JPH10101689A - New metallocene compound and polymerization of olefin or diene using the compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound consisting of a specific metallocene compound containing a cyclopentadienyl group and a fluorenyl group, capable of giving syndiotactic polymers and useful as a catalyst for the polymerization of α-olefins or dienes, etc. SOLUTION: This is a new metallocene compound expressed by formula I [R<1> and R<2> are each H, an alkyl or an aryl; R<3> is an alkyl or a siliconcontaining alkyl; R<4> to R<8> are each H, an alkyl, an aryl or a silicon- containing alkyl; M is a metal of the group 4 of the Periodic Table; Y is a divalent carbon or silicon; X is a halogen, an alkyl or an anionic ligand; (m) is an integer of 1-3]. The compound has a Cs-symmetric structure capable of synthesizing syndiotactic α-olefin polymers and is useful as a catalyst for the polymerization of olefins and dienes, etc. The compound is obtained by reacting a cyclopentadiene of formula II with a fluorene derivative of formula III (L is an alkali metal) and subsequently reacting the reaction product with a halide, etc., of a metal of the group 4 of the Periodic Table.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel metallocene compound and a method for polymerizing an olefin or a diene using the same. More specifically, the present invention relates to a metallocene compound having a specific Cs symmetric structure and a method for polymerizing an olefin or a diene using the metallocene compound.

[0002]

2. Description of the Related Art As homogeneous catalysts for olefin polymerization, so-called metallocene compounds are well known. A method of polymerizing an olefin using a normal metallocene compound, particularly a method of stereoregularly polymerizing an α-olefin,
Since reported by W. Kaminsky et al. (Angew. Che
m., 97, 507 (1985)) Many improvements have been made. As an example of these improvements, metallocene compounds having a C ₂ symmetric structure in which some of the hydrogens of cyclopentadienyl in the ligand portion of the metallocene compound have been substituted with alkyl have been reported. Attempts to improve the stereoregularity of chic polymers are common (Yamazaki et al., Chemistry Letters, 1
853 (1989), JP-A-4-268307). Many similar attempts have been reported to improve the stereoregularity of an olefin polymer by using a metallocene compound having an ethylenebisindenyl derivative having a C ₂ symmetric structure as a ligand (for example, Organometall).
ics, 13, 954 (1994), J. Organmet.Chem., 288, 63 (1
985) etc.).

On the other hand, JA Ewen found that a metallocene compound obtained by crosslinking cyclopentadienyl and fluorenyl having a Cs symmetric structure with dimethylmethane polymerizes an α-olefin with syndiotactic stereoregularity. (J. Am. Chem. Soc. 110 , 6255 (1988)). As a modification of this metallocene, instead of fluorenyl, 2,7-
Attempts have been made to further control the stereoregularity by introducing di-tert-butylfluorenyl (JP-A-4-69394).

[0004]

However, this C
A metallocene compound which introduces a substituent into cyclopentadienyl of a metallocene compound having an s symmetric structure and has a Cs symmetric structure to synthesize a syndiotactic α-olefin polymer has not been found.

Accordingly, an object of the present invention is to provide a metallocene compound and a method for polymerizing an olefin or a diene using the metallocene compound as a polymerization catalyst.

[0006]

Means for Solving the Problems The present inventors have solved the above-mentioned problems, and have developed a novel metallocene compound having a Cs symmetric structure for synthesizing a syndiotactic α-olefin polymer, and a polymerization method using the same. The present invention has been completed by diligent studies.

That is, the novel metallocene compound of the present invention is represented by the following formula [1].

[0008]

Embedded image (Wherein R ¹ and R ² are selected from hydrogen, alkyl and aryl, R ³ is alkyl or silicon-containing alkyl,
R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are selected from hydrogen, alkyl, aryl, and silicon-containing alkyl;
A metal selected from the group, Y is divalent carbon or silicon, X is a halogen, alkyl or anionic ligand, which may be the same or different, and m is an integer of 1-3 . Further, the present invention is a method for polymerizing an olefin or a diene, comprising polymerizing an olefin or a diene using the metaceron compound represented by the above formula [1].

