The obtained solid was washed with 40 ml of methylene chloride, filtered through a glass filter, and the solid precipitated by concentrating the methylene chloride solution was separated with a glass filter to obtain the desired product [dimethylsilylene (2-methyl-4,5- 0.96 g of benzo-1-indenyl) (9-fluorenyl) zirconium dichloride] was obtained as an orange powder.

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (δ value, CDCl ₃ , 90 MHz) 1.44 (s, 3H), 1.54 (s, 3H), 2.3
7 (s, 3H), 6.99 to 8.00 (m, 15H)

[0219]

[Production Example 3] [Synthesis of dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride] The internal volume was 100 ml. After charging 50 ml of diethyl ether and 5.57 g (20 mmol) of 2,7-di-t-butyl-9-fluorene into the reactor, n-butyllithium solution in hexane (1.67 mmol) was cooled under ice cooling. / Ml) 12.0 ml was added dropwise over 10 minutes, and the mixture was stirred at room temperature for 10 hours to obtain a mixed solution E.

40 ml of diethyl ether and 41.2 g of dimethyldichlorosilane were placed in a reactor having an internal volume of 200 ml.
(320 mmol), and then the above mixture E under ice cooling.
Was added dropwise over 1 hour, and the mixture was further stirred at room temperature for 1 hour. After diethyl ether and dimethyldichlorosilane were distilled off under reduced pressure, 100 ml of methylene chloride was added and stirred, and solids were removed using a glass filter. From the obtained methylene chloride solution, methylene chloride was distilled off under reduced pressure, the pressure was reduced with a vacuum pump, and the solvent was further distilled off to obtain an orange viscous oil.

50 ml of diethyl ether and 3.88 g (20 mmol) of 2,6-dimethyl-4,5-benzoindene were placed in a reactor having an internal volume of 100 ml, and then n-butyllithium was dissolved in hexane under ice cooling. (1.67 mmol / m
l) Add 12.0 ml dropwise over 10 minutes and add 1 more at room temperature.
After stirring for 3 hours, a mixed solution F was obtained.

40 ml of the orange viscous oil diethyl ether solution obtained in the above reaction was placed in a reactor having an internal volume of 200 ml, and the mixture F was added dropwise under ice cooling for 30 minutes, and the mixture was stirred at room temperature. It was stirred for another day. The obtained reaction solution was poured into a saturated aqueous solution of ammonium chloride, the ether layer was washed with water, and dried over anhydrous magnesium sulfate. After concentrating the ether layer, it was separated and purified by silica gel column chromatography (developing solution; n-hexane) to give the desired product [dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2 , 7-Di-t-butyl-9-fluorene)] 4.8 g
(Yield: 45%) was obtained as a slightly yellow amorphous solid.

In a reactor having an internal volume of 100 ml, 50 ml of diethyl ether and the dimethylsilylene (2,6-
After adding 1.69 g (3.2 mmol) of dimethyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorene), n-butyllithium was added under ice cooling. 3.8 ml of a hexane solution (1.67 mmol / ml) was added dropwise over 10 minutes, and the reaction was further continued at room temperature for 1 hour and under reflux for 30 minutes. The resulting dark yellow slurry solution was cooled to -60 ° C and 0.75 g (3.2 mmol) zirconium tetrachloride was added.
Was added little by little. The temperature was raised naturally to room temperature, and the mixture was further stirred at room temperature for 12 hours.

The solid formed was filtered through a glass filter. After 10 ml of diethyl ether was added to the obtained solid to wash it, it was filtered under reduced pressure. The obtained solid was washed with 40 ml of methylene chloride, filtered through a glass filter, and the solid precipitated by concentrating the methylene chloride solution was separated with a glass filter to obtain the desired product [dimethylsilylene (2,6-dimethyl-4, 5-benzo-1-indenyl) (2,7-di-t
-Butyl-9-fluorenyl) zirconium dichloride]
1.02 g was obtained as an orange powder.

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (δ value, CDCl ₃ , 90 MHz) 1.24 (s, 9H), 1.35 (s, 9H), 1.4
3 (s, 3H), 1.56 (s, 3H), 2.36
(S, 3H), 2.50 (s, 3H), 7.01-8.
02 (m, 12H)

[0226]

[Production Example 4] [Synthesis of dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride] ] Internal volume is 100
ml reactor, 50 ml of diethyl ether, 2,7-di-t
After charging 5.57 g (20 mmol) of -butyl-9-fluorene, 12.0 ml of a hexane solution of n-butyllithium (1.67 mmol / ml) was added dropwise over 10 minutes under ice-cooling at room temperature. After further stirring for 10 hours, a mixed solution G was obtained.

40 ml of diethyl ether and 41.2 g of dimethyldichlorosilane were placed in a reactor having an internal volume of 200 ml.
(320 mmol), and then the mixture G under ice cooling.
Was added dropwise over 1 hour, and the mixture was further stirred at room temperature for 1 hour. After diethyl ether and dimethyldichlorosilane were distilled off under reduced pressure, 100 ml of methylene chloride was added and stirred, and solids were removed using a glass filter. From the obtained methylene chloride solution, methylene chloride was distilled off under reduced pressure, the pressure was reduced with a vacuum pump, and the solvent was further distilled off to obtain an orange viscous oil.

50 ml of diethyl ether and 4.16 g (20 mmol) of 2,7-dimethyl-4,5- (2-methyl-benzo) indene were placed in a reactor having an internal volume of 100 ml.
Under ice-cooling, 12.0 ml of a hexane solution of n-butyllithium (1.67 mmol / ml) was added dropwise over 10 minutes, and the mixture was further stirred for 13 hours at room temperature to obtain a mixed solution H.

40 ml of a diethyl ether solution of the orange viscous oil obtained in the above reaction was placed in a reactor having an inner volume of 200 ml, and the mixed solution H was added dropwise to the mixture under ice cooling for 30 minutes. It was stirred for another day. The obtained reaction solution was poured into a saturated aqueous solution of ammonium chloride, the ether layer was washed with water, and dried over anhydrous magnesium sulfate. After concentrating the ether layer, it was separated and purified by silica gel column chromatography (developing solution; n-hexane) to give the desired product [dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo)-]. 5.2 g (yield; 48%) of 1-indenyl) (2,7-di-t-butyl-9-fluorene)] was obtained as a slightly yellow amorphous solid.

In a reactor having an internal volume of 100 ml, 50 ml of diethyl ether and the dimethylsilylene (2,7-
Dimethyl-4,5- (2-methyl-benzo) -1-indenyl)
(2,7-di-t-butyl-9-fluorene) 1.73 g (3.2
(3 mmol), and then 3.8 ml of hexane solution of n-butyllithium (1.67 mmol / ml) under ice cooling.
The mixture was added dropwise over 0 minutes, and the reaction was further continued at room temperature for 1 hour and under reflux for 30 minutes. The obtained dark yellow slurry solution was -6
It was cooled to 0 ° C. and 0.75 g (3.2
(Mmol) was added in small portions. The temperature was raised naturally to room temperature, and the mixture was further stirred at room temperature for 12 hours.

The solid formed was filtered through a glass filter. After 10 ml of diethyl ether was added to the obtained solid to wash it, it was filtered under reduced pressure. The solid obtained was washed with 40 ml of methylene chloride, filtered through a glass filter, and the solid precipitated by concentrating the methylene chloride solution was separated with a glass filter to obtain the desired product [dimethylsilylene (2,7-dimethyl-4, 0.94 g of 5- (2-methyl-benzo) -1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride] was obtained as an orange powder.

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (δ value, CDCl ₃ , 90 MHz) 0.69 (s, 9H), 1.36 (s, 9H), 1.5
6 (s, 3H), 1.69 (s, 3H), 2.24
(S, 3H), 2.47 (s, 3H), 2.57 (s,
3H), 6.71 to 8.40 (m, 11H)

[0233]

[Production Example 5] [Synthesis of dimethylsilylene ( 2-n-propyl-4- (9-phenanthryl) -1-indenyl) (9-fluorenyl) zirconium dichloride] Synthesis of dimethyl (9-fluorenyl) silane chloride A four-necked flask was equipped with a reflux tube, a thermometer, and a dropping funnel, and was thoroughly purged with nitrogen and dried. To this, fluorene (5.00 g, 30 mmol) and dehydrated ether (100 ml) were added, and a hexane solution of n-butyllithium (30 mmol) was added dropwise over 30 minutes while stirring at -10 ° C. After dripping, slowly warm up to room temperature,
Stir at room temperature for 4 hours. The reaction liquid became a yellow slurry. This was added dropwise to a dichlorodimethylsilane (18.24 ml, 150 mmol) / dehydrated ether (100 ml) solution with stirring at -10 ° C over 1 hour, and the mixture was naturally heated and then stirred overnight. Add the solution to a glass filter (G-
By pressure filtration in 5) to remove lithium chloride, the solvent in the filtrate and unreacted dichlorodimethylsilane are removed under reduced pressure, reslurry in dehydrated hexane (100 ml) and pressurized with a glass filter (G-5). Filtration gave a white powder (3.30 g, 43% yield).

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (CDCl ₃ ); 7.2-8.0 (m, 8
H), 4.1 (s, 1H), 0.15 (s, 6H) dimethyl (2-n-propyl-4- (9-phenanthryl) -1-i
Synthesis of Ndenyl) (9-fluorenyl) silane A 200 ml four-necked flask was equipped with a reflux tube, a thermometer, and a dropping funnel, and was thoroughly purged with nitrogen and dried. 2-n-
Propyl-4- (9-phenanthryl) indene (1.60
g, 4.78 mmol) and dehydrated ether (20 ml) were added, and a hexane solution of n-butyllithium (5.02 mmol) was added dropwise with stirring at -40 ° C. After the dropping, this was slowly warmed to room temperature naturally. After stirring at room temperature for 7 hours, the white slurry changed to a yellow slurry and a brown slurry, and then changed to a yellow slurry. Dehydrated ether (30m
l) was added, and the mixture was stirred at 0 ° C. and dimethyl (9-fluorenyl) silane chloride (1.24 g,
5.02 mmol) was added, and the mixture was stirred at room temperature overnight. The reaction liquid became a yellow slurry. Then, N-methyl-2-pyrrolidone (0.1 g) was added, and the mixture was further stirred for 3 hours, and then changed into an orange solution. This is ether (100m
l) and saturated aqueous ammonium chloride solution (100 ml) were added, and the mixture was transferred to a separatory funnel and the organic layer was separated, washed with saturated aqueous ammonium chloride solution, water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was removed (yellow oil) and purification by column chromatography (solvent: hexane) gave a white oil. When this was depressurized with a vacuum pump, it foamed and solidified, and a white powder (2.02 g, yield 76
%) Was obtained.

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (CDCl ₃ , 90 MHz); 7.0-9.
0 (m, 20H), 6.2 (d, 1H), 4.3 (d,
1H), 3.9 (br, 1H), 2.1 to 2.5 (t,
2H), 1.0 to 1.6 (br, 2H), 0.6 to 1.
0 (t, 3H), -0.2 to -0.4 (d, 6H) dimethylsilylene (2-n-propyl-4- (9-phenanthriline)
) -1-Indenyl) (9-fluorenyl) zirconium
Synthesis of dichloride A Schlenk bottle of 50 ml was equipped with a dropping funnel, and was thoroughly purged with nitrogen and dried. Dimethyl (2-n-propyl-4- (9-phenanthryl) -1-indenyl) (9-fluorenyl) silane synthesized above (0.80 g, 1.44
mmol) and dehydrated ether (20 ml), and-78
With stirring at ℃, n-butyllithium in hexane (3.0
2 mmol) was added dropwise. After the dropping, this was slowly warmed to room temperature naturally. When the mixture was stirred at room temperature for 8 hours, the yellow solution became a yellow-colored slurry and then a brown slurry. This was again stirred at −78 ° C. to obtain zirconium tetrachloride (0.33
5 g, 1.44 mmol) was added, and after dropwise addition, the temperature was slowly raised to room temperature. After stirring overnight at room temperature, a red slurry resulted. The mixture was filtered under pressure with a glass filter (G-5) to remove ether, and the residue was quickly washed with dehydrated dichloromethane (the residue was lithium chloride). The solvent of the filtrate thus obtained was removed and reslurried with dehydrated hexane (25 ml) to obtain a glass filter (G-
5), and the target metallocene is red powder (39
7 mg, yield 39%).

[0236]

[Production Example 6] [Synthesis of ethylene (9-fluorenyl) (2-methyl-1-indenyl) zirconium dichloride] Reflux tube, thermometer,
2-Methylindene (4.5 g, 34.6 mmol) and dehydrated ether (50 ml) were placed in a 200 ml four-necked flask equipped with a dropping funnel, and a solution of n-butyllithium in hexane (1.61 mol / 1.61 mol / Liter, 23.7
(ml, 38.1 mmol) was added dropwise over 1 hour, and the temperature was naturally raised to room temperature over 6 hours. The reaction became a yellow-orange slurry.

Next, in a 500 ml four-necked flask equipped with a reflux tube, a thermometer and a dropping funnel, 1,2-dibromoethane (3
2.5 g, 0.173 mol), dehydrated ether (100
ml) was added, and the whole amount of the above reaction product was added with a pipette at 0 ° C. over 1 hour, followed by stirring at room temperature for 15 hours. The obtained yellow transparent solution was poured into 300 ml of water to separate an ether layer, and the water layer was extracted with ether (100 ml × 3), and the organic layers were combined and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained yellow-brown oil was purified by column chromatography (300 g of silica gel, developed with hexane) to obtain the desired product as a yellow-white transparent liquid [3- (2-bromoethyl) -2.
-Methylindene] was obtained 6.25 g (yield 76%).

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (CDCl ₃ , 90 MHz) 1.8 to 2.6 (m, 2H), 1.93 (s, 3H),
2.8 to 3.2 (m, 2H), 3.3 (br, 1H),
6.32 (s, 1H), 6.6-7.4 (m, 4H).

300 equipped with reflux tube, thermometer, dropping funnel
Fluorene (2.11 g, 1
2.7 mmol) and dehydrated ether (60 ml),
Hexane solution of n-butyllithium (1.61mo
1 / liter, 8.7 ml, 14.0 mmol) was added dropwise over 1 hour and then refluxed for 2 hours. The reaction became dark red transparent. This was cooled to -78 ° C (yellow slurry) and 3- (2-bromoethyl) -2-methylindene (3
What melt | dissolved g, 12.7 mmol) in dehydrated ether (20 ml) was dripped over 1 hour, Then, it heated up to room temperature naturally and stirred for 15 hours. The reaction gradually became a yellow slurry.

The reaction product was poured into a saturated aqueous solution of ammonium chloride (300 ml) to separate an ether layer. The aqueous layer was extracted with ether (100 ml × 3), and the organic layers were combined and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained white-yellow powder was reslurried with hexane (200 ml) and filtered to obtain the desired product of white powder [1- (9-fluorenyl) -2- (2-methyl-1-indenyl) ethane. ] To 2.
50 g was obtained (61% yield).

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (CDCl ₃ , 90 MHz) 1.3 to 1.9 (m, 4H), 1.92 (s, 3H),
3.12 (br, 1H), 3.88 (br, 1H),
6.48 (s, 1H), 7.0-7.9 (m, 12
H).

300 equipped with reflux tube, thermometer, dropping funnel
1- (9-fluorenyl) -2- (2-
Methyl-1-indenyl) ethane (1.0 g, 3.10 m
mol) and dehydrated ether (100 ml), and-78
Hexane solution of n-butyllithium at 1.6 ° C (1.61 mol
/ Liter, 4.04 ml, 6.51 mmol) 30
The mixture was added dropwise over a period of 5 minutes, and the temperature was naturally raised to 0 ° C over 5 hours, and the mixture was stirred at 0 ° C for 3 hours. The reaction product became a yellow slurry.

The reaction was then cooled to -78 ° C and zirconium tetrachloride (0.760g, 3.26mmol) was added over 15 minutes. After that, the temperature rises naturally to room temperature,
It was stirred for 12 hours. Obtained reaction product (orange yellow slurry)
Was filtered through a glass filter (G-5), and the residue was washed with dehydrated ether (100 ml). The orange solid remaining on the filter was washed with dehydrated dichloromethane (300 ml), filtered, and the solvent in the filtrate was evaporated to give a red orange solid (1.
20 g) was obtained. This solid was washed with dehydrated dichloromethane (100 ml) and filtered to give a reddish orange powder of the target product [ethylene (9-fluorenyl) (2-methyl-1-
Indenyl) zirconium dichloride] is 0.650
g was obtained (yield 43%).

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (CDCl ₃ , 90 MHz) 2.20 (s, 3H), 3.8 to 4.4 (m, 4H),
6.24 (s, 1H), 6.9 to 8.0 (m, 12)
H).

[0245]

Production Example 7 [Dimethylsilylene (9-fluorenyl) (2-methyl-1-
Synthesis of indenyl) zirconium dichloride] A reactor having an inner volume of 100 ml was charged with 20 ml of diethyl ether and 3.3 g (20 mmol) of fluorene, and then n-butyllithium hexane solution (1.61 mmol) was added under ice cooling. / Ml) 12.4 ml was added dropwise over 10 minutes and the mixture was stirred at room temperature for 10 hours to obtain a mixed solution I.

40 ml of diethyl ether and 41.2 g of dimethyldichlorosilane were placed in a reactor having an internal volume of 200 ml.
(320 mmol), and then the mixture I under ice cooling.
Was added dropwise over 1 hour, and the mixture was further stirred at room temperature for 1 hour. After diethyl ether and dimethyldichlorosilane were distilled off under reduced pressure, 100 ml of methylene chloride was added and stirred, and solids were removed using a glass filter. From the resulting methylene chloride solution, methylene chloride was distilled off under reduced pressure, the pressure was reduced with a vacuum pump, and the solvent was further distilled off to obtain 5.0 g of an orange oil.

In a reactor having an internal volume of 100 ml, 40 ml of diethyl ether and 2.18 g of 2-methylindene (16.
(8 mmol), and then n-butyllithium hexane solution (1.61 mmol / ml) 10.4 ml under ice cooling.
Was added dropwise over 10 minutes, and the mixture was stirred at room temperature for another 13 hours to obtain a mixed solution J.

40 ml of a diethyl ether solution containing 5.0 g of the orange oil obtained in the above reaction was placed in a reactor having an inner volume of 200 ml, and then the mixture J was mixed with 1.5 parts of the mixture under ice cooling.
The mixture was added dropwise over time, and the mixture was stirred at room temperature for another day. The obtained reaction solution was poured into a saturated aqueous solution of ammonium chloride, the ether layer was washed with water, and dried over anhydrous magnesium sulfate. After concentrating the ether layer, it was separated and purified by silica gel column chromatography (developing solution; n-hexane) to obtain the desired product [dimethylsilylene (9-fluorenyl) (2-methyl
-1-Indene)] 2.65 g (yield; 45%) was obtained as a white powder.

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (CDCl ₃ , 90 MHz) -4.3 (d, 6H), 2.2 (s, 3H), 3.7.
(S, 1H), 4.2 (s, 1H), 6.7 (s, 1
H), 7.0-8.0 (m, 12H).

In a reactor having an internal volume of 100 ml, 50 ml of diethyl ether and 1.35 g of dimethylsilylene (9-fluorenyl) (2-methyl-1-indene) obtained above.
(3.8 mmol), and then n-butyllithium hexane solution (1.60 mmol / ml) under ice cooling 4.8
ml was added dropwise over 10 minutes, and the reaction was further continued at room temperature for 1 hour and under reflux for 2 hours. The resulting yellow slurry solution was cooled to -60 ° C and 0.90 g of zirconium tetrachloride was added.
(3.8 mmol) was added in small portions. The temperature was raised naturally to room temperature, and the mixture was further stirred at room temperature for 12 hours.

After further refluxing with ether for 1 hour, the produced solid was filtered through a glass filter. The obtained solid was washed with 30 ml of diethyl ether, and the diethyl ether solution was filtered under reduced pressure. The obtained solid was washed with 100 ml of n-hexane and then filtered through a glass filter to give 1.58 g of the desired product [dimethylsilylene (9-fluorenyl) (2-methyl-1-indenyl) zirconium dichloride] in a brick color. Obtained as a powder.

[0252]

Production Example 8 [Diphenylsilylene (9-fluorenyl) (2-methyl-1
-Synthesis of indenyl) zirconium dichloride] In a reactor having an internal volume of 100 ml, 30 ml of diethyl ether,
After charging 3.3 g (20 mmol) of fluorene, 12.4 ml of a hexane solution of n-butyllithium (1.61 mmol / ml) was added dropwise over 10 minutes under ice cooling, and the mixture was further stirred at room temperature for 10 hours. . The obtained reaction solution was concentrated and solidified under reduced pressure, and the pressure was reduced with a vacuum pump and dried to obtain a yellow lithium salt.