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, R ¹ and R ² in the above formula [1] are selected from hydrogen, alkyl and aryl.
Specific examples of alkyl include methyl, ethyl or isopropyl or tert-butyl, cyclohexyl, and mentyl, and specific examples of aryl include phenyl, tolyl, and naphthyl. Also, Y
Is divalent carbon or silicon; R ¹ and R ² are bonded to Y; for example, methylene, dimethylmethylene, diisopropylmethylene, methyl tert-butylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, diphenylmethylene, dinaphthylmethylene Or dimethylsilylene, diisopropylsilylene, methyl te
It comprises rt-butylsilylene, dicyclohexylsilylene, methylcyclohexylsilylene, diphenylsilylene, dinaphthylsilylene and the like.

In the present invention, R ³ in the formula [1] is alkyl or silicon-containing alkyl, and specific examples of alkyl include methyl, ethyl or isopropyl or tert-butyl. Specific examples include trimethylsilyl, dimethylethylsilyl and cyclohexyldimethylsilyl. R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are selected from hydrogen, alkyl, aryl and silicon-containing alkyl, and specific examples of alkyl include methyl, ethyl, propyl or isopropyl, 2-methylpropyl or te
rt-butyl or cyclohexyl, norbornyl, menthyl and the like. Specific examples of aryl include phenyl, tolyl, naphthyl and the like. Also,
Specific examples of the silicon-containing alkyl include trimethylsilyl, dimethylethylsilyl and the like.

In the present invention, M in the formula [1] is a metal selected from Group 4 of the periodic table, and examples of M include titanium, zirconium and hafnium. X is a halogen, alkyl or anionic ligand, which may be the same or different. Specific examples of halogen include fluorine, chlorine, bromine and iodine, specific examples of alkyl include methyl, ethyl, butyl or isopropyl or tert-butyl, and specific examples of an anionic ligand include Organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine or diphenylmethylphosphine, or alkoxy such as methoxy or tert-butoxy or phenoxy, or tetrahydrofuran (THF) diethyl ether, dioxane, 1,2-dimethoxyethane and the like Ethers.

In the present invention, a ligand which is a precursor of the metallocene compound represented by the general formula [1], for example, 9-dimethyl (3,4-dimethylcyclopentadienyl) methyl-
Fluorene, 9-dimethyl (2,3,4,5-tetramethylcyclopentadienyl) methyl-fluorene, 9-
Diphenyl (3,4-dimethylcyclopentadienyl)
Methyl-fluorene, 9-diphenyl (2,3,4,5
-Tetramethylcyclopentadienyl) methyl-fluorene, 9-dimethyl (3,4-dimethylcyclopentadienyl) silyl-fluorene, 9-dimethyl ((2,
3,4,5-tetramethylcyclopentadienyl) silyl-fluorene, 9-diphenyl (3,4-dimethylcyclopentadienyl) silyl-fluorene, 9-diphenyl (2,3,4,5-tetramethylcyclo (Pentadienyl) silyl-fluon is represented by the formula [2]

[0013]

Embedded image (In the formula, R ^{1 to} R ⁸ and Y are the same as in the formula [1], and L is an alkali metal.) Or the formula [3]

[0014]

Embedded image (Wherein R ^{1 to} R ⁸ and Y are the same as those in the formula [1], L is an alkali metal, and Z is a halogen).

As the alkali metal in the above reaction, lithium, sodium or potassium is particularly preferably used, and as the halogen, fluorine, chlorine, bromine and iodine are mentioned. Also, the above reaction
Aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, decalin or aromatic hydrocarbons such as benzene, toluene and xylene or tetrahydrofuran (THF), diethyl ether, dioxane, 1,2-
In an organic solvent of an ether such as dimethoxyethane, -80
The reaction can be performed in a temperature range of from ° C to the boiling point of the solvent.

The ligand which is a precursor of the metallocene compound of the formula [1] obtained by the reaction of the formula [2] or [3] may be an alkali metal such as lithium, sodium, potassium or the like, or sodium hydride, Alkali metal hydride such as potassium or methyl lithium, butyl lithium,
In an organic alkali metal such as phenyllithium and an organic solvent such as the above-mentioned aliphatic hydrocarbon, aromatic hydrocarbon or ether, a reaction temperature is brought into contact with the solvent in a range of -80 ° C to the boiling point of the solvent to form a dialkali metal salt. Dialkali metal salts and halides of metals selected from Group 4 of the periodic table, specifically trivalent or tetravalent titanium fluorides, chlorides,
Bromides or iodides or their complexes with ethers such as THF, diethyl ether, dioxane or 1,2-dimethoxyethane, or zirconium tetrafluoride, chloride, bromide and iodide or their ether complexes, or hafnium Of tetrafluoride, chloride,
The metallocene compound of the formula [1] can be synthesized by reacting with bromide and iodide or an ether complex thereof. The reaction between the dialkali metal salt and the metal halide of Group 4 metal of the periodic table is preferably carried out by an equimolar reaction, and can be carried out in an organic solvent at a reaction temperature of -80 ° C to the boiling point of the solvent. Examples of the organic solvent used include aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane and decalin, or aromatic hydrocarbons such as benzene, toluene and xylene, or ethers such as THF, diethyl ether, dioxane and dimethoxyethane. Halogenated hydrocarbons such as dichloromethane and chloroform are preferably used.