In a reactor having an internal volume of 200 ml, 150 ml of n-hexane and 6.6 g (26 g of diphenyldichlorosilane) were added.
Mmol), and the lithium salt was added under ice cooling,
After the temperature was raised to room temperature, stirring was continued for 12 hours. The generated solid is removed using a glass filter,
The obtained filtrate was concentrated. The precipitated solid was filtered with a glass filter to obtain 4.51 g (yield: 59%) of the target product [9- (chlorodiphenylsilyl) fluorene] as a white powder.

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (CDCl ₃ , 90 MHz) 4.58 (s, 1H), 7.0 to 7.90 (m, 18)
H).

40 mL of diethyl ether and 1.53 g of 2-methylindene (11.
(7 mmol), 7.3 ml of a hexane solution of n-butyllithium (1.61 mmol / ml) was added dropwise over 10 minutes under ice cooling, and the mixture was stirred at room temperature for 10 hours to obtain a mixed solution K. It was

50 ml of diethyl ether, 4.51 g (11.8 mmol) of 9- (chlorodiphenylsilyl) fluorene and 144 mg (1.2 mmol) of copper thiocyanate were placed in a reactor having an internal volume of 200 ml, and then cooled with ice. The mixed solution K was added dropwise under 1 hour, and the mixture was further reacted at room temperature for 15 hours. After the reaction was completed, the precipitated solid was removed with a glass filter. The obtained filtrate is concentrated and solidified, and reslurry washed with 30 ml of diethyl ether to obtain the desired product [diphenylsilylene (9-fluorenyl) (2-methyl
-1-Indene)] 2.10 g (yield; 37%) was obtained as a white powder.

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (CDCl ₃ , 90 MHz) 1.98 (s, 3H), 4.42 (s, 1H), 4.9
6 (s, 1H), 6.20 (s, 1H), 6.60 ~
8.40 (m, 22H).

In a reactor having an internal volume of 100 ml, 50 ml of diethyl ether and the diphenylsilylene (9-
Fluorenyl) (2-methyl-1-indene) 1.50 g
(3.15 mmol) and then n-butyllithium hexane solution (1.60 mmol / ml) under ice cooling.
9 ml was added dropwise over 10 minutes, and the mixture was refluxed for 1 hour at room temperature under reflux for 2 hours.
The reaction was continued for a further hour. The resulting yellow slurry solution was cooled to -60 ° C and 0.73 g of zirconium tetrachloride was added.
(3.15 mmol) was added in small portions. The temperature was raised naturally to room temperature, and the mixture was further stirred at room temperature for 12 hours.

After further refluxing with ether for 1 hour, the produced solid was filtered through a glass filter. The obtained solid was washed with 30 ml of diethyl ether, and the diethyl ether solution was filtered under reduced pressure. The solid obtained was washed with 100 ml of n-hexane and then filtered through a glass filter to give 1.80 g of the desired product [diphenylsilylene (9-fluorenyl) (2-methyl-1-indenyl) zirconium dichloride] in orange color. Obtained as a powder.

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (CDCl ₃ , 90 MHz) 2.12 (s, 3 H), 6.70 to 8.40 (m, 13
H).

[0261]

[Production Example 9] [Synthesis of ethylene (9-fluorenyl) (1-indenyl) zirconium dichloride] A 300 ml four-necked flask equipped with a reflux tube, a thermometer and a dropping funnel was charged with an indene (10
g, 86.1 mmol), dehydrated ether (100 ml)
, And a hexane solution of n-butyllithium (1.61 mol / liter, 59 ml, 94.7 mm) at -78 ° C.
ol) was added dropwise over 30 minutes, and then the temperature was naturally raised to room temperature over 3 hours. The reaction became orange and transparent.

Next, in a 1-liter four-necked flask equipped with a reflux tube, a thermometer and a dropping funnel, 1,2-dibromoethane (8
1 g, 0.431 mol), dehydrated ether (150 m
1) was added, the whole amount of the above reaction product was added dropwise at 0 ° C. over 2 hours, and then the mixture was stirred at room temperature for 15 hours. The obtained yellow transparent solution was poured into 300 ml of water to separate an ether layer, and the water layer was extracted with ether (100 ml × 3), and the organic layers were combined and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained yellowish brown oil was purified by column chromatography (silica gel 500 g, developed with hexane) to obtain 16.36 g of the target compound [3- (2-bromoethyl) indene] as a light green yellow transparent liquid. (Yield 85%).

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (CDCl ₃ , 90 MHz) 1.8 to 2.6 (m, 2H), 3.40 (t, J = 1.
9Hz, 2H), 3.5 to 3.8 (m, 1H), 6.4
8 (d, J = 1.6 Hz, 1H), 6.83 (d, J =
1.6 Hz, 1H), 7.1-7.6 (m, 4H).

300 equipped with reflux tube, thermometer, dropping funnel
Fluorene (3.72 g, 2
2.4 mmol) and dehydrated ether (100 ml) were added, and a solution of n-butyllithium in hexane (1.61) was added at 0 ° C.
mol / liter, 15.3 ml, 24.6 mmol)
Was added dropwise over 1 hour and then refluxed for 2 hours. The reaction became dark red transparent. This was cooled to −78 ° C. (yellow slurry) and 3- (2-bromoethyl) indene (5 g, 2
What melt | dissolved 2.4 mmol) in dehydrated ether (50 ml) was dripped over 1 hour, Then, it heated naturally to room temperature and stirred for 15 hours. The reaction product gradually became an orange-yellow transparent homogeneous solution. This was poured into a saturated aqueous solution of ammonium chloride (200 ml) to separate the ether layer, and the aqueous layer was extracted with ether (100 ml × 3), and the organic layers were combined and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained white-yellow semisolid was purified by column chromatography (400 g of silica gel, developed with hexane) to give the desired product of white powder [1- (9-fluorenyl) -2- (1-indenyl) ethylene. ] Was obtained (yield 49%).

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (CDCl ₃ , 90 MHz) 1.1 to 2.6 (m, 4H), 3.35 (br, 1
H), 3.97 (br, 1H), 6.48 (d, J =
1.6 Hz, 1 H), 6.83 (d, J = 1.6 Hz,
1H), 7.1-8.0 (m, 12H) FD-MS 308 (M ⁺ ) In a 100 ml four-necked flask equipped with a reflux tube, thermometer and dropping funnel, 1- (9-fluorenyl) -2. -(1-Indenyl)
Ethylene (1.0 g, 3.24 mmol) and dehydrated ether (50 ml) were added, and a solution of n-butyllithium in hexane (1.61 mol / liter, 4.2 m) was added at -78 ° C.
1, 6.80 mmol) were added dropwise over 1 hour, the temperature was naturally raised over 5 hours, and the mixture was further refluxed for 1 hour. The reaction became an orange-yellow slurry.

The reaction was then cooled to -78 ° C and zirconium tetrachloride (0.792g, 3.40mmol) was added over 15 minutes. After that, the temperature rises naturally to room temperature,
It was stirred for 12 hours. Obtained reaction product (orange yellow slurry)
Was filtered through a glass filter (G-5), and the residue was washed with dehydrated ether (50 ml). The orange solid remaining on the filter was washed with dehydrated dichloromethane (150 ml),
After filtration and evaporation of the solvent of the filtrate, a red-orange solid (1.29
g) was obtained. This solid was dehydrated with hexane (100 m
When it was reslurried with l) and filtered, 0.924 g of the target product [ethylene (9-fluorenyl) (1-indenyl) zirconium dichloride] as a reddish orange powder was obtained (yield 61%).

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (CDCl ₃ , 90 MHz) 3.7 to 4.4 (m, 4H), 6.20 (d, J = 0.
8 Hz, 1 H), 6.35 (d, J = 0.8 Hz, 1
H), 6.9-8.1 (m, 12H).

[0268]

Production Example 10 [Dimethylsilylene (9-fluorenyl) (2-methyl-4-
Synthesis of phenyl-1-indenyl) zirconium dichloride] A 100 ml four-necked flask equipped with a reflux tube, a thermometer, and a dropping funnel was sufficiently replaced with nitrogen to dry it. 2-Methyl-4-phenylindene (1.50 g, 7.%) produced by the method described in JP-A-6-100579.
27 mmol), dehydrated diethyl ether (40 m
l) was added, and n-butyllithium n-
A hexane solution (7.63 mmol) was added dropwise. After the dropping, the solution was slowly warmed to room temperature and then stirred at room temperature overnight. As a result, the slurry concentration became high and stirring became impossible. The dehydrated diethyl ether (1
0 ml), and then with stirring at 0 ° C., 1.88 of dimethylsilylfluorenylmonochloride synthesized in Preparation Example 6 was added.
g (7.27 mmol) was added and stirred at room temperature for 12 hours to obtain a yellow slurry. Diethyl ether (100 ml) and saturated ammonium chloride aqueous solution (100 ml) were added to this yellow slurry, the mixture was transferred to a separatory funnel and the organic phase was separated, and the organic phase was washed with a saturated ammonium chloride aqueous solution, water and saturated saline in this order. It was dried over magnesium sulfate. The solvent was removed and column chromatography (solvent:
n-hexane) to obtain 1.75 g (yield: 56%) of pale yellow powder.

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (CDCl ₃ , 90 MHz) -0.35 (d, 6H), 2.2 (s, 3H), 3.8
(T, 1H), 4.2 (s, 1H), 6.8 (s, 2
H), 6.9-7.9 (m, 16H).

A 50 ml reactor equipped with a dropping funnel was thoroughly purged with nitrogen and dried. Dimethylsilylene (9-fluorenyl) (2-methyl, 4-phenyl-1-indene) (0.80 g, 1.87 mmol) synthesized above,
Add dehydrated diethyl ether (20 ml) at -78 ° C.
n-Butyllithium n-hexane solution (3.93mmo
l) was added dropwise. After the dropping, the temperature of this solution was slowly raised to room temperature. Next, after stirring for 12 hours at room temperature, 0 ° C
Zirconium tetrachloride (0.435 g, 1.8
7 mmol) was added dropwise, and after the addition, the temperature was slowly raised to room temperature. Then, after stirring at room temperature for 8 hours, the obtained red slurry was filtered through a glass filter, and the obtained solid was quickly washed with dry dichloromethane. After removing the solvent of the obtained filtrate and reslurrying with 40 ml of dehydrated hexane, it was filtered with a glass filter to obtain the target compound 56.
0 mg was obtained as a red powder (yield: 51%).