Specific examples of the above-mentioned metallocene compound in the present invention are shown below. However, the metallocene compound is not particularly limited as long as it is a metallocene compound having a Cs symmetric structure as described above.

Dimethylmethylene (3,4-dimethylcyclopentadienyl) fluorenyl zirconium dichloride, dimethylmethylene (3,4-dimethylcyclopentadienyl) (2,7-dimethylfluorenyl) zirconium dichloride, dimethylmethylene (3,4-dimethylcyclopentadienyl) (2,7-diisopropylfluorenyl) zirconium dichloride, dimethylmethylene (3,4-dimethylcyclopentadienyl)
(2,7-di-tert-butylfluorenyl) zirconium dichloride, dimethylmethylene (3,4-dimethylcyclopentadienyl) (2,7-dicyclohexylfluorenyl) zirconium dichloride, dimethylmethylene (3,4- Dimethylcyclopentadienyl)
(2,7-diphenylfluorenyl) zirconium dichloride, dimethylmethylene (3,4-dimethylcyclopentadienyl) [2,7-di (trimethylsilyl) fluorenyl] zirconium dichloride, dimethylmethylene (3,4-dimethylcyclopenta Dienyl) (2,
3,6,7-tetramethylfluorenyl) zirconium dichloride, dimethylmethylene (3,4-dimethylcyclopentadienyl) [2,7-dimethyl-3,6-di (trimethylsilyl) fluorenyl] zirconium dichloride, dimethylmethylene (2,3,4,5-tetramethylcyclopentadienyl) fluorenylzirconium dichloride, dimethylmethylene (2,3,4,5-
Tetramethylcyclopentadienyl) (2,7-dimethylfluorenyl) zirconium dichloride, dimethylmethylene (2,3,4,5-tetramethylcyclopentadienyl) (2,7-diisopropylfluorenyl) zirconium dichloride , Dimethylmethylene (2,3,
4,5-tetramethylcyclopentadienyl) (2,7
-Di-tert-butylfluorenyl) zirconium chloride, dimethylmethylene (2,3,4,5-tetramethylcyclopentadienyl) (2,7-dicyclohexylfluorenyl) zirconium dichloride, dimethylmethylene (2,3 4,5-tetramethylcyclopentadienyl) (2,7-diphenylfluorenyl) zirconium chloride, dimethylmethylene (2,3,4
5-tetramethylcyclopentadienyl) [2,7-di (trimethylsilyl) fluorenyl] zirconium dichloride, dimethylmethylene (3,4-dimethylcyclopentadienyl) (2,3,6,7-tetramethylfluorenyl) ) Zirconium dichloride, dimethylmethylene (2,3,4,5-tetramethylcyclopentadienyl) [2,7-dimethyl-3,6-di (trimethylsilyl) fluorenyl] zirconium dichloride or diphenylmethylene (3,4-dimethyl) Cyclopentadienyl) fluorenylzirconium dichloride, diphenylmethylene (3,4-dimethylcyclopentadienyl) (2,7-dimethylfluorenyl) zirconium dichloride, diphenylmethylene (3,4-dimethylcyclopentadienyl) (2,7-diisopropyl fluorenyl) zirconium dichloride, diphenylmethylene (3,4-dimethyl cyclopentadienyl) (2,7
-Di-tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3,4-dimethylcyclopentadienyl) (2,7-dicyclohexylfluorenyl) zirconium dichloride, diphenylmethylene (3,4-dimethylcyclopentadienyl) ) (2,
7-diphenylfluorenyl) zirconium dichloride, diphenylmethylene (3,4-dimethylcyclopentadienyl) [2,7-di (trimethylsilyl) fluorenyl] zirconium dichloride, diphenylmethylene (3,4-dimethylcyclopentadienyl) (2,
3,6,7-tetramethylfluorenyl) zirconium dichloride, diphenylmethylene (3,4-dimethylcyclopentadienyl) [2,7-dimethyl-3,6-
Di (trimethylsilyl) fluorenyl] zirconium dichloride, diphenylmethylene (2,3,4,5-tetramethylcyclopentadienyl) fluorenylzirconium dichloride, diphenylmethylene (2,3
4,5-tetramethylcyclopentadienyl) (2,7
-Dimethylfluorenyl) zirconium dichloride,
Diphenylmethylene (2,3,4,5-tetramethylcyclopentadienyl) (2,7-diisopropylfluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetramethylcyclopentadienyl) ( 2,7-di-tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (2,7
3,4,5-tetramethylcyclopentadienyl)
(2,7-dicyclohexylfluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5
-Tetramethylsilopentadienyl) (2,7-diphenylfluorenyl) zirconium dichloride, dimethylmethylene (2,3,4,5-tetramethylcyclopentaenyl) [2,7-di (trimethylsilyl) fluorenyl] zirconium Dichloride, diphenylmethylene (3,4-dimethylcyclopentadienyl) (2,3
6,7-tetramethylfluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetramethylcyclopentadienyl) [2,7-dimethyl-
3,6-di (trimethylsilyl) fluorenyl] zirconium dichloride, dimethylsilylene (3,4-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (3,4-dimethylcyclopentadienyl) (2,7- Dimethylfluorenyl) zirconium dichloride, dimethylsilylene (3,4-dimethylcyclopentadienyl) (2,7-
Diisopropylfluorenyl) zirconium dichloride, dimethylsilylene (3,4-dimethylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, dimethylsilylene (3,4-dimethylcyclopentadienyl) ) (2,7-
Dicyclohexylfluorenyl) zirconium dichloride, dimethylsilylene (3,4-dimethylcyclopentadienyl) (2,7-diphenylfluorenyl) zirconium dichloride, dimethylsilylene (3,4-dimethylcyclopentadienyl) [2 7-di (trimethylsilyl) fluorenyl] zirconium dichloride,
Dimethylsilylene (3,4-dimethylcyclopentadienyl) (2,3,6,7-tetramethylfluorenyl)
Zirconium dichloride, dimethylsilylene (3,4
-Dimethylcyclopentadienyl) [2,7-dimethyl-3,6-di (trimethylsilyl) fluorenyl] zirconium dichloride, dimethylsilylene (2,3
4,5-tetramethylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (2,7-dimethylfluorenyl) zirconium dichloride, dimethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (2,7-diisopropylfluorenyl) zirconium dichloride, dimethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (2 7-di-tert-butylfluorenyl) zirconium dichloride, dimethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (2,7-dicyclohexylfluorenyl) zirconium dichloride, dimethylsilylene (2, 3,4
5-tetramethylcyclopentadienyl) (2,7-diphenylfluorenyl) zirconium dichloride, dimethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) [2,7-di (trimethylsilyl) fluorenyl Zirconium dichloride, dimethylsilylene (3,4-dimethylcyclopentadienyl) (2,
3,6,7-tetramethylfluorenyl) zirconium dichloride, dimethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) [2,7-dimethyl-3,6-di (trimethylsilyl) fluorenyl] Zirconium dichloride or diphenylsilylene (3,
4-dimethylcyclopentadienyl) fluorenylzirconium dichloride, diphenylsilylene (3,4-
Dimethylcyclopentadienyl) (2,7-dimethylfluorenyl) zirconium dichloride, diphenylsilylene (3,4-dimethylcyclopentadienyl)
(2,7-diisopropylfluorenyl) zirconium dichloride, diphenylsilylene (3,4-dimethylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, diphenylsilylene (3,4- Dimethylcyclopentadienyl)
(2,7-dicyclohexylfluorenyl) zirconium dichloride, diphenylsilylene (3,4-dimethylcyclopentadienyl) (2,7-diphenylfluorenyl) zirconium dichloride, diphenylsilylene (3,4-dimethylcyclopentadienyl) Enil) [2,7
-Di (trimethylsilyl) fluorenyl] zirconium dichloride, diphenylsilylene (3,4-dimethylcyclopentadienyl) (2,3,6,7-tetramethylfluorenyl) zirconium dichloride, diphenylsilylene (3,4-dimethylcyclo Pentadienyl)
[2,7-dimethyl-3,6-ditrimethylsilyl) fluorenyl] zirconium dichloride, diphenylsilylene (2,3,4,5-tetramethylcyclopentadienyl) fluorenyl zirconium dichloride, diphenylsilylene (2,3, 4,5-tetramethylcyclopentadienyl) (2,7-dimethylfluorenyl) zirconium dichloride, diphenylsilylene (2,
3,4,5-tetramethylcyclopentadienyl)
(2,7-diisopropylfluorenyl) zirconium dichloride, diphenylsilylene (2,3,4,5-
Tetramethylcyclopentadienyl) (2,7-di-t
tert-butylfluorenyl) zirconium dichloride, diphenylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (2,7-dicyclohexylfluorenyl) zirconium dichloride, diphenylsilylene (2,3,4, 5-tetramethylcyclopentadienyl) (2,7-diphenylfluorenyl) zirconium dichloride, dimethylsilylene (2,3,4,
5-tetramethylcyclopentadienyl) [2,7-di (trimethylsilyl) fluorenyl] zirconium dichloride, diphenylsilylene (3,4-dimethylcyclopentadienyl) (2,3,6,7-tetramethylfluorenyl ) Zirconium dichloride, diphenylmethylene (2,3,4,5-tetramethylcyclopentadienyl) [2,7-dimethyl-3,6-di (trimethylylsilyl) fluorenyl] zirconium dichloride, or Dimethylmethylene (3,4-dimethylcyclopentadienyl) fluorenyl zirconium dimethyl, such as the above metallocene compound in which chloride is converted to methyl, or dimethylmethylene (3,4-
The above metallocene compound in which chloride is converted to trimethylphosphine such as dimethylcyclopentadienyl) fluorenylzirconium bis (trimethylphosphine), or such as dimethylmethylene (3,4-dimethylcyclopentadienyl) fluorenyldimethoxyzirconium And the above metallocene compound in which THF is coordinated, such as dimethylmethylene (3,4-dimethylcyclopentadienyl) fluorenylzirconium dichloride / THF. Further, the above metallocene compounds in which zirconium of the above metallocene compounds is made of titanium or hafnium are also exemplified.