[0271]

Production Example 11 [Synthesis of ethylene (2,7-di-t-butyl-9-fluorenyl) (2-methyl-1-indenyl) zirconium dichloride] 2,7-di-t-butyl-9-fluorene Synthesis In a 100 ml four-necked flask equipped with a reflux tube, a thermometer and a dropping funnel, fluorene (3.4 g, 20.5 mmo) was added.
l), 2,6-di-t-butyl-p-cresol (4.4 g, 2
0.0 mmol) and nitromethane (30 ml),
With stirring in a water bath (10 ° C), anhydrous aluminum chloride (4
A solution obtained by dissolving g) in nitromethane (6 ml) was added dropwise (dropping time 1 hour, the reaction solution gradually became a purple hetero state). After stirring for 3 hours, the reaction solution was put in 300 ml of ice water, transferred to a separatory funnel, the organic layer was separated, and then the aqueous layer was extracted with ether (200 ml × 3) to combine the organic layers. Using an evaporator and an oil pump, the ether and nitromethane were completely distilled off, and the residue was converted to ether (20
0 ml) and dissolve in 10% aqueous sodium hydroxide solution (1
After washing with 50 ml × 3), it was dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained white-yellow powder was recrystallized from methanol to give white-yellow needle-shaped crystals (3.5
g, yield 63%).

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (CDCl ₃ , 90 MHz); 1.38
(S, 18H), 3.86 (s, 2H), 7.2-7.
Synthesis of 8 (m, 6H) 3- (2-bromoethyl) -2-methylindene In a 200 ml four-necked flask equipped with a reflux tube, a thermometer and a dropping funnel, 2-methylindene (4.5 g, 34.6 mm).
ol) and dehydrated ether (50 ml) at -78 ° C.
A hexane solution of n-butyllithium (1.61 mol / liter, 23.7 ml, 38.1 mmol) was added dropwise over 1 hour, and then naturally warmed to room temperature over 6 hours. The reaction became a yellow-orange slurry.

Next, in a 500 ml four-necked flask equipped with a reflux tube, a thermometer and a dropping funnel, 1,2-dibromoethane (3
2.5 g, 0.173 mol), dehydrated ether (100
ml), and the total amount of the anion slurry prepared above is set to 0.
The mixture was added at 1 ° C over 1 hour, and then stirred at room temperature for 15 hours. Transfer the obtained yellow transparent solution to 300 ml of water,
The ether layer was separated, and the aqueous layer was extracted with ether (100 ml).
X3) and the organic layers were combined and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained yellowish brown oil was purified by column chromatography (solvent: hexane) to obtain the desired product (6.25 g, yield 76%) as a yellowish white transparent liquid.

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (CDCl ₃ , 90 MHz); 1.8-2.
6 (m, 2H), 1.93 (s, 3H), 2.8-3.
2 (m, 2H), 3.3 (br, 1H), 6.32
(S, 1H), 6.6 to 7.4 (m, 4H) 1- (2,7-di-t-butyl-9-fluorenyl) -2- (2-methyl-
Synthesis of 1-indenyl) ethylene In a 100 ml four-necked flask equipped with a reflux tube, a thermometer and a dropping funnel, 2,7-di-t-butylfluorene (1.18 g,
4.22 mmol) and dehydrated ether (30 ml) were added, and n-butyllithium hexane solution (1.67) was added at 0 ° C.
(mol / liter, 2.8 ml, 4.64 mmol) was added dropwise over 1 hour, and then the mixture was stirred at room temperature for 7 hours. The reaction product became reddish orange and transparent. This was cooled to −78 ° C. (yellow-orange slurry), and 3- (2-bromoethyl) -2-methylindene (1 g, 4.22 mmol) dissolved in dehydrated ether (10 ml) was added dropwise over 30 minutes. ,
Then, the temperature was raised naturally to room temperature and the mixture was stirred for 15 hours. The reaction was gradually a yellow slurry. This was transferred to a saturated aqueous solution of ammonium chloride (200 ml), the ether layer was separated, the aqueous layer was extracted with ether (100 ml × 2), and the organic layers were combined and dried over anhydrous magnesium sulfate.
The solvent was distilled off, and the obtained white-yellow powder was mixed with hexane (1
(00 ml) and reslurried, and filtered to obtain the desired product as a white powder (1.70 g, yield 93%).

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (CDCl ₃ , 90 MHz); 1.3-1.
9 (m, 4H), 1.40 (s, 18H), 1.91
(Br, 3H), 3.08 (br, 1H), 3.85
(Br, 1H), 6.48 (br, 1H), 7.0
7.9 (m, 10H) ethylene (2,7-di-t-butyl-9-fluorenyl) (2-methyl
Synthesis of ru-1-indenyl) zirconium dichloride In a 300 ml four-necked flask equipped with a reflux tube, a thermometer and a dropping funnel, 1- (2,7-di-t-butyl-9-fluorenyl) -2-
(2-Methyl-1-indenyl) ethylene (0.5 g, 1.
15 mmol) and dehydrated ether (50 ml),
Hexane solution of n-butyllithium (1.67m
(ol / liter, 1.45 ml, 2.42 mmol) was added dropwise over 30 minutes, and the temperature was naturally raised to room temperature over 15 hours. The reaction became an orange-yellow slurry.

The reaction was then cooled to -78 ° C and zirconium tetrachloride (0.282g, 1.21mmol) was added over 15 minutes. After that, the temperature rises naturally to room temperature,
It was stirred for 12 hours. Obtained reaction product (orange yellow slurry)
Was filtered under pressure with a glass filter (G-5), and the residue was washed with dehydrated ether (20 ml × 2). The solvent of the filtrate was distilled off with an oil pump to obtain a red-orange solid, and this solid was washed with dehydrated hexane (10 ml × 2) to obtain a red-orange powder target product (0.300 g, yield 44%). It was

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (CDCl ₃ , 90 MHz): 1.2 to 1.
4 (m, 18H), 2.20 (s, 3H), 3.6-
4.2 (m, 4H), 6.10 (s, 1H), 6.8-
7.8 (m, 10H)

[0278]

[Production Example 12] [Synthesis of dimethylsilylene (3-methyl-1-indenyl) (9-fluorenyl) zirconium dichloride] Synthesis of dimethyl (9-fluorenyl) silane chloride In a 1-liter four-necked flask, a reflux tube and a thermometer , Equipped with a dropping funnel, thoroughly replaced with nitrogen and dried. To this, fluorene (5.00 g, 30 mmol) and dehydrated ether (100 ml) were added, and a hexane solution of n-butyllithium (30 mmol) was added dropwise over 30 minutes while stirring at -10 ° C. After dripping, slowly warm up to room temperature,
Stir at room temperature for 4 hours. The reaction liquid became a yellow slurry. This was added dropwise to a dichlorodimethylsilane (18.24 ml, 150 mmol) / dehydrated ether (100 ml) solution with stirring at -10 ° C over 1 hour, and the mixture was naturally heated and then stirred overnight. Add the solution to a glass filter (G-
By pressure filtration in 5) to remove lithium chloride, the solvent in the filtrate and unreacted dichlorodimethylsilane are removed under reduced pressure, reslurry in dehydrated hexane (100 ml) and pressurized with a glass filter (G-5). Filtration gave a white powder (3.30 g, 43% yield).

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (CDCl ₃ ); 7.2-8.0 (m, 8
H), 4.1 (s, 1H), 0.15 (s, 6H) dimethyl (1-indenyl) (9-fluorenyl) silane
A 200 ml four-necked flask equipped with a reflux tube, a thermometer and a dropping funnel was thoroughly replaced with nitrogen and dried. Indene (3.00 g, 25.8 mmol) and dehydrated ether (40 ml) were added to this, and a hexane solution of n-butyllithium (25.8 mmol) was added dropwise with stirring at 0 ° C. After the dropping, this was slowly warmed to room temperature naturally. 2 at room temperature
Stir for hours. The reaction solution became an orange solution. 0 again
Dimethyl (9-fluorenyl) silane chloride (6.69 g, 25.8 mmo) synthesized above under stirring at ℃.
l) was added, and after dropwise addition, the temperature was slowly raised to room temperature. After stirring at room temperature for 2 hours, a yellow slurry resulted. Ether (100 ml) and saturated aqueous ammonium chloride solution (100 ml) were added to this, the mixture was transferred to a separatory funnel and the organic layer was separated. The aqueous layer was extracted with ether (100 ml x 3) and the organic layers were combined and saturated brine was added. It was washed and dried over anhydrous magnesium sulfate. The solvent was removed and the residue was purified by column chromatography (solvent: hexane) to give a white powder (4.70).
g, yield 54%).

NMR spectrum data of the obtained compound
Is shown below.¹ H-NMR (CDCl₃); 7.2-8.0 (m, 12
H), 6.9 (m, 1H), 6.3 (dd, 1H),
4.1 (s, 1H), 3.6 (t, 1H), -0.2
(S, 3H), -0.4 (s, 3H)Dimethyl (3-methyl-1-indenyl) (9-fluoreni
Le) Synthesis of silane A 200 ml four-necked flask is equipped with a reflux tube, thermometer, and dripping leakage.
The flask was equipped with a dovetail and thoroughly replaced with nitrogen to dry. Above this
Dimethyl (1-indenyl) (9-fluorenyl synthesized in
) Silane (2.00 g, 5.91 mmol), dehydrated
Add ether (50 ml) and stir at -40 ℃ under n-butyl
Add hexane solution of rulithium (6.21 mmol)
did. After dropping, slowly warm it to room temperature.
It was A yellow solution resulted after stirring overnight. This again
Methyl iodide (3.78 g, 26.
6 mmol) was added, and after dropwise addition, the solution was slowly cooled to room temperature.
The temperature rose. It was stirred at room temperature for one day. The reaction solution is orange
It became liquid. Ether (100 ml), saturated ammonium chloride
Aqueous nickel solution (100 ml) was added and transferred to a separatory funnel.
Separate the machine layer, wash with water and saturated saline solution, and dry with anhydrous magnesium sulfate.
Dried with sium. Remove the solvent and perform column chromatography.
Purified with Raffy (solvent: hexane), two isomers
(One is a colorless transparent liquid, the other is a yellow liquid) (total
1.85 g, yield 89%) was obtained.