In the present invention, the olefin polymerized by using the metallocene compound is preferably an α-olefin having 2 to 20 carbon atoms, particularly preferably 2 to 20 carbon atoms.
To 10 to 10 α-olefins. Specific examples include ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, vinylcyclohexane, styrene and the like. Further, examples include cyclic olefins such as norbornene, methylnobornene, tetracyclododecene, and methyltetracyclododecene, and silicon-containing olefins such as allyltrimethylsilane and vinyltrimethylsilane. As the diene, a diene having 4 to 20 carbon atoms such as butadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, and dicyclopentadiene is preferable. Further, these olefins and dienes may be polymerized alone or in combination of two or more.

In the present invention, the aluminoxane used in combination with the olefin polymerization using the above metallocene compound is represented by the following formula [4]

[0021]

Embedded image Or equation [5]

[0022]

Embedded image (In these formulas, R ⁹ may be the same or different and is alkyl having 1 to 6 carbons, aryl having 6 to 18 carbons, or hydrogen, and p is an integer of 2 to 50, preferably 10 to 35. ) Is used.

The ratio of the aluminoxane represented by the above formulas [4] and [5] to the metallocene compound is from 1 to 10,000 as aluminum / metallocene.
It is generally a molar ratio. When using the above aluminoxane, it is also possible to use an organic aluminum compound having 1 to 20 carbon atoms in combination, and in this case, good performance can be obtained with a relatively small amount of aluminoxane. Examples of such organoaluminum compounds include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-sec-butylaluminum; dimethylaluminum chloride, diethylaluminum chloride, Examples thereof include propylaluminum chloride, diisopropylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, and di-sec-butylaluminumchloride.

In the present invention, when the metallocene compound is used to polymerize an olefin, the metallocene compound used in combination is converted into a cationic compound, and an ionic compound and an organoaluminum compound which generate stable counter anion species are As the ionic compound, as a specific example,
Triphenylcarbenium tetrakis (pentafluorophenyl) borate, ferrocenium tetrakis (pentafluorophenyl) borate, N, N-dimethylammonium tetrakis (pentafluorophenyl) borate, tri-n-butylammonium tetrakis (pentafluorophenyl) borate And carbenium borane such as triethylammonium tetrakis (phenyl) borate and tri-n-butylammonium tetra (phenyl) borate, metalabran, ammonium borane and the like.
It is exemplified in Japanese Patent Publication No. 502036. The ratio of the ionic compound to the metallocene compound is preferably 0.1 to 10 times the molar ratio of the ionic compound to the metallocene compound. As the organic aluminum compound, an organic aluminum compound having preferably 1 to 20 carbon atoms is preferably used in combination. For example, trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n
-Butyl aluminum, triisobutyl aluminum,
Examples thereof include tri-n-butylaluminum, dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisopropylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, and di-sec-butylaluminum chloride. The ratio of the organoaluminum compound to the metallocene compound is preferably 1 to 10,000 times as organoaluminum compound / metallocene compound.

In the present invention, the polymerization can be carried out by a bulk polymerization method or a gas phase polymerization method in addition to the ordinary solvent polymerization method, and the polymerization temperature is usually -100 to 200 ° C, preferably -100 ° C.
20-100 ° C. The polymerization pressure is not particularly limited, and is preferably normal pressure to 50 kg / cm ² .

[0026]

The present invention will be further described below with reference to examples, but the present invention is not limited to these examples.

In the present invention, the molecular weight distribution index (P
DI) and the stereoregularity (rrrr) of the polymer were measured by the following methods.

Molecular weight distribution index (PDI) : PDI = Mw
/ Mn: Number average molecular weight (Mn) and weight average molecular weight (Mw) were measured by gel permission chromatography under the following conditions.

Measuring device: Waters 150CVplu
s, column: Shodex GPC AD-80 M / S (exclusion limit: 2 × 10 ⁷ ), mobile phase: trichlorobenzene, column temperature: 135 ° C., measurement flow rate: 1.0 ml / min,
Sample concentration: 0.2 wt / vol%, injector capacity: 0.200 ml, detector: differential refractometer and viscometer, standard sample: stereoregularity (rrrr) of polystyrene standard polymer : measured under the following conditions. Pentad fraction measuring device showing stereoregularity based on polymer side chain methyl group by ¹³ C / NMR spectrum: JEOL JNM-EX270, solvent: trichlorobenzene / deuterated benzene mixed solution, measuring temperature: 125
° C, sample concentration: 100 mg / ml Example 1 [Synthesis of dimethylmethylene (3,4-dimethylcyclopentadienyl) fluorenylzirconium dichloride] (1) 3,4,6,6-tetramethylfulvene under ice cooling With 1,2-dimethylcyclopentadiene (5.7
2 g, 61 mmol) in THF (100 ml) was added to a solution of methyllithium in diethyl ether (44 ml, 6 ml).
4 mmol) was added dropwise under a nitrogen atmosphere, and 6
Stirred for hours. After removing the solvent from the reaction mixture under reduced pressure, the residue was washed with pentane and dried to give a colorless solid. Further, THF (1
50 ml) THF in which 23 ml of acetone is dissolved
(40 ml) The solution was added dropwise under a nitrogen atmosphere, stirred for 5 hours, and a saturated aqueous solution of ammonium chloride (60 ml) was added. After drying the separated organic phase over magnesium sulfate,
After filtration, the solvent was removed from the filtrate under reduced pressure to obtain 3.81 g of yellow crystals. The analytical values are shown below.

¹ H-NMR (90 MHz, CDCl ₃ ,
6.18 (s, 2H), 2.09
(S, 6H), 1.99 (s, 6H) (2) 9-dimethyl (3,4-dimethylcyclopentadienyl) methyl-fluorene Fluorene (4.72 g, 28.4 mmol) under ice cooling
Was added dropwise to a THF (100 ml) solution of methyl lithium in a diethyl ether solution (20.5 ml, 28.4 ml) under a nitrogen atmosphere, and the mixture was further stirred at room temperature for 6 hours. −
At 78 ° C., 3,4,6,6
-Tetramethylfulvene (3.81 g, 28.4 mmol
A solution of l) in THF (40 ml) was added dropwise under a nitrogen atmosphere, the mixture was stirred at room temperature for 20 hours, and a saturated aqueous ammonium chloride solution (40 ml) was added. The separated red organic phase was dried over magnesium sulfate, filtered, and the solvent was removed from the filtrate under reduced pressure to obtain an orange solid. This solid was recrystallized from chloroform / methanol to obtain 4.50 g of colorless crystals. The analytical values are shown below.