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (CDCl ₃ ); 2 isomers (A: B = 4:
1) Isomer A 7.2-8.0 (m, 12H), 6.5 (d, 1H),
4.1 (s, 1H), 3.6 (dd, 1H), 1.2
(D, 3H), 0.1 (d, 6H), isomer B 7.2-8.0 (m, 12H), 6.1 (d, 1H),
4.0 (s, 1H), 3.6 (dd, 1H), 2.1
(S, 3H), -0.3 (d, 6H) dimethylsilylene (3-methyl-1-indenyl) (9-fur
Synthesis of oleenyl) zirconium dichloride A Schlenk bottle of 50 ml was equipped with a dropping funnel, and was thoroughly replaced with nitrogen and dried. Dimethyl (3-methyl-1-indenyl) (9-fluorenyl) silane (0.80 g, 2.27 mmol) synthesized above and dehydrated ether (2
(0 ml) was added, and a hexane solution of n-butyllithium (4.76 mmol) was added dropwise with stirring at -78 ° C. After the dropping, this was slowly warmed to room temperature naturally. After stirring overnight, the yellow solution became a red solution. Again -78
Zirconium tetrachloride (0.53 g, 2.2
7 mmol) was added, and after dropwise addition, the temperature was slowly raised to room temperature. Stir overnight at room temperature. The reaction liquid became a red slurry. The mixture was filtered under pressure with a glass filter (G-5) to remove ether, and the residue was quickly washed with dehydrated dichloromethane (the residue was lithium chloride). The solvent of the filtrate thus obtained was removed and reslurried with dehydrated hexane (25 ml) to obtain a glass filter (G-
The target metallocene was obtained as an orange powder (330 mg, yield 28%) by pressure filtration in 5).

[0282]

Production Example 13 [Ethylene (2-methyl-4-phenyl-1-indenyl) (9-
Synthesis of Fluorenyl) zirconium dichloride] of 3- (2-bromomethyl) -2-methyl-7-phenylindene
A 200 ml four-necked flask equipped with a reflux tube, a thermometer and a dropping funnel was thoroughly replaced with nitrogen and dried. To this, 2-
Methyl-4-phenylindene (2.50 g, 12.12)
mmol) and dehydrated ether (50 ml) were added, and n-butyllithium hexane solution (12.73) was stirred at 0 ° C.
(mmol) was added dropwise over 30 minutes. After the dropping, the temperature was slowly raised to room temperature and the mixture was stirred at room temperature for 4 hours. The reaction solution was a yellow slurry. This was added dropwise to a dibromoethane (5.22 ml, 60.6 mmol) / dehydrated ether (20 ml) solution with stirring at 0 ° C. over 1 hour, the temperature was naturally raised, and the mixture was stirred overnight at room temperature. The reaction solution was a yellow solution. This was added with ether (100 ml) and saturated aqueous ammonium chloride solution (100 ml), transferred to a separatory funnel and the organic layer was separated, washed with saturated aqueous ammonium chloride solution, water and saturated brine, and dried over anhydrous magnesium sulfate. The yellow oil obtained by removing the solvent was purified by column chromatography (solvent: hexane) to obtain a pale yellow oil (3.00 g, yield 79%).

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (CDCl ₃ , 90 MHz); 2.0-2.
8 (m, 2H), 2.1 (s, 3H), 3.0 to 3.8.
(M, 2H), 3.5 (br, 1H), 6.7 (s, 1
H), 7.1-7.8 (m, 8H) 1- (9-fluorenyl) -2- (2-methyl-4-phenyl-1-y)
Synthesis of Ndenyl) ethylene A 200 ml four-necked flask was equipped with a reflux tube, a thermometer, and a dropping funnel, and was thoroughly purged with nitrogen and dried. To this, fluorene (1.29 g, 7.76 mmol) and dehydrated ether (25 ml) were added, and a hexane solution of n-butyllithium (8.15 mmol) was added dropwise over 30 minutes while stirring at 0 ° C. After the dropping, the temperature was slowly raised to room temperature and the mixture was stirred at room temperature for 1.5 hours. The reaction solution became a brown slurry. Then, under stirring at 0 ° C, 3- (2-bromomethyl)
-2-Methyl-7-phenylindene (2.42 g, 7.73)
(mmol) / dehydrated ether (40 ml) solution was added dropwise over 1 hour, the temperature was raised naturally, and the mixture was stirred overnight at room temperature, and the reddish purple solution became a dark orange solution. This is ether (100
ml) and saturated aqueous ammonium chloride solution (100 ml) were added, the mixture was transferred to a separatory funnel and the organic layer was separated, washed with saturated aqueous ammonium chloride solution, water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was removed and purification by column chromatography (solvent: hexane) gave an orange oil. When this was depressurized with a vacuum pump, it foamed and solidified to obtain a pale orange powder (1.10 g, yield 36%).

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (CDCl ₃ , 90 MHz); 1.3-1.
9 (m, 4H), 1.91 (br, 3H), 3.08
(Br, 1H), 3.85 (br, 1H), 6.48
(Br, 1H), 7.0-7.9 (m, 10H) ethylene (2-methyl-4-phenyl-1-indenyl) (9-phenyl)
Synthesis of louenyl) zirconium dichloride A Schlenk bottle of 50 ml was equipped with a dropping funnel, and was thoroughly replaced with nitrogen and dried. 1- (9-fluorenyl) -2- (2-methyl-4-phenyl-1-indenyl) synthesized above
Ethylene (0.50 g, 1.25 mmol) and dehydrated ether (20 ml) were added, and a hexane solution of n-butyllithium (2.63 mmol) was added dropwise with stirring at -78 ° C. After the dropping, this was slowly warmed to room temperature naturally.
Upon stirring overnight at room temperature, the yellow-orange solution changed to a brown solution and became a brown-orange slurry via a dark-orange slurry. Again-
With stirring at 78 ° C., zirconium tetrachloride (0.307 g,
1.31 mmol) was added, and after dropwise addition, the temperature was slowly raised to room temperature. When stirred overnight at room temperature, the ocher slurry became an orange slurry. Glass filter (G-
In 5), the mixture was filtered under pressure to remove ether, and the residue was quickly washed with dehydrated dichloromethane (the residue was lithium chloride). The solvent of the filtrate obtained in this manner was removed, reslurried with dehydrated hexane (30 ml) and filtered with a glass filter (G-5) to obtain the target metallocene as a red-orange powder (320 mg, yield 46%). .

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (CDCl ₃ , 90 MHz); 2.20
(S, 3H), 3.6 to 4.2 (m, 4H), 6.10
(S, 1H), 6.8 to 8.0 (m, 16H)

[0286]

Production Example 14 [Dimethylsilylene (2-methyl-4-i-propyl-7-methyl
Synthesis of 1-indenyl) (9-fluorenyl) zirconium dichloride] Synthesis of dimethyl (9-fluorenyl) silane chloride A 1-liter four-necked flask was equipped with a reflux tube, a thermometer, and a dropping funnel, and was sufficiently replaced with nitrogen. Dried. To this, fluorene (5.00 g, 30 mmol) and dehydrated ether (100 ml) were added, and a hexane solution of n-butyllithium (30 mmol) was added dropwise over 30 minutes while stirring at -10 ° C. After dripping, slowly warm up to room temperature,
Stir at room temperature for 4 hours. The reaction liquid became a yellow slurry. This was added dropwise to a dichlorodimethylsilane (18.24 ml, 150 mmol) / dehydrated ether (100 ml) solution with stirring at -10 ° C over 1 hour, and the mixture was naturally heated and then stirred overnight. Add the solution to a glass filter (G-
By pressure filtration in 5) to remove lithium chloride, the solvent in the filtrate and unreacted dichlorodimethylsilane were removed under reduced pressure, and reslurried with dehydrated hexane (100 ml),
Pressure filtration was performed with a glass filter (G-5) to obtain a white powder (3.30 g, yield 43%).

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (CDCl ₃ ); 7.2-8.0 (m, 8
H), 4.1 (s, 1H), 0.15 (s, 6H) dimethyl (2-methyl-4-i-propyl-7-methyl-1-indene)
Synthesis of (nyl) (9-fluorenyl) silane A 100 ml four-necked flask was equipped with a reflux tube, a thermometer, and a dropping funnel, and was thoroughly purged with nitrogen and dried. 2-methyl-4-i-propyl-7-methylindene (1.50 g,
8.06 mmol) and dehydrated ether (25 ml) were added, and a hexane solution of n-butyllithium (8.46 mmol) was added dropwise with stirring at -78 ° C. After the dropping, this was slowly warmed to room temperature naturally. Upon stirring at room temperature overnight, the colorless solution became a white slurry, then a light yellow slurry, and then a yellow slurry. The reaction solution was stirred at 0 ° C., the dimethyl (9-fluorenyl) silane chloride (2.06 g, 8.06 mmol) synthesized above was added, and the mixture was stirred at room temperature for 1.5 hours. This is ether (100 ml),
A saturated ammonium chloride aqueous solution (100 ml) was added, the mixture was transferred to a separatory funnel and the organic layer was separated, washed with a saturated ammonium chloride aqueous solution, water and saturated saline, and dried over anhydrous magnesium sulfate. The yellow oil obtained by removing the solvent was purified by column chromatography (solvent: hexane) to obtain a yellow oil (1.50 g, yield 46%).

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (CDCl ₃ , 90 MHz); 6.6 to 8.
0 (m, 11H), 4.2 (s, 1H), 3.7 (s,
1H), 2.65 to 3.05 (m, 1H), 2.45
(S, 3H), 2.25 (s, 3H), 1.1 to 1.3
(D, 6H), -0.35 (d, 6H) dimethylsilylene (2-methyl-4-i-propyl-7-methyl-1)
-Indenyl) (9-fluorenyl) zirconium dichloride
Synthesis of Lido A Schlenk bottle of 50 ml was equipped with a dropping funnel, and was thoroughly purged with nitrogen and dried. Dimethyl (2-methyl-4-i-propyl-7-methyl-1-indenyl) (9
-Fluorenyl) silane (0.80 g, 1.96 mmo
l) and dehydrated ether (20 ml) were added, and the mixture was stirred at −78 ° C. to prepare a hexane solution of n-butyllithium (4.11 mm).
ol) was added dropwise. After the dropping, this was slowly warmed to room temperature naturally. When stirred overnight, the lemon yellow solution passed through a bright yellow solution to a reddish brown solution. Zirconium tetrachloride (0.456 g, 1.96 mm) under stirring at -78 ° C.
ol) was added, and after the addition, the temperature was slowly raised to room temperature. Stir at room temperature for 8 hours. The reaction liquid became a red slurry. The mixture was filtered under pressure with a glass filter (G-5) to remove ether, and the residue was quickly washed with dehydrated dichloromethane (the residue was lithium chloride). The solvent of the filtrate thus obtained was removed, and dehydrated hexane (30 m
l) was reslurried and filtered through a glass filter (G-4) to obtain the desired metallocene as a red powder (50 mg, yield 4%).