¹ H-NMR (90 MHz, CDCl ₃ ,
7.72 (d, 2H), 7.35 (d
d, 2H), 7.21 (dd, 2H), 7.17 (d.
2H), 5.86 (s, 1H), 4.08 (s, 1
H), 3.07 (s, 2H), 2.00 (s, 3H),
1.89 (s, 3H), 1.62 (s, 6H) (3) Dimethylmethylene (3,4-dimethylcyclopentadienyl) fluorenyl zirconium dichloride 9-dimethyl (3,4- Dimethylcyclopentadienyl) methyl-fluorene (2.41 g, 8 mmol)
l) A solution of methyllithium in diethyl ether (11.7 ml, 16.4 mmol) in THF (80 ml) solution
Was added dropwise under a nitrogen atmosphere, and the mixture was further stirred at room temperature for 16 hours. Then, this reaction solution was added to a THF (100 ml) solution of zirconium tetrachloride 2THF complex (3.02 g, 8 mmol) cooled to -78 ° C under a nitrogen atmosphere, stirred at -78 ° C for 8 hours, and then stirred at room temperature for 24 hours. did. The solvent was removed from this reaction solution under reduced pressure to obtain an orange solid. The solid was extracted with dichloromethane, filtered through celite, the solvent was removed from the filtrate under reduced pressure, washed with pentane and toluene, and recrystallized from dichloromethane to obtain 0.73 g of orange crystals. The analytical values are shown below.

¹ NMR (90 MHz, CDCl ₃ , TM
8, 17 (d, 2H), 7.80 (d, 2)
H), 7.53 (dd, 2H), 7.24 (dd, 2
H), 5.39 (s, 2H), 2.33 (s, 6H),
1.91 (s, 6H) Elemental analysis: Calculated C: 59.98, H: 4.82, Analytical value C: 60.36, H: 4.92 Example 2 [Polymerization of propylene] Sufficient nitrogen substitution 1 liter of dry toluene was charged into the resulting 2 liter autoclave, and after purging with propylene, 24 mmol of methylaluminoxane in terms of aluminum (manufactured by Toso-Akzo Co., Ltd.) was charged. After propylene was charged to 3 kg / cm ² -G at 20 ° C., a toluene solution of 5.6 mg (0.012 mmol) of the orange solid obtained in Example 1 was propylene-pressurized, and the pressure was kept constant at 20 ° C. for 1 hour. Polymerized. After the polymerization, propylene was degassed, the solvent was removed, and the residue was washed with heptane and dried under vacuum at 80 ° C. for 6 hours. The obtained polymer was 12 g, Mw = 73000, P
DI = 2.3 and rrrr = 0.45.

Example 3 [Polymerization of propylene] Propylene was prepared in the same manner as in Example 2 except that 0.012 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate and 8 mmol of triethylaluminum were used instead of methylaluminoxane. Polymerization was performed. The obtained polymer was 10 g, Mw = 82200, PDI = 2.0, r
rrr = 0.44.

Example 4 [Synthesis of diphenylsilylene (3,4-dimethylcyclopentadienyl) fluorenylzirconium dichloride] (1) 9-chlorodiphenylsilyl-fluorene Fluorene (9.97 g, 60 mmol) under ice-cooling A solution of n-butyllithium in hexane (38 ml, 62.7 mmol) was added dropwise to a solution of the above in diethyl ether (150 ml) under a nitrogen atmosphere, followed by stirring at room temperature for 4 hours. The solvent was removed from the reaction solution under reduced pressure, and washed with hexane to obtain a pale yellow solid. This solid was dissolved in diethyl ether (100 ml) and dichlorodiphenylsilane (22.8 g, 90 mmol) in ether (100 m
1) The mixture was added dropwise to the solution at room temperature at room temperature, and the mixture was stirred overnight. Thereafter, the mixture was filtered, and the filtrate was concentrated and cooled to obtain 18.1 g of pale yellow crystals. The analytical values are shown below.

¹ H-NMR (90 MHz, CDCl ₃ ,
7.74 (d, 2H), 7.31
(S, 10H), 7.42-7.13 (m, 6H),
4.55 (s, 1H) (2) 9-Diphenyl (3,4-dimethylcyclopentadienyl) silyl-fluorene THF (100 ml) of 9-chlorodiphenylsilyl-fluorene (5.75 g, 15 mmol) at room temperature.
1,2-Dimethylcyclopentadienyllithium (1.65 ml, 16.5 mmol) was added to the solution under a nitrogen atmosphere, and the mixture was stirred overnight. A saturated aqueous ammonium chloride solution (40 ml) was added, and the separated organic phase was dried over magnesium sulfate, filtered, and the solvent was removed from the filtrate under reduced pressure to obtain a yellow solid. The solid was recrystallized from hot hexane to give 3.90 g of colorless crystals. The analytical values are shown below.