[0289]

Production Example 15 [Dimethylsilylene (2,3-dimethyl-1-indenyl) (9
-Synthesis of fluorenyl) zirconium dichloride] Synthesis of dimethyl (9-fluorenyl) silane chloride A 1-liter four-necked flask was equipped with a reflux tube, a thermometer, and a dropping funnel, and was thoroughly purged with nitrogen and dried. To this, fluorene (5.00 g, 30 mmol) and dehydrated ether (100 ml) were added, and a hexane solution of n-butyllithium (30 mmol) was added dropwise over 30 minutes while stirring at -10 ° C. After dripping, slowly warm up to room temperature,
Stir at room temperature for 4 hours. The reaction liquid became a yellow slurry. This was added dropwise to a dichlorodimethylsilane (18.24 ml, 150 mmol) / dehydrated ether (100 ml) solution with stirring at -10 ° C over 1 hour, and the mixture was naturally heated and then stirred overnight. Add the solution to a glass filter (G-
By pressure filtration in 5) to remove lithium chloride, the solvent in the filtrate and unreacted dichlorodimethylsilane were removed under reduced pressure, and reslurried with dehydrated hexane (100 ml),
Pressure filtration was performed with a glass filter (G-5) to obtain a white powder (3.30 g, yield 43%).

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (CDCl ₃ ); 7.2-8.0 (m, 8
H), 4.1 (s, 1H), 0.15 (s, 6H) 1,2-Dimethylindene synthesis 200 ml four-necked flask equipped with a reflux tube, thermometer and dropping funnel, and sufficiently replaced with nitrogen. And dried. Methylmagnesium bromide (3.0 mol / liter ether solution) (16.9 ml, 50.7 mmol) and dehydrated ether (50 ml) were added to this, and 2-methyl-1-indanone (3.70 g, 25 .3 mmol) /
Dehydrated ether (20 ml) was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 2 hours, transferred to ice water, transferred to a separating funnel, and the organic layer was separated. The water layer is ether (100 m
The mixture was extracted with 1 × 3) and the organic layers were combined, washed with a saturated aqueous solution of ammonium chloride, water and saturated saline, and dried over anhydrous magnesium sulfate. Remove the solvent to remove 1,2-dimethyl-1-
Hydroxy-indene was obtained. 30 ml of this
The solution was dissolved in water, 0.1 g of p-toluenesulfonic acid was added, and water was refluxed for 3 hours. Transfer the organic layer to a separatory funnel, wash with saturated aqueous ammonium solution, water, and saturated saline,
It was dried over anhydrous magnesium sulfate. Remove the solvent,
Purification by column chromatography (solvent: hexane) gave a pale yellow solution (2.70 g (GC94%), yield 74
%) Was obtained.

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (CDCl ₃ ); 7.1 to 7.6 (m, 4
H), 3.2 (s, 2H), 2.0 (s, 6H) dimethyl (2,3-dimethyl-1-indenyl) (9-fluorene
Synthesis of Nyl) silane A 200 ml four-necked flask was equipped with a reflux tube, a thermometer, and a dropping funnel, and was thoroughly purged with nitrogen and dried. 1,2-Dimethylindene (1.60 g, 1
1.09 mmol) and dehydrated ether (40 ml) were added, and a hexane solution of n-butyllithium (11.6 mmol) was added dropwise with stirring at 0 ° C. After the dropping, this was slowly warmed to room temperature naturally. Stirring overnight at room temperature resulted in a milky white slurry. The dimethyl (9-fluorenyl) silane chloride (2.72 g, 10.51 mmol) synthesized above was added to this under stirring at 0 ° C., and the mixture was stirred at room temperature for 2 hours. The reaction liquid became a yellow slurry. N-Methyl-2-pyrrolidine (0.1 g) was added thereto, and the mixture was stirred at room temperature for 1.5 hours. This is ether (100m
l) and saturated aqueous ammonium chloride solution (100 ml) were added, and the mixture was transferred to a separatory funnel and the organic layer was separated, washed with saturated aqueous ammonium chloride solution, water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was removed and the residue was purified by column chromatography (solvent: hexane) to give a yellow powder (1.1
0 g, yield 27%) was obtained.

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (CDCl ₃ , 90 MHz); 6.7-8.
0 (m, 12H), 4.5 (s, 1H), 3.6 (t,
1H), 2.0 (s, 6H), -0.4 (s, 6H) dimethylsilylene (2,3-dimethyl-1-indenyl) (9-
Synthesis of fluorenyl) zirconium dichloride A Schlenk bottle of 50 ml was equipped with a dropping funnel, and was thoroughly purged with nitrogen and dried. Dimethyl (2,3-dimethyl-1-indenyl) (9-fluorenyl) silane (0.80 g, 2.18 mmol) and dehydrated ether (15 ml) synthesized above were added to this, and the mixture was stirred at −78 ° C. and n -Butyllithium in hexane (4.58 mmol) was added dropwise.
After the dropping, this was slowly warmed to room temperature naturally. When stirred at room temperature for 8 hours, the pale yellow solution became a yellow slurry through the yellow solution. Zirconium tetrachloride (0.509 g, 2.18 mmol) was added again with stirring at −78 ° C.,
After the dropping, the temperature was slowly raised to room temperature. After stirring overnight at room temperature, the reaction solution became a red slurry. Pressurize with a glass filter (G-5) to remove ether,
The residue was quickly washed with dehydrated dichloromethane (the residue was lithium chloride). The solvent of the filtrate thus obtained was removed, reslurried with dehydrated hexane (30 ml) and filtered with a glass filter (G-5) to obtain the desired metallocene as a red powder (427 mg, yield 37%).

[0293]

Reference Example 1 Preparation of catalyst solution Dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di-t-
Butyl-9-fluorenyl) zirconium dichloride (Compound a) was added in an amount of 5.8 mg, and 1.57 ml of a toluene solution of methylaluminoxane (MAO) (Al; 1.1 mol / liter) and 2.76 ml of toluene were added thereto. Thus, a catalyst solution was obtained.

Polymerization 600 ml of hexane and 1-octene-1 were placed in a stainless steel autoclave having an internal volume of 2 liters, which had been sufficiently replaced with nitrogen.
50 ml was charged and the temperature in the system was raised to 130 ° C.
Subsequently, 1 mmol of triisobutylaluminum (TIBA) and 1.0 ml of the catalyst solution prepared above (Zr
0.002 mmol) was injected with ethylene to initiate polymerization. Then, the total pressure was kept at 30 kg / cm ² -G by continuously supplying only ethylene, and polymerization was carried out at 140 ° C. for 8 minutes. After the polymerization was stopped by adding a small amount of ethanol to the system, unreacted ethylene was purged. The polymer was deposited by pouring the obtained polymer solution into a large excess of methanol. The polymer was collected by filtration and dried at 130 ° C. under reduced pressure overnight. As a result, MFR is 0.21g
/ 10 minutes, and 61.3 g of an ethylene / 1-octene copolymer having a density of 0.898 g / cm ³ was obtained. The results are shown in Table 1.

[0295]

Reference Example 2 600 ml of hexane and
Charge 1-octene 400ml and keep the system temperature at 130 ℃.
The temperature was raised to. Subsequently, 1 mmol of triisobutylaluminum and 1.0 ml of the catalyst solution prepared above (Zr
0.002 mmol) was injected with ethylene to initiate polymerization. Then, the total pressure was maintained at 30 kg / cm ² -G by continuously supplying only ethylene, and polymerization was carried out at 140 ° C. for 15 minutes. After the polymerization was stopped by adding a small amount of ethanol to the system, unreacted ethylene was purged. The polymer was deposited by pouring the obtained polymer solution into a large excess of methanol. The polymer is recovered by filtration and at 130 ° C
Dried under reduced pressure overnight. As a result, MFR is 0.47
75.7 g of an ethylene / 1-octene copolymer having a density of g / 10 minutes and a density of 0.875 g / cm ³ was obtained. The results are shown in Table 1.

[0296]

Reference Example 3 Instead of the compound a in Reference Example 1 , dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (9-fluorenyl) zirconium dichloride (Compound b) synthesized in Production Example 2 was used. Was used to prepare an ethylene / 1-octene copolymer in the same manner as in Reference Example 1 except that the polymerization time was 30 minutes. The results are shown in Table 1.

[0297]

Reference Example 4 Instead of the compound a in Reference Example 1 , dimethylsilylene (2,6-dimethyl-4,5, synthesized in Production Example 3 was used.
-Benz-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride (Compound c) was used, and ethylene 1 was prepared in the same manner as in Reference Example 1 except that the polymerization time was 15 minutes. -Octene copolymer was prepared. The results are shown in Table 1.

[0298]

Reference Example 6 Instead of the compound a in Reference Example 1 , dimethylsilylene (2,7-dimethyl-4,5, synthesized in Production Example 4 was used.
- (2-methyl - benzo) -1-indenyl) (2,7-di -t- butyl-9-fluorenyl) using zirconium dichloride (compound d), except that the polymerization time was 15 minutes as in Reference Example 1 Similarly, an ethylene / 1-octene copolymer was produced.
The results are shown in Table 1.

[0299]

Reference Example 6 Instead of the compound a in Reference Example 1 , dimethylsilylene (2-n-propyl-4-) synthesized in Production Example 5 was used.
An ethylene / 1-octene copolymer was produced in the same manner as in Reference Example 1 except that (9-phenanthryl) -1-indenyl) (9-fluorenyl) zirconium dichloride (Compound e) was used and the polymerization time was 15 minutes. did. The results are shown in Table 1.

[0300]

[Reference Example 7] Preparation of catalyst solution n-hexane 5 m was put in a glass flask sufficiently replaced with nitrogen.
1 ml, and 1 ml of a toluene solution of dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride (compound a) (as Zr 0.002 mmol) and 1 ml of a toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate (0.0 as B).
(04 mmol) was added to obtain a catalyst solution.

Polymerization 600 ml of hexane and 1-octene 1 were placed in a stainless steel autoclave having an internal volume of 2 liters, which had been sufficiently replaced with nitrogen.
50 ml was charged and the temperature in the system was raised to 130 ° C.
Subsequently, triisobutylaluminum (TIBA) 0.
Polymerization was initiated by forcing 5 mmol and the catalyst solution prepared above with ethylene. After that, the total pressure is 30 kg / c by continuously supplying only ethylene.
Polymerization was carried out at 140 ° C. for 30 minutes while maintaining m ² -G. After the polymerization was stopped by adding a small amount of ethanol to the system, unreacted ethylene was purged. The polymer was deposited by pouring the obtained polymer solution into a large excess of methanol. The polymer was collected by filtration and dried at 130 ° C. under reduced pressure overnight. As a result, MF
R is 0.51 g / 10 minutes and density is 0.892 g / c
98.8 g of an ethylene / 1-octene copolymer having m ³ and Mw / Mn of 2.0 was obtained.

[0302]

Comparative Example 1 As in Example 1, except that dimethylsilylene (1-indenyl) (9-fluorenyl) zirconium dichloride (Compound x) was used in place of the compound a, and the polymerization time was 30 minutes. Similarly ethylene-1
An octene copolymer was produced. As a result, MFR is 1
There were obtained 17.7 g of an ethylene / 1-octene copolymer having a density of 5.9 g / 10 minutes, a density of 0.920 g / cm ³ and an Mw / Mn of 2.3. The results are shown in Table 1.

[0303]

[Table 1]

[0304]

[Reference Example 8] 400 ml of purified toluene was charged into a glass reactor having an internal volume of 2 liters, which had been sufficiently purged with nitrogen, and ethylene (100 liters / hour) was passed through the reactor to obtain 800 ml / min.
It was kept at 70 ° C. for 10 minutes while stirring by rotation. Next, 4 ml of a toluene solution containing 0.80 mg of methylaluminoxane in terms of aluminum atom and 0.0008 mg of ethylene (9-fluorenyl) (2-methyl-1-indenyl) zirconium dichloride in terms of zirconium atom. Charged. After polymerization was carried out at 80 ° C. and normal pressure for 5 minutes, a small amount of isopropanol was added to terminate the polymerization. After the reaction, the reaction solution was poured into 400 ml of a dilute hydrochloric acid methanol solution, the solvent residue was removed, and the obtained polymer was dried under reduced pressure overnight. The obtained ethylene homopolymer was 7.53 g. The results are shown in Table 2.

[0305]

Reference Example 9 In place of ethylene (9-fluorenyl) (2-methyl-1-indenyl) zirconium dichloride in Reference Example 8 , dimethylsilylene (9-
Ethylene was polymerized in the same manner as in Reference Example 8 except that fluorenyl) (2-methyl-1-indenyl) zirconium dichloride was used. The obtained ethylene homopolymer was 6.00 g. The results are shown in Table 2.

[0306]

Reference Example 10 In place of ethylene (9-fluorenyl) (2-methyl-1-indenyl) zirconium dichloride in Reference Example 8 , diphenylsilylene (9-fluorenyl) (2-methyl-1-methyl) synthesized in Production Example 8 was used. Ethylene was polymerized in the same manner as in Reference Example 8 except that indenyl) zirconium dichloride was used. The obtained ethylene homopolymer was 0.7 g. The results are shown in Table 2.

[0307]

[Reference Example 11] Instead of ethylene (9-fluorenyl) (2-methyl-1-indenyl) zirconium dichloride in Reference Example 8 , dimethylsilylene (9-fluorenyl) (2-methyl-4-) synthesized in Production Example 10 was used. Reference example except that phenyl-1-indenyl) zirconium dichloride was used
Ethylene was polymerized in the same manner as 8 . The obtained ethylene homopolymer was 1.38 g. The results are shown in Table 2.

[0308]

Comparative Example 2 Instead of ethylene (9-fluorenyl) (2-methyl-1-indenyl) zirconium dichloride in Reference Example 8 , ethylene (9-fluorenyl) (1-indenyl) zirconium dichloride synthesized in Production Example 9 was used. Ethylene was polymerized in the same manner as in Reference Example 8 except that it was used. The obtained ethylene homopolymer was 0.85 g. The results are shown in Table 2.

[0309]

Comparative Example 3 Instead of ethylene (9-fluorenyl) (2-methyl-1-indenyl) zirconium dichloride in Reference Example 8 , dimethylsilylene (9- was synthesized by the method described in JP-A-5-345793. Fluorenyl)
Ethylene was polymerized in the same manner as in Reference Example 8 except that (1-indenyl) zirconium dichloride was used. The obtained ethylene homopolymer was 0.98 g. The results are shown in Table 2.

[0310]

[Table 2]

[0311]

Reference Example 12 Ethylene (9-fluorenyl) (2-methyl-1-indenyl) zirconium dichloride was added in an amount of 0.0087 milligram atom in terms of zirconium to a glass flask sufficiently replaced with nitrogen, and a toluene solution of methylaluminoxane was added thereto. A catalyst solution was obtained by adding 1.57 ml of (Al; 1.1 mol / liter) and 2.76 ml of toluene.

[0312] 850 ml of hexane and
Charge 150 ml of 1-octene and keep the system temperature at 130 ° C.
The temperature was raised to. Subsequently, 1 mmol of triisobutylaluminum and 1.0 ml of the catalyst solution prepared above (Zr
0.002 mmol) was injected with ethylene to initiate polymerization. Then, the total pressure was maintained at 30 kg / cm ² -G by continuously supplying only ethylene, and polymerization was performed at 140 ° C. for 30 minutes. After the polymerization was stopped by adding a small amount of ethanol to the system, unreacted ethylene was purged. The polymer was deposited by pouring the obtained polymer solution into a large excess of methanol. The polymer is recovered by filtration and at 130 ° C
Dried under reduced pressure overnight. As a result, 17.1 g of an ethylene / 1-octene copolymer was obtained. The results are shown in Table 3.

[0313]

Reference Example 13 In Reference Example 12 , ethylene (2-methyl
Reference Example 12 except that dimethylsilylene (2-methyl-1-indenyl) (9-fluorenyl) zirconium dichloride synthesized in Production Example 7 was used instead of -1-indenyl) (9-fluorenyl) zirconium dichloride. Similarly, ethylene and 1-octene were polymerized. The obtained ethylene / 1-octene copolymer was 15.7 g. The results are shown in Table 3.

[0314]

Reference Example 14 In Reference Example 12 , ethylene (2-methyl
Reference Example 12 except that diphenylsilylene (2-methyl-1-indenyl) (9-fluorenyl) zirconium dichloride synthesized in Production Example 8 was used in place of -1-indenyl) (9-fluorenyl) zirconium dichloride. Similarly, ethylene and 1-octene were polymerized. The obtained ethylene / 1-octene copolymer was 23.5 g.
The results are shown in Table 3.

[0315]

Reference Example 15 In Reference Example 12 , ethylene (2-methyl
-1-Indenyl) (9-fluorenyl) zirconium dichloride was used instead of dimethylsilylene (2-methyl-4-phenyl-1-indenyl) (9-fluorenyl) zirconium dichloride synthesized in Production Example 10. reference
In the same manner as in Example 12 , ethylene and 1-octene were polymerized. The ethylene / 1-octene copolymer obtained was 21.8.
It was g. The results are shown in Table 3.

[0316]

Reference Example 16 In Reference Example 12 , ethylene (2-methyl
In place of -1-indenyl) (9-fluorenyl) zirconium dichloride, ethylene (2-methyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride synthesized in Production Example 11 was used. Reference examples other than those used
In the same manner as in 12 , ethylene and 1-octene were polymerized.
The obtained ethylene / 1-octene copolymer was 12.2 g. The results are shown in Table 3.

[0317]

Reference Example 17 In Reference Example 12 , ethylene (2-methyl
Reference Example 12 except that dimethylsilylene (3-methyl-1-indenyl) (9-fluorenyl) zirconium dichloride synthesized in Production Example 12 was used instead of -1-indenyl) (9-fluorenyl) zirconium dichloride. Similarly, ethylene and 1-octene were polymerized. The obtained ethylene / 1-octene copolymer was 26.8 g.
The results are shown in Table 3.

[0318]

Reference Example 18 In Reference Example 12 , ethylene (2-methyl
Reference was made except that ethylene (2-methyl-4-phenyl-1-indenyl) (9-fluorenyl) zirconium dichloride synthesized in Production Example 13 was used in place of -1-indenyl) (9-fluorenyl) zirconium dichloride. In the same manner as in Example 12 , ethylene and 1-octene were polymerized. The obtained ethylene / 1-octene copolymer was 8.4 g.
The results are shown in Table 3.

[0319]

Reference Example 19 In Reference Example 12 , ethylene (2-methyl
In place of -1-indenyl) (9-fluorenyl) zirconium dichloride, dimethylsilylene (9-fluorenyl) (2-methyl-4-i-propyl-1-indenyl) zirconium dichloride synthesized in Preparation Example 14 was used. Sun other than
Ethylene and 1-octene were polymerized in the same manner as in Consideration 12 . The ethylene / 1-octene copolymer obtained was 13.1.
It was g. The results are shown in Table 3.

[0320]

Reference Example 20 In Reference Example 12 , ethylene (2-methyl
-1-Indenyl) (9-fluorenyl) zirconium dichloride was replaced with dimethylsilylene (2,3-dimethyl-1-indenyl) (9-fluorenyl) synthesized in Preparation Example 15.
Reference Example 12 except that zirconium dichloride was used
Ethylene and 1-octene were polymerized in the same manner as in. The obtained ethylene / 1-octene copolymer was 27.5 g. The results are shown in Table 3.

[0321]

Comparative Example 4 In Reference Example 12 , ethylene (2-methyl-1
Ethylene was polymerized in the same manner as in Reference Example 12 except that ethylene (1-indenyl) (9-fluorenyl) zirconium dichloride synthesized in Production Example 9 was used instead of -indenyl) (9-fluorenyl) zirconium dichloride. . The ethylene / 1-octene copolymer obtained was 17.
It was 7 g. The results are shown in Table 3.