¹ H-NMR (90 MHz, CDCl ₃ ,
7.59 (d, 2H), 7.14
(S, 10H), 7.30-7.11 (m, 6H),
6.12 (s, 2H), 4.54 (s, 1H), 3.9
0 (br, 1H), 1.61 (s, 6H) (3) diphenylsilylene (3,4-dimethylcyclopentadienyl) fluorenyl zirconium dichloride 9-diphenyl (3,4-dimethylcyclohexane) under ice-cooling (Pentadienyl) silyl-fluorene (2.86 g, 6.5
mmol) in THF (80 ml) and methyllithium in diethyl ether (13 ml, 13.3 mmol).
1) was added dropwise under a nitrogen atmosphere, and the mixture was further stirred at room temperature for 16 hours. Then, the reaction solution was cooled to −78 under a nitrogen atmosphere.
Zirconium tetrachloride 2THF complex (2.45 g, 6.5 mmol) cooled to THF (120 m
l) The mixture was added to the solution, and the mixture was stirred at -78 ° C for 8 hours and then at room temperature for 24 hours. The solvent was removed from this reaction solution under reduced pressure to obtain an orange solid. The solid was extracted with dichloromethane, filtered through celite, the solvent was removed from the filtrate under reduced pressure, washed with pentane and hexane, and recrystallized from dichloromethane / hexane to obtain 0.57 g of orange crystals. . The analytical values are shown below.

¹ H-NMR (90 MHz, CDCl ₃ ,
8, 14 (d, 2H), 7.68-
7.24 (m, 14H), 6.82 (dd, 2H),
5.57 (s, 2H), 2.14 (s, 6H) Example 5 [Polymerization of propylene] As in Example 2, 1 liter of dry toluene was charged into a 2 liter autoclave sufficiently purged with nitrogen. , Then after propylene substitution,
24 mmol of methylaluminoxane in terms of aluminum (manufactured by Toso-Aguso Co., Ltd.) was charged. 3K at 20 ° C
g / cm ² -G of propylene, and then 7.2 mg (0.012 mm) of the orange solid obtained in Example 4.
ol) in toluene with propylene,
Polymerization was carried out at 0 ° C. for 1 hour. After polymerization, propylene is degassed,
After removing the solvent and washing with heptane, 80 ° C. under vacuum,
Dried for 6 hours. The polymer obtained was 16 g, M
w = 98000, PDI = 2.6, rrrr = 0.43
Met.

[0038]

The novel metallocene compound of the present invention can produce a syndiotactic stereoregular polyolefin by using it as a polymerization catalyst for olefins, and is extremely valuable industrially.

[Brief description of the drawings]

FIG. 1 is a ¹ H-NMR spectrum of dimethylmethylene (3,4-dimethylcyclopentadienyl) fluorenylzirconium dichloride obtained in Example 1.

Claims (7)

[Claims] (1) Formula 1 (Wherein R ¹ and R ² are selected from hydrogen, alkyl and aryl, R ³ is alkyl or silicon-containing alkyl,
R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are selected from hydrogen, alkyl, aryl, and silicon-containing alkyl;
A metal selected from the group, Y is divalent carbon or silicon, X is a halogen, alkyl or anionic ligand, which may be the same or different, and m is an integer of 1-3 . ). 2. R ¹ , R ² and R ³ are methyl, R ⁴ , R
^5. The metallocene compound according to claim 1, wherein ⁵ , R ⁶ , R ⁷ and R ⁸ are hydrogen, M is zirconium, Y is carbon, X is chlorine, and m is 2. 3. R ¹ and R ² are phenyl, R ³ is methyl,
^{R 4, R 5, R 6} , R 7 and R ⁸ are hydrogen, M is zirconium, Y is silicon, X is chlorine, metallocene compound according to claim 1 m is 2. 4. A method for polymerizing an olefin or a diene, comprising polymerizing an olefin or a diene using the metallocene compound according to claim 1. 5. The method according to claim 4, wherein the metatheron compound according to any one of claims 1 to 3 and an aluminoxane are used in combination. 6. A combination use of the metaceron compound according to any one of claims 1 to 3, an ionic compound which converts the compound into a cationic compound to generate a stable counter anion species, and an organoaluminum compound. The method according to claim 4. 7. The method according to claim 4, wherein the olefin is an α-olefin having 2 to 20 carbon atoms.