[0322]

[Table 3]

[0323]

[Reference Example 21] 400 ml of purified toluene was charged into a glass reactor having an internal volume of 2 liters, which had been sufficiently purged with nitrogen, and propylene was passed at a rate of 100 liters per hour at 45 ° C while stirring at 800 rpm. Hold for 10 minutes.
Then, 2.88 mg of triisobutylaluminum in terms of aluminum was charged. further,
Methylaluminoxane is 3.5 in terms of aluminum atom
0 milligram atom and ethylene (9-fluorenyl) (2-
4 ml of a toluene solution containing 0.010 mg of zirconium atom-converted methyl-1-indenyl) zirconium dichloride was charged. After polymerizing at 50 ° C. and normal pressure for 15 minutes, add a small amount of isopropanol,
The polymerization was stopped. After the reaction, dilute hydrochloric acid in methanol 40
The reaction solution was poured into 0 ml, the solvent residue was removed, and the obtained polymer was dried under reduced pressure overnight. The obtained propylene homopolymer was 2.2 g. The results are shown in Table 4.

[0324]

Reference Example 22 Instead of ethylene (9-fluorenyl) (2-methyl-1-indenyl) zirconium dichloride in Reference Example 21 , dimethylsilylene (9-fluorenyl) (2-methyl-1-methyl) synthesized in Production Example 7 was used. Propylene was polymerized in the same manner as in Reference Example 21 except that indenyl) zirconium dichloride was used. The obtained propylene homopolymer was 3.8 g. The results are shown in Table 4.

[0325]

Reference Example 23 In place of ethylene (9-fluorenyl) (2-methyl-1-indenyl) zirconium dichloride in Reference Example 21 , diphenylsilylene (9-fluorenyl) (2-methyl-1-) synthesized in Production Example 8 was used. Propylene was polymerized in the same manner as in Reference Example 21 except that indenyl) zirconium dichloride was used. The obtained propylene homopolymer was 0.1 g. The results are shown in Table 4.

[0326]

Comparative Example 5 Instead of ethylene (9-fluorenyl) (2-methyl-1-indenyl) zirconium dichloride in Reference Example 21 , ethylene (9-fluorenyl) (1-indenyl) zirconium dichloride synthesized in Production Example 9 was used. Propylene was polymerized in the same manner as in Reference Example 21 except that it was used, but no propylene polymer was obtained. The results are shown in Table 4.

[0327]

Comparative Example 6 Instead of ethylene (9-fluorenyl) (2-methyl-1-indenyl) zirconium dichloride in Reference Example 21 , dimethylsilylene (9- was synthesized by the method described in JP-A-5-345793. Propylene was polymerized in the same manner as in Reference Example 21 except that fluorenyl) (1-indenyl) zirconium dichloride was used. The obtained propylene homopolymer was in a trace amount.
The results are shown in Table 4.

[0328]

[Table 4]

[0329]

[Reference Example 24] Preparation of solid catalyst component 50 ml of 3.0 g of silica dried at 250 ° C for 10 hours
The suspension was made into toluene and then cooled to 0 ° C. Then, a toluene solution of methylaluminoxane (Al = 1.
(29 mmol / ml) (17.8 ml) was added dropwise over 30 minutes. At this time, the temperature in the system was kept at 0 ° C. Continue to 0
The reaction was performed at 30 ° C. for 30 minutes, then the temperature was raised to 95 ° C. over 30 minutes, and the reaction was performed at that temperature for 4 hours. Then, the temperature was lowered to 60 ° C., and the supernatant was removed by the decantation method.

The solid component thus obtained was washed twice with toluene and then resuspended in 50 ml of toluene. Dimethyl silylene bis (2,6-dimethyl-
4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride in toluene solution (Z
r = 0.0233 mmol / ml) 4.9 ml at 20 ° C.
Was added dropwise over 30 minutes. Then, the temperature was raised to 80 ° C., and the reaction was performed at that temperature for 2 hours. Then, the supernatant liquid was removed, and the solid catalyst containing 2.1 mg of zirconium per 1 g was obtained by washing twice with hexane.

Preparation of Prepolymerized Catalyst 4 g of the solid catalyst obtained above was resuspended in 200 ml of hexane. To this system, 5.0 ml of a decane solution of triisobutylaluminum (1 mmol / ml) and 0.36 g of 1-hexene were added, and prepolymerization of ethylene was carried out at 35 ° C. for 2 hours to obtain 2.0 mg per 1 g of the solid catalyst. A prepolymerized catalyst containing zirconium and having 3 g of polyethylene prepolymerized was obtained.

Polymerization Into a stainless steel autoclave with an internal volume of 2 liters, which had been sufficiently replaced with nitrogen, 1 liter of dehydrated and purified hexane was charged, and the system was replaced with ethylene.

Next, the inside of the system was heated to 60 ° C., and 1.53 mmol of triisobutylaluminum, 20 ml of 1-hexene, and 0.23 mg atom in terms of zirconium atom were added to the prepolymerization catalyst prepared as described above.

After that, ethylene was introduced, and the total pressure was 8 kg /
Polymerization was initiated as cm ² -G. Then, only the mixed gas was replenished, the total pressure was kept at 8 kg / cm ² -G, and polymerization was carried out at 70 ° C. for 1.5 hours.

After the completion of polymerization, the polymer was filtered and dried at 80 ° C. overnight. As a result, 323 g of an ethylene / 1-hexene copolymer having an Mw / Mn of 1.99 was obtained.

[0336]

[Reference Example 25] Reference Example 2 except that ethylene was changed to a mixed gas of ethylene and hydrogen (hydrogen content; 0.1 mol%)
As in 4 , the intrinsic viscosity [η] was 1.29 dl / g.
Thus, 120 g of an ethylene / 1-hexene copolymer having a density of 0.948 g / cm ³ was obtained.

[0337]

[Reference Example 26] Reference except that 1-hexene was not added
In the same manner as in Example 24 , 202 g of an ethylene polymer having Mw / Mn of 2.20 was obtained.

[0338]

[Reference Example 27] Example except that ethylene was changed to a mixed gas of ethylene and hydrogen (hydrogen content; 0.46 mol%)
24 , the intrinsic viscosity [η] is 1.59 dl / g
Thus, 108 g of an ethylene polymer having a density of 0.973 g / cm ³ was obtained.

[Brief description of drawings]

FIG. 1 is an explanatory view showing a process for preparing an olefin polymerization catalyst according to the present invention.

FIG. 2 is an explanatory view showing a step of preparing an olefin polymerization catalyst used in a second method for producing an olefin polymer according to the present invention.

─────────────────────────────────────────────────── ─── Continuation of front page (31) Priority claim number Japanese Patent Application No. 7-300324 (32) Priority date November 17, 1995 (November 17, 1995) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 7-344258 (32) Priority date December 28, 1995 (December 28, 1995) (33) Country of priority claim Japan (JP) (31) Priority claim number Japanese Patent Application No. 7-344259 (32) Priority date December 28, 1995 (December 28, 1995) (33) Priority claiming country Japan (JP) (56) Reference JP-A-8-165310 (JP, A) JP-A-5-239082 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 4/64-4/658 CA (STN)

Claims (9)

(57) [Claims] 1. (A-1) a transition metal compound represented by the following general formula (1), (B) an organoaluminum oxy compound (B-1), and / or (B-2) a transition metal compound A catalyst for olefin polymerization characterized by comprising a compound which reacts with (A-1) to form an ion pair, and optionally (C) an organoaluminum compound; (In the formula, M is titanium, zirconium, or hafnium, R ¹ may be the same or different from each other, is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and R ¹ is At least two adjacent groups of the groups shown are, together with the carbon atoms to which they are attached,
Forming an aromatic ring or an aliphatic ring [in this case, R
^The ring formed by ¹ has a total of 4 to 20 carbon atoms including the carbon atom to which R ¹ is bound], R ² may be the same or different from each other, and are a hydrogen atom, a halogen atom and a carbon atom. An alkyl group having 1 to 10 atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, and 8 to 40 carbon atoms An arylalkenyl group, an alkylaryl group having 7 to 40 carbon atoms,
It is a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, R ¹ and R ² may be the same or different, and R ³ is a hydrogen atom, a halogen atom or a carbon atom. Number is 1 to 1
An alkyl group of 0, an aryl group having 6 to 20 carbon atoms,
Alkenyl group having 2 to 10 carbon atoms, 7 carbon atoms
˜40 arylalkyl group, C 8-40 arylalkenyl group, C 7-40 alkylaryl group, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group or phosphorus-containing group. R ⁴ is a methyl group, X ¹ and X ² may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or 1 carbon atom. To 20 halogenated hydrocarbon groups, oxygen-containing groups, sulfur-containing groups or nitrogen-containing groups, Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, or 2 having 1 to 20 carbon atoms. Divalent halogenated hydrocarbon group, divalent silicon-containing group, divalent germanium-containing group, divalent tin-containing group, -O-, -CO-, -S-, -SO-, -S.
^{_{O 2 -, - NR 5 -}} , - P (R 5) -, - P (O) (R
⁵⁾ -, - BR ⁵ - or -AlR ⁵ - [proviso R ⁵ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms] Is). 2. A particulate carrier, (A-1) a transition metal compound represented by the general formula (1) according to claim 1, (B) an organoaluminum oxy compound (B-1), and / or Alternatively, (B-2) a catalyst for olefin polymerization, which comprises a compound that reacts with the transition metal compound (A-1) to form an ion pair, and optionally (C) an organoaluminum compound. 3. A fine particle carrier, (A-1) a transition metal compound represented by the general formula (1) according to claim 1, (B) an organoaluminum oxy compound (B-1), and / or Or (B-2) a solid catalyst component carrying a compound that reacts with the transition metal compound (A-1) to form an ion pair, and (C) an organoaluminum compound, if necessary, with an olefin. An olefin polymerization catalyst, which is formed by prepolymerization. 4. An olefin polymer obtained by homopolymerizing olefins or copolymerizing two or more kinds of olefins in the presence of the olefin polymerization catalyst according to any one of claims 1 to 3. Manufacturing method. 5. The method for producing an olefin polymer according to claim 4 , wherein the olefin to be homopolymerized is ethylene, and the two or more olefins are ethylene and an α-olefin having 3 to 20 carbon atoms. 6. The method for producing an olefin polymer according to claim 4 , wherein the olefin to be homopolymerized is propylene, and the two or more olefins are propylene and an α-olefin other than propylene. 7. An olefin polymer produced by the method for producing an olefin polymer according to claim 4 . 8. An ethylene polymer produced by the method for producing an olefin polymer according to claim 5 . 9. A propylene-based polymer produced by the method for producing an olefin polymer according to claim 6 .